CN106378201A - Preparation method of denitration catalyst adopting active carbon-TiO2 as carrier - Google Patents
Preparation method of denitration catalyst adopting active carbon-TiO2 as carrier Download PDFInfo
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- CN106378201A CN106378201A CN201610796676.5A CN201610796676A CN106378201A CN 106378201 A CN106378201 A CN 106378201A CN 201610796676 A CN201610796676 A CN 201610796676A CN 106378201 A CN106378201 A CN 106378201A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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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- 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
- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a preparation method of a denitration catalyst adopting carbon-TiO2 as a carrier. The denitration catalyst includes active carbon, TiO2, MoO2, Cr2O3, MnO2, SnO2, ZrO2, a lubricant and heteropolyacid. The preparation method comprises the following steps: mixing a titanium salt solution and an electrolyte solution, adding active carbon, dipping, ageing, transferring the obtained solution to a hydrothermal kettle, and carrying out a reaction to obtain the carrier; and uniformly mixing MoO2, Cr2O3, MnO2, SnO2, ZrO2 and the heteropolyacid, adding the carrier, and dipping to prepare the denitration catalyst. The denitration catalyst has the advantages of low activation temperature, high thermal stability and hydrothermal stability, wide active temperature window, high denitration efficiency and long life, and the preparation method has the advantages of simplicity, strong maneuverability and production cost reduction.
Description
Technical field
The invention belongs to catalyst field, more particularly, to one kind is with activated carbon-TiO2System for the denitrating catalyst of carrier
Preparation Method.
Background technology
Nitrogen oxides are very serious to the pollution of environment, and nitrogen oxides are the basis of nitric acid type acid rain, are to form light again
One of chemical fumes, the main matter damaging the ozone layer；Nitrogen oxides also have very strong toxicity, can cause pole to health
Macrolesion.In recent years, with economic fast development, the discharge capacity of nitrogen oxides pollution thing increases sharply, severe contamination life
State environment, it has also become the environmental problem of global concern.
By the discharge capacity of its nitrogen oxides being controlled in thermal power plant and industrial furnace De-NO_x, its
The denitration of middle selective catalytic reduction (SCR) is one of most widely used, gas denitrifying technology that technology is the most ripe in the world,
Its technological core is to employ denitrating catalyst, has the advantages that reaction temperature is relatively low, purifying rate is high, reliable.Flat board
Formula catalyst is a very important class in this kind of catalyst, has the higher market share.
The mechanical performance of denitrating catalyst is used for the life-span and has a significant impact, and the flying dust in flue gas constantly washes away catalyst
Surface may result in catalyst large area to peel off and cave in, thus greatly shortening catalyst life.Additionally, China will welcome big rule
The inactivation denitrating catalyst regeneration market of mould, the regeneration of inactivation denitrating catalyst is not only advantageous to environmental conservation, saves material,
Realize the cycling and reutilization of resource, and reduce denitration cost, avoid causing the two of the serious waste of resource and environment simultaneously
Secondary pollution, State Council exists《With regard to accelerating development the suggestion of energy-conserving and environment-protective industry》In, clearly propose denitration to be greatly developed and urge
Agent regeneration techniques.If catalytic mechanical performance is not good, the phenomenons such as serious peeling are occurred to will be unable to carry out in use
Regeneration, this partial catalyst must be processed as danger wastes, and processing cost is high and environmental pollution is serious.
Content of the invention
It is an object of the invention to provide a kind of denitration efficiency is high and stability is strong with activated carbon-TiO2Denitration for carrier
The preparation method of catalyst.
Technical scheme：The denitrating catalyst with activated carbon-TiO2 as carrier for the present invention, includes former as follows by weight
Material：Activated carbon 200-250 part, TiO2 20-40 part, MoO2 10-30 part, Cr2O3 5-20 part, MnO2 20-30 part, SnO2
2-12 part, ZrO2 9-27 part, lubricant 17-35 part and heteropoly acid 6-15 part.Preferably, the parts by weight of lubricant can be 25-
32 parts, it at least includes polyurea grease, epoxy resin, polyacrylate, fatty acid amide, Oleic acid, carboxylic acid, esters of silicon acis or fluorine
One of oil；The parts by weight of heteropoly acid can be 10-15 part, and it may include 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicon
Acid；The parts by weight of activated carbon are 225-245 part；The parts by weight of MoO2 are 15-25 part.
The method of the denitrating catalyst with activated carbon-TiO2 as carrier for the present invention preparation comprises the steps：
(1) presoma titanium salt solution and the activated carbon of TiO2 are weighed by weight, by titanium salt solution and electrolyte solution
After mixing, it is added thereto to activated carbon dipping, after ageing 15-35h, mixed liquor is transferred in water heating kettle, then at 120-160 DEG C
Under the conditions of react 12-15h, through filtering, washing, be dried, after roasting, that is, activated carbon-TiO2 carrier be obtained；
(2) weigh MoO2, Cr2O3, MnO2, SnO2, ZrO2, lubricant and heteropoly acid by weight, by MoO2,
After Cr2O3, MnO2, SnO2, ZrO2 and heteropoly acid mixing, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry
Material, this slurry is mixed with lubricant, drying, after roasting, that is, denitrating catalyst is obtained.
The titanium salt of the present invention can be preferably metatitanic acid, titanium tetrachloride, titanyl sulfate or titanium acetylacetone.
Application in denitration for the aforesaid denitrating catalyst with activated carbon-TiO2 as carrier is also in the protection model of the present invention
Within enclosing.
Beneficial effect：Compared with prior art, the remarkable advantage of the present invention is：This denitrating catalyst has relatively low rising and lives
Temperature, its heat stability and hydrothermal stability are strong, active temperature windows width, denitration efficiency are high, and catalyst life is long；Meanwhile,
The preparation method of the present invention is simple, workable, reduces production cost.
Specific embodiment
With reference to embodiment, technical scheme is described further.
Embodiment 1
Raw material：225 parts of activated carbon, 30 parts of TiO2,15 parts of MoO2,15 parts of Cr2O3,25 parts of MnO2,8 parts of SnO2,
20 parts of ZrO2,32 parts of polyurea grease and 10 parts of 12- tungstophosphoric acid.
Preparation method：(1) weigh presoma metatitanic acid solution and the activated carbon of TiO2, metatitanic acid solution and electrolyte solution are mixed
After conjunction, it is added thereto to activated carbon dipping, after ageing 20h, mixed liquor is transferred in water heating kettle, more anti-under the conditions of 130 DEG C
Answer 13h, after filtration, washing, drying, roasting, that is, activated carbon-TiO2 carrier is obtained；
(2) MoO2, Cr2O3, MnO2, SnO2, ZrO2, polyurea grease and 12- tungstophosphoric acid are weighed by weight, will
After MoO2, Cr2O3, MnO2, SnO2, ZrO2 and 12- tungstophosphoric acid mixes, add above-mentioned prepared carrier, dipping, prepared denitration is urged
Agent slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, 4h is dried at 100 DEG C, 450 DEG C of air gas
Roasting 9h under atmosphere, that is, be obtained denitrating catalyst.
Embodiment 2
Raw material：235 parts of activated carbon, 60 parts, 28 parts of TiO2,25 parts of MoO2,10 parts of Cr2O3, MnO222 part, SnO2 10
Part, 15 parts of ZrO2,25 parts of lubricant and 15 parts of 12- tungstosilicic acid, wherein, lubricant is epoxy resin and polyacrylate.
Preparation method：(1) presoma titanium tetrachloride solution and the activated carbon of TiO2 are taken, by titanium tetrachloride solution and electrolyte
After solution mixing, it is added thereto to activated carbon dipping, after ageing 30h, mixed liquor is transferred in water heating kettle, then in 140 DEG C of bars
React 14h under part, through filtering, washing, be dried, after roasting, that is, activated carbon-TiO2 carrier be obtained；
(2) weigh MoO2, Cr2O3, MnO2, SnO2, ZrO2, lubricant and 12- tungstosilicic acid by weight, by MoO2,
After Cr2O3, MnO2, SnO2, ZrO2 and 12- tungstosilicic acid mixes, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst
Slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, 3h is dried at 110 DEG C, under 430 DEG C of air atmospheres
Roasting 12h, that is, be obtained denitrating catalyst.
Embodiment 3
Raw material：245 parts of activated carbon, 20 parts of TiO2,30 parts of MoO2,5 parts of Cr2O3,30 parts of MnO2,2 parts of SnO2,
27 parts of ZrO2,17 parts of lubricant and 15 parts of 12- molybdenum silicic acid, wherein, lubricant is fatty acid amide and Oleic acid.
Preparation method：(1) presoma titanyl sulfate solution and the activated carbon of TiO2 are taken, by titanyl sulfate solution and electrolyte
After solution mixing, it is added thereto to activated carbon and dipping, after ageing 15h, mixed liquor is transferred in water heating kettle, then at 120 DEG C
Under the conditions of react 12h, through filtering, washing, be dried, after roasting, that is, activated carbon-TiO2 carrier be obtained；
(2) by after the mixing of MoO2, Cr2O3, MnO2, SnO2, ZrO2 and 12- molybdenum silicic acid, above-mentioned prepared carrier, leaching are added
Stain, prepared denitrating catalyst slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, at 95 DEG C, 6h is dried,
Roasting 10h under 410 DEG C of air atmospheres, that is, be obtained denitrating catalyst.
Embodiment 4
Raw material：240 parts of activated carbon, 40 parts of TiO2,10 parts of MoO2,20 parts of Cr2O3,20 parts of MnO2,12 parts of SnO2,
9 parts of ZrO2,35 parts of lubricant and 6 parts of 12- molybdenum silicic acid, wherein, lubricant is carboxylic acid, esters of silicon acis and fluorocarbon oil.
Preparation method：(1) presoma acetylacetone,2,4-pentanedione titanium solution and the activated carbon of TiO2 are taken, by acetylacetone,2,4-pentanedione titanium solution and electricity
After electrolyte solution mixing, it is added thereto to activated carbon and dipping, after ageing 35h, mixed liquor is transferred in water heating kettle, then
React 15h under the conditions of 160 DEG C, through filtering, washing, be dried, after roasting, that is, activated carbon-TiO2 carrier be obtained；
(2) by after the mixing of MoO2, Cr2O3, MnO2, SnO2, ZrO2 and 12- molybdenum silicic acid, above-mentioned prepared carrier, leaching are added
Stain, prepared denitrating catalyst slurry, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, at 95 DEG C, 6h is dried,
Roasting 10h under 410 DEG C of air atmospheres, that is, be obtained denitrating catalyst.
The denitrating catalyst of embodiment 1-4 preparation is put in fixed-bed micro-reactor and is evaluated, in this reactor
Temperature be 400 DEG C, simulated flue gas consist of NO concentration be 450ppm, NH3 concentration be 450ppm, O2 content be 5%, vapor
Content is 5%, and remaining is that N2, gas volume air speed 30000h-1, and entrance NO concentration are detected by flue gas analyzer.Obtain
Experimental result as shown in table 1.
The denitration efficiency synopsis of the denitrating catalyst that 1-4 is obtained implemented by table 1
As shown in Table 1, not only denitration efficiency is high for the denitrating catalyst that embodiment 1-4 is obtained, and it has relatively low rising and lives
Temperature, heat-flash stability and hydrothermal stability are strong, its active temperature windows width, life-span length simultaneously.
Claims (10)
1. one kind is prepared with activated carbon-TiO2Method for the denitrating catalyst of carrier is it is characterised in that comprise the steps：
(1) weigh TiO by weight2Presoma titanium salt solution and activated carbon, by titanium salt solution and electrolyte solution mixing
Afterwards, it is added thereto to activated carbon dipping, after ageing 15-35h, mixed liquor is transferred in water heating kettle, then in 120-160 DEG C of condition
Lower reaction 12-15h, after filtration, washing, drying, roasting, that is, is obtained activated carbon-TiO2Carrier；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid, by MoO2、Cr2O3、MnO2、
SnO2、ZrO2And heteropoly acid mix after, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry, by this slurry with
Lubricant mixes, drying, after roasting, that is, denitrating catalyst is obtained.
2. preparation according to claim 1 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
In step (1), described titanium salt is metatitanic acid, titanium tetrachloride, titanyl sulfate or titanium acetylacetone.
3. preparation according to claim 1 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
In step (2), described lubricant at least includes polyurea grease, epoxy resin, polyacrylate, fatty acid amide, Oleic acid, carboxylic
One of acid, esters of silicon acis or fluorocarbon oil.
4. preparation according to claim 1 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
In step (2), described heteropoly acid includes 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid.
5. preparation according to claim 1 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
In step (1) and (2), the mass fraction of each component is as follows：
Activated carbon 200-250 part, TiO220-40 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22-
12 parts, ZrO29-27 part, lubricant 17-35 part and heteropoly acid 6-15 part.
6. preparation according to claim 5 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
The parts by weight of described activated carbon are 225-245 part.
7. preparation according to claim 5 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
Described parts by weight are 60-70 part.
8. preparation according to claim 5 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
Described MoO2Parts by weight be 15-25 part.
9. preparation according to claim 5 is with activated carbon-TiO2Method for the denitrating catalyst of carrier it is characterised in that
The parts by weight of described lubricant are 25-32 part.
10. preparation according to claim 5 is with activated carbon-TiO2For the method for the denitrating catalyst of carrier, its feature exists
In the parts by weight of described heteropoly acid are 10-15 part.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610796676.5A CN106378201A (en) | 2016-08-31 | 2016-08-31 | Preparation method of denitration catalyst adopting active carbon-TiO2 as carrier |
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| CN201610796676.5A CN106378201A (en) | 2016-08-31 | 2016-08-31 | Preparation method of denitration catalyst adopting active carbon-TiO2 as carrier |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376886A (en) * | 2017-09-06 | 2017-11-24 | 北方民族大学 | One kind dipping hydro-thermal method synthesis active carbon from coal load TiO2The method of composite |
| CN109603807A (en) * | 2018-11-29 | 2019-04-12 | 中北大学 | A kind of modified activated carbon Ce-Nb/TiO2@AC efficient cryogenic desulphurization denitration catalyst and preparation method thereof |
| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
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| CN101474565A (en) * | 2009-01-06 | 2009-07-08 | 上海瀛正科技有限公司 | Honeycomb type SCR denitration catalyst as well as preparation method thereof and equipment |
| JP2013180286A (en) * | 2012-03-05 | 2013-09-12 | Mitsubishi Heavy Ind Ltd | Denitration catalyst for treating exhaust gas and method for treating exhaust gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101474565A (en) * | 2009-01-06 | 2009-07-08 | 上海瀛正科技有限公司 | Honeycomb type SCR denitration catalyst as well as preparation method thereof and equipment |
| JP2013180286A (en) * | 2012-03-05 | 2013-09-12 | Mitsubishi Heavy Ind Ltd | Denitration catalyst for treating exhaust gas and method for treating exhaust gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376886A (en) * | 2017-09-06 | 2017-11-24 | 北方民族大学 | One kind dipping hydro-thermal method synthesis active carbon from coal load TiO2The method of composite |
| CN109603807A (en) * | 2018-11-29 | 2019-04-12 | 中北大学 | A kind of modified activated carbon Ce-Nb/TiO2@AC efficient cryogenic desulphurization denitration catalyst and preparation method thereof |
| CN109603807B (en) * | 2018-11-29 | 2021-09-28 | 中北大学 | Modified activated carbon Ce-Nb/TiO2@ AC low-temperature efficient desulfurization and denitrification catalyst and preparation method thereof |
| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
| CN110508275B (en) * | 2019-08-21 | 2022-08-26 | 上海应用技术大学 | Mesoporous material loaded manganese dioxide catalyst and preparation method thereof |
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Application publication date: 20170208 |