CN106311333A - Application of catalyst using activated carbon as carrier in denitration - Google Patents

Application of catalyst using activated carbon as carrier in denitration Download PDF

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Publication number
CN106311333A
CN106311333A CN201610800063.4A CN201610800063A CN106311333A CN 106311333 A CN106311333 A CN 106311333A CN 201610800063 A CN201610800063 A CN 201610800063A CN 106311333 A CN106311333 A CN 106311333A
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Prior art keywords
catalyst
parts
activated carbon
acid
application
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CN201610800063.4A
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Chinese (zh)
Inventor
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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Priority to CN201610800063.4A priority Critical patent/CN106311333A/en
Publication of CN106311333A publication Critical patent/CN106311333A/en
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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
    • B01J23/16—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
    • 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

Abstract

The invention discloses application of a catalyst using activated carbon as a carrier in denitration. The catalyst comprises the following raw materials: activated carbon, MoO2, Cr2O3, MnO2, SnO2, ZrO2, a lubricating agent and heteropolyacid. A preparation method comprises the following steps: soaking the activated carbon in an electrolyte solution, after ageing, transferring into a hydrothermal kettle, and reacting to obtain the carrier; and after MoO2, Cr2O3, MnO2, SnO2, ZrO2 and the heteropolyacid are mixed evenly, adding the carrier, and soaking to obtain the catalyst. The catalyst has the advantages that the denitration catalyst has low activating temperature, thermal stability and hydrothermal stability of the catalyst are high, an activation temperature window is wide, denitration efficiency is high, and the service life of the catalyst is long. Meanwhile, the preparation method is simple, operability is high, and the production cost is reduced.

Description

The application in denitration of the catalyst with activated carbon as carrier
Technical field
The invention belongs to catalyst field, particularly relate to the application in denitration of the catalyst with activated carbon as carrier.
Background technology
Nitrogen oxides is very serious to the pollution of environment, and nitrogen oxides is the basis of nitric acid type acid rain, is again to form light One of chemical fumes, the main matter damaged the ozone layer；Nitrogen oxides also has the strongest toxicity, health can be caused pole Macrolesion.In recent years, along 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 Middle selective catalytic reduction (SCR) denitration is one of gas denitrifying technology the most most widely used, that technology is the most ripe, Its technological core is to employ denitrating catalyst, has the advantages such as 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 and peels off and cave in, thus is greatly shortened 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 the two of serious waste and the environment causing resource simultaneously Secondary pollution, State Council, in " suggestion about accelerating development energy-conserving and environment-protective industry ", clearly proposes denitration to be greatly developed and urges Agent regeneration techniques.If catalytic mechanical performance is the best, the phenomenons such as serious peeling are in use occurred to will be unable to carry out Regeneration, this partial catalyst must process as danger wastes, and processing cost is high and environmental pollution is serious.
Summary of the invention
It is an object of the invention to provide the application in denitration of the catalyst with activated carbon as carrier.
Technical scheme: the present invention denitrating catalyst with activated carbon as carrier, includes following raw material by weight: activity Charcoal 200-250 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22-12 part, ZrO29-27 part, lubrication Agent 17-35 part and heteropoly acid 6-15 part.Preferably, the parts by weight of lubricant can be 25-32 part, and it at least includes that polyureas lubricates One in fat, epoxy resin, polyacrylate, fatty acid amide, oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil；The weight of heteropoly acid Number can be 10-15 part, and it can include 12-tungstophosphoric acid, 12-tungstosilicic acid or 12-molybdenum silicic acid；The parts by weight of activated carbon are 225- 245 parts；MoO2Parts by weight be 15-25 part.
The method of the present invention preparation denitrating catalyst with activated carbon as carrier comprises the steps:
(1) activated carbon is added in electrolyte solution and impregnates, after ageing 15-35h, mixed liquor is transferred in water heating kettle, Under the conditions of 120-160 DEG C, react 12-15h again, through filtering, wash, being dried, after roasting, i.e. prepare absorbent charcoal carrier；
(2) MoO is weighed by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid, by MoO2、Cr2O3、 MnO2、SnO2、ZrO2And after heteropoly acid mixing, add above-mentioned prepared carrier, and dipping, prepare denitrating catalyst slurry, by this slurry Material mixes with lubricant, and drying, after roasting, i.e. prepares denitrating catalyst.
The application in denitration of the above-mentioned catalyst with activated carbon as carrier is also within protection scope of the present invention.
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.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is described further.
Embodiment 1
Raw material: activated carbon 225 parts, MoO215 parts, Cr2O315 parts, MnO225 parts, SnO28 parts, ZrO220 parts, polyureas Grease 32 parts and 12-tungstophosphoric acid 10 parts.
Preparation method: activated carbon is added dipping in electrolyte solution by (1), after ageing 20h, mixed liquor is transferred to hydro-thermal In still, then under the conditions of 130 DEG C, react 13h, through filtering, wash, being dried, after roasting, i.e. prepare absorbent charcoal carrier；
(2) MoO is weighed by weight2、Cr2O3、MnO2、SnO2、ZrO2, polyurea grease and 12-tungstophosphoric acid, will MoO2、Cr2O3、MnO2、SnO2、ZrO2And after the mixing of 12-tungstophosphoric acid, add above-mentioned prepared carrier, and dipping, prepare denitration catalyst Agent slurry, mixes this slurry with lubricant, is coated on rustless steel steel mesh, is dried 4h, 450 DEG C of air atmospheres at 100 DEG C Lower roasting 9h, i.e. prepares denitrating catalyst.
Embodiment 2
Raw material: activated carbon 235 parts, MoO225 parts, Cr2O310 parts, MnO222 parts, SnO210 parts, ZrO215 parts, profit Lubrication prescription 25 parts and 12-tungstosilicic acid 15 parts, wherein, lubricant is epoxy resin and polyacrylate.
Preparation method: activated carbon is added dipping in electrolyte solution by (1), after ageing 30h, mixed liquor is transferred to hydro-thermal In still, then under the conditions of 140 DEG C, react 14h, through filtering, wash, being dried, after roasting, i.e. prepare absorbent charcoal carrier；
(2) MoO is weighed by weight2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and 12-tungstosilicic acid, by MoO2、 Cr2O3、MnO2、SnO2、ZrO2And after the mixing of 12-tungstosilicic acid, add above-mentioned prepared carrier, and dipping, prepare denitrating catalyst slurry Material, mixes this slurry with lubricant, is coated on rustless steel steel mesh, is dried 3h, roasts under 430 DEG C of air atmospheres at 110 DEG C Burn 12h, i.e. prepare denitrating catalyst.
Embodiment 3
Raw material: activated carbon 245 parts, MoO230 parts, Cr2O35 parts, MnO230 parts, SnO22 parts, ZrO227 parts, lubrication Agent 17 parts and 12-molybdenum silicic acid 15 parts, wherein, lubricant is fatty acid amide and oleic acid.
Preparation method: activated carbon is added dipping in electrolyte solution by (1), after ageing 15h, mixed liquor is transferred to hydro-thermal In still, then under the conditions of 120 DEG C, react 12h, through filtering, wash, being dried, after roasting, i.e. prepare absorbent charcoal carrier；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after the mixing of 12-molybdenum silicic acid, add above-mentioned prepared carrier, leaching Stain, prepares denitrating catalyst slurry, is mixed with lubricant by this slurry, is coated on rustless steel steel mesh, is dried 6h at 95 DEG C, Roasting 10h under 410 DEG C of air atmospheres, i.e. prepares denitrating catalyst.
Embodiment 4
Raw material: activated carbon 240 parts, MoO210 parts, Cr2O320 parts, MnO220 parts, SnO212 parts, ZrO29 parts, lubrication Agent 35 parts and 12-molybdenum silicic acid 6 parts, wherein, lubricant is carboxylic acid, esters of silicon acis and fluorocarbon oil.
Preparation method: activated carbon is added dipping in electrolyte solution by (1), after ageing 35h, mixed liquor is transferred to hydro-thermal In still, then under the conditions of 160 DEG C, react 15h, through filtering, wash, being dried, after roasting, i.e. prepare absorbent charcoal carrier；
(2) by MoO2、Cr2O3、MnO2、SnO2、ZrO2And after the mixing of 12-molybdenum silicic acid, add above-mentioned prepared carrier, leaching Stain, prepares denitrating catalyst slurry, is mixed with lubricant by this slurry, is coated on rustless steel steel mesh, is dried 6h at 95 DEG C, Roasting 10h under 410 DEG C of air atmospheres, i.e. prepares denitrating catalyst.
Denitrating catalyst embodiment 1-4 prepared is put into fixed-bed micro-reactor and is evaluated, in this reactor Temperature be 400 DEG C, it is 450ppm, NH that simulated flue gas consists of NO concentration3Concentration is 450ppm, O2Content is 5%, steam Content is 5%, and remaining is N2, gas volume air speed 30000h-1, and import department's 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 prepares implemented by table 1
As shown in Table 1, the denitrating catalyst not only denitration efficiency that embodiment 1-4 prepares is high, and it has relatively low rising and lives Temperature, heat-flash stability and hydrothermal stability are strong, and its active temperature windows width, life-span are long simultaneously.

Claims (7)

1. the application in denitration of the catalyst with activated carbon as carrier, it is characterised in that it includes the group of following parts by weight Point:
Activated carbon 200-250 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22-12 part, ZrO2 9- 27 parts, lubricant 17-35 part and heteropoly acid 6-15 part.
Application the most according to claim 1, it is characterised in that: described lubricant at least includes polyurea grease, asphalt mixtures modified by epoxy resin One in fat, polyacrylate, fatty acid amide, oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil.
Application the most according to claim 1, it is characterised in that: described heteropoly acid include 12-tungstophosphoric acid, 12-tungstosilicic acid or 12-molybdenum silicic acid.
Application the most according to claim 1, it is characterised in that: the parts by weight of described activated carbon are 225-245 part.
Application the most according to claim 1, it is characterised in that: described MoO2Parts by weight be 15-25 part.
Application the most according to claim 1, it is characterised in that: the parts by weight of described lubricant are 25-32 part.
Application the most according to claim 1, it is characterised in that: the parts by weight of described heteropoly acid are 10-15 part.
CN201610800063.4A 2016-08-31 2016-08-31 Application of catalyst using activated carbon as carrier in denitration Pending CN106311333A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109759100A (en) * 2019-02-22 2019-05-17 湘潭大学 The preparation method and the application in glycerol liquid phase catalytic hydrogenation reaction of molybdenum oxide and the co-modified supported ruthenium C catalyst of phosphotungstic acid

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
CN102950008A (en) * 2011-08-29 2013-03-06 中国石油化工股份有限公司 Composite smoke SCR (selective catalytic reduction) denitrification 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
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
CN102950008A (en) * 2011-08-29 2013-03-06 中国石油化工股份有限公司 Composite smoke SCR (selective catalytic reduction) denitrification 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
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
CN109759100A (en) * 2019-02-22 2019-05-17 湘潭大学 The preparation method and the application in glycerol liquid phase catalytic hydrogenation reaction of molybdenum oxide and the co-modified supported ruthenium C catalyst of phosphotungstic acid
CN109759100B (en) * 2019-02-22 2022-03-18 湘潭大学 Preparation method of molybdenum oxide and phosphotungstic acid co-modified supported ruthenium-carbon catalyst and application of catalyst in liquid-phase catalytic hydrogenation reaction of glycerol

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Application publication date: 20170111