CN106390995A - Denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as carrier - Google Patents

Denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as carrier Download PDF

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Publication number
CN106390995A
CN106390995A CN201610796769.8A CN201610796769A CN106390995A CN 106390995 A CN106390995 A CN 106390995A CN 201610796769 A CN201610796769 A CN 201610796769A CN 106390995 A CN106390995 A CN 106390995A
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attapulgite
carrier
tio
parts
green grass
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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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Priority to CN201610796769.8A priority Critical patent/CN106390995A/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
    • 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
    • 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
    • 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
    • B01D53/90—Injecting reactants
    • 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
    • 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
    • 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

Abstract

The invention discloses a denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as a carrier. The denitration catalyst comprises following raw materials: attapulgite, cordierite honeycomb ceramic, TiO2, MoO2, Cr2O3, MnO2, SnO2, ZrO2, a lubricating agent, and heteropolyacid. A preparation method comprises following steps: a titanium salt solution and an electrolyte solution are mixed so as to obtain a mixture; attapulgite and cordierite honeycomb ceramic are added into the mixture for dipping; aging is carried out; an obtained mixed solution is delivered into a hydrothermal vessel for reaction so as to obtain the carrier; MoO2, Cr2O3, MnO2, SnO2, ZrO2, and heteropolyacid are uniformly mixed so as to obtain a mixed material; the carrier is added into the mixed material for dipping so as to obtain the denitration catalyst. The denitration catalyst possesses following advantages: light-off temperature of the preparation method is relatively low; thermal stability and hydrothermal stability of the denitration catalyst are high; active temperature window is wide; denitration efficiency is high; catalyst service life is long; and in addition, the preparation method is simple, operability is high, and production cost is reduced.

Description

One kind is with attapulgite-violet green grass or young crops ceramic honey comb-TiO2Denitrating catalyst for carrier
Technical field
The invention belongs to catalyst field, more particularly, to one kind are with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For carrier Denitrating catalyst.
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 attapulgite-violet green grass or young crops ceramic honey comb- TiO2Denitrating catalyst for carrier.
Technical scheme：The present invention is with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, by weight Part meter includes the following raw material：Attapulgite 100-120 part, violet green grass or young crops ceramic honey comb 50-80 part, TiO220-40 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.Preferably, the parts by weight of lubricant can be 25-32 part, and it at least includes polyurea grease, epoxy resin, polyacrylic acid One of ester, fatty acid amide, Oleic acid, carboxylic acid, esters of silicon acis or fluorocarbon oil；The parts by weight of heteropoly acid can be 10-15 part, and it can Including 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid；The parts by weight of attapulgite are 105-115 part；Violet green grass or young crops ceramic honey comb Parts by weight be 60-70 part；MoO2Parts by weight be 15-25 part.
Present invention preparation is with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier method include as Lower step：
(1) weigh TiO by weight2Presoma titanium salt solution, attapulgite and violet green grass or young crops ceramic honey comb, titanium salt is molten After liquid and electrolyte solution mixing, it is added thereto to attapulgite and violet cuckoo wasp nest cerdip, after ageing 15-35h, will mix Liquid is transferred in water heating kettle, then reacts 12-15h under the conditions of 120-160 DEG C, after filtration, washing, drying, roasting, that is, is obtained Attapulgite-violet green grass or young crops ceramic honey comb-TiO2Carrier；
(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.
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：105 parts of attapulgite, violet 70 parts of ceramic honey comb of green grass or young crops, TiO230 parts, MoO215 parts, Cr2O315 parts, MnO2 25 parts, SnO28 parts, ZrO220 parts, 32 parts of polyurea grease and 10 parts of 12- tungstophosphoric acid.
Preparation method：(1) by TiO2Presoma metatitanic acid solution, attapulgite and violet green grass or young crops ceramic honey comb, by metatitanic acid solution After electrolyte solution mixing, it is added thereto to attapulgite and violet cuckoo wasp nest cerdip, after ageing 20h, mixed liquor is turned Move in water heating kettle, then react 13h under the conditions of 130 DEG C, through filtering, washing, be dried, after roasting, that is, attapulgite-violet be obtained Blue or green ceramic honey comb-TiO2Carrier；
(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：115 parts of attapulgite, violet 60 parts of ceramic honey comb of green grass or young crops, TiO228 parts, MoO225 parts, Cr2O310 parts, MnO2 22 parts, SnO210 parts, ZrO215 parts, 25 parts of lubricant and 15 parts of 12- tungstosilicic acid, wherein, lubricant is epoxy resin and poly- third Olefin(e) acid ester.
Preparation method：(1) by TiO2Presoma titanium tetrachloride solution, attapulgite and violet green grass or young crops ceramic honey comb, by tetrachloro After changing titanium solution and electrolyte solution mixing, it is added thereto to attapulgite and violet cuckoo wasp nest cerdip, after ageing 30h, will Mixed liquor is transferred in water heating kettle, then reacts 14h under the conditions of 140 DEG C, through filtering, washing, is dried, after roasting, that is, is obtained recessed Convex rod stone-violet green grass or young crops ceramic honey comb-TiO2Carrier；
(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 attapulgite, violet 80 parts of ceramic honey comb of green grass or young crops, TiO220 parts, MoO230 parts, Cr2O35 parts, MnO2 30 parts, SnO22 parts, ZrO227 parts, 17 parts of lubricant and 15 parts of 12- molybdenum silicic acid, wherein, lubricant is fatty acid amide and oil Acid.
Preparation method：(1) by TiO2Presoma titanyl sulfate solution, attapulgite and violet green grass or young crops ceramic honey comb, by sulphuric acid After oxygen titanium solution and electrolyte solution mixing, it is added thereto to attapulgite and violet cuckoo wasp nest cerdip, after ageing 15h, will Mixed liquor is transferred in water heating kettle, then reacts 12h under the conditions of 120 DEG C, through filtering, washing, is dried, after roasting, that is, is obtained recessed Convex rod stone-violet green grass or young crops ceramic honey comb-TiO2Carrier；
(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 3
Raw material：120 parts of attapulgite, violet 50 parts of ceramic honey comb of green grass or young crops, TiO240 parts, MoO210 parts, Cr2O320 parts, MnO2 20 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 fluorine Oil.
Preparation method：(1) by TiO2Presoma acetylacetone,2,4-pentanedione titanium solution, attapulgite and violet green grass or young crops ceramic honey comb, by second After acyl acetone titanium solution and electrolyte solution mixing, it is added thereto to attapulgite and violet cuckoo wasp nest cerdip, is aged 35h Afterwards, mixed liquor is transferred in water heating kettle, then reacts 15h under the conditions of 160 DEG C, after filtration, washing, drying, roasting, that is, make Obtain attapulgite-violet green grass or young crops ceramic honey comb-TiO2Carrier；
(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 (8)

1. one kind is with attapulgite-violet green grass or young crops ceramic honey comb-TiO2Denitrating catalyst for carrier is it is characterised in that by weight Including the following raw material：Attapulgite 100-120 part, violet green grass or young crops ceramic honey comb 50-80 part, TiO220-40 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 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its feature It is：Described lubricant at least includes polyurea grease, epoxy resin, polyacrylate, fatty acid amide, Oleic acid, carboxylic acid, silicon One of acid esters or fluorocarbon oil.
3. according to claim 1 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its feature It is：Described heteropoly acid includes 12- tungstophosphoric acid, 12- tungstosilicic acid or 12- molybdenum silicic acid.
4. according to claim 1 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its feature It is：The parts by weight of described attapulgite are 105-115 part.
5. according to claim 1 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its feature It is：The parts by weight of described violet green grass or young crops ceramic honey comb are 60-70 part.
6. according to claim 1 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its feature It is：Described MoO2Parts by weight be 15-25 part.
7. according to claim 1 and 2 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its It is characterised by：The parts by weight of described lubricant are 25-32 part.
8. according to claim 1 or 3 with attapulgite-violet green grass or young crops ceramic honey comb-TiO2For the denitrating catalyst of carrier, its It is characterised by：The parts by weight of described heteropoly acid are 10-15 part.
CN201610796769.8A 2016-08-31 2016-08-31 Denitration catalyst taking attapulgite-cordierite honeycomb ceramic-TiO2 as carrier Withdrawn CN106390995A (en)

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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
CN101862648A (en) * 2010-06-03 2010-10-20 石磊 SCR deNOx catalyst added with attapulgite 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
CN101862648A (en) * 2010-06-03 2010-10-20 石磊 SCR deNOx catalyst added with attapulgite 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

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