CN105126818B - A kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration and preparation method thereof - Google Patents
A kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of wear-resisting anti-poisoning SCR denitration, including mixing, once old, filtering pre-extruded, secondary old, extrusion molding, one-level drying, secondary drying, roasting, cutting and end face cure step.The present invention has the advantages that wearability is strong, compression strength is high, anti-poisoning capability strong, is readily extruded shaping, denitration activity is good, long lifespan；By adding montmorillonitic clay instead of partial-titanium tungsten powder, cost of material is reduced, while improving aperture and the pore-size distribution of catalyst, beneficial to the scattered of active material, catalyst surface acidity can also be increased, denitration performance is improved；It is additionally added catalyst reclaimed materials and carrys out waste material in effective remanufacture, it is to avoid the fixed-end forces of production waste material saves cost simultaneously.The denitrifying oxide processing that present invention may be broadly applicable under the complicated flue gas operating mode such as apparatus of thermo-electric power boiler, glass furnace, cement kiln, chemical industry and steel plant.
Description
Technical field
The present invention relates to catalyst field, more particularly to a kind of preparation of wear-resisting anti-poisoning honeycomb fashion SCR denitration
Method.
Background technology
The nitrogen oxides of the burning generation of fossil fuel, is almost NO and NO entirely2, and it is expected that in 30 ~ 50 years of future,
Energy general layout of China's energy-consuming based on coal will not change, this primary energy production and consumption knot based on coal
Structure brings serious problem of environmental pollution, and China's NOx emission has reached 22,730,000 tons within 2010, as a result of these trends, NOx rows
35,400,000 tons are high-volume up in the year two thousand thirty, control NOx discharge has become pollution control major tasks.With power industry
Development and automobile quantity increase, NOx discharge is increasing, and NOx can not only form acid rain, and can and hydrocarbon
Generate photochemical fog, also participate in the destruction of ozone layer, be also produce the fine particles pollution such as PM2.5 and gray haze major reason it
One, huge threat is constituted to health and ecological environment.
The control dynamics of NOx emission are increased during China " 12 ", simple low-NO_x combustion technology can not expire
Sufficient NOx discharge standard, flue gas SCR technology（SCR）It is maximally effective removing NOx method, it is high performance to urge
Agent is the key in SCR denitration, and existing most of denitrating catalysts have easy to wear, blocking, poisoning, efflorescence in use
The problems such as cause the lost of life, and specific surface area, porosity are low causes catalytic efficiency low, and it is big also to there is catalyst amount, production
The defects such as high expensive, therefore, a kind of anti-wear performance of exploitation is good, the denitration that anti-poisoning capability is strong, denitration efficiency is high and cost is low
Catalyst is urgent problem to be solved in SCR denitration.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of wear-resisting anti-poisoning SCR denitration, denitration can be improved
Wear-resisting, the anti-poisoning performance of catalyst, improves its denitration efficiency and service life.
The object of the invention to solve the technical problems is achieved through the following technical solutions.A kind of wear-resisting anti-poisoning
The preparation method of SCR denitration, including mixing, once it is old, filtering pre-extruded, secondary old, extrusion molding, one-level do
Dry, secondary drying, roasting, cutting and end face cure step.
1）Described mixing process includes the following six stage：
（1）First stage：Kneading machine is under stopped status, by the titanium tungsten powder of 300 ~ 400 parts by weight, 70 ~ 150 parts by weight
Titanium tungsten silica flour, the catalyst reclaimed materials of 30 ~ 80 parts by weight, the ammonium paramolybdate of 5 ~ 30 parts by weight；Under the positive stirring at low speed of rotor
Add the stearic acid of 0.8 ~ 2.0 parts by weight, the lactic acid of 5 ~ 10 parts by weight, 280 ~ 350 parts by weight of deionized water and 25 ~ 40 parts by weight
Concentration is 18% ~ 25%（Mass percent）Ammoniacal liquor in kneading machine, positive strong stirring lower at a high speed is uniform；
（2）Second stage：Kneading machine is under stopped status, by the titanium tungsten powder of 70 ~ 150 parts by weight, the illiteracy of 40 ~ 60 parts by weight
De- stone clay is added in kneading machine.The lower deionized water and 3 ~ 15 parts by weight for adding 10 ~ 30 parts by weight is dense in positive stirring at low speed
Spend for 18% ~ 25%（Mass percent）Ammoniacal liquor in kneading machine, material is warming up to 90 DEG C ~ 98 under positive high-speed stirred
DEG C, then open intake valve and air bleeding valve carries out dehumidifier, intake valve and drain tap are opened during dehumidifier；
（3）Phase III：Under the positive lower-speed state of kneading machine, by the ammonium metavanadate solution of 40 ~ 60 parts by weight, 2.5 ~
The deionized water of the kapok of 4.0 parts by weight, the glass fibre of 25 ~ 40 parts by weight and 10 ~ 25 parts by weight is added in batch mixer, so
Positive high-speed stirred is uniform afterwards；
（4）Fourth stage：In the reverse low speed of kneading machine（350rpm）Under state, by the CMC of 0.8 ~ 2.0 parts by weight（Carboxylic first
Base cellulose）, 1.5 ~ 4.5 parts by weight PEO（PEO）Added with the deionized water of 8 ~ 15 parts by weight in kneading machine, instead
To at a high speed（750rpm）Stir；
（5）5th stage：Under the reverse lower-speed state of kneading machine, by the carboxymethyl cellulose of 0.8 ~ 2.0 parts by weight and
The PEO of 1.5 ~ 4.5 parts by weight is added in kneading machine, and then reverse high-speed stirred is uniform；
（6）6th stage：According to the Testing index of mixing material, the deionized water of 1 ~ 10 parts by weight is added into kneading machine
Ammoniacal liquor progress with 1 ~ 10 parts by weight is quenched, moisture, pH value, shrinkage factor and the plasticity of material is reached after standard requirement from mixing
Motor spindle unloads the material kneaded.
After the above-mentioned mixing first stage terminates, the moisture of mixed material is 40% ~ 42%, and pH value is 9.0 ~ 10.0；Mixing the
After two-stage terminates, the moisture of mixed material is 24% ~ 26%, and pH value is 8.0 ~ 9.0；After the mixing phase III terminates, mixture
The moisture of material is 27% ~ 29%, and pH value is 8.3 ~ 9.2；Knead after the 5th stage terminated, mixed material moisture is in 27 ~ 30%, pH value
7.8 ~ 8.6；Knead after the 6th stage terminated, mixed material moisture is 28 ~ 30%, and pH value is replaced 8.0 ~ 8.6 with extrusion force
Plasticity of slurry value be 1600 ~ 2200N.
The described stage of mixing first to the 6th is carried out in same kneading machine, and high-energy rotator and star are provided with inside kneading machine
Rake, first to the phase III is Positive work, the 4th to the 6th stage antiport.
The titanium tungsten powder crystal type is Detitanium-ore-type, and its main component is TiO2：93% ~ 96%, WO3：4.5% ~ 5.5%, compare surface
Product is 80 ~ 100m2/ g, 1.0 ~ 3.5um of average grain diameter；Titanium tungsten silica flour crystal formation is Detitanium-ore-type, and its main component is TiO2：85%~
90%, WO3：4.5% ~ 5.5%, SiO2：4.0% ~ 6.0%, specific surface area is 95 ~ 115 m2/ g, 1.0 ~ 3.5um of average grain diameter；Cover de-
Stone clay main component is SiO2：58% ~ 65%, Al2O3%：18% ~ 24%, Fe2O3：2% ~ 6%, MgO：2%~6%；Catalyst reclaimed materials
Average grain diameter in 5 ~ 20um.
Described ammonium metavanadate solution is the ammonium metavanadate of 50 ~ 200 parts by weight, the MEA of 60 ~ 220 parts by weight and
The deionized water of 500 ~ 700 parts by weight temperature be 55 ~ 95 DEG C, preparing tank motor speed be to prepare under 35r/min, metavanadic acid
Ammonium salt solution density is 1.0 ~ 1.5g/ml, and the concentration of ammonium metavanadate is titrated with l ferrous ammonium sulfate solution.
2）In described once old step, after material is packed with plastic bag sealing, be positioned over temperature for 10 ~ 30 DEG C, it is wet
Degree is more than in 60% ageing silo, once old 10 ~ 48h.
3）In described filtering preliminary extrusion step, will be once old after material filtered on filtering pre-extruded machine after pre- squeeze
Go out squarely block, its extrusion temperature is not higher than 45 DEG C, and filtering stainless (steel) wire mesh size is 1 × 3mm,
4）In described secondary old step, lump material is sealed in plastic box after filtering pre-extruded, is in temperature
10 ~ 30 DEG C, humidity be more than 60% ageing silo in, secondary old 10 ~ 36h.
5）In described extrusion molding step, extruded velocity is 1 ~ 1.5m/min, and pressure is 2.5 ~ 5.5MPa, and temperature is less than
30 DEG C, vacuum is less than -0.096MPa, a width of 155.5 ~ 157.5mm in extrusioning catalyst section, and length is 400 ~ 1300mm.
6）In described one-level drying steps, preformed catalyst is wrapped into the carton with sponge liner, drying is placed in small
On car and be pushed into hothouse, dry indoor temperature from 25 ± 5 DEG C gradually rise up to 60 ± 5 DEG C, humidity from 90 ± 5% gradually under
20 ± 5% are down to, arid cycle is 7 ~ 12 days.
7）In described secondary drying step, the dried catalyst of one-level is taken out out of carton and overlays secondary drying
Be 60 ± 5 DEG C, the progress F.D drying of humidity 20 ± 5% time in temperature in Che Shang, feeding tunnel cave, drying time for 12 ~
24h, it is 0.5% ~ 3.0% to dry rear catalyst moisture.
8）In described calcination stepses, the catalyst after secondary drying is arranged side by side on mesh-belt kiln, sequentially passes through heating
Section I, constant temperature zone I, warming-up section II, constant temperature zone II, five sections of cooling section；Each zone temperatures are respectively：Warming-up section I：From entrance
Room temperature rises to 170 ~ 200 DEG C, heating-up time 5h；Constant temperature zone I：The constant temperature 4h at 170 ~ 200 DEG C；Warming-up section II：From 170 ~ 200 DEG C
It is warming up to 600 ~ 625 DEG C, heating-up time 9h；Constant temperature zone II：The constant temperature 5.5h at 600 ~ 625 DEG C；Cooling section：From 600 ~ 625 DEG C
It is cooled to 50 ~ 80 DEG C, cool time 9h；Exhaust static pressure is -80Pa ~ -30Pa.
9）In described cutting and end face cure step, calcined catalyst both ends of the surface are cut, are catalyzed after cutting
Dip time of the agent one end in hardening bath is 20 ~ 50s, and dipping height is 10 ~ 30mm；Hardening bath be phosphate dihydrogen aluminum solution or
Person's aluminum sulfate solution, phosphate dihydrogen aluminum solution is 1.4 ~ 1.6g/ml in 25 DEG C of lower densities, and aluminum sulfate solution is in 25 DEG C of lower densities
1.0~1.4g/ml。
Compared with prior art, the present invention has the advantages that：
The present invention provides a kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration, overcomes existing most of denitrating catalysts
There are problems that in use it is easy to wear, block, poisoning, cause its service life shorten, specific surface area and porosity drop
It is low, cause catalytic efficiency to decline, also there is that catalyst amount is big, the defect such as production cost is higher.The catalyst has wearability
By force, compression strength is high, anti-poisoning capability is strong, the advantages of be readily extruded shaping, good denitration activity, long lifespan；Cover de- by adding
Stone clay replaces partial-titanium tungsten powder, cost of material is reduced, while aperture and the pore-size distribution of catalyst are improved, beneficial to activity
Disperseing for material, can also increase catalyst surface acidity, improve denitration performance；Catalyst reclaimed materials is additionally added effectively to reclaim
Waste material in production, it is to avoid the fixed-end forces of production waste material save cost simultaneously；In addition, the honeycomb prepared by above-mentioned steps
Formula SCR denitration, according to different operating condition designs, can be widely used in apparatus of thermo-electric power boiler, glass furnace, cement kiln, change
Denitrifying oxide processing under the complexity flue gas operating mode such as work and steel plant.
Embodiment
The present invention is further elaborated with reference to embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
Embodiment prepared by the wear-resisting anti-poisoning honeycomb fashion SCR denitration of the present invention is as follows：
First, preparation method
1）The preparation of catalyst reclaimed materials：By the catalyst waste material after cutting through crushing, existing again at the beginning of crushing material system
Dry method is levigate under 900r/min, detected with laser fineness gage its average grain diameter is 7.6um.
2）It is prepared by ammonium metavanadate solution：500L deionized waters are added into ammonium metavanadate solution preparing tank, start stirring electricity
Machine, is steam heated to 30 DEG C, then adds 73kg MEAs, is heated to 75 DEG C under 30r/min stirrings, adds the inclined vanadium of 61kg
Sour ammonium powder, is heated with stirring to 95 DEG C and is incubated 1h, and it is 730L to add deionized water to volume, is cooled to after 60 DEG C, with drop
The method of determining detect ammonium metavanadate solution concentration be 0.091kg/L.
3）Mixing：It is divided into six stages, specific embodiment is as follows：
（1）First stage：Kneading machine is under stopped status, by 320kg titanium tungsten powder, 80kg titanium tungsten silica flour, 50kg
Catalyst reclaimed materials, 15kg ammonium paramolybdate are added in kneading machine.In positive low speed（350rpm）Rotate the hard of lower addition 1.5kg
Resin acid, 7.5kg lactic acid, 320L deionized waters, 32L ammoniacal liquor in kneading machine, it is positive at a high speed（750rpm）Lower strong stirring
Uniformly, detect that material moisture is that 41.2%, pH is 9.5 after must kneading；
（2）Second stage：Kneading machine adds 80kg titanium tungsten powder, 40kg montmorillonitic clay mixed under stopped status
In mill, the lower deionized water for adding 15L and 7L ammoniacal liquor are in kneading machine in positive stirring at low speed, in positive high-speed stirred
It is lower that material is warming up to 92 DEG C, then open intake valve and air bleeding valve and carry out dehumidifier, detected after dehumidifier material moisture is
24.6%, pH are 8.6；
（3）Phase III：Under the positive lower-speed state of kneading machine, 55L ammonium metavanadate solution, 3.5kg kapok are starched,
32kg glass fibre and 15L deionized water are added in batch mixer, and then positive high-speed stirred is uniform, is measured after stirring
Material moisture is that 27.6%, pH is 8.9；
（4）Fourth stage：In the reverse low speed of kneading machine（350rpm）Under state, by 1.4kg CMC, 3.0kg PEO and
10L deionized water is added in kneading machine, reversely at a high speed（750rpm）Stir；
（5）5th stage：Mixing is added under the reverse lower-speed state of kneading machine, then by 0.8kg CMC and 2.0kg PEO
In machine, then reverse high-speed stirred is uniform, and it is 7.9 that the moisture of material is measured after stirring for 27.2%, pH；
（6）6th stage：According to the Testing index of mixing material, 10L deionized water and 5L is added into kneading machine
Ammoniacal liquor progress is quenched, moisture, pH value, shrinkage factor and the plasticity of material is reached that standard unloads mixing after requiring from mixing motor spindle
Good material.Material Testing index result after mixing terminates is as shown in table 1
Table 1 kneads material Testing index result
| Testing index | Moisture（180 DEG C, %） | pH | Shrinkage factor（6mm rods, %） | Plasticity（In terms of force value, N） |
| Testing result | 28.4 | 8.4 | 2.9 | 1850 |
4）It is once old：By after mixing material load polybag interior sealing it is good, be put into 20 DEG C of temperature, humidity 75% it is old
Rotten room 18h, to reduce the residual stress of pug and make internal moisture more uniform.
5）Filter pre-extruded：Pug after will be old filters out bulky grain on the filter equipped with stainless steel mesh, so
It is extruded into lump material on pre-extruded machine afterwards.
6）It is secondary old：By the cake mass of pre-extruded loaded in sealed plastic box, 20 DEG C, the ageing silo of humidity 75%
Secondary old 15h.
7）Shaping extrusion：Pug extrusion molding in vacuum-extruder after extrusion will be filtered, extrusion hole count is 18 × 18,
Extruded velocity is 1.1m/min, and pressure is 3.5MPa, and temperature is 16.8 DEG C, and vacuum is -0.096MPa, extrusioning catalyst section
A width of 155.6mm, the moist catalysis honeycomb type semi-finished product that length is 820mm are cut into automatic gas cutting machine.
8）One-level is dried：Extrusion aftershaping catalyst is pressed from both sides to packing table top with manipulator and wrapped with the carton with sponge
Dress, is placed on drying cart, is pushed into drying room, is slowly dried under certain temperature and humidity, and detection subtracts daily in the drying process
Rate and shrinkage factor again, loss of weight stop one-level when reaching 20 ± 2% and dried.The parameters such as drying temperature, humidity are as shown in table 2.
The one-level drying parameter of table 2
| Time/h | 24 | 48 | 72 | 96 | 120 | 144 | 168 | 192 | 216 |
| Temperature/DEG C | 25±5 | 30±5 | 30±5 | 40±5 | 45±5 | 50±5 | 55±5 | 60±5 | 60±5 |
| Humidity/% | 90±5 | 85±5 | 80±5 | 75±5 | 70±5 | 60±5 | 45±5 | 30±5 | 20±5 |
9）Secondary drying：One-level drying rear catalyst is taken out out of carton, is placed on secondary drying car and sends into tunnel
In kiln, temperature be 60 ± 5 DEG C, humidity be 20 ± 5% times progress forced air drying 15h, it is 2.3% to dry rear catalyst moisture.
10）Roasting：Catalyst after secondary drying is placed on mesh-belt kiln, laterally longitudinal direction is maintained a certain distance, with
Exempt from mutually collision, catalyst sequentially passes through warming-up section I：From inlet's temperature rise to 185 DEG C, heating-up time 5h；Constant temperature zone I：185
Constant temperature 4h at DEG C；Warming-up section II：610 DEG C, heating-up time 9h are warming up to from 185 DEG C；Constant temperature zone II：The constant temperature 5.5h at 610 DEG C；
Cooling section：60 DEG C, cool time 9h are cooled to from 610 DEG C；Discharge duct static pressure is -80Pa ~ -30Pa.
11）Cutting：Catalyst after roasting directly delivers to cutting machine with automation equipment, is automatically cut into by design
800mm, the remaining garbage collection of cutting is in ash can, and cutting dust and soot blowing dust are collected with cloth dust collector, waste material and returns
Dust is received to recycle.
12）End face is hardened：25s, dipping height in catalyst one end immersion phosphate dihydrogen aluminum solution after soot blowing will be cut
For 20cm, pile up and air-dried in disk stripping after taking-up.
2nd, performance detection
Main component and performance detection to catalyst are detected.Tear strength be sample size be 10 × 10 holes,
Height of specimen is 10cm, air velocity：15 ± 2m/s, quartz sand concentration：50 ± 5%, quartz sand average grain diameter is 40 ~ 50 mesh, is surveyed
Test agent tests 2h measure with comparative sample under conditions of connecting；Denitration performance is that, in 370 DEG C of flue-gas temperature, air speed is
2.3m/s, ammonia nitrogen mol ratio is that 0.85, NO is 220ppm, SO2For 950ppm, O2For 3.5%, H2O is 9.6%, and remaining is N2, knot
Fruit is as shown in table 3.
The catalyst component of table 3 and properties testing result
Embodiment 2
Embodiment prepared by the wear-resisting anti-poisoning honeycomb fashion SCR denitration of the present invention is as follows：
First, preparation method
1）The preparation of catalyst reclaimed materials：By the catalyst waste material after cutting through crushing, existing again at the beginning of crushing material system
Dry method is levigate under 900r/min, detected with laser fineness gage its average grain diameter is 8.1um.
2）It is prepared by ammonium metavanadate solution：500L deionized waters are added into ammonium metavanadate solution preparing tank, start mixer,
30 DEG C are steam heated to, 180kg MEAs are then added, 75 DEG C is heated under 30r/min stirrings, adds the inclined vanadium of 157kg
Sour ammonium powder, is heated with stirring to 95 DEG C and is incubated 1h, then it is 730L to add deionized water to volume into tank, and solution is cooled to 60
After DEG C, detect that ammonium metavanadate solution concentration is 0.2154kg/L with titration.
3）Mixing：It is divided into six stage completions, specific embodiment is as follows：
（1）First stage：Kneading machine is under stopped status, by 350kg titanium tungsten powder, 95kg titanium tungsten silica flour, 30kg
Catalyst reclaimed materials, 20kg ammonium paramolybdate are added in kneading machine.In positive low speed（350rpm）Rotate the hard of lower addition 1.8kg
Resin acid, 10kg lactic acid, 290L deionized waters, 35L ammoniacal liquor in kneading machine, it is positive at a high speed（750rpm）Lower strong stirring is equal
It is even, detect that material moisture is that 40.7%, pH is 9.8 after must kneading respectively with Moisture Meter and pH meter；
（2）Second stage：Kneading machine adds 95kg titanium tungsten powder, 50kg montmorillonitic clay mixed under stopped status
In mill, the lower deionized water for adding 20L and 10L ammoniacal liquor are in kneading machine in positive stirring at low speed, in positive high-speed stirred
It is lower that material is warming up to 94 DEG C, then open intake valve and air bleeding valve and carry out dehumidifier, detected after dehumidifier material moisture is
25.2%, pH are 8.8；
（3）Phase III：Under the positive lower-speed state of kneading machine, 55L ammonium metavanadate solution, 3.8kg kapok are starched,
35kg glass fibre and 18L deionized water are added in batch mixer, and then positive high-speed stirred is uniform, is measured after stirring
Material moisture is that 28.2%, pH is 9.0；
（4）Fourth stage：In the reverse low speed of kneading machine（350rpm）Under state, by 1.0kg CMC, 2.6kg PEO and
15L deionized waters are added in kneading machine, reversely at a high speed（750rpm）Stir；
（5）5th stage：Mixing is added under the reverse lower-speed state of kneading machine, then by 1.2kg CMC and 2.5kg PEO
In machine, then reverse high-speed stirred is uniform, and it is 8.4 that the moisture of material is measured after stirring for 27.9%, pH；
（6）6th stage：According to the Testing index of mixing material, into kneading machine, the progress of addition 10L deionized waters is quenched,
Moisture, pH value, shrinkage factor and the plasticity of material is set to reach the material for unloading and kneading from mixing motor spindle after standard requirement.Mixing
Material Testing index result afterwards is as shown in table 4
Table 4 kneads material Testing index result
| Testing index | Moisture（180 DEG C, %） | pH | Shrinkage factor（6mm rods, %） | Plasticity（In terms of force value, N） |
| Testing result | 29.5 | 8.3 | 3.0 | 1920 |
4）It is once old：By after mixing material load polybag interior sealing it is good, be put into 25 DEG C of temperature, humidity 80% it is old
Rotten room once old 20h, to reduce pug residual stress and uniform water.
5）Filter pre-extruded：Pug after will be old filters out bulky grain on the filter equipped with stainless steel mesh, so
It is extruded into lump material on pre-extruded machine afterwards.
6）It is secondary old：By the cake mass of pre-extruded loaded in sealed plastic box, 25 DEG C, the ageing silo of humidity 80%
Secondary old 10h.
7）Shaping extrusion：Pug extrusion molding in vacuum-extruder after extrusion will be filtered, extrusion hole count is 20 × 20,
Extruded velocity is 1.2m/min, and pressure is 3.8MPa, and temperature is 17.2 DEG C, and vacuum is -0.096MPa, extrusioning catalyst section
A width of 155.4mm, the moist catalysis honeycomb type semi-finished product that length is 1020mm are cut into automatic gas cutting machine.
8）One-level is dried：Extrusion aftershaping catalyst is pressed from both sides to packing table top with manipulator and wrapped with the carton with sponge
Dress, is placed on drying cart, is pushed into drying room, is slowly dried under certain temperature and humidity, and detection subtracts daily in the drying process
Rate and shrinkage factor again, loss of weight stop one-level when reaching 20 ± 2% and dried.The parameters such as drying temperature, humidity are as shown in table 5.
The one-level drying parameter of table 5
| Time/h | 24 | 48 | 72 | 96 | 120 | 144 | 168 | 192 | 216 |
| Temperature/DEG C | 25±5 | 30±5 | 35±5 | 40±5 | 45±5 | 50±5 | 55±5 | 60±5 | 60±5 |
| Humidity/% | 90±5 | 85±5 | 80±5 | 70±5 | 65±5 | 50±5 | 45±5 | 30±5 | 20±5 |
9）Secondary drying：One-level drying rear catalyst is taken out out of carton, is placed on secondary drying car and sends into tunnel
In kiln, temperature be 60 ± 5 DEG C, humidity be 20 ± 5% times progress forced air drying 16h, it is 2.1% to dry rear catalyst moisture.
10）Roasting：Catalyst after secondary drying is placed on mesh-belt kiln, laterally longitudinal direction is maintained a certain distance, with
Exempt from mutually collision, catalyst sequentially passes through warming-up section I：From inlet's temperature rise to 195 DEG C, heating-up time 5.5h；Constant temperature zone I：
Constant temperature 4h at 195 DEG C；Warming-up section II：618 DEG C, heating-up time 9h are warming up to from 195 DEG C；Constant temperature zone II：The constant temperature at 618 DEG C
5.5h；Cooling section：70 DEG C, cool time 9h are cooled to from 618 DEG C；Discharge duct static pressure is -80Pa ~ -30Pa.
11）Cutting：Catalyst after roasting directly delivers to cutting machine with automation equipment, by design length surface trimming
Into 1000mm, the remaining garbage collection of cutting is in ash can, and cutting dust and soot blowing dust are collected with cloth dust collector, waste material and
Dust is reclaimed to recycle.
12）End face is hardened：25s in catalyst one end immersion aluminum sulfate solution after soot blowing will be cut, dipping height is
Pile up and air-dried in disk stripping after 20cm, taking-up.
2nd, performance detection
Main component and performance detection to catalyst are detected.Tear strength be sample size be 10 × 10 holes,
Height of specimen is 10cm, air velocity：15 ± 2m/s, quartz sand concentration：50 ± 5%, quartz sand average grain diameter is 40 ~ 50 mesh, is surveyed
Test agent tests 2h measure with comparative sample under conditions of connecting；Denitration performance is that, in 370 DEG C of flue-gas temperature, air speed is
2.3m/s, ammonia nitrogen mol ratio is that 0.85, NO is 220ppm, SO2For 950ppm, O2For 3.5%, H2O is 9.6%, and remaining is N2, knot
Fruit is as shown in table 6.
The catalyst component of table 6 and properties testing result
Finally it should be noted that above preferred embodiment is merely illustrative of the technical solution of the present invention rather than to the present invention
The limitation of protection domain, completely and is clearly described although present disclosure has been made with regard to its disclosed embodiment,
But it is not limited only to this.It will be understood by those within the art that, without departing from the scope of the present invention, pass through
The guidance of these statements can modify or equivalent substitution to technical scheme, without departing from the technology of the present invention side
The spirit and scope of case.
Claims (7)
1. a kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method, it is characterised in that including mixing, once it is old,
Filter pre-extruded, secondary old, extrusion molding, one-level drying, secondary drying, roasting, cutting and end face cure step；
The mixing divides the stage following six：
（1）First stage：Kneading machine is under stopped status, by the titanium tungsten powder of 300 ~ 400 parts by weight, the titanium tungsten of 70 ~ 150 parts by weight
Silica flour, the catalyst reclaimed materials of 30 ~ 80 parts by weight, the ammonium paramolybdate of 5 ~ 30 parts by weight are added in kneading machine；Stirred in positive low speed
Mix the lower stearic acid for adding 0.8 ~ 2.0 parts by weight, the lactic acid of 5 ~ 10 parts by weight, the deionized water of 280 ~ 350 parts by weight, 25 ~ 40
Parts by weight concentration for 18wt% ~ 25wt% ammoniacal liquor in kneading machine, positive strong stirring lower at a high speed is uniform；
（2）Second stage：Kneading machine is under stopped status, by the titanium tungsten powder of 70 ~ 150 parts by weight, the montmorillonite of 40 ~ 60 parts by weight
Clay is added in kneading machine, and the deionized water and 3 ~ 15 parts by weight concentration that 10 ~ 30 parts by weight are added under positive stirring at low speed are
Material is warming up to 90 DEG C ~ 98 DEG C by 18wt% ~ 25wt% ammoniacal liquor in kneading machine under positive high-speed stirred, then open into
Air valve and air bleeding valve carry out dehumidifier；
（3）Phase III：Under the positive lower-speed state of kneading machine, by the ammonium metavanadate solution of 40 ~ 60 parts by weight, 2.5 ~ 4.0 weights
Kapok slurry, the glass fibre of 25 ~ 40 parts by weight and 10 ~ 25 parts by weight of deionized water for measuring part are added in batch mixer, then positive
High-speed stirred is uniform；
（4）Fourth stage：Under the reverse lower-speed state of kneading machine, by the carboxymethyl cellulose of 0.8 ~ 2.0 parts by weight, 1.5 ~ 4.5
The deionized water of the PEO of parts by weight and 8 ~ 15 parts by weight is added in kneading machine, and reverse high-speed stirred is uniform；
（5）5th stage：Under the reverse lower-speed state of kneading machine, then by the carboxymethyl cellulose of 0.8 ~ 2.0 parts by weight and 1.5 ~
The PEO of 4.5 parts by weight is added in kneading machine, and then reverse high-speed stirred is uniform；
（6）6th stage：According to mixing material Testing index, into kneading machine add 1 ~ 10 parts by weight deionized water and 1 ~
The ammoniacal liquor of 10 parts by weight carry out it is quenched, it is quenched after the material kneaded is unloaded from mixing motor spindle；
It is described it is once old be to be positioned over temperature for 10 ~ 30 DEG C, high humidity after the material that will be kneaded is packed with plastic bag sealing
In in 60% ageing silo, once old 10 ~ 48h；
The filtering pre-extruded be will be once old after material filtered on filtering pre-extruded machine after pre-extruded squarely it is block,
Its extrusion temperature is not higher than 45 DEG C, and filtering stainless steel mesh mesh size is 1 × 3mm；
It is described it is secondary it is old be filtering pre-extruded after lump material is sealed in plastic box, temperature be 10 ~ 30 DEG C, high humidity
In in 60% ageing silo, secondary old 10 ~ 36h；
The extrusion molding be by it is secondary it is old after lump material input vacuum-extruder in extrusion molding, extruded velocity be 1 ~
1.5m/min, pressure is 2.5 ~ 5.5MPa, and temperature is 10 ~ 30 DEG C, and vacuum is less than -0.096MPa, and extrusioning catalyst section is wide
For 155.5 ~ 157.5mm, length is 400 ~ 1300mm；
It is to wrap into preformed catalyst in the carton with sponge liner that the one-level, which is dried, is placed on dry dolly and is pushed into drying
Interior, dries indoor temperature from 25 ± 5 DEG C through periodicity at the uniform velocity heating and thermostatic process, finally rises to 60 ± 5 DEG C；Humidity is from 90
± 5%, through periodicity at the uniform velocity wet down and constant humidity process, is finally down to 20 ± 5%；Whole arid cycle is 7 ~ 12 days；
The secondary drying is to take out the dried catalyst of one-level out of carton to overlay on secondary drying car, sends into tunnel
It is 60 ± 5 DEG C, 20 ± 5% times progress F.D dryings of humidity in temperature, drying time is 12 ~ 24h, is catalyzed after drying in kiln
Agent moisture is 0.5% ~ 3.0%；
It is described roasting be by the catalyst after secondary drying sequentially pass through warming-up section I, constant temperature zone I, warming-up section II, constant temperature zone II,
Five roasting sections of cooling section；Each zone temperatures are respectively：Warming-up section I：From inlet's temperature rise to 170 ~ 200 DEG C, heating-up time
5h；Constant temperature zone I：The constant temperature 4h at 170 ~ 200 DEG C；Warming-up section II：600 ~ 625 DEG C, heating-up time are warming up to from 170 ~ 200 DEG C
9h；Constant temperature zone II：The constant temperature 5.5h at 600 ~ 625 DEG C；Cooling section：50 ~ 80 DEG C, cool time 9h are cooled to from 600 ~ 625 DEG C；
Exhaust static pressure is -80Pa ~ -30Pa；
It is to be cut calcined catalyst both ends of the surface that the cutting and end face, which are hardened, and cutting rear catalyst one end is in hardening bath
In dip time be 20 ~ 50s, dipping height be 10 ~ 30mm；Hardening bath be phosphate dihydrogen aluminum solution or aluminum sulfate solution, its
Density of the phosphate dihydrogen aluminum solution at 25 DEG C is 1.4 ~ 1.6g/ml, and density of the aluminum sulfate solution at 25 DEG C is 1.0 ~ 1.4g/
ml。
2. wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method according to claim 1, it is characterised in that mixed
After the refining first stage terminates, the moisture of mixed material is 40% ~ 42%, and pH value is 9.0 ~ 10.0；After mixing second stage terminates, mix
Moisture after compound material dehumidifier is 24% ~ 26%, and pH value is 8.0 ~ 9.0；After the mixing phase III terminates, the moisture of mixed material exists
27% ~ 29%, pH value is 8.3 ~ 9.2；Knead after the 5th stage terminated, mixed material moisture is 27 ~ 30%, and pH value is 7.8 ~ 8.6；
Knead after the quenched end of the 6th stage, mixed material moisture is 28 ~ 30%, and pH value is in 8.0 ~ 8.6, the pug replaced with extrusion force
Plasiticity index is 1600 ~ 2200N.
3. wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method according to claim 1, it is characterised in that mixed
First to the 6th stage of refining is carried out in same kneading machine, is harrowed inside kneading machine provided with high-energy rotator and star, the first to the 3rd rank
Section is Positive work, the 4th to the 6th stage antiport.
4. wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method according to claim 1, it is characterised in that institute
Titanium tungsten powder crystal type is stated for Detitanium-ore-type, its main component is TiO2：93% ~ 96%, WO3：4.5% ~ 5.5%, specific surface area be 80 ~
100m2/ g, 1.0 ~ 3.5um of average grain diameter；The titanium tungsten silica flour crystal formation is Detitanium-ore-type, and its main component is TiO2：85% ~ 90%,
WO3：4.5% ~ 5.5%, SiO2：4.0% ~ 6.0%, specific surface area is 95 ~ 115 m2/ g, 1.0 ~ 3.5um of average grain diameter；It is described to cover de-
Stone clay main component is SiO2：58% ~ 65%, Al2O3%：18% ~ 24%, Fe2O3：2% ~ 6%, MgO：2%~6%；The catalyst is returned
The average grain diameter of rewinding is in 5 ~ 20um.
5. wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method according to claim 1, it is characterised in that institute
With ammonium metavanadate, the MEA of 60 ~ 220 parts by weight and 500 ~ 700 parts by weight that ammonium metavanadate solution is 50 ~ 200 parts by weight
Deionized water temperature be 55 ~ 95 DEG C, preparing tank motor speed be to prepare under 35r/min, ammonium metavanadate solution density is
1.0 ~ 1.5g/ml, solution concentration is titrated with l ferrous ammonium sulfate solution.
6. wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method according to claim 1, it is characterised in that institute
It is 350rpm to state positive low speed to refer to that kneading machine rotates forward rotating speed, positive to refer to that kneading machine rotating forward rotating speed is 750rpm at a high speed, described
Reverse low speed refers to that kneading machine reverse is 350rpm, and it is 750rpm that kneading machine reverse is reversely referred at a high speed.
7. a kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration, it is characterised in that it is as described in any one of claim 1 ~ 6
The catalyst that wear-resisting anti-poisoning honeycomb fashion SCR denitration preparation method is prepared.
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