CN107158799A - A kind of composite filtering material fiber and preparation method for SCR dedusting denitrations - Google Patents
A kind of composite filtering material fiber and preparation method for SCR dedusting denitrations Download PDFInfo
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- CN107158799A CN107158799A CN201710486860.4A CN201710486860A CN107158799A CN 107158799 A CN107158799 A CN 107158799A CN 201710486860 A CN201710486860 A CN 201710486860A CN 107158799 A CN107158799 A CN 107158799A
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- fiber
- filtering material
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- dedusting
- composite filtering
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- 239000000835 fiber Substances 0.000 title claims abstract description 146
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000001914 filtration Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000008595 infiltration Effects 0.000 claims abstract description 22
- 238000001764 infiltration Methods 0.000 claims abstract description 22
- 230000032683 aging Effects 0.000 claims abstract description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 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
- 238000001994 activation Methods 0.000 claims abstract description 12
- 238000009841 combustion method Methods 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 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 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [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 12
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000012545 processing Methods 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 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
- 235000011114 ammonium hydroxide Nutrition 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
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 20
- 150000004706 metal oxides Chemical class 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 9
- 238000005470 impregnation Methods 0.000 abstract description 8
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 4
- 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
- 238000005516 engineering process Methods 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
- 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
- 230000004913 activation Effects 0.000 description 4
- 150000001875 compounds Chemical class 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
- 230000033228 biological regulation Effects 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
- 241000143437 Aciculosporium take Species 0.000 description 2
- 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
- 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
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 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
- 150000002466 imines Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 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
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000007613 environmental effect 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
- 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical group 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
-
- B01J35/58—
-
- 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
Abstract
The invention discloses a kind of preparation method of the composite filtering material fiber for SCR dedusting denitrations, 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 infiltrations, 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, finally progress activation process produces the composite filtering material fiber for SCR dedusting denitrations.Mn, Ce, Zr oxide and fiber secure bond can be made, and it is more uniform reactive metal oxides is disperseed in the fibre, NO in removing coal-fired flue-gas while the difunctional composite filtering material being made into by the fiber can realize trap particulate matterx。
Description
Technical field
The present invention relates to locate after the pollutant dust of the building material industry 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 denitrations.
Background technology
Nitrogen oxides can jeopardize health while environmental destruction is caused, and be a kind of to endanger extremely wide big
Gas pollutant.The coal-burning boiler of the wherein industry such as electric power, building materials is the important sources of discharged nitrous oxides.Selective catalysis is also
Former method (Selective Catalytic Reduction, SCR) is most widely used, technology most ripe coal-burning boiler denitration skill
Art, with denitration efficiency height, stable and reliable operation, selectivity it is good many advantages, such as, occupation rate reaches 90% in actual applications
More than. NH3For, using reducing agent the most universal, SCR technical characterstic determines that denitration device is exported in current SCR technology
To inevitably there is not sufficiently reactive NH3, i.e. the escaping of ammonia.If there is oxysulfide in flue gas, the NH of escape3Easily in tail
Portion's flue reacts the stronger ammonium sulfate/ammonium hydrogen sulfate of generation cohesiveness, so as to cause back-end ductwork burn into block.If
SCR catalytic denitration materials are coupled in downstream equipment (sack cleaner) again, escape NH is realized in suitable temperature window3With
NO is not reducedxFurther reaction, then be expected in effectively processing escape NH3While, further improve system denitration efficiency.
Field is post-processed in coal-fired flue-gas, efficiency of dust collection is high, secondary pollution is small, siccative is easily returned due to possessing for sack cleaner
The performances such as receipts, application at home and abroad is more and more wider, accounts for cleaner is applied in market 80%.Sack cleaner is to dedusting
The demand of filter media fibre is huge, and especially multifunctional composite fiber has wide market prospects.China is to the coal-fired pot of every profession and trade
Fire grate, which is put, proposes requirements at the higher level, and the industry coal-burning boiler such as steel, cement, glass, ceramics is the main source of atmosphere pollution,
Also it is to administer emphasis, China's steel annual production is prepared standard more than 900,000,000 tons, according to Baosteel sack cleaner and adjusted, and need to remove altogether
63,000,000 square metres of dirt filtrate, need to change 18,000,000 square metres of filtrate every year, therefore, and dedusting filter media fibre market prospects are especially
It is expected.Being arranged in sack cleaner after SCR device, according to boiler type and application field difference, its running temperature window more
Mouth is normal between 150~250 DEG C, approximate with common low-temperature SCR technology application widget, if realizing that low-temperature SCR is urged here
Change 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 improve system denitration effect
Rate.
In recent years, correlative study of Mn, Ce, Zr etc. the oxide 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 more with TiO2、Al2O3, based on the solid material such as activated carbon.No
The relevant report of the coupling of Mn, Ce, Zr etc. oxide and dedusting filter media fibre.
The content of the invention
Directly soaked using active oxidation species in patent CN104941319A, CN103252135A, CN105315000A
Stain carrying method prepares composite filtering material, but the present inventor has found to use above-mentioned direct impregnation method will by studying
Mn, Ce, Zr etc. oxide with fiber couple the fiber filtering of preparation, and its active component and fibres bond are insecure, hold
Easy powder of detached, industrial production difficulty is 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 denitrations
The preparation method of filter media fibre is closed, Mn, Ce, Zr oxide and fiber secure bond can be made, pair being made into by the fiber
NO in removing coal-fired flue-gas while function and service filtrate can realize trap particulate matterx。
To achieve these goals, the technical scheme is that：
A kind of preparation method of composite filtering material fiber for SCR dedusting denitrations, water is dissolved in by 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
Carry out ultrasonic wave added infiltration a period of time, immersed after the fiber after infiltration is drained dipper precipitation 15 in alkaline solution B~
70min, aging is carried out after the fiber after dipper precipitation is taken out, and the fiber after aging is carried out into microwave combustion method, finally carried out
Activation process produces the composite filtering material fiber for SCR dedusting denitrations.
The present invention enables to metal ion preferably to enter to first by fiber impregnation into salting liquid by ultrasound
In the gap of fiber, so that metal ion more can be uniformly dispersed on fiber, metal ion then will be soaked with 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 strengthened and existed
Bond strength on fiber, and reactive metal oxides are more uniformly dispersed on fiber, so as to improve fiber
Catalytic performance.
Meanwhile, fiber is a kind of larger molecular organicses, and it is easily degraded and dissolved in the basic conditions, not only compromises
The structure of fiber, and the metal ion impregnated in the fibre can be dissociateed from fiber to come, it can not be finally combined
Filter media fibre.The present invention is by many experiments, and regulation alkaline solution A pH is 8~12, and controls the infiltrating time of fiber, energy
Enough ensure that fiber does not produce irreversible structural failure in alkaline solution A, and enable under the alkalescence condition precipitation
Metallic compound wrapping portion fiber afterwards, prevents further destruction of the alkaline matter to fibre structure, so as to finally be lived
The composite filtering material fiber for SCR dedusting denitrations that property component is firmly loaded.
The second object of the present invention is to provide composite filtering material fiber prepared by a kind of above-mentioned preparation method.Prepared with the fiber
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 invention are as follows：
1. the present invention uses brand-new precoating depositing technology, realize manganese, cerium, Zirconium oxide on a variety of organic fiber surfaces
Firm load, under the process conditions, metallic atom is with fiber formation strong interaction, and the oxide ultimately formed is scattered equal
Denitration efficiency that is even, difficult for drop-off and possessing stabilization；The technological process is simple, cost is low, is conducive to filtrate manufacturing enterprise rapid
Input large-scale production.
2. the application of the composite filtering material fiber produced by the present invention for SCR dedusting denitrations can realize dedusting denitrating technique
Upper integration, while solving the problems, such as the escaping of ammonia, greatly improves system denitration efficiency, to promoting the row such as new round steel, building materials
The regulation of industry fire coal boiler fume has positive role, and application prospect is extensive.
Embodiment
It is noted that described further below is all exemplary, it is intended to provide further instruction to the application.Unless another
Indicate, all technologies used herein and scientific terminology are with logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe 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 odd number shape
Formula is also intended to include plural form, additionally, it should be understood that, when in this manual use term "comprising" and/or
During " comprising ", it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Heretofore described manganese salt is that cation is that manganese ion can be dissolved in the compound of water, such as manganese nitrate, sulfuric acid
Manganese, manganese acetate etc..
Heretofore described cerium salt is that cation is that cerium ion can be dissolved in the compound of water, such as cerous nitrate, sulfuric acid
Cerium, cerous acetate etc..
Heretofore described zirconates is that cation is that zirconium ion can be dissolved in the compound of water, such as zirconium nitrate, sulfuric acid
Zirconium etc..
As background technology is introduced, there is active component insecure, easy efflorescence with fibres bond in the prior art
The deficiency come off, in order to solve technical problem as above, present applicant proposes a kind of composite filtering material for SCR dedusting denitrations
The preparation method of fiber.
There is provided a kind of system of the composite filtering material fiber for SCR dedusting denitrations for a kind of exemplary embodiment of the application
Preparation Method, manganese salt, cerium salt and zirconates are dissolved in the water and prepare salting liquid A, the alkaline solution B that pH is 8~12 are prepared, by fibre
Dimension immersion carries out ultrasonic wave added infiltration a period of time in impregnation process, the fiber after infiltration is drained to salting liquid A infiltrations
15~70min of dipper precipitation in immersion alkaline solution B, carries out aging, after aging after the fiber after dipper precipitation is taken out afterwards
Fiber carry out microwave combustion method, finally carry out activation process and produce composite filtering material fiber for SCR dedusting denitrations.
The present invention enables to metal ion preferably to enter to first by fiber impregnation into salting liquid by ultrasound
In the gap of fiber, so that metal ion more can be uniformly dispersed on fiber, metal ion then will be soaked with 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 strengthened and existed
Bond strength on fiber, and reactive metal oxides are more uniformly dispersed on fiber, so as to improve fiber
Catalytic performance.
Meanwhile, fiber is a kind of larger molecular organicses, and it is easily degraded and dissolved in the basic conditions, not only compromises
The structure of fiber, and the metal ion impregnated in the fibre can be dissociateed from fiber to come, it can not be finally combined
Filter media fibre.The present invention is by many experiments, and regulation alkaline solution A pH is 8~12, and controls the infiltrating time of fiber, energy
Enough ensure that fiber does not produce irreversible structural failure in alkaline solution A, and enable under the alkalescence condition precipitation
Metallic compound wrapping portion fiber afterwards, prevents further destruction of the alkaline matter to fibre structure, so as to finally be lived
The composite filtering material fiber for SCR dedusting denitrations that property component is firmly loaded.
It is preferred that, the alkaline solution B is ammoniacal liquor, sodium hydroxide solution, sal volatile or sodium carbonate liquor.
It is preferred that, the mol ratio of manganese ion, cerium ion and zirconium ion in described salting liquid A is 1~8:1~4:1~
4。
It is preferred that, described is 30~80min by the time that fiber is immersed to salting liquid A infiltrations.
It is preferred that, the time of ultrasonic wave added infiltration is 5~30min.Ultrasonic wave added infiltration time less than fiber immerse to
Salting liquid A infiltrating time.
It is preferred that, the time of the aging is 2~6h.
It is preferred that, the aging is to carry out aging in air atmosphere after the fiber after dipper precipitation is taken out.
It is preferred that, the time of the microwave combustion method is 10~40min, microwave power 100-600W, per 300s microwaves hair
Raw time 75-225s.
It is preferred that, 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.
It is preferred that, the activation process is that fiber is placed in into 150~250 DEG C of a period of times.
It is further preferred that the time of the activation process is 2~8h.
Present invention also provides composite filtering material fiber prepared by a kind of above-mentioned preparation method.With the filtrate of fiber preparation both
Energy dedusting, moreover it is possible to catalytic denitration.
Present invention also provides a kind of filtrate, there is above-mentioned composite filtering material fiber to prepare.
Present invention also provides the application of a kind of above-mentioned composite filtering material fiber or filtrate in dedusting denitration.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail with comparative example.
Embodiment 1：
The composite filtering material fiber for SCR dedusting denitrations by substrate of polyimide fiber, step is as follows：
Step one：Weigh 50wt% manganese nitrate solution 14.32g, six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums
4.29g is dissolved in deionized water 250mL, is stirred, and obtains solution A.Take 25wt% ammonia spirit 16mL, using go from
Sub- water is settled to 200mL, is uniformly mixing to obtain solution B (pH is 10).
Step 2：Polyimide fiber is immersed into solution A 40min, ultrasonic wave added time 7min, afterwards by the polyamides of infiltration
Imine fiber takes out from solution A, takes out fiber after solution B, dipper precipitation 21min are immersed after draining, is placed in air atmosphere old
Change 4h.
Step 3：Fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition：Microwave work(
Rate 200W, every 20s microwave time of origins 10s；105 DEG C of drying and processing 5h of air blast drying baker are placed in afterwards.Drying is completely gathered
Imide fiber is placed in Muffle furnace, and heat treatment activation 4h, obtains firmly metal oxide-loaded double work(under the conditions of 250 DEG C
Can composite fibre #1.
Embodiment 2
The present embodiment is same as Example 1, and difference is, the present embodiment 50wt% manganese nitrate solution 3.58g, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 4.29g, obtain firmly metal oxide-loaded difunctional composite fibre #2.
Embodiment 3
The present embodiment is same as Example 1, and difference is, the present embodiment 50wt% manganese nitrate solution 3.58g, six
Nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g, obtain firmly metal oxide-loaded difunctional composite fibre #3.
Embodiment 4：
The composite filtering material fiber for SCR dedusting denitrations by substrate of PTFE fiber, step is as follows：
Step one：Weigh 50wt% manganese nitrate solution 14.32g, six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums
4.29g is dissolved in deionized water 250mL, is stirred, and obtains solution A.Take 25wt% ammonia spirit 16mL, using go from
Sub- water is settled to 200mL, is uniformly mixing to obtain solution B (pH is 11).
Step 2：PTFE fiber is immersed into solution A 30min, ultrasonic wave added time 7min, it is afterwards that the PTFE of infiltration is fine
Dimension is taken out from solution A, takes out fiber after solution B, dipper precipitation 15min are immersed after draining, is placed in air atmosphere aging 4h.
Step 3：Fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition：Microwave work(
Rate 200W, every 20s microwave time of origins 10s；105 DEG C of drying and processing 5h of air blast drying baker are placed in afterwards.It will dry complete
PTFE fiber is placed in Muffle furnace, the heat treatment activation 4h under the conditions of 250 DEG C, obtains firmly metal oxide-loaded difunctional
Composite fibre #4.
Embodiment 5
The present embodiment is same as Example 4, and difference is, the present embodiment 50wt% manganese nitrate solution 3.58g, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 4.29g, obtain firmly metal oxide-loaded difunctional composite fibre #5.
Embodiment 6
The present embodiment is same as Example 4, and difference is, the present embodiment 50wt% manganese nitrate solution 3.58g, six
Nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g, obtain firmly metal oxide-loaded difunctional composite fibre #6.
Embodiment 7：
The composite filtering material fiber for SCR dedusting denitrations by substrate of PTFE fiber, step is as follows：
Step one：Weigh 50wt% manganese nitrate solution 14.32g, six nitric hydrate cerium 17.36g, five nitric hydrate zirconiums
4.29g is dissolved in deionized water 250mL, is stirred, and obtains solution A.Sodium hydroxide 16g is weighed, deionized water is dissolved in and fixed
Hold to 200mL, stirring is completely dissolved to sodium hydrate solid, obtains homogeneous solution B (pH is 12).
Step 2：PTFE fiber is immersed into solution A 50min, ultrasonic wave added time 7min, it is afterwards that the PTFE of infiltration is fine
Dimension is taken out from solution A, takes out fiber after solution B, dipper precipitation 15min are immersed after draining, is placed in air atmosphere aging 4h.
Step 3：Fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition：Microwave work(
Rate 400W, every 30s microwave time of origins 10s；105 DEG C of drying and processing 5h of air blast drying baker are placed in afterwards.It will dry complete
PTFE fiber is placed in Muffle furnace, the heat treatment activation 4h under the conditions of 250 DEG C, obtains firmly metal oxide-loaded difunctional
Composite fibre #7.
Embodiment 8
The present embodiment is same as Example 4, and difference is, the present embodiment 50wt% manganese nitrate solution 3.58g, six
Nitric hydrate cerium 17.36g, five nitric hydrate zirconium 17.16g, obtain firmly metal oxide-loaded difunctional composite fibre #8.
Embodiment 9
The present embodiment is same as Example 4, and difference is, the present embodiment 50wt% manganese nitrate solution 14.32g,
Six nitric hydrate cerium 4.34g, five nitric hydrate zirconium 17.16g, obtain firmly metal oxide-loaded difunctional composite fibre #
9。
Embodiment 10：
The composite filtering material fiber for SCR dedusting denitrations by substrate of polyimide fiber, step is as follows：
Step one：Weigh 50wt% manganese nitrate solution 3.58g, six nitric hydrate cerium 4.34g, five nitric hydrate zirconiums
4.29g is dissolved in deionized water 250mL, is stirred, and obtains solution A.Ammonium carbonate 19.2g is weighed, deionized water is dissolved in and fixed
Hold to 200mL, stirring is completely dissolved to ammonium carbonate solid, obtains homogeneous solution B (pH is 9).
Step 2：Polyimide fiber is immersed into solution A 60min, ultrasonic wave added time 20min, afterwards by the poly- of infiltration
Imide fiber takes out from solution A, takes out fiber after solution B, dipper precipitation 50min are immersed after draining, is placed in air atmosphere
Aging 4h.
Step 3：Fiber after aging is placed in microwave reactor, microwave combustion method 20min, reaction condition：Microwave work(
Rate 300W, every 30s microwave time of origins 10s；105 DEG C of drying and processing 5h of air blast drying baker are placed in afterwards.It will dry complete
PTFE fiber is placed in Muffle furnace, the heat treatment activation 4h under the conditions of 250 DEG C, obtains firmly metal oxide-loaded difunctional
Composite fibre #10.
Embodiment 11
The present embodiment is same as in Example 10, and difference is, when the present embodiment changes infiltration of the fiber in solution A
Between be 80min, infiltrating time is 30min in B solution, obtains firmly metal oxide-loaded difunctional composite fibre #
11。
Embodiment 12
The present embodiment is same as in Example 10, and difference is, 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 firmly metal oxide-loaded difunctional compound fibre
Tie up #12.
Embodiment 13
The present embodiment is same as in Example 10, and difference is, the present embodiment changes the ammonium carbonate 19.2g in step one
For sodium carbonate 21.2g, firmly 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 is：125~250 DEG C of reaction temperature, the 000h of air speed 30-1, NH3Concentration 500ppm, NO concentration 500ppm,
O2Concentration 3.5%, N2For Balance Air.As a result it is as shown in table 1.
Table 1 is used for the composite filtering material fiber denitration activity test result of SCR dedusting denitrations
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
In deionized water 250mL, stir, obtain solution A.The sodium hydroxide solution that preparation pH is 13 is as solution B, by polyamides
Imine fiber immerses solution A 40min, ultrasonic wave added time 7min, afterwards takes the polyimide fiber of infiltration from solution A
Go out, solution B, dipper precipitation 21min, polyimide fiber dissolving, it is impossible to use are immersed after draining.
Comparative example 2
This comparative example is same as Example 1, and difference is, prepare pH for 7.5 sal volatile as solution B,
The fiber prepared by the comparative example does not have the performance of catalytic denitration.
The preferred embodiment of the application is the foregoing is only, the application is not limited to, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made it is any
Modification, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of preparation method of composite filtering material fiber for SCR dedusting denitrations, it is characterized in that, by manganese salt, cerium salt and zirconates
It is dissolved in the water and prepares salting liquid A, prepares the alkaline solution B that pH is 8~12, fiber is immersed to salting liquid A and infiltrated, in infiltration
During carry out ultrasonic wave added infiltration a period of time, dipper precipitation 15 in alkaline solution B is immersed after the fiber after infiltration is drained
~70min, aging is carried out after the fiber after dipper precipitation is taken out, and the fiber after aging is carried out into microwave combustion method, most laggard
Row activation process produces the composite filtering material fiber for SCR dedusting denitrations.
2. preparation method as claimed in claim 1, it is characterized in that, the alkaline solution B is ammoniacal liquor, sodium hydroxide solution, carbon
Acid ammonium solution or sodium carbonate liquor；
Or, the mol ratio of manganese ion in described salting liquid A, cerium ion and zirconium ion is 1~8:1~4:1~4.
3. preparation method as claimed in claim 1, it is characterized in that, the time of ultrasonic wave added infiltration is 5~30min；
Or, it is described by fiber immerse to salting liquid A infiltrate time be 30~80min.
4. preparation method as claimed in claim 1, it is characterized in that, the time of the aging is 2~6h；
Or, the aging is to carry out aging in air atmosphere after the fiber after dipper precipitation is taken out.
5. preparation method as claimed in claim 1, it is characterized in that, the time of the microwave combustion method is 10~40min, microwave
Power 100-600W, per 300s microwave time of origins 75-225s.
6. preparation method as claimed in claim 1, it is characterized in that, activated again after being dried after microwave combustion method；
It is preferred that, the condition of the drying is 105 DEG C of drying and processing 5h.
7. preparation method as claimed in claim 1, it is characterized in that, the activation process is that fiber is placed in into 150~250 DEG C one
The section time；
It is preferred that, the time of the activation process is 2~8h.
8. composite filtering material fiber prepared by a kind of any described preparation method of claim 1~7.
9. a kind of filtrate, it is characterized in that, it is prepared by the composite filtering material fiber having the right described in requirement 8.
10. a kind of the answering in dedusting denitration of the filtrate described in composite filtering material fiber or claim 9 described in claim 8
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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