CN109174142A - A kind of low temperature SCR denitration catalyst and its preparation method and application - Google Patents
A kind of low temperature SCR denitration catalyst and its preparation method and application Download PDFInfo
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- CN109174142A CN109174142A CN201810942130.5A CN201810942130A CN109174142A CN 109174142 A CN109174142 A CN 109174142A CN 201810942130 A CN201810942130 A CN 201810942130A CN 109174142 A CN109174142 A CN 109174142A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
Abstract
The present invention relates to catalyst preparation technical fields, specifically disclose a kind of low temperature SCR denitration catalyst and its preparation method and application.The catalyst includes following component: V by percentage to the quality2O5: 1-4%, Fe2O3: 0.1-2%, WO3: 1-5%, Sb2O3: 1-3%, Nb2O5: 0.02-0.3%, P2O5: 0.2-1.9%, TiO2: 76-86% and inactive ingredients: 5-15%.Catalyst provided by the invention is within the scope of 160-450 DEG C of wide warm area, and under the conditions of aqueous sulfur-containing smoke gas, denitration efficiency can reach 85%-100%, has excellent water resistant resistance to SO_2, and SO2Conversion ratio < 1%, the escaping of ammonia rate < 3ppm, the indexs such as compression strength are all satisfied national standard GBT31587-2015 requirement.
Description
Technical field
The present invention relates to catalyst preparation technical field more particularly to a kind of low temperature SCR denitration catalyst and its preparation sides
Method and application.
Background technique
Nitrogen oxides is as a kind of atmosphere pollution, and from a wealth of sources, coal and oil combustion gas can all generate a large amount of nitrogen oxygen
Compound, nitrogen and oxygen also will form nitrogen oxides through thunder and lightning provocative reaction in atmosphere.Nitrogen oxides can not only pollute ring
Border causes soil acidification, and endangers human health, causes respiratory disease and pneumonia etc..With national environmental consciousness
Raising and increasing of the government to air contaminant treatment dynamics, the nitrogen oxides contained in industrial tail gas must be controlled to be marked in country
Below quasi- and provincial standard.Standard GB/T 13223-2011 regulation coal-fired boiler tail gas discharged nitrous oxides value is no more than
100mg/m3, Gas Generator Set is down to 50mg/m3.Individual places are stringenter to the emission control of nitrogen oxides, Shandong Province's regulation combustion
Coal burning boiler discharged nitrous oxides value is no more than 50mg/m3.In addition, national standard GB13271-2014 provides Industrial Boiler tail gas nitrogen oxidation
Object discharge value is no more than 200mg/m3.And NOx content is generally in 1000-3200mg/m in boiler smoke3, boiler smoke temperature one
As between 160-300 DEG C, traditional medium temperature vanadium tungsten Titanium series catalyst is unable to satisfy denitration requirement.Conventional boiler plant area equipment is tight
It gathers, for UTILIZATION OF VESIDUAL HEAT IN and scrap build difficulty, low temperature SCR denitration catalyst has wide application market.Currently, low temperature
The raw material preparation cost of SCR denitration is high, and industrial application value is little.With γ-Al2O3For carrier, manganese ferrocerium oxide
For the catalyst of active constituent, low temperature water resistant resistance to SO_2 is poor, and practical application has little significance.Steamer is as marine main traffic work
Tool, the pollutant of exhaust emissions also can not be ignored, " GB 15097-2016 engine of boat and ship tailpipe emission limit value and
Measurement method " in regulation steamer exhaust emissions hydrocarbon (CH) and nitrogen oxides (NOx) total content no more than 7.5g/
KWh.The atmosphere pollution of 1 steamer discharge is equal to 500,000 lorries, and (230-450 DEG C) of steamer diesel engine vent gas temperature variation
Greatly, NOx concentration is in 800ppm or so, flue gas SO2Content is in 1000ppm or more.As environmental protection organization of the world is to steamer diesel engine
The pollutant attention degree of exhaust emissions is reinforced, so the SCR for developing a kind of steamer diesel engine vent gas denitration of high resistance to SO_2 is urged
Agent is of great significance.
Summary of the invention
For the problem of existing catalyst cost high and low temperature water resistant resistance to SO_2 difference, the present invention provides a kind of low temperature SCR denitration
Catalyst.
And the present invention also provides a kind of preparation methods of low temperature SCR denitration catalyst.
And the present invention also provides a kind of applications of low temperature SCR denitration catalyst.
To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 1-4%,
Fe2O3: 0.1-2%, WO3: 1-5%, Sb2O3: 1-3%, Nb2O5: 0.02-0.3%, P2O5: 0.2-1.9%, TiO2: 76-86%
And inactive ingredients: 5-15%.
Remaining inactive ingredients include silica, calcium oxide, aluminum oxide etc..
Compared with the existing technology, low temperature SCR denitration catalyst provided by the invention, has the advantage that
(1) catalyst provided by the invention is using V-W-Sb-Nb-P-Fe-Ox as active component, with titania support:
V2O5It is active constituent, V2O5Effect: the main active substances of denitration, accelerate denitration reaction process；
WO3It is active constituent, WO3Effect: with V2O5Interaction makes catalyst have resistance to SO_2, with TiO2Interaction
Improve the thermal stability of catalyst；
Sb2O3It is active constituent, Sb2O3Effect be: with V2O5Interaction improves the denitration activity of catalyst, and improves
The N of catalyst2Selectivity；
Nb2O5It is active constituent, Nb2O5Effect be: the acidity of catalyst is improved, with V2O5It interacts and improves catalyst
Denitration activity；
P2O5It is that active constituent is, P2O5Effect be: with V2O5And Nb2O5Interaction improves vanadium series catalyst to N2's
Selectivity reduces denitrating catalyst to SO2Oxidation；
Fe2O3It is that active constituent is, Fe2O3Effect be: increase the acidity of catalyst, with V2O5、Sb2O3、WO3Phase interaction
With the denitration activity for improving catalyst；
(2) catalyst provided by the invention is within the scope of 160-450 DEG C of wide warm area, under the conditions of aqueous sulfur-containing smoke gas,
Denitration efficiency can reach 85%-100%, have excellent water resistant resistance to SO_2, and SO2Conversion ratio < 1%, the escaping of ammonia rate < 3ppm,
The indexs such as compression strength are all satisfied national standard GBT 31587-2015 requirement.At 3 years or more, mechanical life existed catalyst chemical lifetime
10 years or more, it is able to satisfy the requirement of industrial applications.
(3) catalyst provided by the invention is also applied for coking kiln, rubbish especially suitable for steamer diesel engine vent gas denitration
Rubbish incinerator, glass furnace, cement kiln, ceramic kiln, industrial silicon, the industrial tail gas denitration such as steel mill.
Specifically, it is preferable that the catalyst raw material according to parts by weight, including following component:
Titanium dioxide: 55-70 parts, ammonium metavanadate-monoethanolamine solution: 6-25 parts, tungsten salt: 0.8-4 parts, antimonic salt: 1.8-5.5
Part, ferric nitrate: 0.3-5 parts, niobium oxalate: 0.1-1.7 parts, triammonium phosphate: 0.6-6 parts, montmorillonite: 0.5-4 parts, lactic acid: 0.5-
2.5 parts, urea: 0.5-2.5 parts, paper is fine: 0.1-1.5 parts, glass fibre: and 3-10 parts, stearic acid: 1-4 parts, hydroxylmethyl cellulose
Element: 0.1-1.5 parts and polyoxyethylene: 0.1-1.5 parts.
Catalyst provided by the invention forms strong interaction using titanium dioxide as carrier between V-W-Sb-Nb-P-Fe, tool
There is synergistic effect, there is very high denitration and de- CH activity at low temperature, and there is excellent water resistant resistance to SO_2.Montmorillonite has
Dispersion and the effect for improving pug state, lactic acid and urea can adjust the viscosity and plasticity of pug, and hydroxymethyl cellulose is dispersion
Agent, polyoxyethylene are binder, can adjust the end-state of pug, keep pug evenly dispersed at coccoid, are conducive to pug and turn
It moves, stearic effect is to make to reduce the frictional force between pug and mold, is extruded conducive to pug.
Specifically, it is preferable that the ammonium metavanadate-monoethanolamine solution includes the component of following parts by weight: metavanadic acid
Ammonium: 24-26 parts, monoethanolamine: 28-32 parts, water: 43-47 parts.
Preferably, the ammonium metavanadate-monoethanolamine solution is to mix ammonium metavanadate, monoethanolamine and water, in 68-72
3-5h is stirred under conditions of DEG C to obtain.
Preferably, the titanium dioxide is to vulcanize ultra-fine anatase thpe white powder, wherein by percentage to the quality, containing are as follows: SO31-
4%, titanium dioxide 96-99%.
Preferably, the partial size D50 of the ultra-fine anatase thpe white powder of vulcanization is less than 1 μm.
Preferably, the tungsten salt is at least one of ammonium metatungstate or ammonium paratungstate.
Preferably, the antimonic salt is at least one of antimony acetate or nitric acid antimony.
Further, the present invention also provides the preparation methods of above-mentioned low temperature SCR denitration catalyst, and the preparation method is at least
The following steps are included:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
27-30wt%, pH value 7.2-9 are mixed, and are eventually adding hydroxymethyl cellulose and polyoxyethylene is kneaded, obtain pug；
Step b, the pug being kneaded is sealed it is aging, it is aging after pug be extruded into honeycomb shape catalyst, after extrusion
Catalyst by dry, calcining, obtain low temperature SCR denitration catalyst.
Specifically, it is preferable that 120-300min is mixed in the step a.
Preferably, compounding conditions in the step a are as follows: temperature is 30-80 DEG C, revolving speed 500-800rpm.
Preferably, aging condition in the step b are as follows: temperature is 20-40 DEG C, the time are as follows: 10-14h.
Preferably, in the step b extrusion pressure in 3-5MPa.
Preferably, drying condition in the step b are as follows: temperature is 60-90 DEG C, drying time are as follows: 6-9d.
Preferably, calcination condition in the step b are as follows: temperature is 400-630 DEG C, calcination time are as follows: 5-14h.
Further, the present invention also provides above-mentioned low temperature SCR denitration catalysts in 160-450 DEG C of temperature range flue gas
Application in denitration.
Catalyst provided by the invention is also applied for coking kiln, rubbish especially suitable for steamer diesel engine vent gas denitration
Incinerator, glass furnace, cement kiln, ceramic kiln, industrial silicon, the industrial tail gas denitration such as steel mill.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment provides in order to better illustrate the present invention, is illustrated below by embodiment is further.
Embodiment 1
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 1%,
Fe2O3: 2%, WO3: 5%, Sb2O3: 3%, Nb2O5: 0.2%, P2O5: 1.9%, TiO2: 76% and inactive ingredients: 10.9%.
Above-mentioned low temperature SCR denitration catalyst, raw material according to parts by weight, including following component: titanium dioxide: 55.4 parts, partially
Ammonium vanadate-monoethanolamine solution: 6 parts, tungsten salt: 4 parts, antimonic salt: 5.5 parts, ferric nitrate: 5 parts, niobium oxalate: 1.2 parts, triammonium phosphate:
6 parts, montmorillonite: 4 parts, lactic acid: 0.5 part, urea: 2.5 parts, paper is fine: 1.5 parts, glass fibre: and 6 parts, stearic acid: 1 part, hydroxyl first
Base cellulose: 0.4 part, polyoxyethylene: 0.1 part.
Above-mentioned tungsten salt is ammonium metatungstate；Above-mentioned antimonic salt is antimony acetate；Above-mentioned titanium dioxide is that mass percent is SO3: 1%,
Titanium dioxide: the ultra-fine anatase thpe white powder of 99% vulcanization；Above-mentioned ammonium metavanadate-monoethanolamine solution is by 25 parts of metavanadic acids
Ammonium, 30 parts of monoethanolamine and 45 parts of water mixing, stir 4h under conditions of 70 DEG C and obtain.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
27wt%, pH value 8, is mixed 180min in kneading machine, is eventually adding hydroxymethyl cellulose and polyoxyethylene at 30 DEG C
Under the conditions of be kneaded with the revolving speed of 800rpm, obtain pug；
Step b, the pug being kneaded is sealed into aging 12h after pre- squeeze at 20 °C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, and catalyst of the extrusion pressure after 4.1MPa, extrusion is in 80 DEG C of dry 7d, after dry
In 400 DEG C of calcining at constant temperature 14h, low temperature SCR denitration catalyst is obtained.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
Embodiment 2
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 1.2%,
Fe2O3: 0.1%, WO3: 3.8%, Sb2O3: 2.5%, Nb2O5: 0.3%, P2O5: 1.54%, TiO2: 81% and inactive ingredients:
9.56%.
Above-mentioned low temperature SCR denitration catalyst, raw material according to parts by weight, including following component: titanium dioxide: 61.2 parts, partially
Ammonium vanadate-monoethanolamine solution: 10 parts, tungsten salt: 3 parts, antimonic salt: 4 parts, ferric nitrate: 0.3 part, niobium oxalate: 1.7 parts, tricresyl phosphate
Ammonium: 4 parts, montmorillonite: 2 parts, lactic acid: 1 part, urea: 0.5 part, paper is fine: 0.5 part, glass fibre: and 10 parts, stearic acid: 1 part, hydroxyl
Methylcellulose: 0.3 part, polyoxyethylene: 0.5 part.
Above-mentioned tungsten salt is ammonium metatungstate；Above-mentioned antimonic salt is the mixture of the antimony acetate that mass ratio is 2:1 and nitric acid antimony；It is above-mentioned
Titanium dioxide is that mass percent is SO3: 2%, titanium dioxide: the ultra-fine anatase thpe white powder of 98% vulcanization；Above-mentioned ammonium metavanadate-
Monoethanolamine solution is to mix 24 parts of ammonium metavanadates, 32 parts of monoethanolamine and 43 parts of water, and 3h is stirred under conditions of 72 DEG C and is obtained
It arrives.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
30wt%, pH value 9, is mixed 120min in kneading machine, is eventually adding hydroxymethyl cellulose and polyoxyethylene at 60 DEG C
Under the conditions of be kneaded with the revolving speed of 600rpm, obtain pug；
Step b, the pug being kneaded is sealed into aging 10h after pre- squeeze under the conditions of 40 DEG C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, catalyst of the extrusion pressure after 3MPa, extrusion in 60 DEG C of dry 9d, it is dry after
500 DEG C of calcining at constant temperature 10h, obtain low temperature SCR denitration catalyst.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
Embodiment 3
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 1.3%,
Fe2O3: 0.8%, WO3: 2.7%, Sb2O3: 2.1%, Nb2O5: 0.02%, P2O5: 0.72%, TiO2: 86% and nonactive group
Point: 6.36%.
Above-mentioned low temperature SCR denitration catalyst, raw material according to parts by weight, including following component: titanium dioxide: 70 parts, inclined vanadium
Sour ammonium-monoethanolamine solution: 11 parts, tungsten salt: 2 parts, antimonic salt: 3.5 parts, ferric nitrate: 2 parts, niobium oxalate: 0.1 part, triammonium phosphate: 2
Part, montmorillonite: 0.5 part, lactic acid: 0.5 part, urea: 0.5 part, paper is fine: 0.1 part, glass fibre: and 3 parts, stearic acid: 4 parts, hydroxyl first
Base cellulose: 0.1 part, polyoxyethylene: 0.8 part.
Above-mentioned tungsten salt is ammonium paratungstate；Above-mentioned antimonic salt is nitric acid antimony；Above-mentioned titanium dioxide is that mass percent is SO3: 3%,
Titanium dioxide: the titanium dioxide of the 97% ultra-fine anatase titanium dioxide of vulcanization；Above-mentioned ammonium metavanadate-monoethanolamine solution is by 26 parts of metavanadic acids
Ammonium, 28 parts of monoethanolamine and 47 parts of water mixing, stir 5h under conditions of 68 DEG C and obtain.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
28wt%, pH value 7.2, is mixed 300min in kneading machine, is eventually adding hydroxymethyl cellulose and polyoxyethylene 80
It is kneaded under the conditions of DEG C with the revolving speed of 500rpm, obtains pug；
Step b, the pug being kneaded is sealed into aging 14h after pre- squeeze under the conditions of 30 DEG C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, catalyst of the extrusion pressure after 5MPa, extrusion in 90 DEG C of dry 6d, it is dry after
550 DEG C of calcining at constant temperature 10h, obtain low temperature SCR denitration catalyst.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
Embodiment 4
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 3.3%,
Fe2O3: 1.2%, WO3: 1.8%, Sb2O3: 1.9%, Nb2O5: 0.15%, P2O5: 0.2%, TiO2: 78% and inactive ingredients:
13.45%.
Above-mentioned low temperature SCR denitration catalyst, raw material according to parts by weight, including following component: titanium dioxide: 58.5 parts, partially
Ammonium vanadate-monoethanolamine solution: 20 parts, tungsten salt: 1 part, antimonic salt: 2 parts, ferric nitrate: 3 parts, niobium oxalate: 0.8 part, triammonium phosphate:
0.6 part, montmorillonite: 1 part, lactic acid: 2.5 parts, urea: 1 part, paper is fine: 0.1 part, glass fibre: and 5 parts, stearic acid: 2 parts, hydroxyl first
Base cellulose: 0.1 part, polyoxyethylene: 1.5 parts.
Above-mentioned tungsten salt is ammonium paratungstate；Above-mentioned antimonic salt is the mixture of the antimony acetate that mass ratio is 1:2 and nitric acid antimony；It is above-mentioned
Titanium dioxide is that mass percent is SO3: 4%, titanium dioxide: the ultra-fine anatase thpe white powder of 96% vulcanization；Above-mentioned ammonium metavanadate-
Monoethanolamine solution is to mix 25 parts of ammonium metavanadates, 30 parts of monoethanolamine and 45 parts of water, and 5h is stirred under conditions of 68 DEG C and is obtained
It arrives.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
29wt%, pH value 7.5, is mixed 150min in kneading machine, is eventually adding hydroxymethyl cellulose and polyoxyethylene 40
It is kneaded under the conditions of DEG C with the revolving speed of 700rpm, obtains pug；
Step b, the pug being kneaded is sealed into aging 13h after pre- squeeze under the conditions of 24 DEG C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, catalyst of the extrusion pressure after 6MPa, extrusion in 70 DEG C of dry 8d, it is dry after
620 DEG C of calcining at constant temperature 13.5h, obtain low temperature SCR denitration catalyst.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
Embodiment 5
A kind of low temperature SCR denitration catalyst, the catalyst include following component: V by percentage to the quality2O5: 4%,
Fe2O3: 1.8%, WO3: 1%, Sb2O3: 1%, Nb2O5: 0.15%, P2O5: 0.31%, TiO2: 80% and inactive ingredients:
11.74%.
Above-mentioned low temperature SCR denitration catalyst, raw material according to parts by weight, including following component: titanium dioxide: 60.1 parts, partially
Ammonium vanadate-monoethanolamine solution: 25 parts, tungsten salt: 0.8 part, antimonic salt: 0.8 part, ferric nitrate: 4 parts, niobium oxalate: 0.8 part, tricresyl phosphate
Ammonium: 1 part, montmorillonite: 0.8 part, lactic acid: 0.5 part, urea: 0.5 part, paper is fine: 0.1 part, glass fibre: and 3 parts, stearic acid: 1 part,
Hydroxymethyl cellulose: 1.5 parts, polyoxyethylene: 0.1 part.
Above-mentioned tungsten salt is ammonium paratungstate；Above-mentioned antimonic salt is the mixture of the antimony acetate that mass ratio is 1:1 and nitric acid antimony；It is above-mentioned
Titanium dioxide is that mass percent is SO3: 4%, titanium dioxide: the ultra-fine anatase thpe white powder of 96% vulcanization；Above-mentioned ammonium metavanadate-
Monoethanolamine solution is to mix 25 parts of ammonium metavanadates, 30 parts of monoethanolamine and 45 parts of water, and 4h is stirred under conditions of 68 DEG C and is obtained
It arrives.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, tricresyl phosphate
Ammonium, montmorillonite, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, adjust water content and are
29wt%, pH value 7.5, is mixed 250min in kneading machine, is eventually adding hydroxymethyl cellulose and polyoxyethylene 50
It is kneaded under the conditions of DEG C with the revolving speed of 600rpm, obtains pug；
Step b, the pug being kneaded is sealed into aging 11h after pre- squeeze under the conditions of 24 DEG C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, and catalyst of the extrusion pressure after 4.8MPa, extrusion is in 80 DEG C of dry 7d, after dry
In 620 DEG C of calcining at constant temperature 5h, low temperature SCR denitration catalyst is obtained.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
Technical solution in order to better illustrate the present invention is done by comparative example and the embodiment of the present invention into one further below
The comparison of step.
Comparative example 1
Comparative example of the present invention provides a kind of low temperature SCR denitration catalyst, raw material according to parts by weight, including following component:
Titanium dioxide: 55.4 parts, ammonium metavanadate-monoethanolamine solution: 6 parts, tungsten salt: 4 parts, niobium oxalate: 1.2 parts, montmorillonite: 4 parts, cream
Acid: 0.5 part, urea: 2.5 parts, paper is fine: 1.5 parts, glass fibre: 6 parts, stearic acid: 1 part, hydroxymethyl cellulose: 0.4 part, gathering
Ethylene oxide: 0.1 part.
Above-mentioned tungsten salt is ammonium metatungstate；Above-mentioned titanium dioxide is that mass percent is SO3: 1%, titanium dioxide: 99% sulphur
Change ultra-fine anatase thpe white powder；Above-mentioned ammonium metavanadate-monoethanolamine solution is by 25 parts of ammonium metavanadates, 30 parts of monoethanolamine and 45
Part water mixing, stirs 4h under conditions of 70 DEG C and obtains.
Above-mentioned low temperature SCR denitration catalyst the preparation method comprises the following steps:
Step a, it is de- that ultra-fine anatase thpe white powder, ammonium metavanadate-monoethanolamine solution, tungsten salt, niobium oxalate, illiteracy will be vulcanized
Then stone, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing add water and ammonium hydroxide, adjusting water content is 27wt%,
PH value is 8, and 180min is mixed in kneading machine, be eventually adding hydroxymethyl cellulose and polyoxyethylene under the conditions of 30 DEG C with
The revolving speed of 800rpm is kneaded, and obtains pug；
Step b, the pug being kneaded is sealed into aging 12h after pre- squeeze at 20 °C, it is aging after pug squeezing
Machine is extruded into 18 hole honeycomb shape products out, and catalyst of the extrusion pressure after 4.1MPa, extrusion is in 80 DEG C of dry 7d, after dry
In 620 DEG C of calcining at constant temperature 5h, low temperature SCR denitration catalyst is obtained.
The catalyst prepared is cut into the hole 3*3, length is the catalyst of 50cm long, carries out denitration activity and all other
Detection.
The characteristic for the low temperature SCR denitration catalyst that embodiment provides in order to better illustrate the present invention, below by embodiment
1,2,3,4,5 denitration performance detection is carried out with low temperature SCR denitration catalyst prepared by comparative example 1, testing result is as follows.
Flue gas condition: O26%, NO 320ppm, H2O 10%, SO2200ppm, CH 20ppm, remaining is nitrogen；CH at
Point: volume ratio is the mixture of the methacrylaldehyde of 4:2:1:1:1, benzene, toluene, 1- butylene, paraxylene.
NOx inlet and outlet reading instrument are Testo-350 flue gas analyzer；CH entrance and exit reading uses makings
Combined instrument (Japanese Shimadzu GCMS-QP2010SE) analysis.
1 denitration efficiency of table
From table 1, it is apparent that low temperature SCR denitration catalyst provided in an embodiment of the present invention, in 160-450 DEG C of width
Within the scope of warm area, under the conditions of water sulfur-containing smoke gas, denitration efficiency can reach 88%-100%, have excellent water resistant resistance to SO_2, and
SO2Conversion ratio < 1%, the escaping of ammonia rate < 3ppm.
Low temperature SCR denitration catalyst prepared by embodiment 1,2,3,4,5 carries out intensity test, GBT 31587-
2015 regulations: honeycomb catalyst axial compression strength >=2MPa, radial crushing strength >=0.4MPa, test result are as shown in table 2.
2 resistance to compression result of table
From table 2 it can be seen that catalyst prepared by the present invention meets national standard GBT 31587-2015 regulation.
Low temperature SCR denitration catalyst prepared by embodiment 1,2,3,4,5 carries out specific surface area test, and test result is as follows
Shown in table 3.
3 specific surface area of table
| Number | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Specific surface area m2/g | 55.83 | 53.9 | 57.48 | 55.03 | 56.1 |
From table 3 it can be seen that specific surface area of catalyst prepared by the present invention is greater than 53m2/ g or more.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of low temperature SCR denitration catalyst, it is characterised in that: the catalyst includes following component by percentage to the quality:
V2O5: 1-4%, Fe2O3: 0.1-2%, WO3: 1-5%, Sb2O3: 1-3%, Nb2O5: 0.02-0.3%, P2O5: 0.2-1.9%,
TiO2: 76-86% and inactive ingredients: 5-15%.
2. low temperature SCR denitration catalyst as described in claim 1, it is characterised in that: the catalyst raw material is in parts by weight
Meter, including following component:
Titanium dioxide: 55-70 parts, ammonium metavanadate-monoethanolamine solution: 6-25 parts, tungsten salt: 0.8-4 parts, antimonic salt: 1.8-5.5 parts,
Ferric nitrate: 0.3-5 parts, niobium oxalate: 0.1-1.7 parts, triammonium phosphate: 0.6-6 parts, montmorillonite: 0.5-4 parts, lactic acid: 0.5-2.5
Part, urea: 0.5-2.5 parts, paper is fine: 0.1-1.5 parts, glass fibre: and 3-10 parts, stearic acid: 1-4 parts, hydroxymethyl cellulose:
0.1-1.5 parts and polyoxyethylene: 0.1-1.5 parts.
3. low temperature SCR denitration catalyst as claimed in claim 2, it is characterised in that: the ammonium metavanadate-monoethanolamine solution
Component including following parts by weight: ammonium metavanadate: 24-26 parts, monoethanolamine: 28-32 parts, water: 43-47 parts.
4. low temperature SCR denitration catalyst as claimed in claim 3, it is characterised in that: the ammonium metavanadate-monoethanolamine solution
To mix ammonium metavanadate, monoethanolamine and water, 3-5h is stirred under conditions of 68-72 DEG C and is obtained.
5. low temperature SCR denitration catalyst as described in claim 1, it is characterised in that: the titanium dioxide is to vulcanize ultra-fine rutile titania
Type titanium dioxide, wherein by percentage to the quality, containing are as follows: SO31-4%, titanium dioxide 96-99%.
6. low temperature SCR denitration catalyst as claimed in claim 5, it is characterised in that: the ultra-fine anatase thpe white powder of vulcanization
Partial size D50 less than 1 μm.
7. low temperature SCR denitration catalyst as described in claim 1, it is characterised in that: the tungsten salt is ammonium metatungstate or secondary tungsten
At least one of sour ammonium；And/or
The antimonic salt is at least one of antimony acetate or nitric acid antimony.
8. the preparation method of the described in any item low temperature SCR denitration catalysts of claim 1-7, it is characterised in that: the preparation
Method at least includes the following steps:
Step a, by titanium dioxide, ammonium metavanadate-monoethanolamine solution, tungsten salt, antimonic salt, ferric nitrate, niobium oxalate, triammonium phosphate, illiteracy
De- stone, lactic acid, urea, paper fibre, glass fibre, stearic acid mixing, then add water and ammonium hydroxide, and adjusting water content is 27-
30wt%, pH value 7.2-9 are mixed, and are eventually adding hydroxymethyl cellulose and polyoxyethylene is kneaded, obtain pug；
Step b, by the pug being kneaded seal it is aging, it is aging after pug be extruded into honeycomb shape catalyst, urging after extrusion
Agent passes through drying and calcination, obtains low temperature SCR denitration catalyst.
9. the preparation method of low temperature SCR denitration catalyst as claimed in claim 8, it is characterised in that: mixed in the step a
Stir 120-300min；And/or
Compounding conditions in the step a are as follows: temperature is 30-80 DEG C, revolving speed 500-800rpm；And/or
Aging condition in the step b are as follows: temperature is 20-40 DEG C, the time are as follows: 10-14h；And/or
Extrusion pressure is in 3-5MPa in the step b；And/or
Drying condition in the step b are as follows: temperature is 60-90 DEG C, drying time are as follows: 6-9d；And/or
Calcination condition in the step b are as follows: temperature is 400-620 DEG C, calcination time are as follows: 5-14h.
10. low temperature SCR denitration catalyst as described in any one of claims 1 to 7 flue gas in 160-450 DEG C of temperature range is de-
Application in nitre.
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| CN114392758A (en) * | 2022-01-11 | 2022-04-26 | 河南康宁特环保科技股份有限公司 | High-vanadium denitration catalyst and preparation method thereof |
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