CN110898829A - Composite filter material with synergistic removal function of nitrogen oxides and dioxins and preparation method thereof - Google Patents
Composite filter material with synergistic removal function of nitrogen oxides and dioxins and preparation method thereof Download PDFInfo
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- CN110898829A CN110898829A CN201911072461.9A CN201911072461A CN110898829A CN 110898829 A CN110898829 A CN 110898829A CN 201911072461 A CN201911072461 A CN 201911072461A CN 110898829 A CN110898829 A CN 110898829A
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- polyethylene glycol
- nitrogen oxides
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- 239000000463 material Substances 0.000 title claims abstract description 125
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000002013 dioxins Chemical class 0.000 title claims abstract description 18
- 230000002195 synergetic effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000000428 dust Substances 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 230000010355 oscillation Effects 0.000 claims description 10
- 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
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 6
- 229910016978 MnOx Inorganic materials 0.000 claims description 5
- -1 di (diisooctyl phosphoryl) ethylene titanate Chemical compound 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
- 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
- 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
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 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
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- 229920000784 Nomex Polymers 0.000 claims description 2
- 229920001108 Polyimide P84 Polymers 0.000 claims description 2
- 239000004763 nomex Substances 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003546 flue gas Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 1
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 238000000520 microinjection Methods 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 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
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- 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
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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
- B01J23/16—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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- 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
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Health & Medical Sciences (AREA)
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- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a composite filter material with a function of cooperatively removing nitrogen oxides and dioxins and a preparation method thereof, belongs to the field of composite filter materials, and aims to remove dust in flue gas and simultaneously remove NOx and dioxins in the flue gas. The specific method comprises the following steps: soaking a template agent mixed with vanadium, cerium and titanium oxide on the air outlet side of the filter material, carrying out suction filtration on the dust facing side of the filter material to load an NOx catalyst, and drying to remove the template agent to obtain the composite filter material. The filter material prepared by the method effectively avoids NH3The influence on catalytic oxidation of dioxin and the long service life of the composite filter bag,the pollutant removing effect is good.
Description
Technical Field
The invention relates to a functional composite filter material, in particular to a composite filter material with a function of cooperatively removing nitrogen oxides and dioxins and a preparation method thereof.
Background
NOx is one of the main pollution sources causing air pollution and has great harm to human health and ecological environment. NO stimulates eyes and respiratory system of human body to induce canceration; oxidation of NO to NO in air2Reacting with ultraviolet to form photochemical smog; a large amount of nitrogen oxides are dissolved in rain and snow to form nitric acid rain, which erodes crops and buildings. Dioxins are a generic name for two classes of tricyclic aromatic organic compounds, the most carcinogenic potential substances discovered to date. Excessive ingestion by humans produces irreversible teratogenic, carcinogenic, and mutagenic "triprodogenic" effects.
As the use of the waste incineration power generation process in the disposal of household waste is more and more widespread, secondary pollution including dust, heavy metals, SOx, NOx, dioxin and the like generated in the waste incineration process becomes an important factor limiting the development thereof. In recent years, laws and regulations for environmental protection are gradually perfected, emission standards of conventional pollutants are stricter, and trace pollutants such as dioxin are also included in a monitoring range.
At present, the pollutants are generally controlled by adopting a single removal method, so that the occupied area of the flue gas treatment equipment of a factory is large, and the treatment cost is high. Therefore, a multifunctional filter material capable of removing dust, nitrogen oxide and dioxin simultaneously is researched and developed, so that the removal of the three pollutants can be completed when the flue gas passes through the bag type dust collector, and the equipment and operation cost are greatly saved.
A large number of researches show that the traditional vanadium and titanium commercial SCR catalyst has a very high effect of removing dioxin at the temperature of more than 200 ℃, but the flue gas contains high-concentration NH3The catalyst loses dioxin removal activity in a short time, however, the SCR technology often adopts NH3As a reductant to remove NOx, and the process requires NH3Is generally higher to ensure adequate reduction of NOx.
Disclosure of Invention
The invention provides a composite filter material with a function of cooperatively removing nitrogen oxides and dioxins and a preparation method thereof aiming at the existing technical problems.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a functional filter material for synergistically removing nitrogen oxides and dioxins comprises the following steps:
a. dissolving chelate titanate and polyethylene glycol in water to form a solution a, and then dissolving V2O5、CeO2And TiO2Adding the mixture into the solution a, performing ultrasonic oscillation for 2-4 hours, and stirring for 10-12 hours after oscillation to obtain emulsion a;
b. pouring the emulsion a into a vessel, wherein the liquid level height is 1/5-1/2 of the height of the filter material, the filter material is dipped into the emulsion a with the dust-facing surface upward, so that the upper surface of the filter material is not immersed into the emulsion a, the filter material is taken out before the upper surface of the filter material is wet, the filter material is dried for 2-4h and weighed at the temperature of 80-110 ℃, and the dipping step is repeated until the loading amount a of the catalyst on the filter material reaches 100 plus 150g/m2；
c. Dissolving polyethylene glycol in water to form a solution b, adding at least one of oxides of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum into the solution b, ultrasonically dispersing for 2-4h, and stirring for 10-12h to form an emulsion b;
d. putting the filter material catalyst prepared in the step b into a Buchner funnel with the dust facing surface facing upwards, slowly pouring the emulsion b, adjusting the relative vacuum degree to be-10 to-30 kPa for suction filtration, and enabling the denitration catalyst to be loaded on the dust facing side of the filter material, wherein the catalyst loading amount b is 150-2；
e. And d, drying the filter material treated in the step d in an oven at the temperature of 200-250 ℃ for 10-15h to finish the preparation of the composite filter material.
The technical scheme of the invention is as follows: in the step a, the filter material is a high-temperature-resistant filter material of a bag-type dust collector, and is made of one or more of PPS, Nomex, P84 and PTFE. Preferably, the method comprises the following steps: the filter material is P84 filter material.
The technical scheme of the invention is as follows: in the step a, the polyethylene glycol is at least one of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600; the chelate titanate is di (diisooctyl pyrophosphoryl) methyl glycolate, di (diisooctyl phosphoryl) ethylene titanate or di (diisooctyl phosphoryl) methyl glycolate.
The technical scheme of the invention is as follows: in the step a, the mass ratio of the chelating titanate to the polyethylene glycol to the water is 0.1-10: 1-30: 80-95; preferably: the mass ratio of the chelating titanate to the polyethylene glycol to the water is 0.1-5: 5-20: 80-95.
The technical scheme of the invention is as follows: in the step a, the molar ratio of V to Ce is 1:1, and TiO2Is of mass V2O5-CeO2/TiO275-95% of the total mass of the catalyst; preferably: v2O5、CeO2And TiO2The mass ratio of the mixture to the solution a is 1-5: 100.
the technical scheme of the invention is as follows: in the step c, the mass ratio of the polyethylene glycol to the water is 0.1-5: 95 to 99.9.
The technical scheme of the invention is as follows: in the step c, the molar ratio of the metal oxide is 3:2 MnOx and CeO2And metal oxide and solution b substanceThe amount ratio is 0.1-5: 100.
The filter material base cloth layer is a high-temperature resistant filter material of the bag type dust collector, and the catalyst layer is divided into a primary catalyst layer for removing NOx and a secondary catalyst layer for removing dioxin.
In some specific embodiments: the filter material is prepared by the following method:
a. dissolving chelate titanate and polyethylene glycol in water to form a solution a, and then dissolving V2O5、CeO2And TiO2Adding the mixture into the solution a, performing ultrasonic oscillation for 2-4 hours, and stirring for 10-12 hours after oscillation to obtain emulsion a;
b. pouring the emulsion a into a vessel, wherein the liquid level height is 1/5-1/2 of the height of the filter material, the filter material is dipped into the emulsion a with the dust-facing surface upward, so that the upper surface of the filter material is not immersed into the emulsion a, the filter material is taken out before the upper surface of the filter material is wet, the filter material is dried for 2-4h and weighed at the temperature of 80-110 ℃, and the dipping step is repeated until the loading amount a of the catalyst on the filter material reaches 100 plus 150g/m2；
c. Dissolving polyethylene glycol in water to form a solution b, adding at least one of oxides of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum into the solution b, ultrasonically dispersing for 2-4h, and stirring for 10-12h to form an emulsion b;
d. putting the filter material catalyst prepared in the step b into a Buchner funnel with the dust facing surface facing upwards, slowly pouring the emulsion b, adjusting the relative vacuum degree to be-10 to-30 kPa for suction filtration, and enabling the denitration catalyst to be loaded on the dust facing side of the filter material, wherein the loading amount b is 150-2；
e. And d, drying the filter material treated in the step d in an oven at the temperature of 200-250 ℃ for 10-15h to finish the preparation of the composite filter material.
The technical scheme of the invention is as follows: the particle size of the metal oxide in the catalyst is 150-250 μm.
The invention has the beneficial effects that:
(1)NH3is greatly consumed in the process of catalyzing and degrading NOx, and the subsequent influence on catalyzing and oxidizing dioxin is reduced.
(2) Before the filtration, the emulsion mixed with the secondary catalyst is loaded on the air outlet side of the filter material, the aperture of the air outlet filter material is reduced, and primary catalyst particles in the filtration process are intercepted and loaded on the dust facing side of the filter material.
(3) And e, drying the filter material, fixing primary catalyst particles on one hand, removing the template agent on the gas outlet side of the filter material on the other hand, increasing pore channels of the catalyst, increasing the contact area with gas and improving the catalytic effect.
(4) The catalyst loaded by adopting the suction filtration method has the characteristic that the loading capacity is gradually increased from the dust facing surface to the middle layer of the filter material, the wear resistance of the composite filter material is effectively improved, and the service life is prolonged.
Drawings
FIG. 1 is a schematic diagram of a composite filter of example 1.
A denitration layer A and a dioxin removal layer B.
Fig. 2 is a testing device for denitration and dioxin removal of the composite filter material.
Wherein: 1.N2Bottle, 2.O2Bottle, 3.NH3The device comprises a bottle, 4. a NO bottle, 5. a pressure reducing valve, 6. a mass flow meter, 7. a micro-injection pump, 8. a gasification mixing chamber, 9. a quartz tube, 10. a composite filter material, 11. a tube furnace and 12. a flue gas analyzer.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
a. 1g (1 wt%) of bis (diisooctyl pyrophosphoryl) methylhydroxyacetic acid titanate and 15g (15 wt%) of polyethylene glycol 400 were dissolved in 84g (84 wt%) of distilled water, and 4g of TiO ion silica having a particle size of 150-2、CeO2And V2O5In which V and Ce are present in a molar ratio of 1:1, TiO2Is of mass V2O5-CeO2/TiO290 percent of the total mass of the catalyst. And after mixing, ultrasonically oscillating for 3 hours, and stirring for 12 hours by using a magnetic stirrer to uniformly disperse catalyst particles in the emulsion to obtain emulsion a.
b. Pouring the emulsion a into a vessel, wherein the liquid level is 1mm, cutting the filter material into 5cm round pieces, dipping the filter material into the emulsion with the dust facing side facing upwards, wherein the liquid level is just half of the thickness of the filter material, dipping for 3 minutes, taking out the filter material before the upper surface of the filter material is wetted, drying for 4 hours at 105 ℃, weighing, and increasing the mass of the filter material by 0.4821 g. Repeating the dipping operation of the step b, weighing after drying for 4h, increasing the mass of the filter material by 1.0182g, and calculating to obtain the catalyst loading a of 104g/m2。
c. 0.5g (1%) of polyethylene glycol 400 was dissolved in 49.5g (99%) of water, and 0.2945g of MnOx and CeO each having a particle size of 150-2(molar ratio is 3:2), adding the mixture into the solution, carrying out ultrasonic dispersion for 2 hours, and stirring for 6 hours to form emulsion b.
d. C, placing the filter material prepared in the step c into a Buchner funnel with the dust facing surface facing upwards, slowly pouring the emulsion, adjusting the relative vacuum degree to be-20 kPa for suction filtration, and enabling the denitration catalyst to be loaded on the dust facing side of the filter material, wherein the catalyst loading amount b is 150g/m2。
e. And (3) drying the filter material in an oven at 240 ℃ for 12h to finish the preparation of the composite filter material, as shown in figure 1.
The test method comprises the following steps:
the device of fig. 2 was used to test the effects of denitration and dioxin removal of the composite filter material. The testing device consists of a simulation gas, a mass flowmeter, a gasification mixing chamber, a quartz tube reactor and a flue gas analyzer. The inner diameter of the quartz tube is 2.4cm, the outer diameter is 3cm, the prepared filter cloth is cut into a wafer with the diameter of 3cm, the silicon rubber is adhered to the position of the tube opening, and the quartz tube with the inner diameter of 3.2cm is sleeved outside the quartz tube. As shown in fig. 2, the reactor was sealed and fixed and then placed in a tube furnace. The simulated flue gas composition is phi (NO) ═ phi (NH)3)＝0.06％，Φ(O2)＝11％，N2The dioxin is simulated by gaseous chlorobenzene as balance gas, the concentration of liquid chlorobenzene entering mixed gas is controlled to be 500ppm by a micro-injection pump, the liquid chlorobenzene is gasified into gas by a gasification chamber and is mixed with other gases, the filtering wind speed is 1m/min, and the reaction temperature is controlled to be 240 ℃. NOx concentration was measured using a KM9106 flue gas analyzer and chlorobenzene concentration was measured by GC126N gas chromatograph.
The effect of the composite filter material in removing pollutants is calculated by the following formula:
NOx removal rate (initial NOx concentration-post-reaction NOx concentration)/initial NOx concentration × 100%
Dioxin removal rate (initial chlorobenzene concentration-after-reaction chlorobenzene concentration)/initial chlorobenzene concentration × 100%
And (3) testing results:
example 2
a. 0.2g (0.2 wt%) of bis (diisooctyl pyrophosphoryl) methylhydroxyacetic acid titanate and 10g (10 wt%) of polyethylene glycol 200 were dissolved in 89.8g (89.8 wt%) of distilled water, and 2g of TiO 250m in each case2、CeO2And V2O5In which V and Ce are present in a molar ratio of 1:1, TiO2The mass of (b) is 90% of the total mass of the catalyst system. After mixing, the mixture is subjected to ultrasonic oscillation for 2 hours, and is stirred by a magnetic stirrer for 11 hours, so that catalyst particles are uniformly dispersed in the emulsion.
b. Pouring the emulsion into a vessel, wherein the liquid level is 1mm, cutting the filter material into 5cm round pieces, dipping the filter material into the emulsion with the dust facing side facing upwards, wherein the liquid level is just half of the thickness of the filter material, dipping for 3 minutes, taking out the filter material before the upper surface of the filter material is wet, drying for 4 hours at 105 ℃, weighing, and increasing the mass of the filter material by 0.6108 g. Soaking the filter material for 2 minutes again, drying for 4 hours, weighing, increasing the mass of the filter material by 1.4145g, and calculating to obtain the catalyst loading a of 118g/m2。
c. 0.6g (1.2%) of polyethylene glycol 400 was dissolved in 49.4g (98.8%) of water, and 0.3927g of MnOx, CeO having particle sizes of 150-250 μm each were weighed2(the molar ratio is 3:2), adding the mixture into the solution, carrying out ultrasonic dispersion for 2 hours, and stirring for 12 hours to form emulsion.
d. Putting the filter material prepared in the step b into a Buchner funnel with the dust facing surface upward, slowly pouring the emulsion, adjusting the relative vacuum degree to be-15 kPa for suction filtration, and loading the denitration catalyst on the dust facing side of the filter material, wherein the catalyst loading amount b is 200g/m2。
e. And (3) drying the filter material in a 240 ℃ oven for 12h to finish the preparation of the composite filter material.
The test method was the same as in example 1
Example 3
a. 0.2g (0.2 wt%) of bis (diisooctyl pyrophosphoryl) methylhydroxyacetic acid titanate and 8g (10 wt%) of polyethylene glycol 600 were dissolved in 91.8g (91.8 wt%) of distilled water, and 2g of TiO with particle size of 150 μm2、CeO2And V2O5In which V and Ce are present in a molar ratio of 1:1, TiO2The mass of (b) is 90% of the total mass of the catalyst system. After mixing, the mixture is subjected to ultrasonic oscillation for 2 hours, and is stirred for 10 hours by a magnetic stirrer, so that catalyst particles are uniformly dispersed in the emulsion.
b. Pouring the emulsion into a vessel, wherein the liquid level is 1mm, cutting the filter material into 5cm round pieces, dipping the filter material into the emulsion with the dust facing side facing upwards, the liquid level is just half of the thickness of the filter material, dipping for 3 minutes, taking out the filter material before the upper surface of the filter material is wetted, drying for 4 hours at 105 ℃, weighing, increasing the mass of the filter material by 1.4340g, and calculating to obtain the catalyst loading a of 143g/m2。
c. 0.8g (1.6%) of polyethylene glycol 400 was dissolved in 49.2g (98.4%) of water, and 0.9909g of MnOx, CeO having particle sizes of 150-250 μm each were weighed2(the molar ratio is 3:2), adding the mixture into the solution, carrying out ultrasonic dispersion for 2 hours, and stirring for 12 hours to form emulsion.
d. Putting the filter material prepared in the step b into a Buchner funnel with the dust facing surface upward, slowly pouring the emulsion, adjusting the relative vacuum degree to be-15 kPa for suction filtration, and loading the denitration catalyst on the dust facing side of the filter material, wherein the catalyst loading amount b is 250g/m2。
e. And (3) drying the filter material in a 240 ℃ oven for 12h to finish the preparation of the composite filter material.
The test method was the same as in example 1.
Claims (10)
1. A preparation method of a functional filter material for synergistically removing nitrogen oxides and dioxins is characterized by comprising the following steps: the method comprises the following steps:
a. dissolving chelate titanate and polyethylene glycol in water to form a solution a, and then dissolving V2O5、CeO2And TiO2Adding the mixture into the solution a, performing ultrasonic oscillation for 2-4 hours, and stirring for 10-12 hours after oscillation to obtain emulsion a;
b. pouring the emulsion a into a vessel, wherein the liquid level height is 1/5-1/2 of the height of the filter material, the filter material is dipped into the emulsion a with the dust-facing surface upward, so that the upper surface of the filter material is not immersed into the emulsion a, the filter material is taken out before the upper surface of the filter material is wet, the filter material is dried for 2-4h and weighed at the temperature of 80-110 ℃, and the dipping step is repeated until the loading amount a of the catalyst on the filter material reaches 100 plus 150g/m2；
c. Dissolving polyethylene glycol in water to form a solution b, adding at least one of oxides of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum into the solution b, ultrasonically dispersing for 2-4h, and stirring for 10-12h to form an emulsion b;
d. putting the filter material catalyst prepared in the step b into a Buchner funnel with the dust facing surface facing upwards, slowly pouring the emulsion b, adjusting the relative vacuum degree to be-10 to-30 kPa for suction filtration, and enabling the denitration catalyst to be loaded on the dust facing side of the filter material, wherein the catalyst loading amount b is 150-2；
e. And d, drying the filter material treated in the step d in an oven at the temperature of 200-250 ℃ for 10-15h to finish the preparation of the composite filter material.
2. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step a, the filter material is a high-temperature-resistant filter material of a bag-type dust collector, and is made of one or more of PPS, Nomex, P84 and PTFE.
3. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 2, which is characterized in that: the filter material is P84 filter material.
4. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step a, the polyethylene glycol is at least one of polyethylene glycol 200, polyethylene glycol 400 and polyethylene glycol 600; the chelate titanate is di (diisooctyl pyrophosphoryl) methyl glycolate, di (diisooctyl phosphoryl) ethylene titanate or di (diisooctyl phosphoryl) methyl glycolate.
5. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step a, the mass ratio of the chelating titanate to the polyethylene glycol to the water is 0.1-10: 1-30: 80-95; preferably: the mass ratio of the chelating titanate to the polyethylene glycol to the water is 0.1-5: 5-20: 80-95.
6. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step a, the molar ratio of V to Ce is 1:1, and TiO2Is of mass V2O5-CeO2/TiO275-95% of the total mass of the catalyst; preferably: v2O5、CeO2And TiO2The mass ratio of the mixture to the solution a is 1-5: 100.
7. the preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step c, the mass ratio of the polyethylene glycol to the water is 0.1-5: 95 to 99.9.
8. The preparation method of the filter material for synergistically removing the nitrogen oxides and the dioxins according to claim 1, which is characterized in that: in the step c, the molar ratio of the metal oxide is 3:2 MnOx and CeO2The mass ratio of the metal oxide to the solution b is 0.1-5: 100.
9. The filter material for synergistically removing nitrogen oxides and dioxins as claimed in claim 1, wherein: the filter material base cloth layer is a high-temperature resistant filter material of the bag type dust collector, and the catalyst layer is divided into a primary catalyst layer for removing NOx and a secondary catalyst layer for removing dioxin.
10. The filter material for synergistically removing nitrogen oxides and dioxins according to claim 9, wherein: the filter material is prepared by the following method:
a. dissolving chelate titanate and polyethylene glycol in water to form a solution a, and then dissolving V2O5、CeO2And TiO2Adding the mixture into the solution a, performing ultrasonic oscillation for 2-4 hours, and stirring for 10-12 hours after oscillation to obtain emulsion a;
b. pouring the emulsion a into a vessel, wherein the liquid level height is 1/5-1/2 of the height of the filter material, the filter material is dipped into the emulsion a with the dust-facing surface upward, so that the upper surface of the filter material is not immersed into the emulsion a, the filter material is taken out before the upper surface of the filter material is wet, the filter material is dried for 2-4h and weighed at the temperature of 80-110 ℃, and the dipping step is repeated until the loading amount a of the catalyst on the filter material reaches 100 plus 150g/m2；
c. Dissolving polyethylene glycol in water to form a solution b, adding at least one of oxides of manganese, iron, cerium, copper, nickel, zirconium, cobalt and molybdenum into the solution b, ultrasonically dispersing for 2-4h, and stirring for 10-12h to form an emulsion b;
d. putting the filter material catalyst prepared in the step b into a Buchner funnel with the dust facing surface facing upwards, slowly pouring the emulsion b, adjusting the relative vacuum degree to be-10 to-30 kPa for suction filtration, and enabling the denitration catalyst to be loaded on the dust facing side of the filter material, wherein the loading amount b is 150-2；
e. And d, drying the filter material treated in the step d in an oven at the temperature of 200-250 ℃ for 10-15h to finish the preparation of the composite filter material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115337712A (en) * | 2022-07-29 | 2022-11-15 | 北京工业大学 | Filter material for preparing load low-temperature SCR catalyst by suction filtration method, detection and application |
| CN116747874A (en) * | 2023-08-18 | 2023-09-15 | 天河（保定）环境工程有限公司 | SCR denitration catalyst for cooperatively removing dioxin and preparation method thereof |
Families Citing this family (4)
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| CN111659410B (en) * | 2020-06-24 | 2022-11-29 | 南京溙科新材料科技有限公司 | Porous ceramic membrane dedusting, denitration and dioxin removal catalyst taking blast furnace slag as raw material and preparation method thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170491A (en) * | 1999-12-17 | 2001-06-26 | Hitachi Zosen Corp | Method for hardening treatment of catalyst edge part |
| CN103182305A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Three-way catalyst and preparation method for same |
| CN104998467A (en) * | 2015-07-02 | 2015-10-28 | 辽宁鸿盛环境技术集团股份有限公司 | Filter material with denitration and dioxin-removal effects and preparation method thereof |
| CN105013249A (en) * | 2015-07-02 | 2015-11-04 | 辽宁鸿盛环境技术集团股份有限公司 | Nitre and dioxin-removal PPS composite felt functional filtering material and preparation method thereof |
| WO2016053637A1 (en) * | 2014-09-29 | 2016-04-07 | Basf Corporation | Preparation and applications of hydrophobic materials |
| 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 |
| CN107213899A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of rich CO2Synthesising gas systeming carbinol integral catalyzer and preparation method thereof |
| CN107213900A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of synthesis gas preparing dimethy ether integral catalyzer and preparation method thereof |
| CN109289330A (en) * | 2018-11-14 | 2019-02-01 | 北京建筑材料科学研究总院有限公司 | A kind of sheet stock and its manufacturing method integrating dust removal by filtration and catalytic denitration |
-
2019
- 2019-07-24 CN CN201910669473.3A patent/CN110465288A/en active Pending
- 2019-11-05 CN CN201911072461.9A patent/CN110898829B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001170491A (en) * | 1999-12-17 | 2001-06-26 | Hitachi Zosen Corp | Method for hardening treatment of catalyst edge part |
| JP3837627B2 (en) * | 1999-12-17 | 2006-10-25 | 日立造船株式会社 | Method for curing the end of the catalyst |
| CN103182305A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Three-way catalyst and preparation method for same |
| WO2016053637A1 (en) * | 2014-09-29 | 2016-04-07 | Basf Corporation | Preparation and applications of hydrophobic materials |
| CN104998467A (en) * | 2015-07-02 | 2015-10-28 | 辽宁鸿盛环境技术集团股份有限公司 | Filter material with denitration and dioxin-removal effects and preparation method thereof |
| CN105013249A (en) * | 2015-07-02 | 2015-11-04 | 辽宁鸿盛环境技术集团股份有限公司 | Nitre and dioxin-removal PPS composite felt functional filtering material and preparation method thereof |
| CN107213899A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of rich CO2Synthesising gas systeming carbinol integral catalyzer and preparation method thereof |
| CN107213900A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of synthesis gas preparing dimethy ether integral catalyzer and preparation method thereof |
| 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 |
| CN109289330A (en) * | 2018-11-14 | 2019-02-01 | 北京建筑材料科学研究总院有限公司 | A kind of sheet stock and its manufacturing method integrating dust removal by filtration and catalytic denitration |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115337712A (en) * | 2022-07-29 | 2022-11-15 | 北京工业大学 | Filter material for preparing load low-temperature SCR catalyst by suction filtration method, detection and application |
| CN115337712B (en) * | 2022-07-29 | 2024-04-12 | 北京工业大学 | Filter material for preparing supported low-temperature SCR catalyst by suction filtration method, detection and application |
| CN116747874A (en) * | 2023-08-18 | 2023-09-15 | 天河（保定）环境工程有限公司 | SCR denitration catalyst for cooperatively removing dioxin and preparation method thereof |
| CN116747874B (en) * | 2023-08-18 | 2024-01-09 | 天河（保定）环境工程有限公司 | SCR denitration catalyst for cooperatively removing dioxin and preparation method thereof |
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