CN105327612A - Flue gas low-temperature combined desulfurization and denitration technology method - Google Patents
Flue gas low-temperature combined desulfurization and denitration technology method Download PDFInfo
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Abstract
The invention discloses a flue gas low-temperature combined desulfurization and denitration technology method mainly including the steps: flue gas after dedusting having a purification temperature and humidity meeting desulfurization conditions is sent into a desulfurization tower to flow through a desulfurization catalyst bed, sulfur dioxide in the flue gas is oxidized into sulfur trioxide under the action of a catalyst, and sulfur trioxide acts with water in the flue gas to generate sulfuric acid; the desulfurization catalyst bed is regenerated through progressively-decreased sulfuric acid concentration gradient washing; the flue gas after desulfurization is sent into a denitration conditioning work section, is dehumidified and heated, and is adjusted to meet requirements of a denitration technology; the flue gas after dehumidification and heating is sent into a mixing tower and is mixed with injected ammonia gas, the mixed flue gas mixed with the ammonia gas is sent into a denitration tower to flow through a denitration catalyst bed, and NOx, NH3 and O2 in the mixed flue gas are converted into N2 and water under the action of a denitration catalyst. The problems that a conventional flue gas desulfurization and denitration technology is narrow in flue gas applicable scope, high in heating energy consumption, high in running cost and the like are overcome.
Description
Technical field
The invention belongs to flue gases purification field, be specifically related to the combined desulfurization and denitrification process method removing sulfur dioxide in flue gas and nitrogen oxide, for the purified treatment of industrial smoke.
Background technology
Sulfur dioxide and nitrogen oxide are the major pollutants of air, are also the Focal point and difficult points of air contaminant treatment and environmental protection.In recent years, in order to control sulfur dioxide and discharged nitrous oxides, a lot of country of the world has all put into effect a large amount of laws and regulations and has been controlled its discharge, and increasingly strict to the control of sulfur dioxide and discharged nitrous oxides.
Pollutant sulfur dioxide in air and nitrogen oxide are mainly derived from the flue gas after petrochemical industry substance combustion.Up to the present, flue gas desulfurization and denitrification controls sulfur dioxide and the most effective technology of nitrogen oxides pollution.
Flue gas desulfurization technique is mainly divided into wet desulphurization and the large class of dry desulfurization two.So-called wet desulphurization, main method is that the sulfur dioxide sprayed in lime white and flue gas reacts the calcium sulfate gypsum generating pulpous state, because the calcium sulfate gypsum impurity of pulpous state is more, cannot effectively utilize at present, therefore wet method removes the sulfur dioxide in flue gas, not only investment is large, and operating cost is high, but also can produce secondary pollution.These shortcomings seriously constrain promoting the use of and development of wet method.So-called dry flue gas desulphurization is that application powdery or granular absorbent, adsorbent or catalyst are to remove the SO in flue gas
2.Advantage is that technical process is simple, without sewage, dirty acid treatment problem, energy consumption is low, and particularly after purification, flue-gas temperature is higher, is conducive to chimney exhaust diffusion, " white cigarette " phenomenon can not be produced, flue gas after purification does not need post bake, and corrosivity is little, and its shortcoming is that desulfuration efficiency is lower, equipment is huge, investment is large, floor space is large, and operating technology requires high.
The control of current domestic nitrogen oxide mainly relies on low NO
xcombustion control technology, the problem that the denitration technology ubiquity denitration efficiency of commercial Application is lower, can not meet the strict discharge standard of China.Take the denitration engineering project that selective catalytic reduction reaction (SCR) technology is built, adopt denitrating catalyst to be high temperature denitrating catalyst, denitrating technique adopts traditional high-temperature high dust arrangement usually, before being arranged in dust-removing desulfurating apparatus by denitration catalyst reactor, reaction temperature is generally about 350 DEG C.When adopting this arrangement, the cost transformed original production workshop section is higher, and catalyst exposure is in the complicated flue gas of the grey high-sulfur of height, easily weares and teares, poisoning, affect catalyst life.
There is bibliographical information, have developed the low-temperature denitration catalyst that Applicable temperature is 160 DEG C ~ 240 DEG C.Adopt this low-temperature denitration catalyst to carry out denitration to flue gas, technology arrangement mode has two kinds, one be denitration catalyst reaction bed is arranged in deduster after, before desulphurization reaction bed; Another kind be denitration catalyst reaction bed is arranged in desulphurization reaction bed after.For front a kind of arrangement, advantage directly to remove nitrogen oxides in effluent, do not need to carry out dehumidifying heating to flue gas, floor space is little, but denitrating catalyst has strict demand to the dust content in flue gas and content of sulfur dioxide, and content of sulfur dioxide in flue gas is usually all higher, therefore, this kind of arrangement flue gas that can be suitable for is considerably less.For rear a kind of arrangement, although flue gas content of sulfur dioxide after desulfurization is low, the requirement of denitrating catalyst to sulfur dioxide in flue gas content can be met, but the temperature of flue gas after desulfurization only has 50 DEG C ~ 70 DEG C, and denitrating flue gas needs to carry out 160 DEG C ~ 240 DEG C operating temperatures, therefore need the temperature of flue gas to be heated to 160 DEG C ~ 240 DEG C by 50 DEG C ~ 70 DEG C, this just causes heating energy consumption high, flue gas desulfurization and denitrification operating cost is high, and the enthusiasm that enterprise governance is polluted is not high.
Summary of the invention
For the deficiency that the flue gas desulfurization and denitrification of prior art exists, the present invention aims to provide a kind of new flue gas low-temperature combined desulfurization and denitrification process method, the problems such as to overcome the flue gas narrow application range of existing flue gas desulfurization and denitration technique existence, or heating energy consumption is high, and operating cost is high.
Flue gas low-temperature combined desulfurization and denitrification process method provided by the invention, mainly comprises:
(1) flue gas desulfurization workshop section, flue gas dust content, temperature and humidity being met desulfurization requirement sends into desulfurizing tower, it is made to flow through desulphurization catalyst bed, sulfur dioxide in flue gas, oxygen are oxidized to sulfur trioxide under the catalysed oxidn of catalyst, water effect in sulfur trioxide and flue gas generates sulfuric acid, and the flue gas after desulfurization sends into the modified workshop section of denitration, and desulfurization operations temperature is 50 DEG C ~ 150 DEG C, preferably 60 DEG C ~ 120 DEG C, particularly preferably 70 DEG C ~ 100 DEG C; Relative humidity is 6% ~ 12%;
(2) desulphurization catalyst bed regenerative section, sulfur dioxide in flue gas concentration after desulfurization reaches designing requirement concentration, stop desulfurization operation, with sulfuric acid solution and clear water, descending concentrations gradient wash is carried out to desulphurization catalyst bed, and the cleaning solution after this washing step washing in the operation of this regeneration cycle is used as the washing liquid of the last washing step in regeneration cycle operation next time, purge beds with air again with after clear water washing, the activity of catalyst is recovered;
(3) the modified workshop section of denitration, the flue gas after desulfurization sends into dehumidifying tower successively, heater carries out dehumidifying, heating respectively, the temperature of flue gas and relative humidity is adjusted to the process conditions meeting denitration and require;
(4) mix workshop section, the flue gas after dehumidifying, heating sends into the ammonia of mixing column and feeding, air mixes, the addition of ammonia meets the amount with the reaction of nitrogen oxides demand in flue gas in denitrification process;
(5) denitration workshop section, is mixed with the flue gas gaseous mixture feeding denitrating tower of ammonia, air, makes it flow through denitrating catalyst bed, nitrogen oxide NO in gaseous mixture
xwith NH
3, O
2n is converted under the catalytic action of denitrating catalyst
2and water, discharge from denitrating tower, denitration operating temperature is 80 DEG C ~ 158 DEG C.
In technique scheme of the present invention, desulfurization condition requirement is met for dust content after dedusting, temperature is or/and humidity can not meet the flue gas of desulfurization condition requirement, flue gas is before the desulfurization of feeding desulfurization workshop section, needing first flue gas to be sent into desulfurization tempering tower carries out modified, and the temperature of flue gas is met desulfurization condition requirement or/and humidity is adjusted to.Oxygen content in flue gas generally can desulfurization condition requirement, when the oxygen content that the oxygen content in flue gas is required to meet lower than desulfurization condition, generally take flue gas carry out desulfurization modified before, oxygen content in flue gas is adjusted to by passing into a certain amount of air the oxygen content meeting desulfurization condition requirement.
In technique scheme of the present invention, desulfurization workshop section is provided with the desulfurizing tower being no less than 2 independent operations, wherein a part of tower desulfurization operation, and a part of tower regeneration runs.Be typically provided with the desulfurizing tower of 4 independent operations, a part of tower desulfurization operation, a part of tower regeneration.Specifically according to the situation of sulfur dioxide in flue gas content, three towers parallel connections or series connection desulfurization operations can be taked to run, and a tower regenerative operation runs, and also can be that two towers parallel connections or desulfurization operations of connecting are run, two tower regenerative operations run.
In technique scheme of the present invention, when the sulfur dioxide concentration in flue gas after desulfurization rises to 50 ~ 100mg/Nm
3time, tower desulfurization operation need be stopped, needing to carry out regenerative operation to desulfurizing agent bed.Desulfurizing agent bed regenerative operation, preferentially selects the sulfuric acid solution of 4 kinds of variable concentrations and clear water to carry out descending concentrations gradient wash to beds successively by the height of sulfuric acid concentration.
In technique scheme of the present invention, the dehumidifying tower that the flue gas after desulfurization sends into the modified workshop section of denitration dehumidifies, and preferentially takes step-down condensation method to carry out dehumidification to flue gas.
In technique scheme of the present invention, NH in flue gas gaseous mixture
3with NO
xmol ratio general control in (1 ~ 1.5): 1 scope.Ammonia in mixed flue gas and air are preferably by 1:(2 ~ 5) volume ratio first mix after send into mixing column again, with send into flue gas mix again.Ammonia and air dilute in tower in ammonia and mix, and the ammonia source of ammonia is liquefied ammonia; Air is the pure air through filtering.
In technique scheme of the present invention, the desulphurization catalyst used take Carbon Materials as carrier, with the low temperature composite desulfate catalyst that nickel, titanium, cerium etc. are active component, by country of Sichuan University flue-gas desulfurizing engineering Technical Research Center Development and Production, sell towards the society, the name of product is called SO
2low temperature catalyst, reactivity temperature 50-150 DEG C, SO
2concentration accommodation 600-7000mg/m
3, conversion ratio can reach more than 99%.
In technique scheme of the present invention, the denitrating catalyst used take active carbon as carrier, with cerium, metal oxide for active component, be equipped with the denitration low temperature catalyst that adhesive is made, by country of Sichuan University flue-gas desulfurizing engineering Technical Research Center Development and Production, sell towards the society, the name of product is called NO
xlow temperature catalyst, reactivity temperature 80-158 DEG C, NO
xconcentration accommodation 500-2000mg/m
3, conversion ratio can reach more than 80%.
Flue gas low-temperature combined desulfurization and denitrification process method provided by the invention is by novel low-temp desulfurization catalysis method and low temperature NH
3-SCR method combine formed a kind of combined desulfurization and denitrification process.Desulfurization adopts new type low temperature catalysis method can realize the regeneration of flue gas desulfurization and desulfurizing agent, and carry out in the regenerative process of desulfurizing agent at a desulfurizing tower, do not affect the flue gas desulfurization process of other desulfurizing towers, ensure that the efficiency of desulfurization, and by-product sulfuric acid produces, in unharmful substance entered environment, its production process environmental protection, can realize recycling of resource.Denitration adopts low temperature NH
3-SCR, have stable, efficiency is high, low power consumption and other advantages.Choose suitable ammonia nitrogen ratio, both ensure that higher denitration activity, and also can not cause more NH
3escape.Before desulfurization is placed in denitration by present invention process, and before denitration, desulfurization dehumidifying is carried out to flue gas, reduce moisture and sulphur to the impact of denitrating catalyst activity, the long-term Effec-tive Function of denitrating catalyst can be ensured, running time can reach 3 years, does not need to carry out regeneration process to denitrating catalyst.In addition, denitration operating temperature of the present invention is only 80 DEG C ~ 158 DEG C, than the denitration operating temperature 160 DEG C ~ 248 DEG C of existing low-temperature denitration technology, temperature reduces greatly, flue gas is heated to 80 DEG C ~ 158 DEG C denitration operating temperatures by temperature 50 C ~ 150 after desulfurization DEG C by the present invention, the temperature amplitude of heat temperature raising reduces greatly, reduces heating energy consumption and operating cost.The flue gas low-temperature combined desulfurization and denitrification process method that the present invention proposes, has desulfurization and denitration efficiency is high, stable, technique is simple, and floor space is little, and capital expenditure is few, convenient management, the advantages such as production cost is low, have significant economic and environmental benefit and wide application prospect.
Accompanying drawing explanation
Fig. 1 is low temperature combined desulfurization and denitrification process flow chart of the present invention.
Label in figure is respectively: 1-purges air pump, 2-butterfly valve, and 3-dehumidifies tower, and 4-heater, 5-mixing column, 6-denitrating tower, 7-ammonia diluter, 8-liquefied ammonia, 9-blower fan, 10-regenerated liquid delivery pump, 11-regenerates liquid pool, 12-desulfurizing tower, 13-tempering tower, 14-blower fan.
Detailed description of the invention
Be embodied as example with present invention process in coke-oven plant of Wuhai of Inner Mongolia below, further illustrate the present invention, but therefore do not limit the present invention among described scope of embodiments.The flue-gas temperature of this coke-oven plant is about 150 DEG C, and humidity of flue gas meets the requirement of sulfur removal technology to moisture, requires that the discharge gas content of sulfur dioxide after desulphurization denitration process is not higher than 50mg/Nm
3, the content of nitrogen oxide is not higher than 100mg/Nm
3.
The technological process of the present embodiment as shown in Figure 1.The desulphurization system of the present embodiment uses four desulfurizing towers, four desulfurizing towers control by the control butterfly valve 2 on flue gas turnover air pipe the flue gas flow entering desulfurizing tower, and according to the size of smoke discharge amount and the height of sulfur dioxide in flue gas content, four desulfurizing towers can be arranged as different parallel waies, series system, realize desulfurization operations and regenerative operation, switch between desulfurization and regeneration, and stop.
The operation of desulphurization system, flue gas sends into desulfurization tempering tower by blower fan 14, the data obtained by the temperature sensor arranged in tempering tower and humidity sensor are learnt, the flue-gas temperature of about 150 DEG C meets desulfurization temperature conditional request, water capacity meets the conditional request of sulfur removal technology to moisture, therefore does not need to carry out the process of heating humidification to flue gas.Flue gas enters in desulfurizing tower 12, adopts the design of bottom in and top out.Flue gas flows through the low-temp desulfurization beds in tower, sulfur dioxide in flue gas, oxygen are oxidized to sulfur trioxide under the catalysed oxidn of catalyst, water effect in sulfur trioxide and flue gas generates sulfuric acid, on a catalyst, the flue gas after desulfurization is delivered to denitrating system after discharging from desulfurizing tower top in attachment.
When the content of sulfur dioxide in the flue gas of discharging from desulfurizing tower is greater than about 50mg/Nm
3time, the low-temp desulfurization beds in desulfurizing tower is regenerated.First close the smoke entrance of desulfurizing tower by controlling butterfly valve 2 during regeneration, the dilute sulfuric acid extracted successively in four different washing liquid pools 11 of concentration by regenerated liquid delivery pump 10 carries out gradient wash, dilute sulfuric acid about the purge column 15min of each concentration, finally rinse about 15min with clear water, the dilute sulfuric acid that after washing, concentration increases flows back in corresponding washing liquid pool.Cleaning solution as accessory substance is the sulfuric acid solution that concentration increases gradually, removes after sulfuric acid concentration increases to 30%.
Low-temp desulfurization beds, after rinsing regeneration, is opened and is purged air pump 1, purges desulfurizing tower more than beds 6h, can complete the regeneration of desulfurizing tower with air.Through the desulfurizing tower of this process recovers, normally can run more than 70h, and maintain desulfurization degree and be greater than 95%.Be provided with the thief hatch of flue gas analyzer at the smoke entrance of desulfurizing tower, when exporting sulfur dioxide concentration and being increased to designing requirement, by the duty regulating corresponding butterfly valve to switch tower, carry out regenerative operation subsequently.
Flue gas after desulfurization enters dehumidifying tower 3, dehumidifying tower takes step-down dehumidification by condensation method to dehumidify, and namely takes flue gas to send into a larger space, its pressure and temperature are reduced, make the condensate moisture in flue gas, condensed water is constantly discharged from the osculum of dehumidifying tower bottom.Dehumidifying tower serves minimizing flue gas moisture, slows down the effect of blower fan 9 and follow-up equipment corrosion, and can reduce the impact of moisture on denitrating catalyst activity.
Flue gas after dehumidifying enters heater 4, enters mixing column after flue-gas temperature being risen to about 140 DEG C, fully mixes at blender 5 with the ammonia after the dilution of injecting from ammonia diluter 7.Mixed flue gas enters denitrating tower 6.Denitrating tower is provided with two, and two denitrating towers take alternate run mode to arrange, flue gas after denitrating tower denitration from smoke stack emission.The concentration of the nitrogen oxides in effluent of ammonia injection rate according to flue gas analyzer, by ammonia nitrogen mol ratio 1:1, by regulating the flowmeter connecting ammonia bottle 8, control the ammonia flow of the system that enters, and 3 times that control that diluent air flow is ammonia flow, run with this understanding, denitration efficiency is stabilized in more than 80%, and ammonia flood rate is lower.
The actual operation parameters of the present embodiment all reaches the requirement of design technology.
Although below describe the specific embodiment of the present invention in conjunction with the embodiments, it will be understood by those of skill in the art that these only illustrate, protection scope of the present invention is that claims limit.Those skilled in the art, under the prerequisite not deviating from principle of the present invention and essence, can make various changes or modifications to these embodiments, but these change and amendment all falls into protection scope of the present invention.
Claims (10)
1. a flue gas low-temperature combined desulfurization and denitrification process method, is characterized in that mainly comprising:
(1) desulfurization workshop section, flue gas dust content, temperature and humidity being met desulfurization condition requirement sends into desulfurizing tower, it is made to flow through desulphurization catalyst bed, sulfur dioxide in flue gas, oxygen are oxidized to sulfur trioxide under the catalysed oxidn of catalyst, water effect in sulfur trioxide and flue gas generates sulfuric acid, flue gas after desulfurization sends into the modified workshop section of denitration, and flue gas desulfurization operating temperature is 50 DEG C ~ 150 DEG C, and relative humidity is 6% ~ 12%;
(2) desulphurization catalyst bed regenerative section, SO 2 from fume concentration after desulfurization reaches designing requirement concentration, stop desulfurization operation, with dilution heat of sulfuric acid and clear water, descending concentrations gradient wash is carried out to desulphurization catalyst bed, and the cleaning solution after this washing step washing in the operation of this regeneration cycle is used as the washing liquid of the last washing step in regeneration cycle operation next time, purge beds with air again with after clear water washing, the activity of catalyst is recovered;
(3) the modified workshop section of denitration, the flue gas after desulfurization sends into dehumidifying tower successively, heater carries out dehumidifying, heating respectively, the temperature of flue gas and relative humidity is adjusted to and meets denitrating technique requirement;
(4) mix workshop section, the flue gas after dehumidifying, heating sends into the ammonia of mixing column and injection, air mixes, the injection rate of ammonia is to meet the demand with the reaction of nitrogen oxides in flue gas in denitrification process;
(5) denitration workshop section, is mixed with the mixed flue gas feeding denitrating tower of ammonia, air, makes it flow through denitrating catalyst bed, the nitrogen oxide NO in mixed flue gas
xwith NH
3, O
2n is converted under the catalytic action of denitrating catalyst
2and water, discharge from denitrating tower, denitration operating temperature is 80 DEG C ~ 158 DEG C.
2. flue gas low-temperature combined desulfurization and denitrification process method according to claim 1, it is characterized in that, for temperature after udst separation or/and humidity does not meet the flue gas of desulfurization condition requirement, sent into desulfurization tempering tower, by temperature or/and humidity is adjusted to meet desulfurization condition requirement.
3. flue gas low-temperature combined desulfurization and denitrification process method according to claim 1, it is characterized in that, desulfurization workshop section is provided with the desulfurizing tower being no less than 2 independent operations, a part of tower desulfurization operation, and a part of tower regeneration runs.
4. flue gas low-temperature combined desulfurization and denitrification process method according to claim 2, it is characterized in that, desulfurization workshop section is provided with the desulfurizing tower of 4 independent operations, a part of tower desulfurization operation, a part of tower regeneration.
5. according to the flue gas low-temperature combined desulfurization and denitrification process method one of Claims 1-4 Suo Shu, it is characterized in that, when the sulfur dioxide concentration in flue gas after desulfurization is more than 50 ~ 100mg/Nm
3time, stop desulfurization operation, regenerative operation is carried out to desulfurizing agent bed.
6. according to the flue gas low-temperature combined desulfurization and denitrification process method one of Claims 1-4 Suo Shu, it is characterized in that, successively descending concentrations gradient wash is carried out to beds with the sulfuric acid solution of 4 kinds of variable concentrations and clear water by the height of sulfuric acid concentration.
7. according to the flue gas low-temperature combined desulfurization and denitrification process method one of Claims 1-4 Suo Shu, it is characterized in that, the flue gas after desulfurization is sent into dehumidifying tower and is taked step-down condensation method to carry out dehumidification to flue gas.
8., according to the flue gas low-temperature combined desulfurization and denitrification process method one of Claims 1-4 Suo Shu, it is characterized in that, the NH in mixed flue gas
3with NO
xmol ratio be (1 ~ 1.5): 1.
9., according to the flue gas low-temperature combined desulfurization and denitrification process method one of Claims 1-4 Suo Shu, it is characterized in that, ammonia and air are by 1:(2 ~ 5) volume ratio mix after send into mixing column again.
10. flue gas low-temperature combined desulfurization and denitrification process method according to claim 9, it is characterized in that, ammonia mixes in ammonia diluter with air, and the ammonia source of ammonia is liquefied ammonia, and air is the air purified after filtration.
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| CN110102299A (en) * | 2019-04-29 | 2019-08-09 | 华东理工大学 | A kind of desulphurization denitration dual purpose catalyst and its application |
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| CN110394056A (en) * | 2019-08-30 | 2019-11-01 | 华能国际电力股份有限公司 | Industrial boiler flue gas dehumidification, desulfurization and denitrification system and method |
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| CN110898626A (en) * | 2019-12-17 | 2020-03-24 | 无锡市华星电力环保工程有限公司 | Low-temperature flue gas denitration desulfurization washing system |
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