CN106669390B - A kind of denitration process method of the process tail gas containing NOx - Google Patents

A kind of denitration process method of the process tail gas containing NOx Download PDF

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CN106669390B
CN106669390B CN201510740292.7A CN201510740292A CN106669390B CN 106669390 B CN106669390 B CN 106669390B CN 201510740292 A CN201510740292 A CN 201510740292A CN 106669390 B CN106669390 B CN 106669390B
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branch
tank
tail gas
absorbing liquid
liquid
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CN106669390A (en
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张雁玲
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B01D—SEPARATION
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    • 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
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
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    • 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
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • 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
    • 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
    • B01D53/79—Injecting reactants
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2221/00—Applications of separation devices
    • B01D2221/14—Separation devices for workshops, car or semiconductor industry, e.g. for separating chips and other machining residues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2251/00—Reactants
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    • B01D2251/206—Ammonium compounds
    • B01D2251/2067—Urea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
    • B01D2252/2053—Other nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a kind of denitration process 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, residual exhaust introduces secondary oxidation device and carries out oxidation processes, the absorbing liquid of reactor is divided into branch 1 and branch 2 out, branch 1 is recycled back to primary cycle tank, branch 2 enters secondary cycle tank, with absorbing liquid hybrid reaction in secondary cycle tank, the absorbing liquid after reaction is divided into branch 1 ' and branch 2 ' after secondary cycle pumps；(3) branch 1 ' and the tail gas after secondary oxidation introduce efficient absorption tower respectively, tail gas is handled through absorbing liquid absorption, absorbing liquid returns to secondary cycle tank and is recycled, branch 2 ' enters primary cycle tank, with be recycled after absorbing liquid hybrid reaction in primary cycle tank, the qualified discharge after demisting of tail gas after processing.This method good absorption effect, high concentrate NOx technology tail gas after processing meet qualified discharge requirement, efficiently and without " three wastes " discharge.

Description

A kind of denitration process method of the process tail gas containing NOx
Technical field
The present invention relates to technical field of air pollution control, and in particular to a kind of denitration process side of the process tail gas containing NOx Method, the process tail gas processing that and content high especially suitable for NOx concentration easily fluctuates.
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
In view of the deficiencies of the prior art, the invention proposes a kind of denitration process method of process tail gas containing NOx, this method Good absorption effect, high concentrate NOx technology tail gas after processing meet qualified discharge requirement, efficiently and without " three wastes " discharge.
The denitration process 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, residual exhaust introduces secondary oxidation device and carries out oxidation processes, and the absorbing liquid of reactor is divided into branch 1 and branch 2, branch 1 out It is recycled back to primary cycle tank, branch 2 enters absorbing liquid hybrid reaction in secondary cycle tank, with secondary cycle tank, the suction after reaction It receives liquid and is divided into branch 1 ' and branch 2 ' after secondary cycle pumps；
(3) branch 1 ' and the tail gas after secondary oxidation introduce efficient absorption tower respectively, and tail gas is handled through absorbing liquid absorption, inhale It receives liquid and returns to the recycling of secondary cycle tank, branch 2 ' enters absorbing liquid hybrid reaction in primary cycle tank, with primary cycle tank After be recycled, the qualified discharge after demisting of tail gas after processing.
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) rotating packed bed reactor is equipped with frequency control motor, can turn to bed Speed is adjusted, 50~5000rpm of adjustable range, preferably 200~3000rpm.
In the method for the present invention, the absorbing liquid of primary cycle tank described in step (2) is the urea that mass concentration is 5% ~ 30% Aqueous solution.
In the method for the present invention, the absorbing liquid hybrid reaction condition of process tail gas described in step (2) and primary cycle tank are as follows: 5~40 DEG C of temperature, preferably 15~25 DEG C, 5~50L/m of liquid-gas ratio3, preferably 10~25L/m3, reaction mass stops in reactor Time is 1~500 second, preferably 5~100 seconds.
In the method for the present invention, secondary oxidation device described in step (2) 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 (2) 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, the absorbing liquid in step (2) the secondary cycle tank is the aciduria of mass concentration 5%~30% Plain aqueous solution, pH value are 1~6, preferably 2~5.
In the method for the present invention, 2 volume flow of branch described in step (2) be revolving bed absorbing liquid total flow (branch 1 with 2 flow summation of branch) 1/10~2/3, preferably 1/5~1/2；2 ' the volume flow of branch is secondary cycle total pump flow 1/10~2/3, preferably the 1/5~1/2 of (branch 1 ' and 2 ' flow summation of branch)；It is preferred that the flow phase of branch 2 and branch 2 ' Match, i.e., adjusts the flow of branch 2 and branch 2 ' by the level chain of firsts and seconds circulating tank.
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.
Absorption treatment conditions in the method for the present invention, in efficient absorption tower described in step (3) are as follows: absorb temperature 50~90 DEG C, preferably 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, urea is added to required concentration, continues cycling through use.
In the method for the present invention, one piece of weir divider is preferably provided in the primary cycle tank, weir divider, which is fixed on, to follow Ring pot bottom is long 1/6~1/2, preferably 1/5~1/3 of tank away from tank outlet distance, and weir divider height is circulating tank height 1/2~5/6, preferably 2/3~4/5, branch 2 ' is sufficiently mixed with circulation pot liquid and contacts, and passes through weir divider overflow to circulation Tank outlet enters high-gravity rotating bed through primary cycle pump；The lower section of 2 ' inlet side of branch in primary cycle tank is preferably set There is liquid distributor, branch 2 ' comes into full contact with and reacts with circulation pot liquid after liquid distributor homogenizing distribution；Wherein institute One piece of weir divider is preferably provided in the secondary cycle tank stated, it is tank that weir divider, which is fixed on circulation pot bottom away from tank outlet distance, Long 1/6~1/2, preferably 1/5~1/3, weir divider height are the 1/2~5/6, preferably 2/3~4/5 of circulating tank height, branch Road 2 is sufficiently mixed with circulation pot liquid and contacts, and is exported by weir divider overflow to circulating tank, enters through circulating pump and efficiently inhales Receive tower；It is preferably provided with liquid distributor below 2 inlet side of branch in secondary cycle tank, branch 2 is equal through liquid distributor It comes into full contact with and reacts with circulation pot liquid after changing distribution.
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 denitration process method of the process tail gas of the present invention containing NOx is suitable for the various works that NOx content is stable or fluctuates Skill tail 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 during being somebody's turn to do through secondary oxidative treatments are mixed with acid urea liquid, the HNO that NOx is formed2And HNO3With CO(NH2)2And the NH that part urea primary water solution obtains2COONH4(aminoquinoxaline) is reacted, what generation can discharge CO2And 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. Wherein, primary cycle tank controls HNO2The low temperature environment being stabilized, the control of secondary cycle tank promote the hydrolysis of urea moiety primary For NH2COONH4High-temperature acidic environment forms circulation through branch 2 and branch 2 ' between primary cycle tank and secondary cycle tank Circuit makes to be easy to there are the two of different condition kind component, i.e. low temperature is rich in HNO2And HNO3Primary cycle tank solution with rich in urine Plain primary hydrolysate NH2COONH4Secondary cycle tank solution mix and react, ensure that the HNO in urea liquid2And HNO3It fills Divide and is reduced to CO2And N2And it is discharged.The process handles NOx compared with the urea absorption solution of single condition, has the following advantages: increasing The big removal effect of urea reduction NOx, greatly reduces in whole system because of HNO2The side reaction of the by-products NO gases such as decomposition, Make labile HNO2Sufficiently reaction, to make to be absorbed by liquid absorption but the NOx not yet restored completely is sufficiently reduced to N2, protect While demonstrate,proving absorbing liquid cyclic absorption effect, the NOx desorption outlet release in system absorbing liquid has also been reduced or avoided.
(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 denitration process method and process flow chart of process tail gas containing NOx of the invention.
1- stair oxidation device 2- rotating packed bed reactor 3- secondary oxidation device 4- efficient absorption tower 5- mono- in figure Grade circulating tank 6- secondary cycle tank 7- primary cycle pump 8- secondary cycle pumps the high-gravity rotating bed liquid distributor 10- of 9- The high-gravity rotating bed high-gravity rotating bed motor 12- primary cycle tank liquid distributor 13- primary cycle tank of bed 11- overflows Flow partition 14- secondary cycle tank liquid distributor 15- second reactor weir divider 16- demister.
Specific embodiment
The denitration process method of the process tail gas of the invention containing NOx is done specifically below in conjunction with Detailed description of the invention and embodiment It is bright, but be 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 7 conveyings come is after the homogenizing distribution of high-gravity rotating bed liquid distributor 9 under the effect of high-gravity rotating bed bed 10 Efficient absorption NOx gas；Treated tail gas the enters secondary oxidation device 3 of rotating packed bed reactor 2, 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 8 conveying of secondary cycle pump comes；It is super 2 liquid-phase outlet of gravity reactor is connect with primary cycle tank 5 and secondary cycle tank 6 respectively, goes 6 solution of secondary cycle tank through second level Entering tank body after the homogenizing distribution of circulating tank liquid distributor 14, the liquid for being homogenized distribution comes into full contact with and reacts with solution in tank, It is exported through 15 overflow of secondary cycle tank weir divider to circulating tank, by 8 conveying of secondary cycle pump；Secondary cycle pumps 8 entrances and two Grade circulating tank 6 connects, and outlet is connect with efficient absorption tower 4 and primary cycle tank 5 respectively, goes 5 solution of primary cycle tank through level-one Entering tank body after the homogenizing distribution of circulating tank liquid distributor 12, the liquid for being homogenized distribution comes into full contact with and reacts with solution in tank, It is exported through 13 overflow of primary cycle tank weir divider to circulating tank, rotating packed bed reactor 2 is delivered to by primary cycle pump 7 Cyclic absorption process tail gas；The gaseous phase outlet of efficient absorption tower 4 is connect with demister 16, and the liquid phase under demisting condensation returns to second level Circulating tank 6, 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 exported away from tank in primary cycle tank and secondary cycle tank Distance be tank it is long 1/4 at set highly as the weir divider of tank high 4/5.
Embodiment 1
To tolerance Q=3000Nm3/ h, NOx concentration 20000mg/m3, wherein NO concentration is 11000mg/m3Technique tail Gas is handled.Process tail gas initially enters stair oxidation device, and stair oxidation device uses O2For oxidant, O2Adding amount is 15m3/ H, oxidization time 20 seconds.Tail gas enters rotating packed bed reactor after oxidation processes, what rotating packed bed reactor used Absorbing liquid is the urea liquid of mass concentration 25%, treatment conditions are as follows: 15 DEG C of temperature, revolving bed revolving speed 2000rpm, liquid-gas ratio 20 L/m3, through this grade treated NOx removal rate up to 70%~83%.The liquid-phase outlet of rotating packed bed reactor enters second level Circulating tank volume flow is reactor absorbing liquid total flow 1/3, and it is to pass through liquid at tank high 3/5 that secondary cycle tank, which controls liquid level, Position interlocking adjusts the flow of circulation secondary cycle tank to primary cycle tank.Second level is introduced through supergravity reactor treated tail gas Oxidator, secondary oxidation device use O2Oxidation processes, O are for oxidant2Adding amount is 8m3/ h, oxidization time 35 seconds.Through second level Tail gas enters efficient absorption tower after oxidation processes, and absorbing liquid used is mass concentration 25%, the acid urea liquid that pH is 4, processing Condition are as follows: 65 DEG C of temperature, liquid-gas ratio 7L/m3, tail gas is discharged after demisting after processing.Process tail gas NOx after processing is total Removal efficiency supplements urea 94% or more, periodically into absorbing liquid, and (when absorbing liquid mass concentration is lower than 17%, supplement concentration is extremely 25%), after system stable operation 360h, still ensure that process tail gas after processing meets national emission standard, it is entire processed Journey is discharged without " three wastes ".
Embodiment 2
To tolerance Q=9000Nm3/ h, NOx concentration 5000mg/m3, wherein NO concentration is 3200mg/m3Process tail gas It is handled.Stair oxidation device uses O3For oxidant, O3Adding amount is 8m3/ h, oxidization time 10 seconds.It is high-gravity rotating bed anti- The absorbing liquid for answering device to use is the urea liquid of mass concentration 15%, treatment conditions are as follows: and 20 DEG C of temperature, revolving bed revolving speed 900rpm, 12 L/ m of liquid-gas ratio3, through this grade treated NOx removal rate up to 75%~80%.The liquid phase of rotating packed bed reactor goes out It is reactor absorbing liquid total flow 1/5 that mouth, which enters secondary cycle tank volume flow, and it is high by 2/3 for tank that secondary cycle tank controls liquid level Place adjusts the flow of circulation secondary cycle tank to primary cycle tank by level chain.Through supergravity reactor treated tail Gas introduces secondary oxidation device, and secondary oxidation device uses O3Oxidation processes, O are for oxidant3Adding amount is 5m3/ h, oxidization time 15 Second.Tail gas enters efficient absorption tower after secondary oxidative treatments, and absorbing liquid used is mass concentration 15%, and the acid urea that pH is 3 is molten Liquid, treatment conditions are as follows: temperature 70 C, liquid-gas ratio 5L/m3, tail gas is discharged after demisting after processing.Technique tail after processing The total removal efficiency of gas NOx supplements urea into absorbing liquid 91% or more, periodically and (when absorbing liquid mass concentration is lower than 10%, supplements Concentration after system stable operation 450h, still ensures that process tail gas after processing meets national emission standard, entirely to 15%) Treatment process is discharged without " three wastes ".
Embodiment 3
To tolerance Q=5000Nm3/ h, NOx concentration 11000mg/m3, wherein NO concentration is 8200mg/m3Process tail gas It is handled.Stair oxidation device uses O3For oxidant, O3Adding amount is 10m3/ h, oxidization time 12 seconds.It is high-gravity rotating bed anti- The absorbing liquid for answering device to use is the urea liquid of mass concentration 20%, treatment conditions are as follows: and 20 DEG C of temperature, revolving bed revolving speed 1500rpm, 15 L/ m of liquid-gas ratio3, through this grade treated NOx removal rate up to 72%~82%.Rotating packed bed reactor Liquid-phase outlet enter secondary cycle tank volume flow be reactor absorbing liquid total flow 1/4, secondary cycle tank control liquid level At tank high 3/4, the flow of circulation secondary cycle tank to primary cycle tank is adjusted by level chain.At supergravity reactor Tail gas after reason introduces secondary oxidation device, and secondary oxidation device uses O3Oxidation processes, O are for oxidant3Adding amount is 6m3/ h, oxygen Change the time 15 seconds.Tail gas enters efficient absorption tower after secondary oxidative treatments, and absorbing liquid used is mass concentration 20%, and pH is 2.5 Acid urea liquid, treatment conditions are as follows: 75 DEG C of temperature, liquid-gas ratio 6.5L/m3, tail gas is discharged after demisting after processing.Through locating The total removal efficiency of process tail gas NOx after reason supplements urea 93% or more, periodically (when absorbing liquid mass concentration is low into absorbing liquid When 13%, supplement concentration after system stable operation 400h, still ensures that process tail gas after processing meets country to 20%) Discharge standard, entire treatment process are discharged without " three wastes ".
Comparative example 1
Same as Example 1, difference does not set absorbing liquid pipeloop, reaction process between level-one, secondary cycle tank And treatment effect comparison is as follows:
After handling 50 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 17% by 25%, and secondary storage tank urea concentration is down to 19% by 25%；Level-one storage tank urea is dense in comparative example 1 Degree is down to 20% by 25%, and secondary storage tank urea concentration is down to 23% by 25%.Hereafter, each circulating tank urea of regular replenishment, makes it Absorbing liquid urea quality concentration maintains 25% or so, and after handling 270 h, NOx concentration is more than in the final emission of comparative example 1 300mg/m3, can not achieve qualified discharge, after circulation fluid is by supplement urea in embodiment 1, remained to after 360 h of stable operation Guarantee that tail gas after processing meets national emission standard.

Claims (17)

1. one kind contains NOxThe denitration process method of process tail gas, it is characterised in that including following content: (1) higher concentration NO will be containedx Process tail gas introduce stair oxidation device carry out oxidation processes；(2) by the process tail gas after stair oxidation and from primary cycle The absorbing liquid of tank introduces rotating packed bed reactor respectively, in rotating packed bed reactor, process tail gas and absorbing liquid Hybrid reaction, part NO in process tail gasxIt is absorbed, residual exhaust introduces secondary oxidation device and carries out oxidation processes, out reactor Absorbing liquid be divided into branch 1 and branch 2, branch 1 is recycled back to primary cycle tank, and branch 2 enters secondary cycle tank, with secondary cycle Absorbing liquid hybrid reaction in tank, the absorbing liquid after reaction are divided into branch 1 ' and branch 2 ' after secondary cycle pumps；(3) branch 1 ' and Tail gas after secondary oxidation introduces efficient absorption tower respectively, and tail gas is handled through absorbing liquid absorption, and absorbing liquid returns to secondary cycle tank It is recycled, branch 2 ' enters in primary cycle tank, with primary cycle tank to be recycled after absorbing liquid hybrid reaction, after processing Tail gas after demisting qualified discharge；The absorbing liquid of primary cycle tank described in step (2) is the urea of mass concentration 5% ~ 30% Aqueous solution；The absorbing liquid hybrid reaction condition of process tail gas described in step (2) and primary cycle tank are as follows: 5~40 DEG C of temperature, liquid Gas is than 5~50L/m3, reaction mass residence time in reactor is 1~500 second；In step (2) the secondary cycle tank Absorbing liquid is the acid aqueous solution of urea of mass concentration 5%~30%, and pH value is 1~6；In efficient absorption tower described in step (3) Absorption treatment conditions are as follows: absorb 50~90 DEG C of temperature, liquid-gas ratio be 2~30L/m3。
2. denitration process method described in accordance with the claim 1, it is characterised in that: stair oxidation device described in step (1) is pipe Road form or one of independent tank body or tower-shaped formula, oxidant used are O2Or O3, provided by oxygen or ozone generator；Its The additional amount of middle oxidant is 0.5:1~5:1 with the molar ratio of NO in terms of O element.
3. denitration process method described in accordance with the claim 1, it is characterised in that: oxidation processes condition described in step (1) are as follows: It 10~200 DEG C of temperature, stops oxidization time 1~100 second.
4. denitration process method described in accordance with the claim 1, it is characterised in that: step (2) the high-gravity rotating bed reaction Device is one of parallel type, reverse-flow and cross-current type.
5. denitration process method described in accordance with the claim 1, it is characterised in that: step (2) the high-gravity rotating bed reaction Device is equipped with frequency control motor, bed revolving speed is adjusted, 50~5000rpm of adjustable range.
6. denitration process method described in accordance with the claim 1, it is characterised in that: secondary oxidation device described in step (2) is pipe Road form or one of independent tank body or tower-shaped formula, oxidant used are O2Or O3, provided by oxygen or ozone generator；Its The additional amount of middle oxidant is 0.5:1~5:1 with the molar ratio of NO in terms of O element.
7. denitration process method described in accordance with the claim 1, it is characterised in that: secondary oxidative treatments item described in step (2) Part are as follows: 10~200 DEG C of temperature, stop oxidization time 1~100 second.
8. denitration process method described in accordance with the claim 1, it is characterised in that: 2 volume flow of branch described in step (2) is The 1/10~2/3 of revolving bed absorbing liquid total flow out；2 ' the volume flow of branch is the 1/10 of secondary cycle total pump flow ~2/3.
9. denitration process method described in accordance with the claim 1, it is characterised in that: the body of step (2) branch 2 and branch 2 ' Product flow matches, and the flow of branch 2 and branch 2 ' is adjusted by the level chain of firsts and seconds circulating tank.
10. denitration process method described in accordance with the claim 1, it is characterised in that: efficient absorption tower described in step (3) is bulging One of bubble column, spray column, packed tower and rotating stream tray scrubber.
11. denitration process method described in accordance with the claim 1, it is characterised in that: the primary cycle tank and secondary cycle tank Equipped with urea filler, absorbing liquid mass concentration declines 1~10 percentage point, adds urea to required concentration, continuing cycling through makes With.
12. denitration process method described in accordance with the claim 1, it is characterised in that: one piece of setting in the primary cycle tank Weir divider, 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 The 1/2~5/6 of circulating tank height, branch 2 ' are sufficiently mixed with circulation pot liquid and contact, and pass through weir divider overflow to circulation Tank outlet enters high-gravity rotating bed through primary cycle pump.
13. denitration process method described in accordance with the claim 1, it is characterised in that: the 2 ' entrance one of branch in primary cycle tank The lower section of side is equipped with liquid distributor, and branch 2 ' comes into full contact with after liquid distributor homogenizing distribution with circulation pot liquid simultaneously anti- It answers.
14. denitration process method described in accordance with the claim 1, it is characterised in that: one piece of setting in the secondary cycle tank Weir divider, 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 The 1/2~5/6 of circulating tank height, branch 2 are sufficiently mixed with circulation pot liquid and contact, and pass through weir divider overflow to circulating tank Outlet, enters efficient absorption tower through circulating pump.
15. denitration process method described in accordance with the claim 1, it is characterised in that: 2 inlet side of branch in secondary cycle tank Lower section be equipped with liquid distributor, branch 2 comes into full contact with and reacts with circulation pot liquid after liquid distributor homogenizing distribution.
16. denitration process method described in accordance with the claim 1, it is characterised in that: the efficient absorption tower gaseous phase outlet pipeline Demister is set, and treated, and tail gas is discharged after demisting is handled, and the demister is cylindrical tube, and inside setting is cylindric Sieve prevents purified gas entrainment.
17. denitration process method described in accordance with the claim 1, it is characterised in that: the higher concentration NOxProcess tail gas in NOxConcentration is 1000~50000mg/m3Process tail gas.
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CN109406711A (en) * 2018-10-17 2019-03-01 华电电力科学研究院有限公司 A kind of device for absorbing tail gas and its tail gas absorption method for SCR denitration performance detection
CN111467946A (en) * 2020-04-22 2020-07-31 运城学院 NO in preparation process of molecular sieve catalystxMethod for treating exhaust gas
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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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