CN106000312B - A kind of flue gas multiple pollutant cooperation-removal agent for dense-phase tower technique - Google Patents
A kind of flue gas multiple pollutant cooperation-removal agent for dense-phase tower technique Download PDFInfo
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Abstract
The present invention provides a kind of flue gas multiple pollutant cooperation-removal agent for dense-phase tower technique, belongs to smoke comprehensive and administers field of material technology.The cooperation-removal agent is using breeze as raw material, and by roasting, cooling down, nitrogen atmosphere is surface-treated breeze, continues to roast, the final breeze that modified activation is made, i.e. cooperation-removal agent.The present invention can realize the desulfurization of flue gas, take off N, dedusting, removing heavy-metal, de- bioxin simultaneously, the cost of flue gas multiple pollutant removing be effectively reduced, the step of breeze also has been carried out the cyclic utilization of waste, and has eliminated regeneration.Breeze is by filling N2Surface treatment activation is carried out, not only effectively prevents breeze in the case that closed, relatively-high temperature easily explodes the problem of, also effectively evenly opens the acupoint on breeze surface, its absorption property is made to enhance 3 times or more.Scavenger preparation method of the present invention is simple, good adsorption performance, and the treatment of wastes with processes of wastes against one another, realizes the cyclic utilization of waste.
Description
Technical field
The present invention relates to smoke comprehensives to administer field of material technology, particularly relates to a kind of flue gas for dense-phase tower technique
Multi-pollutant cooperation-removal agent.
Background technology
While rapid economic development, the improvement of pollutant is very urgent in China, and haze is that each is Chinese in recent years
The pain of the people especially Beijing-Tianjin Ji people mind.Sulfur dioxide, nitrogen oxides and pellet are the main compositions of haze.
The suspended particulate substance of different-grain diameter in haze, can cause health different influences.Particle is thinner, and the chance being inhaled into is got over
Greatly, it is stronger in the in vivo activity of people, it is bigger to the harm of human body.Due to taking place frequently for haze weather, air contaminant treatment industry
Standard, national standard are stepping up, the proposition of near-zero release concept especially in recent years, most enterprises all towards this
Direction is close, and dust concentration effectively controls, by efficient cleaner.
Steel industry and power industry are the sources of pollutant emission, thus coal-burning boiler and iron and steel enterprise's smoke gas treatment into
Various regions Environmental Protection Agency mainlys grasp in recent years focus.New steel is put into effect within 2015 in the Hebei province of steel emission reduction maximum
Emission of industrial pollutants standard, steel and iron industry sintered particles object, sulfur dioxide, discharged nitrous oxides will be respectively plus tight in new standard
To 50,180 and 300mg/m3, blast furnace ironmaking particulate matter, sulfur dioxide, discharged nitrous oxides are limited to 20,80 and 300mg/m3,
Steel-making lime kiln white clouds stone kiln roasting particle object, sulfur dioxide, discharged nitrous oxides are limited to 30,80 and 400mg/m3, it is strict in
National standard.It is promulgated in face of new standard, most of iron and steel enterprises of China cannot or can not fully meet discharge standard requirement, compel
It is essential and wants upgrading.Only it is the requirement that meet new Air Pollutant Emission limit value in Hebei province according to measuring and calculating, it is following annual
Put into 30,000,000,000 yuan for transform and equipment operation, disposal of pollutants administer wide market.In terms of denitration, new standard
Discharged nitrous oxides concentration will all be performed by defining to all fired power generating units in 2015 is not higher than 200mg/m in key area3, it is non-
Key area 400mg/m3Limit value.The newly-increased unit of key area came into effect 200mg/m from 20103Emission limit.
Dense-phase tower technique is due to the stable, bed that do not collapse, circulating ratio is high and desulfuration efficiency is high, is always that industry is half-dried
The leading technique of method desulfurization.The present invention will change used reagent in dense-phase tower, and the breeze after activation is used for wherein, real
Existing multi-pollutant collaboration removal.
There is presently no application example and patent of the breeze in fume treatment, the patent being documented all concentrates on work
Property charcoal and activated coke desulfurization denitration in terms of, activated carbon and activated coke itself are expensive, and for fume treatment when work
Journey is invested and operating cost is high.Activated carbon and the patent of activated coke desulfurization denitration have at present, Chinese patent：
" a kind of desulphurization denitration changes by CN200910083045.9 " a kind of method for preparing desulphurizing activated coke ", CN201410851400.3
Property activated coke and preparation method thereof ", CN201010124815.2 " a kind of desulphurization denitration activated coke and preparation method thereof ",
" one kind is de- by CN201210400062.2 " a kind of activated coke desulfurization technique and its device " and CN201210250671.4
Sulphur activated coke and preparation method thereof ", but be to disclose the method for modifying of breeze and for flue gas multiple pollutant in these patents
The use of removing etc..Research and development are cheap, efficient, flue gas multiple pollutant cooperation-removal agent is current industrial smoke pollution control skill
The hot spot of art.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of de- for the flue gas multiple pollutant collaboration of dense-phase tower technique
Except agent, the problems such as expensive, relatively inefficient in industrial smoke multi-pollutant collaboration governance process is solved, the present invention is applicable in
In dense-phase tower technique.The cooperation-removal agent is the breeze of modified activation, is made by following steps：
(1) coke leftover bits and pieces --- breeze of the grain size in below 3mm is prepared, as raw material；
(2) breeze is roasted into 30-60min in 200 DEG C, the rotary calciner of 50-100 turns/min；
(3) after the breeze cooling 1h after step (2) is roasted, when temperature is down to 95-105 DEG C, lead in rotary calciner
Enter nitrogen, when nitrogen content reaches more than 99% in rotary calciner, stop nitrogen charging, close rotary calciner door, and will return
Turn calciner temperature to adjust to not heated condition, rotating speed is adjusted to 200r/min, starts to be surface-treated breeze, in nitrogen ring
1h is handled under border；
(4) continue rotary calciner being warming up to 500 DEG C, be calcined in rotating speed is the rotary calciner of 50-100 turns/min
30-60min；
(5) it is repeated once according to step (3), the final breeze that modified activation is made, i.e. cooperation-removal agent.
Wherein, breeze specific surface area that is modified, activating is 800-1000m2/ g, Sulfur capacity 28-49%.It is modified, activation
Breeze is at 80-120 DEG C, SO2Removal efficiency be more than 98.8%, NOxRemoval efficiency be more than 85%, the removal efficiency of dust is more than
97.7%th, Hg is He the removal efficiency of bioxin reaches 100%.
During the cooperation-removal agent use, fresh breeze need not be supplemented, considerably reduces intricate operation degree and drop
Low operating cost.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
The present invention can realize the desulfurization of flue gas, take off N, dedusting, removing heavy-metal, Tuo bioxin simultaneously, effectively reduce cigarette
Breeze has also been carried out the cyclic utilization of waste by the cost of gas multi-pollutant removing, and the step of eliminate regeneration.Breeze is by filling
N2Surface treatment activation is carried out, not only effectively prevents breeze in the case that closed, relatively-high temperature easily explodes the problem of, is also had
Effect equably opens the acupoint on breeze surface, its absorption property is made to enhance 3 times or more.Scavenger preparation method letter of the present invention
Single, good adsorption performance, and the treatment of wastes with processes of wastes against one another, realize the cyclic utilization of waste.The multi-pollutant cooperation-removal agent is suitable for close
Relevant tower process, and the manufacturing cost of scavenger is reduced, improve the removal efficiency of pollutant.
Specific embodiment
To make the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with specific implementation
Example is described in detail.
The present invention provides a kind of flue gas multiple pollutant cooperation-removal agent for dense-phase tower technique.
Breeze after activation enters as multi-pollutant cooperation-removal agent in dense-phase tower, with smoke contacts during simultaneously
Desulphurization denitration removing heavy-metal and dioxin, the process of breeze removing pollutant is the mistake of chemisorbed and physical absorption while effect
Journey.Physical absorption is primarily referred to as adsorbing by the hole on breeze surface after activation and internal capillary, so as to which pollutant be retained
In breeze；And chemisorbed is to be consolidated pollutant by features such as the oxygen-containing functional group on breeze surface and polar surfaces oxides
It is scheduled in breeze.The breeze of adsorption saturation is parsed by heating, and the breeze after parsing goes successively to dense-phase tower and carries out more pollutions
Object collaboration removal.It is more preferable compared with the pollutant removal of the breeze used for the first time by nonexpondable breeze, because by cigarette
The abrasion of gas and resolving, breeze grain size smaller, specific surface area increase, and the grain size of dense-phase tower requirement scavenger is smaller more
It is good.Therefore breeze need not supplement substantially, not only realize the treatment of wastes with processes of wastes against one another, also effectively reduce cost so that multi-pollutant cooperates with
It is suitable with desulphurization cost to remove cost.
It is illustrated with reference to specific embodiment.
Embodiment 1
Take grain size that it is roasted 30min in 200 DEG C, the rotary calciner of 50 turns/min for 3mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue rotary calciner being warming up to 500 DEG C, in the rotary calciner that rotating speed is 50 turns/min
Middle calcining 30min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, most
The breeze be modified afterwards, activated.Breeze specific surface area after activation is 801m2/ g, Sulfur capacity 28%.
Embodiment 2
Take grain size that it is roasted 30min in 200 DEG C, the rotary calciner of 50 turns/min for 2mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue roasting furnace temperature elevation to 500 DEG C, forged in the rotary calciner for being 50 turns/min in rotating speed
Burn 30min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, finally
To the breeze of modification, activation.Breeze specific surface area after activation is 837m2/ g, Sulfur capacity 35%.
Embodiment 3
Take grain size that it is roasted 60min in 200 DEG C, the rotary calciner of 100 turns/min for 2mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue roasting furnace temperature elevation to 500 DEG C, in the rotary calciner for being 100 turns/min in rotating speed
Calcine 60min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, finally
The breeze be modified, activated.Breeze specific surface area after activation is 856m2/ g, Sulfur capacity 35%.
Embodiment 4
Take grain size that it is roasted 60min in 200 DEG C, the rotary calciner of 100 turns/min for 2mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue roasting furnace temperature elevation to 500 DEG C, forged in the rotary calciner for being 50 turns/min in rotating speed
Burn 60min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, finally
To the breeze of modification, activation.Breeze specific surface area after activation is 951m2/ g, Sulfur capacity 44%.
Embodiment 5
Take grain size that it is roasted 60min in 200 DEG C, the rotary calciner of 100 turns/min for 1mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue roasting furnace temperature elevation to 500 DEG C, forged in the rotary calciner for being 50 turns/min in rotating speed
Burn 60min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, finally
To the breeze of modification, activation.Breeze specific surface area after activation is 982m2/ g, Sulfur capacity 49%.
Embodiment 6
Take grain size that it is roasted 30min in 200 DEG C, the rotary calciner of 50 turns/min for 1mm breeze 10kg first
Afterwards, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.Then fire door is turned off, and in rotary calciner
The nitrogen that purity is 99.99% is passed through, when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes back
Turn roasting fire door.In-furnace temperature is shown as 90 DEG C at this time, and rotating speed is adjusted to 200r/min, starts to be surface-treated breeze,
After handling 1h in a nitrogen environment, continue roasting furnace temperature elevation to 500 DEG C, forged in the rotary calciner for being 50 turns/min in rotating speed
Burn 30min.Fire door is opened after closing roaster 1h, after 1h, in-furnace temperature is down to 102 DEG C, repeats inflated with nitrogen step, finally
To the breeze of modification, activation.Breeze specific surface area after activation is 954m2/ g, Sulfur capacity 43%.
Embodiment 7
This embodiment is the contrast test under the conditions of not nitrogen charging.Grain size is taken first as 1mm breeze 10kg, by it at 200 DEG C,
After roasting 30min in the rotary calciner of 50 turns/min, fire door is then opened, after being cooled to 1h, breeze temperature is down to 98 DEG C.
Continue rotary calciner being warming up to 500 DEG C, 30min is calcined in the rotary calciner for being 50 turns/min in rotating speed.Close roasting
Fire door is opened after stove 1h, after 1h, in-furnace temperature is down to 102 DEG C, finally obtains the breeze of modified activation.Breeze after activation
Specific surface area is 310m2/ g, Sulfur capacity 15%.
Activation breeze and comparative sample made in embodiment 1-7 are fitted into batches in small-sized dense-phase tower and tested, is tried
The weight for testing activated coke breeze used is 7.5kg, and dense-phase tower volume is：0.125m3；Booster fan parameter is：Flow 75m3/ h,
Pressure 3000Pa；Set in tower stirring chain rotating speed as：1440r/h；Cloth bag size is：Diameter 130mm, height 1200mm, shares three
Bar cloth bag, cloth bag material are common Bi Dafu cloth bags.Simulated flue gas is passed through, smoke components are：NO200mg/L、SO23000mg/
L, 10%H2O, 16%O2、0.5μg/m3Hg steam, 0.5ng/m3Bioxin, dust 100mg/L, N2For Balance Air, gas componant
It is detected by the gas analyzer S720EX of SICK companies, Hg is He bioxin detects again after first sampling.Specific testing result such as 1 institute of table
Show.
As known from Table 1, in several embodiments, it is not much different for the removal effect of heavy metal, bioxin and dust.It is right
In SO2For NO, grain size is smaller and soak time is longer, and removal effect is better.But in view of grain size is small and soak time
The long economic problems brought, therefore in practical operation, control activation condition according to specific exhanst gas outlet concentration requirement, passing through
An optimal equalization point is taken between Ji and removal efficiency.
The more pollution synergetic scavenger effects of 1 this patent of table
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (3)
1. a kind of flue gas multiple pollutant cooperation-removal agent for dense-phase tower technique, it is characterised in that：The cooperation-removal agent is
Modified, activation breeze, is made by following steps：
（1）Prepare breeze of the grain size in below 3mm, as raw material；
（2）Breeze is roasted into 30-60min in 200 DEG C, the rotary calciner of 50-100 turns/min；
（3）By step（2）After breeze cooling 1h after roasting, when temperature is down to 95-105 DEG C, nitrogen is passed through in rotary calciner
Gas when nitrogen content reaches more than 99% in rotary calciner, stops nitrogen charging, closes rotary calciner door, and revolution is roasted
Furnace temperature is adjusted to not heated condition, and rotating speed is adjusted to 200r/min, is started to be surface-treated breeze, be located in a nitrogen environment
Manage 1h；
（4）Continue rotary calciner being warming up to 500 DEG C, 30- is calcined in rotating speed is the rotary calciner of 50-100 turns/min
60min；
（5）According to step（3）It is repeated once, the final breeze that modified activation is made；
The flue gas multiple pollutant that the cooperation-removal agent is applicable in contains SO2、NOx, dust, Hg is He bioxin.
2. the flue gas multiple pollutant cooperation-removal agent according to claim 1 for dense-phase tower technique, it is characterised in that：
The modification, the breeze specific surface area of activation are 800-1000m2/ g, Sulfur capacity 28-49%.
3. the flue gas multiple pollutant cooperation-removal agent according to claim 1 for dense-phase tower technique, it is characterised in that：
The modification, the breeze of activation are at 80-120 DEG C, SO2Removal efficiency be more than 98.8%, NOxRemoval efficiency be more than 85%, dust
Removal efficiency is more than 97.7%, Hg He the removal efficiency of bioxin reaches 100%.
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| CN105561781A (en) * | 2015-12-14 | 2016-05-11 | 重庆大学 | Method for removing NOx in sintering flue gas through low-temperature SCR (Selective Catalytic Reduction) catalyst |
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