CN113769573B - Method for removing NO and VOCs in flue gas - Google Patents
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Abstract
A method for removing NO and VOCs in flue gas adopts an ozone generator to manufacture ozone, ozone and flue gas are respectively introduced into a buffer tower, so that the ozone and the flue gas are fully mixed in the buffer tower to form mixed gas, and then the mixed gas is sequentially introduced into an oxidation tower, an absorption tower and an ozone destructor and then discharged; the oxidation tower is filled with a catalyst and water, and when the mixed gas enters the oxidation tower, the mixed gas is fully oxidized by ozone under the adsorption and catalysis actions of the catalyst; a spraying device is arranged in the absorption tower, and the mixed gas in the absorption tower is sprayed by the spraying device to absorb NO 2 、CO 2 And an absorber for HCl. The invention mixes ozone and smoke to oxidize NO and VOCs in the smoke, the oxidation products are absorbed by the absorbent in the absorption tower, and unreacted ozone is decomposed in the ozone destructor, so that the discharged gas does not produce secondary pollution to the atmosphere, and the purification rate is high, and the invention belongs to the technical field of air pollution control.
Description
Technical Field
The invention relates to the technical field of air pollution control, in particular to a method for removing NO and VOCs in flue gas.
Background
The flue gas of biomass boiler, garbage and sludge incineration flue gas are equivalent to contain a large amount of Nitrogen Oxides (NO) x ) And Volatile Organic Compounds (VOCs). NO (NO) x And VOCs not only directly pollute the air, but also cause photochemical smog and secondary particulate matters (such as PM 2.5 ) And ozone generation, which causes deterioration of air quality and harm to life health. With a series of harsh NO x And VOCs emission standard, NO x And control of VOCs present a significant challenge.
The flue gas denitration mainly comprises a selective catalytic reduction method, a non-selective catalytic reduction method and the like. The VOCs removing method includes absorption method, adsorption method, catalytic oxidation method, biological method, etc. To save the floor space of the flue gas treatment facilities and the investment operation cost, NO x The technology of cooperative control of multiple pollutants of VOCs becomes a research hotspot. CN201810069060.7 discloses a manganese-based catalyst for efficiently purifying nitrogen oxides and dioxins in a synergistic manner, and for catalytic reduction of NO x Is used for simultaneously catalyzing and oxidizing dioxin. CN111229238A discloses an ordered porous perovskite catalyst which can catalyze the oxidation of NO and toluene simultaneously. These patents all utilize gas-solid two-phase catalytic reactions to achieve simultaneous removal of NO and VOCs, but are prone to carbon deposition byproducts, resulting in catalyst deactivation. ZL103721550B discloses a wet method simultaneous desulfurization and denitrification VOCs absorbent, which utilizes a gas-liquid two-phase reaction to realize simultaneous removal of three pollutants, but the absorbent needs to be continuously supplemented, the operation cost is relatively high, and the removal rate of insoluble VOCs is low. It can be seen that the prior art is difficult to stably, efficiently and inexpensively cooperatively remove the NO and VOCs in the flue gas.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims at: the method for removing NO and VOCs in the flue gas is efficient and does not generate secondary pollution.
In order to achieve the above object, the present invention adopts the following techniquesThe operation scheme is as follows: a method for removing NO and VOCs in flue gas adopts an ozone generator to manufacture ozone, ozone and flue gas are respectively introduced into a buffer tower, so that the ozone and the flue gas are fully mixed in the buffer tower to form mixed gas, and then the mixed gas is sequentially introduced into an oxidation tower, an absorption tower and an ozone destructor and then discharged; the oxidation tower is filled with a catalyst and water, and when the mixed gas enters the oxidation tower, the mixed gas is fully oxidized by ozone under the adsorption and catalysis actions of the catalyst; a spraying device is arranged in the absorption tower, and the mixed gas in the absorption tower is sprayed by the spraying device to absorb NO 2 、CO 2 And an absorber for HCl. The temperature of the solid waste incineration flue gas such as household garbage after dust removal and desulfurization is generally 100-200 ℃, water in an oxidation tower can be heated to 40-90 ℃, NO and VOCs in the flue gas are fully oxidized by ozone in the oxidation tower, oxidation products are absorbed in an absorption tower, and then the mixed gas passes through an ozone destructor to decompose and discharge unreacted ozone in the mixed gas.
Preferably, the oxidation tower is a bubbling tower, the oxidation tower comprises a gas distributor, the gas distributor is positioned at the bottom of the oxidation tower, the top of the oxidation tower is provided with a gas outlet, and the mixed gas enters the oxidation tower through the gas distributor and forms bubbles in water, is fully oxidized under the action of a catalyst and is discharged from the gas outlet.
Preferably, the oxidation column comprises a heat insulating layer.
As a preferred form, the absorbent is Ca (OH) 2 And CaSO 3 Is a mixed solution of (a) and (b).
Preferably, the catalyst is a carbon-based catalyst, the catalyst is in a powder form and is uniformly distributed in water, the particle size of the catalyst is less than 200 meshes, and the metal loading is 1-10wt.%.
In the oxidation tower, the catalyst has the functions of improving the mass transfer efficiency of reactant molecules and catalyzing ozone oxidation, and the efficient and simultaneous removal of NO and VOCs is realized. The powdery carbon-based catalyst can change the interface effect of gas-liquid two phases, increase the gas-liquid contact area, reduce the gas-liquid film resistance and improve NO, VOCs, O 3 Gas-liquid mass transfer efficiency in water. The hydrophobic porous carbon-based catalyst can adsorb NO, VOCs, O 3 Enhancing intermolecular grafting of reactantsContact and oxidation reactions. The surface of the carbon-based catalyst has rich active oxygen groups, can promote ozone adsorption and decomposition to generate high-activity oxygen species such as more polyhydroxy free radicals, superoxide free radicals and the like, has selectivity for oxidation of ozone, has low mineralization rate of organic matters, is nonselective for oxidation of hydroxy free radicals, and can deeply remove VOCs with complex components. Thus, on the one hand, NO can be oxidized by ozone/high active oxygen species to nitric acid or NO with higher solubility 2 The nitrogen oxides with the same valence state, on the other hand, VOCs can be oxidized into small molecular organic acid and other products, and finally mineralized into CO 2 And H 2 O, etc.
The purpose of the liquid phase catalytic ozonation method is to eliminate the negative influence of carbon deposit and chlorine poisoning in the oxidation process of VOCs. In the gas-solid two-phase catalytic reaction, the generated organic byproducts are deposited on the surface of the catalyst in the form of carbon deposit to occupy active sites and pores, so that the catalyst is deactivated, and in addition, the chlorine-containing volatile organic matters in the flue gas generate chloride (CCl) in the catalytic oxidation reaction 4 HCl, etc.), poisoning the catalyst active site results in deactivation. In the gas-liquid-solid three-phase catalytic reaction system, the generated organic byproducts and chlorides are not easy to deposit on the surface of the catalyst to form carbon deposit and poison active components under the action of hydraulic force, so that the carbon deposit deactivation and the chlorine poisoning deactivation of the catalyst are effectively slowed down, and the defects of gas-solid phase catalysis are overcome.
In the absorption tower, the absorbent is Ca (OH) 2 And CaSO 3 The mixed solution of (2) is reacted as follows, and the oxidation product NO generated by the oxidation tower 2 、CO 2 HCl and the like are further absorbed by the absorbent, so that the synergistic pollution and carbon reduction are realized, and secondary pollution is avoided.
2NO 2 +SO 3 2- +H 2 O→2H + +2NO 2 - +SO 4 2-
2NO 2 +CO 2 +2HCl+3Ca(OH) 2 +O 3 →CaCO 3 +Ca(NO 3 ) 2 +CaCl 2 +O 2 +4H 2 O
As a preference, the carbon-based catalyst is prepared by the following method:
firstly, selecting biomass as a raw material, and preparing the biomass into powder;
secondly, soaking powdery biomass in a metal salt solution, and stirring to form a mixed solution;
thirdly, drying the mixed solution, and then placing the dried mixed solution in an inert atmosphere for pyrolysis to obtain biochar;
and fourthly, physically activating the biochar under the action of oxidizing gas to obtain the carbon-based catalyst.
Preferably, in the first step, the biomass is one or more of straw, wood, bamboo, fruit shell, and sawdust.
Preferably, in the second step, the metal salt solution is prepared by dissolving metal salt in deionized water, wherein the metal element in the metal salt is one or more of transition metal Mn, fe, co, cu, ni and rare earth metals Ce and Sm, and the metal salt is one or more of nitrate, chloride and acetate; stirring by a magnetic stirrer, wherein the temperature of the solution is controlled to be 25-60 ℃ during stirring, and the stirring time is 12-24h.
Preferably, in the third step, the drying temperature is 80-110 ℃ and the drying time is 12-24 hours; the pyrolysis heating rate is 5-15 ℃/min, the pyrolysis final temperature is 500-700 ℃, and the pyrolysis final temperature retention time is 1-3h; in the fourth step, the oxidizing gas includes H 2 O、CO 2 One or more of oxygen, the activation temperature is 600-900 ℃, and the activation time is 1-3h.
The specific surface area of the carbon-based catalyst manufactured by the method is generally 400-800m 2 And/g, the adsorption capacity is large, and the catalyst has the functions of promoting gas-liquid mass transfer, adsorption and catalysis; the metal plays a role of a catalyst in the biological carbon activation process, reduces the physical activation temperature and improves the activation effect.
The supported carbon-based catalyst prepared by the traditional impregnation method has the advantages that metal particles are easy to agglomerate and poor in dispersibility, the carbon-based catalyst generated in situ is adopted, the dispersity of the metal particles is high, the atomic layers are highly mixed, and the interaction is strong; when the traditional supported metal catalyst is used for liquid phase catalysis, metal is easy to dissolve out in a solution, so that the activity is reduced and secondary pollution is caused.
In general, the invention has the following advantages:
1. the method adopts liquid phase catalytic ozonation and wet absorption to remove NO and VOCs in the flue gas, has high removal rate of NO and VOCs which can be higher than 80 percent at the same time, and has long service life because the catalyst is not easy to be deactivated by carbon deposit and chlorine poisoning in a gas-liquid-solid three-phase catalytic reaction system.
2. The carbon-based catalyst suitable for liquid phase catalytic ozonation is prepared in situ, has the advantages of simple preparation, low cost, no toxicity, low metal dissolution rate, dispersed active ingredients, high mixing of different metals and low physical activation temperature, and has the functions of promoting gas-liquid mass transfer, adsorption and catalysis.
3. The oxidation tower fully utilizes the heat of the flue gas without additional heat source, and an absorption tower is arranged behind the oxidation tower to oxidize the NO product 2 、CO 2 HCl is absorbed, so that the synergistic pollution reduction and carbon reduction are realized, and secondary pollution is avoided. Therefore, the invention has the advantages of simplicity, high efficiency, safety, reliability, wide adaptability, no secondary pollution, low energy consumption and low operation cost.
Drawings
FIG. 1 is a schematic diagram of an apparatus for use in a method for removing NO and VOCs from flue gas.
Wherein, 1 is an ozone generator, 2 is a buffer tower, 3 is an oxidation tower, 4 is an absorption tower, 5 is an ozone destructor, 6 is water, 7 is an insulating layer, 8 is a gas distributor, and 9 is a circulating pump.
Detailed Description
The invention will be described in further detail with reference to the drawings and the detailed description.
Example 1
As shown in figure 1, a method for removing NO and VOCs in flue gas adopts an ozone generator 1 to manufacture ozone, and the ozone and the flue gas are respectively introduced into a buffer tower 2 so as to lead the ozone and the flue gas to be in slow releaseFully mixing in the flushing tower to form mixed gas, and then sequentially introducing the mixed gas into the oxidation tower 3, the absorption tower 4 and the ozone destructor 5 for discharging; the oxidation tower is filled with a catalyst and water 6, and when the mixed gas enters the oxidation tower, the mixed gas is fully oxidized by ozone under the adsorption and catalysis of the catalyst; a spraying device is arranged in the absorption tower, and the mixed gas in the absorption tower is sprayed by the spraying device to absorb NO 2 、CO 2 And an absorber for HCl.
The oxidation tower is a bubbling tower, the oxidation tower comprises a gas distributor 8, the gas distributor is positioned at the bottom of the oxidation tower, the top of the oxidation tower is provided with an exhaust port, and the mixed gas enters the oxidation tower through the gas distributor and forms bubbles in water, and is fully oxidized under the action of a catalyst and then is discharged from the exhaust port.
The oxidation tower comprises a heat-insulating layer 7.
The buffer tower is provided with a flue gas inlet, an ozone inlet and a buffer tower outlet, the outlet of the ozone generator is connected with the ozone inlet through a pipeline, the buffer tower outlet is positioned at the top of the buffer tower, the buffer tower outlet is connected with a gas distributor through a pipeline, the absorption tower is provided with an absorption tower inlet, an absorption tower outlet and an absorbent circulating outlet, the spraying device comprises a spray head, the absorbent circulating outlet is connected with the spraying device through a circulating pump 9, an exhaust port on the oxidation tower is connected with the absorption tower inlet through a pipeline, and the absorption tower outlet is connected with the inlet of the ozone destructor through a pipeline.
The absorbent is Ca (OH) 2 And CaSO 3 Is a mixed solution of (a) and (b).
The catalyst is a carbon-based catalyst, the catalyst is in a powder form and is uniformly distributed in water under the drive of bubbles, the particle size of the catalyst is less than 200 meshes, and the metal loading amount is 1-10wt.%.
The carbon-based catalyst is prepared by the following method:
firstly, selecting biomass as a raw material, and preparing the biomass into powder;
secondly, soaking powdery biomass in a metal salt solution, and stirring to form a mixed solution;
thirdly, drying the mixed solution, and then placing the dried mixed solution in an inert atmosphere for pyrolysis to obtain biochar;
and fourthly, physically activating the biochar under the action of oxidizing gas to obtain the carbon-based catalyst.
In the first step, the biomass is one or more of straw, wood, bamboo, fruit shell and sawdust.
In the second step, the metal salt solution is prepared by dissolving metal salt in deionized water, wherein the metal element in the metal salt is one or more of transition metal Mn, fe, co, cu, ni and rare earth metal Ce and Sm, and the metal salt is one or more of nitrate, chloride and acetate; stirring by a magnetic stirrer, wherein the temperature of the solution is controlled to be 25-60 ℃ during stirring, and the stirring time is 12-24h.
In the third step, the drying temperature is 80-110 ℃ and the drying time is 12-24 hours; the pyrolysis heating rate is 5-15 ℃/min, the pyrolysis final temperature is 500-700 ℃, and the pyrolysis final temperature retention time is 1-3h.
In the fourth step, the oxidizing gas includes H 2 O、CO 2 One or more of oxygen, the activation temperature is 600-900 ℃, and the activation time is 1-3h.
The catalyst is specifically CoO x AC catalyst (wherein AC is activated carbon), preparation process: 0.8g of cobalt nitrate hexahydrate was weighed into 100mL of deionized water, 10g of powdered coconut shell was added to the cobalt nitrate solution, stirred continuously at 60℃for 12 hours, and dried at 105℃for 12 hours. At N 2 Heating to 600 ℃ at 10 ℃ per minute in the atmosphere, and then staying for 1h to obtain Co/AC. Then use CO 2 Activating at 800 deg.C for 1 hr to obtain CoO x AC catalyst, ground to a particle size of less than 200 mesh.
Oxidation reaction conditions in the oxygen column: water 1L, catalyst 3g, NO 100ppm, toluene (VOCs representative) 50ppm, O 3 100-1200ppm，O 2 10vol.％，N 2 Balance, total flow of flue gas is 1L/min, and reaction temperature is 60 ℃.
Under the oxidation reaction conditions, the reaction effect is measured: the NO conversion rate can reach 84.2%, and the toluene conversion rate can reach 91.0%.
Example two
The catalyst is specifically CeO x The catalyst used in the reaction of the catalyst,the preparation process comprises the following steps: 1.67g of cerium nitrate hexahydrate was weighed into 100mL of deionized water, 10g of powdered coconut shell was added to the cerium nitrate solution, stirred continuously at 60℃for 12 hours, and dried at 105℃for 12 hours. At N 2 Heating to 600 ℃ at 10 ℃ per minute in the atmosphere, and then staying for 1h to obtain Ce/AC. Then use CO 2 Activating at 800 deg.c for 1 hr to obtain CeO x AC catalyst, ground to a particle size of less than 200 mesh.
Oxidation reaction conditions in the oxygen column: water 1L, catalyst 3g, NO 100ppm, toluene (VOCs representative) 50ppm, O 3 100-1200ppm，O 2 10vol.％，N 2 Balance, total flow of flue gas is 1L/min, and reaction temperature is 60 ℃.
Under the oxidation reaction conditions, the reaction effect is measured: the NO conversion rate can reach 82.7%, and the toluene conversion rate can reach 88.2%.
The non-implemented part of this embodiment is the same as the first embodiment.
Example III
The catalyst is FeO x AC catalyst, preparation process: 1.67g of ferric nitrate nonahydrate was weighed into 100mL of deionized water, 10g of powdered coconut shell was added to the ferric nitrate solution, stirring was continued at 60℃for 12h, and the mixture was dried at 105℃for 12h. At N 2 Heating to 600 ℃ at 10 ℃ per minute in the atmosphere, and then staying for 1h to obtain Fe/AC. Then use CO 2 Activating at 800 deg.C for 1 hr to obtain FeO x AC catalyst, ground to a particle size of less than 200 mesh.
Oxidation reaction conditions in the oxygen column: water 1L, catalyst 3g, NO 100ppm, toluene (VOCs representative) 50ppm, O 3 100-1200ppm，O 2 10vol.％，N 2 Balance, total flow of flue gas is 1L/min, and reaction temperature is 60 ℃.
Under the oxidation reaction conditions, the reaction effect is measured: the NO conversion rate can reach 83.1%, and the toluene conversion rate can reach 86.9%.
The non-implemented part of this embodiment is the same as the first embodiment.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. A method for removing NO and VOCs in flue gas, which is characterized by comprising the following steps: ozone is manufactured by adopting an ozone generator, ozone and smoke are respectively introduced into a buffer tower, so that the ozone and the smoke are fully mixed in the buffer tower to form mixed gas, and then the mixed gas is sequentially introduced into an oxidation tower, an absorption tower and an ozone destructor and then discharged;
the oxidation tower is filled with a catalyst and water, and when the mixed gas enters the oxidation tower, the mixed gas is fully oxidized by ozone under the adsorption and catalysis actions of the catalyst;
a spraying device is arranged in the absorption tower, and the absorbent capable of absorbing NO2, CO2 and HCl is sprayed to the mixed gas in the absorption tower through the spraying device;
the catalyst is a carbon-based catalyst, the catalyst is in a powder form and is uniformly distributed in water under the action of bubbles, the particle size of the catalyst is less than 200 meshes, and the metal loading amount is 1-10 wt%;
the oxidation tower is a bubbling tower, the oxidation tower comprises a gas distributor, the gas distributor is positioned at the bottom of the oxidation tower, the top of the oxidation tower is provided with an exhaust port, and the mixed gas enters the oxidation tower through the gas distributor and forms bubbles in water, is fully oxidized under the action of a catalyst and is discharged from the exhaust port;
the carbon-based catalyst is prepared by the following method:
firstly, selecting biomass as a raw material, and preparing the biomass into powder;
secondly, soaking powdery biomass in a metal salt solution, and stirring to form a mixed solution;
thirdly, drying the mixed solution, and then placing the dried mixed solution in an inert atmosphere for pyrolysis to obtain biochar;
step four, physically activating the biochar under the action of oxidizing gas to obtain a carbon-based catalyst;
in the second step, the metal salt solution is prepared by dissolving metal salt in deionized water, wherein the metal element in the metal salt is one or more of transition metal Mn, fe, co, cu, ni and rare earth metal Ce and Sm, and the metal salt is one or more of nitrate, chloride and acetate.
2. A method of removing NO and VOCs from flue gas according to claim 1, wherein: the oxidation tower comprises an insulating layer.
3. A method of removing NO and VOCs from flue gas according to claim 1, wherein: the absorbent is a mixed solution of Ca (OH) 2 and CaSO 3.
4. A method of removing NO and VOCs from flue gas according to claim 1, wherein: in the first step, the biomass is one or more of straw, wood, bamboo, fruit shell and sawdust.
5. A method of removing NO and VOCs from flue gas according to claim 1, wherein: in the second step, stirring by a magnetic stirrer, wherein the temperature of the solution is controlled to be 25-60 ℃ during stirring, and the stirring time is 12-24 hours.
6. A method of removing NO and VOCs from flue gas according to claim 1, wherein: in the third step, the drying temperature is 80-110 ℃ and the drying time is 12-24 hours; the pyrolysis heating rate is 5-15 ℃/min, the pyrolysis final temperature is 500-700 ℃, and the pyrolysis final temperature retention time is 1-3h;
in the fourth step, the oxidizing gas comprises one or more of H2O, CO and oxygen, the activation temperature is 600-900 ℃, and the activation time is 1-3H.
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