CN106475147A - Application in denitration for the catalyst with aluminium oxide as carrier - Google Patents

Application in denitration for the catalyst with aluminium oxide as carrier Download PDF

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Publication number
CN106475147A
CN106475147A CN201610780907.3A CN201610780907A CN106475147A CN 106475147 A CN106475147 A CN 106475147A CN 201610780907 A CN201610780907 A CN 201610780907A CN 106475147 A CN106475147 A CN 106475147A
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Prior art keywords
catalyst
parts
aluminium oxide
application
acid
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CN201610780907.3A
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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 CN201610780907.3A priority Critical patent/CN106475147A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14Phosphorus; Compounds thereof
    • B01J27/186Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19Molybdenum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts 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
    • B01J23/32Manganese, technetium or rhenium
    • B01J23/34Manganese
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/20Metals or compounds thereof
    • B01D2255/209Other metals
    • B01D2255/2092Aluminium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/65Catalysts not containing noble metals

Abstract

The invention discloses application in denitration for the catalyst with aluminium oxide as carrier, this catalyst includes the following raw material:Aluminium oxide, MoO2、Cr2O3、MnO2、SnO2、ZrO2, lubricant and heteropoly acid;Preparation method is to add aluminium oxide in electrolyte solution to impregnate, and is transferred in water heating kettle, reaction after ageing, that is, carrier is obtained;By MoO2、Cr2O3、MnO2、SnO2、ZrO2And after heteropoly acid mixes, adding above-mentioned carrier, dipping is obtained catalyst.Advantage is that this denitrating catalyst has relatively low light-off temperature, and 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.

Description

Application in denitration for the catalyst with aluminium oxide as carrier
Technical field
The invention belongs to catalyst field, application in denitration for the catalyst more particularly, to aluminium oxide as carrier.
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 catalyst with aluminium oxide as carrier.
Technical scheme:The denitrating catalyst with aluminium oxide as carrier for the present invention, includes the following raw material by weight:Oxidation Aluminum 75-150 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 polyureas lubrication One of 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 may include 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid;The parts by weight of aluminium oxide are 90- 110 parts;MoO2Parts by weight be 15-25 part.
The method of the denitrating catalyst with aluminium oxide as carrier for the present invention preparation comprises the steps:
(1) aluminium oxide is added in electrolyte solution and impregnates, after ageing 15-35h, mixed liquor is transferred in water heating kettle, React 12-15h again under the conditions of 120-160 DEG C, through filtering, washing, be dried, after roasting, that is, alumina support be obtained;
(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 above-mentioned catalyst with aluminium oxide as carrier is in the application in denitration 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.
Specific embodiment
With reference to embodiment, technical scheme is described further.
Embodiment 1
Raw material:90 parts of aluminium oxide, MoO215 parts, Cr2O315 parts, MnO225 parts, SnO28 parts, ZrO220 parts, polyureas 32 parts of grease and 10 parts of 12- tungstophosphoric acid.
Preparation method:(1) aluminium oxide is added in electrolyte solution and impregnate, after ageing 20h, mixed liquor is transferred to hydro-thermal In kettle, then react 13h under the conditions of 130 DEG C, through filtering, washing, be dried, after roasting, that is, alumina support be obtained;
(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:95 parts of aluminium oxide, MoO225 parts, Cr2O310 parts, MnO222 parts, SnO210 parts, ZrO215 parts, lubrication 25 parts of agent and 15 parts of 12- tungstosilicic acid, wherein, lubricant is epoxy resin and polyacrylate.
Preparation method:(1) aluminium oxide is added in electrolyte solution and impregnate, after ageing 30h, mixed liquor is transferred to hydro-thermal In kettle, then react 14h under the conditions of 140 DEG C, through filtering, washing, be dried, after roasting, that is, alumina support be obtained;
(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:100 parts of aluminium oxide, MoO230 parts, Cr2O35 parts, MnO230 parts, SnO22 parts, ZrO227 parts, lubrication 17 parts of agent and 15 parts of 12- molybdenum silicic acid, wherein, lubricant is fatty acid amide and Oleic acid.
Preparation method:(1) aluminium oxide is added in electrolyte solution and impregnate, after ageing 15h, mixed liquor is transferred to hydro-thermal In kettle, then react 12h under the conditions of 120 DEG C, through filtering, washing, be dried, after roasting, that is, alumina support be obtained;
(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:110 parts of aluminium oxide, MoO210 parts, Cr2O320 parts, MnO220 parts, SnO212 parts, ZrO29 parts, lubrication 35 parts of agent and 6 parts of 12- molybdenum silicic acid, wherein, lubricant is carboxylic acid, esters of silicon acis and fluorocarbon oil.
Preparation method:(1) aluminium oxide is added in electrolyte solution and impregnate, after ageing 35h, mixed liquor is transferred to hydro-thermal In kettle, then react 15h under the conditions of 160 DEG C, through filtering, washing, be dried, after roasting, that is, alumina support be obtained;
(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 catalyst with aluminium oxide as carrier is it is characterised in that it includes the group of following parts by weight Point:
Aluminium oxide 75-150 part, MoO210-30 part, Cr2O35-20 part, MnO220-30 part, SnO22-12 part, 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 aluminium oxide are 90-110 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.
CN201610780907.3A 2016-08-31 2016-08-31 Application in denitration for the catalyst with aluminium oxide as carrier Withdrawn CN106475147A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110274607A1 (en) * 2010-05-04 2011-11-10 Technical University Of Denmark Vanadia-supported zeolites for scr of no by ammonia
CN102527404A (en) * 2011-12-30 2012-07-04 湖南大学 Medium/low temperature SCR (Selective Catalytic Reduction) denitration catalyst with gamma-Al2O3 as carrier 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
US20110274607A1 (en) * 2010-05-04 2011-11-10 Technical University Of Denmark Vanadia-supported zeolites for scr of no by ammonia
CN102527404A (en) * 2011-12-30 2012-07-04 湖南大学 Medium/low temperature SCR (Selective Catalytic Reduction) denitration catalyst with gamma-Al2O3 as carrier 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵琳琳等: "V-W/TiO2/γ-Al2O3催化剂催化还原NO的研究", 《环境科学与技术》 *

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