CN109316954A - A method of utilizing multilayer catalytic degradation sintering flue gas pollutant - Google Patents
A method of utilizing multilayer catalytic degradation sintering flue gas pollutant Download PDFInfo
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- CN109316954A CN109316954A CN201811257393.9A CN201811257393A CN109316954A CN 109316954 A CN109316954 A CN 109316954A CN 201811257393 A CN201811257393 A CN 201811257393A CN 109316954 A CN109316954 A CN 109316954A
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/26—Drying gases or vapours
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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Abstract
The invention discloses a kind of methods using multilayer catalytic degradation sintering flue gas pollutant, belong to flue gas pollutant processing technology field.The sintering flue gas that sintering process generates in the present invention moves up in admission line along air inlet, and the movement of horizontal direction subsidiary conduit is continued by filter plate, it is moved in catalyst filter cylinder into the sintering flue gas in subsidiary conduit through collapsible tube, the V-Ce-Ti catalyst layer in catalyst filter cylinder carries out catalytic degradation to the pollutant in sintering flue gas；The present invention is passed through in catalyst filter cylinder by the sintering flue gas for generating sintering process, is successively handled the pollutant in sintering flue gas, and the content of pollutant in sintering flue gas can be reduced, and reduces pollution of the pollutant to environment.
Description
Technical field
The present invention relates to flue gas pollutant processing technology fields, utilize multilayer catalytic degradation more specifically to a kind of
The method of sintering flue gas pollutant.
Background technique
The development of steel and iron industry is that tremendous contribution is made in China's economic growth, while steel and iron industry is also Chinese national economy
Pillar industry, but China's steel and iron industry Environmental Protection Level is low, so that pollutant discharge amount is high, the maximum of iron and steel enterprise is dirty
Dye source is exactly to come from sintering flue gas, and the typical pollutant in sintering flue gas mainly includes dust, SO2, dioxin pollution object etc.,
Nitrogen oxides, dioxin removing sulfuldioxide mainly have three classes in sintering flue gas both at home and abroad at present, and the first kind is to utilize raw materials for sintering sulphur
The lone pair electrons of sulphur form complex compound inhibition dioxin generation with catalyst and react in compound, or utilize sulfur dioxide, ammonia
Group is reacted with chloride ion, reduces chlorine source and dioxin is inhibited to generate, although the method effect is that above have preferable suppression to PCDD
System, but it is very low to the inhibitory effect of PCDF, and sulfide cannot be removed；Second class is active carbon adsorption, utilizes active carbon
Porous adsorption capacity, achieve the effect that adsorbing and removing dioxin, but activated carbon method equipment investment operating cost is high, after absorption
Active carbon how to handle be also new problem；Third class is that selective catalytic reduction takes off dioxin, and key is to select
Although suitable catalyst, vanadium Ti-base catalyst can achieve higher dioxin removal efficiency, but at high price；Catalyst window
Mouth temperature is unreasonable, and sintering flue gas needs to be again heated to 300-450 DEG C or so and carries out de- dioxin, and two evils can occur for this temperature
The generation again of English；The V that catalyst after reaction contains2O5For extremely toxic substance, there are serious pollution, such as where to environment and biology
Catalyst after reason reaction is also new problem, and the country has more than 1000 iron ore sintering processes at present, possesses de- two and dislikes
English equipment less than 10.Therefore, it is there is an urgent need to study the pollutant removing technology being directed in sintering flue gas in present society
Steel industry clean manufacturing provides strong guarantee, and to ensuring that clean environment and human health have far reaching significance.
Through retrieving, the title of innovation and creation are as follows: sintering flue gas processing system and method (number of patent application:
CN201110449648.3, the applying date: 2012.07.18), it is used for synchronized desulfuring, denitration, removal of impurities and relieving haperacidity, and the system packet
Include: flue gas system, ammonia injection system, smoke processing system and acid making system, flue gas system include main exhauster and chimney；Flue gas
Processing system includes adsorption tower and Analytic Tower；The main exhauster and ammonia injection system of flue gas system are connected with adsorption tower respectively；Flue gas
The Analytic Tower of processing system is connected with acid making system；The adsorption tower of smoke processing system is connected with the chimney of flue gas system.The Shen
Please case be disadvantageous in that: must be in a heated condition to pollutant process, cannot be within the temperature range of sintering flue gas exports
Catalytic degradation is carried out to the pollutant in sintering flue gas.
Through retrieving, the title of innovation and creation are as follows: a kind of sintering plant smoke gas comprehensive treatment system and method and apply (patent Shen
Please number: CN201510903174.3, the applying date: 2015.12.09), this method includes successively taking off high sulfur contained high temoperature flue gas
Nitre processing, dust removal process, then cool down to the high sulfur contained high temoperature flue gas through denitration process, dust removal process, then carry out to it
Desulfurization process is discharged after finally heating to the flue gas through desulfurization process；Low sulfur-bearing low-temperature flue gas is dusted processing, then
By treated, flue gas is discharged；While cleaning flue gases, and recovery waste heat and waste heat can reasonably distribute again sharp
With improving the thermal efficiency of sintering system, realize energy-saving and emission-reduction.This application is disadvantageous in that: being needed by repeatedly removing
Journey, it is complicated for operation, while the dioxin in sintering flue gas cannot be removed, environmental pollution is more serious.
Summary of the invention
1. technical problems to be solved by the inivention
The deficiency that it is an object of the invention to overcome the method effect for being catalyzed emission reduction sintering flue gas in the prior art poor,
A kind of method using multilayer catalytic degradation sintering flue gas pollutant is improved, under cryogenic to the pollution in sintering flue gas
Object cleans, and sintering flue gas is avoided to enter atmosphere, it is possible to further avoid causing secondary pollution to environment.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of method using multilayer catalytic degradation sintering flue gas pollutant of the invention, the sintering cigarette that sintering process generates
Gas moves up in admission line along air inlet, and continues the movement of horizontal direction subsidiary conduit by filter plate, into subsidiary conduit
Interior sintering flue gas moves in catalyst filter cylinder through collapsible tube, and the V-Ce-Ti catalyst layer in catalyst filter cylinder is to sintering cigarette
Pollutant in gas carries out catalytic degradation.
Preferably, the specific steps are as follows: step 1: sintering flue gas moves upwards after entering admission line, and in deflector
Subsidiary conduit is moved under guiding role, sintering flue gas is turned to when flowing into subsidiary conduit by admission line；Step 2: burning
Knot flue gas moves downward in subsidiary conduit, and moves in catalyst filter cylinder by collapsible tube；Step 3: sintering flue gas into
After entering in catalyst filter cylinder, successively pass through molecular sieve layer and V-Ce-Ti catalyst layer, at the same vibrator to catalyst filter cylinder into
Row vibration, sintering flue gas are flowed out after catalyst filter cylinder catalytic degradation by the outlet of bottom.
Preferably, in step 1, sintering flue gas is filtered when entering subsidiary conduit by admission line by filter plate.
Preferably, in step 3, sintering flue gas is successively urged by molecular sieve layer, denitration after entering in catalyst filter cylinder
Agent layer and V-Ce-Ti catalyst layer.
Preferably, in step 3, molecular sieve layer accommodates 5A molecular sieve catalyst, and the pollutant in flue gas is in molecular sieve layer
It is adsorbed.
Preferably, in step 3, denitration catalyst oxidant layer accommodates Co-Mn-Ce catalyst, the NO in flue gasXIn denitration catalyst
By Co-Mn-Ce catalytic degradation in oxidant layer.
Preferably, in step 3, V-Ce-Ti catalyst layer accommodates VaCebTicOxCatalyst, the NO in flue gasXIt is disliked with two
English is in V-Ce-Ti catalyst layer by VaCebTicO catalytic degradation.
Preferably, the granularity of 5A molecular sieve catalyst is 8~12mm in molecular sieve layer；Co-Mn-Ce in denitration catalyst oxidant layer
The degree of catalyst is 4~5mm；V in V-Ce-Ti catalyst layeraCebTicThe granularity of O catalyst is 1~2mm.
Preferably, the V-Ce-Ti catalyst is VaCebTicOxCatalyst, wherein the oxide mass ratio of V and Ce be
The oxide mass of 0.5~1, Ce and Ti ratio are 0.05~0.16.
Preferably, the tall and big layer in molecular sieve layer of the layer of V-Ce-Ti catalyst layer is high.
3. beneficial effect
Using technical solution provided by the invention, compared with existing well-known technique, there is following remarkable result:
(1) a kind of method using multilayer catalytic degradation sintering flue gas pollutant of the invention, the burning that sintering process generates
Knot flue gas moves up in admission line along air inlet, and continues the movement of horizontal direction subsidiary conduit by filter plate, into auxiliary
Sintering flue gas in pipeline moves in catalyst filter cylinder through collapsible tube, and the V-Ce-Ti catalyst layer in catalyst filter cylinder is to burning
The pollutant tied in flue gas carries out catalytic degradation, can clean under cryogenic to the pollutant in sintering flue gas, letter
Change removal step, avoids generating secondary pollution；
(2) a kind of method using multilayer catalytic degradation sintering flue gas pollutant of the invention, sintering flue gas are urged in entrance
After in agent filter cylinder, successively pass through molecular sieve layer, denitration catalyst oxidant layer and V-Ce-Ti catalyst layer, molecular sieve layer can remove
Remove the H in sintering flue gas2O and SO2, prevent the catalyst poisoning in denitration catalyst oxidant layer and V-Ce-Ti catalyst layer, catalyst
Catalyst combination energy efficient cryogenic in filter cylinder removes the pollutant in sintering flue gas；
(3) a kind of method using multilayer catalytic degradation sintering flue gas pollutant of the invention, V-Ce-Ti catalyst layer
The tall and big layer in molecular sieve layer of layer is high, and the layer of the catalyst three times in catalyst filter cylinder is high different, can control sintering flue gas and exists
Residence time in catalyst filter cylinder preferably removes the pollutant in sintering flue gas；
Detailed description of the invention
Fig. 1 is a kind of overall structure diagram of the device of layering removing sintering flue gas pollutant；
Fig. 2 is the structural schematic diagram of deflector and collapsible tube of the invention；
Fig. 3 is the structural schematic diagram of catalyst filter cylinder of the invention；
Fig. 4 is mixed liquor A whipping process structural schematic diagram of the invention；
Fig. 5 is the filter plate schematic diagram of the embodiment of the present invention 2；
Fig. 6 is a kind of flow chart of method using multilayer catalytic degradation sintering flue gas pollutant of the invention.
Label declaration in schematic diagram:
100, catalyst filter cylinder；110, molecular sieve layer；120, denitration catalyst oxidant layer；130, V-Ce-Ti catalyst layer；140,
Strainer；
200, admission line；210, filter plate；220, deflector；221, upper end；222, lower end；230, vertical angle；
300, vibrator；
400, subsidiary conduit；410, collapsible tube；
A00, reaction kettle；Point is added dropwise in A01, solution；A10, whirlpool face；A11, swirl center；A12, whirlpool edge.
Specific embodiment
Hereafter detailed description of the present invention and example embodiment are more fully understood in combination with attached drawing, wherein of the invention
Element and feature are identified by appended drawing reference.
Structure depicted in this specification attached drawing, ratio, size etc., only to cooperate the revealed content of specification,
So that those skilled in the art understands and reads, enforceable qualifications are not intended to limit the invention, therefore do not have technology
On essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size can be generated not influencing the present invention
The effect of and the purpose that can reach under, should all still fall in the range of disclosed technology contents obtain and can cover.Together
When, cited such as "upper", "lower", "left", "right", " centre " term in this specification are merely convenient to the clear of narration,
Rather than to limit enforceable range, relativeness is altered or modified, under the content of no substantial changes in technology, when also regarding
For the enforceable scope of the present invention；In addition to this, it is not independent from each other between each embodiment of the invention, but can be with
It is combined.
Embodiment 1
As shown in connection with fig. 6, a kind of method using multilayer catalytic degradation sintering flue gas pollutant of the present embodiment, it is sintered
The sintering flue gas that journey generates moves up in admission line 200 along air inlet, and continues horizontal direction auxiliary tube by filter plate 210
Road 400 moves, and moves in catalyst filter cylinder 100 into the sintering flue gas in subsidiary conduit 400 through collapsible tube 410, catalyst
V-Ce-Ti catalyst layer 130 in filter cylinder 100 carries out catalytic degradation to the pollutant in sintering flue gas.It is above-mentioned a kind of using more
Specific step is as follows for the method for layer catalytic degradation sintering flue gas pollutant:
Step 1: sintering flue gas moves upwards after entering admission line 200, and moves under the guiding role of deflector 220
To subsidiary conduit 400, sintering flue gas is turned to when flowing into subsidiary conduit 400 by admission line 200；Detailed step are as follows:
Sintering flue gas is filtered, when sintering flue gas passes through filter when entering subsidiary conduit 400 by admission line 200 by filter plate 210
When plate 210 is moved to subsidiary conduit 400, the air inlet of subsidiary conduit 400 is connected with the gas outlet of admission line 200, works as sintering
When containing particulate matter in flue gas, the partial size of particulate matter is greater than the diameter of filter plate 210, so that particulate matter is under the blocking of filter plate 210
Without can enter in subsidiary conduit 400, while filter plate 210 is inclined at the top of admission line 200, and particulate matter is not easy to adhere to
Filter plate 210 is caused to be blocked on the surface of filter plate 210, to hinder sintering flue gas to enter in subsidiary conduit 400, and particulate matter
Under the effect of gravity and towards movement at the air inlet of admission line 200, promote sintering flue gas and particulate separation, it can
To improve the catalytic effect of sintering flue gas.
Step 2: sintering flue gas moves downward in subsidiary conduit 400, and moves to catalyst filter cylinder by collapsible tube 410
In 100；
Step 3: sintering flue gas successively passes through molecular sieve layer 110 and V-Ce-Ti after entering in catalyst filter cylinder 100
Catalyst layer 130, while vibrator 300 vibrates catalyst filter cylinder 100, sintering flue gas is catalyzed through catalyst filter cylinder 100
It is flowed out after degradation by the outlet of bottom.Detailed description is: sintering flue gas is after entering in catalyst filter cylinder 100, successively
By molecular sieve layer 110, denitration catalyst oxidant layer 120 and V-Ce-Ti catalyst layer 130, molecular sieve layer 110 accommodates 5A molecular sieve
Catalyst, the pollutant in flue gas are adsorbed in molecular sieve layer 110.After sintering flue gas enters catalyst filter cylinder 100, first pass through point
Sub- screen layers 110.5A molecular sieve catalyst is filled in molecular sieve layer 110, which is a kind of calcium A type alumino-silicate, can
To adsorb the substance that cut off diameter in sintering flue gas is not more than 5A, it is mainly used for adsorbing the H in flue gas2O and SO2, and molecular sieve layer
The granularity of 5A molecular sieve catalyst is 8~12mm in 110, and the granularity of 5A molecular sieve catalyst is 8mm, molecular sieve in the present embodiment
The a height of 1m of layer of layer 110.Further, sintering flue gas enters denitration catalyst oxidant layer 120, and denitration catalyst oxidant layer 120 accommodates Co-
Mn-Ce catalyst, the NO in flue gasXBy Co-Mn-Ce catalytic degradation in denitration catalyst oxidant layer 120, Co-Mn-Ce catalyst
Granularity is 4~5mm, the preferred 4mm of granularity of Co-Mn-Ce catalyst, a height of 1.5m of layer, Co-Mn-Ce catalyst in the present embodiment
Partial size be less than 5A molecular sieve catalyst partial size, 5A molecular sieve catalyst can be prevented to be mixed into Co-Mn-Ce catalyst.Sintering
Flue gas continues to move downwardly to V-Ce-Ti catalyst layer 130, is filled with V in V-Ce-Ti catalyst layer 130aCebTicOxCatalysis
Agent, and VaCebTicOxThe partial size of catalyst is 2~3mm, a height of 1.8m of layer.
The NO at 200 air inlet of admission line is detected simultaneouslyXConcentration 313mg/m-3, dioxin concentration is 0.86ng/
m-3, then detect the NO at 100 bottom gas outlet of catalyst filter cylinderXConcentration 187mg/m-3, dioxin concentration is 0.25ng/
m-3；NOXEmission reduction efficiency reach 40.26%；The emission reduction efficiency of dioxin reaches 70.93%；To realize NOXAnd dioxin
Joint emission reduction.
Referring to figs. 1 and 2, the device of a kind of layering of the invention removing sintering flue gas pollutant, including air inlet pipe
Road 200, subsidiary conduit 400 and catalyst filter cylinder 100.The bottom of admission line 200 is provided with air inlet, the air inlet and sintering
Large flue is connected, and the sintering flue gas generated in sintering process enters in admission line 200 through air inlet；The admission line 200
Gas outlet is arranged in top, is provided with filter plate 210 on the gas outlet, and the top droop of admission line 200 is provided with deflector
220。
The sintering flue gas that sintering process generates moves up in admission line 200 along air inlet, and continues along air inlet pipe
Road 200 moves upwards, and the top droop of admission line 200 is provided with deflector 220, while the top setting of admission line 200
Gas outlet, when sintering flue gas moves near deflector 220, sintering flue gas moves under the guiding role of deflector 220
The upper end 221 of filter plate 210, deflector 220 is connected with the top of filter plate 210；The lower end 222 of deflector 220 and air inlet pipe
The side wall in road 200 is connected, and the lower end 222 of deflector 220 is lower than the bottom of filter plate 210, while also avoiding sintering flue gas
It is moved downward under the double action of deflector 220 and air-flow along admission line 200, it is ensured that the sintering generated in sintering process
Flue gas can enter filter plate 210；Angle between filter plate 210 and deflector 220 is α, and the value range of α is 30~75 °, this implementation
Middle α value is 45 °, and deflector 220 can prevent sintering flue gas from moving at the vertical angle 230 of admission line 200 and condensing attachment
On 230 surface of vertical angle, the device of multilayer removing sintering flue gas pollutant is avoided to cause to be lost.
When sintering flue gas is moved by filter plate 210 to subsidiary conduit 400, the air inlet and air inlet pipe of subsidiary conduit 400
The gas outlet in road 200 is connected, and when containing particulate matter in sintering flue gas, the partial size of particulate matter is greater than the diameter of filter plate 210, so that
Particulate matter is without can enter in subsidiary conduit 400 under the blocking of filter plate 210, while filter plate 210 is inclined at admission line
200 top, particulate matter are not easy to be attached to the surface of filter plate 210 and filter plate 210 are caused to be blocked, thus hinder sintering flue gas into
Enter in subsidiary conduit 400, and particulate matter promotees under the effect of gravity and towards movement at the air inlet of admission line 200
Make sintering flue gas and particulate separation, the catalytic effect of sintering flue gas can be improved.400 lower part of subsidiary conduit is provided with collapsible tube
410, subsidiary conduit 400 is connected by collapsible tube 410 with the top of catalyst filter cylinder 100, and catalyst filter cylinder 100 is set to auxiliary
The bottom of pipeline 400, collapsible tube 410 is in the truncated cone shape stood upside down, it is ensured that between subsidiary conduit 400 and catalyst filter cylinder 100
Seamless connection, so that in sintering flue gas entire motion to catalyst filter cylinder 100.
Further, the top of catalyst filter cylinder 100 is provided with strainer 140, and the outside of catalyst filter cylinder 100 is provided with vibration
Dynamic device 300.For sintering flue gas after entering in catalyst filter cylinder 100, vibrator 300 vibrates catalyst filter cylinder 100, burns
Flue gas is tied to be flowed out after 100 catalytic degradation of catalyst filter cylinder by the outlet of bottom.When vibration, strainer 140 can prevent catalyst
Catalyst in filter cylinder 100 is shaked out because of vibration outside catalyst filter cylinder 100, so that catalyst content is lossy.
A kind of method using multilayer catalytic degradation sintering flue gas pollutant of the invention, the sintering cigarette that sintering process generates
Gas moves up in admission line 200 along air inlet, and continues horizontal direction subsidiary conduit 400 by filter plate 210 and move, and enters
Sintering flue gas in subsidiary conduit 400 moves in catalyst filter cylinder 100 through collapsible tube 410, the V- in catalyst filter cylinder 100
Ce-Ti catalyst layer 130 carries out catalytic degradation to the pollutant in sintering flue gas.This method can be under cryogenic to sintering
Pollutant in flue gas cleans, so that catalysis process simplification, catalyst denaturation is produced caused by can also avoiding because of high temperature
Raw extremely toxic substance, and then generate secondary pollution.
It is worth noting that specific preparation process is as follows for above-mentioned V-Ce-Ti catalyst:
Step 1: butyl titanate, glacial acetic acid and dehydrated alcohol are mixed, adds cerous nitrate and stir evenly obtained mixing
Liquid A；
Step 2: by oxalic acid obtained oxalic acid solution soluble in water, then ammonium metavanadate is added to oxalic acid solution obtained and is made
Mixed liquid B；
Step 3: mixed liquid B is added dropwise in mixed liquor A, gel is made；
Step 4: by V is made after the drying of above-mentioned gel, calciningaCebTicOxCatalyst.
VaCebTicOxCatalyst is made using sol-gal process one-step method, it can be ensured that ensures the element of institute's additive
Match constant, raising production efficiency.And allow the V-Ce-Ti catalyst being prepared on cryogenic conditions (about 200 DEG C of left sides
It is right) catalytic treatment is carried out to the sintering flue gas generated in sintering process, it can be to the dioxin and nitrogen oxides in sintering flue gas
Removal effect is played, while reducing the discharge of the dioxin in sintering flue gas and nitrogen oxides.
The mass ratio of water in butyl titanate and oxalic acid solution is 3.5~4, can be added dropwise to by mixed liquid B
Uniform and stable gel is formed during mixed liquor A, in mixed liquor A, provides basis to prepare catalyst；Ammonium metavanadate and grass
The mass ratio of acid solution is 0.028~0.035, can metavanadic acid is uniformly dissolved in oxalic acid solution, so that will mix
Close liquid B be added dropwise to during mixed liquor A, react it is more abundant, enable V more evenly, be effectively adhere on Ce-Ti carrier, into
And the catalytic effect of catalyst can be improved.In the present embodiment, the mass ratio of the water in butyl titanate and oxalic acid solution is
3.8, the mass ratio of ammonium metavanadate and oxalic acid solution is 0.032.Therefore the dosage of the present embodiment concrete component are as follows: butyl titanate
38.36g, glacial acetic acid 15g, dehydrated alcohol 40g, cerous nitrate 1.26g, oxalic acid 0.40g, water 10g, ammonium metavanadate 0.32g.This implementation
The specific preparation step of example are as follows:
Step 1: butyl titanate 38.36g, glacial acetic acid 15g and dehydrated alcohol mixing 40g are added cerous nitrate stirring
Uniformly obtained mixed liquor A；Glacial acetic acid and butyl titanate are mixed, butyl titanate dissolves in glacial acetic acid first and water
Solution coordination forms stable Ti (OH)x(OAc)y(wherein x+y=4) complex, wherein glacial acetic acid not only has butyl titanate molten
Solution effect, and play catalytic action；
Oxalic acid solution is made Step 2: the oxalic acid of 0.40g is dissolved in the water of 10g, then is added to oxalic acid solution obtained
Mixed liquid B is made in ammonium metavanadate, so that ammonium metavanadate is completely dissolved in oxalic acid solution；Mixed liquid B is gradually being added drop-wise to mixed liquor A
During, butyl titanate is reacted with water, and gradually complete hydrolysis is [Ti (OH)6]2-Jelly, and make Ce3+It is adsorbed on
After Ti jelly surface forms Ce-Ti carrier, V is then being attached to Ce-Ti carrier.
Step 3: mixed liquid B is added dropwise in mixed liquor A, while mixed liquor A is stirred；Mixed liquid B is added dropwise to mixed
Close the step in liquid A specifically:
Step (1): control magneton revolving speed is 180~220r/min, while being added dropwise to mixed liquid B with 3 drops/sec of speed
In mixed liquor A；The time for adding of step (1) is t1=1min；
Step (2): keeping magneton revolving speed constant, while adjusting the speed that mixed liquid B is added dropwise, and will be mixed with 1 drop/sec of speed
Liquid B is closed to be added dropwise in mixed liquor A；The time for adding of step (2) is t2=2min；So that being added dropwise by mixed liquid B
The early period of mixed liquor A quickly forms gel, after quickly forming gel, by the way that mixed liquid B is added dropwise under slower speed, so that
React relatively stable, so that gel prepares relatively uniform stabilization.
Step (3): raising magneton revolving speed to 280~320r/min, and change the speed that mixed liquid B is added dropwise, with 2 drops/sec
Speed mixed liquid B is added dropwise in mixed liquor A completely, be made gel；It is further illustrated: forming colloidal sol in the early stage
When, suitably slow down rate of addition, so that mixed liquor A gradually forms colloidal sol, and guarantees that the sol ingredient generated is uniformly distributed；When
When the hydrolysis of butyl titanate, polycondensation reaction are carried out to a certain extent, colloidal particle concentration is not further added by, at this moment shear rate
Variation no longer influences hydrolytic-polymeric reaction, and the variation of viscosity is unrelated with shear rate at this time, shows the feature of Newton type fluid,
It being cross-linked with each other between colloidal particle later, colloidal sol gradually to gel transition, forms certain network structure, and mobility is deteriorated, this
When increase with shear rate, bigger to the destructiveness of cross-linked network, so that apparent viscosity reduces, fluid shows false modeling
Property type characteristic of fluid, the network cross-linked of last whole system forms gel together, therefore setting procedure (2) and step (3)
Rate of addition first reduce and improve afterwards.
It is worth noting that: as shown in figure 5, mixed liquid B is added dropwise in mixed liquor A, while mixed liquor A is stirred
Mix, mixed liquor A surface forms whirlpool face A10, and solution is added dropwise point A01 and is located at the whirlpool face surface A10, and solution dropwise addition point A01 away from
It is D1 with a distance from swirl center A11 from whirlpool face A10, whirlpool edge A12 of the point A01 at the top of the A10 of whirlpool face is added dropwise in solution
Distance is D2, and D1 > D2, and mixed liquid B is quickly mixed with mixed liquor A, promotes mixed liquid B quickly and mixed liquor A
It carries out reaction and forms gel, and micelle is reset, chaotic space structure is formed, so that is be prepared urges
The more uniform stabilization of agent, improves the catalytic effect of catalyst.
Step 4: above-mentioned gel is stood 12h, gel is dried after the completion of standing under conditions of 100 DEG C, is dried
Gel is ground after the completion, then the powder after grinding is put into oxidizing roasting in not closed Muffle furnace, oxidizing roasting
Temperature is 400~500 DEG C, and V-Ce-Ti catalyst is made after roasting, and wherein the maturing temperature of the present embodiment is 450 DEG C, when roasting
Between be 3h.The V-Ce-Ti catalyst being prepared is VaCebTicOxCatalyst, wherein the oxide mass ratio of V and Ce is 0.5
The oxide mass of~1, Ce and Ti ratio are 0.05~0.16, wherein V in the present embodimentaCebTicOxV, Ce, Ti in catalyst
The mass ratio of oxide is 1:1:18, and detects the VaCebTicOxThe specific surface area of catalyst is 95.7219m2/g。
The catalyst of powdery will be obtained after V-Ce-Ti catalyst obtained grinding, then by its binder with 2%~10%
Mixing granulation, wherein the binder used is polymer alumina, the proportion of binder is 2%, then above-mentioned mixing granulation is obtained
Catalyst be made beaded catalyst, the diameter of beaded catalyst is 2.0mm~3.0mm, under same catalyst volume,
Grain catalyst has biggish surface area, while also there are gaps between beaded catalyst and beaded catalyst, so that particle is urged
Agent can be contacted sufficiently with sintering flue gas, and carry out catalytic degradation to sintering flue gas.
It is worth noting that, it is complete to can be prepared by Ce-Ti carrier using one-step method in the step of preparation V-Ce-Ti catalyst
At initial reaction, production cost and production time can be greatlyd save.Mixed liquid B, which is added dropwise in mixed liquor A, is made gel, colloidal sol
Gel method mainly hydrolyzes to form gel by butyl titanate, be added deionized water it is excessive or it is very few can not all be formed it is solidifying
Glue.In addition, all reagent orders of addition can all influence the formation of colloidal sol.Therefore the present invention in, all procedure parameters and
Chemical constituent is to be mutually related, and any change of these parameters will not most possibly generate target capabilities value.
Embodiment 2
The basic content of the present embodiment with embodiment 1, as shown in figure 3, the difference is that: in catalyst filter cylinder 100 by
It is disposed with molecular sieve layer 110 and V-Ce-Ti catalyst layer 130 under, is additionally provided with denitration in catalyst filter cylinder 100 and urges
Agent layer 120, the denitration catalyst oxidant layer 120 are set between molecular sieve layer 110 and V-Ce-Ti catalyst layer 130.
It is worth noting that as shown in figure 4, be provided with angle γ between filter plate 210 and vertical direction, the value of angle γ
Range is 10~15 °, in the present embodiment, and the value of angle γ is 15 °, sintering flue gas of the invention by admission line 200 into
It when entering subsidiary conduit 400, is filtered by filter plate 210, angle γ, angle γ is provided between filter plate 210 and vertical direction
Value range be 10~15 °, in the present embodiment, the value of angle γ is 30 °, when sintering flue gas by filter plate 210 to auxiliary
Pipeline 400 move when, the air inlet of subsidiary conduit 400 is connected with the gas outlet of admission line 200, when in sintering flue gas contain
When grain object, the partial size of particulate matter is greater than the diameter of filter plate 210, so that particulate matter is auxiliary without can enter under the blocking of filter plate 210
It helps in pipeline 400, while filter plate 210 is inclined at the top of admission line 200, particulate matter is not easy to be attached to filter plate 210
Surface and cause filter plate 210 be blocked, to hinder sintering flue gas to enter in subsidiary conduit 400, and particulate matter is in self gravity
Under the action of and towards moving at the air inlet of admission line 200, promote sintering flue gas and particulate separation, sintering can be improved
The catalytic effect of flue gas.
After sintering flue gas enters catalyst filter cylinder 100, molecular sieve layer 110 is first passed through.Filled with 5A points in molecular sieve layer 110
Sub- sieve catalyst, the 5A molecular sieve are a kind of calcium A type alumino-silicates, can adsorb cut off diameter in sintering flue gas and be not more than 5A's
Substance is mainly used for adsorbing the H in flue gas2O and SO2, and the partial size of 5A molecular sieve catalyst is 1cm, the layer of molecular sieve layer 110
A height of 1m.
Further, sintering flue gas enters denitration catalyst oxidant layer 120, is filled with Co-Mn-Ce in denitration catalyst oxidant layer 120
Catalyst, can remove the part NOx in sintering flue gas, and the partial size of the Co-Mn-Ce catalyst is 4~5mm, a height of 1.5m of layer,
The partial size of Co-Mn-Ce catalyst is less than the partial size of 5A molecular sieve catalyst, and 5A molecular sieve catalyst can be prevented to be mixed into Co-Mn-Ce
In catalyst.Specific preparation process is as follows for Co-Mn-Ce catalyst:
S100, the CoCl for taking 4g2·6H2O, the MnCl of 12g2·4H2O, the Ce (NO of 1g3)3·6H2O, 1480g deionization
Water, and it is mixed to get catalyst activity component A；
S200,23 g oxalic acid and 550g water are taken, and is mixed to prepare oxalic acid aqueous solution B；
When S300,20 DEG C, catalyst activity component A is stirred, the revolving speed for controlling magneton is 200r/min, when stirring
Between 30min；
When S400,20 DEG C, oxalic acid aqueous solution B is stirred, the revolving speed for controlling magneton is 200r/min, mixing time
30min；
S500, under conditions of being evenly heated stirring, oxalic acid solution B is added dropwise in catalyst activity component A, it is heavy to be made
Shallow lake solution C；
S600, precipitation solution C obtained is stirred into cooling, and precipitation solution C is washed using deionized water, is taken out
Filter, process in triplicate, then with ethanol solution are washed precipitation solution C, are filtered, the step in triplicate, by institute
The precipitation solution C obtained is dried for 24 hours at 70 DEG C, and oxidizing roasting under the conditions of keeping the temperature 3 hours after being warming up to 400 DEG C obtains after cooling
Catalyst fines are ground into 60 mesh.
S700, catalyst fines obtained are uniformly mixed with certain binder, are 5mm's in being rolled into diameter on pellet processing machine
Spherical catalyst, then formed after 100 DEG C of dryings of low temperature.
Using a kind of device of layering removing sintering flue gas pollutant of the present embodiment, 200 air inlet of admission line is detected
The NO at placeXConcentration 328mg/m-3, dioxin concentration is 0.91ng/m-3, then detect 100 bottom gas outlet of catalyst filter cylinder
The NO at placeXConcentration 53mg/m-3, dioxin concentration is 0.27ng/m-3；NOXEmission reduction efficiency reach 80.79%；Dioxin
Emission reduction efficiency reach 70.33%；To realize NOXWith the joint emission reduction of dioxin.
The present invention is described in detail above in conjunction with specific exemplary embodiment.It is understood, however, that can not take off
It is carry out various modifications in the case where from the scope of the present invention being defined by the following claims and modification.Detailed description and drawings
Should be to be considered only as it is illustrative and not restrictive, if there is any such modifications and variations, then they all will
It falls into the scope of the present invention described herein.In addition, Development Status and meaning that background technique is intended in order to illustrate this technology,
It is not intended to limit the present invention or the application and application field of the invention.
Claims (10)
1. a kind of method using multilayer catalytic degradation sintering flue gas pollutant, it is characterised in that:
The sintering flue gas that sintering process generates moves up in admission line (200) along air inlet, and by filter plate (210) after
Continuous horizontal direction subsidiary conduit (400) movement, moves to through collapsible tube (410) into the sintering flue gas in subsidiary conduit (400) and urges
In agent filter cylinder (100), V-Ce-Ti catalyst layer (130) in catalyst filter cylinder (100) to the pollutant in sintering flue gas into
Row catalytic degradation.
2. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 1, it is characterised in that:
Specific step is as follows:
Step 1: sintering flue gas moves upwards after entering admission line (200), and moves under the guiding role of deflector (220)
To subsidiary conduit (400), sintering flue gas is turned to when flowing into subsidiary conduit (400) by admission line (200)；
Step 2: sintering flue gas moves downward in subsidiary conduit (400), and moves to catalyst filter cylinder by collapsible tube (410)
(100) in；
Step 3: sintering flue gas successively passes through molecular sieve layer (110) and V-Ce-Ti after entering in catalyst filter cylinder (100)
Catalyst layer (130), while vibrator (300) vibrates catalyst filter cylinder (100), sintering flue gas is through catalyst filter cylinder
(100) it is flowed out after catalytic degradation by the outlet of bottom.
3. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 2, it is characterised in that:
In step 1, sintering flue gas is filtered when entering subsidiary conduit (400) by admission line (200) by filter plate (210).
4. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 2, it is characterised in that:
In step 3, sintering flue gas successively passes through molecular sieve layer (110), denitrating catalyst after entering in catalyst filter cylinder (100)
Layer (120) and V-Ce-Ti catalyst layer (130).
5. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 4, it is characterised in that:
In step 3, molecular sieve layer (110) accommodates 5A molecular sieve catalyst, and the pollutant in flue gas is inhaled in molecular sieve layer (110)
It is attached.
6. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 4, it is characterised in that:
In step 3, denitration catalyst oxidant layer (120) accommodates Co-Mn-Ce catalyst, the NO in flue gasXIn denitration catalyst oxidant layer (120)
It is middle by Co-Mn-Ce catalytic degradation.
7. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 4, it is characterised in that:
In step 3, V-Ce-Ti catalyst layer (130) accommodates VaCebTicOxCatalyst, the NO in flue gasXWith dioxin in V-Ce-Ti
By V in catalyst layer (130)aCebTicO catalytic degradation.
8. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 4, it is characterised in that:
The granularity of 5A molecular sieve catalyst is 8~12mm in molecular sieve layer (110)；Co-Mn-Ce is catalyzed in denitration catalyst oxidant layer (120)
The degree of agent is 4~5mm；V in V-Ce-Ti catalyst layer (130)aCebTicThe granularity of O catalyst is 1~2mm.
9. a kind of method using multilayer catalytic degradation sintering flue gas pollutant according to claim 6, it is characterised in that:
The V-Ce-Ti catalyst is VaCebTicOxCatalyst, wherein the oxide mass ratio of V and Ce is the oxygen of 0.5~1, Ce and Ti
Compound mass ratio is 0.05~0.16.
10. a kind of method using multilayer catalytic degradation sintering flue gas pollutant, feature according to claim 2-9 exist
In: the tall and big layer in molecular sieve layer (110) of the layer of V-Ce-Ti catalyst layer (130) is high.
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