CN107158799B - A kind of composite filtering material fiber and preparation method for SCR dedusting denitration - Google Patents
A kind of composite filtering material fiber and preparation method for SCR dedusting denitration Download PDFInfo
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- 239000000835 fiber Substances 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000001914 filtration Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000032683 aging Effects 0.000 claims abstract description 21
- 230000008595 infiltration Effects 0.000 claims abstract description 20
- 238000001764 infiltration Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 238000009938 salting Methods 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 14
- 238000009841 combustion method Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 150000000703 Cerium Chemical class 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- -1 cerium ion Chemical class 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 20
- 150000004706 metal oxides Chemical class 0.000 abstract description 20
- 238000005470 impregnation Methods 0.000 abstract description 8
- 239000011572 manganese Substances 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- 239000003546 flue gas Substances 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000013618 particulate matter Substances 0.000 abstract description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000012501 ammonium carbonate Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- RWACICCRNCPMDT-UHFFFAOYSA-N cerium sulfuric acid Chemical compound [Ce].S(O)(O)(=O)=O RWACICCRNCPMDT-UHFFFAOYSA-N 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- XIFFNSGJZPAYQJ-UHFFFAOYSA-N sulfuric acid;zirconium Chemical compound [Zr].OS(O)(=O)=O XIFFNSGJZPAYQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of preparation methods of composite filtering material fiber for SCR dedusting denitration, by manganese salt, cerium salt and zirconates, which are dissolved in the water, prepares salting liquid A, prepare the alkaline solution B that pH is 8~12, fiber is immersed to salting liquid A and is infiltrated, ultrasonic wave added infiltration a period of time is carried out in impregnation process, 15~70min of dipper precipitation in alkaline solution B is immersed after fiber after infiltration is drained, aging is carried out after fiber after dipper precipitation is taken out, fiber after aging is subjected to microwave combustion method, it finally carries out being activated up to the composite filtering material fiber of SCR dedusting denitration is used for.It can make the oxide and fiber secure bond of Mn, Ce, Zr, and it is more uniform so that reactive metal oxides is dispersed in the fibre, NO in removing coal-fired flue-gas while can realizing trap particulate matter by the difunctional composite filtering material that the fiber is made intox。
Description
Technical field
The present invention relates to after the pollutant dust of the building material industries such as coal-burning power plant and cement, glass, ceramics, nitrogen oxides
A kind of reason field, and in particular to composite filtering material fiber and preparation method for SCR dedusting denitration.
Background technique
Nitrogen oxides can jeopardize human health while causing ecological environment destruction, be it is a kind of endanger it is extremely wide big
Gas pollutant.Wherein the coal-burning boiler of the industries such as electric power, building materials is the important sources of discharged nitrous oxides.Selective catalytic reduction
Method (Selective Catalytic Reduction, SCR) is coal-burning boiler denitration technology most widely used, that technology is most mature,
Have denitration efficiency height, stable and reliable operation, selectivity it is good many advantages, such as, in practical applications occupation rate reach 90% with
On.NH3To apply reducing agent the most universal in current SCR technology, the technical characterstic of SCR determines that denitration device outlet will not
It is evitable that there are not sufficiently reactive NH3, i.e. the escaping of ammonia.If there are oxysulfide, the NH of escape in flue gas3Easily in tail portion cigarette
Road, which reacts with it, generates the stronger ammonium sulfate/ammonium hydrogen sulfate of cohesiveness, so that back-end ductwork burn into be caused to block.As can under
SCR catalytic denitration material is coupled again in trip equipment (sack cleaner), realizes escape NH in suitable temperature window3With not also
Former NOxFurther reaction, then be expected to be effectively treated escape NH3While, further increase system denitration efficiency.
Field is post-processed in coal-fired flue-gas, and high dust collection efficiency, secondary pollution be small, siccative easily returns due to having for sack cleaner
The performances such as receipts, application at home and abroad is more and more wider, accounts for about cleaner is applied in market 80%.Sack cleaner filters dedusting
Expect that the demand of fiber is huge, especially multifunctional composite fiber has a vast market foreground.China is to every profession and trade coal-burning boiler
Discharge proposes requirements at the higher level, and the industries coal-burning boiler such as steel, cement, glass, ceramics is the main source of atmosphere pollution, is also
Emphasis is administered, China's steel annual output is more than 900,000,000 tons, prepares standard according to Baosteel sack cleaner and calculates, total that dedusting is needed to filter
Expect 63,000,000 square metres, need to change 18,000,000 square metres of filtrate every year, therefore, dedusting filter media fibre market prospects are especially seen
It is good.Sack cleaner is arranged in after SCR device more, and according to boiler type and application field difference, running temperature window is normal
It is approximate with common low-temperature SCR technical application window between 150~250 DEG C, as can realizing that low-temperature SCR is catalyzed material here
The efficient coupling of material and dedusting filter media fibre, will effectively solve the problems, such as above-mentioned the escaping of ammonia and greatly improves system denitration efficiency.
In recent years, the correlative study that the oxide of Mn, Ce, Zr etc. are used as low-temperature SCR catalyst active specy has obtained state
The extensive concern of inside and outside scholar, but the selection of relevant carriers is mostly with TiO2、Al2O3, based on the solid materials such as active carbon.Do not have Mn,
The relevant report of the coupling of the oxide and dedusting filter media fibre of Ce, Zr etc..
Summary of the invention
Active oxidation species are all made of in patent CN104941319A, CN103252135A, CN105315000A directly to soak
Stain carrying method prepares composite filtering material, however the present inventor will using above-mentioned direct impregnation method by research discovery
The oxide of Mn, Ce, Zr etc. couple with fiber the fiber filtering of preparation, and active component is insecure with fibres bond, hold
Easy powder of detached, industrial production difficulty are larger.
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of answering for SCR dedusting denitration
The preparation method for closing filter media fibre, can make the oxide and fiber secure bond of Mn, Ce, Zr, be made by the fiber double
NO in removing coal-fired flue-gas while function and service filtrate can realize trap particulate matterx。
To achieve the goals above, the technical solution of the present invention is as follows:
A kind of preparation method of the composite filtering material fiber for SCR dedusting denitration, is dissolved in water for manganese salt, cerium salt and zirconates
In prepare salting liquid A, prepare pH be 8~12 alkaline solution B, by fiber immerse to salting liquid A infiltrate, in impregnation process into
Row ultrasonic wave added infiltration a period of time, 15~70min of dipper precipitation in alkaline solution B is immersed after the fiber after infiltration is drained,
Aging is carried out after fiber after dipper precipitation is taken out, the fiber after aging is subjected to microwave combustion method, is finally carried out at activation
It manages up to the composite filtering material fiber of SCR dedusting denitration is used for.
The present invention enables to metal ion that can preferably enter to first by fiber impregnation into salting liquid, by ultrasound
In the gap of fiber, so that metal ion can be more uniform is dispersed on fiber, it then will be soaked with metal ion again
Fiber impregnation into aqueous slkali so that finely dispersed reactive metal oxides can be made on fiber, due to first impregnating
Metal ion enter in fiber gap, then metal ion is precipitated, reactive metal oxides can not only be reinforced and existed
Bond strength on fiber, and make reactive metal oxides are more uniform to be dispersed on fiber, to improve fiber
Catalytic performance.
Meanwhile fiber is a kind of larger molecular organics, under alkaline condition, is easy to degrade and dissolve, not only compromise
The structure of fiber, and the metal ion of dipping in the fibre can be dissociateed to come from fiber, it is finally unable to get compound
Filter media fibre.For the present invention by many experiments, the pH for adjusting alkaline solution A is 8~12, and controls the infiltrating time of fiber, energy
Enough ensure that fiber does not generate irreversible structural failure in alkaline solution A, and enables to precipitate under the alkaline condition
Metallic compound wrapping portion fiber afterwards prevents further destruction of the alkaline matter to fibre structure, to finally be lived
The composite filtering material fiber for SCR dedusting denitration that property component securely loads.
The second object of the present invention is to provide a kind of composite filtering material fiber of above-mentioned preparation method preparation.With fiber preparation
Filtrate can dedusting, moreover it is possible to catalytic denitration.
The third object of the present invention is to provide a kind of filtrate, has above-mentioned composite filtering material fiber to prepare.
The fourth object of the present invention is to provide a kind of application of above-mentioned composite filtering material fiber or filtrate in dedusting denitration.
Compared with prior art, the beneficial effects of the present invention are:
1. the present invention uses completely new precoating depositing technology, realize manganese, cerium, Zirconium oxide on a variety of organic fiber surfaces
Secured load, under the process conditions, metallic atom and fiber form strong interaction, and finally formed oxide dispersion is equal
It is even, not easily to fall off and have stable denitration efficiency；The process flow is simple, at low cost, and it is rapid to be conducive to filtrate manufacturing enterprise
Investment large-scale production.
2. dedusting denitrating technique may be implemented in the application of the composite filtering material fiber produced by the present invention for SCR dedusting denitration
Upper integration while solving the problems, such as the escaping of ammonia, greatly improves system denitration efficiency, to rows such as propulsion new round steel, building materials
The regulation of industry fire coal boiler fume has positive effect, and application prospect is extensive.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
Heretofore described manganese salt is the compound that can be dissolved in water that cation is manganese ion, such as manganese nitrate, sulfuric acid
Manganese, manganese acetate etc..
Heretofore described cerium salt is the compound that can be dissolved in water that cation is cerium ion, such as cerous nitrate, sulfuric acid
Cerium, cerous acetate etc..
Heretofore described zirconates is the compound that can be dissolved in water that cation is zirconium ion, such as zirconium nitrate, sulfuric acid
Zirconium etc..
As background technique is introduced, exist in the prior art that active component and fibres bond are insecure, are easy dusting
The deficiency to fall off, in order to solve technical problem as above, present applicant proposes a kind of composite filtering material for SCR dedusting denitration is fine
The preparation method of dimension.
A kind of exemplary embodiment of the application provides a kind of system of composite filtering material fiber for SCR dedusting denitration
Manganese salt, cerium salt and zirconates are dissolved in the water and prepare salting liquid A by Preparation Method, the alkaline solution B that pH is 8~12 are prepared, by fiber
It immerses to salting liquid A and infiltrates, ultrasonic wave added infiltration a period of time is carried out in impregnation process, is soaked after the fiber after infiltration is drained
Enter 15~70min of dipper precipitation in alkaline solution B, aging is carried out after the fiber after dipper precipitation is taken out, by the fibre after aging
Dimension carries out microwave combustion method, finally carries out being activated up to the composite filtering material fiber of SCR dedusting denitration is used for.
The present invention enables to metal ion that can preferably enter to first by fiber impregnation into salting liquid, by ultrasound
In the gap of fiber, so that metal ion can be more uniform is dispersed on fiber, it then will be soaked with metal ion again
Fiber impregnation into aqueous slkali so that finely dispersed reactive metal oxides can be made on fiber, due to first impregnating
Metal ion enter in fiber gap, then metal ion is precipitated, reactive metal oxides can not only be reinforced and existed
Bond strength on fiber, and make reactive metal oxides are more uniform to be dispersed on fiber, to improve fiber
Catalytic performance.
Meanwhile fiber is a kind of larger molecular organics, under alkaline condition, is easy to degrade and dissolve, not only compromise
The structure of fiber, and the metal ion of dipping in the fibre can be dissociateed to come from fiber, it is finally unable to get compound
Filter media fibre.For the present invention by many experiments, the pH for adjusting alkaline solution A is 8~12, and controls the infiltrating time of fiber, energy
Enough ensure that fiber does not generate irreversible structural failure in alkaline solution A, and enables to precipitate under the alkaline condition
Metallic compound wrapping portion fiber afterwards prevents further destruction of the alkaline matter to fibre structure, to finally be lived
The composite filtering material fiber for SCR dedusting denitration that property component securely loads.
Preferably, the alkaline solution B is ammonium hydroxide, sodium hydroxide solution, sal volatile or sodium carbonate liquor.
Preferably, the molar ratio of the manganese ion in the salting liquid A, cerium ion and zirconium ion be 1~8:1~4:1~
4。
Preferably, the time that fiber is immersed to salting liquid A infiltration is 30~80min.
Preferably, the time of ultrasonic wave added infiltration is 5~30min.Ultrasonic wave added infiltration time less than fiber immerse to
The infiltrating time of salting liquid A.
Preferably, the time of the aging is 2~6h.
Preferably, the aging is to carry out aging in air atmosphere after taking out the fiber after dipper precipitation.
Preferably, the time of the microwave combustion method is 10~40min, microwave power 100-600W, every 300s microwave hair
Raw time 75-225s.
Preferably, it is activated again after being dried after microwave combustion method.
It is further preferred that the condition of the drying is 105 DEG C of drying and processing 5h.
Preferably, described be activated is that fiber is placed in 150~250 DEG C of a period of times.
It is further preferred that the time of the activation processing is 2~8h.
Present invention also provides a kind of composite filtering material fibers of above-mentioned preparation method preparation.Both with the filtrate of fiber preparation
Energy dedusting, moreover it is possible to catalytic denitration.
Present invention also provides a kind of filtrates, have above-mentioned composite filtering material fiber to prepare.
Present invention also provides a kind of application of above-mentioned composite filtering material fiber or filtrate in dedusting denitration.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment and comparative example of body.
Embodiment 1:
Using polyimide fiber as the composite filtering material fiber for SCR dedusting denitration of substrate, steps are as follows:
Step 1: manganese nitrate solution 14.32g, the six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums of 50wt% are weighed
4.29g is dissolved in deionized water 250mL, is stirred evenly, and solution A is obtained.The ammonia spirit 16mL for taking 25wt%, using deionization
Water is settled to 200mL, is uniformly mixing to obtain solution B (pH 10).
Step 2: polyimide fiber is immersed into solution A 40min, ultrasonic wave added time 7min, later by the polyamides of infiltration
Imine fiber takes out from solution A, and solution B is immersed after draining, fiber is taken out after dipper precipitation 21min, it is old to be placed in air atmosphere
Change 4h.
Step 3: the fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition: microwave function
Rate 200W, every 20s microwave time of origin 10s；Be placed on 105 DEG C of drying and processing 5h of air blast drying box.Drying is completely gathered
Imide fiber is placed in Muffle furnace, and heat treatment activation 4h under the conditions of 250 DEG C is obtained securely metal oxide-loaded difunctional
Composite fibre #1.
Embodiment 2
The present embodiment is same as Example 1, the difference is that, the manganese nitrate solution 3.58g of the present embodiment 50wt%, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 4.29g obtain securely metal oxide-loaded difunctional composite fibre #2.
Embodiment 3
The present embodiment is same as Example 1, the difference is that, the manganese nitrate solution 3.58g of the present embodiment 50wt%, six
Nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g obtain securely metal oxide-loaded difunctional composite fibre #3.
Embodiment 4:
Using PTFE fiber as the composite filtering material fiber for SCR dedusting denitration of substrate, steps are as follows:
Step 1: manganese nitrate solution 14.32g, the six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums of 50wt% are weighed
4.29g is dissolved in deionized water 250mL, is stirred evenly, and solution A is obtained.The ammonia spirit 16mL for taking 25wt%, using deionization
Water is settled to 200mL, is uniformly mixing to obtain solution B (pH 11).
Step 2: PTFE fiber is immersed into solution A 30min, ultrasonic wave added time 7min, later by the PTFE fiber of infiltration
It is taken out from solution A, solution B is immersed after draining, takes out fiber after dipper precipitation 15min, be placed in air atmosphere aging 4h.
Step 3: the fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition: microwave function
Rate 200W, every 20s microwave time of origin 10s；Be placed on 105 DEG C of drying and processing 5h of air blast drying box.It will dry complete
PTFE fiber is placed in Muffle furnace, and heat treatment activation 4h under the conditions of 250 DEG C is obtained securely metal oxide-loaded difunctional multiple
Condensating fiber #4.
Embodiment 5
The present embodiment is same as Example 4, the difference is that, the manganese nitrate solution 3.58g of the present embodiment 50wt%, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 4.29g obtain securely metal oxide-loaded difunctional composite fibre #5.
Embodiment 6
The present embodiment is same as Example 4, the difference is that, the manganese nitrate solution 3.58g of the present embodiment 50wt%, six
Nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g obtain securely metal oxide-loaded difunctional composite fibre #6.
Embodiment 7:
Using PTFE fiber as the composite filtering material fiber for SCR dedusting denitration of substrate, steps are as follows:
Step 1: manganese nitrate solution 14.32g, the six nitric hydrate cerium 17.36g, five nitric hydrate zirconiums of 50wt% are weighed
4.29g is dissolved in deionized water 250mL, is stirred evenly, and solution A is obtained.Sodium hydroxide 16g is weighed, deionized water is dissolved in and is determined
Hold to 200mL, stirring is completely dissolved to sodium hydrate solid, obtains homogeneous solution B (pH 12).
Step 2: PTFE fiber is immersed into solution A 50min, ultrasonic wave added time 7min, later by the PTFE fiber of infiltration
It is taken out from solution A, solution B is immersed after draining, takes out fiber after dipper precipitation 15min, be placed in air atmosphere aging 4h.
Step 3: the fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition: microwave function
Rate 400W, every 30s microwave time of origin 10s；Be placed on 105 DEG C of drying and processing 5h of air blast drying box.It will dry complete
PTFE fiber is placed in Muffle furnace, and heat treatment activation 4h under the conditions of 250 DEG C is obtained securely metal oxide-loaded difunctional multiple
Condensating fiber #7.
Embodiment 8
The present embodiment is same as Example 4, the difference is that, the manganese nitrate solution 3.58g of the present embodiment 50wt%, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 17.16g obtain securely metal oxide-loaded difunctional composite fibre #8.
Embodiment 9
The present embodiment is same as Example 4, the difference is that, the manganese nitrate solution 14.32g of the present embodiment 50wt%,
Six nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g obtain securely metal oxide-loaded difunctional composite fibre #
9。
Embodiment 10:
Using polyimide fiber as the composite filtering material fiber for SCR dedusting denitration of substrate, steps are as follows:
Step 1: manganese nitrate solution 3.58g, the six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums of 50wt% are weighed
4.29g is dissolved in deionized water 250mL, is stirred evenly, and solution A is obtained.Ammonium carbonate 19.2g is weighed, deionized water is dissolved in and is determined
Hold to 200mL, stirring is completely dissolved to ammonium carbonate solid, obtains homogeneous solution B (pH 9).
Step 2: immersing solution A 60min, ultrasonic wave added time 20min for polyimide fiber, later by the poly- of infiltration
Imide fiber takes out from solution A, and solution B is immersed after draining, fiber is taken out after dipper precipitation 50min, is placed in air atmosphere
Aging 4h.
Step 3: the fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition: microwave function
Rate 300W, every 30s microwave time of origin 10s；Be placed on 105 DEG C of drying and processing 5h of air blast drying box.It will dry complete
PTFE fiber is placed in Muffle furnace, and heat treatment activation 4h under the conditions of 250 DEG C is obtained securely metal oxide-loaded difunctional multiple
Condensating fiber #10.
Embodiment 11
The present embodiment is same as in Example 10, the difference is that, when the present embodiment changes infiltration of the fiber in solution A
Between be 80min, infiltrating time is 30min in B solution, obtains securely metal oxide-loaded difunctional composite fibre #11.
Embodiment 12
The present embodiment is same as in Example 10, the difference is that, when the present embodiment changes infiltration of the fiber in solution A
Between be changed to 60min, infiltrating time is changed to 40min in B solution, obtains securely metal oxide-loaded difunctional compound fibre
Tie up #12.
Embodiment 13
The present embodiment is same as in Example 10, the difference is that, the present embodiment changes the step the ammonium carbonate 19.2g in one
For sodium carbonate 21.2g, securely metal oxide-loaded difunctional composite fibre #13 is obtained.
SCR denitration active testing is carried out to 13 catalyst samples on the fixed bed Benitration reactor of laboratory, denitration is anti-
The test condition answered are as follows: 125~250 DEG C of reaction temperature, 30 000h of air speed-1, NH3Concentration 500ppm, NO concentration 500ppm, O2
Concentration 3.5%, N2For Balance Air.The results are shown in Table 1.
Table 1 is used for the composite filtering material fiber denitration activity test result of SCR dedusting denitration
Comparative example 1
The manganese nitrate solution 14.32g, six nitric hydrate cerium 4.34g, five nitric hydrate zirconium 4.29g for weighing 50wt% are dissolved in
It in deionized water 250mL, stirs evenly, obtains solution A.Preparing pH is 13 sodium hydroxide solution as solution B, by polyamides Asia
Amine fiber immerses solution A 40min, and ultrasonic wave added time 7min later takes out the polyimide fiber of infiltration from solution A,
Solution B, dipper precipitation 21min are immersed after draining, polyimide fiber dissolution is not available.
Comparative example 2
This comparative example is same as Example 1, the difference is that, prepare the sal volatile that pH is 7.5 as solution B,
There is no the performances of catalytic denitration for the fiber prepared by the comparative example.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field
For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair
Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (12)
1. a kind of preparation method of the composite filtering material fiber for SCR dedusting denitration, characterized in that by manganese salt, cerium salt and zirconates
It is dissolved in the water and prepares salting liquid A, prepare the alkaline solution B that pH is 8~12, fiber is immersed to salting liquid A and is infiltrated, is being infiltrated
Ultrasonic wave added infiltration a period of time is carried out in the process, and dipper precipitation 15 in alkaline solution B is immersed after the fiber after infiltration is drained
~70min carries out aging after taking out the fiber after dipper precipitation, and the fiber after aging is carried out microwave combustion method, most laggard
Row is activated to be used for the composite filtering material fiber of SCR dedusting denitration.
2. preparation method as described in claim 1, characterized in that the alkaline solution B is ammonium hydroxide, sodium hydroxide solution, carbon
Acid ammonium solution or sodium carbonate liquor；
Or, the molar ratio of manganese ion, cerium ion and zirconium ion in the salting liquid A is 1~8:1~4:1~4.
3. preparation method as described in claim 1, characterized in that the time of ultrasonic wave added infiltration is 5~30min；
Or, the time that fiber is immersed to salting liquid A infiltration is 30~80min.
4. preparation method as described in claim 1, characterized in that the time of the aging is 2~6h；
Or, the aging is to carry out aging in air atmosphere after taking out the fiber after dipper precipitation.
5. preparation method as described in claim 1, characterized in that the time of the microwave combustion method is 10~40min, microwave
Power 100-600W, every 300s microwave time of origin 75-225s.
6. preparation method as described in claim 1, characterized in that activated again after being dried after microwave combustion method.
7. preparation method as claimed in claim 6, characterized in that the condition of the drying is 105 DEG C of drying and processing 5h.
8. preparation method as described in claim 1, characterized in that the activation processing is that fiber is placed in 150~250 DEG C one
The section time.
9. preparation method as claimed in claim 8, characterized in that the time of the activation processing is 2~8h.
10. a kind of composite filtering material fiber of any preparation method preparation of claim 1~9.
11. a kind of filtrate, characterized in that prepared by composite filtering material fiber described in any one of claim 10.
12. filtrate answering in dedusting denitration described in a kind of composite filtering material fiber described in any one of claim 10 or claim 11
With.
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| PCT/CN2017/106879 WO2018233159A1 (en) | 2017-06-23 | 2017-10-19 | Difunctional composite filter medium fiber and preparation method therefor |
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| CN108926911B (en) * | 2018-06-26 | 2021-02-26 | 清华大学盐城环境工程技术研发中心 | Preparation method of denitration and demercuration integral filter material |
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