CN108144601A - A kind of SCR ultralow temperature denitrating catalyst and preparation method thereof - Google Patents
A kind of SCR ultralow temperature denitrating catalyst and preparation method thereof Download PDFInfo
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- CN108144601A CN108144601A CN201810111570.6A CN201810111570A CN108144601A CN 108144601 A CN108144601 A CN 108144601A CN 201810111570 A CN201810111570 A CN 201810111570A CN 108144601 A CN108144601 A CN 108144601A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of SCR ultralow temperature denitrating catalysts and preparation method thereof.SCR denitration includes component：40~60wt% of titanium dioxide, silica 1~10wt%, 10~20wt% of tantalum pentoxide, 5~15wt% of 10~20wt% of manganese dioxide, 10~20wt% of molybdenum trioxide and vanadic anhydride.Preparation method includes step：It is kneaded, is aging, filtering the processes such as pre- crowded, extrusion molding, primary drying, redrying, calcining, cutting, packaging.SCR denitration of the present invention has the effect used under ultra-low temperature surroundings, and use temperature range reaches 100~450 DEG C, and denitration efficiency is up to more than 80%；SCR denitration of the present invention has good water resistant poisoning capability, and operational efficiency reaches 82% under 20% moisture content；Sulfur oxidation rate is less than 0.8%；Alkali resistant metal poisoning ability is strong, and technique prepares the features such as being simply easy to industrialization.
Description
Technical field
The invention belongs to catalyst material fields, are specifically related to a kind of SCR ultralow temperature denitrating catalyst and its preparation side
Method.
Background technology
Nitrogen oxides (NOX) generally include NO, NO2And N2O etc., exhaust gas, heat power station essentially from motor vehicles
The industrial processes production of the high-temp combustion and nitric acid, nitrogenous fertilizer, explosive of the fossil fuel of exhaust gas, marine exhaust and other industry
Raw.NOXLung can be stimulated to lead to human respiratory system's disease, can also result in depletion of the ozone layer and greenhouse effects, and and SO2One
Rising can cause acid rain to cause cultivated land degradation and damage of building etc..Therefore China is strengthened by forms such as laws and regulations to each
Kind NOXThe disposal of pollutants of emission source is limited.With the sustainable growth of Electricity Demand, the installed capacity of power plants
Also it increases rapidly, therefore also brings NOXThe problem of disposal of pollutants aggravates.In addition, the fuel economy due to diesel engine
With excellent power performance, China is continued to increase using the motor vehicles ownership of diesel engine, at the same time ship power
More than 90% all uses diesel engine.
At present, it is main both at home and abroad to carry out exhaust gas from diesel vehicle and power plant boiler, steel by the way of SCR denitration is post-processed
NO in factory and cement plant furnace flueXControl.SCR catalyst is the core of SCR denitration device, and prevailing operating temperatures section exists
300~400 DEG C, the performance requirement of catalyst is denitration efficiency height, and thermal stability is good, and alkali resistant metal poisoning power is strong, SO2Conversion ratio
The features such as low.In recent years, V2O5-WO3/TiO2Catalyst is widely used as firepower due to good active, preferable thermal stability
In power plant, cement plant, steel plant's denitrating flue gas.But 300 DEG C of the minimum temperature in use of SCR denitration of current power plant is low
Warm catalyst technology can only achieve 160 DEG C or more.For being currently much of that, glass run flue gas temperature for glass and coking industry
Spend minimum also with regard to 200 DEG C, and minimum 180 DEG C or so of coke-oven plant's flue gas running temperature.But for steel sintering machine tail gas come
It says, due to usually only 120 DEG C or so of sintering machine exhaust temperature, common low temperature catalyst can only accomplish 160 DEG C of flue-gas temperature
It could use above, under the conditions of these low-temperature flue gas, select General low temperature catalyst that can only show and flue-gas temperature is heated to 160
DEG C or more, it is calculated with electrical heating by exhaust gas volumn 200000Nm3/ h flue gases are warming up to 160 DEG C from 120 DEG C needs power consumption daily
300kw, year power consumption can reach 90000kw, increase operating cost.In summary discuss, this field need one kind can be low
The denitrating catalyst used under the conditions of temperature.
Invention content
In order to solve the above technical problem, the present invention provides a kind of SCR denitration formulas and preparation method thereof.This is urged
Agent cold operation and can play denitration function, and denitration efficiency is high, there is good water resistant poisoning capability, and sulfur oxidation rate is small, resist
The features such as alkali metal poisoning capability is strong, and preparation process is simple.
In order to achieve the object of the present invention, present invention employs following technical schemes：
A kind of SCR denitration, including following components by weight percent：40~60wt% of titanium dioxide, silica 1~
10wt%, 10~20wt% of tantalum pentoxide, 10~20wt% of manganese dioxide, the oxidations of 10~20wt% of molybdenum trioxide and five two
5~15wt% of vanadium.
A kind of preparation method of the SCR denitration, includes the following steps：
Step 1 is kneaded：
Titanium silica flour, oxidation tantalum powder, stearic acid particles are added in kneading machine and stirred evenly by step 1.1, backward institute
It states and deionized water, ammonium hydroxide and lactic acid is sequentially added in kneading machine and stirs evenly acquisition pug；The ammonia concn for 18~
22wt%, the titanium silica flour, oxidation tantalum powder, stearic acid particles, deionized water, the weight ratio of ammonium hydroxide and lactic acid for (50~
70):(10~20):(0.1~1):(20~35):(1~10):(0.1~1)；
Step 1.2, stirring keep the temperature 5~10min to the pug under 85~95 DEG C of states, and it is straight to carry out cooling dehumidifier later
To the 20~30wt% of pug moisture content；
Step 1.3 is uniformly added into polypropylene fibre and glass fibre in the pug and forms mixture A, described poly-
Tacryl accounts for 0.2~1wt% of mixture A total weights, and the glass fibre accounts for 4~6wt% of mixture A total weights；
Step 1.4 is uniformly added into living solution A, living solution B and living solution C-shaped into the mixture A successively
Into mixture B；The living solution A be manganese nitrate solution, the living solution B be Ammoniun Heptamolybdate Solution, the living solution C
For monoethanolamine and the mixed solution of ammonium metavanadate；In the manganese nitrate solution manganese nitrate account for mixture B total weights 0.4~
2.4wt%, ammonium heptamolybdate accounts for 0.4~2.4wt% of mixture B total weights, the mixed solution in the Ammoniun Heptamolybdate Solution
Middle monoethanolamine accounts for 0.4~1.2wt% of mixture B total weights, and ammonium metavanadate accounts for mixture B total weights in the mixed solution
1.2~3.6wt%；
Step 1.5 is uniformly added into ammonia type carboxymethyl cellulose and polyethylene glycol oxide formation mixing into the mixture B
Expect C；The ammonia type carboxymethyl cellulose, polyethylene glycol oxide account for 0.1~1wt% of mixture C total weights respectively；
Step 1.6 simultaneously adjusts the clay sculpture value of the mixture C to 20~35
It is step 2, aging：By the mixture C seal and with it is aging under the conditions of 18~22 DEG C, 75~85wt% of relative humidity
Obtain aging material within 22~26 hours；
Step 3, filtering are pre- crowded：The aging material is pushed with extruder and pass through sieve processing realize aging material comb with
And impurity removal；
Step 4, extrusion molding：The aging material is extruded into the catalyst with setting shape of hygrometric state with extruder
Moulded pottery not yet put in a kiln to bake；
Step 5, primary drying：It is put into after the moulded pottery not yet put in a kiln to bake is wrapped with carton in drying box and carries out heated-air drying, the mud
Drying early period of base experience, mid-term drying and terminal drying stage；
3~4 days drying times of early period, early period and gradually rise 28~35 DEG C of drying temperature, when early period is dried in drying box
Relative humidity continuously decreases and 1.5~2.5wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake after 70~90wt%, drying early period is controlled to shrink
Rate 2~3%；
It 3~4 days mid-term drying times, 35~50 DEG C of mid-term drying temperature and gradually rises, when mid-term is dried in drying box
Relative humidity is continuously decreased and is controlled in 40~65wt%, and 6~8wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake shrinking percentage 3 after mid-term drying~
3.5%；
It 2.5~3.5 days terminal drying time, 55~60 DEG C of terminal drying temperature and gradually rises, when terminal drying is dried
Relative humidity continuously decreases and 15~17wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake after 10~30wt%, terminal drying is controlled to receive in case
Shrinkage does not change；
Step 6, redrying：The carton dismounting on the moulded pottery not yet put in a kiln to bake surface after primary drying is continued to be put into, heat is carried out in hothouse
Air-dry dry, 55~65 DEG C of drying temperature, 8~12wt% of dry indoor relative humidity, 6~12 hours drying times；
Step 7, calcining：Moulded pottery not yet put in a kiln to bake after redrying is calcined 0.8~1.2 hour under the conditions of 180~220 DEG C successively,
It calcines 1.5~2.5 hours under the conditions of 350~450 DEG C, is calcined 2.5~3.5 hours under the conditions of 500~600 DEG C, obtain SCR
Denitrating catalyst product.
Step 8, cutting, packaging.
Further, titanium silica flour in the step 1, the grain size for aoxidizing tantalum powder are 5~20 microns.
Further, in the step 1 X ray of titanium silica flour 160 ± 10 millimeters of peak height, titanium silica flour specific surface area 90 ±
10m2/ g, titanium silica flour constituent content are：1 ± 0.2wt% of silica, 99 ± 0.7wt% of titanium dioxide, sodium oxide molybdena are less than
0.01wt%, potassium oxide are less than 0.01wt%, four 1.5~3.5wt% of sulfur oxide less than 0.01wt%, di-iron trioxide.
The beneficial effects of the present invention are：
SCR denitration of the present invention has the effect that is used under ultra-low temperature surroundings, and use temperature range reaches 100~
450 DEG C, and denitration efficiency is up to more than 80%；In addition SCR denitration of the present invention has good water resistant poisoning capability,
Operational efficiency reaches 82% under 20% moisture content；Sulfur oxidation rate is less than 0.8%；Alkali resistant metal poisoning ability is strong, and technique prepares letter
The features such as being singly easy to industrialization.
Description of the drawings
Fig. 1 for SCR denitration of the present invention using when denitration efficiency vary with temperature curve graph.
Fig. 2 for SCR denitration of the present invention using when sulfur oxidation rate vary with temperature curve graph.
Specific embodiment
More specific detail is made to technical solution of the present invention with reference to embodiment：
Titanium silica flour used in the present invention is anatase titanium dioxide titanium silica flour, and silicon content 1wt% is scientific and technological by super color environmental friendly material
Co., Ltd produces, trade mark apre-cat S.Since the crystalline form of anatase thpe white powder is space regular octahedron structure, formed
Particle has very big smoke contacts face, while anatase thpe white powder has the function of that good load active material is good
The carrier of active material.160 ± 10 millimeters of the peak height of the X ray of the titanium silica flour product, 90 ± 10m of titanium silica flour specific surface area2/
G, titanium silica flour constituent content are：1 ± 0.2wt% of silica, 99 ± 0.7wt% of titanium dioxide, sodium oxide molybdena are less than 0.01wt%, oxygen
Change potassium and be less than 0.01wt%, four 1.5~3.5wt% of sulfur oxide less than 0.01wt%, di-iron trioxide.
Embodiment 1
Step 1 is kneaded：
Titanium silica flour, oxidation tantalum powder, stearic acid particles are added in kneading machine and stirred evenly, mixing time by step 1.1
5min, 200 turns/mim of mixing speed；The backward kneading machine in sequentially add deionized water, (concentration 20wt% is left for ammonium hydroxide
It is right) and lactic acid and acquisition pug is stirred evenly, mixing time 20min, 750 turns/mim of mixing speed；The titanium silica flour, oxidation
Tantalum powder, stearic acid particles, deionized water, the weight ratio of ammonium hydroxide and lactic acid are 60:15:0.5:28:5:0.5；The titanium silica flour,
The grain size for aoxidizing tantalum powder is 5~20 microns.
The addition sequence of liquid adjuvants deionized water, ammonium hydroxide and lactic acid follows principle from more to less, this avoid
Powder material will measure few liquid adjuvants due to water absorbing properties and adsorb in some regions so that the pug of mixing out is unable to reach very
Performance well.The effect of the ammonium hydroxide is dispersant, and the effect of lactic acid is antifoaming agent.
Step 1.2, high-speed stirred (750 turns/mim) to the pug keep the temperature 8min under 90 DEG C of states, it is therefore an objective to ensure
Stearic acid, which fully melts, to be attached on material, and material is made to have certain demolding performace, carries out cooling dehumidifier later until described
Pug moisture content 25wt%, it is therefore an objective to so that pug is in granular form in order to (the glass fibre and poly- of fibrous matter in subsequent step
Ethylene oxide) be uniformly added into.
Step 1.3 is uniformly added into polypropylene fibre and glass fibre in the pug and forms mixture A, described poly-
Tacryl accounts for the 0.5wt% of mixture A total weights, and the glass fibre accounts for the 5wt% of mixture A total weights；Polypropylene is fine
The effect of dimension and glass fibre is at the time of molding so that pug can improve the anti-of product with certain mechanical strength after sintering
Pressure energy power.
Step 1.4 is uniformly added into living solution A, living solution B and living solution C-shaped into the mixture A successively
Into mixture B；The mixture A is in the less state of moisture, and the addition of living solution brings a large amount of liquid into mixture A
Body so that granular material becomes pug state again, while also ensures that the carrier that the active constituent of addition is disperseed with molecular forms
On the surface of particle.
The living solution A is manganese nitrate solution, and the living solution B is Ammoniun Heptamolybdate Solution, and the living solution C is
The mixed solution of monoethanolamine and ammonium metavanadate；Manganese nitrate accounts for the 1.2wt% of mixture B total weights in the manganese nitrate solution,
Ammonium heptamolybdate accounts for the 1.2wt% of mixture B total weights in the Ammoniun Heptamolybdate Solution, and monoethanolamine accounts for mixed in the mixed solution
The 0.8wt% of material B total weights is closed, ammonium metavanadate accounts for the 2.5wt% of mixture B total weights in the mixed solution.
So that activearm under the strong positive interference of activearm liquid (M1, M2, M3 solution) tantalum element in tantalum oxide of the present invention
Acid key mapping in liquid is stronger, so as to which nitrogen oxides and ammonia at a lower temperature can be anti-when contacting active component
Nitrogen and water should be resolved into；Simultaneously because the acid key mapping of active component is reinforced, active component and nitrogen oxides and ammonia
Affinity also just increase, nitrogen oxides passes through contact of the moisture film with active component with ammonia when water content is higher in flue gas
Ability just increases, strong so as to embody catalyst water resistant poisoning capability.Tantalum element is strong in the tantalum oxide that the present invention also utilizes
Positive key mapping so that alkali metal cation ingredient is difficult close to active component, in the alkali metal for reducing active component in flue gas
Poison.
Step 1.5 is uniformly added into ammonia type carboxymethyl cellulose and polyethylene glycol oxide formation mixing into the mixture B
Expect C；The ammonia type carboxymethyl cellulose, polyethylene glycol oxide account for the 0.5wt% of mixture C total weights respectively.Polyethylene glycol oxide into
Cause pug that there is certain mechanical strength during type, hole position (pore creating material) is left after sintering, while the effect of polyethylene glycol oxide is
Pug water-retaining agent, ensureing pug, moisture is not easy to lose in process afterwards, and the effect of ammonia type carboxymethyl cellulose is to improve
The flexibility of pug is convenient for the normal molding of pug.
Step 1.6 adjusts the clay sculpture value of the mixture C to 30.
It is step 2, aging：The mixture C is sealed and was obtained with aging 24 hours under the conditions of 20 DEG C, relative humidity 80wt%
Obtain aging material.The Free water in pug after mixing is more uniform over time under the influence of the capillary effect of pore
Change.
Step 3, filtering are pre- crowded：The aging material with screw extruder is pushed and passes through sieve processing and realizes aging material
Combing and the removal of impurity；The aperture 0.6mm*1.5mm of the sieve.
Step 4, extrusion molding：The aging material is squeezed out with screw extruder, by the honeycomb ceramics mould of certain specification
The SCR catalyst moulded pottery not yet put in a kiln to bake of the hygrometric state of certain length is cut into after tool.
Step 5, primary drying：It is put into after the moulded pottery not yet put in a kiln to bake is wrapped with carton in drying box and carries out heated-air drying, the mud
Drying early period of base experience, mid-term drying and terminal drying stage；Primary drying technique according to the form below carries out：
Moulded pottery not yet put in a kiln to bake dehydration when being to avoid drying early period with the purpose that carton is wrapped by moulded pottery not yet put in a kiln to bake when dry is shunk too fast and is caused
Cracking.Early period, drying was that a weight-loss ratio slows down, and allowed the process of moulded pottery not yet put in a kiln to bake natural mode health, and moulded pottery not yet put in a kiln to bake is allowed gently to spend dangerous period,
The process of season cracking is avoided, moulded pottery not yet put in a kiln to bake weight-loss ratio 2wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 2.5% after drying early period realize the one of moulded pottery not yet put in a kiln to bake
It is secondary qualitative；Mid-term drying is the excessive period of primary drying, and moulded pottery not yet put in a kiln to bake realizes that the acceleration of moisture is lost in, while at this in the period
The appearance type shape of moulded pottery not yet put in a kiln to bake is fixed after phase, moulded pottery not yet put in a kiln to bake weight-loss ratio 7wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 3.2% after mid-term drying；Latter stage
Dry major function is the rapidly losing of realization moisture, and moulded pottery not yet put in a kiln to bake weight-loss ratio 16wt%, moulded pottery not yet put in a kiln to bake shrinking percentage do not change after terminal drying.
Step 6, redrying：The carton dismounting on the moulded pottery not yet put in a kiln to bake surface after primary drying is continued to be put into, heat is carried out in hothouse
Air-dry dry, 60 DEG C of drying temperature, dry indoor relative humidity 10wt%, 9 hours drying times；Redrying realizes the fast of moulded pottery not yet put in a kiln to bake
Fast dehydration knows that moisture content is 0, and the weight-loss ratio of moulded pottery not yet put in a kiln to bake is by 17wt% to 23wt%.
Step 7, calcining：Moulded pottery not yet put in a kiln to bake after redrying is calcined 1 hour under the conditions of 200 DEG C successively, under the conditions of 400 DEG C
Calcining 2 hours, is calcined 3 hours under the conditions of 550 DEG C, obtains SCR denitration product.
Step 8, cutting, packaging.The SCR denitration product can cut into the SCR of setting length as needed
Denitrating catalyst monomer, and more SCR denitration monomers are assembled into solid catalyst modular unit with module cage, it is convenient
The installation at scene is also simplified while transport.
Calcine purpose：1st, so that the decomposition of polyethylene glycol oxide leaves hole position；2nd, manganese nitrate is decomposed into manganese dioxide, is urged
One of main active material of agent；3rd, ammonium metavanadate decomposes to obtain vanadic anhydride, obtains one of main active material of catalyst；4th, seven
Ammonium molybdate decomposes to obtain molybdenum trioxide, obtains one of main active material of catalyst；5 titanium white powder sinterings improve the pressure resistance of product
Degree and wear-resisting property.
Embodiment 2
Step 1 is kneaded
Titanium silica flour, oxidation tantalum powder, stearic acid particles are added in kneading machine and stirred evenly, mixing time by step 1.1
5min, 200 turns/mim of mixing speed；The backward kneading machine in sequentially add deionized water, (concentration 20wt% is left for ammonium hydroxide
It is right) and lactic acid and acquisition pug is stirred evenly, mixing time 20min, 750 turns/mim of mixing speed；The titanium silica flour, oxidation
Tantalum powder, stearic acid particles, deionized water, the weight ratio of ammonium hydroxide and lactic acid are 50:10:0.1:20:1:0.1.
Step 1.2, high-speed stirred (750 turns/mim) to the pug keep the temperature 5min under 85 DEG C of states, are dropped later
Warm dehumidifier is until the pug moisture content 20wt%.
Step 1.3 is uniformly added into polypropylene fibre and glass fibre in the pug and forms mixture A, described poly-
Tacryl accounts for the 0.2wt% of mixture A total weights, and the glass fibre accounts for the 4wt% of mixture A total weights.
Step 1.4 is uniformly added into living solution A, living solution B and living solution C-shaped into the mixture A successively
Into mixture B；The living solution A be manganese nitrate solution, the living solution B be Ammoniun Heptamolybdate Solution, the living solution C
For monoethanolamine and the mixed solution of ammonium metavanadate；Manganese nitrate accounts for mixture B total weights in the manganese nitrate solution
0.4wt%, ammonium heptamolybdate accounts for the 0.4wt% of mixture B total weights in the Ammoniun Heptamolybdate Solution, single second in the mixed solution
Hydramine accounts for the 0.4wt% of mixture B total weights, and ammonium metavanadate accounts for the 1.2wt% of mixture B total weights in the mixed solution.
Step 1.5 is uniformly added into ammonia type carboxymethyl cellulose and polyethylene glycol oxide formation mixing into the mixture B
Expect C；The ammonia type carboxymethyl cellulose, polyethylene glycol oxide account for the 0.1wt% of mixture C total weights respectively.
Step 1.6 adjusts the clay sculpture value of the mixture C to 20.
It is step 2, aging：The mixture C is sealed and was obtained with aging 22 hours under the conditions of 18 DEG C, relative humidity 75wt%
Obtain aging material.
Step 3, filtering are pre- crowded：The aging material with screw extruder is pushed and passes through sieve processing and realizes aging material
It combs and impurity removes.
Step 4, extrusion molding：The aging material is squeezed out with screw extruder, by the honeycomb ceramics mould of certain specification
The SCR catalyst moulded pottery not yet put in a kiln to bake of the hygrometric state of certain length is cut into after tool.
Step 5, primary drying：It is put into after the moulded pottery not yet put in a kiln to bake is wrapped with carton in drying box and carries out heated-air drying, the mud
Drying early period of base experience, mid-term drying and terminal drying stage；Drying process is pressed table in embodiment 1 and is carried out：Early period is dried
Moulded pottery not yet put in a kiln to bake weight-loss ratio 1.5wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 2% afterwards；Moulded pottery not yet put in a kiln to bake weight-loss ratio 6wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 3% after mid-term drying；End
Moulded pottery not yet put in a kiln to bake weight-loss ratio 15wt%, moulded pottery not yet put in a kiln to bake shrinking percentage do not change after phase drying.
Step 6, redrying：The carton dismounting on the moulded pottery not yet put in a kiln to bake surface after primary drying is continued to be put into, heat is carried out in hothouse
Air-dry dry, 55 DEG C of drying temperature, dry indoor relative humidity 8wt%, 6 hours drying times.
Step 7 is calcined：Moulded pottery not yet put in a kiln to bake after redrying is calcined 0.8 hour under the conditions of 180 DEG C successively, in 350 DEG C of conditions
Lower calcining 1.5 hours, is calcined 2.5 hours under the conditions of 500 DEG C, obtains SCR denitration product.
Step 8, cutting, packaging.
Embodiment 3
Step 1 is kneaded：
Titanium silica flour, oxidation tantalum powder, stearic acid particles are added in kneading machine and stirred evenly, mixing time by step 1.1
5min, 200 turns/mim of mixing speed；The backward kneading machine in sequentially add deionized water, (concentration 20wt% is left for ammonium hydroxide
It is right) and lactic acid and acquisition pug is stirred evenly, mixing time 20min, 750 turns/mim of mixing speed；The titanium silica flour, oxidation
Tantalum powder, stearic acid particles, deionized water, the weight ratio of ammonium hydroxide and lactic acid are 70:20:1:20:10:1.
Step 1.2, high-speed stirred (750 turns/mim) to the pug keep the temperature 10min under 95 DEG C of states, are dropped later
Warm dehumidifier is until the pug moisture content 30wt%.
Step 1.3 is uniformly added into polypropylene fibre and glass fibre in the pug and forms mixture A, described poly-
Tacryl accounts for the 1wt% of mixture A total weights, and the glass fibre accounts for the 6wt% of mixture A total weights.
Step 1.4 is uniformly added into living solution A, living solution B and living solution C-shaped into the mixture A successively
Into mixture B；The living solution A be manganese nitrate solution, the living solution B be Ammoniun Heptamolybdate Solution, the living solution C
For monoethanolamine and the mixed solution of ammonium metavanadate；Manganese nitrate accounts for mixture B total weights in the manganese nitrate solution
2.4wt%, ammonium heptamolybdate accounts for the 2.4wt% of mixture B total weights in the Ammoniun Heptamolybdate Solution, single second in the mixed solution
Hydramine accounts for the 1.2wt% of mixture B total weights, and ammonium metavanadate accounts for the 3.6wt% of mixture B total weights in the mixed solution.
Step 1.5 is uniformly added into ammonia type carboxymethyl cellulose and polyethylene glycol oxide formation mixing into the mixture B
Expect C；The ammonia type carboxymethyl cellulose, polyethylene glycol oxide account for the 1wt% of mixture C total weights respectively.
Step 1.6 adjusts the clay sculpture value of the mixture C to 35.
It is step 2, aging：The mixture C is sealed and was obtained with aging 26 hours under the conditions of 22 DEG C, relative humidity 85wt%
Obtain aging material.
Step 3, filtering are pre- crowded：The aging material with screw extruder is pushed and passes through sieve processing and realizes aging material
It combs and impurity removes.
Step 4, extrusion molding：The aging material is squeezed out with screw extruder, by the honeycomb ceramics mould of certain specification
The SCR catalyst moulded pottery not yet put in a kiln to bake of the hygrometric state of certain length is cut into after tool.
Step 5, primary drying：It is put into after the moulded pottery not yet put in a kiln to bake is wrapped with carton in drying box and carries out heated-air drying, the mud
Drying early period of base experience, mid-term drying and terminal drying stage；Drying process is pressed table in embodiment 1 and is carried out：Early period is dried
Moulded pottery not yet put in a kiln to bake weight-loss ratio 2.5wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 3% afterwards；Moulded pottery not yet put in a kiln to bake weight-loss ratio 8wt%, moulded pottery not yet put in a kiln to bake shrinking percentage 3.5% after mid-term drying；
Moulded pottery not yet put in a kiln to bake weight-loss ratio 17wt%, moulded pottery not yet put in a kiln to bake shrinking percentage do not change after terminal drying.
Step 6, redrying：The carton dismounting on the moulded pottery not yet put in a kiln to bake surface after primary drying is continued to be put into, heat is carried out in hothouse
Air-dry dry, 65 DEG C of drying temperature, dry indoor relative humidity 12wt%, 12 hours drying times.
Step 7, calcining：Moulded pottery not yet put in a kiln to bake after redrying is calcined 1.2 hours under the conditions of 220 DEG C successively, in 450 DEG C of conditions
Lower calcining 2.5 hours, is calcined 3.5 hours under the conditions of 600 DEG C, obtains SCR denitration product.
Step 8, cutting, packaging.
The SCR denitration product that above-described embodiment prepares after testing, including following components content：Dioxy
Change 40~60wt% of titanium, silica 1~10wt%, 10~20wt% of tantalum pentoxide, 10~20wt% of manganese dioxide, three oxygen
Change 5~15wt% of 10~20wt% of molybdenum and vanadic anhydride.
The SCR denitration product that the present invention prepares is cut into the model of size 150mm*150mm*1000mm
It is tested into pilot test system, simulation steel sintering machine smoke components are：NOXContent 1500mg/Nm3、H2O content 7wt%, CO2Contain
Measure 12wt%, O2Content 8wt%, N2Content 72wt%, S content 0.5wt%, flue gas flow rate 3000/h, the SCR denitration catalysis
Agent product performance result is as shown in Figure 1, 2.
Claims (4)
1. a kind of SCR denitration, it is characterised in that including following components by weight percent：40~60wt% of titanium dioxide, titanium dioxide
1~10wt% of silicon, 10~20wt% of tantalum pentoxide, 10~20wt% of manganese dioxide, 10~20wt% of molybdenum trioxide and five
5~15wt% of V 2 O.
2. a kind of preparation method of SCR denitration as described in claim 1, it is characterised in that include the following steps：
Step 1 is kneaded：
Titanium silica flour, oxidation tantalum powder, stearic acid particles are added in kneading machine and stirred evenly by step 1.1, it is backward described mixed
Deionized water, ammonium hydroxide and lactic acid are sequentially added in mill and stirs evenly acquisition pug；The ammonia concn for 18~
22wt%, the titanium silica flour, oxidation tantalum powder, stearic acid particles, deionized water, the weight ratio of ammonium hydroxide and lactic acid for (50~
70):(10~20):(0.1~1):(20~35):(1~10):(0.1~1)；
Step 1.2, stirring keep the temperature 5~10min to the pug under 85~95 DEG C of states, carry out cooling dehumidifier later until institute
State 20~30wt% of pug moisture content；
Step 1.3 is uniformly added into polypropylene fibre and glass fibre formation mixture A, the polypropylene in the pug
Fiber accounts for 0.2~1wt% of mixture A total weights, and the glass fibre accounts for 4~6wt% of mixture A total weights；
Step 1.4, be uniformly added into successively into the mixture A living solution A, living solution B and living solution C formed it is mixed
Close material B；The living solution A is manganese nitrate solution, and the living solution B is Ammoniun Heptamolybdate Solution, and the living solution C is single
The mixed solution of ethanol amine and ammonium metavanadate；In the manganese nitrate solution manganese nitrate account for mixture B total weights 0.4~
2.4wt%, ammonium heptamolybdate accounts for 0.4~2.4wt% of mixture B total weights, the mixed solution in the Ammoniun Heptamolybdate Solution
Middle monoethanolamine accounts for 0.4~1.2wt% of mixture B total weights, and ammonium metavanadate accounts for mixture B total weights in the mixed solution
1.2~3.6wt%；
Step 1.5 is uniformly added into ammonia type carboxymethyl cellulose and polyethylene glycol oxide formation mixture C into the mixture B；
The ammonia type carboxymethyl cellulose, polyethylene glycol oxide account for 0.1~1wt% of mixture C total weights respectively；
Step 1.6 simultaneously adjusts the clay sculpture value of the mixture C to 20~35
It is step 2, aging：The mixture C is sealed and under the conditions of 18~22 DEG C, 75~85wt% of relative humidity aging 22~
Obtain aging material within 26 hours；
Step 3, filtering are pre- crowded：The aging material with extruder is pushed and passes through sieve processing and realizes that aging material combs and miscellaneous
Matter removes；
Step 4, extrusion molding：The aging material is extruded into the catalyst mud with setting shape of hygrometric state with extruder
Base；
Step 5, primary drying：It is put into after the moulded pottery not yet put in a kiln to bake is wrapped with carton in drying box and carries out heated-air drying, the moulded pottery not yet put in a kiln to bake warp
Go through dry early period, mid-term drying and terminal drying stage；
3~4 days drying times of early period, early period and gradually rise 28~35 DEG C of drying temperature, opposite in drying box when early period is dried
Humidity is continuously decreased and is controlled in 70~90wt%, and 1.5~2.5wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake shrinking percentage 2 after drying early period~
3%；
It 3~4 days mid-term drying times, 35~50 DEG C of mid-term drying temperature and gradually rises, it is opposite in drying box when mid-term is dried
Humidity is continuously decreased and is controlled in 40~65wt%, and 6~8wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake shrinking percentage 3 after mid-term drying~
3.5%；
It 2.5~3.5 days terminal drying time, 55~60 DEG C of terminal drying temperature and gradually rises, during terminal drying in drying box
Relative humidity continuously decreases and controls 15~17wt% of moulded pottery not yet put in a kiln to bake weight-loss ratio, moulded pottery not yet put in a kiln to bake shrinking percentage after 10~30wt%, terminal drying
Do not change；
Step 6, redrying：The carton dismounting on the moulded pottery not yet put in a kiln to bake surface after primary drying is continued to be put into, hot air drying is carried out in hothouse
It is dry, 55~65 DEG C of drying temperature, 8~12wt% of dry indoor relative humidity, 6~12 hours drying times；
Step 7, calcining：Moulded pottery not yet put in a kiln to bake after redrying is calcined 0.8~1.2 hour under the conditions of 180~220 DEG C successively, 350
It calcines 1.5~2.5 hours under the conditions of~450 DEG C, is calcined 2.5~3.5 hours under the conditions of 500~600 DEG C, obtain SCR denitration
Catalyst prod.
Step 8, cutting, packaging.
3. the preparation method of SCR denitration as described in claim 1, it is characterised in that：Titanium silica flour, oxygen in the step 1
The grain size for changing tantalum powder is 5~20 microns.
4. the preparation method of SCR denitration as described in claim 1, it is characterised in that：The X of titanium silica flour in the step 1
160 ± 10 millimeters of the peak height of ray, 90 ± 10m of titanium silica flour specific surface area2/ g, titanium silica flour constituent content are：Silica 1 ±
0.2wt%, 99 ± 0.7wt% of titanium dioxide, sodium oxide molybdena are less than 0.01wt%, potassium oxide less than 0.01wt%, di-iron trioxide
Less than 0.01wt%, four 1.5~3.5wt% of sulfur oxide.
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Application publication date: 20180612 |