CN106391133A - Application of denitration catalyst with activated carbon-TiO2 as carrier in denitration - Google Patents

Application of denitration catalyst with activated carbon-TiO2 as carrier in denitration Download PDF

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CN106391133A
CN106391133A CN201610794290.0A CN201610794290A CN106391133A CN 106391133 A CN106391133 A CN 106391133A CN 201610794290 A CN201610794290 A CN 201610794290A CN 106391133 A CN106391133 A CN 106391133A
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activated carbon
parts
denitration
carrier
application
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史和生
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Nanjing Wo Yu Chemical Co Ltd
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Nanjing Wo Yu Chemical Co Ltd
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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
    • 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
    • B01J23/16—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
    • B01J23/28—Molybdenum
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/65—Catalysts not containing noble metals
    • 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)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention discloses to an application of a denitration catalyst with activated carbon-TiO2 as a carrier in denitration; the denitration catalyst comprises the following raw materials: activated carbon, TiO2, MoO2, Cr2O3, MnO2, SnO2, ZrO2, a lubricant and heteropolyacid. A preparation method comprises the steps of mixing a titanium salt solution and an electrolyte solution, then adding activated carbon to the mixture, impregnating, aging, then transferring to a hydrothermal kettle, and carrying out a reaction, to prepare a carrier; mixing evenly MoO2, Cr2O3, MnO2, SnO2, ZrO2 and heteropolyacid, adding the carrier, and impregnating to prepare the denitration catalyst. The denitration catalyst has the advantages of relatively low activation temperature, strong thermal stability and hydrothermal stability, wide active temperature window, high denitration efficiency, and long service life of the catalyst; and at the same time, the preparation method is simple, the operability is high, and the production cost is reduced.

Description

With activated carbon-TiO2Application in denitration for the denitrating catalyst for carrier
Technical field
The invention belongs to catalyst field, more particularly, to the denitrating catalyst with activated carbon-TiO2 as carrier is in denitration Application.
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 application in denitration for the denitrating catalyst with activated carbon-TiO2 as carrier.
Technical scheme：The present invention is with activated carbon-TiO2For the denitrating catalyst of carrier, include former as follows by weight Material：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.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；MoO2Parts by weight be 15-25 part.
The present invention is prepared with activated carbon-TiO2Method for the denitrating catalyst of carrier comprises the steps：
(1) weigh TiO by weight2Presoma titanium salt solution and activated carbon, 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-TiO be obtained2Carrier；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid, by MoO2、Cr2O3、 MnO2、SnO2、ZrO2And after heteropoly acid mixes, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry, this is starched Material 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.
Aforesaid with activated carbon-TiO2For carrier application in denitration for the denitrating catalyst 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, TiO230 parts, MoO215 parts, Cr2O315 parts, MnO225 parts, SnO28 parts, ZrO2 20 parts, 32 parts of polyurea grease and 10 parts of 12- tungstophosphoric acid.
Preparation method：(1) weigh TiO2Presoma metatitanic acid solution and activated carbon, 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-TiO is obtained2Carrier；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, polyurea grease and 12- tungstophosphoric acid, will MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- tungstophosphoric acid mixes, add above-mentioned prepared carrier, dipping, prepared denitration catalyst 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 atmospheres Lower roasting 9h, that is, be obtained denitrating catalyst.Embodiment 2
Raw material：235 parts of activated carbon, 60 parts, TiO228 parts, MoO225 parts, Cr2O310 parts, MnO222 parts, SnO210 Part, ZrO215 parts, 25 parts of lubricant and 15 parts of 12- tungstosilicic acid, wherein, lubricant is epoxy resin and polyacrylate.
Preparation method：(1) take TiO2Presoma titanium tetrachloride solution and activated carbon, 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-TiO be obtained2Carrier；
(2) weigh MoO by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and 12- tungstosilicic acid, by MoO2、 Cr2O3、MnO2、SnO2、ZrO2And after 12- tungstosilicic acid mixes, add above-mentioned prepared carrier, dipping, prepared denitrating catalyst slurry Material, this slurry is mixed with lubricant, is coated on rustless steel steel mesh, 3h is dried at 110 DEG C, roasts under 430 DEG C of air atmospheres Burn 12h, that is, denitrating catalyst is obtained.Embodiment 3
Raw material：245 parts of activated carbon, TiO220 parts, MoO230 parts, Cr2O35 parts, MnO230 parts, SnO22 parts, ZrO2 27 parts, 17 parts of lubricant and 15 parts of 12- molybdenum silicic acid, wherein, lubricant is fatty acid amide and Oleic acid.
Preparation method：(1) take TiO2Presoma titanyl sulfate solution and activated carbon, 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-TiO be obtained2Carrier；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- molybdenum silicic acid mixes, add above-mentioned prepared carrier, leaching 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, TiO240 parts, MoO210 parts, Cr2O320 parts, MnO220 parts, SnO212 parts, ZrO29 parts, 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) take TiO2Presoma acetylacetone,2,4-pentanedione titanium solution and activated carbon, 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-TiO be obtained2Carrier；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after 12- molybdenum silicic acid mixes, add above-mentioned prepared carrier, leaching 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, NH3Concentration is 450ppm, O2Content is 5%, vapor Content is 5%, and remaining is N2, gas volume air speed 30000h-1, and entrance NO concentration 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 (7)

1. application in denitration for the denitrating catalyst with activated carbon-TiO2 as carrier is it is characterised in that it includes following weight The component of number：
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.
2. according to claim 1 application it is characterised in that：Described lubricant at least includes polyurea grease, asphalt mixtures modified by epoxy resin One of fat, polyacrylate, fatty acid amide, Oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil.
3. according to claim 1 application it is characterised in that：Described heteropoly acid include 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid.
4. according to claim 1 application it is characterised in that：The parts by weight of described activated carbon are 225-245 part.
5. according to claim 1 application it is characterised in that：Described MoO2Parts by weight be 15-25 part.
6. according to claim 1 application it is characterised in that：The parts by weight of described lubricant are 25-32 part.
7. according to claim 1 application it is characterised in that：The parts by weight of described heteropoly acid are 10-15 part.
CN201610794290.0A 2016-08-31 2016-08-31 Application of denitration catalyst with activated carbon-TiO2 as carrier in denitration Withdrawn CN106391133A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101185886A (en) * 2007-11-21 2008-05-28 北京博奇电力科技有限公司 SCR denitration catalyst and preparation method thereof
CN103861628A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Flue-gas denitration catalyst incapable of being deactivated by basic metallic oxides, preparation method thereof and applications thereof
CN104128188A (en) * 2014-08-15 2014-11-05 安徽省元琛环保科技有限公司 Denitration catalyst used in waste incineration power plant and preparation method thereof
CN105688974A (en) * 2016-01-11 2016-06-22 大唐南京环保科技有限责任公司 Denitration catalyst with SBA-15/TiO2 serving as carrier and preparing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101185886A (en) * 2007-11-21 2008-05-28 北京博奇电力科技有限公司 SCR denitration catalyst and preparation method thereof
CN103861628A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Flue-gas denitration catalyst incapable of being deactivated by basic metallic oxides, preparation method thereof and applications thereof
CN104128188A (en) * 2014-08-15 2014-11-05 安徽省元琛环保科技有限公司 Denitration catalyst used in waste incineration power plant and preparation method thereof
CN105688974A (en) * 2016-01-11 2016-06-22 大唐南京环保科技有限责任公司 Denitration catalyst with SBA-15/TiO2 serving as carrier and preparing method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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