CN107913696A - A kind of denitrating catalyst of anti-oxidizing sulfur dioxide and preparation method thereof - Google Patents
A kind of denitrating catalyst of anti-oxidizing sulfur dioxide and preparation method thereof Download PDFInfo
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- CN107913696A CN107913696A CN201610884196.4A CN201610884196A CN107913696A CN 107913696 A CN107913696 A CN 107913696A CN 201610884196 A CN201610884196 A CN 201610884196A CN 107913696 A CN107913696 A CN 107913696A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of denitrating catalyst of anti-oxidizing sulfur dioxide and preparation method thereof, by weight percentage, the catalyst contains titanium dioxide 80~98%, molybdenum trioxide 1~10%, vanadic anhydride 0.3~5%, titanium source presoma is formed solution by silica 0.1%~5%, preparation method (1)；(2) molybdenum source presoma is formed into solution, and is mixed with the solution of (1)；(3) (2) resulting solution pH, filtering are adjusted；(4) deionized water is added in filter cake obtained by (3), adds vanadium source precursor solution, combination drying, roasting；(5) molybdenum source precursor solution is mixed with the powder of (4), adds pore-creating auxiliary agent, it is dry；(6) desciccate of (5) is impregnated in silicon source precursor solution, roasted.Denitrating catalyst prepared by the present invention can not only resist in flue gas barium oxide in its surface nonuniform deposition, but also can be while high catalytic performance is ensured with low sulfur dioxide/sulphur trioxide conversion rate.
Description
Technical field
The present invention relates to a kind of catalyst for denitrating flue gas of anti-oxidizing sulfur dioxide and preparation method thereof, especially one kind is supported
Uneven denitrating catalyst of vanadium deposition and preparation method thereof in anti-flue gas, which belongs to New Inorganic Materials technical field.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly stringent.China《" 12th Five-Year Plan " section
Can the comprehensive programme of work of emission reduction》Middle regulation：By 2015, national discharged nitrous oxides total amount declined 10% than 2010.
The GB13223-2001 that 2011 Nian9Yue State Ministry of Environmental Protection promulgate《Fossil-fuel power plant atmospheric pollutant emission standard》Thermal power plant NOx is arranged
Put concentration and make more strict requirements：Provide the coal-burning boiler that the 3rd period created, and extended, reconstructing, NOx highests allow to discharge
Concentration is 100mg/m3.What State Ministry of Environmental Protection promulgated《Petroleum refining industry pollutant emission standard》It is required that：On July 1st, 2015
Rise, nitrogen oxides requires to be less than 200mg/m in newly-built catalytic cracking unit discharge regenerated flue gas3, special emission limit requires small
In 100mg/m3, on July 1st, 2017, existing enterprise also performed the standard.In numerous gas denitrifying technologies, selective catalysis is also
The technology that it is still international mainstream that former method (Selective Catalytic Reduction, SCR), which is, its NOxRemoval efficiency is reachable
To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just have developed in the eighties in last century
For a series of denitrating catalysts of coal characteristics, boiler type etc., many R＆D institutions of China are coal-fired for China with enterprise
Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.
CN201010537130 proposes the method that denitrating catalyst is prepared using hydrothermal method, first by titanium source presoma
Mixed with molybdenum source presoma, be placed in autoclave and carry out hydro-thermal reaction, be filtered, washed and dried to obtain titanium molybdenum powder denitration catalyst
Agent, while the elements such as vanadium and molybdenum can be also introduced, prepare multi-metal-oxide catalyst.Catalyst activity component prepared by this method
Crystal grain is small, specific surface area is larger, but by being sufficiently mixed process material aggregation extent of the same race may be caused higher due to no
Phenomenon occurs, and certain influence is had on catalyst activity.
CN201110345605 proposes a kind of preparation method of denitrating catalyst, and molybdenum is sequentially added into metatitanic acid slurry
Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, stand, separate, drying is catalyzed
Agent powder.This method technique is simple, cost is low, but ammonium metavanadate is added with solid, and the dissolubility of vanadium is still to be tested, and vanadium disperses
Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst performance.
CN201210400949 proposes a kind of preparation method of titanium dioxide-molybdenum trioxide composite granule, by para-molybdic acid
Ammonium salt solution is added in metatitanic acid slurries, and directly vacuum drying obtains finished product after stirring.This method technique is simple, but titanium-molybdenum
Mixing intensity is relatively low, can have a certain impact to the performance of material.
In conclusion the preparation of denitrating catalyst is directed to the mixing of Multimetal oxide, hybrid mode and technique
Difference can not distinguish the denitration performance of catalyst, NO completelyxConversion ratio can reach more than 90%, illustrate special metal oxygen
The catalytic activity of compound is higher, and scattered inequality can still obtain higher NOxConversion ratio.The quality of catalyst overall performance is also
Need to be verified from otherwise characterization, while the preparation of catalyst will also take into account the operability of industry amplification.
The content of the invention
It is a primary object of the present invention to provide a kind of denitrating catalyst of anti-oxidizing sulfur dioxide and preparation method thereof, with
Overcome in the prior art that denitrating catalyst activated centre in flue gas is unbalanced, resistance to SO_2 is poor and active unstable lack
Fall into.
The object of the present invention is achieved like this, a kind of preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide, should
Method for preparing catalyst includes the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) molybdenum source presoma is dissolved to form solution, and is uniformly mixed with the solution of (1)；
(3) solution ph to alkalescence, precipitates, filtering, washs to obtain filter cake after mixing obtained by regulating step (2)；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, add vanadium source precursor solution, mixing is equal
After even, directly it is dried, roasts, forms powder；
(5) the powder mixing pulp by the solution that molybdenum source presoma is formed with step (4), after stirring, adds pore-creating to help
Agent, after secondary agitation, sealing and standing, drying；And
(6) desciccate of step (5) is impregnated in silicon source precursor solution, dry afterwards, roasting, forms denitration and urge
Agent.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, titanium in the step (1)
Source presoma is titanyl sulfate or metatitanic acid, and the acid is inorganic acid, and the solution of formation is with TiO2Meter, content is preferably 15~
40g/L。
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, the molybdenum source presoma
For ammonium paramolybdate or ammonium molybdate, the molybdenum source presoma is with MoO3Meter, titanium source presoma is with TiO2Count, before molybdenum source used in step (2)
The mass ratio for driving body and titanium source presoma is preferably 2.0~5.0:100；Molybdenum source presoma used and titanium source forerunner in step (5)
Body mass ratio is preferably 0.5~2:100.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, the step (2) and step
Suddenly for the mode being uniformly mixed in (4) using stirring or supersonic oscillations, the time is both preferably 0.5~3h, is adjusted in the step (3)
It is preferably ammonium hydroxide to save pH value medicament, and pH value is more than 9.0 after adjusting, in the step (5) mixing time be both preferably 10~
60min, the sealing and standing time is preferably 8~30h in the step (5), in the step (6) dip time be preferably 5~
20s。
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, vanadium source presoma
Vanadium source presoma is ammonium metavanadate in solution, and vanadium source presoma is with V2O5Meter, the titanium source presoma is with TiO2Meter, vanadium source
The mass ratio of presoma dosage and titanium source presoma dosage is preferably 0.5~2.0:100.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, slurry in the step (4)
Shape thing water quality content is preferably 35~55%, and slurry water quality content is preferably 25~40% in the step (5), described
Silicon source precursor solution is the alcoholic solution of ethyl orthosilicate in step (6), wherein ethyl orthosilicate mass content be preferably 3~
15%.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, the titanium source presoma
With TiO2Count, pore-creating auxiliary agent is the mass ratio of polyethylene glycol oxide or sesbania powder, addition and titanium source presoma in the step (5)
Preferably 0.3~1.0:100.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, the step (4) and step
Suddenly calcination temperature is both preferably 400~650 DEG C in (6), and roasting time is both preferably 4~10h.
The preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide of the present invention, wherein, the inorganic acid is preferred
For sulfuric acid or nitric acid.
, should present invention also offers catalyst prepared by the preparation method of the denitrating catalyst of above-mentioned anti-oxidizing sulfur dioxide
Catalyst is vanadium system O composite metallic oxide catalyst, 40~120m of specific surface area2/ g, by weight percentage, wherein containing two
Titanium oxide is 80~98%, containing molybdenum trioxide 1~10%, containing vanadic anhydride 0.3~5%, containing silica 0.1%~5%.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and molybdenum atom is mixed in molecule rank, cause subsequently to be co-precipitated
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves at the same time
Titanium dioxide crystal turns brilliant temperature, beneficial to the performance of catalytic activity；
(2) vanadium source is added when titanium dioxide-molybdenum trioxide co-precipitation material does not roast, in titanium-molybdenum particle surface infiltration
Deeper, connection is closer, disperses evenly, fired rear catalyst activity is more stable；
(3) the vanadium molybdenum titanium powder material prepared is into after crossing once roasting, and covers one layer of molybdenum trioxide on its surface, at the same time
Pore-creating auxiliary agent is added, catalyst particle surface is also possessed while there is the attachment of more molybdenum oxides nanometer level microporous, both may be used
To resist heavy metals of flue gases in its surface nonuniform deposition, and it can ensure high catalyst performance.
(4) non-after baking catalyst is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas can also be hindered to contact catalyst
The activated centre of layer, reduces the oxidation of sulfur dioxide.
Embodiment
Elaborate below to the embodiment of the present invention：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of actual conditions is not specified in example, usually according to normal condition.
Titanium source precursor solution：
In the present invention, solution is formed in titanium source presoma vitriolization, there is no particular restriction to titanium source presoma, usually limit
It is set to titanyl sulfate or metatitanic acid, with TiO in titanium source precursor solution2Meter, titanium source presoma content is 15~40g/L.It is if small
In 15g/L, then solution is too dilute, and the combination of other materials is more loose, and production efficiency is relatively low；If more than 40g/L, then due to dense
Du Taigao and reduced with the mixing intensities of other materials, cause to merge bad.
Each material proportion in denitrating catalyst：
In the present invention, denitrating catalyst mainly includes titanium source presoma, molybdenum source presoma, vanadium source presoma, silicon source forerunner
Body and pore-creating auxiliary agent, if molybdenum source presoma is less, can influence the scattered and catalyst low-temperature stability of active material vanadium, cause
Catalyst performance is poor；If polyethylene glycol oxide amount is more, absorption of the molybdenum trioxide in particle surface can be influenced, is influenced if very little
Catalyst surface porosity.
Catalyst sample and catalytic cracking spent catalyst hybrid technique：Screening takes 20 after the fresh catalyst of preparation is crushed
~40 mesh powders；40~60 mesh powders are taken after catalytic cracking spent catalyst screening, and barium oxide contains in catalytic cracking spent catalyst
Amount about 1%.Two kinds of powders in mass ratio 1:1 mixing, in air atmosphere, at 350 DEG C, mixes 24h, screens out catalyst afterwards
Powder is evaluated.Fresh catalyst is contacted in mixed process with waste acetic acid, can be by waste acetic acid
In active material vanadium it is non-uniform be transferred on fresh catalyst, cause fresh catalyst surface reactive material barium oxide collection
Middle accumulation, causes catalyst Topically active to strengthen, and then can increase the SO of catalyst2/SO3Conversion ratio, it is whole to reduce denitrating catalyst
Body performance.
Stationary state NOxConversion ratio appreciation condition：Air speed 20000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2
For 1000mg/Nm3, ammonia nitrogen ratio be 1, water content 10%.
NOx、SO2Method for measurement of concentration：Flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
SO2/SO3Conversion ratio assay method：Wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Following embodiments are that the present invention is illustrated, and " % " described in embodiment and comparative example refers to quality percentage and contain
Amount.
Embodiment 1：
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 35g/L solution, add
Containing with MoO3The molybdenum ammonium solution of 22.5g is counted, ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 9.5, has been precipitated
Quan Hou, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 4.5g
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, 8h is roasted at 620 DEG C；Powder is again after roasting
With with MoO3Aqueous 30% slurry is made in the ammonium molybdate solution of meter 7.5g, and 4g polyethylene glycol oxides, stirring are added after stirring
40min, sealing and standing 24h, drying；The catalyst powder of drying is inserted into 15s in the ethanol solution containing ethyl orthosilicate 10%,
Denitrating catalyst is obtained after filtering, drying, 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and giving up with catalytic cracking containing vanadium is urged
Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Comparative example 1：
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 35g/L solution, add
Containing with MoO3The molybdenum ammonium solution of 22.5g is counted, ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 10, precipitation is complete
Afterwards, filter, wash；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 4.5g's
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, roasts 8h and obtains denitrating catalyst at 620 DEG C；
Above-mentioned gained fresh catalyst and evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1
Data.
Embodiment 2
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 30g/L solution, add
Containing with MoO3The ammonium molybdate solution of 22.5g is counted, ammonium hydroxide is gradually added after supersonic oscillations 1.5h and adjusts pH value to 10, precipitation is complete
Afterwards, filter, wash；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 4.5g's
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, 8h is roasted at 600 DEG C；After roasting powder again with
With MoO3Aqueous 35% slurry is made in the ammonium molybdate solution of meter 5g, addition 3.5g polyethylene glycol oxides after stirring, stirring 30min,
Sealing and standing 16h, drying；The catalyst powder of drying is inserted into 10s in the ethanol solution containing ethyl orthosilicate 5%, filtering, dry
Denitrating catalyst is obtained after dry, 600 DEG C of roastings.Above-mentioned gained fresh catalyst and mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Close rear catalyst to evaluate respectively, the results are shown in Table 1 data.
Comparative example 2
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 30g/L solution, add
Containing with MoO3The molybdenum ammonium solution of 22.5g is counted, ammonium hydroxide is gradually added after supersonic oscillations 1.5h adjusts pH value and precipitated to 9.0
Quan Hou, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 4.5g
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, 8h is roasted at 600 DEG C；Powder is again after roasting
With with MoO3Aqueous 35% slurry is made in the ammonium molybdate solution of meter 5g, and denitration is obtained after stirring 30min, drying, 600 DEG C of roastings
Catalyst.Above-mentioned gained fresh catalyst and evaluate, tie respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst
Fruit is shown in Table 1 data.
Embodiment 3
It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 30g/L solution, addition contains
With MoO3The ammonium molybdate solution of 20g is counted, ammonium hydroxide is gradually added after supersonic oscillations 1h and adjusts pH value to 9.5, after precipitation is complete, mistake
Filter, washing；Material after washing is spent into ion water making into the slurry that moisture content is 45% again, is added with V2O5Count the metavanadic acid of 5g
Ammonium salt solution, supersonic oscillations 1h while stirring, after convection drying, 6h is roasted at 550 DEG C；After roasting powder again with MoO3Meter
Aqueous 30% slurry is made in the ammonium molybdate solution of 5g, and 3g polyethylene glycol oxides, stirring 30min, sealing and standing are added after stirring
20h, drying；The catalyst powder of drying is inserted into 6s in the ethanol solution containing ethyl orthosilicate 8%, filtering, dry, 550 DEG C
Denitrating catalyst is obtained after roasting.Above-mentioned gained fresh catalyst and it is catalyzed after being mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Agent is evaluated respectively, the results are shown in Table 1 data.
Comparative example 3
Technique used presses CN201110345605 embodiments 1, and metatitanic acid dust technology is disperseed to be beaten, is filtered to neutrality,
Add water metatitanic acid mashing is scattered, obtained metatitanic acid slurry.Ammonium tungstate, ammonium molybdate and vanadium are sequentially added in metatitanic acid slurry
Sour ammonium, it is respectively 1/100,1/100 and 0.1/100 to make the mass ratio of three kinds of ammonium salts and metatitanic acid, is then used mixed material super
Sound wave mashing allows the ammonium salt of addition to dissolve, is scattered, ammonium salt is fully adsorbed to metatitanic acid surface, with nitre acid for adjusting pH value extremely
5.0.Stand, dry, 300 DEG C of heat treatment 4h obtain catalyst.Above-mentioned gained fresh catalyst and give up with catalytic cracking containing vanadium
Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 4
It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 20g/L solution, addition contains
With MoO3Count the molybdenum ammonium solution of 15g, be gradually added after supersonic oscillations 1h ammonium hydroxide adjust pH value to 10.5 precipitations completely after,
Filtering, washing；The slurry that moisture content is 40% is made with distilled water in material after washing again, is added with V2O5Count the metavanadic acid of 5g
Ammonium salt solution, supersonic oscillations 1h while stirring, after convection drying, 6h is roasted at 500 DEG C；After roasting powder again with MoO3Meter
Aqueous 28% slurry is made in the ammonium molybdate solution of 3.5g, and 2.5g polyethylene glycol oxides are added after stirring, and stirring 40min, sealing are quiet
Put 20h, drying；The catalyst powder of drying is inserted into 5s in the ethanol solution containing ethyl orthosilicate 13%, filtering, drying, 500
DEG C roasting after obtain denitrating catalyst.Above-mentioned gained fresh catalyst and urge after being mixed with catalytic cracking vanadium-containing wasting catalyst high temperature
Agent is evaluated respectively, the results are shown in Table 1 data.
Comparative example 4
Technique used presses CN103143396 embodiments 1, a kind of honeycomb type flue gas denitration catalyst, with the raw material of parts by weight
Extruded shaping, sintering form：83 parts of nano-titanium dioxide, 8.3 parts of nano silicon dioxide, ammonium metatungstate are with WO3Count 10 weight
Part, ammonium metavanadate are with V2O5Count 1 parts by weight, 6.7 parts of glass fibre, 0.42 part of extrusion aid, 0.17 part of cellulose, polyethylene glycol oxide
0.25 part, 0.17 part of sesbania powder.Honeycombed catalyst is evaluated through being crushed to 20~40 mesh.Above-mentioned gained fresh catalyst and
Evaluated respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst, the results are shown in Table 1 data.
Embodiment 5：
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 35g/L solution, add
Containing with MoO3The molybdenum ammonium solution of 10.0g is counted, ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 9.5, has been precipitated
Quan Hou, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 2.5g
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, 8h is roasted at 620 DEG C；Powder is again after roasting
With with MoO3Aqueous 30% slurry is made in the ammonium molybdate solution of meter 2.5g, and 4g polyethylene glycol oxides, stirring are added after stirring
40min, sealing and standing 24h, drying；The catalyst powder of drying is inserted into 15s in the ethanol solution containing ethyl orthosilicate 3%,
Denitrating catalyst is obtained after filtering, drying, 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and giving up with catalytic cracking containing vanadium is urged
Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
Embodiment 6：
It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, and formation contains TiO2For 35g/L solution, add
Containing with MoO3The molybdenum ammonium solution of 25g is counted, ammonium hydroxide is gradually added after supersonic oscillations 2h and adjusts pH value to 9.5, precipitation is complete
Afterwards, filter, wash；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, is added with V2O5Count 10g's
Ammonium metavanadate solution, supersonic oscillations 1.5h while stirring, after convection drying, 8h is roasted at 620 DEG C；After roasting powder again with
With MoO3Aqueous 30% slurry is made in the ammonium molybdate solution of meter 10g, and 4g polyethylene glycol oxides, stirring 40min, close are added after stirring
Envelope stands 24h, drying；The catalyst powder of drying is inserted into 15s in the ethanol solution containing ethyl orthosilicate 15%, filtering, dry
Denitrating catalyst is obtained after dry, 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and with catalytic cracking vanadium-containing wasting catalyst high temperature
Mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.
1 embodiment of table and comparative example evaluating data contrast table
Embodiment prepares 40~120m of specific surface area of catalyst2/ g, by weight percentage, wherein being 80 containing titanium dioxide
~98%, containing molybdenum trioxide 1~10%, containing vanadic anhydride 0.3~5%, containing silica 0.1%~5%；Pass through embodiment
Found with comparative example：The denitrating catalyst of the preventing from heavy metal deposition of embodiment has good effect, preliminary by ultrasonic wave in situ
Mixing, makes the mixing rank of active material reach molecule rank, through being co-precipitated the nano particle slightly evacuated, then in particle table
Face and shallow-layer introduce barium oxide, and catalyst intermediate is obtained after roasting, then strengthens introducing again under the action of pore-creating auxiliary agent
Co-catalyst, up to final catalyst after roasting, NO in evaluating catalystxConversion ratio ammonia nitrogen ratio be 1 when, up to 99% with
On, and catalyst sulfur dioxide/sulphur trioxide conversion rate is relatively low, through with after catalytic cracking vanadium-containing wasting catalyst mixed processing,
SO2/SO3Conversion ratio illustrates catalyst surface almost without the polycrystalline deposition of barium oxide, catalyst is produced almost without increase
Function admirable；In denitrating catalyst preparation method, if being handled without (5) (6) step, only retain vanadium molybdenum titanium after roasting for the first time and urge
Agent sample, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio has increased slightly；If in the processing of (5) step
Pore-creating auxiliary agent is not added with, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio also has increased slightly；If without
(6) impregnation steps of step, the SO of catalyst2/SO3Conversion ratio is higher.In short, the fresh denitrating catalyst of the invention prepared and place
Catalyst after reason with the conditions of when evaluating, SO2/SO3Conversion ratio is lower than other comparative examples, has good anti-flue gas
The effect of middle heavy metal deposition.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom and molybdenum atom is mixed in molecule rank, cause subsequently to be co-precipitated
During the crystal that produces, lattice defect is more, and mixed-metal oxides particle diameter is small and homogeneous, bigger than surface, improves at the same time
Titanium dioxide crystal turns brilliant temperature, beneficial to the performance of catalytic activity；
(2) vanadium source is added when titanium dioxide-molybdenum trioxide co-precipitation material does not roast, in titanium-molybdenum particle surface infiltration
Deeper, connection is closer, disperses evenly, fired rear catalyst activity is more stable；
(3) the vanadium molybdenum titanium powder material prepared is into after crossing once roasting, and covers one layer of molybdenum trioxide on its surface, at the same time
Pore-creating auxiliary agent is added, catalyst particle surface is also possessed while there is the attachment of more molybdenum oxides nanometer level microporous, both may be used
To resist heavy metals of flue gases in its surface nonuniform deposition, and it can ensure high catalyst performance.
(4) non-after baking catalyst is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas can also be hindered to contact catalyst
The activated centre of layer, reduces the oxidation of sulfur dioxide.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
- A kind of 1. preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide, it is characterised in that the method for preparing catalyst bag Include following steps：(1) titanium source presoma is dissolved in acid and forms solution；(2) molybdenum source presoma is dissolved to form solution, and is uniformly mixed with the solution of (1)；(3) solution ph to alkalescence, precipitates, filtering, washs to obtain filter cake after mixing obtained by regulating step (2)；(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, added vanadium source precursor solution, be uniformly mixed Afterwards, directly it is dried, roasts, forms powder；(5) the powder mixing pulp by the solution that molybdenum source presoma is formed with step (4), after stirring, adds pore-creating auxiliary agent, and two After secondary stirring, sealing and standing, drying；And(6) desciccate of step (5) is impregnated in silicon source precursor solution, dry afterwards, roasting, forms denitration catalyst Agent.
- 2. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Titanium source presoma is titanyl sulfate or metatitanic acid in step (1), and the acid is inorganic acid, and the solution of formation is with TiO2Meter, content For 15~40g/L.
- 3. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Molybdenum source presoma is ammonium paramolybdate or ammonium molybdate, and the molybdenum source presoma is with MoO3Meter, titanium source presoma is with TiO2Meter, step (2) The mass ratio of molybdenum source presoma and titanium source presoma used is 2.0~5.0:100；Molybdenum source presoma and titanium used in step (5) Source forerunner's body mass ratio is 0.5~2:100.
- 4. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described The mode being uniformly mixed in step (2) and step (4) is 0.5~3h using stirring or supersonic oscillations, time, the step (3) it is ammonium hydroxide that pH value medicament is adjusted in, and pH value is more than 9.0 after adjusting, and mixing time is 10~60min in the step (5), The sealing and standing time is 8~30h in the step (5), and dip time is 5~20s in the step (6).
- 5. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Vanadium source presoma is ammonium metavanadate in the precursor solution of vanadium source, and vanadium source presoma is with V2O5Meter, the titanium source presoma with TiO2The mass ratio of meter, vanadium source presoma dosage and titanium source presoma dosage is 0.5~2.0:100.
- 6. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Slurry water quality content is 35~55% in step (4), and slurry water quality content is 25~40% in the step (5), Silicon source precursor solution is the alcoholic solution of ethyl orthosilicate in the step (6), wherein ethyl orthosilicate mass content for 3~ 15%.
- 7. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Titanium source presoma is with TiO2Meter, pore-creating auxiliary agent be polyethylene glycol oxide or sesbania powder in the step (5), addition and titanium source forerunner The mass ratio of body is 0.3~1.0:100.
- 8. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 1, it is characterised in that described Calcination temperature is 400~650 DEG C in step (4) and step (6), and roasting time is 4~10h.
- 9. the preparation method of the denitrating catalyst of anti-oxidizing sulfur dioxide according to claim 2, it is characterised in that described Inorganic acid is sulfuric acid or nitric acid.
- 10. catalysis prepared by the preparation method of the denitrating catalyst of any one of claim 1 to the 9 anti-oxidizing sulfur dioxide Agent, the catalyst are vanadium system O composite metallic oxide catalyst, 40~120m of specific surface area2/ g, by weight percentage, wherein It is 80~98% containing titanium dioxide, containing molybdenum trioxide 1~10%, containing vanadic anhydride 0.3~5%, containing silica 0.1%~ 5%.
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| CN114308010A (en) * | 2021-12-23 | 2022-04-12 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
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| CN114308010B (en) * | 2021-12-23 | 2023-11-03 | 江苏金聚合金材料有限公司 | Preparation and application of titanium dioxide loaded molybdenum trioxide and vanadium pentoxide catalyst |
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