CN110124677A - Denitrating catalyst and preparation method thereof - Google Patents
Denitrating catalyst and preparation method thereof Download PDFInfo
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- CN110124677A CN110124677A CN201910551312.4A CN201910551312A CN110124677A CN 110124677 A CN110124677 A CN 110124677A CN 201910551312 A CN201910551312 A CN 201910551312A CN 110124677 A CN110124677 A CN 110124677A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006104 solid solution Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005751 Copper oxide Substances 0.000 claims abstract description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000019738 Limestone Nutrition 0.000 claims 1
- 239000006028 limestone Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910001868 water Inorganic materials 0.000 abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 229910001200 Ferrotitanium Inorganic materials 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
This application discloses a kind of denitrating catalysts, including titanium dioxide and vanadic anhydride, and vanadic anhydride is in the form of ionic bond in conjunction with titanium dioxide.Disclosed herein as well is a kind of preparation methods of denitrating catalyst, comprising: (1), synthesis containing vanadic anhydride, tungstic acid, ferric oxide, copper oxide solid solution；(2), solid solution and auxiliary agent are mixed, and successively obtains denitrating catalyst through filtering, extrusion, drying and roasting.The ferrotitanium based low-temperature denitration catalyst that the present invention prepares is increased dramatically in the denitration performance and water resistant resistance to SO_2 of worst cold case；Volumetric usage no longer needs to be promoted flue-gas temperature when reducing, running, and reduces engineering cost and operating cost.
Description
Technical field
This application involves a kind of denitrating catalysts and preparation method thereof, it is especially useful in coke-oven plant denitrating flue gas field.
Background technique
Coke-oven plant's flue gas emission feature is mainly shown as low temperature, and general 160~200 DEG C of temperature, conventional normal-temperature catalyst is
It is unable to satisfy low-temperature denitration requirement, general 300~420 DEG C of room temperature denitrating catalyst operating temperature.
Currently, some scholars are developing low-temperature denitration catalyst in the market, but due to the compound in flue gas there are sulphur
And there are vapor, in use for some time, the accumulation of sulfate causes the blocking of catalyst to catalyst, and must not be again to cigarette
Air lift high-temperature carries out the recycled sinter to sulfate to 350 DEG C or so, due to the control inaccuracy and control to clogging
The unstability of system causes this mode and there are problems when in use, needs constantly to improve flue-gas temperature in addition,
Operating cost is caused to be significantly increased.
Summary of the invention
The purpose of the present invention is to provide a kind of denitrating catalyst and preparation method thereof, solve to exist in prior art scheme
Worst cold case under denitration performance difference and resistance to SO_2, water-resistance difference problem.
To achieve the above object, the invention provides the following technical scheme:
The embodiment of the present application discloses a kind of denitrating catalyst, including titanium dioxide and vanadic anhydride, vanadic anhydride with
The form of ionic bond is in conjunction with titanium dioxide.
Preferably, further include ferric oxide and copper oxide in above-mentioned denitrating catalyst, ferric oxide and copper oxide with
The form of ionic bond is in conjunction with titanium dioxide.
Disclosed herein as well is a kind of preparation methods of denitrating catalyst, comprising:
(1), synthesize containing vanadic anhydride, tungstic acid, ferric oxide, copper oxide solid solution；
(2), solid solution and auxiliary agent are mixed, and successively obtains denitrating catalyst through filtering, extrusion, drying and roasting.
Preferably, in the preparation method of above-mentioned denitrating catalyst, step (1) includes: that titanium tungsten is added in a kettle
The pressure of powder, reaction kettle is 1.6~10MPa, sequentially adds vanadic sulfate, molysite and mantoquita.
Preferably, in the preparation method of above-mentioned denitrating catalyst, WO in titanium tungsten powder3Mass percentage content be
5%.
Preferably, in the preparation method of above-mentioned denitrating catalyst, titanium tungsten powder, vanadic sulfate, molysite and mantoquita are added
Mass ratio be 75~90:5~10:2~8:3~8.
Preferably, in the preparation method of above-mentioned denitrating catalyst, step (1) includes:
S1, addition titanium tungsten powder is heated, is pressurizeed and stirred in a kettle, and speed of agitator is 100~500r/min, temperature
Degree is 40~50 DEG C, and pressure is 3~10MPa, and mixing time is 0.1~0.5h；
S2, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into ferrous acid iron, 0.3~0.6h of used time is forced into 3 after adding
~10MPa continues to stir, and speed of agitator is 100~500r/min, and temperature is 40~50 DEG C, and mixing time is 1~3h；
S3, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into vanadic sulfate, 0.3~0.6h of used time is forced into after adding
5~10MPa lifts temperature to 100~110 DEG C, continues to stir, and speed of agitator is 100~500r/min, and mixing time is 1~3h；
S4, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into copper nitrate, 0.3~0.6h of used time is forced into 6 after adding
~10MPa lifts temperature to 110~120 DEG C, continues to stir, and speed of agitator is 100~500r/min, and mixing time is 1~3h；
S5, it being forced into 6~10MPa, lifts temperature to 110~120 DEG C, continue to stir, speed of agitator is 100~500r/min,
Mixing time is 2~4h；
S6, blowing, and be dried, calcine, crushing and obtain required solid solution, drying condition is 100~150 DEG C, dry
Time is 2~6h, and calcination condition is 300~400 DEG C, and calcination time is 3~5h, and smashed product granularity is that average grain diameter is
0.5~2 μm.
Preferably, in the preparation method of above-mentioned denitrating catalyst, step (2) includes: to be made with the solid solution of step (1)
For basis material, while sequentially adding basis material, glass fibre, wood pulp, binder, silica, wollastonite, deionized water
And ammonium hydroxide, the mass ratio of addition is 50~65:5~8:1~5:0.5~2:3~5:1~3:20~30:5~10, is mixed
It closes, filtering, squeeze out, dry and roasting, mixed revolving speed is 200~400r/min, and the time is 4~6h, the pressure 4 of filtering~
6MPa, the pressure of extrusion are 4~6MPa, and drying condition is 50~60 DEG C, and drying time is 168~240h, maturing temperature 450
~550 DEG C, calcining time is 20~30h.
Compared with the prior art, the advantages of the present invention are as follows: the ferrotitanium based low-temperature denitration catalyst that the present invention prepares,
The denitration performance and water resistant resistance to SO_2 of worst cold case are increased dramatically；Volumetric usage no longer needs to promote cigarette when reducing, running
Temperature degree reduces engineering cost and operating cost.
Detailed description of the invention
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in application, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 show the flow chart of the preparation method of denitrating catalyst in the specific embodiment of the invention.
Specific embodiment
The present invention is described further by the following example: according to following embodiments, the present invention may be better understood.
However, as it will be easily appreciated by one skilled in the art that specific material ratio, process conditions and its result described in embodiment are only used
In illustrating the present invention, without the present invention described in detail in claims should will not be limited.
The present embodiment process program is the synthetic method of basis material by titanium dioxide, realizes vanadic anhydride, three
Tungsten oxide, ferric oxide, copper oxide etc. synthesize solid solution, make the V as active constituent2O5Pass through ionic bond and TiO2In conjunction with together
When ferric oxide, copper oxide is also in the form of ionic bond and TiO2In conjunction with this extremely stable combination greatly improved
The catalyst worst cold case denitration performance and water resistant resistance to SO_2,.
Solid solution is a kind of material that chemical property is sufficiently stable, and crystal phase is kept completely in practical applications, solid solution
Preparation method be in middle pressure reaction kettle addition titanium tungsten powder (WO3Mass percentage content be 5%), the pressure of reaction kettle is
1.6~10MPa sequentially adds preceding extract vanadic sulfate, the ferric nitrate, copper nitrate of vanadic anhydride, ferric oxide, copper oxide.
The mass ratio that titanium tungsten powder, vanadic sulfate, ferric nitrate, copper nitrate are added is 75~90:5~10:2~8:3~8,
Iron, copper can also be added in the form of acetate or oxalates.
It being heated, is pressurizeed and stirred firstly, titanium tungsten powder is added in a kettle, speed of agitator is 100~500r/min,
Temperature is 40~50 DEG C, and pressure is 3~10MPa, and mixing time is 0.1~0.5h.
Later, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into ferrous acid iron, 0.3~0.6h of used time is forced into after adding
3~10MPa continues to stir along above-mentioned revolving speed, temperature, and mixing time is 1~3h.
Thereafter, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into vanadic sulfate, 0.3~0.6h of used time pressurizes after adding
To 5~10MPa, 100~110 DEG C are lifted temperature to, continues to stir along above-mentioned revolving speed, mixing time is 1~3h.
Followed by, after being decompressed to standard atmospheric pressure, it is slowly uniformly added into copper nitrate, 0.3~0.6h of used time pressurizes after adding
To 6~10MPa, 110~120 DEG C are lifted temperature to, continues to stir along above-mentioned revolving speed, mixing time is 1~3h.
Finally, be forced into 6~10MPa, 110~120 DEG C are lifted temperature to, continues to stir along above-mentioned revolving speed, mixing time is 2~
4h。
Terminate blowing after above-mentioned steps, and be dried, calcine, crushing and obtain required solid solution, drying condition for 100~
150 DEG C, drying time is 2~6h, and calcination condition is 300~400 DEG C, and calcination time is 3~5h.Smashed product granularity is
Average grain diameter is 0.5~2 μm, and maximum particle diameter is 3~5 μm.
The preparation method of ferrotitanium based low-temperature denitration catalyst is sequentially added simultaneously using above-mentioned solid solution as basis material
Basis material, glass fibre, wood pulp, binder, silica, wollastonite, deionized water and ammonium hydroxide etc., the quality percentage of addition
Ratio is 50~65:5~8:1~5:0.5~2:3~5:1~3:20~30:5~10, is mixed, filtered, squeezed out, dried
And roasting.Mixed revolving speed is 200~400r/min, and the time is 4~6h, and 4~6MPa of pressure of filtering, the pressure of extrusion is 4
~6MPa, drying condition are 50~60 DEG C, and drying time is 168~240h, and calcination temperature is 450~550 DEG C, and calcination time is
20~30h.
Since vanadic anhydride, ferric oxide, copper oxide and titanium dioxide are the combinations in the form of ionic bond, so this
The solid solution of kind combination preparation is extremely stable, to the ferrotitanium based low-temperature denitration catalyst prepared, in worst cold case
Denitration performance and water resistant resistance to SO_2 are increased dramatically.
It is verified below by way of performance of the practical application to above-mentioned catalysis material.
Application is Certain Coking Plant, 1,300,000 tons of annual output, exhaust gas volumn 300000Nm3/ h, 170 DEG C of flue-gas temperature,
Sulfur dioxide concentration 100mg/Nm3Water vapour content 10%, nitrogen oxides entrance concentration 1700mg/Nm3, denitration efficiency requirement >=
94%, nitrogen oxides exit concentration requirement≤100mg/Nm3,
Gas bypass pilot-plant is established in the coke-oven plant, by mass flowmenter, makes flue gas flow in pilot-plant
2000Nm3/ h, parameter such as table 1.
1 gas bypass pilot-plant smoke components of table
| Gas | NOx | SO2 | H2O | O2 | N2 |
| Concentration | 1700mg/Nm3 | 100mg/Nm3 | 10% | 8% | 73% |
Catalyst amounts 64,4 layers of catalyst vertical direction arrangement, every layer of catalyst arrangement 4 × 4, every stressor layer
Loss≤100pa.
Comparative example
Commercially available low-temperature denitration catalyst,
Catalyst specification 150mm × 150mm × 400mm, 4/cm of hole count2, V2O5Mass concentration 5.0%.
Embodiment 1
Catalyst specification 150mm × 150mm × 400mm, 4/cm of hole count2, Fe2O3Mass concentration 2%, V2O5Mass concentration
5.0%.
Embodiment 2
Catalyst specification 150mm × 150mm × 400mm, 4/cm of hole count2, Fe2O3Mass concentration 3%, V2O5Mass concentration
5.0%.
Different embodiments join table 2~5 to the removal rate of pollutant.
The removal rate of 2 nitrogen oxides of table
Test condition: exhaust gas volumn 2000Nm3/h,NH3/NOx=0.9446, NOx1700mg/Nm3, SO25mg/Nm3, 8vol%
O2, 10vol%H2O
The removal rate of 3 nitrogen oxides of table
Test condition: exhaust gas volumn 2000Nm3/ h, NH3/NOx=0.9446, NOx1700mg/Nm3, SO2100mg/Nm3,
8vol%O2, 0vol%H2O
The removal rate of 4 nitrogen oxides of table
Test condition: exhaust gas volumn 2000Nm3/ h, NH3/ NOx=0.9446, NOx1700mg/Nm3, SO2100mg/Nm3,
8vol%O2, 10vol%H2O
The removal rate of 5 nitrogen oxides of table
Test condition: exhaust gas volumn 2000Nm3/ h, NH3/ NOx=0.9446, NOx1700mg/Nm3, SO2100mg/Nm3,
8vol%O2, 10vol%H2O
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show with closely related structure and/or processing step according to the solution of the present invention, and be omitted little with relationship of the present invention
Other details.
Finally, it is to be noted that, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.
Claims (9)
1. a kind of denitrating catalyst, which is characterized in that including titanium dioxide and vanadic anhydride, vanadic anhydride is with ionic bond
Form is in conjunction with titanium dioxide.
2. denitrating catalyst according to claim 1, which is characterized in that further include ferric oxide and copper oxide, three oxidations
Iron and copper oxide are in the form of ionic bond in conjunction with titanium dioxide.
3. denitrating catalyst according to claim 2, which is characterized in that the matter of vanadic anhydride, ferric oxide, copper oxide
Measure ratio 1~5:1~5:1~5.
4. a kind of preparation method of denitrating catalyst characterized by comprising
(1), synthesize containing vanadic anhydride, tungstic acid, ferric oxide, copper oxide solid solution；
(2), solid solution and auxiliary agent are mixed, and successively obtains denitrating catalyst through filtering, extrusion, drying and roasting.
5. the preparation method of denitrating catalyst according to claim 4, which is characterized in that step (1) includes: in reaction kettle
The pressure of middle addition titanium tungsten powder, reaction kettle is 1.6 ~ 10MPa, sequentially adds vanadic sulfate, molysite and mantoquita.
6. the preparation method of denitrating catalyst according to claim 5, which is characterized in that WO in titanium tungsten powder3Quality percentage
It is 5% than content.
7. the preparation method of denitrating catalyst according to claim 5, which is characterized in that titanium tungsten powder, vanadic sulfate, molysite
It is 75~90:5~10:2~8:3~8 with the mass ratio that mantoquita is added.
8. the preparation method of denitrating catalyst according to claim 5, which is characterized in that step (1) includes:
S1, addition titanium tungsten powder is heated, is pressurizeed and stirred in a kettle, and speed of agitator is 100 ~ 500r/min, and temperature is
40 ~ 50 DEG C, pressure is 3 ~ 10MPa, and mixing time is 0.1 ~ 0.5h；
S2, after being decompressed to standard atmospheric pressure, slowly it is uniformly added into ferrous acid iron, 0.3 ~ 0.6h of used time, it is forced into 3 after adding ~
10MPa continues to stir, and speed of agitator is 100 ~ 500r/min, and temperature is 40 ~ 50 DEG C, and mixing time is 1 ~ 3h；
S3, after being decompressed to standard atmospheric pressure, slowly it is uniformly added into vanadic sulfate, 0.3 ~ 0.6h of used time, it is forced into 5 after adding ~
10MPa lifts temperature to 100 ~ 110 DEG C, continues to stir, and speed of agitator is 100 ~ 500r/min, and mixing time is 1 ~ 3h；
S4, after being decompressed to standard atmospheric pressure, slowly it is uniformly added into copper nitrate, 0.3 ~ 0.6h of used time, it is forced into 6 after adding ~
10MPa lifts temperature to 110 ~ 120 DEG C, continues to stir, and speed of agitator is 100 ~ 500r/min, and mixing time is 1 ~ 3h；
S5, it is forced into 6 ~ 10MPa, lifts temperature to 110 ~ 120 DEG C, continue to stir, speed of agitator is 100 ~ 500r/min, mixing time
For 2 ~ 4h；
S6, blowing, and be dried, calcine, crushing and obtain required solid solution, drying condition is 100 ~ 150 DEG C, and drying time is
2 ~ 6h, calcination condition are 300 ~ 400 DEG C, and calcination time is 3 ~ 5h, and smashed product granularity is that average grain diameter is 0.5 ~ 2 μm.
9. the preparation method of denitrating catalyst according to claim 5, which is characterized in that step (2) includes: with step
(1) solid solution sequentially adds basis material, glass fibre, wood pulp, binder, silica, silicon as basis material
Lime stone, deionized water and ammonium hydroxide, the mass ratio of addition are 50 ~ 65:5 ~ 8:1 ~ 5:0.5 ~ 2:3 ~ 5:1 ~ 3:20 ~ 30:5 ~ 10, into
Row mixing filtering, squeezes out, dry and roasting, and mixed revolving speed is 200 ~ 400r/min, and the time is 4 ~ 6h, and the pressure 4 of filtering ~
6MPa, the pressure of extrusion are 4 ~ 6MPa, and drying condition is 50 ~ 60 DEG C, and drying time is 168 ~ 240h, maturing temperature is 450 ~
550 DEG C, calcining time is 20 ~ 30h.
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