CN106861673B - A kind of denitrating catalyst and preparation method thereof - Google Patents

A kind of denitrating catalyst and preparation method thereof Download PDF

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CN106861673B
CN106861673B CN201510923102.5A CN201510923102A CN106861673B CN 106861673 B CN106861673 B CN 106861673B CN 201510923102 A CN201510923102 A CN 201510923102A CN 106861673 B CN106861673 B CN 106861673B
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catalyst
solution
denitrating catalyst
source presoma
ammonium
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CN201510923102.5A
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CN106861673A (en
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巫树锋
贾媛媛
唐中华
李扬
李常青
江岩
郭珺
刘发强
刘光利
梁宝锋
杨岳
王军
何琳
张媛
李晶蕊
荣树茂
文善雄
周霞
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中国石油天然气股份有限公司
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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
    • B01J23/30—Tungsten
    • 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
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/02—Solids
    • B01J35/10—Solids characterised by their surface properties or porosity
    • 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 and preparation method thereof, titanium source presoma vitriolization is formed solution by (1)；(2) tungsten source presoma is soluble in water, and add it in the solution of step (1)；(3) after to step (2) acquired solution supersonic oscillations, pH value to more than 9.0 is adjusted with ammonium hydroxide, is precipitated, is filtered, washing；(4) deionized water is added in filter cake obtained by the step (3), is tuned into pulpous state, be added vanadium source precursor solution, after supersonic oscillations, be directly dried, roast, form powder；And (5) by the powder of step (4) and ammonium metatungstate solution mixing pulp, after stirring, addition polymerization ethylene oxide, after secondary agitation, sealing and standing, drying, roasting form denitrating catalyst.Denitrating catalyst prepared by the present invention can not only resist in flue gas barium oxide in its surface nonuniform deposition, but also can guarantee high catalyst performance, and catalytic performance is more stable.

Description

A kind of denitrating catalyst and preparation method thereof

Technical field

The present invention relates to a kind of preparation method of catalyst for denitrating flue gas, vanadium is deposited not in especially a kind of resistance flue gas Equal denitrating catalyst preparation method, the invention belong to New Inorganic Materials technical field.

Background technique

Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China's " " 12th Five-Year Plan " section Can emission reduction comprehensive programme of work " in regulation: by 2015, the decline 10% in than 2010 of national discharged nitrous oxides total amount. The GB13223-2001 " fossil-fuel power plant atmospheric pollutant emission standard " that 2011 Nian9Yue State Ministry of Environmental Protection promulgate arranges thermal power plant NOx Put concentration and made more strict requirements: the regulation third period is newly-built, extends, the coal-burning boiler of reconstruction, and NOx highest allows to discharge Concentration is 100mg/m3." petroleum refining industry pollutant emission standard " requirement that State Ministry of Environmental Protection promulgates: on July 1st, 2015 It rises, creates nitrogen oxides in catalytic cracking unit discharge regenerated flue gas and require to be less than 200mg/m3, special emission limit requires small In 100mg/m3, on July 1st, 2017, existing enterprise also executed the standard.In numerous gas denitrifying technologies, selective catalysis is also Former method (Selective Catalytic Reduction, SCR) is the technology for being still international mainstream, NOxRemoval efficiency is reachable To 80%~90%.Wherein, denitrating catalyst is the core of SCR technology, and developed country just has developed in the eighties in last century For a series of denitrating catalysts of coal characteristics, boiler type etc., many R&D institutions, China and enterprise are coal-fired for China Boiler and catalytic cracking flue gas situation have also carried out a series of research, and develop some denitrating catalysts.

CN201010537130 proposes the method for preparing denitrating catalyst using hydrothermal method, first by titanium source presoma It is mixed with tungsten source presoma, is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried to obtain titanium tungsten powder denitration catalyst Agent, while the elements such as vanadium and molybdenum can be also introduced, prepare multi-metal-oxide catalyst.The catalyst activity component of this method preparation Crystal grain is small, specific surface area is larger, but since by being sufficiently mixed process, it is higher not may cause material aggregation extent of the same race Phenomenon occurs, and has certain influence to catalyst activity.

CN201110345605 proposes a kind of preparation method of denitrating catalyst, sequentially adds tungsten into metatitanic acid slurry Sour ammonium, ammonium molybdate and ammonium metavanadate, ultrasonic wave mashing, then pH value is adjusted to 4.0~6.5, it stands, separate, drying is catalyzed Agent powder.It is this method simple process, at low cost, but ammonium metavanadate is added with solid, the dissolubility of vanadium is still to be tested, vanadium dispersion Although activity very high, SO when uneven2/SO3Conversion ratio can be higher, influences catalyst service performance.

CN201210400949 proposes a kind of preparation method of titanium dioxide-tungstic acid composite granule, by para-tungstic acid Ammonium salt solution is added in metatitanic acid slurries, and directly vacuum drying obtains finished product after stirring.This method simple process, but titanium-tungsten Mixing intensity is lower, 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 90% or more, illustrate special metal oxygen The catalytic activity of compound is higher, and dispersion unevenness can still obtain higher NOxConversion ratio.The superiority and inferiority of catalyst overall performance is also It needs to be verified from otherwise characterization, while the preparation of catalyst will also take into account the operability of industry amplification.

Summary of the invention

The main purpose of the present invention is to provide a kind of denitrating catalysts and preparation method thereof, are taken off in the prior art with overcoming Denox catalyst activated centre in high-temperature flue gas is unbalanced, the unstable defect of activity.

The object of the present invention is achieved like this, and a kind of preparation method of denitrating catalyst, this method comprises the following steps:

(1) titanium source presoma vitriolization is formed into solution；

(2) tungsten source presoma is soluble in water, and add it in the solution of step (1)；

(3) after to step (2) acquired solution supersonic oscillations, pH value to more than 9.0 is adjusted with ammonium hydroxide, is precipitated, filtering is washed It washs；

(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, vanadium source precursor solution, ultrasonic wave is added It after oscillation, is directly dried, roasts, form powder；And

(5) by the powder of step (4) and ammonium metatungstate solution mixing pulp, after stirring, addition polymerization ethylene oxide is secondary After stirring, sealing and standing, drying, roasting form denitrating catalyst.

The preparation method of denitrating catalyst of the present invention, wherein the titanium source presoma be preferably titanyl sulfate or Metatitanic acid, the step (1) form solution with TiO2Meter, content is preferably 15~40g/L.

The preparation method of denitrating catalyst of the present invention, wherein tungsten source presoma be preferably ammonium paratungstate or Ammonium metatungstate, the step (2) obtains in solution, with WO3And TiO2Mass ratio meter, preferably 2.0~5.0:100.

The preparation method of denitrating catalyst of the present invention, wherein ultrasonic wave shakes in the step (3) and step (4) Swinging the time is both preferably 0.5~3h, and mixing time is both preferably 10~60min in the step (5), close in the step (5) Sealing time of repose is preferably 8~30h.

The preparation method of denitrating catalyst of the present invention, wherein vanadium source presoma in the precursor solution of the vanadium source Preferably ammonium metavanadate, the vanadium source presoma dosage is with V2O5Meter, the titanium source presoma dosage is with TiO2Meter, V2O5And TiO2 Mass ratio is preferably 0.5~2.0:100.

The preparation method of denitrating catalyst of the present invention, wherein slurry water content is preferably in the step (4) 35~55%.

The preparation method of denitrating catalyst of the present invention, wherein the dosage of ammonium metatungstate solution in the step (5) With WO3Meter, the titanium source presoma dosage is with TiO2Meter, WO3And TiO2Mass ratio is preferably 0.5~2.0:100.

The preparation method of denitrating catalyst of the present invention, wherein slurry water content is preferably in the step (5) 25~40%.

The preparation method of denitrating catalyst of the present invention, wherein the titanium source presoma dosage is with TiO2Meter, it is described The additional amount of polyethylene glycol oxide in step (5), with and TiO2Mass ratio indicate be preferably 0.3~1.0:100.

The preparation method of denitrating catalyst of the present invention, wherein maturing temperature in the step (4) and step (5) Both preferably 400~650 DEG C, calcining time is both preferably 4~10h.

It is prepared by the preparation method of above-mentioned denitrating catalyst the present invention also provides a kind of denitrating catalyst.

Beneficial effects of the present invention:

(1) using the method mixed in situ, titanium atom and tungsten atom is mixed in molecule rank, causes subsequent co-precipitation The crystal generated in the process, lattice defect is more, and mixed-metal oxides partial size is small and uniform, and specific surface is big, improves simultaneously Titanium dioxide crystal turns brilliant temperature, conducive to the performance of catalytic activity；

(2) mixed method is assisted using ultrasonic wave, keeps the mixing of various materials atomic level more uniform；

(3) vanadium source addition when titanium dioxide-tungstic acid co-precipitation material does not roast, in titanium-tungsten particle surface penetration Deeper, connection is closer, and dispersion more evenly, it is more stable to be fired rear catalyst activity；

(4) the vanadium tungsten titanium powder material prepared covers one layer of tungstic acid into after once roasting excessively, and on its surface, simultaneously It joined polyethylene glycol oxide, possess catalyst particle surface also while there is the attachment of more tungsten oxides nanometer level microporous, both Barium oxide can be resisted in flue gas in its surface nonuniform deposition, and can guarantee high catalyst performance.

Specific embodiment

Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation Test method without specific conditions 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 limits It is set to titanyl sulfate or metatitanic acid, with TiO in titanium source precursor solution2Meter, titanium source presoma content are 15~40g/L.If small In 15g/L, then solution is too dilute, and the combination of other materials is more loose, and production efficiency is lower；If more than 40g/L, then due to dense Du Taigao and with the mixing intensity of other materials reduce, cause to merge bad.

Each material proportion in denitrating catalyst:

In the present invention, denitrating catalyst mainly includes titanium source presoma, tungsten source presoma, vanadium source presoma, ammonium metatungstate And polyethylene glycol oxide, respectively with TiO2、WO3、V2O5、WO3, polyethylene glycol oxide note, mass ratio be 100:2.0~5.0:0.5~ 2.0:0.5~2.0:0.3~1.0 will affect the dispersion of active material vanadium, lead to catalyst performance if tungsten source presoma is less It can be poor；If ammonium metatungstate is less, lead to that SO cannot be effectively reduced2/SO3Conversion ratio；It, can shadow if polyethylene glycol oxide amount is more Tungstic acid is rung in the absorption of particle surface, influences catalyst surface porosity if very little.

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, barium oxide contains in catalytic cracking spent catalyst Amount about 1%.Two kinds of powders 1:1 in mass ratio mixing, in air atmosphere, at 350 DEG C, mixing for 24 hours, screens out catalyst later Powder is evaluated.It, can be by waste acetic acid in fresh catalyst and waste acetic acid contact mixed process In active material vanadium it is non-uniform be transferred on fresh catalyst, lead to fresh catalyst surface reactive material barium oxide collection Middle accumulation causes catalyst Topically active to enhance, and then will increase the SO of catalyst2/SO3It is whole to reduce denitrating catalyst for conversion ratio Body performance.

NOxConversion ratio evaluation condition: air speed 4000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2For 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 measuring method: wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/ T998-2006)。

Following embodiment is illustrated to of the invention, and " % " described in embodiment and comparative example refers to that quality percentage contains Amount.

Embodiment 1:

It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g Ammonium salt solution forms and contains TiO2For 35g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 9.5, precipitating After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 620 DEG C；Powder after roasting Body is again and with WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 7.5g, and 4g polyethylene glycol oxide, stirring are added after stirring 40min, sealing and standing for 24 hours, drying, obtain denitrating catalyst after 620 DEG C of roasting 8h.Above-mentioned gained fresh catalyst and with catalysis Cracking vanadium-containing wasting catalyst 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, is added containing with WO3Count the para-tungstic acid of 22.5g Ammonium salt solution forms and contains TiO2For 35g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 2h and adjusts pH value to 10, precipitating After completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h and obtain denitration at 620 DEG C Catalyst；It above-mentioned gained fresh catalyst and evaluates, ties respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst Fruit is shown in Table 1 data.

Embodiment 2

It will contain with TiO2The titanyl sulfate of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3Count the para-tungstic acid of 22.5g Ammonium salt solution forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1.5h and adjusts pH value to 10, sinks After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 600 DEG C；Powder after roasting Body is again and with WO3Aqueous 35% slurry is made in the ammonium metatungstate solution of meter 5g, and 3.5g polyethylene glycol oxide, stirring are added after stirring Denitrating catalyst is obtained after 30min, sealing and standing 16h, drying, 600 DEG C of roastings.It above-mentioned gained fresh catalyst and is split with catalysis Change vanadium-containing wasting catalyst high temperature mixing 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, is added containing with WO3Count the para-tungstic acid of 22.5g Ammonium salt solution forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1.5h and adjusts pH value to 9.0 heavy After forming sediment completely, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 50% at moisture content again, is added with V2O5Meter The ammonium metavanadate solution of 4.5g, supersonic oscillations 1.5h while stirring after convection drying, roast 8h at 600 DEG C；Powder after roasting Body is again and with WO3Aqueous 35% slurry is made in the ammonium metatungstate solution of meter 5g, after stirring 30min, drying, 600 DEG C of roastings To denitrating catalyst.It above-mentioned gained fresh catalyst and is commented respectively with catalytic cracking vanadium-containing wasting catalyst high temperature mixing rear catalyst Valence the results are shown in Table 1 data.

Embodiment 3

It will contain with TiO2The metatitanic acid of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3The ammonium paratungstate for counting 20g is molten Liquid forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 9.5, precipitating is complete Afterwards, it is filtered, washed；Material after washing is spent into the slurry that ion water making is 45% at moisture content again, is added with V2O5Count the inclined of 5g Ammonium Vanadate Solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 550 DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 5g, and 3g polyethylene glycol oxide, stirring 30min, sealing are added after stirring Denitrating catalyst is obtained after standing 20h, drying, 550 DEG C of roastings.It above-mentioned gained fresh catalyst and urges with catalytic cracking containing vanadium is useless Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.

Comparative example 3

Technique used presses CN201110345605 embodiment 1, and metatitanic acid dust technology is dispersed mashing, is filtered to neutrality, It adds water for metatitanic acid to be beaten and disperse, metatitanic acid slurry is made.Ammonium tungstate, ammonium molybdate and vanadium are sequentially added in metatitanic acid slurry Sour ammonium, making the mass ratio of three kinds of ammonium salts and metatitanic acid is respectively 1/100,1/100 and 0.1/100, is then used mixed material super Sound wave mashing allows the ammonium salt of addition to dissolve, disperse, and so that ammonium salt is sufficiently adsorbed to metatitanic acid surface, extremely with nitre acid for adjusting pH value 5.0.It stands, dry, 300 DEG C of heat treatment 4h obtain catalyst.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking 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, is added containing with WO3The ammonium paratungstate for counting 15g is molten Liquid forms and contains TiO2For 20g/L mixed solution, ammonium hydroxide is gradually added after supersonic oscillations 1h, and to adjust pH value complete to 10.5 precipitatings Afterwards, it is filtered, washed；The slurry that moisture content is 40% is made with distilled water in material after washing again, is added with V2O5Count the inclined vanadium of 5g Acid ammonium solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 500 DEG C；Powder is again and with WO after roasting3 Aqueous 28% slurry is made in the ammonium metatungstate solution of meter 3.5g, and 2.5g polyethylene glycol oxide, stirring 40min, close are added after stirring Envelope obtains denitrating catalyst after standing 20h, drying, 500 DEG C of roastings.Above-mentioned gained fresh catalyst and useless containing vanadium with catalytic cracking Catalyst high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.

Comparative example 4

Technique used presses CN103143396 embodiment 1, a kind of honeycomb type flue gas denitration catalyst, with the raw material of parts by weight Through extrusion molding, be sintered: 83 parts of nano-titanium dioxide, 8.3 parts of nano silica, 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 crushed to 20~40 mesh and is evaluated.Above-mentioned gained fresh catalyst and It is 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 metatitanic acid of meter 500g is dissolved in sulfuric acid solution, is added containing with WO3The ammonium metatungstate for counting 20g is molten Liquid forms and contains TiO2For 30g/L mixed solution, it is gradually added ammonium hydroxide after supersonic oscillations 1h and adjusts pH value to 10.5, has precipitated Quan Hou is filtered, washed；The slurry that moisture content is 40% is made with distilled water in material after washing again, is added with V2O5Count the inclined of 4g Ammonium Vanadate Solution, supersonic oscillations 1h while stirring after convection drying, roast 6h at 550 DEG C；After roasting powder again with WO3Aqueous 30% slurry is made in the ammonium metatungstate solution of meter 5g, and 3g polyethylene glycol oxide, stirring 40min, sealing are added after stirring Denitrating catalyst is obtained after standing 20h, drying, 550 DEG C of roastings.It above-mentioned gained fresh catalyst and urges with catalytic cracking containing vanadium is useless Agent high temperature mixing rear catalyst is evaluated respectively, the results are shown in Table 1 data.

1 embodiment and comparative example of table evaluates data contrast table

Found by embodiment and comparative example: the denitrating catalyst that the resistance vanadium deposition of embodiment is uneven has good effect Fruit, it is preliminary by ultrasonic wave mixing in situ, so that the mixing rank of active material is reached molecule rank, is slightly evacuated through co-precipitation Nano particle, then introduce barium oxide in particle surface and shallow-layer, catalyst intermediate obtained after roasting, then in pore creating material Strengthen the co-catalyst for being introduced into and hindering barium oxide nonuniform deposition in gas phase under the action of (polyethylene glycol oxide) again, after roasting i.e. Obtain final catalyst, NO in evaluating catalystxConversion ratio when ammonia nitrogen ratio is 1, up to 99% or more, through containing with catalytic cracking After vanadium dead catalyst mixed processing, SO2/SO3Conversion ratio illustrates catalyst surface almost without increase almost without vanadium oxygen is generated The polycrystalline of compound deposits, and catalyst performance is excellent；In denitrating catalyst preparation method, if handling without second step, only retain the Vanadium tungsten titanium catalyst sample after primary roasting, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio slightly increases Add；If pore creating material is not added in second step processing, after catalytic cracking vanadium-containing wasting catalyst mixed processing, SO2/SO3Conversion ratio is also slightly There is increase.In short, fresh denitrating catalyst prepared by the present invention and treated when catalyst evaluates under the conditions of same, SO2/SO3 Conversion ratio is lower than other comparative examples, has the effect of barium oxide nonuniform deposition in good anti-flue gas.

Beneficial effects of the present invention:

(1) using the method mixed in situ, titanium atom and tungsten atom is mixed in molecule rank, causes subsequent co-precipitation The crystal generated in the process, lattice defect is more, and mixed-metal oxides partial size is small and uniform, and specific surface is big, improves simultaneously Titanium dioxide crystal turns brilliant temperature, conducive to the performance of catalytic activity.

(2) mixed method is assisted using ultrasonic wave, keeps the mixing of various materials atomic level more uniform.

(3) vanadium source addition when titanium dioxide-tungstic acid co-precipitation material does not roast, in titanium-tungsten particle surface penetration Deeper, connection is closer, and dispersion more evenly, it is more stable to be fired rear catalyst activity；

(4) the vanadium tungsten titanium powder material prepared covers one layer of tungstic acid into after once roasting excessively, and on its surface, simultaneously It joined polyethylene glycol oxide, possess catalyst particle surface also while there is the attachment of more tungsten oxides nanometer level microporous, both Barium oxide can be resisted in flue gas in its surface nonuniform deposition, and can guarantee high catalyst performance.

Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art It all should belong to the protection scope of the claims in the present invention.

Claims (9)

1. a kind of preparation method of denitrating catalyst, which is characterized in that this method comprises the following steps:
(1) titanium source presoma vitriolization is formed into solution, titanium source presoma is in the solution with TiO2Meter, content are 15~40g/ L；
(2) tungsten source presoma is soluble in water, and add it in the solution of step (1)；
(3) after to step (2) acquired solution supersonic oscillations, pH value to more than 9.0 is adjusted with ammonium hydroxide, is precipitated, is filtered, washing；
(4) deionized water is added in the filter cake obtained by step (3), is tuned into pulpous state, vanadium source precursor solution, supersonic oscillations are added Afterwards, it is directly dried, roasts, form powder；And
(5) by the powder of step (4) and ammonium metatungstate solution mixing pulp, after stirring, addition polymerization ethylene oxide, secondary agitation Afterwards, sealing and standing, drying, roasting form denitrating catalyst；
Wherein, titanium source presoma, tungsten source presoma, vanadium source presoma, ammonium metatungstate and polyethylene glycol oxide, respectively with TiO2、WO3、 V2O5、WO3With polyethylene glycol oxide meter, mass ratio is 100:2.0~5.0:0.5~2.0:0.5~2.0:0.3~1.0.
2. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the titanium source presoma is sulfuric acid Oxygen titanium or metatitanic acid.
3. the preparation method of denitrating catalyst according to claim 1, which is characterized in that tungsten source presoma is secondary tungsten Sour ammonium or ammonium metatungstate.
4. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the step (3) and step (4) The middle supersonic oscillations time is 0.5~3h, and mixing time is 10~60min in the step (5), in the step (5) The sealing and standing time is 8~30h.
5. the preparation method of denitrating catalyst according to claim 1, which is characterized in that in the precursor solution of the vanadium source Vanadium source presoma is ammonium metavanadate.
6. the preparation method of denitrating catalyst according to claim 1, which is characterized in that slurry in the step (4) Water content is 35~55%.
7. the preparation method of denitrating catalyst according to claim 1, which is characterized in that slurry in the step (5) Water content is 25~40%.
8. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the step (4) and step (5) Middle maturing temperature is 400~650 DEG C, and calcining time is 4~10h.
9. a kind of denitrating catalyst is prepared by the preparation method of the described in any item denitrating catalysts of claim 1 to 8.
CN201510923102.5A 2015-12-14 2015-12-14 A kind of denitrating catalyst and preparation method thereof CN106861673B (en)

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