CN108246283A - A kind of denitrating catalyst and preparation method thereof - Google Patents
A kind of denitrating catalyst and preparation method thereof Download PDFInfo
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- CN108246283A CN108246283A CN201810150394.7A CN201810150394A CN108246283A CN 108246283 A CN108246283 A CN 108246283A CN 201810150394 A CN201810150394 A CN 201810150394A CN 108246283 A CN108246283 A CN 108246283A
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- 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
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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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- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
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- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20769—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/0283—Flue gases
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Abstract
The present invention relates to gas denitrifying technology field, more particularly, to a kind of denitrating catalyst and preparation method thereof.The preparation method of the denitrating catalyst, includes the following steps：(a) vanadium-containing compound is dissolved in solvent, is concentrated to give the concentrate of vanadium-containing compound；(b) concentrate of the mixed solution of carrier, Tungstenic compound and molybdate compound, vanadium-containing compound is uniformly mixed, mediates, is molded, calcines, obtain the denitrating catalyst.The activity load for the denitrating catalyst that the present invention is prepared is high, can be prepared the high catalyst prod of content of vanadium, and the load capacity of vanadium coordinates other active components, make the temperature range of 160 400 DEG C of ranges of denitrating catalyst applicable for temperature up to 8% 10%.
Description
Technical field
The present invention relates to gas denitrifying technology field, more particularly, to a kind of denitrating catalyst and preparation method thereof.
Background technology
Nitrogen oxides (NOX) it is a kind of atmosphere pollution with high risks.NO in airXAlmost there is more than half
It is as produced by man-made pollution source, is mainly derived from production, fossil fuels such as coal, oil, natural gas used in life
Burning is one of noxious material in the industry such as electric power, chemistry, national defence and the equipment such as boiler and internal combustion engine institute discharge gas.
NOXIt is most with quantity caused by fuel combustion process, account for about 30%, wherein about 70% derives from the direct burning of coal.Greatly
NO in gasXCertain injury can all be caused, such as form acid rain, photochemical fog to health and animals and plants existence, because
And it is badly in need of administering.But NOXWater solubility and reactivity it is poor, administer relatively difficult, technology requirement is high.
Include selective catalytic reduction (SCR) and selective non-catalytic reduction method (SNCR) in the prior art.Though SNCR
It is so simple for process, but temperature requirement is too high, and denitration efficiency is unsatisfactory.SCR is that industrial most widely used one kind takes off
Nitre technology, ideally removal efficiency is up to more than 90%.But for some special flue gases, since operating load is low or
Boiler characteristics itself so that denitrification apparatus inlet temperature is low, is unable to reach the requirement of conventional scr denitrating catalyst, removal efficiency
It is only capable of reaching about 65%, and catalyst life is short.
In view of this, it is special to propose the present invention.
Invention content
The first object of the present invention is to provide a kind of preparation method of denitrating catalyst, to solve to exist in the prior art
Denitrating catalyst temperature in use it is high, the problem of Applicable temperature narrow range, denitration removal efficiency is low, also, the preparation method work
Skill is simple, suitable for industrialization；Pass through the high conjunction with catalyst of activity load for the catalyst that the preparation method is prepared
Lattice rate is high, and greatly improves the physical strength and activity stability of catalyst.
The second object of the present invention is to provide a kind of denitrating catalyst, the activity load of the denitrating catalyst
Height, qualification rate is high, and microcosmic specific surface area is greatly improved, and catalytic activity is high, broad application temperature range；Also,
The physical strength of catalyst is high, and activity stability is good, long lifespan.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of denitrating catalyst, includes the following steps：
(a) vanadium-containing compound is dissolved in solvent, is concentrated to give the concentrate of vanadium-containing compound；
(b) concentrate of the mixed solution of carrier, Tungstenic compound and molybdate compound, vanadium-containing compound is mixed equal
It is even, it mediates, molding, calcine, obtain the denitrating catalyst.
In the prior art, in the catalyst for producing high content of vanadium, vanadium solubility is low, and vanadium precursor is unevenly distributed, production
The obtained microcosmic trepanning of catalyst is few, and active site is few, causes the qualification rate of catalyst that production obtains extremely low (less than 70%),
Catalytic activity is unstable, short life.
Then the present invention is concentrated, can uniformly be divided by the way that vanadium-containing compound is dissolved in solvent in advance again
The concentrate of scattered vanadium-containing compound, concentrate are uniformly mixed with carrier and other active components, make the catalyst being prepared
Middle content of vanadium is high, greatly improves the activity load of catalyst, while catalyst prod qualification rate is up to more than 95%.Gao Han
The vanadium of amount coordinates tungsten and molybdenum so that the catalyst can adapt to 160-400 DEG C of temperature range, under cryogenic still
Keep excellent catalytic activity.
Preferably, the solvent in the step (a) includes monoethanolamine.
Preferably, the solvent in the step (a) is the aqueous solution of monoethanolamine.It is furthermore preferred that the monoethanolamine
The mass fraction of monoethanolamine is 15-25%, preferably 18-22%, more preferably 20% in aqueous solution.
Preferably, the vanadium-containing compound includes one or both of ammonium metavanadate and vanadic anhydride.It is furthermore preferred that
The vanadium-containing compound is ammonium metavanadate.
Ammonium ion in ammonium metavanadate can interact with the amino of monoethanolamine in solvent, ensure that ammonium metavanadate exists
Stability in solution avoids ammonium metavanadate dispersion uneven, in the concentrate for being concentrated to give the higher ammonium metavanadate of concentration,
It is still able to ensure the dispersing uniformity and stability of ammonium metavanadate, so as to make active component in the catalyst prod being prepared
It is uniformly dispersed, improves catalyst activity stability.And it is possible to which the high catalyst prod of content of vanadium is prepared, cooperation is other
Active component widens the Acclimation temperature width of the denitrating catalyst, is applicable to the temperature range of 160-400 DEG C of range.
Content for vanadium in raising catalyst in the prior art, is directly mixed, but prepare using vanadic anhydride with carrier
Obtained catalyst activity dispersion is uneven, and specific surface area is low, and activity is low, and waste product is more, and product qualification rate is low.
Preferably, in the step (a) vanadium-containing compound using vanadium count with the mass ratio of solvent as (1-2) ﹕ 10, preferably
(1.5-2) ﹕ 10.
Preferably, in the step (a), vanadium-containing compound is dissolved in solvent, is warming up to 90-98 DEG C, stirring until
Solution is clarified, and is cooled to 75-80 DEG C, stirs distillation and concentration.It is furthermore preferred that the concentration rate is 0.5-0.9, preferably 0.7-
0.8。
Preferably, the mass ratio of tungsten and molybdenum is 1 ﹕ (1- in the mixed solution of the Tungstenic compound and molybdate compound
10).By adjusting the ratio of tungsten and molybdenum, the denitrating catalyst is made to be adapted to the denitration reaction of Different hypothermia.
Preferably, the Tungstenic compound includes ammonium metatungstate and ammonium paratungstate, preferably ammonium metatungstate.
Preferably, the molybdate compound includes ammonium heptamolybdate.
The dissolubility of ammonium metatungstate and ammonium heptamolybdate is good, and uniformity is good, and acid-base value is easily controllable, makes what is be prepared
The stability of catalyst is good.
Preferably, the mixed solution of the carrier, Tungstenic compound and molybdate compound is in terms of tungsten and molybdenum, vanadium-containing compound
Each parts by weight of the concentrate in terms of vanadium be respectively 58-68 parts, 3-4 parts, 4-9 parts.Preferably 60-65 parts, 3.2-3.8 parts,
5.5-8.4 part.
Preferably, the carrier includes one or more in titanium dioxide, cordierite and montmorillonite.It is furthermore preferred that institute
It states carrier and includes titanium dioxide and cordierite.It is further preferred that the mass ratio of the titanium dioxide and cordierite is (20-
22) ﹕ (1-3).
Preferably, the carrier passes through surface preparation.It is furthermore preferred that the surface preparation includes：By carrier impregnation
It is mixed in ammonium hydroxide.The mass ratio of the ammonium hydroxide and carrier is 1 ﹕ (3-7).It is further preferred that the mass fraction of the ammonium hydroxide
For 5%-25%, preferably 6%-12%.
The moisture retention of the carriers such as titanium dioxide is poor, after the processing of ammonium hydroxide impregnation surface, improves surface moisture retention, avoids out
It splits, neutralizes the polarity of carrier, make the infiltration of uniform moisture that can fully mix combination with other materials, improve in carrier surface
The physical strength of catalyst extends the service life.
Preferably, the calcination temperature is 430-600 DEG C, and the calcination time is 16-48h.
The present invention also provides the denitrating catalysts that a kind of preparation method of aforementioned denitrating catalyst is prepared.
Compared with prior art, beneficial effects of the present invention are：
(1) the activity load of the denitrating catalyst obtained by the preparation method of the present invention is high, and vanadium can be prepared and contain
High catalyst prod is measured, the load capacity of vanadium coordinates other active components, make denitrating catalyst applicable for temperature up to 8%-10%
The temperature range of 160-400 DEG C of range；
(2) the microcosmic specific surface area of denitrating catalyst of the invention is greatly improved, up to 90m2/g；
(3) physical strength of denitrating catalyst of the invention is high, transverse strength ＞ 1.5MPa, longitudinal strength ＞ 4.5MPa,
Catalyst stability is good.
Specific embodiment
Technical scheme of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiment is part of the embodiment of the present invention, instead of all the embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel all other embodiments obtained without making creative work belong to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, the condition suggested according to normal condition or manufacturer carry out.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
The present invention provides a kind of preparation methods of denitrating catalyst, include the following steps：
(a) vanadium-containing compound is dissolved in solvent, is concentrated to give the concentrate of vanadium-containing compound；
(b) concentrate of the mixed solution of carrier, Tungstenic compound and molybdate compound, vanadium-containing compound is mixed equal
It is even, it mediates, molding, calcine, obtain the denitrating catalyst.
In a preferred embodiment of the invention, the solvent in the step (a) includes monoethanolamine.
In a preferred embodiment of the invention, the solvent in the step (a) is the aqueous solution of monoethanolamine.More preferably
, in the aqueous solution of the monoethanolamine mass fraction of monoethanolamine be 15-25%, preferably 18-22%, more preferably
20%.
Monoethanolamine can coordinate with vanadium-containing compound, improve the dispersing uniformity and stability of vanadium-containing compound, improve
The uniformity for the catalyst being prepared, so as to improve denitration catalyst activity.
In a preferred embodiment of the invention, the vanadium-containing compound includes one in ammonium metavanadate and vanadic anhydride
Kind or two kinds.It is furthermore preferred that the vanadium-containing compound is ammonium metavanadate.
Ammonium ion in ammonium metavanadate can interact with the amino of monoethanolamine in solvent, ensure that ammonium metavanadate exists
Stability in solution avoids ammonium metavanadate dispersion uneven；In the concentrate for being concentrated to give the higher ammonium metavanadate of concentration,
It is still able to ensure the dispersing uniformity and stability of ammonium metavanadate, so as to make active component in the catalyst prod being prepared
It is uniformly dispersed, improves catalyst activity stability.And it is possible to which the high catalyst prod of content of vanadium is prepared, cooperation is other
Active component widens the Acclimation temperature width of the denitrating catalyst, is applicable to the temperature range of 160-400 DEG C of range.
In an of the invention preferred embodiment, in the step (a) vanadium-containing compound in terms of vanadium with the mass ratio of solvent
For (1-2) ﹕ 10, preferably (1.5-2) ﹕ 10.
In a preferred embodiment of the invention, in the step (a), vanadium-containing compound is dissolved in solvent, is heated up
To 90-98 DEG C, stirring is cooled to 75-80 DEG C until solution clarification, stirs distillation and concentration.It is furthermore preferred that the concentration rate is
0.5-0.9, preferably 0.7-0.8.
In a preferred embodiment of the invention, the carrier includes one kind in titanium dioxide, cordierite and montmorillonite
It is or a variety of.It is furthermore preferred that the carrier includes titanium dioxide and cordierite.It is further preferred that the titanium dioxide and violet are green
The mass ratio of stone is (20-22) ﹕ (1-3).
Coordinated using titanium dioxide and cordierite, the physical strength of catalyst can be effectively improved, and work can be improved
Property the load capacity of the component and stability of permanent load, improve catalyst activity.
In a preferred embodiment of the invention, tungsten and molybdenum in the mixed solution of the Tungstenic compound and molybdate compound
Mass ratio be 1 ﹕ (1-10).
By adjusting the ratio of tungsten and molybdenum, the different denitrating catalyst of optimum activity reaction temperature can be obtained, is suitable for
Different reaction conditions.
In a preferred embodiment of the invention, the Tungstenic compound includes ammonium metatungstate and ammonium paratungstate, preferably
Ammonium metatungstate.
In a preferred embodiment of the invention, the molybdate compound includes ammonium heptamolybdate.
The dissolubility of ammonium metatungstate and ammonium heptamolybdate is good, and uniformity is good, and acid-base value is easily controllable, makes what is be prepared
The stability of catalyst is good.
In an of the invention preferred embodiment, the mixed solution of the carrier, Tungstenic compound and molybdate compound with
Tungsten and molybdenum meter, vanadium-containing compound each parts by weight of the concentrate in terms of vanadium be respectively 58-68 parts, 3-4 parts, 4-9 parts.Preferably
60-65 parts, 3.2-3.8 parts, 5.5-8.4 parts.
Within the above range, it can ensure that on carrier, no waste product generates uniform load to greatest extent for tungsten, molybdenum and vanadium,
Reduce cost.
In a preferred embodiment of the invention, the carrier passes through surface preparation.It is furthermore preferred that the surface is located in advance
Reason includes：Carrier impregnation is mixed in ammonium hydroxide.The mass ratio of the ammonium hydroxide and carrier is 1 ﹕ (3-7).It is further preferred that institute
The mass fraction for stating ammonium hydroxide is 8%-15%.
The moisture retention of the carriers such as titanium dioxide is poor, after the processing of ammonium hydroxide impregnation surface, improves surface moisture retention, avoids out
It splits, improves the physical strength of catalyst, extend the service life.
In a preferred embodiment of the invention, the calcination temperature is 430-600 DEG C, and the calcination time is 16-
48h。
The present invention also provides the denitrating catalysts that a kind of preparation method of aforementioned denitrating catalyst is prepared.
Embodiment 1
The preparation method of denitrating catalyst described in the present embodiment, includes the following steps：
(a) aqueous solution of monoethanolamine for being mixed to get 20g monoethanolamine and 80g deionized waters, adds in 23g thereto
Ammonium metavanadate is warming up to 95 ± 3 DEG C, and stirring 40-90min is until solution is clarified；Then temperature is reduced to 75-80 DEG C, is maintained
At a temperature of this, distillation and concentration is stirred, concentration rate 0.75 obtains the concentrate of vanadium-containing compound.
(b) 60g titanium dioxide and 9g cordierites are taken, is mixed with the ammonium hydroxide and 10g deionized waters that 5g mass fractions are 25%,
Carrier is pre-processed (or mix ammonium hydroxide and deionized water, it is mixed again with carrier after being made into the ammonium hydroxide of certain mass score
It closes)；
Prepare the mixed solution of Tungstenic compound and molybdate compound：Take 2.7g ammonium metatungstates and 3.1g ammonium heptamolybdates common
It adds in appropriate amount of deionized water, ammonium metatungstate and ammonium heptamolybdate is made all to dissolve, wherein in the mixed solution, Tungstenic compound
With the mass ratio of tungsten in molybdate compound (being counted using tungsten) and molybdenum (being counted using molybdenum) as 1 ﹕ 1；
The mixed solution of Tungstenic compound and molybdate compound is added in above-mentioned carrier and ammonia water mixture, is then added again
After the concentrate of the vanadium-containing compound obtained in the step of entering the 6.7g in terms of vanadium (a), carry out mixed at high speed and be placed in kneader
30min is mediated, is sieved by high density sieve, is then placed in drying chamber and dried in the shade using extruder for shaping.It is placed in 550 DEG C
Lower calcining obtains the denitrating catalyst for 24 hours.
Embodiment 2
The preparation method of denitrating catalyst described in the present embodiment, includes the following steps：
(a) aqueous solution of monoethanolamine for being mixed to get 25g monoethanolamine and 75g deionized waters, adds in 46g thereto
Ammonium metavanadate is warming up to 93 ± 3 DEG C, and stirring 40-90min is until solution is clarified；Then temperature is reduced to 75-80 DEG C, is maintained
At a temperature of this, distillation and concentration is stirred, concentration rate 0.9 obtains the concentrate of vanadium-containing compound.
(b) 60g titanium dioxide and 9g cordierites are taken, is mixed with the ammonium hydroxide and 10g deionized waters that 5g mass fractions are 25%,
Carrier is pre-processed (or mix ammonium hydroxide and deionized water, it is mixed again with carrier after being made into the ammonium hydroxide of certain mass score
It closes)；
Prepare the mixed solution of Tungstenic compound and molybdate compound：Take 2.7g ammonium metatungstates and 3.1g ammonium heptamolybdates common
It adds in appropriate amount of deionized water, ammonium metatungstate and ammonium heptamolybdate is made all to dissolve, wherein in the mixed solution, Tungstenic compound
With the mass ratio of tungsten in molybdate compound (being counted using tungsten) and molybdenum (being counted using molybdenum) as 1 ﹕ 1；
The mixed solution of Tungstenic compound and molybdate compound is added in above-mentioned carrier and ammonia water mixture, is then added again
After the concentrate of the vanadium-containing compound obtained in the step of entering the 9g in terms of vanadium (a), progress mixed at high speed, which is placed in kneader, pinches
30min is closed, is sieved by high density sieve, is then placed in drying chamber and dried in the shade using extruder for shaping.It is placed at 500 DEG C
Calcining obtains the denitrating catalyst for 24 hours.
Embodiment 3
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the Tungstenic compound
It is 1 ﹕ 3 with the mass ratio of tungsten and molybdenum in the mixed solution of molybdate compound.
Embodiment 4
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the Tungstenic compound
It is 1 ﹕ 5 with the mass ratio of tungsten and molybdenum in the mixed solution of molybdate compound.
Embodiment 5
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the Tungstenic compound
It is 1 ﹕ 7 with the mass ratio of tungsten and molybdenum in the mixed solution of molybdate compound.
Embodiment 6
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the Tungstenic compound
It is 1 ﹕ 10 with the mass ratio of tungsten and molybdenum in the mixed solution of molybdate compound.
Embodiment 7
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the carrier, tungstenic
The mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound each parts by weight in terms of vanadium point
It Wei not be 58 parts, 3 parts, 4 parts.
Embodiment 8
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the carrier, tungstenic
The mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound each parts by weight in terms of vanadium point
It Wei not be 68 parts, 4 parts, 9 parts.
Embodiment 9
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the carrier, tungstenic
The mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound each parts by weight in terms of vanadium point
It Wei not be 60 parts, 3.2 parts, 5.5 parts.
Embodiment 10
The preparation method of the present embodiment reference implementation example 1, differs only in：In the step (b), the carrier, tungstenic
The mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound each parts by weight in terms of vanadium point
It Wei not be 65 parts, 3.8 parts, 8.4 parts.
Embodiment 11
The preparation method of the present embodiment reference implementation example 1, differs only in：Carrier is pre- without surface in the step (b)
Processing.
Embodiment 12
The preparation method of the present embodiment reference implementation example 1, step (b) the carrier total amount is constant, differs only in：Carrier
For the titanium dioxide and cordierite that mass ratio is 22 ﹕ 1.
Embodiment 13
The preparation method of the present embodiment reference implementation example 1, step (b) the carrier total amount is constant, differs only in：It is described
Carrier is only titanium dioxide.
Embodiment 14
The preparation method of the present embodiment reference implementation example 1, step (b) the carrier total amount is constant, differs only in：It is described
Carrier is the titanium dioxide and montmorillonite that mass ratio is 20 ﹕ 3.
Embodiment 15
The preparation method of the present embodiment reference implementation example 1, differs only in：The calcination temperature is 430 DEG C, the calcining
Time is 48h.
Embodiment 16
The preparation method of the present embodiment reference implementation example 1, differs only in：The calcination temperature is 600 DEG C, the calcining
Time is 16h.
Embodiment 17
The preparation method of the present embodiment reference implementation example 1, differs only in：Monoethanolamine is water-soluble in the step (a)
The mass fraction of monoethanolamine is 15% in liquid.
Embodiment 18
The preparation method of the present embodiment reference implementation example 1, differs only in：Ammonium metavanadate is in terms of vanadium in the step (a)
Mass ratio with solvent is 1.5 ﹕ 10.
Embodiment 19
The preparation method of the present embodiment reference implementation example 1, differs only in：Ammonium metavanadate is in terms of vanadium in the step (a)
Mass ratio with solvent is 1.8 ﹕ 10.
Embodiment 20
The preparation method of the present embodiment reference implementation example 1, differs only in：Vanadium-containing compound is five in the step (a)
V 2 O.
Embodiment 21
The preparation method of the present embodiment reference implementation example 1, differs only in：Dissolving vanadium-containing compound in the step (a)
Solvent be deionized water.
Embodiment 22
The preparation method of the present embodiment reference implementation example 1, differs only in：Concentration rate is 0.5 in the step (a).
Embodiment 23
The preparation method of the present embodiment reference implementation example 1, differs only in：Concentration rate is 0.7 in the step (a).
Embodiment 24
The preparation method of the present embodiment reference implementation example 1, differs only in：Concentration rate is 0.8 in the step (a).
Embodiment 25
The preparation method of the present embodiment reference implementation example 1, differs only in：The mass ratio of the ammonium hydroxide and carrier is 1 ﹕ 3,
The mass fraction of the ammonium hydroxide is 8%.
Embodiment 26
The preparation method of the present embodiment reference implementation example 1, differs only in：The mass ratio of the ammonium hydroxide and carrier is 1 ﹕ 7,
The mass fraction of the ammonium hydroxide is 15%.
Embodiment 27
Calcine technology described in the present embodiment drying and calcining in rotary furnace, temperature control point, installation air hose and wind in rotary furnace
The position of machine is specially：
Temperature control point is respectively in kiln body position and relevant temperature：(0m, 0 DEG C), (1m, 40 DEG C), (4.3m, 140 DEG C),
(7.7m, 180 DEG C), (10.8m, 180 DEG C), (15m, 360 DEG C), (17.7m, 450 DEG C), (20.7m, 550 DEG C), (22.8m, 550
DEG C), (24.35m, 550 DEG C), (27.5m, 550 DEG C), (30m, 500 DEG C), (31.5m, 440 DEG C), (32.8m, 360 DEG C),
(34.5m, 250 DEG C), (35.9m, 160 DEG C), (37.2m, 130 DEG C), (39m, 60 DEG C)；
Air hose is respectively in kiln body position：1.5m, 2.75m, 4m, 5.25m, 6.5m, 7.75m, 9m, 10.3m, 11.5m,
12.8m, 14m, 15.25m, 16.5m, 17.75m, 19m, 20.25m, 21.5m, 22.75m, 24m, 25.25m, 26.5m, 27.8m,
29m, 30.3m, 31.5m, 32.75m, 34m, 35.25m；
Wind turbine position and quantity are respectively：(13.5m, 1), (22.25m, 1), (27.5m, 2).
Pass through the calcine technology of above-mentioned process parameter control so that the uniformity of obtained denitrating catalyst is good, specific surface
Product is big, and micro-property is good, remote super existing catalyst.
Comparative example 1
The raw material dosage of 1 reference implementation example 1 of comparative example, difference lies in vanadium-containing compound uses vanadic anhydride, will contain
Vfanadium compound, Tungstenic compound and molybdate compound directly with carrier mixed-forming, obtain catalyst.
Comparative example 2
The raw material dosage of 2 reference implementation example 1 of comparative example, difference lies in do not add molybdate compound.Vanadium-containing compound is adopted
With vanadic anhydride, by vanadium-containing compound, Tungstenic compound directly with carrier mixed-forming, catalyst is obtained.
Comparative example 3
The raw material dosage of 3 reference implementation example 1 of comparative example, difference lies in do not add Tungstenic compound.Vanadium-containing compound is adopted
With vanadic anhydride, by vanadium-containing compound, molybdate compound directly with carrier mixed-forming, catalyst is obtained.
Experimental example 1
For the catalyst that comparative illustration various embodiments of the present invention and comparative example obtain, to each embodiment and comparative example
The performance of obtained catalyst is tested, and test result is shown in Table 1.
The performance test results of catalyst that 1 different disposal of table obtains
Experimental example 2
For the denitration performance for the catalyst that comparative illustration various embodiments of the present invention and comparative example obtain, by each embodiment
And the catalyst that comparative example obtains is used in SCR reactors be evaluated.Carry out simulated flue gas with steel gas cylinder to form, be wrapped in flue gas
Include NO, O2、N2、NH3And SO2, NO and NH3Volume fraction be 0.5%, SO2Volume fraction be 1%, O2Volume fraction be
6%, remaining is N2, reaction velocity 3500h-1, gas flow, composition are adjusted and are controlled by mass flowmenter.Gas analysis is adopted
With German TEST0350-XL flue gas analyzers, the test of data is carried out after each catalyst stable conditions 30min, to ensure
The stability and accuracy of data, test result are shown in Table 2.
The denitration efficiency efficiency test result for the catalyst that 2 different disposal of table obtains
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical features into
Row equivalent replacement；And these modifications or replacement, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of denitrating catalyst, which is characterized in that include the following steps：
(a) vanadium-containing compound is dissolved in solvent, is concentrated to give the concentrate of vanadium-containing compound；
(b) concentrate of the mixed solution of carrier, Tungstenic compound and molybdate compound, vanadium-containing compound is uniformly mixed, pinched
It closes, molding, calcine, obtain the denitrating catalyst.
2. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the solvent in the step (a)
Including monoethanolamine；
Preferably, the solvent in the step (a) is the aqueous solution of monoethanolamine；
It is furthermore preferred that the mass fraction of monoethanolamine is 15-25% in the aqueous solution of the monoethanolamine.
3. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the vanadium-containing compound includes inclined
One or both of ammonium vanadate and vanadic anhydride；
Preferably, the vanadium-containing compound is ammonium metavanadate；
Preferably, vanadium-containing compound is counted with the mass ratio of solvent using vanadium as (1-2) ﹕ 10 in the step (a)；
It is furthermore preferred that vanadium-containing compound is counted with the mass ratio of solvent using vanadium as (1.5-2) ﹕ 10 in the step (a).
4. the preparation method of denitrating catalyst according to claim 1, which is characterized in that in the step (a), vanadium will be contained
Compound is dissolved in solvent, is warming up to 90-98 DEG C, and stirring is cooled to 75-80 DEG C until solution clarification, stirs distillation and concentration；
Preferably, the concentration rate is 0.5-0.9；
It is furthermore preferred that the concentration rate is 0.7-0.8.
5. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the Tungstenic compound and containing molybdenum
The mass ratio of tungsten and molybdenum is 1 ﹕ (1-10) in the mixed solution of compound；
Preferably, the Tungstenic compound includes ammonium metatungstate and ammonium paratungstate, preferably ammonium metatungstate；
Preferably, the molybdate compound includes ammonium heptamolybdate.
6. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the carrier, Tungstenic compound
With the mixed solution of molybdate compound in terms of tungsten and molybdenum, each parts by weight of the concentrate of vanadium-containing compound in terms of vanadium be respectively
58-68 parts, 3-4 parts, 4-9 parts；
Preferably, the mixed solution of the carrier, Tungstenic compound and molybdate compound in terms of tungsten and molybdenum, vanadium-containing compound it is dense
Each parts by weight of the contracting liquid in terms of vanadium are respectively 60-65 parts, 3.2-3.8 parts, 5.5-8.4 parts.
7. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the carrier includes titanium dioxide
It is one or more in titanium, cordierite and montmorillonite；
Preferably, the carrier includes titanium dioxide and cordierite；
It is furthermore preferred that the mass ratio of the titanium dioxide and cordierite is (20-22) ﹕ (1-3).
8. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the carrier is located in advance by surface
Reason；
Preferably, the surface preparation includes：Carrier impregnation is mixed in ammonium hydroxide；
Preferably, the mass ratio of the ammonium hydroxide and carrier is 1 ﹕ (3-7)；
Preferably, the mass fraction of the ammonium hydroxide is 5%-25%.
9. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the calcination temperature is 430-
600 DEG C, the calcination time is 16-48h.
10. the denitrating catalyst that the preparation method of claim 1-9 any one of them denitrating catalysts is prepared.
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