CN109289907A - Alkaline earth metal modified copper-based molecular sieve NH3-SCR catalyst and preparation method thereof - Google Patents
Alkaline earth metal modified copper-based molecular sieve NH3-SCR catalyst and preparation method thereof Download PDFInfo
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- CN109289907A CN109289907A CN201811105284.5A CN201811105284A CN109289907A CN 109289907 A CN109289907 A CN 109289907A CN 201811105284 A CN201811105284 A CN 201811105284A CN 109289907 A CN109289907 A CN 109289907A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 43
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 Alkaline earth metal modified copper Chemical class 0.000 title abstract 3
- 239000010949 copper Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 37
- 150000001879 copper Chemical class 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001447 alkali salts Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 15
- 239000012876 carrier material Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 14
- 229910052878 cordierite Inorganic materials 0.000 description 13
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 11
- 239000007767 bonding agent Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/7615—Zeolite Beta
-
- 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
- B01D53/92—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
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
本发明提供碱土金属改性的铜基分子筛NH3‑SCR催化剂的制备方法，包括将碱土金属盐溶液与分子筛材料混合，进行离子交换，得到碱土金属改性的分子筛载体材料；在改性后的分子筛载体上负载Cu。本发明提供的碱土金属(Mg，Ca，Sr和Ba)改性的铜分子筛NH3‑SCR催化剂的制备方法，显著提高此类催化剂的水热稳定性。
The invention provides a preparation method of an alkaline earth metal modified copper-based molecular sieve NH 3 SCR catalyst, which comprises mixing an alkaline earth metal salt solution with a molecular sieve material, and performing ion exchange to obtain an alkaline earth metal modified molecular sieve carrier material; Cu is loaded on the molecular sieve carrier. The preparation method of the alkaline earth metal (Mg, Ca, Sr and Ba) modified copper molecular sieve NH 3 SCR catalyst provided by the invention can significantly improve the hydrothermal stability of such catalyst.
Description
Technical field
The invention belongs to NH3A kind of SCR catalyst field, and in particular to copper-based molecular sieve NH3The modification of SCR catalyst
And application.
Background technique
Exhaust gas from diesel vehicle is atmosphere pollution NOxOne of main source, it not only results in haze, acid rain, photochemistry
The Heavy environmental pollutions such as smog also endanger the health of the mankind due to being carcinogen.NH3SCR system is efficient, low because of its
The advantages of cost, it has also become one kind can effectively eliminate NO in exhaust gas from diesel vehiclexMost important means, be widely used in Europe
The areas such as beauty, Japan.The traditional NH in China at present3SCR catalyst is with V2O5/WOx-TiO2Based on, but its active temperature windows
Narrow, hydrothermal stability is poor and V2O5Inherently there is bio-toxicity.
Molecular sieve has the characteristics that environmental-friendly, bigger serface and duct are complicated orderly, is conducive to metal species at it
Dispersion in surface and duct is also beneficial to diffusion of the gas molecule in duct, gradually becomes NH3SCR catalyst
One of mainstream carrier material.And it is used for NH3The common molecular sieve type of-SCR system mainly includes MFI (ZSM-5), BEA
(beta) and CHA (SAPO-34 and SSZ-13) etc..But the NH of molecular sieve itself3SCR activity is poor, it is therefore desirable to pass through auxiliary agent
It is metal-modified to meet diesel vehicle NOxThe demand of purified treatment.It is existing research shows that copper-based molecular sieve catalyst is to the diesel oil tailstock
NO in gasxThere is higher NH3- SCR catalytic purification activity, has wide potential application foreground.But molecular sieve is a kind of Asia
Stabilizing material, framework of molecular sieve can collapse at high temperature.In the presence of having water (or vapor) in environment, hydrone meeting
The site Al of molecular sieve is attacked, so that framework of molecular sieve hydrolyzes dealuminzation, to cause the collapsing of skeleton.For diesel vehicle,
Its exhaust temperature is lower than gasoline car, general < 400 DEG C, although there are 10% or so H in tail gas2O, but this is for Cu molecular sieve
Can't there is a problem of for the hydrothermal stability of base catalyst very big.But work as NH3SCR system front end is equipped with DPF
When, temperature can be increased to 600 DEG C or more with moment when regenerating, it could even be possible to reaching 800 DEG C.Although DPF regenerates every time
Time is very short (within a few minutes), but the temporal summation within the entire after-treatment device service life period is longer, this is just right
The high-temperature hydrothermal stability of Cu based molecular sieve catalyst proposes requirement.In many Cu based molecular sieve catalyst, Cu/BEA is urged
Agent possesses more excellent initial activity, but its hydrothermal stability is to be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of copper zeolite NH that different alkaline-earth metal (Mg, Ca, Sr and Ba) are modified3-
The preparation method of SCR catalyst, this method improve such catalyst, the especially hydrothermal stability of Cu/BEA catalyst, are protecting
NO while holding fresh activity, after promoting long-lasting catalytic hydro-thermal processxTransformation efficiency extends catalyst service life.
To achieve the above object, the present invention provides alkali-earth metal modified copper-based molecular sieve NH3The preparation of SCR catalyst
Method, comprising the following steps:
(1) alkali salt is dissolved in the alkali salt for being made into that molar concentration is 0.05~0.2mol/L in deionized water
Solution；Acquired solution is mixed with molecular screen material, stirring carries out ion exchange 1-12h and obtains slurry at 50~90 DEG C, institute
Stating molecular screen material and solution quality ratio is 50~150g/L, and gained slurry is dried to obtain to alkali-earth metal modified molecular sieve
Carrier material；
(2) step (1) alkali-earth metal modified molecular screen material obtained is added in copper salt solution, passes through equal bodies
The Cu of product impregnation molecular sieve quality 1%~3%, is then dried, after drying in oxygen atmosphere or air, 300~600 DEG C
3~6h of lower roasting obtains alkali-earth metal modified copper-based molecular sieve catalyst powder.
Further, the molecular screen material is at least one of the beta type molecular sieve of not copper silica alumina ratio (Si/Al),
Silica alumina ratio is 20-40, preferably 22-28.
Further, the alkali salt is at least one of the salt of element M g, Ca, Sr, Ba, preferably nitric acid
Salt, such as barium nitrate.
Further, step (2) mantoquita is copper nitrate.
Further, step (1) ion-exchange temperature is 60~85 DEG C, and the time is 1~9h；Preferably temperature 75~85
DEG C, 5~7h of time.
Further, step (1) 150~250rpm of ion exchange speed of agitator.
Further, the drying temperature of step (1) slurry is 65~120 DEG C.
Further, step (2) drying condition is 70~150 DEG C of dry 20~26h.
The alkali-earth metal modified copper-based molecular sieve NH of above method preparation provided by the invention3SCR catalyst has
Excellent hydrothermal stability.
Alkali-earth metal modified copper-based molecular sieve catalyst powder of the present invention, when use, need to be prepared into monoblock type catalysis
Agent, the method is as follows:
(1) alkali-earth metal modified copper-based molecular sieve catalyst powder is uniformly mixed with deionized water, bonding agent and is made
Slurries, control slurry solid content are 45~50%；
(2) gained catalyst slurry is coated uniformly on cordierite ceramic honeycomb matrix, controls catalyst fines in base
Upper carrying capacity on body is 150~160g/L；
(3) by the cordierite substrates after coating after 100~120 DEG C of dry 8~12h, the 500-600 DEG C of roasting in Muffle furnace
3~5h is burnt to get integral catalyzer is arrived.
Further, it is Φ 11mm*25mm/400cpsi that the cordierite, which selects specification,.
Compared with prior art, the invention has the following advantages:
1. the present invention is modified copper-based molecular sieve catalyst using base earth metal promoter, copper-based molecular sieve NH is improved3-
The SCR activity of SCR catalyst, the especially hydrothermal stability of Cu/BEA catalyst improve while keeping fresh activity
The NO of Cu/BEA catalyst after long-time hydro-thermal processxTransformation efficiency can effectively extend the service life of catalyst.
2. in the method for the present invention, alkaline-earth metal has alkalinity, that is, there is higher electron donation, be conducive to priming reaction
Object NOx, promote NH3The progress of-SCR reaction, improves Reduction of NOxAbility.
3. by modified copper-based molecular sieve NH3SCR catalyst is coated uniformly on cordierite honeycomb ceramic matrix, system
Standby integral formula catalyst, advantageously reduces the phenomenon that high temperature catalyst falls off.
4. the catalyst of the method for the present invention preparation not only shows preferable catalytic performance, but also simple production process, fit
For industrial requirement.
Detailed description of the invention
Fig. 1 is Cu/BEA catalyst prepared by comparative example 1 and the Cu/BEA that Examples 1 to 4 utilizes different content Ba modified
The fresh activity figure of catalyst.
Fig. 2 is the Cu/ that Cu/BEA catalyst prepared by comparative example 1 and different content Ba prepared by Examples 1 to 4 are modified
BEA catalyst by 600 DEG C of hydro-thermal process for 24 hours after activity figure.
Fig. 3 is Cu/BEA catalyst prepared by comparative example 1 and the Cu/BEA that Examples 1 to 4 utilizes different content Ba modified
Activity figure of the catalyst after 600 DEG C of hydro-thermal process 48h.
Fig. 4 is that the Cu/BEA catalyst that Cu/BEA catalyst prepared by comparative example 1 and Ba prepared by embodiment 3 are modified passes through
Activity figure after 600 DEG C of hydro-thermal process 72h.
Fig. 5 is active assessment device.
Specific embodiment
The present invention will be further described with specific embodiment with reference to the accompanying drawing.
Molecular screen material as described below is mainly the molecular sieve of commercially available industrial mass manufacture, the molecular screen material skeleton
Topology structural code is that International Zeolite Association meeting (IZA) proposes BEA molecular sieve.
Comparative example 1
The unmodified BEA molecular sieve of 10g is taken to be added in copper nitrate solution, according to equi-volume impregnating impregnated zeolite matter
The Cu of percentage 2% is measured, then 600 DEG C of roasting 6h in the Muffle furnace of air atmosphere is placed in after drying for 24 hours at 70 DEG C, obtains
Cu/BEA catalyst fines.
The obtained powder is finally prepared into monoblock type NH3SCR catalyst:
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive Cu/BEA monoblock type NH3SCR catalyst.
Embodiment 1
By Ba (NO3)2It is dissolved in the alkaline-earth metal salt solution for being made into that molar concentration is 0.1mol/L in deionized water；Then will
Acquired solution is mixed with the BEA molecular screen material of unmodified Si/Al=25, and the molecular screen material and solution quality ratio are
100g/L.Heating stirring 2h obtains slurry at 80 DEG C, and by gained slurry, the dry modified BEA of Ba that obtains for 24 hours divides at 70 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ba of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu that impregnated zeolite mass percent is 1%, then for 24 hours, drying is placed in Muffle furnace in air for drying at 70 DEG C
600 DEG C of roasting 6h obtain the modified Cu/BEA catalyst fines of Ba.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive 1%CuBa/BEA monoblock type NH3- SCR is urged
Agent.
Embodiment 2
By Ba (NO3)2It is dissolved in the alkaline-earth metal salt solution for being made into that molar concentration is 0.1mol/L in deionized water；Then will
Acquired solution is mixed with the BEA molecular screen material of unmodified Si/Al=25, and the molecular screen material and solution quality ratio are
100g/L.Heating stirring 4h obtains slurry at 80 DEG C, and by gained slurry, the dry modified BEA of Ba that obtains for 24 hours divides at 70 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ba of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, then at 70 DEG C it is dry for 24 hours, it is dry to be placed in Muffle furnace in air 600
DEG C roasting 6h, obtains the modified Cu/BEA catalyst fines of Ba.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 3
By Ba (NO3)2It is dissolved in deionized water and is made into molar concentration as 0.1mol/L alkaline-earth metal salt solution；Then by institute
It obtains solution to mix with the BEA molecular screen material of unmodified Si/Al=25, the molecular screen material and solution quality ratio are
100g/L.Heating stirring 6h obtains slurry at 80 DEG C, and by gained slurry, the dry modified BEA of Ba that obtains for 24 hours divides at 70 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ba of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, then at 70 DEG C it is dry for 24 hours, it is dry to be placed in Muffle furnace in air 600
DEG C roasting 6h, obtains the modified Cu/BEA catalyst fines of Ba.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 4
By Ba (NO3)2It is dissolved in deionized water and is made into molar concentration as 0.05mol/L alkaline-earth metal salt solution；Then by institute
It obtains solution to mix with the BEA molecular screen material of unmodified Si/Al=25, the molecular screen material and solution quality ratio are
100g/L.Heating stirring 8h obtains slurry at 80 DEG C, and by gained slurry, the dry modified BEA of Ba that obtains for 24 hours divides at 70 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ba of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, then at 70 DEG C it is dry for 24 hours, it is dry to be placed in Muffle furnace in air 600
DEG C roasting 6h, obtains the modified Cu/BEA catalyst fines of Ba.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 5
By BaCl2It is dissolved in deionized water and is made into molar concentration as 0.1mol/L alkaline-earth metal salt solution；Then by gained
Solution is mixed with the BEA molecular screen material of unmodified Si/Al=25, and the molecular screen material and solution quality ratio are
100g/L.Heating stirring 6h obtains slurry at 50 DEG C, and by gained slurry, the dry modified BEA of Ba that obtains for 24 hours divides at 90 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ba of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, then dry 22h, drying are placed in Muffle furnace in oxygen-containing atmosphere at 70 DEG C
In 300 DEG C of roasting 6h, obtain the modified Cu/BEA catalyst fines of Ba.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 6
By Mg (NO3)2It is dissolved in deionized water and is made into molar concentration as 0.2mol/L alkaline-earth metal salt solution；Then by institute
It obtains solution to mix with the BEA molecular screen material of unmodified Si/Al=25, the molecular screen material and solution quality ratio are
100g/L.Heating stirring 6h obtains slurry at 90 DEG C, and by gained slurry, the dry modified BEA of Mg that obtains for 24 hours divides at 100 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Mg of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, the then dry 26h at 70 DEG C are dry to be placed in Muffle furnace in air 500
DEG C 4h obtains the modified Cu/BEA catalyst fines of Mg.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 7
By Ca (NO3)2It is dissolved in deionized water and is made into molar concentration as 0.2mol/L alkaline-earth metal salt solution；Then by institute
It obtains solution to mix with the BEA molecular screen material of unmodified Si/Al=25, the molecular screen material and solution quality ratio are
50g/L.Heating stirring 6h obtains slurry at 70 DEG C, and by gained slurry, the dry modified BEA of Ca that obtains for 24 hours divides at 120 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Ca of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 2%, then dry 22h, drying are placed in Muffle furnace in air at 100 DEG C
600 DEG C of 3h obtain the modified Cu/BEA catalyst fines of Ca.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
Embodiment 8
By Sr (NO3)2It is dissolved in deionized water and is made into molar concentration as 0.2mol/L alkaline-earth metal salt solution；Then by institute
It obtains solution to mix with the BEA molecular screen material of unmodified Si/Al=25, the molecular screen material and solution quality ratio are
150g/L.Heating stirring 6h obtains slurry at 90 DEG C, and by gained slurry, the dry modified BEA of Sr that obtains for 24 hours divides at 70 DEG C
Son sieve carrier material；The modified BEA molecular screen material of the Sr of acquisition is added in copper nitrate solution, equi-volume impregnating is passed through
The Cu of impregnated zeolite mass percent 3%, then for 24 hours, drying is placed in Muffle furnace in air for drying at 150 DEG C
600 DEG C of 6h obtain the modified Cu/BEA catalyst fines of Sr.
Prepare integral catalyzer:
Resulting fine catalyst is uniformly mixed with deionized water, bonding agent, slurries are made, control slurry solid content is
45%, it is coated uniformly on Φ 11mm*25mm/400cpsi cordierite ceramic honeycomb matrix, controlling carrying capacity on catalyst coat is
160g/L, after 120 DEG C of dry 6h, in Muffle furnace 550 DEG C of roasting 5h to get arrive CuBa/BEA monoblock type NH3- SCR catalysis
Agent.
The following are the performance tests of the catalyst of embodiment preparation
1, catalytic activity is tested
NH is carried out in the fixed microreactor continuously flowed of multichannel of laboratory self assembly3SCR conversion efficiency is surveyed
Examination, the exhaust gas from diesel vehicle composition and experiment condition of simulation are shown in Table 1.
The fixed microreactor continuously flowed of the multichannel, by multichannel air inlet pipeline 1, be mounted on every air inlet pipeline
On quality stream measuring device 2, gas mixing pipe road 3, reacting furnace 5, tubular reactor and gas analyzer composition 6, multichannel air inlet pipeline is simultaneously
Connection is connected to gas mixing pipe road, and tubular reactor is entered after mixing, and catalyst 4 is placed in the middle part of tubular reactor, tubular reactor position
In the burner hearth of reacting furnace, it is ensured that be heated evenly in the middle part of tubular type inductor, mixed gas turns in tubular reactor catalyst
After change, into gas analyzer.
Before test, first integral catalyzer is pre-processed for 550 DEG C in reaction gas (simulation exhaust gas from diesel vehicle).Then
Using the method for cooling test, active testing is carried out after each temperature spot balance.Unconverted NO, NO2And N2O uses Fourier
Leaf infrared gas analyser (Thermol Fisher Scientific) is tested.As a result as shown in Figure 1.
Table 1: simulated exhaust gas condition
As can be known from Fig. 1, the fresh activity of the alkali-earth metal modified catalyst that do not have an impact, still shows excellent
NH3SCR activity, the NO in 150-550 DEG C of reaction temperature sectionx(NO can be converted completelyxConversion ratio > 90%).
2, hydrothermal stability is tested
To investigate influence of the addition (modification) of alkaline-earth metal to monoblock type Cu/BEA catalyst hydrothermal stability.It will comparison
The modified Cu/BEA integral catalyzer of the different alkaline-earth metal exchange capacities of Cu/BEA and embodiment the 1-4 preparation of example preparation,
Containing 10vol.%H2In the moving air of O, 600 DEG C of hydrothermal aging different times (24-72h) carry out active testing, reaction gas afterwards
Composition and test method are identical as corresponding part in catalytic activity test.
Test result is shown in Fig. 2-4, and from figure it is found that by 600 DEG C of hydrothermal agings, alkali-earth metal modified catalyst has more
Good catalytic activity, illustrate alkaline-earth metal is added with the hydrothermal stability for being conducive to improve catalyst, enhances the old of Cu/BEA
Change activity and service life.Wherein but the CuBa/BEA (embodiment 3) especially with swap time for 6h to possess superior hydro-thermal steady
Qualitative, after 600 DEG C of hydrothermal aging 72h, at 250 DEG C maximum NOxConversion ratio is 86%, hence it is evident that higher than Cu/BEA's
71% NOxConversion ratio.Meanwhile the former can obtain the NO greater than 80% in 200-550 DEG C of temperature rangexConversion ratio, this
It is significantly wider than 490-550 DEG C of Cu/BEA.
Claims (10)
1. alkali-earth metal modified copper-based molecular sieve NH3The preparation method of SCR catalyst, which comprises the following steps:
(1) alkali salt is dissolved in be made into deionized water molar concentration be 0.05~0.2mol/L alkali salt it is molten
Liquid；Acquired solution is mixed with molecular screen material, stirring carries out ion exchange 1-12h and obtains slurry at 50~90 DEG C, described
Molecular screen material and solution quality ratio are 50~150g/L, gained slurry are dried to obtain alkali-earth metal modified molecular sieve supported
Body material；
(2) step (1) alkali-earth metal modified molecular screen material obtained is added in copper salt solution, by soaking in equal volume
The Cu of stain method impregnated zeolite quality 1%~3%, is then dried, after drying in oxygen-containing atmosphere or air, at 300~600 DEG C
3~6h is roasted, alkali-earth metal modified copper-based molecular sieve catalyst powder is obtained.
2. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, the molecular screen material is at least one of the beta type molecular sieve of not copper silica alumina ratio, silica alumina ratio 20-40, into one
Step is 22-28.
3. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, the alkali salt is at least one of the water soluble salt of element M g, Ca, Sr, Ba.
4. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, step (2) mantoquita is copper nitrate.
5. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, step (1) ion-exchange temperature is 60~85 DEG C, and the time is 1~9h.
6. alkali-earth metal modified copper-based molecular sieve NH according to claim 53The preparation method of SCR catalyst, feature
It is, step (1) ion-exchange temperature is 75~85 DEG C, 5~7h of time.
7. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, step (1) 150~250r/min of ion exchange speed of agitator.
8. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, the drying temperature of step (1) slurry is 65~120 DEG C.
9. alkali-earth metal modified copper-based molecular sieve NH according to claim 13The preparation method of SCR catalyst, feature
It is, step (2) drying condition is 70~150 DEG C of dry 20~26h.
10. the alkali-earth metal modified copper-based molecular sieve NH that in claim 1-9 prepared by any claim the method3-SCR
Catalyst.
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| CN110201708A (en) * | 2019-06-13 | 2019-09-06 | 中自环保科技股份有限公司 | A kind of SCR catalyst and preparation method |
| CN112371166A (en) * | 2020-10-19 | 2021-02-19 | 江苏大学 | Preparation method of secondary modified molecular sieve integrated SCR catalyst |
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