CN102872919B - Preparation process of honeycomb SCR (selective catalytic reduction) denitration catalyst - Google Patents
Preparation process of honeycomb SCR (selective catalytic reduction) denitration catalyst Download PDFInfo
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Abstract
The invention discloses a preparation process of a honeycomb SCR(selective catalytic reduction) denitration catalyst. The preparation process includes steps of (1), subjecting a mixture of raw materials which are mixed proportionally to primary decaying, filtering and pre-extruding the mixture, subjecting the mixture to secondary decaying and finally forming and extruding out a catalyst blank in vacuum; (2), subjecting the catalyst blank formed and extruded in vacuum to primary drying at a temperature ranging from 22-68 DEG C and a humidity ranging from 95-10% gradually; (3), subjecting the catalyst dried primarily to secondary drying at the temperature ranging from 60 DEG C to 105 DEG C within the drying period of 12-24 hours; (4), calcining the catalyst blank dried secondarily at the temperature ranging from 68 DEG C to 600 DEG C for 20-30 hours, and detecting finished products after calcining. The honeycomb SCR denitration catalyst is high in yield and high in strength, manufacturing cost of the catalyst is reduced, and mechanical performance of the catalyst is improved.
Description
Technical field
The present invention relates to denitrating catalyst preparing technical field, be specifically related to a kind of preparation technology of honeycomb-shaped SCR denitrating catalyst.
Background technology
Denitrating flue gas is the method for the minimizing NOx discharge that at present developed country generally adopts in the world, can reach very high NOx removal efficiency, and wherein applying more is SCR and SNCR technology, especially SCR technology, and denitration efficiency can reach more than 90%.SCR has the successful Application achievement of hundreds of and the operating experience of many decades in the world, and Japan and Germany's equipment for denitrifying flue gas of approximately 95% adopt SCR technology, and the method technology maturation, denitration rate be high, non-secondary pollution almost.
The key of SCR denitration technology is catalyst, and its expense accounts for 30%～40% of initial outlay conventionally.The catalyst great majority that adopt in engineering at present, from import, have more increased extra cost.Therefore research and develop high efficiency catalyst and there is very important economic implications and realistic meaning.In general catalyst is by the base material skeleton of catalyst (form), carrier (material that makes active component disperse preferably and to keep) and active component (playing the composition of catalytic action) formation, has honeycomb fashion, the various ways such as board-like, corrugated.Honeycombed catalyst is directly using carrier material itself as base material, to be made into cellular integrated catalyst, and catalyst blank becomes and has active honeycomb-like pore structure through extrusion modling, dry, calcining, at reducing agent NH
3effect under the NOx flowing through in catalyst flue gas is carried out to SCR, generate the N of environmental sound
2and H
2o.
But, because with carrier TiO
2for the catalyst raw material of main body belongs to lean property material, there is certain hydraulicity, easily agglomerating while mixing with water, there is no plasticity, cannot directly by kneading, obtain plastic material, therefore need to add other structural promoter, plastotype agent and binding agent etc. to regulate the plasticity of catalyst blank entirety.Because carrier TiO
2occupy significant proportion, be not generally 55～99wt% not etc., easily there is the problem of cracking in catalyst therefore in dry and calcination process, thereby cause yield rate not high.The cost of material of making catalyst is very expensive, can not repeat again processing after cracking, and therefore yield rate has determined profit margin to a great extent.
The existing patent overwhelming majority is improved from raw material, as adjusted the addition of structural promoter in catalyst, binding agent, or explores new additive, but in addition improved patent is very little by controlling the technological parameter of manufacturing process.Application number is that the drying condition that 200910232040.8 patent has been announced catalyst is: 80 ℃ of temperature keep 2～3 hours, and then keep 3～5 hours 105 ℃ of temperature; Calcination condition is: at 250 ℃, calcine 2～3 hours, then at 450 ℃, calcine 4～5 hours.In dry run, there is no humidity control, the catalyst after extruding is directly put into the dry cracking that is easy at 80 ℃; In addition, in dry and calcination process, temperature span is large, and catalyst is sharply heated, and is also the major reason that causes cracking.
Summary of the invention
The invention provides a kind of preparation technology of honeycomb-shaped SCR denitrating catalyst, for dry and calcining, proposed strict controlled condition, prevent from ftractureing in the dry or calcination process of catalyst, guarantee the yield rate of catalyst, can effectively reduce the cost of manufacture of catalyst.Use this technique can also effectively improve the intensity of catalyst, increased the mechanical performance of catalyst.
A preparation technology for honeycomb-shaped SCR denitrating catalyst, comprising:
(1) by raw material in proportion after batch mixing catalyst blank, catalyst blank is carried out once old, then filter in advance and extrude; It is old that catalyst blank after filtration is extruded in advance carries out secondary, then carries out vacuum forming and extrude;
But in the component of described raw material and mixed proportion prior art thereof, prepare arbitrary formula of honeycomb-shaped SCR denitrating catalyst, in the present invention, as the preferred raw material components of one and proportioning thereof, be: carrier, active component, structural promoter, binding agent, distilled water in mass ratio 1: (0.5～0.75): (0.1～0.25): (0.02～0.04): mix (0.1～0.2);
Described carrier is preferably nano grade titanium tungsten powder and titanium silica flour.Wherein in titanium tungsten powder, contain 5～10% nanoscale WO
3, in titanium silica flour, contain 5～10% nanoscale SiO
2, the mass ratio of titanium tungsten powder and titanium silica flour is 4.6～15.0: 1.
Described active component is preferably manganese acetate, ceria and cupric oxide, and its mass ratio is 1: 0.07～0.25: 0.10～0.35.
Described structural promoter is preferably glass fibre, paper pulp cotton and glycerine, and its mass ratio is 1: 0.08～0.24: 0.20～1.67.
Described binding agent is polyethylene glycol oxide and sodium carboxymethylcellulose, and its mass ratio is 1: 0.40～1.62.
Mixing procedure carries out in mixer, needs material to be carried out to heating and cooling in good time; Material is in heating process, and all valves are all closed; In cooling procedure, according to mixer internal temperature, regulate mixer air inlet and air outlet aperture, now have gas and discharge, realize granulation; The standard of having mixed is mainly to see the moisture of material, plasticity, and moisture is 13～26%, plasticity is 150～300, and all detections are all qualified can discharging.
Once the old time is 8～24h.
Filter in pre-expressing technique, material after once old enters and in filter, carries out mixing and filter, filtering mesh screen is 4～10 orders, needing at set intervals to pull down filter screen cleans, if a batch materials impurity or grit are more, this material need to filter multipass and just can carry out vacuum forming and extrude operation.
The material filtering directly enters the pre-extruder of bottom, and what pre-extruder was extruded is the continuous former material base with certain size; Now material is fully bonded together, and intensity is higher, and wall is smooth, according to specification, cuts into certain length, piles up good seal, puts into old and carries out oldly for the second time, and the old time of secondary is 8～24h.
The present invention carried out twice old, there is following technical advantage: 1) catalyst blank is under dark and damp environment, and by capillarity, the moisture in blank fully permeates, distributes more even; 2) under the condition of abundant aquation, there is further ion-exchange in the active material in catalyst blank, and structural promoter contacts with water to occur to be hydrolyzed and be transformed into clay material for a long time, thereby improves plasticity; 3) particle in catalyst blank is under the condition of abundant aquation, and the corner angle passivation of particle is therefore not easy to occur compared with macroscopic void after burning till; 4) under the effect of bacterium, impel the organic matter in blank to rot, generate organic acid, increased the content of humic-acid-type substances, therefore reduced the acid-base value of blank, improved blank character, increased plasticity; 5) old time length is conducive to aeriferous eliminating in blank, makes blank more closely knit, therefore can increase the viscosity of blank and the intensity of base substrate; 6) old time length is conducive to eliminate the structural stress of each material monomer, can reduce the cracking phenomena of semi-finished product and finished product, and the quality of finished product and yield rate are improved.
Material after secondary is old enters vacuum-extruder by vacuum extruding machine inlet capable, and is extruded into the honeycombed catalyst module with certain size and pitch; Before extruding, first guarantee that mould is clean free from admixture; In extrusion, need to drive cooling water, vavuum pump, 30 ℃ of cooling water temperature <, vacuum pump pressure is-0.20～-0.05MPa, needs often to observe the quality of extrusioning catalyst simultaneously, to determine whether mould stops up; Mould need to be shut down more mold exchange after stopping up, and the mould of obstruction is put into cleaning agent and cleaned; If, because a variety of causes needs, outlet of extruder needs sealing, prevents water loss in extrusion; The catalyst module extruded cuts into the catalyst elements with certain length through wet base cutting machine, then the catalyst of extruding is weighed, and two ends coating, covers lid above catalyst or wrap with carton, treats that next step puts into climatic chamber.
(2) the catalyst blank after vacuum forming is extruded carries out primary drying, in described primary drying process temperature from 22～68 ℃ by gradient increase progressively, humidity successively decreases by gradient from 95～10%; Be to be arid cycle 4～8 days;
Temperature in described primary drying process from 22 ℃ through 8～16h to 24～26 ℃, again through 8～16h to 27～28 ℃, then through 8～16h to 29～30 ℃, then through 8～16h to 31～32 ℃, again through 8～16h to 38～40 ℃, again through 8～16h to 44～45 ℃, then through 8～16h to 48～49 ℃, then through 8～16h to 52～54 ℃, again through 8～16h to 56～58 ℃, again through 8～16h to 64～65 ℃, then through 8～16h to 67～68 ℃, then through 8～16h to 68 ℃.
Preferably, the temperature in described primary drying process is from 22 ℃ through 8～16h to 25 ℃, then through 8～16h to 28 ℃, again through 8～16h to 30 ℃, again through 8～16h to 32 ℃, then through 8～16h to 40 ℃, then through 8～16h to 45 ℃, again through 8～16h to 49 ℃, again through 8～16h to 54 ℃, then through 8～16h to 58 ℃, then through 8～16h to 65 ℃, again through 8～16h to 68 ℃, then through 8～16h to 68 ℃.
Humidity in described primary drying process from 95% through 8～16h to 95%, again through 8～16h to 89～90%, then through 8～16h to 85～86%, then through 8～16h to 81～82%, again through 8～16h to 64～65%, again through 8～16h to 55～56%, then through 8～16h to 47～48%, then through 8～16h to 39～40%, again through 8～16h to 25～26%, again through 8～16h to 18～20%, then through 8～16h to 10%, then through 8～16h to 10%.
Preferably, the humidity in described primary drying process is from 95% through 8～16h to 95%, then through 8～16h to 89%, again through 8～16h to 85%, again through 8～16h to 81%, then through 8～16h to 65%, then through 8～16h to 55%, again through 8～16h to 47%, again through 8～16h to 39%, then through 8～16h to 25%, then through 8～16h to 18%, again through 8～16h to 10%, then through 8～16h to 10%.
Before climatic chamber is enabled, need internal temperature and humidity be set according to above-mentioned drying curve and moisture curve, to remove in catalyst moisture and to prevent catalyst cracking; Temperature from 22～68 ℃ by gradient increase progressively, humidity successively decreases by gradient from 95～10%; Temperature, by electrical heating or Steam Heating, is passed through sensor adjustment; Humidity is to regulate by steam humidification or hydrofuge valve hydrofuge; Be 4～8 days arid cycle; One-level is dry finish after, lid or carton and the film that is coated on two ends are dismantled, treat that next step enters secondary drying; This stage catalyst shrinks very fast, easily causes catalyst cracking, needs very strict control.
(3) the catalyst blank after primary drying is carried out to redrying, described redrying process is the powerful convective drying of constant temperature, 60～105 ℃ of baking temperatures, and be 12～24 hours arid cycle;
Redrying thermal source is hot-air, and baking temperature is 60～105 ℃, there is no humidity requirement; Be 12～24 hours drying time; This stage catalyst shrinks slowly, but weight-loss ratio still continues rising, can accelerate rate of drying.
(4) the catalyst blank after redrying is calcined to obtain to described honeycomb-shaped SCR denitrating catalyst, in described calcination process, temperature increases progressively by gradient from 68～600 ℃; Calcination time is 20～30 hours; After calcining, carry out finished product detection.
In described calcination process temperature from 68 ℃ through 50～70min to 105～107 ℃, again through 50～70min to 167～168 ℃, again through 50～70min to 184～185 ℃, again through 50～70min to 225～226 ℃, again through 100～140min to 258～260 ℃, again through 100～140min to 283～285 ℃, again through 100～140min to 290～291 ℃, again through 50～70min to 303～305 ℃, again through 50～70min to 383～385 ℃, again through 50～70min to 430～431 ℃, again through 50～70min to 450 ℃, again through 100～140min to 450 ℃, again through 150～210min to 448～450 ℃, again through 50～70min to 418～420 ℃, again through 50～70min to 378～380 ℃, again through 50～70min to 343～345 ℃, again through 50～70min to 298～300 ℃, again through 50～70min to 248～250 ℃, again through 50～70min to 198～200 ℃, then naturally cool to room temperature.
Preferably, in described calcination process temperature from 68 ℃ through 50～70min to 105 ℃, again through 50～70min to 167 ℃, again through 50～70min to 184 ℃, again through 50～70min to 226 ℃, again through 100～140min to 260 ℃, again through 100～140min to 283 ℃, again through 100～140min to 291 ℃, again through 50～70min to 303 ℃, again through 50～70min to 385 ℃, again through 50～70min to 431 ℃, again through 50～70min to 450 ℃, again through 100～140min to 450 ℃, again through 150～210min to 450 ℃, again through 50～70min to 420 ℃, again through 50～70min to 380 ℃, again through 50～70min to 345 ℃, again through 50～70min to 300 ℃, again through 50～70min to 250 ℃, again through 50～70min to 200 ℃, then naturally cool to room temperature, 20～30 ℃.
Catalyst is sent in high-temperature calcination stove or Muffle furnace and is calcined, and calcining heat is 68～600 ℃; In calcination process, complete the evaporation of moisture, organic decomposition completely, and the activation process of active material; Calcination time is 20～30 hours.
Calcine complete catalyst by cutting machine or manually cut, forming the catalyst elements of certain length, then in SCR denitrating catalyst evaluating apparatus, carrying out the mensuration of indices.
The preparation technology of honeycomb-shaped SCR denitrating catalyst of the present invention is to moisture, plasticity, temperature, the parameters such as humidity have proposed strict demand, before moulding to catalyst blank carried out twice old, be conducive to strengthen plasticity and the intensity of blank, can also effectively reduce the cracking phenomena of semi-finished product and finished product, after vacuum forming, coating processing is carried out in catalyst two ends, to reduce moisture loss speed, dry run is carried out in two steps, primary drying carries out temperature and humidity control to catalyst, reduce catalyst cracking risk, redrying is that after striping, constant temperature brute force is dried, catalyst can be completed dry within a short period of time, calcination process has adopted the temperature control curve obtaining through pathognomonic feature mode, can effectively remove the organic matter in blank, make active material at high temperature react simultaneously, obtain (80～120 ℃) under low temperature and possess higher denitration efficiency, high-intensity catalyst finished product.
The yield rate of the honeycomb-shaped SCR catalyst that use the present invention makes is more than 90%.The mechanical strength of catalyst is very high simultaneously, get 3 × 3 holes, be of a size of 2.5 × 2.5 × 5cm catalyst of (size after two ends polish), while using the test of YDW-03 type microcomputer controlled electronic anti-folding and anti-pressing testing machine to obtain that intensity is the highest, be longitudinal 2.8MPa, laterally 0.96MPa.The intensity that is 3 × 3 holes equally, be of a size of the commercial catalysts of 2.5 × 2.5 × 5cm is longitudinal 1.8MPa, laterally 0.92MPa.The intensity of catalyst prepared by use this method is apparently higher than commercial catalysts.
The specific embodiment
Embodiment 1
(1) batch mixing.Take 328.6g titanium tungsten powder, 71.4g titanium silica flour, 25.0g cupric oxide, 147.0g manganese acetate, 36.0g ceria, 45.0g glass fibre, 3.6g paper pulp cotton, 50.0g glycerine, 40g distilled water, 4.2g sodium carboxymethylcellulose, 5.2g polyethylene glycol oxide evenly mixes in mixer, get mixed blank, it is 15.3% that use HB43-S halogen moisture teller detects its moisture, use KS-B type micro computer plasticity measurement instrument to detect its plasticity is 225.
(2) once old.Blank is put into sealing bag, be placed in ageing tower and carry out oldly, the time is 12h.
(3) filter and extrude in advance.The blank of old mistake is put into filter and carry out mixing and filter, filtering mesh screen is 10 orders.Remove after impurity, enter pre-extruder, be extruded into cuboid bulk.
(4) secondary is old.The sealing of above-mentioned block blank is carried out old for the second time, the time is 12h.
(5) vacuum extruding.Above-mentioned block blank after secondary is old is put into vacuum forming extruder and extrude, controlling cooling water temperature is 10 ℃, and vacuum pump pressure is-0.15MPa.By die blank, be extruded into honeycombed catalyst module, cut into 10 catalyst, every catalyst is weighed, two ends coating, wraps with carton.
(6) primary drying.Above-mentioned 10 catalyst are put into climatic chamber, by programed temperature curve from 22 ℃ through 12h to 25 ℃, then through 12h to 28 ℃, again through 12h to 30 ℃, again through 12h to 32 ℃, then through 12h to 40 ℃, then through 12h to 45 ℃, again through 12h to 49 ℃, again through 12h to 54 ℃, then through 12h to 58 ℃, then through 12h to 65 ℃, again through 12h to 68 ℃, then through 12h to 68 ℃.
By programme-control moisture curve from 95% through 12h to 95%, again through 12h to 89%, then through 12h to 85%, then through 12h to 81%, again through 12h to 65%, again through 12h to 55%, then through 12h to 47%, then through 12h to 39%, again through 12h to 25%, again through 12h to 18%, then through 12h to 10%, then through 12h to 10%.Total time is 6 days.
(7) redrying.The film that above-mentioned dried 10 catalyst is removed to carton and two ends, is put in redrying case and is dried, and temperature constant is at 68 ℃, and the time is 24h.
(8) calcining.Above-mentioned 10 catalyst after redrying are put into calcining furnace and carry out high-temperature calcination, temperature according to calcining curve from 68 ℃ through 60min to 105 ℃, again through 60min to 167 ℃, again through 60min to 184 ℃, again through 60min to 226 ℃, again through 120min to 260 ℃, again through 120min to 283 ℃, again through 120min to 291 ℃, again through 60min to 303 ℃, again through 60min to 385 ℃, again through 60min to 431 ℃, again through 60min to 450 ℃, again through 120min to 450 ℃, again through 180min to 450 ℃, again through 60min to 420 ℃, again through 60min to 380 ℃, again through 60min to 345 ℃, again through 60min to 300 ℃, again through 60min to 250 ℃, again through 60min to 200 ℃, then in stove, naturally cool to room temperature, obtain catalyst finished product.Calcining curve total time is 25h.
(9) finished product detection.Above-mentioned finished catalyst is detected.10 catalyst are intercepted into 25 × 25 × 50mm, use YDW-03 type microcomputer controlled electronic anti-folding and anti-pressing testing machine to test its intensity, recording longitudinal strength is 2.8MPa, and transverse strength is 0.96MPa, reaches the requirement of industrial catalyst.10 catalyst that use this technique to make do not have cracking phenomena, yield rate 100%.
Embodiment 2
(1) batch mixing.Take 350.0g titanium tungsten powder, 50.0g titanium silica flour, 50.0g cupric oxide, 196.0g manganese acetate, 36.0g ceria, 40.0g glass fibre, 7.2g paper pulp cotton, 20.0g glycerine, 65g distilled water, 8.4g sodium carboxymethylcellulose, 5.2g polyethylene glycol oxide evenly mixes in mixer, get mixed blank, it is 18.6% that use HB43-S halogen moisture teller detects its moisture, use KS-B type micro computer plasticity measurement instrument to detect its plasticity is 197.
(2) once old.Blank is put into sealing bag, be placed in ageing tower and carry out oldly, the time is 24h.
(3) filter and extrude in advance.The blank of old mistake is put into filter and carry out mixing and filter, filtering mesh screen is 4 orders.Remove after impurity, enter pre-extruder, be extruded into cuboid bulk.
(4) secondary is old.The sealing of above-mentioned block blank is carried out old for the second time, the time is 24h.
(5) vacuum extruding.Above-mentioned block blank after secondary is old is put into vacuum forming extruder and extrude, controlling cooling water temperature is 15 ℃, and vacuum pump pressure is-0.10MPa.By die blank, be extruded into honeycombed catalyst module, cut into 10 catalyst, every catalyst is weighed, two ends coating, wraps with carton.
(6) primary drying.Above-mentioned 10 catalyst are put into climatic chamber, by programed temperature curve from 22 ℃ through 16h to 25 ℃, then through 16h to 28 ℃, again through 16h to 30 ℃, again through 16h to 32 ℃, then through 16h to 40 ℃, then through 16h to 45 ℃, again through 16h to 49 ℃, again through 16h to 54 ℃, then through 16h to 58 ℃, then through 16h to 65 ℃, again through 16h to 68 ℃, then through 16h to 68 ℃.
By programme-control moisture curve from 95% through 16h to 95%, again through 16h to 89%, then through 16h to 85%, then through 16h to 81%, again through 16h to 65%, again through 16h to 55%, then through 16h to 47%, then through 16h to 39%, again through 16h to 25%, again through 16h to 18%, then through 16h to 10%, then through 16h to 10%.Total time is 8 days.
(7) redrying.The film that above-mentioned dried 10 catalyst is removed to carton and two ends, is put in redrying case and is dried, and temperature constant is at 80 ℃, and the time is 18h.
(8) calcining.Above-mentioned 10 catalyst after redrying are put into calcining furnace and carry out high-temperature calcination, temperature according to calcining curve from 68 ℃ through 70min to 105 ℃, again through 70min to 167 ℃, again through 70min to 184 ℃, again through 70min to 226 ℃, again through 140min to 260 ℃, again through 140min to 283 ℃, again through 140min to 291 ℃, again through 70min to 303 ℃, again through 70min to 385 ℃, again through 70min to 431 ℃, again through 70min to 450 ℃, again through 140min to 450 ℃, again through 210min to 450 ℃, again through 70min to 420 ℃, again through 70min to 380 ℃, again through 70min to 345 ℃, again through 70min to 300 ℃, again through 70min to 250 ℃, again through 70min to 200 ℃, then naturally cool to room temperature, obtain catalyst finished product.Calcining curve total time is 29.2h.
(9) finished product detection.Above-mentioned finished catalyst is detected.10 catalyst are intercepted into 25 × 25 × 50mm, use YDW-03 type microcomputer controlled electronic anti-folding and anti-pressing testing machine to test its intensity, recording longitudinal strength is 2.3MPa, and transverse strength is 0.82MPa, reaches the requirement of industrial catalyst.10 catalyst that use this technique to make do not have cracking phenomena, yield rate 100%.
Embodiment 3
(1) batch mixing.Take 375.0g titanium tungsten powder, 25.0g titanium silica flour, 25.0g cupric oxide, 245.0g manganese acetate, 18.0g ceria, 30.0g glass fibre, 3.6g paper pulp cotton, 10.0g glycerine, 80g distilled water, 4.2g sodium carboxymethylcellulose, 10.4g polyethylene glycol oxide evenly mixes in mixer, get mixed blank, it is 24.1% that use HB43-S halogen moisture teller detects its moisture, use KS-B type micro computer plasticity measurement instrument to detect its plasticity is 165.
(2) once old.Blank is put into sealing bag, be placed in ageing tower and carry out oldly, the time is 8h.
(3) filter and extrude in advance.The blank of old mistake is put into filter and carry out mixing and filter, filtering mesh screen is 6 orders.Remove after impurity, enter pre-extruder, be extruded into cuboid bulk.
(4) secondary is old.The sealing of above-mentioned block blank is carried out old for the second time, the time is 8h.
(5) vacuum extruding.Above-mentioned block blank after secondary is old is put into vacuum forming extruder and extrude, controlling cooling water temperature is 20 ℃, and vacuum pump pressure is-0.20MPa.By die blank, be extruded into honeycombed catalyst module, cut into 10 catalyst, every catalyst is weighed, two ends coating, wraps with carton.
(6) primary drying.Above-mentioned 10 catalyst are put into climatic chamber, by programed temperature curve from 22 ℃ through 8h to 25 ℃, then through 8h to 28 ℃, again through 8h to 30 ℃, again through 8h to 32 ℃, then through 8h to 40 ℃, then through 8h to 45 ℃, again through 8h to 49 ℃, again through 8h to 54 ℃, then through 8h to 58 ℃, then through 8h to 65 ℃, again through 8h to 68 ℃, then through 8h to 68 ℃.
By programme-control moisture curve from 95% through 8h to 95%, again through 8h to 89%, then through 8h to 85%, then through 8h to 81%, again through 8h to 65%, again through 8h to 55%, then through 8h to 47%, then through 8h to 39%, again through 8h to 25%, again through 8h to 18%, then through 8h to 10%, then through 8h to 10%.Total time is 4 days.
(7) redrying.The film that above-mentioned dried 10 catalyst is removed to carton and two ends, is put in redrying case and is dried, and temperature constant is at 100 ℃, and the time is 12h.
(8) calcining.Above-mentioned 10 catalyst after redrying are put into calcining furnace and carry out high-temperature calcination, temperature according to calcining curve from 68 ℃ through 50min to 105 ℃, again through 50min to 167 ℃, again through 50min to 184 ℃, again through 50min to 226 ℃, again through 100min to 260 ℃, again through 100min to 283 ℃, again through 100min to 291 ℃, again through 50min to 303 ℃, again through 50min to 385 ℃, again through 50min to 431 ℃, again through 50min to 450 ℃, again through 100min to 450 ℃, again through 150min to 450 ℃, again through 50min to 420 ℃, again through 50min to 380 ℃, again through 50min to 345 ℃, again through 50min to 300 ℃, again through 50min to 250 ℃, again through 50min to 200 ℃, then naturally cool to room temperature, obtain catalyst finished product.Calcining curve total time is 20.8h.
(9) finished product detection.Above-mentioned finished catalyst is detected.10 catalyst are intercepted into 25 × 25 × 50mm, use YDW-03 type microcomputer controlled electronic anti-folding and anti-pressing testing machine to test its intensity, recording longitudinal strength is 2.4MPa, and transverse strength is 0.95MPa, reaches the requirement of industrial catalyst.10 catalyst that use this technique to make have a trickle cracking, yield rate 90%.
Comparative example 1
(1) batch mixing.According to the raw material described in embodiment 1 and proportioning thereof, in mixer, evenly mix, get mixed blank, it is 21.63% that use HB43-S halogen moisture teller detects its moisture, use KS-B type micro computer plasticity measurement instrument to detect its plasticity is 192.
(2) old.Blank is put into sealing bag, be placed in ageing tower and carry out oldly, the time is 6h.
(3) filter and extrude in advance.The blank of old mistake is put into filter and carry out mixing and filter, filtering mesh screen is 10 orders.Remove after impurity, enter pre-extruder, be extruded into cuboid bulk.
(4) vacuum extruding.Above-mentioned block blank after secondary is old is put into vacuum forming extruder and extrude, controlling cooling water temperature is 10 ℃, and vacuum pump pressure is-0.15MPa.By die blank, be extruded into honeycombed catalyst module, cut into 10 catalyst, every catalyst is weighed, two ends coating, wraps with carton.
(5) dry.80 ℃ of maintenances of temperature 2～3 hours, and then keep 3～5 hours 105 ℃ of temperature.
(6) calcining.At 250 ℃, calcine 2～3 hours, then at 450 ℃, calcine 4～5 hours.
(7) finished product detection.In 10 catalyst that use this technique to make, there are 4 to occur crackle, yield rate 60%.
Claims (5)
1. a preparation technology for honeycomb-shaped SCR denitrating catalyst, is characterized in that, comprising:
(1) by raw material in proportion after batch mixing catalyst blank, catalyst blank is carried out once old, then filter in advance and extrude; It is old that catalyst blank after filtration is extruded in advance carries out secondary, then carries out vacuum forming and extrude;
(2) the catalyst blank after vacuum forming is extruded carries out primary drying, in described primary drying process temperature from 22～68 ℃ by gradient increase progressively, humidity successively decreases by gradient from 95～10%;
Temperature in primary drying process from 22 ℃ through 8～16h to 24～26 ℃, again through 8～16h to 27～28 ℃, then through 8～16h to 29～30 ℃, then through 8～16h to 31～32 ℃, again through 8～16h to 38～40 ℃, again through 8～16h to 44～45 ℃, then through 8～16h to 48～49 ℃, then through 8～16h to 52～54 ℃, again through 8～16h to 56～58 ℃, again through 8～16h to 64～65 ℃, then through 8～16h to 67～68 ℃, then through 8～16h to 68 ℃;
(3) the catalyst blank after primary drying is carried out to redrying, described redrying process is the powerful convective drying of constant temperature, 60～105 ℃ of baking temperatures, and be 12～24 hours arid cycle;
(4) the catalyst blank after redrying is calcined to obtain to described honeycomb-shaped SCR denitrating catalyst, in described calcination process, temperature increases progressively by gradient from 68～600 ℃; Calcination time is 20～30 hours;
In calcination process temperature from 68 ℃ through 50～70min to 105～107 ℃, again through 50～70min to 167～168 ℃, again through 50～70min to 184～185 ℃, again through 50～70min to 225～226 ℃, again through 100～140min to 258～260 ℃, again through 100～140min to 283～285 ℃, again through 100～140min to 290～291 ℃, again through 50～70min to 303～305 ℃, again through 50～70min to 383～385 ℃, again through 50～70min to 430～431 ℃, again through 50～70min to 450 ℃, again through 100～140min to 450 ℃, again through 150～210min to 448～450 ℃, again through 50～70min to 418～420 ℃, again through 50～70min to 378～380 ℃, again through 50～70min to 343～345 ℃, again through 50～70min to 298～300 ℃, again through 50～70min to 248～250 ℃, again through 50～70min to 198～200 ℃, then in stove, naturally cool to room temperature.
2. preparation technology according to claim 1, it is characterized in that, humidity described in step (2) in primary drying process from 95% through 8～16h to 95%, again through 8～16h to 89～90%, again through 8～16h to 85～86%, again through 8～16h to 81～82%, again through 8～16h to 64～65%, again through 8～16h to 55～56%, then through 8～16h to 47～48%, then through 8～16h to 39～40%, again through 8～16h to 25～26%, again through 8～16h to 18～20%, then through 8～16h to 10%, then through 8～16h to 10%.
3. preparation technology according to claim 1, is characterized in that, described in step (1), once old time is 8～24h.
4. preparation technology according to claim 1, is characterized in that, the old time of secondary described in step (1) is 8～24h.
5. preparation technology according to claim 1, is characterized in that, vacuum forming described in step (1) is extruded and rear catalyst blank carried out to coating.
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