CN110465288A - A kind of cooperation-removal nitrogen oxides and the composite filtering material of dioxin function and preparation method thereof - Google Patents
A kind of cooperation-removal nitrogen oxides and the composite filtering material of dioxin function and preparation method thereof Download PDFInfo
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- CN110465288A CN110465288A CN201910669473.3A CN201910669473A CN110465288A CN 110465288 A CN110465288 A CN 110465288A CN 201910669473 A CN201910669473 A CN 201910669473A CN 110465288 A CN110465288 A CN 110465288A
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- filtrate
- dioxin
- lotion
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- nitrogen oxides
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical group O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000001914 filtration Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000000706 filtrate Substances 0.000 claims abstract description 85
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 239000006210 lotion Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 229910016978 MnOx Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 5
- -1 (diisooctyl phosphoryl) methyl Chemical group 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000009514 concussion Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 229920000784 Nomex Polymers 0.000 claims description 2
- 229920001108 Polyimide P84 Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 239000004763 nomex Substances 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 241000040710 Chela Species 0.000 claims 1
- 229960003511 macrogol Drugs 0.000 claims 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003546 flue gas Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000428 dust Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000003708 ampul Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 238000000520 microinjection Methods 0.000 description 2
- 206010068150 Acoustic shock Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- 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 present invention provides a kind of cooperation-removal nitrogen oxides and composite filtering materials of dioxin function and preparation method thereof, belong to composite filtering material field, it is intended to NOx and dioxin while removing dust in flue gas in removing flue gas.Method particularly includes: by be mixed with vanadium, cerium, titanium oxide template be impregnated in filtrate outlet side, meet dirt side in filtrate and carry out filtering load NOx catalyst, by it is dry remove template agent removing after obtain composite filtering material.The filtrate of this method preparation effectively prevents NH3Influence to catalysis oxidation dioxin, compound filter bag long service life, pollutant removing effect are good.
Description
Technical field
The present invention relates to functional composite filtering materials, and in particular to a kind of cooperation-removal nitrogen oxides and dioxin function are answered
Close filtrate and preparation method thereof.
Background technique
NOx is to cause one of primary pollution source of air pollution, has huge harm to human health and ecological environment.
There is stimulation to the eyes and respiratory system of people in NO, induce canceration；NO is oxidized to NO in air2, react with ultraviolet light
Form photochemical fog；A large amount of nitrogen oxides are dissolved in rain, form nitric acid type acid rain in snow, corrode crops and building.Two dislike
English is the general designation of two class tricyclic aromatic organic compounds, is the substance of the most carcinogenic potential found so far.Human body mistake
Amount intake generates irreversible teratogenesis, carcinogenic and mutagenic " three cause " effect.
As refuse incineration and power generation process uses more and more extensive in Disposal of Domestic, produced in Refuse Incineration Process
Raw secondary pollution, including dust, heavy metal, SOx, NOx and dioxin etc., become an important factor for limiting its development.Closely
The laws and regulations of Nian Lai, environmental protection are gradually perfect, and the discharge standard of Conventional pollution is stringenter, dioxin trace contamination
Object is also included into monitoring range.
Factory smoke processing equipment is caused to be taken up an area generally using the method individually removed the control of these pollutants at present
Area is big, and treatment cost is high.Therefore, researching and developing one kind can be by the multi-functional of dust, nitrogen oxides, dioxin while removing
Filtrate completes the removing of these three types of pollutants when so that the flue gas is passed through sack cleaner, greatly saved equipment and operation at
This.
A large number of studies show that traditional vanadium, titanium system commercialization SCR catalyst have very high take off to dioxin at 200 DEG C or more
Except effect, but as contained high concentration NH in flue gas3Catalyst can be made to lose the activity of de- dioxin in a short time, however, SCR
Technology is often with NH3NOx is removed as reducing agent, and technique requires NH3Concentration it is usually higher, to guarantee that NOx is reduced sufficiently.
Summary of the invention
The present invention be directed to above-mentioned technical problems to provide a kind of cooperation-removal nitrogen oxides and dioxin function
Composite filtering material and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of cooperation-removal nitrogen oxides and dioxin function filter material, method includes the following steps:
A. chelating titanate and polyethylene glycol are dissolved in the water to form solution a, later by V2O5、CeO2And TiO2's
Mixture is added to 2~4h of ultrasonic vibration in previous solu a, and 10~12h is stirred after concussion, obtains lotion a；
B. lotion a is poured in vessel, liquid level is the 1/5~1/2 of filtrate height, and filtrate dust-collecting face is impregnated in upward
In lotion a, so that the upper surface of filtrate is not submerged in lotion a, taken out before filtrate upper surface is wet, 80~110 DEG C of items
Dry 2-4h weighing under part, repeated impregnations step, until load capacity a of the catalyst on filtrate reaches 100-150g/m2；
C. polyethylene glycol is dissolved in the water to form solution b, in the oxide for taking manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum
It is at least one be added in previous solu b, after ultrasonic disperse 2-4h, stirring 10-12h forms lotion b；
D. filtrate catalyst dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion b, adjusted
Relative degree of vacuum is that -10~-30kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, catalyst loadings b
For 150-250g/m2；
E. will be through step d treated filtrate is placed in 200-250 DEG C of baking oven dry 10-15h, i.e. completion composite filtering material
Preparation.
In technical solution of the present invention: in step a filtrate use bag filter high temperature resistance filtration material, material PPS,
One of Nomex, P84, PTFE or a variety of compositions.As preferred: filtrate uses P84 filtrate.
In technical solution of the present invention: polyethylene glycol is polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol in step a
At least one of 600；The chelating titanate is two (diisooctyl pyrophosphoryl base) methyl oxyacetate titanates, two (two
Iso-octyl phosphoryl) metatitanic acid second diester or two (diisooctyl phosphoryl) methyl oxyacetate titanates.
In technical solution of the present invention: the mass ratio of chelating titanate, polyethylene glycol and water is 0.1~10:1 in step a
~30:80~95；It is preferred that: the mass ratio of chelating titanate, polyethylene glycol and water is 0.1~5:5~20:80~95.
In technical solution of the present invention: in step a, the molar ratio of V and Ce are 1:1, TiO2Quality be V2O5-CeO2/TiO2
The 75~95% of catalyst gross mass；It is preferred that: V2O5、CeO2And TiO2Mixture and solution a mass ratio be 1~5:100.
In technical solution of the present invention: in step c, the mass ratio of polyethylene glycol and water is 0.1~5:95~99.9.
In technical solution of the present invention: in step c, metal oxide is the MnOx and CeO that molar ratio is 3:22Mixture,
And metal oxide and solution b mass ratio are 0.1~5:100.
A kind of filtrate of above-mentioned cooperation-removal nitrogen oxides and dioxin function, the filtrate base cloth layer are sack cleaner
High temperature resistance filtration material, Catalytic Layer are divided into a Catalytic Layer of removing NOx and the quadric catalysis layer of removing dioxin.
In some specific technical solutions: the filtrate is prepared via a method which to obtain:
A. chelating titanate and polyethylene glycol are dissolved in the water to form solution a, later by V2O5、CeO2And TiO2's
Mixture is added to 2~4h of ultrasonic vibration in previous solu a, and 10~12h is stirred after concussion, obtains lotion a；
B. lotion a is poured in vessel, liquid level is the 1/5~1/2 of filtrate height, and filtrate dust-collecting face is impregnated in upward
In lotion a, so that the upper surface of filtrate is not submerged in lotion a, taken out before filtrate upper surface is wet, 80~110 DEG C of items
Dry 2-4h weighing under part, repeated impregnations step, until load capacity a of the catalyst on filtrate reaches 100-150g/m2；
C. polyethylene glycol is dissolved in the water to form solution b, in the oxide for taking manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum
It is at least one be added in previous solu b, after ultrasonic disperse 2-4h, stirring 10-12h forms lotion b；
D. filtrate catalyst dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion b, adjusted
Relative degree of vacuum is that -10~-30kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, load capacity b is 150-
250g/m2；
E. will be through step d treated filtrate is placed in 200-250 DEG C of baking oven dry 10-15h, i.e. completion composite filtering material
Preparation.
In technical solution of the present invention: the partial size of metal oxide is 150~250 μm in catalyst.
Beneficial effects of the present invention:
(1)NH3It is largely consumed during catalytic degradation NOx, reduces the subsequent influence to catalysis oxidation dioxin.
(2) before being filtered, the lotion for being mixed with quadric catalysis agent is carried on filtrate outlet side, reduces outlet and surveys
The aperture of filtrate a, catalyst granules during retention filters, makes it be carried on filtrate and meets dirt side.
(3) filtrate is dried in step e, on the one hand fixes a catalyst granules, on the other hand removal filter
The template for expecting gas side out increases the duct of catalyst, increases the area contacted with gas, improves catalytic effect.
(4) it using the catalyst of the method load filtered, shows load capacity and gradually increases from dust-collecting face to filtrate middle layer
More features effectively increases the wearability of composite filtering material, prolongs the service life.
Detailed description of the invention
Fig. 1 is the structure chart of the composite filtering material of embodiment 1.
A layers of denitration layer, B layers of de- dioxin layer.
Fig. 2 is that the denitration of composite filtering material of the invention takes off the test device of dioxin.
Wherein: 1.N2Bottle, 2.O2Bottle, 3.NH3Bottle, 4.NO bottles, 5. pressure reducing valves, 6. mass flowmenters, 7. micro-injection pumps,
8. gasify mixing chamber, 9. quartz ampoules, 10. composite filtering materials, 11. tube furnaces, 12. flue gas analyzers.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, and but the scope of the present invention is not limited thereto:
Embodiment 1
A. 1g (1wt%) two (diisooctyl pyrophosphoryl base) methyl oxyacetate titanate, the poly- second two of 15g (15wt%) are weighed
Alcohol 400 is dissolved in 84g (84wt%) distilled water, and the TiO that 4g partial size is 150-250 μm is added2、CeO2And V2O5Mixing
Object, wherein the molar ratio of V and Ce is 1:1, TiO2Quality be V2O5-CeO2/TiO2The 90% of catalyst gross mass.After mixing
Ultrasonic vibration 3h, and 12h is stirred with magnetic stirrer, it is dispersed in catalyst granules in lotion, obtains lotion a.
B. lotion a is poured in vessel, filtrate is cut into the disc-shaped of 5cm by liquid level 1mm, and dust-collecting face soaks upward
For stain in lotion, liquid level is exactly the half of filtrate thickness, is impregnated 3 minutes, is taken out before filtrate upper surface is wet, 105
Dry 4h, weighing, filtrate quality increase 0.4821g at DEG C.The dip operation of step b is repeated, is weighed after dry 4h, filtrate quality
Increase 1.0182g, can be calculated catalyst loadings a is 104g/m2。
C. 0.5g (1%) polyethylene glycol 400 is dissolved in 49.5g (99%) water, weighing 0.2945g grain diameter is
150-250 μm MnOx, CeO2(molar ratio 3:2) is added in solution, and after ultrasonic disperse 2h, stirring 6h forms lotion b.
D. filtrate dust-collecting face prepared by step c is put in Buchner funnel upward, is poured slowly into lotion, adjust relative vacuum
Degree is that -20kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, catalyst loadings b is 150g/m2。
E. filtrate is placed in 240 DEG C of baking ovens dry 12h, that is, completes the preparation of composite filtering material, as shown in Figure 1.
Test method:
Dioxin effect is taken off to the denitration of composite filtering material using the device of Fig. 2 to test.The test device is by simulation gas
Body, mass flowmenter, gasification mixing chamber, quartz tube reactor and flue gas analyzer composition.Quartzy bore 2.4cm, outer diameter
The filter cloth that preparation is completed is cut into the disk of diameter 3cm, is sticked at nozzle using silicon rubber, in the outer sheath one of quartz ampoule by 3cm
The quartz ampoule of root internal diameter 3.2cm.As shown in Fig. 2, being put into tube furnace after reactor sealing is fixed.Simulated flue gas group becomes
77%N2, 11%O2, 6%NO, 6%NH3, dioxin simulated by gaseous state chlorobenzene, and micro-injection pump control liquid chlorobenzene enters mixing
The concentration of gas is 500ppm, is gasificated into gas by vaporizer and mixes with remaining gas, filtration velocity 1m/min, reaction temperature
Degree control is at 240 DEG C.Using the concentration of KM9106 flue gas analyzer test NOx, chlorobenzene is tested by GC126N gas chromatograph
Concentration.
The effect of composite filtering material removing pollutant is calculated by following formula:
NOx removal rate=(NOx concentration after initial NOx concentration-reaction)/initial NOx concentration × 100%
Dioxin removal efficiency=(chlorobenzene concentration after initial chlorobenzene concentration-reaction)/initial chlorobenzene concentration × 100%
Test result:
Embodiment 2
A. it is poly- that 0.2g (0.2wt%) two (diisooctyl pyrophosphoryl base) methyl oxyacetate titanate, 10g (10wt%) are weighed
Ethylene glycol 200 is dissolved in 89.8g (89.8wt%) distilled water, and the TiO that 2g partial size is 150-250m is added2、CeO2And V2O5
Mixture, wherein the molar ratio of V and Ce be 1:1, TiO2Quality be the 90% of catalyst system gross mass.Surpass after mixing
2h is swung in acoustic shock, and stirs 11h with magnetic stirrer, is dispersed in catalyst granules in lotion.
B. lotion is poured in vessel, filtrate is cut into the disc-shaped of 5cm by liquid level 1mm, and dust-collecting face impregnates upward
In lotion, liquid level is exactly the half of filtrate thickness, is impregnated 3 minutes, is taken out before filtrate upper surface is wet, 105 DEG C
Lower dry 4h, weighing, filtrate quality increase 0.6108g.Filtrate is impregnated 2 minutes again, is weighed after dry 4h, filtrate quality increases
Add 1.4145g, can be calculated catalyst loadings a is 118g/m2。
C. 0.6g (1.2%) polyethylene glycol 400 is dissolved in 49.4g (98.8%) water, weighs 0.3927g grain diameter
It is 150-250 μm MnOx, CeO2(molar ratio 3:2) is added in solution, and after ultrasonic disperse 2h, stirring 12h forms cream
Liquid.
D. filtrate dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion, adjust relative vacuum
Degree is that -15kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, catalyst loadings b is 200g/m2。
E. filtrate is placed in 240 DEG C of baking ovens dry 12h, that is, completes the preparation of composite filtering material.
Test method is same as Example 1
Embodiment 3
A. it is poly- that 0.2g (0.2wt%) two (diisooctyl pyrophosphoryl base) methyl oxyacetate titanate, 8g (10wt%) are weighed
Ethylene glycol 600 is dissolved in 91.8g (91.8wt%) distilled water, and the TiO that 2g partial size is 150-250 μm is added2、CeO2With
V2O5Mixture, wherein the molar ratio of V and Ce be 1:1, TiO2Quality be the 90% of catalyst system gross mass.After mixing
Ultrasonic vibration 2h, and 10h is stirred with magnetic stirrer, it is dispersed in catalyst granules in lotion.
B. lotion is poured in vessel, filtrate is cut into the disc-shaped of 5cm by liquid level 1mm, and dust-collecting face impregnates upward
In lotion, liquid level is exactly the half of filtrate thickness, is impregnated 3 minutes, is taken out before filtrate upper surface is wet, 105 DEG C
Lower dry 4h, weighing, filtrate quality increase 1.4340g, and can be calculated catalyst loadings a is 143g/m2。
C. 0.8g (1.6%) polyethylene glycol 400 is dissolved in 49.2g (98.4%) water, weighs 0.9909g grain diameter
It is 150-250 μm MnOx, CeO2(molar ratio 3:2) is added in solution, and after ultrasonic disperse 2h, stirring 12h forms cream
Liquid.
D. filtrate dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion, adjust relative vacuum
Degree is that -15kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, catalyst loadings b is 250g/m2。
E. filtrate is placed in 240 DEG C of baking ovens dry 12h, that is, completes the preparation of composite filtering material.
Test method is same as Example 1.
Claims (10)
1. a kind of preparation method of cooperation-removal nitrogen oxides and dioxin function filter material, it is characterised in that: this method include with
Lower step:
A. chelating titanate and polyethylene glycol are dissolved in the water to form solution a, later by V2O5、CeO2And TiO2Mixture
It is added to 2~4h of ultrasonic vibration in previous solu a, 10~12h is stirred after concussion, obtains lotion a；
B. lotion a is poured in vessel, liquid level is the 1/5~1/2 of filtrate height, and filtrate dust-collecting face is impregnated in lotion upward
In a, so that the upper surface of filtrate is not submerged in lotion a, taken out before filtrate upper surface is wet, under the conditions of 80~110 DEG C
Dry 2-4h weighing, repeated impregnations step, until load capacity a of the catalyst on filtrate reaches 100-150g/m2；
C. polyethylene glycol is dissolved in the water to form solution b, is taken in the oxide of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum extremely
In a kind of few addition previous solu b, after ultrasonic disperse 2-4h, stirring 10-12h forms lotion b；
D. filtrate catalyst dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion b, adjusted opposite
Vacuum degree is that -10~-30kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, catalyst loadings b is
150-250g/m2；
E. the system of composite filtering material will be completed through step d treated filtrate is placed in 200-250 DEG C of baking oven dry 10-15h
It is standby.
2. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: in step a filtrate use bag filter high temperature resistance filtration material, one of material PPS, Nomex, P84, PTFE or
A variety of compositions.
3. the preparation method of cooperation-removal nitrogen oxides according to claim 2 and the filtrate of dioxin function, feature
Be: filtrate uses P84 filtrate.
4. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: polyethylene glycol is at least one of polyethylene glycol 200, polyethylene glycol 400 and Macrogol 600 in step a；The chela
Mould assembly titanate esters are two (diisooctyl pyrophosphoryl base) methyl oxyacetate titanates, two (diisooctyl phosphoryl) metatitanic acid second diester
Or two (diisooctyl phosphoryl) methyl oxyacetate titanate.
5. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: the mass ratio of chelating titanate, polyethylene glycol and water is 0.1~10:1~30:80~95 in step a；It is preferred that: chelating
The mass ratio of type titanate esters, polyethylene glycol and water is 0.1~5:5~20:80~95.
6. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: in step a, the molar ratio of V and Ce are 1:1, TiO2Quality be V2O5-CeO2/TiO2The 75 of catalyst gross mass~
95%；It is preferred that: V2O5、CeO2And TiO2Mixture and solution a mass ratio be 1~5:100.
7. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: in step c, the mass ratio of polyethylene glycol and water is 0.1~5:95~99.9.
8. the preparation method of cooperation-removal nitrogen oxides according to claim 1 and the filtrate of dioxin function, feature
Be: in step c, metal oxide is the MnOx and CeO that molar ratio is 3:22Mixture, and metal oxide and solution b
Mass ratio is 0.1~5:100.
9. a kind of filtrate of cooperation-removal nitrogen oxides and dioxin function described in claim 1, it is characterised in that: the filtrate
Base cloth layer is sack cleaner high temperature resistance filtration material, and Catalytic Layer is divided into a Catalytic Layer of removing NOx and removes the secondary of dioxin
Catalytic Layer.
10. the filtrate of cooperation-removal nitrogen oxides and dioxin function according to claim 9, it is characterised in that: the filter
Material is prepared via a method which to obtain:
A. chelating titanate and polyethylene glycol are dissolved in the water to form solution a, later by V2O5、CeO2And TiO2Mixture
It is added to 2~4h of ultrasonic vibration in previous solu a, 10~12h is stirred after concussion, obtains lotion a；
B. lotion a is poured in vessel, liquid level is the 1/5~1/2 of filtrate height, and filtrate dust-collecting face is impregnated in lotion upward
In a, so that the upper surface of filtrate is not submerged in lotion a, taken out before filtrate upper surface is wet, under the conditions of 80~110 DEG C
Dry 2-4h weighing, repeated impregnations step, until load capacity a of the catalyst on filtrate reaches 100-150g/m2；
C. polyethylene glycol is dissolved in the water to form solution b, is taken in the oxide of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum extremely
In a kind of few addition previous solu b, after ultrasonic disperse 2-4h, stirring 10-12h forms lotion b；
D. filtrate catalyst dust-collecting face prepared by step b is put in Buchner funnel upward, is poured slowly into lotion b, adjusted opposite
Vacuum degree is that -10~-30kPa is filtered, and so that denitrating catalyst is supported on filtrate and meets dirt side, load capacity b is 150-250g/
m2；
E. the system of composite filtering material will be completed through step d treated filtrate is placed in 200-250 DEG C of baking oven dry 10-15h
It is standby.
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| JP3837627B2 (en) * | 1999-12-17 | 2006-10-25 | 日立造船株式会社 | Method for curing the end of the catalyst |
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| CN106423231A (en) * | 2016-11-07 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Titanium dioxide integral type photocatalyst and preparation method and application thereof |
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