CN107308969A - One kind reduction SO2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and preparation method thereof - Google Patents
One kind reduction SO2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and preparation method thereof Download PDFInfo
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- CN107308969A CN107308969A CN201710436267.9A CN201710436267A CN107308969A CN 107308969 A CN107308969 A CN 107308969A CN 201710436267 A CN201710436267 A CN 201710436267A CN 107308969 A CN107308969 A CN 107308969A
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Classifications
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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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/56—
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
SO is reduced the invention discloses one kind2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and preparation method thereof, and step is as follows：Titanium source presoma is dissolved in acid and forms solution；Tungsten source presoma, phosphorus source precursor, magnesium source precursor are dissolved to form solution respectively；Above solution is well mixed, regulation pH value to 7~12, is precipitated, and filtering then adds deionized water, rare earth precursor solution, after being well mixed, is directly dried, is calcined, grind to form powder；Extrusion aid, solution, the pore creating material of the formation of tungsten source presoma are added in powder, paste is added water into while stirring, nano silicon, glass fibre, binding agent is added, uniform mixing extrudes honeycomb fashion idiosome using extruder；Dried idiosome be first placed in silicon source precursor solution impregnate, it is fired after get product.Honeycomb fashion prepared by the present invention is without vanadium denitration catalyst, and to overcome, denitrating catalyst activated centre in flue gas is unbalanced in the prior art and active unstable defect.
Description
Technical field
SO is reduced the present invention relates to one kind2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and preparation method thereof, especially one
Uneven denitrating catalyst of resistance heavy metals of flue gases deposition and preparation method thereof is planted, the invention belongs to New Inorganic Materials technology
Field.
Background technology
Nitrogen oxides (NOx) it is one of main atmosphere pollution, emission request is increasingly strict.China《" 12 " are saved
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 the national environmental protection of in September, 2011 portion is promulgated《Fossil-fuel power plant atmospheric pollutant emission standard》Thermal power plant NOx is arranged
Put concentration and make more strict requirements：Newly-built the 3rd period, enlarging, the coal-burning boiler of reconstruction are provided, NOx highests allow discharge
Concentration is 100mg/m3.What national environmental protection portion was promulgated《Petroleum refining industry pollutant emission standard》It is required that：On July 1st, 2015
Rise, nitrogen oxides requirement is 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
With the mixing of molybdenum source presoma, it is placed in autoclave and carries out hydro-thermal reaction, be filtered, washed and dried and obtain titanium molybdenum powder denitration catalyst
Agent, while can also introduce the elements such as vanadium and molybdenum, prepares 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, and the performance to material can have a certain impact.
CN103143396B proposes a kind of preparation method of honeycomb type denitrification catalyst, by titanium dioxide, silica,
Active material and into paste, then adding additives, glass etc., last extrusion molding.This method technique is simple, but active material
Distribution it is bad, cause the denitration efficiency of catalyst relatively low.
In summary, the preparation of denitrating catalyst is directed to the mixing of Multimetal oxide, hybrid mode and preparation work
The difference of skill can not distinguish the denitration performance of catalyst, powder catalyst n O completelyxConversion ratio can reach more than 90%, and
Preformed catalyst activity has certain decline, and on the one hand the catalytic activity of explanation special metal oxide is higher, and scattered inequality is still
Higher NO can be obtainedxConversion ratio；On the other hand, shaping of catalyst process also results in catalyst activity reduction.Meanwhile, urge
The quality of agent overall performance also needs to be verified that the preparation of catalyst will also take into account industrial amplification from otherwise sign
The factor such as operability.
The content of the invention
It is a primary object of the present invention to provide a kind of reduction SO2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and its preparation
Method, to overcome, denitrating catalyst activated centre in flue gas is unbalanced in the prior art and active unstable defect.
The object of the present invention is achieved like this, one kind reduction SO2Oxygenation efficiency honeycomb fashion is without vanadium denitration catalyst and its system
Preparation Method, it is characterised in that the method for preparing catalyst comprises the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) tungsten source presoma, phosphorus source precursor, magnesium source precursor are dissolved to form solution respectively, and mixed with the solution of (1)
Close uniform；
(3) well mixed rear solution ph, to 7~12, is precipitated obtained by regulating step (2), and filter cake is washed to obtain in filtering；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, add rare earth precursor solution, mixing is equal
After even, directly it is dried, is calcined, grinds to form powder；
(5) extrusion aid, solution, the pore creating material of the formation of tungsten source presoma are added in powder obtained by step (4), while stirring
Paste is added water into, and adjusts pH value to 7~12；
(6) nano silicon, glass fibre, binding agent are added in lotion obtained by step (5), stir mixing,
Honeycomb fashion idiosome is extruded using extruder；
(7) gained idiosome in step (6) dried, be then placed in silicon source precursor solution and impregnate, it is fired after produce
Finished product.
Titanium source presoma, tungsten source presoma, silicon source presoma, pore creating material, binding agent, extrusion aid are used in the present invention
It is that denitrating catalyst prepares conventional material in the prior art, consumption selects appropriate amount, the present invention also according to process characteristic
It is not any limitation as especially.The present invention also recommended preferred scheme.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (1)
Titanium source presoma is preferably titanyl sulfate or metatitanic acid, and the acid is preferably inorganic acid, and the solution of formation is with TiO2Meter, content is most
It is 15~40g/L well.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (2)
Tungsten source presoma is preferably ammonium metatungstate or ammonium tungstate, and tungsten source presoma is with WO3Meter, titanium source presoma is with TiO2Meter, step
(2) mass ratio of tungsten source presoma and titanium source presoma is preferably 2.0~5.0 in solution after gained is well mixed:100；Step
(5) tungsten source presoma used and titanium source forerunner's body mass ratio used in step (1) are preferably 0.5~2 in:100.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (2)
Before phosphorus source presoma is preferably the one or more in phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and triammonium phosphate, phosphorus source
Body is driven with P2O5Meter, titanium source presoma is with TiO2Meter, it is well mixed obtained by step (2) after in solution before phosphorus source presoma and titanium source
The mass ratio for driving body is preferably 0.1~1.5:100.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (2)
Magnesium source presoma is preferably the one or more in magnesia, magnesium hydroxide, magnesium nitrate and magnesium sulfate, magnesium source presoma with
MgO is counted, and titanium source presoma is with TiO2Meter, it is well mixed obtained by step (2) after magnesium source presoma and titanium source presoma in solution
Mass ratio is preferably 0.01~1.0:100；
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (2) and
The mode being well mixed in step (4) is using stirring, and the time is preferably 0.5~3h.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (3)
Regulation pH value medicament be preferably after ammoniacal liquor, regulation pH value be more than 9.0.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (4)
Grind to form powder, best 0.01~50 μm of powder granule particle diameter.
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, is preferably 30
~360min.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (5)
Extrusion aid is preferably stearic acid or glycerine, addition with TiO2The mass ratio of the titanium source presoma of meter respectively be preferably 0.01~
1.0:100。
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (5)
Pore creating material is preferably the one or more in polyethylene glycol oxide, polymethyl methacrylate, field fine powder, addition with TiO2Meter
Titanium source presoma mass ratio respectively be preferably 0.01~1.0:100.
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium catalyst for denitrating flue gas, the step
(4) middle rare earth presoma is preferably nitric acid rare earth, and rare earth element is lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium
(Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), one kind in lutetium (Lu) or
Several, the rare earth precursor is with Re2O3Meter, titanium source presoma is with TiO2It is dilute in meter, well mixed rear solution obtained by step (4)
The mass ratio of native source presoma and titanium source presoma is 0.1~10:100；
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, it is characterised in that institute
It is preferably 35~55% to state slurry water quality content in step (4).
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (5)
Paste water quality content is preferably 25~40%.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (6)
Nano silicon, glass fibre, binding agent addition with TiO2The mass ratio of the titanium source presoma of meter is preferably 0.1 respectively
~2.5:100th, 1~8:100th, 0.1~1.0:100, during wherein binding agent is preferably carboxymethyl cellulose or hydroxypropyl cellulose
One or two.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (7)
Silicon source precursor solution is the water or alcoholic solution of tetraethyl orthosilicate, and wherein tetraethyl orthosilicate mass content is preferably 3~15%,
Dip time is preferably 5~20s.
Reduction SO of the present invention2In preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (6)
The hole count for extruding honeycomb fashion idiosome section is preferably 3 × 3 holes to 40 × 40 holes, preferably 15 × 15 holes, 18 × 18 holes, 20 × 20
Hole, 21 × 21 holes, 22 × 22 holes, 25 × 25 holes, 30 × 30 holes.
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the step (4) and
Highest sintering temperature is preferably 400~650 DEG C in step (6), and roasting time is preferably 4~10h.
Reduction SO of the present invention2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, the inorganic acid is most
It is sulfuric acid or nitric acid well.
The acting as of binding agent of the present invention is bonded other materials, lotion is formed, beneficial to shaping of catalyst.
Pore creating material of the present invention, leaves in catalyst matrix micro- by the use of its own molecular structure as template, after roasting
Hole, increases the microcellular structure of catalyst.
Extrusion aid of the present invention, using its lubrication to catalyst substrates, improved catalysts extrusion molding performance,
Molding materials are made not glue wall.
Present invention also offers above-mentioned reduction SO2Prepared by preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst urges
Agent, its physical index and composition are preferably：40~120m of specific surface area2/ g, by weight percentage, wherein containing titanium dioxide
For 80~90%, containing tungstic acid 1~10%, containing Re2O30.1~10%, containing phosphorus pentoxide 0.1%~2%, containing magnesia
0.01%~1.5%, containing silica 0.1%~5%, containing alundum (Al2O3) 0.1%~5%.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom, tungsten atom, phosphorus atoms and magnesium atom is made to be mixed in atomic level,
The crystal produced in follow-up coprecipitation process is caused, lattice defect is more, mixed-metal oxides particle diameter is small and homogeneous, compare surface
Greatly, while turn brilliant temperature of titanium dioxide crystal is improved, beneficial to the performance of catalytic activity；
(2) rare earth source is added when titanium dioxide-tungstic acid-phosphorus pentoxide-magnesia co-precipitation material is not calcined,
Permeate deeper in particle surface, connect closer, disperse evenly, fired rear catalyst activity is more preferably；
(3) magnesium oxide is introduced, prioritizing selection can react, reduce with the sulfur dioxide in atmosphere in mixed oxide
The sulfur dioxide chance close to active material, reduces the oxidation of sulfur dioxide.
(4) using phosphorous oxides in the deposition of catalyst microparticle surfaces, increase catalyst surface acidity improves catalyst
Low temperature active.
(5) the catalyst powder material prepared entered after roasting, and covered one layer of tungstic acid on its surface, added simultaneously
Pore-creating auxiliary agent, also possesses nanometer level microporous while making catalyst particle surface that there are more tungsten oxides to adhere to, can both support
Anti- heavy metals of flue gases oxide can ensure high catalyst performance again in its surface nonuniform deposition.
(6) gap of titanium dioxide matrix particle is filled using nanometer silicon dioxide particle, increases the cause of catalyst matrix
Density, and then increase the intensity of calcined catalyst.
(7) using pore creating material, binding agent, the auxiliary agent such as glass fibre by catalyst preparation into excellent activity and intensity
Cellular catalyst, beneficial to its modularization assembling and the long-period stable operation on industrial denitrification apparatus.
(8) non-calcined catalyst idiosome is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of porous, inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas contact can also be hindered to urge
The activated centre of agent layer, reduces SO2Oxygenation efficiency.
(9) use baking modes to be calcined for echelon, can so make moisture and organic principle in catalyst matrix etc. by
Step release, reduces the stress concentration in catalyst roasting process, increases yield rate.
Embodiment
Embodiments of the invention are elaborated below：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 unreceipted actual conditions in example, generally 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, generally limit
It is set in titanyl sulfate or metatitanic acid, titanium source precursor solution with TiO2Meter, titanium source presoma content is 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 relatively low；If more than 40g/L, due to dense
Du Taigao and reduced with the mixing intensities of other materials, cause fusion bad.
Each material proportion in denitrating catalyst：
In the present invention, denitrating catalyst mainly include titanium source presoma, tungsten source presoma, rare earth source presoma, pore creating material,
Binding agent etc., if tungsten source presoma is less, can influence the scattered and catalyst activity stability of main active material, cause catalysis
Agent poor-performing；If rare earth source presoma is less, the Activity and stabill of main active material can be influenceed, causes catalyst performance
It is poor；If pore-creating dosage is more, tungstic acid can be influenceed in the absorption of catalyst particle surface, catalyst pores are influenceed if very little
Gap rate；Binding agent is less, can influence shaping of catalyst, and shaping of catalyst intensity is then influenceed too much；Glass fibre can make to urge too much
Agent is difficult to be molded, and then reduces catalyst strength very little.
Preformed catalyst sample and dust (dust that catalytic cracking flue gas dust or other flues can be made) in flue
Hybrid technique：In air atmosphere, at 350 DEG C, circulation is passed through 40~60 mesh in flue in the fresh catalyst duct of preparation
Heavy metallic oxide content about 1% in dust 24h, catalytic cracking chimney flue dust, takes out catalyst and is evaluated afterwards.It is fresh to urge
Heavy metal in dust with that in flue dust contact process, can be transferred on fresh catalyst, cause fresh catalyst by agent
Surface-active declines, and reduces denitrating catalyst overall performance.
Stationary state NOxConversion ratio appreciation condition：Air speed 5000h-1, 350 DEG C of reaction temperature, air inlet NOxFor 600mg/Nm3、SO2
For 1000mg/Nm3, ammonia nitrogen ratio be that 1, water content is 10%.
NOx、SO2Method for measurement of concentration：Flue gas continuous on-line analysis instrument, Siemens ULTRAMAT23.
The escaping of ammonia assay method：Public places sanitary method of inspection part 2：Chemical pollutant (GBT 18204.2-
2014) indigo spectrophotometry specified in.Change ammonia nitrogen ratio, control outlet NOxConcentration is in 40~50mg/Nm3When measure ammonia
Escape.
SO2/SO3Conversion ratio assay method：Wet desulfurization of flue gas by limestone-gypsum method device performance acceptance test specification (DL/
T998-2006)。
Following examples are that the present invention is illustrated, and " % " described in embodiment and comparative example refers to quality percentage and contained
Amount.
Embodiment 1：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Count 22.5g metatungstic acid
Ammonium, with P2O54.5g phosphoric acid, the magnesium nitrate solution of the 4.5g in terms of MgO is counted, is formed and contains TiO2For 35g/L mixed solutions, 2h is stirred
After be gradually added ammoniacal liquor and adjust pH value to 9.5, precipitation completely after, filtering, washing；Again by material after washing spend ion water making into
Moisture content is 50% slurry, is added with CeO230g cerous nitrate solution is counted, 1.5h is stirred, dries, be calcined 8h at 620 DEG C, then
Grind to form less than 20 μm powders of particle diameter；Powder again with WO3Count 7.5g ammonium metatungstate, 4g stearic acid, 3g polyethylene glycol oxides and
Aqueous 30% lotion is made in deionized water, adjusts pH value to 8.5 with ammoniacal liquor, 5g nano silicons, 17.5g are added after stirring
Glass fibre, 4g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, utilize the hole honeybee of extruder for shaping 6 × 6 afterwards
Socket catalyst idiosome；Obtained after 15s in the ethanol solution containing tetraethyl orthosilicate 10%, 620 DEG C of roasting 8h are inserted after idiosome drying
To honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst with commenting respectively after catalytic cracking flue dust containing heavy metal high temperature contact
Valency, the results are shown in Table 1 data.
Comparative example 1：
Impregnated not in the ethanol solution of tetraethyl orthosilicate, remaining is same as Example 1, will contain with TiO2Count 500g's
Titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Count 22.5g ammonium metatungstate, with P2O5Count 4.5g phosphoric acid, with MgO
4.5g magnesium nitrate solution is counted, is formed and contains TiO2For 35g/L mixed solutions, be gradually added after stirring 2h ammoniacal liquor adjust pH value to
9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added
With CeO230g cerous nitrate solution is counted, 1.5h is stirred, dries, 8h is calcined at 620 DEG C, then grind to form less than 20 μm powders of particle diameter；
Powder again with WO3Aqueous 30% cream is made in meter 7.5g ammonium metatungstate, 4g stearic acid, 3g polyethylene glycol oxides and deionized water
Body, with ammoniacal liquor adjust pH value to 8.5, after stirring add nano silicon (final dioxide-containing silica is same as Example 1),
17.5g glass fibres, 4g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, utilize extruder for shaping 6 × 6 afterwards
Hole cellular catalyst idiosome；After idiosome drying, honeycomb type denitrification catalyst is obtained after 620 DEG C of roasting 8h.Above-mentioned gained is fresh
Catalyst the results are shown in Table 1 data with being evaluated respectively after catalytic cracking flue dust containing heavy metal high temperature contact.
Embodiment 2
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Count 22.5g metatungstic acid
Ammonium, with P2O54.0g phosphoric acid, the magnesium nitrate solution of the 4.0g in terms of MgO is counted, is formed and contains TiO2For 30g/L mixed solutions, stirring
Ammoniacal liquor is gradually added after 1.5h and adjusts pH value to 10, after precipitation is complete, filtering, washing；Again by material deionized water after washing
The slurry that moisture content is 50% is made, adds with CeO225g cerous nitrate solution is counted, 1.5h is stirred, dries, be calcined at 620 DEG C
8h, then grind to form less than 30 μm powders of particle diameter；Powder again with WO3Count 7.5g ammonium metatungstate, 3.5g stearic acid, 3.5g polyoxies
Aqueous 32% lotion is made in change ethene and deionized water, adjusts pH value to 8.0 with ammoniacal liquor, 4.5g nano-silicas are added after stirring
SiClx, 17.5g glass fibres, 4g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, are extruded into using extruder afterwards
The hole cellular catalyst idiosome of type 5 × 5；10s in the ethanol solution containing tetraethyl orthosilicate 5%, 620 DEG C of roastings are inserted after idiosome drying
Honeycomb type denitrification catalyst is obtained after burning 8h.After above-mentioned gained fresh catalyst and catalytic cracking flue dust containing heavy metal high temperature contact
Evaluate respectively, the results are shown in Table 1 data.
Comparative example 2
Pore creating material polyethylene glycol oxide is not added, remaining is same as Example 2, will contain with TiO2Count 500g titanyl sulfate
It is dissolved in sulfuric acid solution, adds and contain with WO3Count 22.5g ammonium metatungstate, with P2O5Count 4.0g phosphoric acid, the 4.0g in terms of MgO
Magnesium nitrate solution, forms and contains TiO2For 30g/L mixed solutions, stir and ammoniacal liquor regulation pH value is gradually added after 1.5h to 10, precipitation
After completely, filtering, washing；Material after washing is spent into ion water making into the slurry that moisture content is 50% again, added with CeO2Meter
25g cerous nitrate solution, stirs 1.5h, dries, 8h is calcined at 620 DEG C, then grind to form less than 30 μm powders of particle diameter；Powder again with
With WO3Meter 7.5g ammonium metatungstate, 3.5g stearic acid and deionized water be made aqueous 32% lotion, with ammoniacal liquor adjust pH value to
8.0,4.5g nano silicons, 17.5g glass fibres, 4g carboxymethyl celluloses are added after stirring, stirring 40min, sealing are quiet
24h is put, the hole cellular catalyst idiosome of extruder for shaping 5 × 5 is utilized afterwards；Inserted after idiosome drying containing tetraethyl orthosilicate
Honeycomb type denitrification catalyst, calcined catalyst matrix breakdown are obtained after 10s in 5% ethanol solution, 620 DEG C of roasting 8h.On
Gained fresh catalyst is stated with being evaluated respectively after catalytic cracking flue dust containing heavy metal high temperature contact, 1 data are the results are shown in Table.
Embodiment 3
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Meter 20g ammonium metatungstate,
With P2O53.5g phosphoric acid, the magnesium nitrate solution of the 3.5g in terms of MgO is counted, is formed and contains TiO2For 30g/L mixed solutions, 1.0h is stirred
After be gradually added ammoniacal liquor and adjust pH value to 9, precipitation completely after, filtering, washing；Again by material after washing spend ion water making into containing
Water rate is 45% slurry, is added with CeO220g cerous nitrate solution is counted, 1.0h is stirred, dries, be calcined 8h at 620 DEG C, then grind
Wear into less than 15 μm powders of particle diameter；Powder again with WO3Count 5g ammonium metatungstate, 3.0g stearic acid, 3.0g polyethylene glycol oxides and
Aqueous 28% lotion is made in deionized water, and pH value is adjusted to 8.2 with ammoniacal liquor, added after stirring 3.5g nano silicons,
22.5g glass fibres, 3g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, afterwards using extruder for shaping 20 ×
20 hole cellular catalyst idiosomes；6s in the ethanol solution containing tetraethyl orthosilicate 8%, 620 DEG C of roasting 8h are inserted after idiosome drying
After obtain honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst after catalytic cracking flue dust containing heavy metal high temperature contact with distinguishing
Evaluate, the results are shown in Table 1 data.
Comparative example 3
Technique used presses CN201110345605 embodiments 1, by the metatitanic acid scattered mashing of dust technology, filters to neutrality,
Add water metatitanic acid mashing is scattered, obtained metatitanic acid slurry.Ammonium tungstate, cerous nitrate, phosphorus are sequentially added in metatitanic acid slurry
The sour ammonium of hydrogen two and magnesium nitrate, make the mass ratio of four kinds of salt and metatitanic acid reach the situation of embodiment 3, make its composition identical, then will
Mixed material stirring to pulp allows the ammonium salt of addition to dissolve, disperseed, and ammonium salt is fully adsorbed to metatitanic acid surface, is adjusted with nitric acid
PH value is to 5.0.Stand, dry, 300 DEG C of heat treatment 4h are to obtain catalyst powder.Grind powder granulating footpath and be less than 15 μm of powders,
Aqueous 28% lotion is made with 3.0g stearic acid, 3.0g polyethylene glycol oxides and deionized water again, with ammoniacal liquor adjust pH value to
8.2,3.5g nano silicons, 22.5g glass fibres, 3g carboxymethyl celluloses are added after stirring, stirring 40min, sealing are quiet
24h is put, the hole cellular catalyst idiosome of extruder for shaping 20 × 20 is utilized afterwards；After idiosome drying, after 620 DEG C of roasting 8h
Obtain honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst with commenting respectively after catalytic cracking flue dust containing heavy metal high temperature contact
Valency, the results are shown in Table 1 data.
Embodiment 4
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Meter 15g ammonium metatungstate,
With P2O53g phosphoric acid, the magnesium nitrate solution of the 3g in terms of MgO is counted, is formed and contains TiO2For 30g/L mixed solutions, after stirring 1.0h by
Step adds ammoniacal liquor and adjusts pH value to 10.5, after precipitation is complete, filtering, washing；Again by material after washing spend ion water making into containing
Water rate is 40% slurry, is added with CeO217.5g cerous nitrate solution is counted, 1.0h is stirred, dries, be calcined 8h at 620 DEG C, then
Grind to form less than 10 μm powders of particle diameter；Powder again with WO3Count 3.5g ammonium metatungstate, 3.0g stearic acid, 3.5g polyoxyethylenes
Aqueous 32% lotion is made in alkene and deionized water, adjusts pH value to 8.2 with ammoniacal liquor, 2.5g nanometer titanium dioxides are added after stirring
Silicon, 15g glass fibres, 3.5g carboxymethyl celluloses, stirring 40min, sealing and standing 24h, utilize extruder for shaping afterwards
18 × 18 hole cellular catalyst idiosomes；5s in the ethanol solution containing tetraethyl orthosilicate 13%, 620 DEG C of roastings are inserted after idiosome drying
Honeycomb type denitrification catalyst is obtained after burning 8h.After above-mentioned gained fresh catalyst and catalytic cracking flue dust containing heavy metal high temperature contact
Evaluate 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
18 × 18 hole cellular catalysts of extruded shaping, sintering are formed：Nano titanium oxide, nano silicon, ammonium metatungstate, nitre
Sour cerium, diammonium hydrogen phosphate and magnesium nitrate, glass fibre, extrusion aid, cellulose, polyethylene glycol oxide, sesbania powder.Catalyst activity is matched somebody with somebody
Side reaches the situation of embodiment 4, makes its composition identical.Above-mentioned gained fresh catalyst and with catalytic cracking vanadium-containing wasting catalyst (LDR
Series) high temperature mixing rear catalyst evaluates respectively, the results are shown in Table 1 data.
Embodiment 5：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Meter 10g ammonium metatungstate,
With P2O51.5g phosphoric acid, the magnesium nitrate solution of the 1.5g in terms of MgO is counted, is formed and contains TiO2For 35g/L mixed solutions, stir after 2h
It is gradually added ammoniacal liquor and adjusts pH value to 9.5, after precipitation is complete, filtering, washing；Again by material after washing spend ion water making into containing
Water rate is 50% slurry, is added with CeO210g cerous nitrate solution is counted, 1.5h is stirred, dries, be calcined 8h at 620 DEG C, then grind
Wear into less than 20 μm powders of particle diameter；Powder again with WO3Count 2.5g ammonium metatungstate, 4g stearic acid, 3g poly-methyl methacrylates
Aqueous 30% lotion is made in ester and deionized water, and pH value is adjusted to 8.5 with ammoniacal liquor, added after stirring 4g nano silicons,
17.5g glass fibres, 4g hydroxypropyl celluloses, stirring 40min, sealing and standing 24h, afterwards using extruder for shaping 25 ×
25 hole cellular catalyst idiosomes；15s in the ethanol solution containing tetraethyl orthosilicate 3%, 620 DEG C of roasting 8h are inserted after idiosome drying
After obtain honeycomb type denitrification catalyst.Above-mentioned gained fresh catalyst after catalytic cracking flue dust containing heavy metal high temperature contact with distinguishing
Evaluate, the results are shown in Table 1 data.
Embodiment 6：
It will contain with TiO2Meter 500g titanyl sulfate is dissolved in sulfuric acid solution, is added and is contained with WO3Meter 25g ammonium metatungstate,
With P2O55g phosphoric acid, the magnesium nitrate solution of the 5g in terms of MgO is counted, is formed and contains TiO2For 35g/L mixed solutions, stir after 2h progressively
Add ammoniacal liquor and adjust pH value to 9.5, after precipitation is complete, filtering, washing；Material after washing is spent into ion water making into moisture content again
For 50% slurry, add with CeO250g cerous nitrate solution is counted, 1.5h is stirred, dries, be calcined 8h at 620 DEG C, then grind to form
Particle diameter is less than 15 μm of powders；Powder again with WO3Count 10g ammonium metatungstate, 4g glycerine, 3g polyethylene glycol oxides and deionized water system
Into aqueous 30% lotion, pH value is adjusted to 8.5 with ammoniacal liquor, added after stirring 4g nano silicons, 17.5g glass fibres,
4g carboxymethyl celluloses, stirring 40min, sealing and standing 24h are catalyzed using the hole honeycomb fashion of extruder for shaping 25 × 25 afterwards
Agent idiosome；10s in the ethanol solution containing tetraethyl orthosilicate 8% is inserted after idiosome drying, and obtaining honeycomb fashion after 620 DEG C of roasting 8h takes off
Denox catalyst.Above-mentioned gained fresh catalyst the results are shown in Table 1 with being evaluated respectively after catalytic cracking flue dust containing heavy metal high temperature contact
Data.
The embodiment of table 1 and comparative example evaluating data contrast table
Found by embodiment and comparative example：The denitrating catalyst of the resistance heavy metal deposition of embodiment has good effect
Really, it is preliminary the mixing rank of active material is reached molecule rank by mixing in situ, through being co-precipitated the nanometer slightly evacuated
Particle, then rare earth oxide is introduced in particle surface and shallow-layer, catalyst intermediate is obtained after roasting, is ground to form after powder,
Strengthen the co-catalyst for being introduced into and hindering that heavy metallic oxide is deposited in gas phase in the presence of pore-creating auxiliary agent again, in nanometer titanium dioxide
NO in formed honeycomb shape denitrating catalyst, evaluating catalyst under the auxiliary of the materials such as silicon, binding agent, structural promoterxConversion ratio
When ammonia nitrogen ratio is 1, up to more than 94%, and catalyst sulfur dioxide/sulphur trioxide conversion rate is relatively low, through containing with catalytic cracking
After heavy metal dusts mixed processing, catalyst activity does not almost weaken, and illustrates that catalyst performance is excellent；It is prepared by denitrating catalyst
In method, if being handled without (5) step, vanadium tungsten titanium catalyst sample after a reservation is calcined for the first time gives up containing vanadium through catalytic cracking and urged
After agent (LDR series) mixed processing, SO2/SO3Conversion ratio has increased slightly；If pore creating material is not added with the processing of (5) step, through catalysis
After cracking vanadium-containing wasting catalyst (LDR series) mixed processing, SO2/SO3Conversion ratio also has increased slightly；If without the leaching of silicon source presoma
Stain step, the SO of catalyst2/SO3Conversion ratio is higher.In a word, the catalysis after the fresh denitrating catalyst for preparing of the present invention and processing
Agent with the conditions of when evaluating, SO2/SO3Conversion ratio is lower than other comparative examples, with good catalytic activity.
Beneficial effects of the present invention：
(1) using the method for mixing in situ, titanium atom, tungsten atom, phosphorus atoms and magnesium atom is made to be mixed in atomic level,
The crystal produced in follow-up coprecipitation process is caused, lattice defect is more, mixed-metal oxides particle diameter is small and homogeneous, compare surface
Greatly, while turn brilliant temperature of titanium dioxide crystal is improved, beneficial to the performance of catalytic activity；
(2) rare earth source is added when titanium dioxide-tungstic acid-phosphorus pentoxide-magnesia co-precipitation material is not calcined,
Permeate deeper in particle surface, connect closer, disperse evenly, fired rear catalyst activity is more preferably；
(3) magnesium oxide is introduced, prioritizing selection can react, reduce with the sulfur dioxide in atmosphere in mixed oxide
The sulfur dioxide chance close to active material, reduces the oxidation of sulfur dioxide.
(4) using phosphorous oxides in the deposition of catalyst microparticle surfaces, increase catalyst surface acidity improves catalyst
Low temperature active.
(5) the catalyst powder material prepared entered after roasting, and covered one layer of tungstic acid on its surface, added simultaneously
Pore-creating auxiliary agent, also possesses nanometer level microporous while making catalyst particle surface that there are more tungsten oxides to adhere to, can both support
Anti- heavy metals of flue gases oxide can ensure high catalyst performance again in its surface nonuniform deposition.
(6) gap of titanium dioxide matrix particle is filled using nanometer silicon dioxide particle, increases the cause of catalyst matrix
Density, and then increase the intensity of calcined catalyst.
(7) using pore creating material, binding agent, the auxiliary agent such as glass fibre by catalyst preparation into excellent activity and intensity
Cellular catalyst, beneficial to its modularization assembling and the long-period stable operation on industrial denitrification apparatus.
(8) non-calcined catalyst idiosome is impregnated using silicon source precursor solution, calcined catalyst surface can be attached
One layer of porous, inorganic silicon, the water repelling property of catalyst can be increased, while sulfur dioxide in flue gas contact can also be hindered to urge
The activated centre of agent layer, reduces SO2Oxygenation efficiency.
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)
1. one kind reduction SO2Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst, it is characterised in that the catalyst preparation
Method comprises the following steps：
(1) titanium source presoma is dissolved in acid and forms solution；
(2) tungsten source presoma, phosphorus source precursor, magnesium source precursor are dissolved to form solution respectively, and mixed with the solution of (1)
It is even；
(3) well mixed rear solution ph, to 7~12, is precipitated obtained by regulating step (2), and filter cake is washed to obtain in filtering；
(4) deionized water is added in filter cake obtained by step (3), is tuned into pulpous state, add rare earth precursor solution, be well mixed
Afterwards, directly it is dried, is calcined, grinds to form powder；
(5) extrusion aid, solution, the pore creating material of the formation of tungsten source presoma are added in powder obtained by step (4), is added water while stirring
With into paste, and pH value is adjusted to 7~12；
(6) nano silicon, glass fibre, binding agent are added in lotion obtained by step (5), stir mixing, utilized
Extruder extrudes honeycomb fashion idiosome；
(7) gained idiosome in step (6) is dried, is then placed in silicon source precursor solution and impregnates, it is fired after get product.
2. preparation method according to claim 1, it is characterised in that tungsten source presoma is with WO in the step (2)3Meter, titanium
Source presoma is with TiO2The mass ratio of tungsten source presoma and titanium source presoma is in meter, well mixed rear solution obtained by step (2)
2.0~5.0:100；Tungsten source presoma used and titanium source forerunner body mass ratio used in step (1) are 0.5~2 in step (5):
100；Phosphorus source presoma is with P in the step (2)2O5Meter, titanium source presoma is with TiO2Meter, it is molten after step (2) gained is well mixed
The mass ratio of phosphorus source presoma and titanium source presoma is 0.1~1.5 in liquid:100；Magnesium source presoma is with MgO in the step (2)
Meter, titanium source presoma is with TiO2The quality of magnesium source presoma and titanium source presoma in meter, well mixed rear solution obtained by step (2)
Than for 0.01~1.0:100.
3. preparation method according to claim 1, it is characterised in that silicon source presoma dip time in the step (7)
For 5~20s.
4. preparation method according to claim 1, it is characterised in that pore creating material is polyethylene glycol oxide, polymethylacrylic acid
One or more in methyl esters, sesbania powder.
5. preparation method according to claim 1, it is characterised in that step (4) the middle rare earth presoma is that nitric acid is dilute
Soil, the rare earth precursor is with Re2O3Meter, titanium source presoma is with TiO2Meter, well mixed rear solution middle rare earth obtained by step (4)
The mass ratio of source presoma and titanium source presoma is 0.1~10:100.
6. preparation method according to claim 1, it is characterised in that nano silicon, glass fibers in the step (6)
Dimension, binding agent addition with TiO2The mass ratio of the titanium source presoma of meter is respectively 0.1~2.5:100th, 1~8:100、0.1
~1.0:100.
7. preparation method according to claim 1, it is characterised in that sintering temperature is equal in the step (4) and step (7)
For 400~650 DEG C, roasting time is 4~40h.
8. preparation method according to claim 1, it is characterised in that in the step (5) extrusion aid addition with TiO2
The mass ratio of the titanium source presoma of meter is respectively 0.01~1.0:100.
9. preparation method according to claim 1, it is characterised in that in the step (5) pore creating material addition with TiO2
The mass ratio of the titanium source presoma of meter is respectively 0.01~1.0:100.
10. the reduction SO described in a kind of any one of claim 1 to 92Preparation method of the oxygenation efficiency honeycomb fashion without vanadium denitration catalyst
The catalyst of preparation, it is characterised in that the catalyst is 40~120m of specific surface area2/ g, by weight percentage, wherein containing two
Titanium oxide is 80~90%, containing tungstic acid 1~10%, containing Re2O30.1~10%, containing phosphorus pentoxide 0.1%~2%, contain
Magnesia 0.01%~1.5%, containing silica 0.1%~5%, containing alundum (Al2O3) 0.1%~5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999790A (en) * | 2019-04-04 | 2019-07-12 | 山东东源新材料科技有限公司 | A kind of low-temperature denitration is without vanadium rare-earth base catalyst and preparation method thereof |
| CN111939950A (en) * | 2019-05-16 | 2020-11-17 | 新淳(上海)环保科技有限公司 | Denitration catalyst for circulating fluidized bed boiler and preparation method thereof |
| CN113117742A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Low-temperature denitration molded catalyst and preparation method thereof |
-
2017
- 2017-06-09 CN CN201710436267.9A patent/CN107308969A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109999790A (en) * | 2019-04-04 | 2019-07-12 | 山东东源新材料科技有限公司 | A kind of low-temperature denitration is without vanadium rare-earth base catalyst and preparation method thereof |
| CN111939950A (en) * | 2019-05-16 | 2020-11-17 | 新淳(上海)环保科技有限公司 | Denitration catalyst for circulating fluidized bed boiler and preparation method thereof |
| CN113117742A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Low-temperature denitration molded catalyst and preparation method thereof |
| CN113117742B (en) * | 2019-12-31 | 2024-02-06 | 中国石油化工股份有限公司 | Low-temperature denitration forming catalyst and preparation method thereof |
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