CN108160107A - The ceramic monolith active coating method of NOx in fabricated in situ removal exhaust gas from diesel vehicle - Google Patents
The ceramic monolith active coating method of NOx in fabricated in situ removal exhaust gas from diesel vehicle Download PDFInfo
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- CN108160107A CN108160107A CN201711475735.XA CN201711475735A CN108160107A CN 108160107 A CN108160107 A CN 108160107A CN 201711475735 A CN201711475735 A CN 201711475735A CN 108160107 A CN108160107 A CN 108160107A
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- China
- Prior art keywords
- ceramic monolith
- molecular sieve
- nox
- dopamine
- active coating
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- 239000000919 ceramic Substances 0.000 title claims abstract description 69
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 35
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229960003638 dopamine Drugs 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 14
- 229920001690 polydopamine Polymers 0.000 claims abstract description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 4
- 230000010148 water-pollination Effects 0.000 claims abstract description 3
- 238000010926 purge Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910016411 CuxO Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- -1 cerium ion Chemical class 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000000969 carrier Substances 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 241000237536 Mytilus edulis Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a kind of ceramic monolith active coating methods that fabricated in situ removes NOx in exhaust gas from diesel vehicle, it is characterised in that：Dopamine solution pretreatment molecular sieves powder is used for the first time, it is allowed to form poly-dopamine in molecular sieve surface, then there is stronger hydrophily and caking property using poly-dopamine, molecular sieve carrier is firmly supported on ceramic monolith, finally by copper ion and transition metal ions Mn+With the coordination of the amino in poly-dopamine, under high-temperature calcination, finally in ceramic monolith surface in situ loaded Cu xO/MxO/N doped molecular sieve mixtures, so as to which the active coating with efficient De NOx effects be made；It has the characteristics that preparation process it is simple, convenient for industrialization continuous production, coating adhesion is strong, activearm distribution is uniform, the active coating of preparation has excellent removal NOx effects.
Description
Technical field
The present invention relates to the ceramic monolith active coating methods that fabricated in situ removes NOx in exhaust gas from diesel vehicle, belong to automobile
Draining technology field especially belongs to the carried catalyst preparation field of exhaust gas from diesel vehicle SCR denitration.
Background technology
It is more and more stringenter to the NOx limit values of emission of diesel engine with the gradually upgrading of environmental regulation, to meet exhaust method
Rule, domestic overwhelming majority main engine plants purify NOx using SCR technology, and principle is to utilize hydrolysis of urea or solid storage ammonia material
When expecting carriers of the NOx in the ammonia and tail gas that generate by being coated with active coating, under the action of active coating, NOx is quick
Nitrogen and water are reduced to by ammonia.Carrier actually in SCR postprocessor is by ceramic monolith, coating and active metal component
Three parts form, and carrier plays the role of supporting coating, active component, provides suitable catalysis reaction channel, activity here
Component is actually catalyst, if without coating, then active component is just without the carrier supported, if do not had on coating
Active component, NOx emission will be exceeded, therefore coating on carrier and active component are essential.
General active component, coating, carrier combine usual two ways, and active component is initially formed catalysis by a kind of mode
Agent powder, is then adhered on ceramic monolith, due between catalyst and ceramic monolith without interaction force, in vehicle
In driving process, particularly the operating mode in mine area, active component are particularly easy to come off from carrier surface；Another way will first apply
Layer is attached to binding agent on carrier, and catalyst then is supported on ceramic monolith by way of electro-deposition or original position again
On, this mode Active components distribution is uniform, and active component is improved with coating binding force, but whether using which kind of mode, by
Between coating and ceramic monolith without interaction force, against the physical action of binding agent, therefore there are still active components
The problem of coming off, it is impossible to inherently solve the problems, such as.If by the direct step fabricated in situ on ceramic monolith of catalyst, not only
Preparation process can be simplified, and from solving the problems, such as coating shedding at all.
Dopamine is the main component of the emplastic of marine mussel class stickiness protide bio secretion, in recent years, in table
Face is modified field using a lot of, but has not seen used in tail gas denitration field.Dopamine by itself sending out under certain condition
Raw polymerisation, the poly-dopamine of formation contains catechol and amino group, and these group expression activitiys are high, can be with ceramics
Carrier forms very high forces with covalent bond and non-covalent bond, and catalyst material is made firmly to be attached to surface.For this purpose, this patent
Mentality of designing be to be allowed to using dopamine solution pretreatment molecular sieves powder form poly-dopamine in molecular sieve surface for the first time,
Then there is the caking property feature that can form very high forces with covalent bond and non-covalent bond with ceramic monolith using poly-dopamine,
Molecular sieve carrier is firmly supported on ceramic monolith, finally by copper ion and transition metal ions Mn+With in poly-dopamine
Amino complexing, under high-temperature calcination, finally ceramic monolith surface in situ synthesize CuxO/MxO/N- doped molecular sieves
Mixture, so as to which the active coating with efficient De-NOx effects be made.
Invention content
The purpose of the present invention is to provide the preparations of the ceramic monolith active coating of fabricated in situ exhaust gas from diesel vehicle removal NOx
Method, have the characteristics that preparation process it is simple, convenient for industrialization continuous production, coating adhesion is strong, activearm distribution is uniform,
The active coating of preparation has excellent removal NOx effects.
To achieve the above object, the technical proposal of the invention is realized in this way：In fabricated in situ removal exhaust gas from diesel vehicle
The ceramic monolith active coating method of NOx, it is characterised in that：For the first time using dopamine solution pretreatment molecular sieves powder, it is allowed to
Poly-dopamine is formed in molecular sieve surface, then there is stronger hydrophily and caking property using poly-dopamine, it will be molecular sieve supported
Body is firmly supported on ceramic monolith, finally by copper ion and transition metal ions Mn+With matching for the amino in poly-dopamine
Position effect, under high-temperature calcination, finally in ceramic monolith surface in situ loaded Cu xO/MxO/N- doped molecular sieve mixtures, from
And the active coating with efficient De-NOx effects is made；It is as follows：
A) micro porous molecular sieve is pre-processed using dopamine solution, obtains PDA- molecular sieve powders, a concentration of 0.08- of dopamine
0.6g/L, for processing mode to continuously stir, temperature is 45-80 DEG C, processing time 8-24h, molecular sieve and dopamine solution system
Mass ratio be 0.1-1.0；
B) uniformly mixed system room temperature ultrasound-leaching containing deionized water, PDA- molecular sieve powders, Ludox, dispersant is used
Stain handles ceramic monolith, and wherein Ludox solid content is 15-40%, and dispersant is industrial alcohol, and PDA- molecular sieve powders are 18-
29 parts, Ludox be 8-32 parts, dispersant is 8-20 parts；
C) b) treated ceramic monolith, in 80-105 DEG C of drying, is finally obtained PDA- points using after compressed air purging
Sub- sieve/ceramic monolith；
D) using active metal solution treatment PDA- molecular sieve powders/ceramic monolith, it is heavy that processing mode is not limited to dipping, electricity
Product mode, 80-105 DEG C of drying, active metal is copper, cerium, iron, one or more of chromium, a concentration of 0.008- of copper ion
0.05mol/L, a concentration of 0-0.01mol/L of cerium ion, a concentration of 0-0.01mol/L of iron, chromium a concentration of 0-
0.01mol/L；
E) by d) treated, carrier removes NOx in exhaust gas from diesel vehicle in 350-500 DEG C of calcining 1-3h to get to fabricated in situ
Ceramic monolith active coating.
The positive effect of the present invention is by the active coating of the fabricated in situ De-NOx on ceramic monolith, suitable for diesel oil
Tail gas denitration, preparation method of the invention not only have preparation process it is simple, convenient for industrialization continuous production, coating adhesion
By force, activearm is distributed uniform feature, and the active coating prepared has excellent in the case where disclosure satisfy that wide temperature window
Remove NOx effects.
Description of the drawings
Fig. 1 is the EDX energy for the ceramic monolith active coating that fabricated in situ prepared by embodiment 1 removes exhaust gas from diesel vehicle NOx
Spectrum.
Fig. 2 is that embodiment 1-5 prepares the expulsion rate survey that position combined diesel oil tail gas removes the ceramic monolith active coating of NOx
Examination installs picture in vibration mechine.
Fig. 3 is that embodiment 1 prepares the NOx activity survey that position combined diesel oil tail gas removes the ceramic monolith active coating of NOx
Test result.
Fig. 4 is preparation principle schematic diagram of the present invention.
Specific embodiment
In following specific example descriptions, a large amount of concrete details are given in order to more deep this hair of understanding
It is bright.It will be apparent, however, to one skilled in the art that the present invention may not need one or more of these details and
It is carried out.
Embodiment 1
A) 300g Sapo-34 molecular sieve powders are weighed, are placed in the dopamine solution of pH=8.0 of the 0.08g/L of a concentration of 300g
In system, 80 DEG C continuously stir processing 8h, and through filtering, 105 DEG C of drying obtain PDA- molecular sieve powders；
B) 18 parts of PDA- molecular sieve powders, 8 parts of Ludox will be contained（Solid content 15%）, 8 parts of ethyl alcohol and deionized water mixing stir
Homogeneous system is mixed, then by system processing ceramic monolith at room temperature, ultrasound-dipping 20min is taken out using compressed air purging
Raffinate；
C) by b) treated, ceramic monolith heats 2min under microwave, according to second of mode ultrasound-impregnation in b)
10min, after compressed air purges raffinate, through 105 DEG C of drying；
D) mixed solution 20L is made into using the cerous acetate of 242g copper nitrates, 63.4g, is handled at room temperature by the way of dipping
Time 15min, PDA- molecular sieve powders/ceramic monolith after taking out purging raffinate and then heated by microwave 2min, impregnate again
Into the mixed liquor of copper acetate and cerous acetate, 10min post-purge raffinates；
E) d) treated carrier is calcined into 3h to get the ceramics of NOx in exhaust gas from diesel vehicle are removed to fabricated in situ in 350 DEG C
Carriers Active coating.
If Fig. 1 is the EDX of the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 1,
It can be seen that each element forms in figure coating；
As shown in Fig. 2, the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 1 is fixed
On vibration mechine, using vibration acceleration 10g, vibration frequency is（100±5）Hz, test period 5h, experiment knot
Honeycomb catalyst finished product is removed after beam and claims its quality, carried catalyst is removed after experiment and claims its quality, coating is computed and takes off
Rate is fallen as shown in table 1, the expulsion rate of 1 prepares coating of embodiment is 0.2%, this shows that coating adhesion is strong, and it is easily de- to solve coating
Fall problem.
As shown in figure 3, the ceramic monolith activity that embodiment 1 is prepared to fabricated in situ removal exhaust gas from diesel vehicle NOx applies
Layer, has carried out micro- anti-test, NO：1000ppm, NH3：1000ppm, O2：5vol %, H2O：10 vol %, N2 Balance Airs, air speed
100000±1000h-1.It can be seen that conversion rate of NOx is up to 98.0%, 150 DEG C of conversion rate of NOx minimum 61.3%, 215~
450 DEG C, conversion rate of NOx can reach more than 85%, it is shown that fine NOx activity disclosure satisfy that each operating mode of diesel vehicle uses and want
It asks.
Comparative example 1
A) 18 parts of molecular sieve powders, 8 parts of Ludox will be contained（Solid content 15%）, 8 parts of ethyl alcohol and deionized water be mixed it is equal
Even system, then by system processing ceramic monolith at room temperature, ultrasound-dipping 20min is taken out residual using compressed air purging
Liquid；
B) by a) treated, ceramic monolith heats 2min under microwave, according to second of mode ultrasound-impregnation in a)
10min, after compressed air purges raffinate, through 105 DEG C of drying；
C) mixed solution 20L is made into using the cerous acetate of 242g copper nitrates, 63.4g, is handled at room temperature by the way of dipping point
Son sieve powder/ceramic monolith, time 15min, after taking out purging raffinate and then heated by microwave 2min, is impregnated into acetic acid again
In the mixed liquor of copper and cerous acetate, 10min post-purge raffinates；
D) by c) treated, carrier is carried in 350 DEG C of calcining 3h to get the ceramics to fabricated in situ removal exhaust gas from diesel vehicle NOx
Body active coating.
Table 1 is embodiment 1, the experiment of the expulsion rate of comparative example 1, is 5h between experiment condition, removes carrier after experiment and urge
Agent coating claims its quality, is computed coating shedding rate as shown in table 1, embodiment 1 is only 0.2%, and comparative example is 2.1%, can
See the effect by poly-dopamine, coating adhesion is strong.
Embodiment 1 is prepared to the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx, has been carried out micro-
Anti- test, NO：1000ppm, NH3：1000ppm, O2：5vol %, H2O：10 vol %, N2 Balance Airs, air speed 100000 ±
1000h-1.It can be seen that conversion rate of NOx is up to 98.0%, and 150 DEG C of conversion rate of NOx minimum 61.3%, 215~450 DEG C, NOx
Conversion ratio can reach more than 85%, it is shown that fine NOx activity disclosure satisfy that each operating mode requirement of diesel vehicle.
Embodiment 2
A) 300g SSZ-13 molecular sieve powders are weighed, are placed in the dopamine solution of pH=8.5 of the 0.6g/L of a concentration of 1000g
In system, 45 DEG C continuously stir processing for 24 hours, and through filtering, 105 DEG C of drying obtain PDA- molecular sieve powders；
B) 29 parts of PDA- molecular sieve powders, 32 parts of Ludox will be contained（Solid content 40%）, 20 parts of ethyl alcohol and deionized water mixing
System is stirred evenly, then by system ultrasound-impregnation ceramic monolith 10min at room temperature, takes out and is blown using compressed air
Sweep raffinate；
C) by b) treated, ceramic monolith is dried in 105 DEG C；
D) mixed solution 20L is made into using the ferric nitrate of 38.7g copper nitrates, 80.8g, PDA- points is loaded in a manner that electricity is heavy
On son sieve powder/ceramic monolith, coating layer thickness 0.08mm；
E) d) treated carrier is calcined into 2h to get the ceramics of NOx in exhaust gas from diesel vehicle are removed to fabricated in situ in 500 DEG C
Carriers Active coating.
As shown in Fig. 2, the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 2
It is fixedly mounted on vibration mechine, using vibration acceleration 10g, vibration frequency is（100±5）Hz, test period 5h, it is real
Honeycomb catalyst finished product is removed after testing and claims its quality, carried catalyst is removed after experiment and claims its quality, is computed applying
Layer expulsion rate is shown in table 1, the expulsion rate of 2 prepares coating of embodiment is 0.10%.
Embodiment 3
A) 300g ZSM5 molecular sieve powders are weighed, are placed in the dopamine solution system of pH=9.0 of the 0.1g/L of a concentration of 900g
In, 60 DEG C continuously stir processing 20h, and through filtering, 100 DEG C of drying obtain PDA- molecular sieve powders；
B) 20 parts of PDA- molecular sieve powders, 15 parts of Ludox will be contained（Solid content 40%）, 10 parts of ethyl alcohol and deionized water mixing
System is stirred evenly, then by system processing ceramic monolith at room temperature, ultrasound-dipping 15min is taken out and blown using compressed air
Sweep raffinate；
C) by b) treated, ceramic monolith heats 2min under microwave, according to second of mode ultrasound-impregnation in b)
5min, after compressed air purges raffinate, through 105 DEG C of drying；
D) mixed solution 20L is made into using the chromium acetate of 121g copper nitrates, 45.8g, is handled at room temperature by the way of dipping
PDA- molecular sieve powders/ceramic monolith, after reaction time 20min, taking-up purge raffinate and then heated by microwave 2min, again
It is impregnated into the mixed liquor of copper acetate and cerous acetate, 10min post-purge raffinates；
E) d) treated carrier is calcined into 3h to get the ceramics of NOx in exhaust gas from diesel vehicle are removed to fabricated in situ in 480 DEG C
Carriers Active coating.
As shown in Fig. 2, the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 2
It is fixedly mounted on vibration mechine, using vibration acceleration 10g, vibration frequency is（100±5）Hz, test period 5h, it is real
Honeycomb catalyst finished product is removed after testing and claims its quality, carried catalyst is removed after experiment and claims its quality, is computed applying
Layer expulsion rate is shown in table 1, the expulsion rate of 3 prepares coating of embodiment is 0.18%.
Embodiment 4
A) 300g Sapo-34 molecular sieve powders are weighed, are placed in the dopamine solution of pH=8.5 of the 0.08g/L of a concentration of 900g
In system, 60 DEG C continuously stir processing 10h, and through filtering, 105 DEG C of drying obtain PDA- molecular sieve powders；
B) 25 parts of PDA- molecular sieve powders, 30 parts of Ludox will be contained（Solid content 20%）, 10 parts of ethyl alcohol and deionized water mixing
System is stirred evenly, then by system processing ceramic monolith at room temperature, ultrasound-dipping 25min is taken out and blown using compressed air
Sweep raffinate；
C) by b) treated, ceramic monolith is dried in 105 DEG C；
D) be made into containing 121g copper nitrates, 20g ferric nitrates, 22g cerous nitrates, chromic nitrate 20g mixed solution 20L, it is heavy using electricity
Long-pending mode handles PDA- molecular sieve powders/ceramic monolith, coating layer thickness 0.1mm；
E) d) treated carrier is calcined into 3h to get the ceramics of NOx in exhaust gas from diesel vehicle are removed to fabricated in situ in 480 DEG C
Carriers Active coating.
As shown in Fig. 2, the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 2
It is fixedly mounted on vibration mechine, using vibration acceleration 10g, vibration frequency is（100±5）Hz, test period 5h, it is real
Honeycomb catalyst finished product is removed after testing and claims its quality, carried catalyst is removed after experiment and claims its quality, is computed applying
Layer expulsion rate is shown in table 1, the expulsion rate of 4 prepares coating of embodiment is 0.20%.
Embodiment 5
A) 300g SSZ-13 molecular sieve powders are weighed, are placed in the dopamine solution of pH=8.5 of the 0.2g/L of a concentration of 1000g
In system, 60 DEG C continuously stir processing 20h, and through filtering, 100 DEG C of drying obtain PDA- molecular sieve powders；
B) 20 parts of PDA- molecular sieve powders, 15 parts of Ludox will be contained（Solid content 40%）, 10 parts of ethyl alcohol and deionized water mixing
System is stirred evenly, then by system processing ceramic monolith at room temperature, ultrasound-dipping 20min is taken out and blown using compressed air
Sweep raffinate；
C) by b) treated, ceramic monolith is dried in 105 DEG C；
D) mixed solution 20L is made into using the cerous acetate of 121g copper nitrates, 32g, handles PDA- at room temperature by the way of dipping
Reaction time 20min, molecular sieve powder/ceramic monolith after taking out purging raffinate and then heated by microwave 2min, impregnates again
Into the mixed liquor of copper acetate and cerous acetate, 10min post-purge raffinates；
E) d) treated carrier is calcined into 2h to get the ceramics of NOx in exhaust gas from diesel vehicle are removed to fabricated in situ in 450 DEG C
Carriers Active coating.
As shown in Fig. 2, the ceramic monolith active coating of fabricated in situ removal exhaust gas from diesel vehicle NOx prepared by embodiment 2
It is fixedly mounted on vibration mechine, using vibration acceleration 10g, vibration frequency is（100±5）Hz, test period 5h, it is real
Honeycomb catalyst finished product is removed after testing and claims its quality, carried catalyst is removed after experiment and claims its quality, is computed applying
Layer expulsion rate is shown in table 1, the expulsion rate of 5 prepares coating of embodiment is 0.15%.
。
Claims (1)
1. the ceramic monolith active coating method of NOx in fabricated in situ removal exhaust gas from diesel vehicle, it is characterised in that：For the first time using more
Bar amine aqueous solution pretreatment molecular sieves powder is allowed to form poly-dopamine in molecular sieve surface, then using poly-dopamine have compared with
Molecular sieve carrier is firmly supported on ceramic monolith by strong hydrophily and caking property, finally by copper ion and transition gold
Belong to ion Mn+With the coordination of the amino in poly-dopamine, under high-temperature calcination, finally loaded in ceramic monolith surface in situ
CuxO/MxO/N- doped molecular sieve mixtures, so as to which the active coating with efficient De-NOx effects be made；Specific steps are such as
Under：
A) micro porous molecular sieve is pre-processed using dopamine solution, obtains PDA- molecular sieve powders, a concentration of 0.08- of dopamine
0.6g/L, for processing mode to continuously stir, temperature is 45-80 DEG C, processing time 8-24h, molecular sieve and dopamine solution system
Mass ratio be 0.1-1.0；
B) uniformly mixed system room temperature ultrasound-leaching containing deionized water, PDA- molecular sieve powders, Ludox, dispersant is used
Stain handles ceramic monolith, and wherein Ludox solid content is 15-40%, and dispersant is industrial alcohol, and PDA- molecular sieve powders are 18-
29 parts, Ludox be 8-32 parts, dispersant is 8-20 parts；
C) b) treated ceramic monolith, in 80-105 DEG C of drying, is finally obtained PDA- points using after compressed air purging
Sub- sieve/ceramic monolith；
D) using active metal solution treatment PDA- molecular sieve powders/ceramic monolith, it is heavy that processing mode is not limited to dipping, electricity
Product mode, 80-105 DEG C of drying, active metal is copper, cerium, iron, one or more of chromium, a concentration of 0.008- of copper ion
0.05mol/L, a concentration of 0-0.01mol/L of cerium ion, a concentration of 0-0.01mol/L of iron, chromium a concentration of 0-
0.01mol/L；
E) by d) treated, carrier removes NOx in exhaust gas from diesel vehicle in 350-500 DEG C of calcining 1-3h to get to fabricated in situ
Ceramic monolith active coating.
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