CN106669383B - The processing method of the process tail gas containing NOx - Google Patents
The processing method of the process tail gas containing NOx Download PDFInfo
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- CN106669383B CN106669383B CN201510740290.8A CN201510740290A CN106669383B CN 106669383 B CN106669383 B CN 106669383B CN 201510740290 A CN201510740290 A CN 201510740290A CN 106669383 B CN106669383 B CN 106669383B
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- 238000000034 method Methods 0.000 title claims abstract description 122
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 101
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 60
- 230000003647 oxidation Effects 0.000 claims abstract description 47
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 41
- 239000004202 carbamide Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000012141 concentrate Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 93
- 230000001590 oxidative effect Effects 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 210000002700 urine Anatomy 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000013589 supplement Substances 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- -1 pharmacy Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YOWAEZWWQFSEJD-UHFFFAOYSA-N quinoxalin-2-amine Chemical compound C1=CC=CC2=NC(N)=CN=C21 YOWAEZWWQFSEJD-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002351 wastewater Substances 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—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
- B01D53/74—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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (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 processing methods of process tail gas containing NOx, including following content: (1) process tail gas containing high concentrate NOx being introduced stair oxidation device and carry out oxidation processes；(2) process tail gas after stair oxidation and the absorbing liquid from primary cycle tank are introduced into rotating packed bed reactor respectively, in rotating packed bed reactor, process tail gas and absorbing liquid hybrid reaction, part NOx is absorbed in process tail gas, and absorbing liquid returns to primary cycle tank and is recycled；(3) treated residual exhaust is absorbed through step (2) introduce secondary oxidation device carry out oxidation processes, absorbing liquid in secondary cycle tank is divided into branch 1 and branch 2 after secondary cycle pumps, tail gas and branch 1 after secondary oxidation introduce efficient absorption tower, tail gas is handled through absorbing liquid absorption, absorbing liquid returns to secondary cycle tank, branch 2 enters absorbing liquid hybrid reaction in primary cycle tank, with primary cycle tank, the qualified discharge after demisting of tail gas after processing.This method urea absorption effect is good, and high concentrate NOx technology tail gas after processing meets qualified discharge requirement, efficiently and without " three wastes " discharges.
Description
Technical field
The present invention relates to technical field of air pollution control, and in particular to a kind of processing method of the process tail gas containing NOx, it is special
It Shi Yongyu not NOx concentration is high and content easily fluctuates process tail gas processing.
Background technique
Nitric acid is a kind of important industrial chemicals, can be used for manufacturing chemical fertilizer, explosive, dyestuff, pharmacy, synthetic fibers, inorganic
The chemical products such as salt.In nitric acid production and it is related to using nitric acid as raw material or the change process of producing product produced by nitroso reaction
In, generally have a generation of NOx process tail gas, such as nitrogen fertilizer plant, explosive wastewater factory, catalyst preparation factory, Organic Chemical Plant are certain
Production process.The characteristics of such tail gas is that NOx concentration is high and content is influenced vulnerable to raw material and operating condition, fluctuation range
Very big, the concentration of NOx is generally 1000~50000mg/m in tail gas3, some up to 80000mg/m3More than, and thermal power plant
NOx content is typically only 400~1500mg/m in different boiler emission flue gases3.Therefore, these features of process tail gas reach it
Mark is administered and causes many troubles, it is more difficult to be administered." discharge standard of air pollutants " (GB16297-1996) requires NOx
Concentration of emission limit value is 240 mg/m3, " nitric acid industry pollutant emission standard " (GB26131-2010) requires existing enterprise certainly
From on April 1st, 2013, enterprise is created from March 1st, 2011, and emission limits of nitrogen oxides is 300 mg/ in atmosphere pollution
m3, especially regional limit value is 200 mg/m3, just to the NOx process tail gas discharge of enterprise, more stringent requirements are proposed for this, it is necessary to adopt
Effective method is taken to handle.
Currently used NOx tail gas disposal technique can generally be divided into two class of dry and wet.Dry method includes absorption method, ammonia
Selective catalytic reduction (SCR), ammine selective noncatalytic reduction (SNCR) etc..Wet process includes water absorption method, lye absorption
Method, oxidative absorption method, reducing absorping method and Absorption via Chemical Complexation etc..Although the processing technique means of NOx are more, it is directed to temperature
The process tail gas that low and NOx concentration is high, content fluctuation range is big, many processing methods are restricted to a certain extent.As inhaled
Attached method adsorbent capacity compared with small, dosage is big, and for high concentrate NOx processing when, exist absorption fuel factor the problems such as；SCR and
SNCR technology needs higher temperature window (generally respectively 200~400 DEG C and 800~1250 DEG C or so of SCR and SNCR), and
For the NOx nitric acid tail gas of high concentration, Yi Bodong, throwing ammonia amount is difficult to control, causes the problems such as energy consumption is high, operating cost is big；Tradition
Absorption process (uses NaOH, Na2CO3Deng) then difficult by liquid phase by-product, it is also easy to produce the limitation of secondary pollution problems.
Urea absorptive method is to utilize urea as absorbent, and NOx generates N after processing2And CO2, can direct emission, master
The reaction wanted are as follows:
NO +NO2 +(NH2)2CO =2N2 +CO2 +2H2O
The advantages of method is that raw material and operating cost are low, and do not generate secondary pollution.But the technology due to being reacted or
Limitation in terms of mass transfer leads to conventional suction technique it is difficult to ensure that atm number, high concentrate NOx technology tail gas once reach after processing
Mark discharge.Current many study uses urea cooperation additive technology progress denitration process, the removal effect of Lai Tigao NOx, though
NOx removal effect so is improved, but due to the complicated components of additive, so the processing of liquid phase by-product or waste liquid must be cooperated
Processing unit increases the complexity and investment operating cost of exhaust gas processing device.CN1986033A discloses a kind of with containing
Chlorine Strong oxdiative and the wet method combined process for desulfurization and denitration for enhancing urea, the technique NOx removal rate is higher, but has useless absorption simultaneously
Liquid generates, and needs to reprocess.The patents such as CN101352647A, CN1986032A equally face the problem of liquid waste processing.
Rotary packed bed conduct absorption equipment is used in CN1830526A to improve mass transfer, but other acidity are added in first order absorption
Or alkaline matter promotes assimilation effect, and by-product nitric acid or nitrite is caused to generate.
Summary of the invention
, NOx concentration low for prior art treatment temperature be high and the easy fluctuating process tail gas of content on deficiency, the present invention mentions
A kind of processing method of process tail gas containing NOx is gone out, this method urea absorption effect is good, high concentrate NOx technology tail after processing
Gas meets qualified discharge requirement, efficiently and without " three wastes " discharges.
The processing method of the process tail gas containing NOx of the invention, including following content:
(1) process tail gas containing high concentrate NOx is introduced into stair oxidation device and carries out oxidation processes；
(2) process tail gas after stair oxidation and the absorbing liquid from primary cycle tank are introduced respectively high-gravity rotating bed
Reactor, in rotating packed bed reactor, process tail gas and absorbing liquid hybrid reaction, part NOx is inhaled in process tail gas
It receives, absorbing liquid returns to primary cycle tank and is recycled；
(3) treated residual exhaust is absorbed through step (2) introduce secondary oxidation device carry out oxidation processes, secondary cycle tank
Interior absorbing liquid is divided into branch 1 and branch 2 after secondary cycle pumps, and the tail gas and branch 1 after secondary oxidation introduce efficient absorption
Tower, tail gas are handled through absorbing liquid absorption, and absorbing liquid returns to secondary cycle tank, and branch 2 enters primary cycle tank, with primary cycle tank
Interior absorbing liquid hybrid reaction, treated tail gas qualified discharge after demisting；Wherein between primary cycle tank and secondary cycle tank
Pans are set, the liquid level of absorbing liquid in primary cycle tank and secondary cycle tank is adjusted by pans.
In the method for the present invention, stair oxidation device described in step (1) can be tube shaped or independent tank body or tower-shaped formula,
Oxidant used is O2Or O3, provided by oxygen or ozone generator；Wherein the additional amount of oxidant according to NO concentration in tail gas into
Row adjustment, oxidant is 0.5:1~5:1 with the molar ratio of NO in terms of O element, preferably 1:1~3.5:1.
In the method for the present invention, oxidation processes condition described in step (1) are as follows: 10~200 DEG C of temperature, preferably 20~100 DEG C,
It stops oxidization time 1~100 second, preferably 5~30 seconds.
In the method for the present invention, various types in the prior art are can be used in step (2) described rotating packed bed reactor
It is high-gravity rotating bed, high-gravity rotating bed scale and form can be determined according to gas operating condition and operating condition, it specifically can be with
Including parallel type, reverse-flow and cross-current type, reverse-flow hypergravity filler revolving bed is preferentially selected.
In the method for the present invention, step (2) the high-gravity rotating bed outfit frequency control motor can carry out bed revolving speed
It adjusts, 50~5000rpm of adjustable range, preferably 200~3000rpm.
In the method for the present invention, absorbing liquid described in step (2) is the aqueous solution of urea of mass concentration 5% ~ 30%.
In the method for the present invention, process tail gas described in step (2) and absorbing liquid hybrid reaction condition are as follows: 5~40 DEG C of temperature,
It is preferred that 15~25 DEG C, 5~50L/m of liquid-gas ratio3, preferably 10~25L/m3, reaction mass residence time in reactor is 1~500
Second, preferably 5~100 seconds.
In the method for the present invention, secondary oxidation device described in step (3) can be tube shaped or independent tank body or tower-shaped formula,
Oxidant used is O2Or O3, provided by oxygen or ozone generator；Wherein the additional amount of oxidant according to NO concentration in tail gas into
Row adjustment, oxidant is 0.5:1~5:1 with the molar ratio of NO in terms of O element, preferably 1:1~4:1.
In the method for the present invention, secondary oxidative treatments condition described in step (3) are as follows: 10~200 DEG C of temperature, preferably 20~
It 100 DEG C, stops oxidization time 1~100 second, preferably 10~40 seconds.
In the method for the present invention, efficient absorption tower described in step (3) can be bubble tower, spray column, packed tower and eddy flow
One of plate tower, preferred filler tower.
In the method for the present invention, absorbing liquid described in step (3) is acid urea liquid, and mass concentration is 5%~30%, pH value
It is 1~6, preferably 2~5.
In the method for the present invention, efficient absorption tower described in step (3) absorbs treatment conditions are as follows: 50~90 DEG C of temperature are absorbed,
It is preferred that 65~80 DEG C, liquid-gas ratio is 2~30L/m3, preferably 5~20L/m3。
In the method for the present invention, the primary cycle tank and secondary cycle tank are equipped with urea filler, to supplement urea, protect
Card system general 1~10 percentage point of the decline of absorbing liquid mass concentration, preferably declines 2~5 percentages to the removal effect of NOx
When point, addition urea to required concentration；The absorbing liquid of primary cycle tank and secondary cycle tank can repeat to follow by supplementing urea
Ring uses.
In the method for the present invention, 2 volume flow of branch described in step (3) is secondary cycle total pump flow (branch 1 and branch
2 flow summations) 1/10~2/3, preferably 1/5~1/2；Wherein be preferably provided in the primary cycle tank one piece of overflow every
Plate, it is long 1/6~1/2, preferably 1/5~1/3 of tank, weir divider that weir divider, which is fixed on circulation pot bottom away from tank outlet distance,
Height is the 1/2~5/6, preferably 2/3~4/5 of circulating tank height, and branch 2 is sufficiently mixed with primary cycle pot liquid and contacts,
It is exported, is entered through primary cycle pump high-gravity rotating bed by weir divider overflow to circulating tank；Branch 2 in primary cycle tank
Be preferably provided with liquid distributor below inlet side, branch 2 after liquid distributor homogenizing distribution with liquid in primary cycle tank
Body comes into full contact with and reacts；The aqueous solution of urea for containing 5% ~ 30% in the pans, is followed by pans to adjust level-one
The liquid level of absorbing liquid is the 1/2~5/6 of tank height, preferably 2/3~4/5 in ring tank and secondary cycle tank；The pans are equipped with
Urea filler, to supplement urea, the absorbing liquid of pans can be used by supplementing urea with repetitive cycling, primary cycle tank
It can also be supplemented by pans with the absorbing liquid concentration of secondary cycle tank.
In the method for the present invention, demister is arranged in the efficient absorption tower gaseous phase outlet pipeline, and treated tail gas is through demisting
It is discharged after processing, the demister is cylindrical tube, and inside is arranged cylindric sieve, prevents purified gas entrainment.
The processing method of the process tail gas of the present invention containing NOx is suitable for the various technique tails that NOx content is stable or fluctuates
Gas denitration process, the preferred NOx concentration of processing gas are 1000~50000mg/m3Process tail gas.
The method of the present invention compared with prior art, has the advantages that
(1) the method for the present invention improves the oxidizability of NOx first, and NOx is made to form the larger NO of solubility2And N2O3, then by low temperature
Urea liquid absorbs to form HNO2And HNO3And and urea reaction；Cooperate rotating packed bed reactor simultaneously, greatly improves
Mass transfer rate coefficient, compared to traditional absorption tower, 1~3 order of magnitude is can be improved in mass tranfer coefficient, greatly improves NOx
Assimilation effect, the process can be such that 60%~85% NOx is absorbed by urea liquid.
(2) second level of the invention is absorbed is handled using efficient absorption tower, and corresponding secondary cycle tank is high-temperature acidic
Urea liquid, the tail gas through secondary oxidative treatments is mixed with urea liquid during being somebody's turn to do, the HNO that NOx is formed2And HNO3With CO
(NH2)2And the NH that part urea primary water solution obtains2COONH4(aminoquinoxaline) is reacted, and the CO that can be discharged is generated2
And N2, can the NOx process tail gas of basic guarantee after processing meet national emission standard.
(3) present invention also adds liquid-liquid reactions area while two-stage solution-air absorbing reaction section removing NOx is arranged,
2 branches of absorbing liquid point in secondary cycle tank, absorbing liquid of the branch 1 as efficient absorption tower, branch 2 remove primary cycle tank, prop up
NH in road 22COONH4With CO (NH2)2HNO in the solution is deposited after low temperature absorption NOx in equal substances and primary cycle tank2And HNO3
Fully reacting is reduced and is reduced because of HNO2The side reaction of the by-products NO gases such as decomposition.It can make in liquid phase in this manner easily
The HNO of decomposition2Reaction is abundant, so that the NOx by solution absorption but not yet restored completely be made sufficiently to be reduced to N2, reduce or keep away
The NOx desorption outlet release in system absorbing liquid is exempted from.
(4) present invention significantly increases NOx removal effect, shortens process flow, and small investment takes up little area, operation at
This is low, and NOx generates N after processing2And CO2, absorbing liquid, which passes through supplement urea, to be recycled, and the method for the present invention can be economical high
Effect carries out processing up to standard to NOx process tail gas, does not have secondary pollution to environment, discharges without " three wastes ".
Detailed description of the invention
Fig. 1 is a kind of processing method process flow chart of process tail gas containing NOx of the invention.
Wherein, 1- stair oxidation device 2- rotating packed bed reactor 3- secondary oxidation device 4- efficient absorption tower 5- mono-
Grade circulating tank 6- pans 7- secondary cycle tank 8- primary cycle pump 9- three-level circulating pump 10- secondary cycle pump 11- is super
The high-gravity rotating bed motor 14- primary cycle tank liquid of the high-gravity rotating bed bed 13- of gravity revolving bed liquid distributor 12-
Body distributor 15- primary cycle tank weir divider 16- demister.
Specific embodiment
It elaborates below in conjunction with Detailed description of the invention and embodiment to the processing method of the process tail gas of the invention containing NOx,
But it is not intended to limit the present invention.
The method of the present invention is realized in this way: process tail gas containing NOx initially enters the progress of stair oxidation device 1
Oxidation processes, gas enters rotating packed bed reactor 2 after processing；In rotating packed bed reactor 2, primary cycle pump
The absorbing liquid that 8 conveyings come is after the homogenizing distribution of high-gravity rotating bed liquid distributor 11 under the effect of high-gravity rotating bed bed 12
Efficient absorption NOx gas；Treated that tail gas enters secondary oxidation device 3 for rotating packed bed reactor 2, and tail gas enters after oxidation
Efficient absorption tower 4；In efficient absorption tower 4, the NOx in tail gas is handled by the absorbing liquid absorption that 10 conveying of secondary cycle pump comes；
Secondary cycle pumps 10 entrances and connect with secondary cycle tank 7, and outlet is connect with efficient absorption tower 4 and primary cycle tank 5 respectively, goes one
Grade 5 solution of circulating tank enters tank body after the homogenizing distribution of primary cycle tank liquid distributor 14, is homogenized in the liquid and tank of distribution
Solution comes into full contact with and reacts, and exports through 15 overflow of primary cycle tank weir divider to circulating tank, by 8 conveying of primary cycle pump；
Primary cycle pumps 8 entrances and connect with primary cycle tank 5, and outlet is connect with rotating packed bed reactor 2 and pans 6 respectively,
Respectively rotating packed bed reactor 2 provides absorbing liquid and guarantees 5 liquid level of primary cycle tank；Pans 6 are recycled by three-level
Pump 9 supplements absorbing liquid to secondary cycle tank 7；The gaseous phase outlet of efficient absorption tower 4 is connect with demister 16, the liquid under demisting condensation
Secondary cycle tank 7 is mutually returned to, through demisting treated exhaust emissions.
Hypergravity filler revolving bed selects reverse-flow filler revolving bed in following embodiment, and two-level absorption tower selects filler
Tower；Stair oxidation device and secondary oxidation device are all made of tube shaped；It is being long 1/4 of tank away from tank outlet distance in primary cycle tank
Place sets height as the weir divider of tank high 4/5, is equipped with liquid distributor in primary cycle tank below 2 inlet side of branch.
Embodiment 1
Tolerance Q=5000Nm3/ h, NOx concentration 8000mg/m3, wherein NO concentration is 5000mg/m3Process tail gas it is first
It is introduced into stair oxidation device, stair oxidation device uses O3For oxidant, O3Adding amount is 8m3/ h, oxidization time 10 seconds.Through level-one
Tail gas enters rotating packed bed reactor after oxidation processes, and the absorbing liquid that rotating packed bed reactor uses is mass concentration
20% urea liquid, treatment conditions are as follows: 15 DEG C of temperature, revolving bed revolving speed 800rpm, 10 L/ m of liquid-gas ratio3, handled through this grade
NOx removal rate afterwards is up to 70~80%.Secondary oxidation device, secondary oxidation device are introduced through supergravity reactor treated tail gas
Using O3Oxidation processes, O are for oxidant3Adding amount is 4m3/ h, oxidization time 15 seconds.Tail gas enters after secondary oxidative treatments
Efficient absorption tower, absorbing liquid used are mass concentration 20%, the acid urea liquid that pH is 3, treatment conditions are as follows: temperature 70 C, liquid
Gas ratio is 7 L/m3, tail gas is discharged after demisting after processing.Absorbing liquid in secondary cycle tank enters level-one through secondary cycle pump
The volume flow of circulating tank is secondary cycle total pump flow 1/4, and absorbing liquid is after the homogenizing distribution of primary cycle tank liquid distributor
It comes into full contact with and reacts into tank body and with solution in tank.The total removal efficiency of process tail gas NOx after processing is determined 90% or more
Phase supplements urea into absorbing liquid, and (when absorbing liquid mass concentration is lower than 15%, supplement concentration is to 20%), system stable operation
After 400h, still ensure that process tail gas after processing meets national emission standard, entire treatment process is discharged without " three wastes ".
Embodiment 2
To tolerance Q=7000Nm3/ h, NOx concentration 12000mg/m3, wherein NO concentration is 7000mg/m3Process tail gas
It is handled.Process tail gas initially enters stair oxidation device, and stair oxidation device uses O2For oxidant, O2Adding amount is 23m3/ h,
Oxidization time 20 seconds.Tail gas enters rotating packed bed reactor after stair oxidation is handled, and rotating packed bed reactor is adopted
Absorbing liquid is the urea liquid of mass concentration 25%, treatment conditions are as follows: 20 DEG C of temperature, revolving bed revolving speed 2000rpm, liquid gas
Than 15 L/ m3, through this grade treated NOx removal rate up to 75%~85%.It is introduced through supergravity reactor treated tail gas
Secondary oxidation device, secondary oxidation device use O2Oxidation processes, O are for oxidant2Adding amount is 10m3/ h, oxidization time 35 seconds.Through
Tail gas enters efficient absorption tower after secondary oxidative treatments, and absorbing liquid used is mass concentration 25%, and the acid urea that pH is 2.5 is molten
Liquid, treatment conditions are as follows: 65 DEG C of temperature, liquid-gas ratio is 9 L/m3, tail gas is discharged after demisting after processing.Suction in secondary cycle tank
Receiving the volume flow that liquid enters primary cycle tank through secondary cycle pump is secondary cycle total pump flow 2/5, and absorbing liquid is followed through level-one
Enter tank body after the homogenizing distribution of ring tank liquid distributor and comes into full contact with and react with solution in tank.Process tail gas after processing
The total removal efficiency of NOx supplements urea into absorbing liquid 92% or more, periodically and (when absorbing liquid mass concentration is lower than 18%, supplements dense
Degree after system stable operation 300h, still ensures that process tail gas after processing meets national emission standard to 25%), entire to locate
Reason process is discharged without " three wastes ".
Embodiment 3
Tolerance Q=2000Nm3/ h, NOx concentration 15000mg/m3, wherein NO concentration is 11000mg/m3Process tail gas
It is handled.Process tail gas initially enters stair oxidation device, and stair oxidation device uses O2For oxidant, O2Adding amount is 15m3/ h,
Oxidization time 22 seconds.Tail gas enters rotating packed bed reactor after stair oxidation is handled, and rotating packed bed reactor is adopted
Absorbing liquid is the urea liquid of mass concentration 22%, treatment conditions are as follows: 25 DEG C of temperature, revolving bed revolving speed 2300rpm, liquid gas
Than 20 L/ m3, through this grade treated NOx removal rate up to 65%~80%.It is introduced through supergravity reactor treated tail gas
Secondary oxidation device, secondary oxidation device use O2Oxidation processes, O are for oxidant2Adding amount is 6m3/ h, oxidization time 30 seconds.Through
Tail gas enters efficient absorption tower after secondary oxidative treatments, and absorbing liquid used is mass concentration 22%, and the acid urea that pH is 3.5 is molten
Liquid, treatment conditions are as follows: temperature 70 C, liquid-gas ratio are 10 L/m3, tail gas is discharged after demisting after processing.In secondary cycle tank
The volume flow that absorbing liquid enters primary cycle tank through secondary cycle pump is secondary cycle total pump flow 3/10, and absorbing liquid is through level-one
Enter tank body after the homogenizing distribution of circulating tank liquid distributor and comes into full contact with and react with solution in tank.Technique tail after processing
The total removal efficiency of gas NOx supplements urea into absorbing liquid 95% or more, periodically and (when absorbing liquid mass concentration is lower than 18%, supplements
Concentration after system stable operation 450h, still ensures that process tail gas after processing meets national emission standard, entirely to 22%)
Treatment process is discharged without " three wastes ".
Comparative example 1
Same as Example 1, difference does not set absorbing liquid pipeloop between level-one, secondary cycle tank and pans,
Reaction process and treatment effect comparison are as follows:
After handling 40 h, tail gas can be realized qualified discharge, level-one in embodiment 1 after embodiment 1 and the processing of comparative example 1
Storage tank urea concentration is down to 15% by 20%, and secondary storage tank urea concentration is down to 17% by 20%；Level-one storage tank urea is dense in comparative example 1
Degree is down to 16% by 20%, and secondary storage tank urea concentration is down to 18% by 20%.Hereafter, each circulating tank urea of regular replenishment, makes it
Absorbing liquid urea quality concentration maintains 20% or so, and after handling 320 h, NOx concentration is more than in the final emission of comparative example 1
350mg/m3, can not achieve qualified discharge, after circulation fluid is by supplement urea in embodiment 1, remained to after 400 h of stable operation
Guarantee that tail gas after processing meets national emission standard.
Claims (15)
1. a kind of processing method of process tail gas containing NOx, it is characterised in that including following content: (1) by the work containing high concentrate NOx
Skill tail gas introduces stair oxidation device and carries out oxidation processes；(2) by the process tail gas after stair oxidation and from primary cycle tank
Absorbing liquid introduces rotating packed bed reactor respectively, and in rotating packed bed reactor, process tail gas is mixed with absorbing liquid
It reacts, part NOx is absorbed in process tail gas, and absorbing liquid returns to primary cycle tank and is recycled；(3) at through step (2) absorption
Residual exhaust after reason introduces secondary oxidation device and carries out oxidation processes, and the absorbing liquid in secondary cycle tank is divided after secondary cycle pumps
For branch 1 and branch 2, tail gas and branch 1 after secondary oxidation introduce efficient absorption tower, and tail gas is handled through absorbing liquid absorption, inhale
It receives liquid and returns to secondary cycle tank, branch 2 enters absorbing liquid hybrid reaction in primary cycle tank, with primary cycle tank, after processing
Tail gas after demisting qualified discharge；Pans wherein are set between primary cycle tank and secondary cycle tank, by pans come
Adjust the liquid level of absorbing liquid in primary cycle tank and secondary cycle tank；Absorbing liquid described in step (2) is mass concentration 5% ~ 30%
Aqueous solution of urea；Process tail gas described in step (2) and absorbing liquid hybrid reaction condition are as follows: 5~40 DEG C of temperature, liquid-gas ratio 5
~50L/m3, reaction mass residence time in reactor is 1~500 second；Absorbing liquid described in step (3) is that acid urea is molten
Liquid, mass concentration are 5%~30%, and pH value is 1~6；Efficient absorption tower described in step (3) absorbs treatment conditions are as follows: absorbs temperature
50~90 DEG C of degree, liquid-gas ratio are 2~30L/m3。
2. according to the method for claim 1, it is characterised in that: stair oxidation device described in step (1) be tube shaped or
One of independent tank body or tower-shaped formula；Oxidant used is O2Or O3, provided by oxygen or ozone generator, oxidant is with O member
The molar ratio of element meter and NO are 0.5:1~5:1.
3. according to the method for claim 1, it is characterised in that: oxidation processes condition described in step (1) are as follows: temperature 10~
It 200 DEG C, stops oxidization time 1~100 second.
4. according to the method for claim 1, it is characterised in that: step (2) rotating packed bed reactor is cocurrent
One of formula, reverse-flow and cross-current type.
5. according to the method for claim 1, it is characterised in that: step (2) the high-gravity rotating bed outfit frequency control
Motor can be adjusted bed revolving speed, 50~5000rpm of adjustable range.
6. according to the method for claim 1, it is characterised in that: secondary oxidation device described in step (3) be tube shaped or
Independent tank body or tower-shaped formula, oxidant used are O2Or O3, provided by oxygen or ozone generator；The wherein additional amount of oxidant
It with the molar ratio of NO is 0.5:1~5:1 in terms of O element.
7. according to the method for claim 1, it is characterised in that: secondary oxidative treatments condition described in step (3) are as follows: temperature
It 10~200 DEG C, stops oxidization time 1~100 second.
8. according to the method for claim 1, it is characterised in that: efficient absorption tower described in step (3) is bubble tower, spray
One of tower, packed tower and rotating stream tray scrubber.
9. according to the method for claim 1, it is characterised in that: 2 volume flow of branch described in step (3) is secondary cycle
The 1/10~2/3 of total pump flow.
10. according to the method for claim 1, it is characterised in that: one piece of weir divider is set in the primary cycle tank,
It is long 1/6~1/2 of tank that weir divider, which is fixed on circulation pot bottom away from tank outlet distance, and weir divider height is circulating tank height
1/2~5/6.
11. according to the method for claim 1, it is characterised in that: the branch 2 in primary cycle tank described in step (3) enters
The lower section of mouth side is equipped with liquid distributor.
12. according to the method for claim 1, it is characterised in that: contain 5% ~ 30% urine in pans described in step (3)
Plain aqueous solution, adjusted by pans the liquid level of absorbing liquid in primary cycle tank and secondary cycle tank tank height 1/2~
5/6。
13. according to the method for claim 1, it is characterised in that: demisting is arranged in the efficient absorption tower gaseous phase outlet pipeline
Device, treated, and tail gas is discharged after demisting is handled, and the demister is cylindrical tube, and cylindric sieve is arranged in inside.
14. being applied to the various works that NOx content is stable or fluctuates according to method described in claim 1 ~ 13 any claim
Skill tail gas denitration process.
15. according to the method for claim 1, it is characterised in that: the process tail gas concentration of the high concentrate NOx is
1000~50000mg/m3。
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| CN103394279A (en) * | 2013-08-15 | 2013-11-20 | 北京化工大学 | System device and method for deeply removing nitric oxide in industrial tail gas |
| CN104338425A (en) * | 2013-08-07 | 2015-02-11 | 北京阳光欣禾科技有限公司 | Technological method for wet-process flue gas denitration |
| CN104826463A (en) * | 2014-02-10 | 2015-08-12 | 中国石油化工股份有限公司 | Process and apparatus for producing sodium hydrosulfide from acidic gas |
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| CN104338425A (en) * | 2013-08-07 | 2015-02-11 | 北京阳光欣禾科技有限公司 | Technological method for wet-process flue gas denitration |
| CN103394279A (en) * | 2013-08-15 | 2013-11-20 | 北京化工大学 | System device and method for deeply removing nitric oxide in industrial tail gas |
| CN104826463A (en) * | 2014-02-10 | 2015-08-12 | 中国石油化工股份有限公司 | Process and apparatus for producing sodium hydrosulfide from acidic gas |
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