CN108246283B - 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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- CN108246283B CN108246283B CN201810150394.7A CN201810150394A CN108246283B CN 108246283 B CN108246283 B CN 108246283B CN 201810150394 A CN201810150394 A CN 201810150394A CN 108246283 B CN108246283 B CN 108246283B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20723—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- 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
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
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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
Abstract
The present invention relates to gas denitrifying technology fields, more particularly, to a kind of denitrating catalyst and preparation method thereof.The preparation method of the denitrating catalyst includes the following steps: that vanadium-containing compound is dissolved in solvent by (a), is concentrated to get 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, forms, calcines, obtain the denitrating catalyst.The activity load for the denitrating catalyst that the present invention is prepared is high, the high catalyst prod of content of vanadium can be prepared, the load capacity of vanadium cooperates other active components, make the temperature range of 160-400 DEG C of range of denitrating catalyst applicable for temperature up to 8%-10%.
Description
Technical field
The present invention relates to gas denitrifying technology fields, more particularly, to a kind of denitrating catalyst and preparation method thereof.
Background technique
Nitrogen oxides (NOX) it is a kind of atmosphere pollution with high risks.NO in atmosphereXAlmost there is more than half
It is to be mainly derived from the fossil fuels such as coal used in production, life, petroleum, natural gas as produced by man-made pollution source
Burning is one of the 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 to human health and animals and plants existence, such as form acid rain, photochemical fog, because
And it is badly in need of administering.But NOXWater solubility and reactivity it is poor, administer relatively difficult, technical requirements are high.
It in the prior art include selective catalytic reduction (SCR) and selective non-catalytic reduction method (SNCR).Though SNCR
Right simple process, but temperature requirement is too high, and denitration efficiency is unsatisfactory.SCR is that industrial most widely used one kind is de-
Nitre technology, ideally removal efficiency is up to 90% or more.But for some special flue gases, since operating load is low or
Boiler characteristics itself makes denitrification apparatus inlet temperature 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, the present invention is specifically proposed.
Summary of the invention
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 it is high using temperature, Applicable temperature narrow range, the low problem of denitration removal efficiency, also, the preparation method work
Skill is simple, is 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, and the service life is long.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of denitrating catalyst, includes the following steps:
(a) vanadium-containing compound is dissolved in solvent, is concentrated to get 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, calcining, obtains the denitrating catalyst.
In the prior art, when producing the catalyst of high content of vanadium, vanadium solubility is low, and vanadium precursor is unevenly distributed, production
The microcosmic aperture of obtained catalyst is few, and active site is few, and the qualification rate for the catalyst for causing production to obtain is extremely low (lower than 70%),
Catalytic activity is unstable, and the service life is short.
Then the present invention is concentrated again, can uniformly be divided by the way that vanadium-containing compound to be dissolved in solvent in advance
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 95% or more.Gao Han
The vanadium of amount cooperates 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, guarantee that ammonium metavanadate exists
Stability in solution avoids ammonium metavanadate dispersion uneven, when being concentrated to get the concentrate of the higher ammonium metavanadate of concentration,
It is still able to guarantee the dispersing uniformity and stability of ammonium metavanadate, 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, cooperate 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.
It is in the prior art the content for improving vanadium in catalyst, directlys adopt vanadic anhydride and mixed with carrier, but prepares
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 in terms of vanadium with the mass ratio of solvent be (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 clarification, 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, adapt the denitrating catalyst 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 pH value is easily controllable, makes to 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 of titanium dioxide, cordierite and montmorillonite or a variety of.It is furthermore preferred that institute
Stating carrier 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 in carrier surface, can sufficiently be combined, be improved with the mixing of other materials
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, the invention has the benefit that
(1) the activity load for the denitrating catalyst that preparation method through the invention obtains is high, and vanadium can be prepared and contain
High catalyst prod is measured, the load capacity of vanadium cooperates 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 solution 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 embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, 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 every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.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 get 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, calcining, obtains 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 cooperate with vanadium-containing compound, improve the dispersing uniformity and stability of vanadium-containing compound, improve
The uniformity for the catalyst being prepared, 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, guarantee that ammonium metavanadate exists
Stability in solution avoids ammonium metavanadate dispersion uneven；When being concentrated to get the concentrate of the higher ammonium metavanadate of concentration,
It is still able to guarantee the dispersing uniformity and stability of ammonium metavanadate, 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, cooperate 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 of titanium dioxide, cordierite and montmorillonite
Or it is 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).
Cooperated using titanium dioxide and cordierite, the physical strength of catalyst can be effectively improved, and can be improved work
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 available optimum activity reaction temperature is suitable for
Different reaction conditions.
In an of the invention preferred embodiment, 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 pH value is easily controllable, makes to 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 guarantee tungsten, molybdenum and the maximum uniform load of vanadium on carrier, no waste product generates,
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: that 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 for the monoethanolamine for being mixed to get 20g monoethanolamine and 80g deionized water, is added 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 cordierite are taken, is mixed with 5g mass fraction for 25% ammonium hydroxide and 10g deionized water,
Carrier is pre-processed and (or by ammonium hydroxide and deionized water mixing, is made into after the ammonium hydroxide of certain mass score again mixed with carrier
It closes)；
It prepares the mixed solution of Tungstenic compound and molybdate compound: taking 2.7g ammonium metatungstate and 3.1g ammonium heptamolybdate common
It is added in appropriate amount of deionized water, dissolves ammonium metatungstate and ammonium heptamolybdate all, wherein in the mixed solution, Tungstenic compound
It is 1 ﹕ 1 with the mass ratio of tungsten in molybdate compound (in terms of tungsten) and molybdenum (in terms of molybdenum)；
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 vanadium-containing compound obtained in the step of entering the 6.7g in terms of vanadium (a), carries out mixed at high speed and be placed in kneader
30min is mediated, is sieved by high density screen cloth, is then placed in drying chamber and is dried in the shade using extruder extrusion molding.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 for the monoethanolamine for being mixed to get 25g monoethanolamine and 75g deionized water, is added 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 cordierite are taken, is mixed with 5g mass fraction for 25% ammonium hydroxide and 10g deionized water,
Carrier is pre-processed and (or by ammonium hydroxide and deionized water mixing, is made into after the ammonium hydroxide of certain mass score again mixed with carrier
It closes)；
It prepares the mixed solution of Tungstenic compound and molybdate compound: taking 2.7g ammonium metatungstate and 3.1g ammonium heptamolybdate common
It is added in appropriate amount of deionized water, dissolves ammonium metatungstate and ammonium heptamolybdate all, wherein in the mixed solution, Tungstenic compound
It is 1 ﹕ 1 with the mass ratio of tungsten in molybdate compound (in terms of tungsten) and molybdenum (in terms of molybdenum)；
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 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, is pinched
30min is closed, is sieved by high density screen cloth, is then placed in drying chamber and is dried in the shade using extruder extrusion molding.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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: in the step (b), the carrier, tungstenic
Each parts by weight that the mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound is 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, difference are only that: in the step (b), the carrier, tungstenic
Each parts by weight that the mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound is 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, difference are only that: in the step (b), the carrier, tungstenic
Each parts by weight that the mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound is 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, difference are only that: in the step (b), the carrier, tungstenic
Each parts by weight that the mixed solution of compound and molybdate compound is in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound is 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, difference are only that: 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, and difference is only that: carrier
The titanium dioxide and cordierite for being 22 ﹕ 1 for mass ratio.
Embodiment 13
The preparation method of the present embodiment reference implementation example 1, step (b) the carrier total amount is constant, and difference is only that: 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, and difference is only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: 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, difference are only that: vanadium-containing compound is dissolved in the step (a)
Solvent be deionized water.
Embodiment 22
The preparation method of the present embodiment reference implementation example 1, difference are only that: concentration rate is 0.5 in the step (a).
Embodiment 23
The preparation method of the present embodiment reference implementation example 1, difference are only that: concentration rate is 0.7 in the step (a).
Embodiment 24
The preparation method of the present embodiment reference implementation example 1, difference are only that: concentration rate is 0.8 in the step (a).
Embodiment 25
The preparation method of the present embodiment reference implementation example 1, difference are only that: 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, difference are only that: the mass ratio of the ammonium hydroxide and carrier is 1 ﹕ 7,
The mass fraction of the ammonium hydroxide is 15%.
Embodiment 27
The drying and calcining in rotary furnace of calcine technology described in the present embodiment, temperature control point, installation air hose and wind in rotary furnace
The position of machine specifically:
Temperature control point is respectively as follows: (0m, 0 DEG C) in kiln body position and relevant temperature, (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 as follows: 1.5m, 2.75m, 4m, 5.25m, 6.5m, 7.75m, 9m, 10.3m, 11.5m in kiln body position,
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；
Blower position and quantity are respectively as follows: (13.5m, 1), (22.25m, 1), (27.5m, 2).
By 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 are that 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 is, does not add molybdate compound.Vanadium-containing compound is adopted
Catalyst is obtained by vanadium-containing compound, Tungstenic compound directly with carrier mixed-forming with vanadic anhydride.
Comparative example 3
The raw material dosage of 3 reference implementation example 1 of comparative example, difference is, does not add Tungstenic compound.Vanadium-containing compound is adopted
Catalyst is obtained by vanadium-containing compound, molybdate compound directly with carrier mixed-forming with vanadic anhydride.
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 for the 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 in SCR reactor for being 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 by mass flowmenter regulation and control.Gas analysis is adopted
With German TEST0350-XL flue gas analyzer, the test of data is carried out after every kind of catalyst stable conditions 30min, to guarantee
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 present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (21)
1. a kind of preparation method of denitrating catalyst, which comprises the steps of:
(a) vanadium-containing compound is dissolved in solvent, is concentrated to get 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, is pinched
It closes, molding, calcining, obtains the denitrating catalyst；
In the step (a), vanadium-containing compound is dissolved in solvent, is warming up to 90-98 DEG C, stirring is until solution clarification, drop
Temperature stirs distillation and concentration to 75-80 DEG C；The concentration rate is 0.7-0.9；
The mass ratio of tungsten and molybdenum is 1 ﹕ (1-10) in the mixed solution of the Tungstenic compound and molybdate compound；
The mixed solution of the carrier, Tungstenic compound and molybdate compound in terms of tungsten and molybdenum, the concentrate of vanadium-containing compound with
Each parts by weight of vanadium meter are respectively 58-68 parts, 3-4 parts, 4-9 parts.
2. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the solvent in the step (a)
Including monoethanolamine.
3. the preparation method of denitrating catalyst according to claim 2, which is characterized in that it is preferred, in the step (a)
Solvent be monoethanolamine aqueous solution.
4. the preparation method of denitrating catalyst according to claim 3, which is characterized in that the aqueous solution of the monoethanolamine
The mass fraction of middle monoethanolamine is 15-25%.
5. 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.
6. the preparation method of denitrating catalyst according to claim 5, which is characterized in that the vanadium-containing compound is inclined vanadium
Sour ammonium.
7. the preparation method of denitrating catalyst according to claim 5, which is characterized in that contain vanadium in the step (a)
It is (1-2) ﹕ 10 with the mass ratio of solvent that object, which is closed, in terms of vanadium.
8. the preparation method of denitrating catalyst according to claim 7, which is characterized in that contain vanadium in the step (a)
It is (1.5-2) ﹕ 10 with the mass ratio of solvent that object, which is closed, in terms of vanadium.
9. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the concentration rate is 0.7-
0.8。
10. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the Tungstenic compound includes
Ammonium metatungstate and ammonium paratungstate.
11. the preparation method of denitrating catalyst according to claim 10, which is characterized in that the Tungstenic compound is inclined
Ammonium tungstate.
12. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the molybdate compound includes
Ammonium heptamolybdate.
13. 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
60-65 parts, 3.2-3.8 parts, 5.5-8.4 parts.
14. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the carrier includes titanium dioxide
One of titanium, cordierite and montmorillonite are a variety of.
15. the preparation method of denitrating catalyst according to claim 14, which is characterized in that the carrier includes titanium dioxide
Titanium and cordierite.
16. the preparation method of denitrating catalyst according to claim 15, which is characterized in that the titanium dioxide and violet are green
The mass ratio of stone is (20-22) ﹕ (1-3).
17. the preparation method of denitrating catalyst according to claim 1, which is characterized in that the carrier is pre- by surface
Processing；The surface preparation includes: that carrier impregnation is mixed in ammonium hydroxide.
18. the preparation method of denitrating catalyst according to claim 17, which is characterized in that the matter of the ammonium hydroxide and carrier
Amount is than being 1 ﹕ (3-7).
19. the preparation method of denitrating catalyst according to claim 17, which is characterized in that the mass fraction of the ammonium hydroxide
For 5%-25%.
20. 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.
21. the denitrating catalyst that the preparation method of the described in any item denitrating catalysts of claim 1-20 is prepared.
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| CN113042031A (en) * | 2021-03-29 | 2021-06-29 | 安徽元琛环保科技股份有限公司 | Preparation method of low-temperature catalyst and prepared catalyst |
| CN114392758A (en) * | 2022-01-11 | 2022-04-26 | 河南康宁特环保科技股份有限公司 | High-vanadium denitration catalyst and preparation method thereof |
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