CN108855120A - Monoblock type metal composite oxide low-temperature denitration catalyst and preparation method thereof - Google Patents
Monoblock type metal composite oxide low-temperature denitration catalyst and preparation method thereof Download PDFInfo
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- CN108855120A CN108855120A CN201810398321.XA CN201810398321A CN108855120A CN 108855120 A CN108855120 A CN 108855120A CN 201810398321 A CN201810398321 A CN 201810398321A CN 108855120 A CN108855120 A CN 108855120A
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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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
Abstract
The present invention relates to a kind of monoblock type metal composite oxide low-temperature denitration catalysts and preparation method thereof, and preparation method includes：By MnO2、V2O5、Fe2O3、CeO2、MoO3It is ground with the titanium tungsten sphere of powder, obtains powder；The powder and water, ammonium hydroxide, stearic acid, lactic acid, glass fibre, hydroxymethyl cellulose and polyethylene glycol oxide are kneaded, discharging obtains mixed raw material；Aging, the pre-extruded by the mixed raw material squeezes out, obtains green body；The green body is dried and is calcined, monoblock type metal composite oxide low-temperature denitration catalyst is obtained.The monoblock type metal composite oxide low-temperature denitration catalyst of the application has good low temperature active, water-resistance, anti-low-sulfur performance and product easily molded；Active constituent with carrier is full and uniform mixes, high yield rate, high mechanical strength, to be more applicable for practical flue gas condition.
Description
Technical field
The present invention relates to a kind of field of denitration catalyst, de- more particularly to a kind of monoblock type metal composite oxide low temperature
Denox catalyst and preparation method thereof.
Background technique
Nitrogen oxides (NOx) it is one of Air Pollutant Discharge, acid rain, photochemical fog can be generated and participate in being formed
PM2.5 etc. in air seriously endangers ecological natural environment and human health.NO in atmospherexBe mainly derived from coal-burning power plant,
Non-electrical Industrial Stoves boiler and moving source automotive emission etc..In numerous NOx abatement technologies, selective catalytic reduction
Method (SCR) is because it is with stable, NOxThe advantages that removal efficiency is high is shown one's talent, and makes SCR technology in NOxEmission reduction field of purification
It is used widely, wherein denitrating catalyst is the core of the technology.As country is to non-electrical industry kiln, boiler NOxDischarge
Limit value is continuously improved, and gradually implements minimum discharge transformation, non-electrical industry NOxEmission reduction faces a severe challenge.Current domestic and international city
The operating temperature of SCR denitration is mostly at 220-420 DEG C on field, it is difficult to which it is low to remove complicated component, temperature applied to flue gas
The non-electrical industry of (180-220 DEG C), therefore, the SCR denitration of efficient cryogenic are non-electrical industry kiln, boiler NOxEmission reduction
Technology there is an urgent need to object.
In low temperature SCR denitration catalyst research field mostly based on Mn base, but under the conditions of low-temp reaction, simple Mn
The poisoning of base catalyst surface sulphur ammonium is more serious, and sulfur resistive water-resistance is poor, and furthermore Mn base honeycomb catalyst is in drying, calcination process
Easily occur green body burst, the quality accidents such as longitudinal crack, Mn base catalyst rarely has full-scale exhaust gas volumn to answer in practical engineering application
Use case.High vanadium denitration catalyst passes through addition Mo element, SO2Conversion ratio significantly reduces, and medium temperature sulfur resistive water-resistance obtains obviously
It is promoted, is graduallyd mature in medium temperature (220-300 DEG C) application field, but its low-temperature denitration activity is poor, if continuing to improve content of vanadium,
There can be SO2The problems such as conversion ratio increases, catalyst green body bursts crushing accident in calcination process, catalyst not only anti-toxicity
It reduces, and yield rate reduces, increased production cost, can eliminate in increasingly dog-eat-dog denitrating catalyst market eventually.Mesh
The preceding denitrating catalyst with high efficient cryogenic denitration activity and good sulfur resistive water-resistance only rests on the laboratory research stage, more
Number catalyst sample is graininess, powdered or cellulor shape, and there are also a distances with practical batch production.Therefore, one is developed
Kind has high efficient cryogenic denitration activity, high N2Selectivity, low SO2The catalyst of the excellent properties such as oxygenation efficiency and the poisoning of strong sulfur resistive ammonium,
It is had a vast market foreground in non-electrical industry " minimum discharge " transformation.
Summary of the invention
It is a primary object of the present invention to provide a kind of novel monoblock type metal composite oxide low-temperature denitration catalyst
And preparation method thereof, the technical problem to be solved is that making it have, good low-temperature denitration activity, sulfur resistive water-resistance, chemistry are steady
Qualitative, thermal stability and mechanical strength, thus more suitable for practical.
The object of the invention to solve the technical problems adopts the following technical solutions to realize.It proposes according to the present invention
A kind of monoblock type metal composite oxide low-temperature denitration catalyst preparation method comprising：
By MnO2、V2O5、Fe2O3、CeO2、MoO3It is ground with the titanium tungsten sphere of powder, obtains powder；
The powder and water, ammonium hydroxide, stearic acid, lactic acid, glass fibre, hydroxymethyl cellulose and polyethylene glycol oxide are mixed
Refining, discharging, obtains mixed raw material；
Aging, the pre-extruded by the mixed raw material squeezes out, obtains green body；
The green body is dried and is calcined, monoblock type metal composite oxide low-temperature denitration catalyst is obtained.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
Ball-milling Time is 2-4h, and the specific surface area of the powder is 120-140m2/g。
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
Mixed raw material, based on parts by weight comprising：
MnO2：3-7 parts；
V2O5：2-4 parts；
Fe2O3：1-5 parts；
CeO2：0.1-0.5 parts；
MoO3：3-5 parts；
Glass fibre：10-15 parts；
Carboxymethyl cellulose：0.4-1 parts；
Polyethylene glycol oxide：0.5-1 parts；
Lactic acid：1-2 parts；
Stearic acid：1-3 parts；
Ammonium hydroxide：3-7 parts；
Water：10-15 parts；
Titanium tungsten powder：100 parts.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
The preparation of mixed raw material includes：Powder is mixed with water, ammonium hydroxide, rotates forward stirring, stearic acid is added, lactic acid stirs to temperature and is
90-95 DEG C, shutdown is cooled to 60-65 DEG C, and glass fibre is added, and after stirring 25-35min, shutdown is cooled to 60-65 DEG C, then plus
Enter carboxymethyl cellulose and polyethylene glycol oxide, stir 30-40min, shutdown is cooled to 50-60 DEG C, reversion discharging.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
The water content of mixed raw material is 25-27wt%, plasticity index 25-28, pH value 7.8-8.5.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
The aging time is 1-7d；
The vacuum degree of the pre-extruded is -0.1~0.08MPa；
The length of the green body is 700-1300mm.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described dry
Dry includes primary drying and redrying；
The primary drying includes：It is warming up to 50-60 DEG C of heat preservation 6-7d with the heating rate of 4-6 DEG C/d, humidity is with 5-
The rate of 6%/d is reduced to 20-40% from 70-90%；The time of the primary drying is 13-16d；
The redrying includes：Be warming up to 60-70 DEG C of heat preservation 2-4h with the heating rate of 0.1-1 DEG C/h, humidity with
The rate of 1-2%/h is reduced to 5-15% from 25-35%；The time of the redrying is 22-24h.
Preferably, the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein described
Calcining includes：It is warming up to 400-550 DEG C of heat preservation 4-5h with the heating rate of 20-30 DEG C/h, then is reduced to the rate of 50-60 DEG C/h
60-80℃；The time of the calcining is 22-24h.
Also the following technical solution is employed for the object of the invention to solve the technical problems to realize.It proposes according to the present invention
A kind of monoblock type metal composite oxide low-temperature denitration catalyst, be prepared by method above-mentioned.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
Preferably, monoblock type metal composite oxide low-temperature denitration catalyst above-mentioned, wherein the monoblock type is compound
The hole count of metal oxide low-temperature denitration catalyst is 16-25.
By above-mentioned technical proposal, monoblock type metal composite oxide low-temperature denitration catalyst of the present invention and preparation method thereof
At least there are following advantages：
The application is with MnO2、V2O5、Fe2O3、CeO2For active component, it is ensured that catalyst have good low temperature activity and
Low temperature sulfur resistive water-resistance, with MoO3SO can be effectively reduced for coagent2Oxygenation efficiency.With the titanium tungsten with large specific surface area
Powder is carrier, it is ensured that catalyst has biggish specific surface area, and for SCR reaction temperature at 180-220 DEG C, 10-20% is aqueous
Amount, 200mg/m3SO2Flue gas in have not less than 85% denitration efficiency.All catalyst raw materials are metal oxidation simultaneously
Object, the catalyst of batch production yield rate with higher and mechanical strength are suitable in cement, glass, ceramics, steel, coke
It is promoted and applied in the Flue Gas Denitrification Engineerings of non-electrical industry such as change.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, with presently preferred embodiments of the present invention, detailed description is as follows below.
Specific embodiment
It is of the invention to reach the technical means and efficacy that predetermined goal of the invention is taken further to illustrate, below in conjunction with
Preferred embodiment, to monoblock type metal composite oxide low-temperature denitration catalyst proposed according to the present invention and preparation method thereof its
Specific embodiment, structure, feature and its effect, detailed description is as follows.In the following description, different " embodiment " or
What " embodiment " referred to is not necessarily the same embodiment.In addition, the special characteristic, structure or feature in one or more embodiments can
It is combined by any suitable form.
A kind of preparation for monoblock type metal composite oxide low-temperature denitration catalyst that one embodiment of the present of invention proposes
Method comprising：
By MnO2、V2O5、Fe2O3、CeO2、MoO32-4h is ground with the titanium tungsten sphere of powder, obtains powder；
Mixing facilities are added in powder and water, ammonium hydroxide, rotate forward stirring, it is 90-95 that addition stearic acid, lactic acid, which are stirred to temperature,
DEG C, shutdown is cooled to 60-65 DEG C, and glass fibre is added, and after stirring 25-35min, shutdown is cooled to 60-65 DEG C, adds carboxylic first
Base cellulose and polyethylene glycol oxide stir 30-40min, and shutdown is cooled to 50-60 DEG C, and reversion discharging obtains mixed raw material；Institute
The water content for the mixed raw material stated is 25-27wt%, plasticity index 25-28, pH value 7.8-8.5.
Preferably, the water content of mixed raw material is 23-28wt%.
The mixed raw material, based on parts by weight comprising：
MnO2：3-7 parts；
V2O5：2-4 parts；
Fe2O3：1-5 parts；
CeO2：0.1-0.5 parts；
MoO3：3-5 parts；
Glass fibre：10-15 parts；
Carboxymethyl cellulose (CMC)：0.4-1 parts；
Polyethylene glycol oxide (PEO)：0.5-1 parts；
Lactic acid：1-2 parts；
Stearic acid：1-3 parts；
Ammonium hydroxide：3-7 parts；
Water：10-15 parts；
Titanium tungsten powder：100 parts.
The mixed raw material is placed in aging in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture
A large amount of evaporations.Aging purpose is that moisture has the sufficient time to be distributed in pug, so as to subsequent extrusion process, the aging time
1-7d.Vacuum mud refining extrusion is carried out after aging, vacuum degree is -0.1-0.08Mpa.Its object is to will be relatively large in pug
Particle filtering fall, the followed by contact between the little particle in pug is more compact, so as to the progress of subsequent extrusion process, in advance
It squeezes out 1-3 times.Large, honeycomb extruder is extruded through after pre-extruded to be squeezed out, as needed choose section be 150 ×
The honeycomb die in the hole 150mm, 13-25 is mounted in extrusion, obtains green body；Use automatic gas cutting machine intercepted length as needed for
The green body of 700-1300mm carries out manual parcel placement to honeycomb body with the packing paper of included sponge.
The green body is dried and is calcined, monoblock type metal composite oxide low-temperature denitration catalyst is obtained.
Preferably, dry includes primary drying and redrying；
Primary drying includes：It is warming up to 50-60 DEG C of heat preservation 6-7d with the heating rate of 4-6 DEG C/d, humidity is with 5-6%/d's
Rate is reduced to 20-40% from 70-90%；The time of the primary drying is 13-16d；
Redrying includes：It is warming up to 60-70 DEG C of heat preservation 2-4h with the heating rate of 0.1-1 DEG C/h, humidity is with 1-2%/h
Rate be reduced to 5-15% from 25-35%；The time of the redrying is 22-24h.
Calcining includes：It is warming up to 400-550 DEG C of heat preservation 4-5h with the heating rate of 20-30 DEG C/h, then with 50-60 DEG C/h's
Rate is reduced to 60-80 DEG C；The time of the calcining is 22-24h.
Another embodiment of the present invention proposes a kind of monoblock type metal composite oxide low-temperature denitration catalyst, by above-mentioned
Method is prepared.Monoblock type metal composite oxide low-temperature denitration catalyst is without obvious crackle, micro-crack, hole count 16-25.
Embodiment 1
A kind of preparation for monoblock type metal composite oxide low-temperature denitration catalyst that one embodiment of the present of invention proposes
Method comprising：
By 20kg MnO2、20kg V2O5、5kg Fe2O3、1kg CeO2、15kg MoO32h is ground with the 500kg titanium tungsten sphere of powder,
Obtain powder, powder specific surface area 130m2/g；
Mixing facilities are added in powder and 40kg deionized water, 15kg20% industrial ammonia, low speed rotates forward stirring, is added
10kg stearic acid, 5kg80% lactic acid solution, starting high-speed stirred to temperature is 90 DEG C after 30min, and shutdown is cooled to 60 DEG C, is added
Enter 50kg glass fibre, after stirring 25min, shutdown is cooled to 60 DEG C, add 3kgCMC and 5kgPEO, high-speed stirred 30min,
Shutdown is cooled to 50 DEG C, and reversion discharging obtains mixed raw material；The moisture of mixed raw material is 24wt%, plasticity index 25, pH value
It is 7.9；
Mixed raw material is placed in aging in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture from largely steaming
Hair.Aging purpose is that moisture has the sufficient time to be distributed in pug, so as to subsequent extrusion process, aging time 1d.It is old
Vacuum mud refining extrusion is carried out after corruption, vacuum degree is -0.08Mpa.Its object is to by the relatively large particle filtering in pug
To fall, the followed by contact between the little particle in pug is more compact, so as to the progress of subsequent extrusion process, pre-extruded 1 time.In advance
It is extruded through large, honeycomb extruder after extrusion to be squeezed out, choosing section as needed is 150 × 150mm, the honeycomb in 18 holes
Mold is mounted in extrusion, obtains green body；Use automatic gas cutting machine intercepted length as needed for the green body of 700mm, use is included
The packing paper of sponge carries out manual parcel placement to honeycomb body；
Green body is placed in primary drying hothouse, temperature setting is 25 DEG C of room temperature and is to slowly warm up to 55 DEG C, heating rate
For 4 DEG C/d, 6d is kept the temperature at 55 DEG C, humidity is adjusted by blower, is slowly dropped to 30%, rate 5%/d from 80%, entire primary
Drying time is 16d.Then honeycomb body is transferred in redrying hothouse, temperature setting is to be to slowly warm up to from 55 DEG C
65 DEG C, heating rate is 0.5 DEG C/h, keeps the temperature 2h at 65 DEG C, and humidity is down to 10%, rate 1%/h from 30%, entire secondary dry
The dry time is 22h.Green body is calcined after drying, calcination-temperature profile is set as being warming up to 450 DEG C from 120 DEG C, heating speed
Degree is 20 DEG C/h, in 450 DEG C of heat preservation 4h, is then cooled to 60 DEG C, cooling rate is 50 DEG C/h, and calcination time 34h is obtained whole
Body formula metal composite oxide low-temperature denitration catalyst.
Another embodiment of the present invention proposes a kind of monoblock type metal composite oxide low-temperature denitration catalyst, by embodiment
1 method is prepared.Monoblock type metal composite oxide low-temperature denitration catalyst is without obvious crackle, micro-crack, hole count 18.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 1 is subjected to low temperature SCR denitration catalyst
It can test：Interception 4 × 4 sample of 20cm be put into the rectangular stainless steel reactor of fixed bed, internal diameter 40mm, simulated flue gas by NO,
NH3、O2And N2It forms, wherein NO 300ppm, NH3For 300ppm, O25%, air speed 6700h-1, face velocity 16m2/ s, reaction temperature
150-300 DEG C of degree reacts flue gas 0 gas analyzer on-line checking of moral Figure 35.In this test condition, the denitration effect of catalyst
Rate is stablized 85% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 1 is subjected to the test of sulfur resistive water repelling property：?
SO is additionally added in simulated flue gas2And vapor, SO2Concentration is 500mg/m3, water vapour content is in 10vol.%, other tests
Condition is constant.In this test condition, the denitration efficiency of catalyst is still stable 82% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 1 is subjected to intensity test, it is axial anti-
Compressive Strength 2.2Mpa, radial crushing strength 0.6Mpa.
Embodiment 2
A kind of preparation for monoblock type metal composite oxide low-temperature denitration catalyst that one embodiment of the present of invention proposes
Method comprising：
By 27.5kg MnO2、16.5kg V2O5、16.5kg Fe2O3、1.65kg CeO2、22kg MoO3With 550kg titanium tungsten
The sphere of powder grinds 3h, obtains powder, powder specific surface area 134m2/g；
Mixing facilities are added in powder and 46kg deionized water, 17kg20% industrial ammonia, low speed rotates forward stirring, is added
5.5kg stearic acid, 8.25kg80% lactic acid solution, starting high-speed stirred to temperature is 92 DEG C after 35min, and shutdown is cooled to 65
DEG C, 50kg glass fibre is added, after stirring 30min, shutdown is cooled to 65 DEG C, adds 4.5kgCMC and 4.5kgPEO, high speed
35min is stirred, shutdown is cooled to 55 DEG C, and reversion discharging obtains mixed raw material；The moisture of mixed raw material is 25wt%, and plasticity refers to
Number is 25, pH value 7.8；
Mixed raw material is placed in aging in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture from largely steaming
Hair.Aging purpose is that moisture has the sufficient time to be distributed in pug, so as to subsequent extrusion process, aging time 1d.It is old
Vacuum mud refining extrusion is carried out after corruption, vacuum degree is -0.09Mpa.Its object is to by the relatively large particle filtering in pug
To fall, the followed by contact between the little particle in pug is more compact, so as to the progress of subsequent extrusion process, pre-extruded 2 times.In advance
It is extruded through large, honeycomb extruder after extrusion to be squeezed out, choosing section as needed is 150 × 150mm, the honeycomb in 22 holes
Mold is mounted in extrusion, obtains green body；Use automatic gas cutting machine intercepted length as needed for the green body of 1000mm, use is included
The packing paper of sponge carries out manual parcel placement to honeycomb body；
Green body is placed in primary drying hothouse, temperature setting is 25 DEG C of room temperature and is to slowly warm up to 55 DEG C, heating rate
For 5 DEG C/d, 7d is kept the temperature at 55 DEG C, humidity is adjusted by blower, is slowly dropped to 30%, rate 5%/d from 80%, entire primary
Drying time is 13d.Then honeycomb body is transferred in redrying hothouse, temperature setting is to be to slowly warm up to from 55 DEG C
65 DEG C, heating rate is 0.5 DEG C/h, keeps the temperature 3h at 65 DEG C, and humidity is down to 10%, rate 1%/h from 30%, entire secondary dry
The dry time is 23h.Green body is calcined after drying, calcination-temperature profile is set as being warming up to 450 DEG C from 120 DEG C, heating speed
Degree is 25 DEG C/h, in 450 DEG C of heat preservation 5h, is then cooled to 60 DEG C, cooling rate is 50 DEG C/h, and calcination time 30h is obtained whole
Body formula metal composite oxide low-temperature denitration catalyst.
Another embodiment of the present invention proposes a kind of monoblock type metal composite oxide low-temperature denitration catalyst, by embodiment
2 method is prepared.Monoblock type metal composite oxide low-temperature denitration catalyst is without obvious crackle, micro-crack, hole count 22.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 2 is subjected to low temperature SCR denitration catalyst
It can test：Interception 4 × 4 sample of 20cm be put into the rectangular stainless steel reactor of fixed bed, internal diameter 40mm, simulated flue gas by NO,
NH3、O2And N2It forms, wherein NO 300ppm, NH3For 300ppm, O25%, air speed 6700h-1, face velocity 14m2/ s, reaction temperature
150-300 DEG C of degree reacts flue gas 0 gas analyzer on-line checking of moral Figure 35.In this test condition, the denitration effect of catalyst
Rate is stablized 89% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 2 is subjected to the test of sulfur resistive water repelling property：?
SO is additionally added in simulated flue gas2And vapor, SO2Concentration is 500mg/m3, water vapour content is in 10vol.%, other tests
Condition is constant.In this test condition, the denitration efficiency of catalyst is still stable 85% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 2 is subjected to intensity test, it is axial anti-
Compressive Strength 2.3Mpa, radial crushing strength 0.5Mpa.
Embodiment 3
A kind of preparation for monoblock type metal composite oxide low-temperature denitration catalyst that one embodiment of the present of invention proposes
Method comprising：
By 42kg MnO2、12kg V2O5、30kg Fe2O3、3kg CeO2、30kg MoO34h is ground with the 600kg titanium tungsten sphere of powder,
Obtain powder, powder specific surface area 138m2/g；
Mixing facilities are added in powder and 50kg deionized water, 20kg20% industrial ammonia, low speed rotates forward stirring, is added
18kg stearic acid, 12kg80% lactic acid solution, starting high-speed stirred to temperature is 95 DEG C after 40min, and shutdown is cooled to 65 DEG C, is added
Enter 90kg glass fibre, after high-speed stirred 35min, shutdown is cooled to 60 DEG C, adds 5kgCMC and 5kgPEO, high-speed stirred
40min, shutdown are cooled to 60 DEG C, and reversion discharging obtains mixed raw material；The moisture of mixed raw material is 26wt%, and plasticity index is
26, pH value 8.2；
Mixed raw material is placed in aging in Bulk plastic case, covers sealing with plastic cloth, prevent pug moisture from largely steaming
Hair.Aging purpose is that moisture has the sufficient time to be distributed in pug, so as to subsequent extrusion process, aging time 1d.It is old
Vacuum mud refining extrusion is carried out after corruption, vacuum degree is -0.08Mpa.Its object is to by the relatively large particle filtering in pug
To fall, the followed by contact between the little particle in pug is more compact, so as to the progress of subsequent extrusion process, pre-extruded 3 times.In advance
It is extruded through large, honeycomb extruder after extrusion to be squeezed out, choosing section as needed is 150 × 150mm, the honeycomb in 25 holes
Mold is mounted in extrusion, obtains green body；Use automatic gas cutting machine intercepted length as needed for the green body of 1200mm, use is included
The packing paper of sponge carries out manual parcel placement to honeycomb body；
Green body is placed in primary drying hothouse, temperature setting is 25 DEG C of room temperature and is to slowly warm up to 55 DEG C, heating rate
For 4 DEG C/d, 7d is kept the temperature at 55 DEG C, humidity is adjusted by blower, is slowly dropped to 30%, rate 6%/d from 80%, entire primary
Drying time is 15d.Then honeycomb body is transferred in redrying hothouse, temperature setting is to be to slowly warm up to from 55 DEG C
65 DEG C, heating rate is 0.5 DEG C/h, keeps the temperature 4h at 65 DEG C, and humidity is down to 10%, rate 1%/h from 30%, entire secondary dry
The dry time is for 24 hours.Green body is calcined after drying, calcination-temperature profile is set as being warming up to 500 DEG C from 120 DEG C, heating speed
Degree is 30 DEG C/h, in 450 DEG C of heat preservation 4h, is then cooled to 60 DEG C, cooling rate is 50 DEG C/h, and calcination time 28h is obtained whole
Body formula metal composite oxide low-temperature denitration catalyst.
Another embodiment of the present invention proposes a kind of monoblock type metal composite oxide low-temperature denitration catalyst, by embodiment
3 method is prepared.Monoblock type metal composite oxide low-temperature denitration catalyst is without obvious crackle, micro-crack, hole count 25.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 3 is subjected to low temperature SCR denitration catalyst
It can test：Interception 4 × 4 sample of 20cm be put into the rectangular stainless steel reactor of fixed bed, internal diameter 40mm, simulated flue gas by NO,
NH3、O2And N2It forms, wherein NO 300ppm, NH3For 300ppm, O25%, air speed 6700h-1, face velocity 16m2/ s, reaction temperature
150-300 DEG C of degree reacts flue gas 0 gas analyzer on-line checking of moral Figure 35.In this test condition, the denitration effect of catalyst
Rate is stablized 92% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 3 is subjected to the test of sulfur resistive water repelling property：?
SO is additionally added in simulated flue gas2And vapor, SO2Concentration is 500mg/m3, water vapour content is in 10vol.%, other tests
Condition is constant.In this test condition, the denitration efficiency of catalyst is still stable 88% or more.
The monoblock type metal composite oxide low-temperature denitration catalyst of embodiment 3 is subjected to intensity test, it is axial anti-
Compressive Strength 2.1Mpa, radial crushing strength 0.6Mpa.
The above described is only a preferred embodiment of the present invention, be not intended to limit the present invention in any form, according to
According to technical spirit any simple modification, equivalent change and modification to the above embodiments of the invention, this hair is still fallen within
In the range of bright technical solution.
Claims (10)
1. a kind of preparation method of monoblock type metal composite oxide low-temperature denitration catalyst, which is characterized in that it includes：
By MnO2、V2O5、Fe2O3、CeO2、MoO3It is ground with the titanium tungsten sphere of powder, obtains powder；
The powder and water, ammonium hydroxide, stearic acid, lactic acid, glass fibre, hydroxymethyl cellulose and polyethylene glycol oxide are kneaded,
Discharging, obtains mixed raw material；
Aging, the pre-extruded by the mixed raw material squeezes out, obtains green body；
The green body is dried and is calcined, monoblock type metal composite oxide low-temperature denitration catalyst is obtained.
2. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the Ball-milling Time is 2-4h, and the specific surface area of the powder is 120-140m2/g。
3. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the mixed raw material, based on parts by weight comprising：
MnO2：3-7 parts；
V2O5：2-4 parts；
Fe2O3：1-5 parts；
CeO2：0.1-0.5 parts；
MoO3：3-5 parts；
Glass fibre：10-15 parts；
Carboxymethyl cellulose：0.4-1 parts；
Polyethylene glycol oxide：0.5-1 parts；
Lactic acid：1-2 parts；
Stearic acid：1-3 parts；
Ammonium hydroxide：3-7 parts；
Water：10-15 parts；
Titanium tungsten powder：100 parts.
4. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the preparation of the mixed raw material includes：Powder is mixed with water, ammonium hydroxide, rotates forward stirring, stearic acid is added, lactic acid stirs
Mixing to temperature is 90-95 DEG C, and shutdown is cooled to 60-65 DEG C, and glass fibre is added, and after stirring 25-35min, shutdown is cooled to 60-
65 DEG C, carboxymethyl cellulose and polyethylene glycol oxide are added, stirs 30-40min, shutdown is cooled to 50-60 DEG C, reversion discharging.
5. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the water content of the mixed raw material is 25-27wt%, plasticity index 25-28, pH value 7.8-8.5.
6. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the aging time is 1-7d；
The vacuum degree of the pre-extruded is -0.1~0.08MPa；
The length of the green body is 700-1300mm.
7. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the drying includes primary drying and redrying；
The primary drying includes：It is warming up to 50-60 DEG C of heat preservation 6-7d with the heating rate of 4-6 DEG C/d, humidity is with 5-6%/d
Rate be reduced to 20-40% from 70-90%；The time of the primary drying is 13-16d；
The redrying includes：It is warming up to 60-70 DEG C of heat preservation 2-4h with the heating rate of 0.1-1 DEG C/h, humidity is with 1-
The rate of 2%/h is reduced to 5-15% from 25-35%；The time of the redrying is 22-24h.
8. the preparation method of monoblock type metal composite oxide low-temperature denitration catalyst according to claim 1, feature
It is, the calcining includes：Be warming up to 400-550 DEG C of heat preservation 4-5h with the heating rate of 20-30 DEG C/h, then with 50-60 DEG C/
The rate of h is reduced to 60-80 DEG C；The time of the calcining is 22-24h.
9. a kind of monoblock type metal composite oxide low-temperature denitration catalyst, which is characterized in that by any one of claim 1-8 institute
The method stated is prepared.
10. monoblock type metal composite oxide low-temperature denitration catalyst according to claim 9, which is characterized in that described
Monoblock type metal composite oxide low-temperature denitration catalyst hole count be 16-25.
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Application publication date: 20181123 |