CN1830526A - Purification technology and equipment of waste gas containing high concentration nitrogen oxide - Google Patents
Purification technology and equipment of waste gas containing high concentration nitrogen oxide Download PDFInfo
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- CN1830526A CN1830526A CN 200610012414 CN200610012414A CN1830526A CN 1830526 A CN1830526 A CN 1830526A CN 200610012414 CN200610012414 CN 200610012414 CN 200610012414 A CN200610012414 A CN 200610012414A CN 1830526 A CN1830526 A CN 1830526A
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- 239000002912 waste gas Substances 0.000 title claims abstract description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 171
- 238000000746 purification Methods 0.000 title claims description 15
- 238000005516 engineering process Methods 0.000 title description 4
- 239000007788 liquid Substances 0.000 claims abstract description 107
- 239000007789 gas Substances 0.000 claims abstract description 85
- 238000010521 absorption reaction Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000007800 oxidant agent Substances 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 12
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 13
- 239000003517 fume Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000010257 thawing Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 description 20
- 230000002378 acidificating effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000002250 absorbent Substances 0.000 description 6
- 230000002745 absorbent Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- -1 electroplating Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002828 nitro derivatives Chemical group 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
A process for cleaning the waste gas containing high-concentration NOx includes such steps as gathering the fume, coming in rotary filler bed, diffusing into rotary filler, spraying the absorptive liquid to filler, countercurrent absorption, mixing the treated gas with oxidant to oxidize NO to NO2, coming in rotary filler bed, absorbing by absorptive liquid, defrosting, and exhausting. Said absorptive liquid can be cyclically used. Its apparatus is also disclosed.
Description
Technical Field
The invention relates to a treatment process of waste gas containing nitrogen oxides, in particular to a process for treating industrial waste gas containing high-concentration nitrogen oxides and corresponding equipment thereof.
Background
A large amount of waste gas containing high-concentration nitrogen oxides, namely commonly called smoke, is generated in China every year due to chemical processes such as nitration reaction, decomposition of nitro compounds, synthesis of nitro compounds, nitric acid production and the like. The related industries comprise chemical fertilizers, electroplating, gunpowder, explosives and other industrial fields. The high-concentration nitrogen oxide refers to nitrogen-containing waste gas which is hundreds to thousands of times higher than common smoke and is dark yellow in color. Compared with common smoke containing a small amount of nitric oxide, the smoke gas has higher harm degree, and causes serious damage to the surrounding environment besides directly harming the bodies and mind of nearby residents. Is one of the pollution gases which are important to be treated in all countries in the world.
At present, the treatment technologies of nitrogen oxides in flue gas mainly include a dry method and a wet method, and the dry treatment technologies include a catalytic reduction method, an adsorption method, an electron beam irradiation method and the like. The catalytic reduction method is to reduce nitrogen oxides into harmless nitrogen by using a reducing agent under the action of a catalyst, the method is mainly used for treating boiler flue gas, the catalytic temperature of the method is generally above 300 ℃, partialheat energy can be recovered in the treatment process, but the investment and the remote expense are high, so the method is difficult to popularize in small and medium-sized enterprises, for example, Chinese patent 99126262, X discloses a method for treating high-concentration nitrogen dioxide waste gas and equipment thereof, namely, a method for burning liquefied gas and gas containing nitrogen dioxide in a special incinerator is adopted. The combustion temperature reaches 800-1400 ℃. The adsorption method for removing nitrogen oxides is to use silica gel, molecular sieve, active carbon and other adsorbents to adsorb nitrogen oxides in waste gas, then desorb the nitrogen oxides and absorb the nitrogen oxides by water or alkali, and the method has large investment, high operation cost and unstable treatment effect due to the reasons of large consumption of the adsorbents, huge equipment, high regeneration frequency and the like, so the method is not widely applied. The electron beam method is to irradiate the burning tail gas with electron beam to make the nitrogen oxide and solid particles in the tail gas form acid mist mixture, and then separate them by electric dust collector. The wet method for treating nitrogen oxide mainly adopts single-stage or two-stage absorption processes of a packed tower, a bubble cap tower, a sieve plate tower and the like. In the aspect of absorbent selection, enterprises use clear water as an absorbent or dilute nitric acid as an absorbent for physical absorption according to the characteristics of respective production; in addition, chemical absorption treatment is carried out by using alkaline liquid such as sodium carbonate and sodium hydroxide as an absorbent. Over the years, researchers have improved on the basis of the prior art, including the attempts of multi-stage absorption by a plurality of towers in series, the use of active fillers and the like, but the effect is very limited, the treatment requirement is difficult to achieve, and the phenomenon of 'yellow smoke' isstill very serious.
Disclosure of Invention
Aiming at the defects of the prior art for treating the waste gas containing the high-concentration nitrogen oxide, the invention provides a purification process of the waste gas containing the high-concentration nitrogen oxide, which takes a rotary packed bed as an absorption reaction device and utilizes the characteristics of the rotary packed bed and a deep oxidation-reduction technology to simplify the purification process of the smoke. The invention also provides equipment for realizing the reaction.
The invention relates to a purification process of waste gas containing high-concentration nitrogen oxides, which comprises the following process steps:
I. the waste gas containing high concentration of nitrogen oxide and absorption liquid A1Or A2Introducing the waste gas and the absorption liquid into a first rotary packed bed respectively through a gas inlet and a liquid inlet, wherein the gas-liquid ratio is 50-1000: 1, and the waste gas and the absorption liquid are subjected to first-stage absorption in the rotary packed bed and then are discharged through a gas outlet and a liquid outlet respectively;
II. The gas treated in the step I enters an oxidation device to be mixed and reacted with an oxidant, the nitric oxide in the waste gas is oxidized into nitrogen dioxide, and the oxidant and the nitric oxide are added according to the corresponding stoichiometric ratio;
III, introducing gas and urea absorption liquid obtained by the reaction in the step II into a second rotary packed bed through a gas inlet and a liquid inlet respectively, reducing and absorbing residual nitrogen oxides in the gas by acidic urea absorption liquid in the rotary packed bed,wherein the gas-liquid ratio introduced into the second rotary packed bed is 50-500: 1, and exhausting clean gas after the reaction from a gas outlet of the rotary packed bed;
the absorption liquid A1Is sodium carbonate or sodium hydroxide aqueous solution; absorption liquid A2Is dilute nitric acid.
In the purification process of the waste gas containing the high-concentration nitrogen oxides, the oxidant is oxygen or ozone, and the oxygen or ozone is directly introduced into a pipeline between the first rotating packed bed and the second rotating packed bed, reacts in the pipeline and then enters the second rotating packed bed.
The purification process of the waste gas containing high-concentration nitrogen oxides is characterized in that the oxidation device is a reaction tank, and the oxidant is 0.1-0.5M hypochlorous acid and/or sodium hypochlorite and/or potassium permanganate solution.
An equipment for realizing the purification process of the waste gas containing high-concentration nitrogen oxides comprises a first rotating packed bed and a second rotating packed bed, the exhaust port of the first rotary packed bed is communicated with the air inlet of the second rotary packed bed through a communicating pipeline, an oxidant generator is connected with the communicating pipeline, the liquid outlet pipeline and the liquid inlet pipeline of the first circulating tank are respectively communicated with the liquid inlet of the first rotary packed bed and the liquid outlet of the first rotary packed bed, a first circulating pump is connected on a pipeline between the liquid inlet of the first rotary packed bed and the first circulating groove, a liquid outlet pipeline and a liquid inlet pipeline of the second circulating groove are respectively communicated with the liquid inlet of the second rotary packed bed and the liquid outlet of the second rotary packed bed, and a second circulating pump is connected on a pipeline between the liquid inlet of the second rotary packed bed and the second circulating groove, and the exhaust port of the second rotary packed bed is connected with an induced draft fan.
The purification equipment for the waste gas containing high-concentration nitrogen oxides is characterized in that a communicating pipeline between the first rotary packed bed and the second rotary packed bed is connected with an oxidation reaction tank.
The purification equipment for the waste gas containing high concentration of nitrogen oxides is characterized in that the oxidant generator is an oxygen or ozone generator.
According to the purification process of the waste gas containing high-concentration nitrogen oxides, the reduction absorption reaction of the waste gas containing nitrogen oxides is carried out in the rotating packed bed, the reaction process is accelerated, and the mass transfer process between gas and liquid is enhanced. The nitrogen oxides in the waste gas are absorbed through the first reaction, oxidation and the second reaction, so that the waste gas containing the nitrogen oxides is deeply purified, and the raw materials used in the reaction and absorption process are all common chemical raw materials, so that the cost is low and the raw materials are easy to obtain. The liquid used in the whole process can be recycled and treated, no waste liquid and waste are generated, and no secondary pollution is caused.
The purification equipment for waste gas containing high-concentration nitrogen oxide adopts the rotating packed bed with simple structure and small volume to replace huge tower equipment in the traditional process. The whole system has compact design, simple and convenient operation, low use and maintenance cost, small occupied area and large operation elasticity. The processing cost can be greatly reduced.
Drawings
FIG. 1 is a flow chart of a process and an apparatus for purifying an exhaust gas containing a high concentration of nitrogen oxides
In the figure, 1-a first rotating packed bed 2-a second rotating packed bed 3-an oxidant generating agent 4-a first rotating packed bed 5-a first liquid distributor 6-a second rotating packed bed 7-a second liquid distributor 8-a second circulating pump 9-a first circulating pump 10-a first rotating packed bed air inlet 11-a first rotating packed bed air outlet 12-a second rotating packed bed air inlet 13-a second rotating packed bed air outlet 15-a first rotating packed bed liquid outlet 16-a second rotating packed bed liquid outlet 17-a first rotating packed bed liquid inlet 18-a second rotating packed bed liquid inlet 20-a first circulating groove 21-a second circulating groove 22-a communicating pipeline
Detailed Description
The process and apparatus for purifying exhaust gas containing high concentration of nitrogen oxides according to the present invention will be described in detail with reference to the accompanying drawings.
The invention relates to a device for realizing the purification process of waste gas containing high-concentration nitrogen oxides, which adopts two sets of rotating packed beds, namely a first rotating packed bed 1 and a second rotating packed bed 2, wherein an exhaust port 11 of the first rotating packed bed 1 is communicated with an air inlet 12 of the second rotating packed bed 2 through a communication pipeline 22, an oxidant generator 3 is also connected to the communication pipeline 22, and the oxidant generator 3 is an oxygen generator such as an oxygen generator or an ozone generator. If liquid oxidant is used, the oxidant generator is an oxidant delivery tank, an oxidation reaction tank is connected in series with the communication pipeline 22 and communicated with the oxidant delivery tank, and the oxidant in the delivery tank is delivered into the reaction tank by a liquid delivery pump. A liquid outlet pipeline and a liquid inlet pipeline of the first circulating groove 20 are respectively communicated with a first rotary packed bed liquid inlet 17 and a first rotary packed bed liquid outlet 15, and a first circulating pump 9 is connected on a pipeline between the first rotary packed bed liquid inlet 17 and the first circulating groove 20. A liquid outlet pipeline and a liquid inlet pipeline of the second circulating groove 21 are respectively communicated with a liquid inlet 18 of the second rotary packed bed and a liquid outlet 16 of the second rotary packed bed, a second circulating pump 8 is connected on a pipeline between the liquid inlet 18 of the second rotary packed bed and the second circulating groove 21, and an exhaust port 13 of the second rotary packed bed 2 is connected with an induced draft fan. The rotary filler power motor of the first and second rotary filler beds is preferably a variable frequency speed control motor. As acid and alkali liquor are involved in the whole reaction process, the corresponding acid and alkali resistant materials are adopted as the system materials.
The invention relates to a purification process of waste gas containing high-concentration nitrogen oxides, which mainly comprises the following three steps:
the first step is an absorption process using an alkaline absorption solution such as 5% -20% sodium carbonate solution, 5% -20% sodium hydroxide solution or an acidic absorption solution such as 1-10% dilute sodium hydroxide solutionNitric acid for absorbing nitrogen oxidesin waste gas containing high concentration of nitrogen oxides, selecting acidic or alkaline absorption liquid in the specific process according to nitrogen oxide composition in the waste gas, selecting acidic absorption liquid if NO content in the waste gas is high, and selecting acidic absorption liquid if NO content in the waste gas is high2If the content is high, selecting alkaline absorption liquid. The two reactions respectively have the following chemical reactions:
(1) the reaction when using sodium hydroxide solution as an absorbent is as follows:
(2) the reaction when dilute nitric acid solution is used as the absorbent is as follows:
the reaction process is a fast process, whether the reaction is completely and fast depends on the diffusion mass transfer process between gas and liquid, and the process is a control step of the whole reaction process.
In order to accelerate the mass transfer process, the invention is realized by utilizing the characteristics of high speed and high efficiency of the rotary packed bed absorption equipment and simple and convenient operation conditions. And introducing the gas containing the nitrogen oxides and the absorption liquid into the first rotating packed bed from a gas inlet 10 and a liquid inlet 17 of the first rotating packed bed 1 respectively, wherein the introduction of the gas containing the nitrogen oxides is realized by negative pressure formed by a draught fan at the tail end of the system on the whole system. The prepared absorption liquid is placed in a first circulation groove 20 and is led into a first rotary pump 9 through a pipelineThe liquid inlet 17 of the rotating packed bed enters the liquid distributor 5 and the first rotating packing 4, and gas-liquid fully contacts in the rotating packing in a countercurrent or cross flow mode. Gas (es)The nitrogen-containing compound in the (B) reacts with the absorption liquid and is absorbed, and NO in the nitrogen-containing compound is2Is substantially absorbed. The gas is discharged from the gas outlet 11 and enters the oxidation step of the second step, and the rich solution after the absorption reaction is recycled.
The rotating speed of the rotating filler in the first rotating filler bed is 100-10000rpm, wherein the selection of the rotating speed of the rotating filler is mainly determined by the treatment capacity of the waste gas, and if the motor of the rotating filler is a variable frequency speed regulating motor, continuous adjustment can be carried out within the rotating speed according to the introduction quantity of the waste gas and the treatment liquid; the gas-liquid ratio entering the first rotating packed bed is 50-1000: 1 (unit/liter). The gas-liquid ratio is selected mainly according to the concentration of nitrogen oxides in the waste gas entering the rotating packed bed and the concentration of the absorption liquid.
The second step of the present invention is an oxidation step: the oxidant is oxygen or ozone, and hydrogen peroxide or potassium permanganate or other strong oxidant water solution can also be adopted. And (3) feeding the gas subjected to the absorption treatment in the step (I) into an oxidation device (a reaction tank) to be mixed with the oxidant and react (if the oxidant is oxygen or ozone, the oxidant can be directly introduced into a pipeline at an exhaust port of the first rotating packed bed, and an oxidation device is not required to be additionally arranged). The main purpose in this step is to oxidize the nitrogen monoxide in the exhaust gas to nitrogen dioxide, wherein the oxidizing agent is added in a corresponding stoichiometric ratio with the nitrogen monoxide; because the general absorption process is only for NO2The absorption rate is high, so that the key factor of the final treatment effect is to improve the oxidation degree of the nitrogen oxide gas through the step.
The following nitrogen oxide gas oxidation process:
The third step of the present invention is still the absorption process of the rotating packed bed: the absorption liquid is acidic urea absorption liquid. Introducing the gas obtained by the reaction in the step (II) and urea absorption liquid into a second rotary packed bed from a gas inlet 12 and a liquid inlet 18 of the second rotary packedbed respectively, wherein the introduced gas-liquid ratio is 50-500: 1 standard gas volume (unit/liter), and nitrogen oxide components in the waste gas after the second oxidation reaction mainly comprise nitrogen dioxide gas and trace nitrogen monoxide and nitrogen trioxide gas, so that the acidic urea absorption liquid is adopted to absorb the nitrogen dioxide in the step. The acidic urea absorption liquid is placed in a second circulation groove 21, is pumped into a liquid inlet 18 of a second rotary packed bed 2 through a pipeline by a second circulation pump 8, sequentially enters a second liquid distributor 7 and a second rotary packing 6, and is absorbed and reacted with the nitrogen oxide-containing waste gas introduced from a gas inlet 12 of the second rotary packed bed in the rotary packing. The rotational speed of the rotary packing is still 100-10000 rpm. The concentration of the acid urea absorption solution is prepared by calculating the reaction equivalence ratio of the two according to the measured (calculated) value of the nitrogen dioxide content in the gas after the second step of reaction. The make-up concentration can also be calculated (adjusted) from the gas-liquid ratio into the rotating packing.
The reaction process of this step is as follows.
The final products after the above reaction are nitrogen, carbon dioxide and water. The acid urea absorption liquid is recycled after being recovered and supplemented with enough concentration.
Through the three steps, the treatment rate of the nitrogen oxides in the waste gas containing high-concentration nitrogen oxides can reach more than 99 percent. Completely reaches the national emission standard.
Example 1 throughput was 700m3H; inlet concentration of about 18000mg/m3The nitrate fume is collected by the gas-collecting hood under the action of the induced draft fan, enters the rotating packed bed 1 from the gas inlet 10, is diffused into the rotating packing 4 under the action of pressure difference, and the rotating speed of the rotating packing is adjusted to 2400 rpm. A dilute nitric acid solution with the concentration of 10 percent is sent from the circulating tank 20 to the liquid distributor 5 of the first rotating packed bed 1 by a circulating pump 9 and sprayed to the inner side of the packing, the gas-liquid ratio is 1/50 (unit/liter), and gas and liquid are in countercurrent contact and absorbed in the packing to remove nitrogen dioxide and part of nitric oxide in the packing. The absorption liquid is recycled, the gas after the first absorption treatment is mixed with ozone generated by the ozone generator 3 in the cavity of the outlet 11, and NO in the gas is oxidized into NO2And then the gas enters a second rotary packed bed 2 through a pipeline, the rotary packing 6 is contacted with an acid urea absorption liquid for absorption, and the treated gas is discharged after passing through a demister. The rotational speed of the packing was 2400rpm, and the liquid-gas ratio was 1/50 (units/liter). The absorption temperature is 20 ℃, the absorption pressure is 1atm, and the gas reaches the GBI6297-1996 first-grade emission standard. In the treatment process, the acidic urea solution is gradually consumed, the urea solution with the reduced concentration is put into an intermediate tank, the urea solution with the concentration meeting the requirement is supplemented to the absorption process for cyclic absorption, and the urea solution is recycled in a closed loop way, so that the waste gas is treated without increasing new pollution.
Example 2
The treatment capacity was 2000m3H; the inlet concentration is about 10000mg/m3The smoke gas with concentration is collected by the gas collecting hood under the action of the induced draft fan and then enters the first rotary packed bed 1 through the gas inlet 10, the sodium carbonate solution with the concentration of 15 percent in the first circulating groove 20 is pumped into the liquid distributor 5 through the liquid inlet 17 by the circulating pump 9 and enters the inner side of the rotary packing 4, and the sodium carbonate solution reacts with the gas from the gas inlet in the rotary packing to remove part of NO in the sodium carbonate solution2The rotating speed of the rotating packing was 2000rpm, and the liquid-gas ratio was 1/50 (units/liter). The gas after absorption treatment is discharged from the exhaust port 11 and enters the lower part of an oxidation tank to perform oxidation reaction with hydrogen peroxide solution (0.2M) in the tank, and NO in the gas is oxidized into NO2Then, howeverThen the waste water is discharged from the top of the tank, enters a pipeline 22 and enters a second rotating packed bed 2 to perform a second absorption reaction with the acidic urea absorption liquid.The absorption temperature is 20 ℃, the absorption pressure is 1atm, and the gas reaches the GBI6297-1996 first-grade emission standard.
Example 3
The treatment capacity was 2000m3H; the inlet concentration is about 10000mg/m3The nitrate fume with concentration is collected by the gas collecting hood under the action of the induced draft fan, enters the first rotary packed bed 1 through the gas inlet 10, and is subjected to absorption reaction with the sodium hydroxide solution entering the rotary packing to remove part of NO in the nitrate fume2The gas after the absorption treatment is mixed and reacted with oxygen from the oxygen generator in the communication line 2 to oxidize the remaining NO therein to NO2Then enters the second rotating packed bed 2 through the gas inlet 12 and carries out absorption reaction with the acidic urea absorption liquid in the rotating packing 6. The rotating packing speed was 1200rpm and the liquid-to-gas ratio was 1/100 (units/liter). The absorption temperature is 20 ℃, the absorption pressure is 1atm, and the gas reaches the GBI6297-1996 first-grade emission standard.
Example 4
The treatment capacity is 10000m3H; the inlet concentration is about 11000mg/m3The nitrate fume with the concentration is collected by the gas-collecting hood under the action of the induced draft fan and then is introduced into the first rotary packed bed 1 for absorption treatment. The concentration of absorption liquid is 20 percent, the liquid-gas ratio is 1/100 (unit/liter), the gas treated by the first rotating packed bed 1 enters an oxidation reaction tank to react with potassium permanganate solution in the tank, and NO in the gas is oxidized into NO2Then the gas enters the second rotating packed bed 2 along a pipeline to perform absorption reaction with the acidic urea absorption liquid and then is discharged. The rotational speed of the packing was 5000rpm, and the liquid-gas ratio was 1/100 (units/liter). The absorption temperature is 20 ℃, the absorption pressure is 1atm, and the gas reaches the GBI6297-1996 first-grade emission standard.
Example 5
The treatment capacity is 10000m3H; the inlet concentration is about 11000mg/m3The nitrate fumewith concentration is collected by the gas collecting hood under the action of the induced draft fan, and then is introduced into the first rotary packed bed 1 to perform absorption reaction with dilute nitric acid solution to remove NO in the nitrate fume2The rotating speed of the filler is 800 rpm; the liquid-gas ratio was 1/500 (units/liter),the absorption temperature is 30 ℃ and the absorption pressure is 1 atm. The rest is the same as in example 1. The treated gas meets GBI6297-1996 primary emission standard.
Example 6
Example 5 the throughput was 20000m3At the time of/h, the liquid-gas ratio is increased to 1/1000 (unit/liter), and the rotating speed of the rotary filler is adjusted to 1300 rpm; other conditions were unchanged. The treated gas can also reach the national standard.
Claims (6)
1. A purification process of waste gas containing high concentration of nitrogen oxides comprises the following steps:
I. the waste gas containing high concentration of nitrogen oxide and absorption liquid A1Or A2Introducing the waste gas and the absorption liquid into a first rotary packed bed respectively through a gas inlet and a liquid inlet, wherein the gas-liquid ratio is 50-1000: 1, and the waste gas and the absorption liquid are subjected to first-stage absorption in the rotary packed bed and then are discharged through a gas outlet and a liquid outlet respectively;
II. The gas treated in the step I enters an oxidation device to be mixed and reacted with an oxidant, the nitric oxide in the waste gas is oxidized into nitrogen dioxide, and the oxidant and the nitric oxide are added according to the corresponding stoichiometric ratio;
III, introducing gas obtained by the reaction in the step II and urea absorption liquid into a second rotary packed bed through a gas inlet and a liquid inlet respectively, reducing and absorbing residual nitrogen oxides in the gas by the urea absorption liquid in the rotary packed bed, wherein the gas-liquid ratio introduced into the second rotary packed bed is 50-500: 1, and exhausting the absorbed gas from a gas outlet of the rotary packed bed;
the absorption liquid A1Is sodium carbonate or sodium hydroxide aqueous solution; absorption liquid A2Is dilute nitric acid.
2. The process according to claim 1, wherein the oxidizing means is a gas pipe, and the oxidizing agent is oxygen or ozone, and the oxygen or ozone is introduced directly into the pipe between the first rotating packed bed and the second rotating packed bed, and reacted therein, and then introduced into the second rotating packed bed.
3. The process for purifying an exhaust gas containing a high concentration of nitrogen oxides as claimed in claim 1, wherein said oxidizing means is a reaction tank and said oxidizing agent is a 0.1-0.5M solution of hypochlorous acid and/or sodium hypochlorite and/or potassium permanganate.
4. An apparatus for realizing the purification process of waste gas containing high concentration nitrogen oxide as claimed in any one of claims 1-3, comprising a first rotary packed bed (1) and a second rotary packed bed (2), wherein the gas outlet (11) of the first rotary packed bed (1) is communicated with the gas inlet (12) of the second rotary packed bed (2) through a communication pipeline (22), an oxidant generator (3) is connected with the communication pipeline (22), the liquid outlet pipeline and the liquid inlet pipeline of a first circulation tank (20) are respectively communicated with a first rotary packed bed liquid inlet (17) and a first rotary packed bed liquid outlet (15), a first circulation pump (9) is connected on the pipeline between the first rotary packed bed liquid inlet (17) and the first circulation tank (20), and the liquid outlet pipeline and the liquid inlet pipeline of a second circulation tank (21) are respectively communicated with a second rotary packed bed liquid inlet (18), A liquid outlet (16) of the second rotary packed bed is communicated, a second circulating pump (8) is connected on a pipeline between a liquid inlet (18) of the second rotary packed bed and a second circulating groove (21), and an exhaust port (13) of the second rotary packed bed (2) is connected with an induced draft fan.
5. An apparatus for purifying an exhaust gas containing a high concentration of nitrogen oxides as claimed in claim 4, characterized in that an oxidation reaction tank is connected to the communication pipe (22) between the first rotating packed bed (1) and the second rotating packed bed (2).
6. An apparatus for purifying an exhaust gas containing a high concentration of nitrogen oxides as claimed in claim 4, characterized in that said oxidant generator (3) is an oxygen or ozone generator.
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