CN109692681A - A method of promoting denitrating catalyst water resistance - Google Patents
A method of promoting denitrating catalyst water resistance Download PDFInfo
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- CN109692681A CN109692681A CN201811480354.5A CN201811480354A CN109692681A CN 109692681 A CN109692681 A CN 109692681A CN 201811480354 A CN201811480354 A CN 201811480354A CN 109692681 A CN109692681 A CN 109692681A
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- carrier
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- new carbon
- roasting
- water resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- Oil, Petroleum & Natural Gas (AREA)
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- Health & Medical Sciences (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
A method of denitrating catalyst water resistance is promoted, field of catalyst preparation is belonged to.Carrier and new carbon are uniformly mixed with ball-milling method by this method first, and modified mixed carrier is made, then loads to metal salt solution on the carrier being modified, roasting prepares catalyst.The present invention prepares carrier with simple ball-milling method, and production method is simple, short preparation period；The addition of new carbon also improves the water-fast activity of catalyst.
Description
Technical field
The present invention relates to a kind of methods for promoting denitrating catalyst water resistance, belong to field of catalyst preparation.
Background technique
With China's industrialization, the fast development of urbanization economy, atmosphere pollution becomes the serious problems being difficult to avoid that.Steel
Iron industry is the second largest high pollution industry after Thermal Power Generation Industry, and the sintering of the sector and pelletizing process can generate a large amount of two
Sulfur oxide, nitrogen oxides and dust.Steel plant's flue gas is after desulfurization process, and flue-gas temperature is at 100 DEG C -200 DEG C.So far it is
Manganese series catalyzer has preferable low temperature active in the catalyst only studied, and active section is 80 DEG C -250 DEG C, meets steel plant
The active window of flue gas pollutant reaction, but manganese series catalyzer water resistance is poor, greatly limits its application, so improving
The water resistance of manganese series catalyzer is just particularly important.New carbon itself has superior hydrophobicity, high-ratio surface
Product, XXX (patent CN108380225A) are prepared for Fe using one-step method1-xCexVO4/TiO2Graphen catalyst, the catalyst
It is demonstrated by preferable sulfur resistive water resistance.In addition, patent CN104759277B arrives stone for metal oxide supported using hydro-thermal method
On black alkene, it is prepared for CeOx-MnOx/ graphen catalyst, the catalyst obtain preferably in 120 DEG C -200 DEG C of temperature range
Low-temperature SCR denitrating flue gas activity, and preferable anti-sulfur dioxide and water resistant poisoning are achieved under 200 DEG C of test condition
Effect.On this basis, the present invention using a series of there is good hydrophobic new carbon to be modified to carrier, make
Standby cost out is less expensive, and operation is simpler, and manufacturing cycle is shorter, is easier to industrialized carrier to improve the water resistance of catalyst
Energy.
Summary of the invention
It is a primary object of the present invention to provide a kind of denitrating catalyst preparation method of promotion water resistance to improve manganese
The status of series catalysts water resistance difference, and cost is reduced on this basis, thus more suitable for application.
The present invention adopts the following technical scheme that:
A method of promoting denitrating catalyst water resistance will be novel using active metal salt solution as precursor solution
The carrier that carbon material was modified, which is added in above-mentioned precursor solution, to be impregnated, and then roasts and catalyst is made；In the catalyst,
Reactive metal oxides account for the 20%-40% of catalyst gross mass；In the carrier that new carbon was modified, new carbon
Account for carrier TiO2The 0.1%-15% of gross mass；Carrier is TiO2, new carbon is expanded graphite, the stone for removing amorphous carbon
One or more of black alkene etc.；Reactive metal oxides include at least the oxidation of manganese, and it is other living to may also include cerium oxide etc.
Property metal oxide.
Further preferably the following steps are included:
The carrier that step 1. preparation new carbon was modified:
That is roasting is pre-processed to commercial new carbon and removes amorphous carbon therein；Then solid-phase ball milling method is used
New carbon after roasting is mixed with carrier, ball milling condition setting: when orientation operation, revolving speed 300-800r/min, ball milling
Between 0.5h-6h, ratio of grinding media to material 20:1；
Step 2. prepares catalyst:
Using active metal salt solution as presoma, it is uniformly mixed solution in 60 DEG C of stirring 0.5h-1.5h, is then slowly added
Enter the carrier of step 1 preparation, 75 DEG C of -85 DEG C of stirrings 2h-3h, ultrasonic 0.5h-2h are dried, 300 DEG C -400 in air atmosphere
DEG C roasting 2h-4h.
It is preferred that: the roasting in step 1 are as follows: lower 300 DEG C of -400 DEG C of roasting 2h-4h of air atmosphere.
The present invention by adopting the above technical scheme, has the following advantages compared with prior art:
1. the carrier being modified by new carbon prepared by solid-phase ball milling method, preparation method is simple, short preparation period,
New carbon and original vector can be made to mix more evenly.
2. reduce preparation cost using new carbon expanded graphite, while the superpower suction-operated of expanded graphite can also
To improve the low-temperature denitration activity of catalyst.
Detailed description of the invention:
Fig. 1: the SEM of new carbon expanded graphite used in the present invention and graphene figure；
(a) figure is the SEM figure of expanded graphite；(b) figure is the SEM figure of graphene.
Fig. 2: the catalyst water resistant activity comparison diagram of Example 1 and Example 2 of the present invention preparation；(test condition:
1000ppm NH3, 1000ppm NO, 6%O2, N2For Balance Air, 3,0000h-1Air speed continuously leads to 10%H at 150 DEG C2O 8h)
Fig. 3: catalyst water resistant activity comparison diagram prepared by the embodiment of the present invention 3 and embodiment 4；(test condition:
1000ppm NH3, 1000ppm NO, 6%O2, N2For Balance Air, 3,0000h-1Air speed continuously leads to 15%H at 150 DEG C2O 8h)
Specific embodiment:
The contents of the present invention are explained below with reference to embodiment, but the present invention is not limited to following embodiments.
Embodiment 1:
Graphene (abbreviation GE, 350 DEG C of roasting 4h of roasting condition), 9.9g TiO after weighing 0.1g roasting respectively2In ball
In grinding jar, TiO is made in ratio of grinding media to material 20:1, Ball-milling Time 2h2- 1%GE carrier.Measure 12.0g 50%Mn (NO3)2Solution
Into container, 30mL deionized water is added, 60 DEG C of stirring 0.5h are then slowly added into 7g TiO2- 1%GE carrier, 80 DEG C are stirred
Mix 2h, ultrasonic 1h, 120 DEG C of drying, 350 DEG C of roasting 4h.30%MnO is madex/TiO2- 1%GE catalyst.
Embodiment 2:
0.5g GE, 9.5g TiO are weighed respectively2In ball grinder, TiO is made in ratio of grinding media to material 20:1, Ball-milling Time 2h2-
5%GE carrier.Measure 12.0g 50%Mn (NO3)2Solution is into container, addition 30mL deionized water, 60 DEG C of stirring 0.5h, so
After be slowly added to 7g TiO2- 5%GE carrier, 80 DEG C of stirrings 2h, ultrasonic 1h, 120 DEG C of drying, 350 DEG C of roasting 4h.It is made
30%MnOx/TiO2- 5%GE catalyst.
Embodiment 3:
Expanded graphite (abbreviation EG, 350 DEG C of roasting 4h of roasting condition), 9.9g TiO after weighing 0.1g roasting respectively2In
In ball grinder, TiO is made in ratio of grinding media to material 20:1, Ball-milling Time 2h2- 1%EG carrier.Measure 12.0g 50%Mn (NO3)2It is molten
30mL deionized water is added into container in liquid, and 60 DEG C of stirring 0.5h are then slowly added into 7g TiO2- 1%EG carrier, 80 DEG C
Stir 2h, ultrasonic 1h, 120 DEG C of drying, 350 DEG C of roasting 4h.30%MnO is madex/TiO2- 1%EG catalyst.
Embodiment 4:
Expanded graphite (abbreviation EG, 350 DEG C of roasting 4h of roasting condition), 9.5g TiO after weighing 0.5g roasting respectively2In
In ball grinder, TiO is made in ratio of grinding media to material 20:1, Ball-milling Time 2h2- 5%EG carrier.Measure 12.0g 50%Mn (NO3)2It is molten
30mL deionized water is added into container in liquid, and 60 DEG C of stirring 0.5h are then slowly added into 7g TiO2- 5%EG carrier, 80 DEG C
Stir 2h, ultrasonic 1h, 120 DEG C of drying, 350 DEG C of roasting 4h.30%MnO is madex/TiO2- 5%EG catalyst.
Claims (5)
1. a kind of method for promoting denitrating catalyst water resistance, which is characterized in that molten by presoma of active metal salt solution
The carrier that new carbon was modified is added in above-mentioned precursor solution and impregnates, then roasts and catalyst is made by liquid；It is described to urge
In agent, reactive metal oxides account for the 20%-40% of catalyst gross mass；It is novel in the carrier that new carbon was modified
Carbon material accounts for carrier TiO2The 0.1%-15% of gross mass；Carrier is TiO2, new carbon is the expansion stone for removing amorphous carbon
One or more of ink, graphene；Reactive metal oxides include at least the oxidation of manganese.
2. a kind of method for promoting denitrating catalyst water resistance described in accordance with the claim 1, which is characterized in that active metal
Oxide further includes cerium oxide.
3. a kind of method for promoting denitrating catalyst water resistance according to claim 1 or 2, which is characterized in that specific
The following steps are included:
The carrier that step 1. preparation new carbon was modified:
That is roasting is pre-processed to commercial new carbon and removes amorphous carbon therein；Then it will be roasted using solid-phase ball milling method
New carbon after burning is mixed with carrier；
Step 2. prepares catalyst:
Using active metal salt solution as presoma, it is uniformly mixed solution in 60 DEG C of stirring 0.5h-1.5h, is then slowly added into step
The carrier of rapid 1 preparation, 75 DEG C of -85 DEG C of stirrings 2h-3h, ultrasonic 0.5h-2h, drying, lower 300 DEG C of -400 DEG C of roastings of air atmosphere
2h-4h。
4. according to the method for claim 3, which is characterized in that the setting of step 1 ball milling condition: orientation operation, 300-800r/
Min, Ball-milling Time 0.5h-6h, ratio of grinding media to material 20:1.
5. according to the method for claim 3, which is characterized in that the roasting in step 1 are as follows: lower 300 DEG C -400 of air atmosphere
DEG C roasting 2h-4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811480354.5A CN109692681A (en) | 2018-12-05 | 2018-12-05 | A method of promoting denitrating catalyst water resistance |
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| CN201811480354.5A CN109692681A (en) | 2018-12-05 | 2018-12-05 | A method of promoting denitrating catalyst water resistance |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371134A (en) * | 2020-12-04 | 2021-02-19 | 上海交通大学 | Preparation method of expanded graphite-based carrier-loaded low-temperature denitration catalyst |
| CN113368898A (en) * | 2021-06-16 | 2021-09-10 | 福州大学 | Method for preparing high-water-resistance filter material by ball milling method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881077A (en) * | 2017-04-25 | 2017-06-23 | 北京工业大学 | A kind of preparation method of low temperature sulfur resistive water resistant denitrating catalyst |
-
2018
- 2018-12-05 CN CN201811480354.5A patent/CN109692681A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881077A (en) * | 2017-04-25 | 2017-06-23 | 北京工业大学 | A kind of preparation method of low temperature sulfur resistive water resistant denitrating catalyst |
Non-Patent Citations (2)
| Title |
|---|
| XINING LU ETC.: "Low-temperature selective catalytic reduction of NOX with NH3 over cerium and manganese oxides supported on TiO2–graphene", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 高凤雨: "Mn基低温NH_3-SCR催化剂的抗水抗硫性能及反应机理研究", 《北京科技大学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371134A (en) * | 2020-12-04 | 2021-02-19 | 上海交通大学 | Preparation method of expanded graphite-based carrier-loaded low-temperature denitration catalyst |
| CN112371134B (en) * | 2020-12-04 | 2022-04-08 | 上海交通大学 | Preparation method of expanded graphite-based carrier-loaded low-temperature denitration catalyst |
| CN113368898A (en) * | 2021-06-16 | 2021-09-10 | 福州大学 | Method for preparing high-water-resistance filter material by ball milling method |
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Application publication date: 20190430 |