CN106391096A - Monolithic catalyst for catalytic degradation of flue gas dioxin from small-sized household refuse incinerator and preparation method thereof - Google Patents
Monolithic catalyst for catalytic degradation of flue gas dioxin from small-sized household refuse incinerator and preparation method thereof Download PDFInfo
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- CN106391096A CN106391096A CN201610690225.3A CN201610690225A CN106391096A CN 106391096 A CN106391096 A CN 106391096A CN 201610690225 A CN201610690225 A CN 201610690225A CN 106391096 A CN106391096 A CN 106391096A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003546 flue gas Substances 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 230000015556 catabolic process Effects 0.000 title claims abstract description 19
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 title abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000779 smoke Substances 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 9
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 9
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 6
- 239000010813 municipal solid waste Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 14
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000037237 body shape Effects 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 230000000638 stimulation Effects 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052680 mordenite Inorganic materials 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 238000004056 waste incineration Methods 0.000 description 12
- 239000003344 environmental pollutant Substances 0.000 description 11
- 231100000719 pollutant Toxicity 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012876 carrier material Substances 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical class [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- -1 carrier Substances 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000256844 Apis mellifera Species 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002977 hyperthermial effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The invention discloses a monolithic catalyst for catalytic degradation of flue gas dioxin from small-sized household refuse incinerator and a preparation method thereof. The preparation method comprises catalyst and assistant formula selection, catalyst carrier selection, smoke suppressing agent and binder selection, integral honeycomb structure formation, and baking and catalyst activation. The catalyst, assistant and smoke suppressing agent comprise V2O5, WO3, MOO3, (NH4)2MOO4, CeO2 and BaSO4, the carrier and binder comprise TiO2, SiO2, NaX-type (13X) mordenite (Na2O, Al2O3, (2.8+/-0.2)SiO2 and (6-7)H2O), glass fibers and silica sol (mSiO2nH2O), the integral honeycomb structure formation process comprises extruding the fully stirred catalyst, assistant and carrier mud to obtain a honeycomb structure through a mold and a press machine, and the baking and catalyst activation process comprises drying the honeycomb structure in the shade at the room temperature, carrying out low temperature baking dehydration and carrying out high temperature calcination to stimulate catalyst activity.
Description
Technical field
The present invention relates to catalyst field, in particular to a kind of two English class catalytic degradation integral catalyzers and its
Preparation method.
Background technology
The domestic existing catalyst with two English class substance decomposition functions, great majority are for station boiler or other industry
Denitration of boiler smoke, desulfurization, incidentally remove two English classes.Be not exclusively used in remove flue gas in two dislike because of the catalyst of pollutant
Product, is more equipped with simple not used for facility, and two evils of incomplete small-sized consumer waste incineration system gas cleaning are divided because of class
Solution catalyst prod.
For adopting honeycomb station boiler or other Industrial Boiler denitrating flue gas, desulfurization, removing two English class catalyst more
Cerdip catalyst liquid is made.Limited by its catalyst content, service life is accordingly shorter.The present invention adopts nano silicon
Participate in catalyst carrier, it not only micro structure be spherical, in cotton-shaped and netted, there is small-size effect, skin effect and macroscopic view
Quantum with drug effect should, and can fully dispersed in the middle of system, enable carrier good slow releasing function.Equally as carrier
Ultra-fine clinoptilolite is the same with nano silicon to have a huge specific surface area, many meso-hole structures, the super absorbability robbed and strange
Different physicochemical property, the powerful Ludox of appropriate bond propertiess is integrated into a whole well-mixed catalyst, carrier,
Catalyst material sinks collection well in mesoporous, and catalytic action is efficiently, persistently.
Because two English pollutant contents in incineration flue gas of household garbage are far above flue gas in power station boiler, small-sized life
Refuse burning system flue gas temperature after the process such as chilling, dedusting, deacidification gas has dropped down to less than 200 DEG C it is desirable to catalyst
Activity is very high, and catalytic reaction temperature is low.The present invention is using the ceria with quick Lacking oxygen diffusivity and nanometer
Titanium dioxide combines, and makes original vanadium-tungsten-Titanium series catalyst effectively improve activity, reduces reaction temperature, strengthens degraded two English classes
Ability, to meet the needs of incineration flue gas of household garbage purification.
Content of the invention
It is an object of the invention to developing one kind to be suitable for consumer waste incineration, particularly small-sized consumer waste incineration system
Flue gas removes the catalyst of two English pollutants.It is currently used for flue gas in power station boiler denitration, de- two English catalyst vanadium-tungsten-
The life-span of Titanium series catalyst, reaction temperature and degradation rate all can not meet small-sized consumer waste incineration system flue gas and remove two English
The needs of pollutant.
The present invention is achieved in that a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation of construction is overall
Formula catalyst it is characterised in that：Including catalyst, auxiliary formula and sorting, catalyst carrier and sorting, smoke suppressant, binding agent
And sorting, shaped using integral honeycomb body, bakee and make with catalyst stimulation technique.
According to a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer of the present invention,
It is characterized in that：Described catalyst, auxiliary formula and sorting：V2O54%～6%, WO36%～8%, CeO2（Nano level superfine）
0.3%～0.5%, BaSO41%～2%, TiO2（Nanoscale, sharp titanium A type）77%～85%.
According to a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer of the present invention,
It is characterized in that：Described catalyst carrier and sorting：SiO2（Inorganic nano level）5%～10%, NaX type（13X）Modenite
（na2o、al2o3、（2.8±0.2）sio2、（6-7）h2o）85%～90%.
According to a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer of the present invention,
It is characterized in that：Described smoke suppressant, binding agent and sorting：MOO32%～3%,（NH4）2MOO41%～2%, remaining is Ludox
（mSiO2nH2O）.
According to a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer of the present invention
Preparation method it is characterised in that：It is the good catalyst of formula, catalyst aid, smoke suppressant and load that integral honeycomb body shapes
Body material（Siccative）It is placed in agitator stirring 1.5h～2h, add that silicon is molten to stir into mud after all materials are sufficiently mixed uniformly
Material.On 20T hydraulic press, pug is squeezed into 150mm × 150mm × 100mm, the block green honeycomb of 36 mesh with mould；
The blank being squeezed into is dried in the shade 48h～72h at normal temperatures, baking oven is put into the blank of blank dehydration substantially and carries out 100 DEG C
Low temperature baking 3h, 5 DEG C of programming rate～8 DEG C/min, 200 DEG C of middle temperature baking 2h, 10 DEG C of programming rate～15 DEG C/min, finally
The honeycomb ceramics having bakeed is put into box Muffle furnace（900℃）Activated at is implemented to catalyst.During 550 DEG C of activation of activationary temperature
Between be 1.5h, 15 DEG C of programming rate～20 DEG C/min.
1st, use for reference vanadium-tungsten-Titanium series catalyst technology of having announced, adjustment formula increases auxiliary agent and adopts nanometer material as far as possible
Material.Catalyst, auxiliary agent, smoke suppressant formula and sorting：V2O54%～6%, WO36%～8%, CeO2（Nano level superfine） 0.3%
～0.5%, BaSO41%～2%, MOO32%～3%+（NH4）2MOO41%～2%, TiO2（Nanoscale, sharp titanium A type）77%～85%.
2nd, catalyst carrier and sorting：SiO2（Inorganic nano level）5%～10%, NaX type（13X）Modenite（na2o、
al2o3、（2.8±0.2）sio2、（6-7）h2o）85%～90%.
3rd, it is the globality binding agent sorting ensureing catalyst：Ludox（mSiO2nH2O）.
4th, integral honeycomb body shapes is the good catalyst of formula, catalyst aid, smoke suppressant and carrier material（Siccative）
It is placed on stirring 1.5h～2h in agitator.（Catalyst+auxiliary agent+smoke suppressant）With the weight of carrier than for 1:4.Treat that all materials are filled
Add after point mix homogeneously that appropriate silicon is molten to stir into pug.With mould on 20T hydraulic press pug be squeezed into 150mm ×
150mm × 100mm, the block green honeycomb of 36 mesh.
5th, the blank being squeezed into is dried in the shade 48h～72h at normal temperatures, baking oven is put into the blank of blank dehydration substantially and carries out
100 DEG C of low temperature baking 3h, 5 DEG C of programming rate～8 DEG C/min, 200 DEG C of middle temperature baking 2h, 10 DEG C of programming rate～15 DEG C/min,
Finally the honeycomb ceramics having bakeed is put into box Muffle furnace（900℃）Activated at is implemented to catalyst.550 DEG C of activationary temperature swashs
Live time is 1.5h, 15 DEG C of programming rate～20 DEG C/min.
The invention discloses a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer and
Its preparation method it is characterised in that：Including catalyst, auxiliary formula and sorting, catalyst carrier and sorting, smoke suppressant, bonding
Agent and sorting, integral honeycomb body shapes, bakees and catalyst stimulation technique and method；Described catalyst, auxiliary agent, smoke suppressant
Including V2O5、WO3、MOO3、（NH4）2MOO4、CeO2、BaSO4；Described carrier, binding agent include TiO2、SiO2、Clinoptilolite
（AmBpO2p·nH2O）, glass fibre, Ludox（mSiO2nH2O）；Described integral honeycomb body shapes, with mould and pressure
Machine is stirring the catalyst of mixing, auxiliary agent, carrier pug are squeezed into honeycomb ceramics；Described baking and catalyst stimulation,
Honeycomb ceramics room temperature is dried in the shade, low temperature bakees dehydration, high-temperature calcination excites catalyst activity.
The purpose of the present invention is that the catalysis being exclusively used in Small-sized living garbage incinerator flue gas removing two English pollutants divides
Solution.Existing market sells the catalyst with catalytic degradation two English class material function, purifies only for flue gas in power station boiler
Denitration, desulfurization, de- two English catalyst.Because boiler oil mostly is coal, oil or natural gas, in flue gas, two English class contents are relative
Not high, catalyst is mainly for being denitration, desulfurization.And in house refuse, have a large amount of plastics, food waste Organic substance, produce big during burning
Measure two English pollutants, even if limiting using Pintsch process, chilling, in flue gas, two English pollutant contents are still larger.
The needs that incineration flue gas of household garbage removes two English pollutants can not be met using the catalyst that flue gas in power station boiler purifies,
The needs of the incomplete small-sized consumer waste incineration system of facility can not be met.Again because of small-sized consumer waste incineration system flue gas
After the control techniquess such as removing dust, removing sour gas, temperature drop is larger, to reach conventional two English class catalyst requirement
Reaction temperature it is necessary to flue gas hyperthermic treatment, so on the one hand increased the manufacturing cost of consumer waste incineration system,
Also the operation cost of incineration treatment of garbage can be increased simultaneously.Small-sized consumer waste incineration system flue gas removes two English needs one kind
Reaction temperature is low, degradation efficiency is high, long-acting（Life-span）Catalyst.Published patent, going back neither one can meet this simultaneously
A little requirements.The present invention uses for reference published vanadium-tungsten-Titanium series catalyst, and from nanocatalyst and carrier material, addition has
Characteristic of appraising at the current rate and the rare earth oxide-CeO of quick Lacking oxygen diffusivity2, make optimal reaction temperature area 130 DEG C～180
DEG C, the life-span >=20000h, air speed ＞ 5000h-1, two English class removal efficiencies reach 95%～98% catalyst it is ensured that urging using this
After agent, small-sized consumer waste incineration system（Day processes house refuse 0.5t～50T）Two English class pollutions in discharge flue gas
Thing content≤0.1ngTEQ/m3.
It is an advantage of the current invention that：This integral type two English class catalysis oxidation honeycomb ceramics, is specifically designed for small-sized house refuse
Gasification burning system flue gas is developed.Have that catalyst content is high, catalyst active sites are many, response speed is fast, and mithridatism is strong, makes
The features such as use life-span length.Cannot be only used for small-sized domestic garbage gasification CIU gas cleaning to process, apply also for other two
English class concentration is big, the complicated gas cleaning of pollutant component.
Brief description
Fig. 1 is catalyst honeycomb size of the present invention
Fig. 2 is Fig. 1 side schematic view.
Specific embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail, and the technical scheme in the embodiment of the present invention is carried out clearly
Chu, it is fully described by it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.
Based on the embodiment in the present invention, it is all that those of ordinary skill in the art are obtained under the premise of not making creative work
Other embodiment, broadly falls into the scope of protection of the invention.
The present invention provides a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation monoblock type to urge by improving
Agent and preparation method thereof, can be practiced as follows；Including catalyst, auxiliary formula and sorting, catalyst carries
Body and sorting, smoke suppressant, binding agent and sorting, integral honeycomb body shapes, bakees and catalyst stimulation technique and method.
Described catalyst, auxiliary agent, smoke suppressant formula and sorting include V2O5(nanoscale) 4%～6%, WO36%～8%,
CeO2（Nano level superfine）0.3%～0.5%, BaSO41%～2%, MOO32%～3%+（NH4）2MOO41%～2%, TiO2（Nanometer
Level, sharp titanium A type）77%～85%.Described nanometer V2O5For layer structure, there is V+、V+3、V+4And V+5Equivalent state, activated
Coordination site, can occur to be coordinated the reaction participation catalytic cycle such as addition, oxidoreduction, coordination elimination, be middle Strong oxdiative thing, can make
Two English class catalysis oxidations.Described auxiliary agent WO3、BaSO4V can be improved2O5Activity, and catalyst can be increased to SO2, HCl, weight
The mithridatism of metal etc..Described Rare-Earth Ce O2Due to have storage and release oxygen property, and this property mainly due to
The Lattice oxygen defect of CeO2 determines.The cubic fluorite structure of CeO2 can be regarded as forming tetragonal lattice by a large amount of oxonium ions,
And every a cube, have a cation to occupy next cubical center.Some aniones may be from four sides
The position of body is voluntarily transferred on the position on octahedron, leaves vacancy on tetrahedron, makes presence in ceria crystal
The oxygen dissociating in a large number, becomes important storage oxygen/oxygen supply material.Again due to being easy between Ce3+ the and Ce4+ ion pair of CeO2 carry out
Conversion is so as to have the redox property of uniqueness.Cerium oxide plays two Main Functions as promoter:One is storage oxygen,
Oxygen is converted into CeO when lacking, and is converted into CeO2 when oxygen excess again;Two is the metal particle controlling in catalyst.Work as CeO2
With sharp state nanometer TiO2In conjunction with the one hand making the V of high degree of dispersion2O5Increase active component, specific surface area, thus increased work
Property, effectively reduce its activation energy simultaneously, reduce catalytic reaction temperature.Described smoke suppressant MOO32%～3%+（NH4）2MOO4It is
A kind of efficient smoke suppressant, can effectively suppress the exhaust gas volumn discharged.
Described catalyst carrier and sorting include SiO2（Inorganic nano level）5%～10%, NaX type（13X）Modenite
（na2o、al2o3、（2.8±0.2）sio2、（6-7）h2o）85%～90%；Described inorganic nano SiO2,Micro structure is spherical, is in
Cotton-shaped and netted quasi- grain structure, specific surface area is huge, the many meso-hole structures in surface and superpower absorbability, also can fully divide
It is scattered in catalyst system and catalyzing, allows catalyst slow release, increase the service life.Described NaX type（13X）Modenite（na2o、
al2o3、（2.8±0.2）sio2、（6-7）h2o）, big to the adsorption capacity of gas, catalyst and smoke pollution gas can be effectively increased
The reaction contact surface of body.Do not ftracture for making catalyst carrier mix pug dry forming, NaX type（13X）Modenite needs to select
300 mesh fine powders.
Described binding agent Ludox（mSiO2nH2O）Adhesive viscosities relatively low, the porous place of water can be permeated,
Therefore all very good with dispersibility when catalyst and carrier mass mixing and permeability.Because colloidal particle is fine（10-20nm),
There is sizable specific surface area, when Ludox moisture evaporation, colloidal particle is firmly attached to body surface, formed between particle
Silica combines, and is good binding agent and catalyst carrier.
Described integral honeycomb body shapes：Including the catalyst that formula is good, catalyst aid, smoke suppressant and carrier material
（Siccative）It is placed on stirring 1.5h～2h in agitator.（Catalyst+auxiliary agent+smoke suppressant）：The weight of carrier is than for 1:4.Wait own
Material is sufficiently mixed and uniformly adds that appropriate silicon is molten to stir into pug afterwards.For ease of large-scale production, with mould on 20T hydraulic press handle
Pug is squeezed into 150mm × 150mm × 100mm, the block green honeycomb of 36 mesh.
Baking is accompanied and catalyst stimulation technique and method：The blank being squeezed into is dried in the shade 48h～72h at normal temperatures, to blank
The blank of basic dehydration is put into baking oven and is carried out 100 DEG C of low temperature baking 3h, 5 DEG C of programming rate～8 DEG C/min, and 200 DEG C of middle temperature bakee
2h, 10 DEG C of programming rate～15 DEG C/min, finally the honeycomb ceramics having bakeed is put into box Muffle furnace（900℃）Real to catalyst
Apply activated at.550 DEG C of activationary times of activationary temperature are 1.5h, 15 DEG C of programming rate～20 DEG C/min.
The principle of this reality invention：On the basis of vanadium-tungsten-Titanium series catalyst, not only adopt nanometer V2O5, also improve formula
Middle V2O5Weight ratio, make two English adsorb on the huge catalyst of specific surface, quickly can urge in catalyst active sites
Oxidation, decomposes two English classes and generates the mineral products such as CO2, H2O, HCl, H2O.Because consumer waste incineration tail gas contains
There are a large amount of HCl, SO2Deng gas, increase cerium and barium sulfate in catalyst aid it is therefore intended that on the one hand significantly strengthening catalyst
Activity, on the other hand improves the mithridatism of catalyst.For the broad-minded feature of consumer waste incineration tail, in catalyst formulation
Add efficient smoke suppressant MOO3With（NH4）2MOO4Mixture.
Because not only two disliking because of pollutant content greatly in small-sized consumer waste incineration system tail gas, also complicated component has
Machine thing, heavy metal contaminants, more much bigger than other industrial tail gas scavenging loss to the waste of catalyst, using conventional honeybee
Nest pottery stain catalyst liquid preparation method, catalyst carrier amount is very limited, and the present invention adopts catalyst formulation material and carrier
Material is mixed with pug, is integrally formed formula honeycomb catalytic body through extruding, baking, greatly improves catalyst content, carrier
In be furnished with slow releasing agent inorganic nano SiO2Extend catalytic body service life further.
It is an advantage of the current invention that：This integral type two English class catalysis oxidation honeycomb ceramics, is specifically designed for small-sized house refuse
Gasification burning system flue gas is developed.Have that catalyst content is high, catalyst active sites are many, response speed is fast, and mithridatism is strong, makes
The features such as use life-span length.Cannot be only used for small-sized domestic garbage gasification CIU gas cleaning to process, apply also for other two
English class concentration is big, the complicated gas cleaning of pollutant component.
Claims (5)
1. a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer it is characterised in that：Including
Catalyst, auxiliary formula and sorting, catalyst carrier and sorting, smoke suppressant, binding agent and sorting, become using integral honeycomb body
Shape, baking are accompanied and are made with catalyst stimulation technique.
2. a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation monoblock type catalysis according to claim 1
Agent it is characterised in that：Described catalyst, auxiliary formula and sorting：V2O54%～6%, WO36%～8%, CeO2（Nanoscale surpasses
Carefully）0.3%～0.5%, BaSO41%～2%, TiO2（Nanoscale, sharp titanium A type）77%～85%.
3. a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation monoblock type catalysis according to claim 1
Agent it is characterised in that：Described catalyst carrier and sorting：SiO2（Inorganic nano level）5%～10%, NaX type（13X）Modenite
（na2o、al2o3、（2.8±0.2）sio2、（6-7）h2o）85%～90%.
4. a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation monoblock type catalysis according to claim 1
Agent it is characterised in that：Described smoke suppressant, binding agent and sorting：MOO32%～3%,（NH4）2MOO41%～2%, remaining is that silicon is molten
Glue（mSiO2nH2O）.
5. a kind of Small-sized living garbage incinerator flue gas two English class catalytic degradation integral catalyzer according to claim 1
Preparation method it is characterised in that：It is the good catalyst of formula, catalyst aid, smoke suppressant and load that integral honeycomb body shapes
Body material（Siccative）It is placed in agitator stirring 1.5h～2h, add that silicon is molten to stir into mud after all materials are sufficiently mixed uniformly
Material；
On 20T hydraulic press, pug is squeezed into 150mm × 150mm × 100mm, the block green honeycomb of 36 mesh with mould；
The blank being squeezed into is dried in the shade 48h～72h at normal temperatures, baking oven is put into the blank of blank dehydration substantially and carries out 100 DEG C
Low temperature baking 3h, 5 DEG C of programming rate～8 DEG C/min, 200 DEG C of middle temperature baking 2h, 10 DEG C of programming rate～15 DEG C/min, finally
The honeycomb ceramics having bakeed is put into box Muffle furnace（900℃）Activated at is implemented to catalyst；
550 DEG C of activationary times of activationary temperature are 1.5h, 15 DEG C of programming rate～20 DEG C/min.
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| CN110124750A (en) * | 2019-04-29 | 2019-08-16 | 南京点元环境科技有限公司 | A kind of material and preparation method thereof for denitrating flue gas processing |
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Application publication date: 20170215 |