CN110523432A - Cu-CHA containing copper zeolite and its catalyst, application - Google Patents
Cu-CHA containing copper zeolite and its catalyst, application Download PDFInfo
- Publication number
- CN110523432A CN110523432A CN201911034501.0A CN201911034501A CN110523432A CN 110523432 A CN110523432 A CN 110523432A CN 201911034501 A CN201911034501 A CN 201911034501A CN 110523432 A CN110523432 A CN 110523432A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- cha
- catalyst
- ssz
- cha molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J29/70—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
- B01J29/723—CHA-type, e.g. Chabazite, LZ-218
-
- 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
- B01J29/86—Borosilicates; Aluminoborosilicates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
This application discloses a kind of Cu-CHA containing copper zeolite and its catalyst and the application in exhaust gas from diesel vehicle processing, belong to catalysis material field.This contains copper zeolite Cu-CHA, and composition includes the zeolite with CHA skeleton structure of the Cu of silicon, aluminium element and 1.65-3.05wt%, further includes the boron of 0.5-1.5wt% in the Cu-CHA molecular sieve, and the Cu-CHA molecular sieve acid amount is 0.25-0.98mmol/g.The sour density of the Cu-CHA molecular sieve of the application, which is up to 0.25-0.98mmol/g and Cu content, has excellent NH as the catalyst of ammine selectivity catalytic reduction down to 1.65-3.05wt%3Storage capacity and good low temperature active, while the generation of CuOx species is not present in high temperature section, it avoids due to NH3Non-selective oxidation bring high temperature active reduce.Cu-CHA molecular sieve catalyst all shows excellent catalytic activity in wider temperature window, take into account low temperature and high temperature active, good catalytic activity is still shown after hydrothermal aging is handled, being applied in exhaust gas from diesel vehicle treatment process has significant performance advantage.
Description
Technical field
Catalysis this application involves a kind of Cu-CHA containing copper zeolite and preparation method thereof, comprising the Cu-CHA containing copper zeolite
Agent and application of the catalyst in motor-driven vehicle gas disposal, the especially application in exhaust gas from diesel vehicle processing, belong to catalysis
Material Field.
Background technique
It include carbon monoxide (CO), hydrocarbon (HC), particulate matter (PM) and nitrogen oxides (NOx) in exhaust gas from diesel vehicle
Four kinds of major pollutants.Wherein, NOx may cause haze, photochemical fog and depletion of the ozone layer.China's automobile is possessed within 2017
Amount reaches 2.08 hundred million, and diesel vehicle only accounts for wherein 9.4%, but the NOx of emission of diesel engine is about motor vehicle emission NOx total amount
70%.Ammine selectivity catalytic reduction (NH3- SCR) it is currently generally acknowledged mainstream exhaust gas from diesel vehicle NOx processing technique.
Catalyst is NH3The core of SCR technology, uses for reference the successful experience in stationary source denitration field, and vanadium series catalyst becomes
First generation exhaust gas from diesel vehicle denitrating catalyst.Vanadium series catalyst has NO high conversion rate, and sulfur tolerance is excellent and at low cost etc.
Many advantages, but since its temperature window is narrow, high-temperature behavior difference and active component vanadium have the disadvantages such as bio-toxicity,
It is unable to satisfy the requirement of six stage emission standard of state.The molecular sieve based catalyst of transition metal load since its activity is high, heat and
Hydrothermal stability is excellent and is considered as state six stages exhaust gas from diesel vehicle NH not comprising advantages such as poisonous components3SCR technology
Ideal catalyst.
Zeolite is by duplicate TO4The crystalline state or quasi- crystalline state that tetrahedron element (or combination of tetrahedron element) is constituted
Aluminosilicate, wherein T most typically is Si and Al.These units are joined together to form in the well-regulated crystal of tool of molecular size
The skeleton in hole and/or channel.Synthesized a plurality of types of synthetic zeolites and every kind all have it is only based on tetrahedron element
The unique framework of display cloth.In rule, each topological classification is assigned with unique trigram by International Zeolite Association (IZA)
Code name (such as " CHA ").
The CHA type Si-Al molecular sieve base catalyst of Cu exchange is real due to its good low temperature active and hydrothermal stability
Existing exhaust gas from diesel vehicle NH3The commercial applications of-SCR process.Generally, the exhaust temperature under diesel vehicle nominal situation be about 200 ~
450 DEG C, cold-start phase exhaust temperature is lower than 200 DEG C, when the regeneration of the grain catcher (DPF) of front end, into SCR module
Tail gas transient temperature can reach 700 DEG C.Therefore, showing good conversion rate of NOx in the temperature window significantly changed is
Important one of the performance indicator of SCR catalyst.
For the Upgrade Problem of low temperature active, the strategy of the prior art is the Cu load capacity for improving CHA molecular sieve, but this
Kind way often leads to the reduction of catalyst high temperature active.This is because part Cu species are in high temperature in high load amount
Under the conditions of can be converted to CuOx, these CuOx do not have catalytic activity to the conversion of NOx, but can be catalyzed NH3It is non-selection
Property oxidation, thus cause catalyst high temperature active reduction.In addition, Cu-CHA molecular sieve catalyst exists under the conditions of high load amount
In use process can due to Cu species transformation and cause the irreversible inactivation of catalytic activity.
Summary of the invention
To solve the above-mentioned problems, one kind Cu-CHA containing copper zeolite and its catalyst is provided and at exhaust gas from diesel vehicle
Application in reason.The sour density of the Cu-CHA molecular sieve of the application is up to 0.25-0.98mmol/g and Cu content down to 1.65-
3.05wt% has excellent NH as the catalyst of ammine selectivity catalytic reduction (abbreviation SCR)3Storage capacity and good
Low temperature active, while high temperature section be not present CuOx species generation, avoid due to NH3Non-selective oxidation bring
High temperature active reduces.Cu-CHA molecular sieve catalyst all shows excellent catalytic activity in wider temperature window, takes into account
Low temperature and high temperature active still show good catalytic activity after hydrothermal aging is handled, and are applied to the diesel oil tailstock
There is significant performance advantage during gas disposal.
According to the one aspect of the application, provide one kind Cu-CHA containing copper zeolite, it includes element silicon, aluminium element and
The aluminosilicate zeolite including CHA skeleton structure of the Cu of 1.65-3.05wt% further includes 0.5- in the Cu-CHA molecular sieve
The boron of 1.5wt%, the Cu-CHA molecular sieve acid amount are 0.25-0.98mmol/g.Further, the Cu-CHA molecular sieve
Acid amount be range lower limit be selected from 0.3mmol/g, 0.35mmol/g, 0.4mmol/g, 0.45mmol/g, 0.5mmol/g,
0.55mmol/g、0.6mmol/g、0.65mmol/g、0.7mmol/g、0.75mmol/g、0.8mmol/g、0.85mmol/g、
0.9mmol/g or 0.95mmol/g, the upper limit be selected from 0.3mmol/g, 0.35mmol/g, 0.4mmol/g, 0.45mmol/g,
0.5mmol/g、0.55mmol/g、0.6mmol/g、0.65mmol/g、0.7mmol/g、0.75mmol/g、0.8mmol/g、
0.85mmol/g, 0.9mmol/g or 0.95mmol/g.Preferably, it includes 1.95-3.05wt%Cu including CHA skeleton knot
The zeolite of structure.
Optionally, the Cu content in the Cu-CHA molecular sieve is 1.95-3.02wt%, the acid of the Cu-CHA molecular sieve
Amount is 0.65-0.96mmol/g.
Optionally, the lower limit of the boron content range is selected from 0.7wt%, 0.9wt%, 1.1wt% or 1.3wt%, the upper limit
Selected from 0.7wt%, 0.9wt%, 1.1wt% or 1.3wt%.
Optionally, the boron atom is located on the skeleton of zeolite.
Optionally, the molar ratio of the silica in the Cu-CHA molecular sieve and aluminium oxide is 13-28.
Optionally, the molar ratio of the silica in the Cu-CHA molecular sieve and aluminium oxide is 18-24.Further,
The lower limit of the molar ratio range of the silica and aluminium oxide is selected from 19,20,21,22 or 23, and the upper limit is selected from 19,20,21,22
Or 23.
Optionally, the Cu-CHA molecular sieve also includes the not metal with Copper Ion Exchange, the metal of non-ion exchange
Content is less than 1000ppm；The metal of the non-ion exchange is selected from least one of alkali metal.Further, it is described not from
The content of the metal of son exchange is less than 500ppm.Further, the content of the metal of the non-ion exchange is less than 100ppm.
Preferably, the metal of the non-ion exchange is sodium or potassium.It is highly preferred that the metal of the non-ion exchange is
Sodium.
Optionally, the grain size of the Cu-CHA molecular sieve is 0.2 ~ 3 μm.Further, the Cu-CHA molecular sieve
Grain size be 0.5 ~ 2.5 μm.Further, the range lower limit of the grain size of the Cu-CHA molecular sieve is selected from 1 μ
M, 1.5 μm or 2 μm, the range limit of the grain size of the Cu-CHA molecular sieve is selected from 1 μm, 1.5 μm or 2 μm.
Optionally, the specific surface area of the Cu-CHA molecular sieve is not less than 500 m2/g.Further, the Cu-CHA points
The specific surface area of son sieve is greater than 500 m2/g。
Optionally, the total pore volume of the Cu-CHA molecular sieve is not less than 0.25 cm3/g.Further, the Cu-CHA points
The total pore volume of son sieve is higher than 0.25 cm3/g。
Optionally, the test method of the acid amount is ammonia Temperature Programmed Desorption.
According to further aspect of the application, the preparation method of the Cu-CHA containing copper zeolite described in one kind is provided,
Include the following steps:
1) providing has the aluminosilicate zeolite of CHA skeleton structure as CHA molecular sieve；
2) the CHA molecular sieve is subjected to NH4 +Or H+Exchange system, which obtains, just exchanges CHA molecular sieve；
3) using liquid-phase ion exchange by copper source introduce it is described just exchange CHA molecular sieve, dry, roasting obtains described
Cu-CHA molecular sieve.
Optionally, the Cu content in the Cu-CHA molecular sieve is 1.65-3.05wt%.
Optionally, the preparation method of the CHA molecular sieve includes:
1) silicon source, silicon source, boron source, template, alkali and deionized water are mixed to get just mixed object；
2) object just will be mixed at autogenous pressures made from step 1), in 150 ~ 200 DEG C of 12 ~ 96 h of crystallization to get the CHA molecule
Sieve；
Wherein, the Al in the just mixed object2O3、SiO2、B2O3, template, OH-And H2The molar ratio of O are as follows: 1:18-32:0.8-
1.7:1.8-3.8:2.4-6.5:200-380；
The template is selected from N, N, at least one of N- trimethyl hydroxide amantadine, benzyl trimethyl amine and choline.
Optionally, the preparation method of the just exchange CHA molecular sieve includes: by the CHA molecular sieve in ammonium salt solution or acid
0.5-20h is mixed at 70-95 DEG C in solution, is separated by solid-liquid separation, washs, it is dry, it obtains just exchanging CHA molecular sieve.
Further, will made from step 1) just mixed object at autogenous pressures, 160 ~ 170 DEG C of 48 ~ 60 h of crystallization to get
The CHA molecular sieve.
Further, the Al in the just mixed object2O3、SiO2、B2O3, template, OH-And H2The molar ratio of O are as follows: 1:20-
28:1.0-1.4:2.2-3.2:2.8-5.6:280-320.
Further, the template is N, N, N- trimethyl hydroxide amantadine.
Optionally, the CHA molecular sieve is SSZ-13 molecular sieve.
Optionally, copper source is selected from least one of copper acetate, copper nitrate and copper sulphate.
Optionally, the temperature of the ion exchange in solution is 20 ~ 90 DEG C.Further, the temperature of the ion exchange in solution
Degree is 50 ~ 80 DEG C.
Optionally, the time of the ion exchange in solution is 0.5 ~ 24 h.Further, the ion exchange in solution when
Between be 2 ~ 7 h.
According to the another aspect of the application, a kind of catalyst is provided comprising Cu-CHA molecular sieve；
The Cu- that the Cu-CHA molecular sieve is selected from any Cu-CHA molecular sieve, is prepared according to any the method
At least one of CHA molecular sieve.
Optionally, the catalyst includes that the Cu-CHA molecular sieve is deposited on the honeycomb substrates.
Preferably, the honeycomb substrates are selected from wall flow substrate or flow through substrate.
Optionally, the catalyst further includes binder, and the binder is zirconium dioxide based binder.
According to another aspect of the application, the answering in ammine selectivity catalytic reduction of catalyst described in one kind is provided
With.
According to another aspect of the application, a kind of waste gas processing method is provided, including makes exhaust gas containing NOx combustion and this
Apply for any catalyst contact.
According to another aspect of the application, a kind of emission-control equipment is provided, it is any described that it includes the application
Catalyst, wherein exhaust gas is transported to the position in exhaust device downstream from diesel engine, reducing agent is added herein, and contain
The waste gas stream of added reducing agent is transported to any catalyst of the application.
In the application, " CHA " refers to the CHA topological classification that (IZA) the structure committee, International Zeolite Association really knows, term
" CHA " refers to topological classification chabasie.Term " including CHA skeleton " refers to that principal crystalline phase is the material of CHA, and there may also be other
Crystalline state, but primary crystallization mutually includes at least about CHA of the CHA of 90wt%, preferably at least about 95wt% and even more desirably at least
The CHA of the CHA of about 97wt% or at least about 99wt% or 100%.
" calcining " refers to the heating material in air, oxygen or inert atmosphere.Implement calcining with decomposing metal salt, promotion catalyst
Removed template method in the micropore of interior metal ion exchanged, the material that catalyst is bonded to matrix and is prepared from here.
" zeolite " refers to skeleton (the i.e. duplicate SiO including aluminium oxide and silica construction4And AlO4Tetrahedron element)
Aluminosilicate molecular sieves also include adulterating other elements in skeleton structure.Under specific synthesis condition, zeolite can be " silicic acid
", refer to that aluminium is only used as impurity presence.
The beneficial effect of the application includes but is not limited to:
1. due to its higher sour density and lower copper content, thus being had according to the Cu-CHA containing copper zeolite of the application
Excellent NH3Storage capacity and good low temperature active, at the same high temperature section be not present CuOx species generation, avoid due to
NH3Non-selective oxidation bring high temperature active reduce.
2. there is more optimized Acidity according to the Cu-CHA molecular sieve catalyst of the application, with existing Cu-CHA points
Son sieve is compared, and weak acid bit quantity increased, and total acid content increased, and the formation of CuOx is suppressed significantly under hot conditions, Cu-
CHA molecular sieve heat and hydrothermal stability are improved.
3. according to the Cu-CHA molecular sieve catalyst of the application in the application that exhaust gas from diesel vehicle is handled, Cu-CHA molecular sieve
Catalyst all shows excellent catalytic activity in wider temperature window, takes into account low temperature and high temperature active, is applied to
There is significant performance advantage in exhaust gas from diesel vehicle treatment process.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 be the invention relates to embodiment 1-3 Cu-SSZ-13 molecular sieve 1-3#XRD spectrogram.
Fig. 2 be the invention relates to comparative example 1-3 Cu-SSZ-13 molecular sieve D1-D3#XRD spectrogram.
Fig. 3 be the invention relates to comparative example 4 Cu-MFI molecular sieve catalyst D4#XRD spectrogram.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
Analysis method is as follows in embodiments herein:
The crystal form of gained sample is analyzed using Rigaku Ultima IV type powder x-ray diffraction.
Using II type Xray fluorescence spectrometer of Rigaku ZSX Primus to the silica alumina ratio and B of gained sample2O3Content
It is analyzed.
Using Agilent company of the U.S. Varian 715-ES type plasma emission spectrometer to the Cu content of gained sample
It is analyzed.
Conversion ratio calculates as follows in embodiments herein:
The conversion ratio of NO=(Reactor inlet NO concentration-reactor outlet NO concentration)/(Reactor inlet NO concentration) * 100%
In embodiments herein, NO conversion ratio is based on nitrogen molal quantity and is calculated.
Embodiments herein is illustrated the performance of Cu-CHA molecular sieve by taking Cu-SSZ-13 molecular sieve as an example, but unlimited
In Cu-SSZ-13 molecular sieve.
According to a kind of embodiment of the application, Na-SSZ-13 molecular sieve is prepared by hydrothermal synthesis first, then to it
Ammonium is carried out to exchange to obtain NH4- SSZ-13 molecular sieve finally carries out the ion exchange in solution of copper to it, obtains Cu-SSZ-13 molecule
Sieve.
1 Cu-SSZ-13 molecular sieve 1# of embodiment
By the N of 220.0 grams of 25wt%, N, N- trimethyl hydroxide amantadine is added in 215.0 grams of deionized waters, is uniformly mixed,
5.6 grams of sodium hydroxides, stirring to abundant dissolution is added thereto again, then by 12.4 grams of aluminium hydroxides, is sufficiently mixed, then thereto
5.8 grams of boric acid are added, 100.0 grams of solid silicones are finally added thereto, 2h is sufficiently stirred.It is poly- that said mixture is transferred to band
In the stainless steel cauldron of tetrafluoroethene liner, be placed in 170 DEG C of baking ovens crystallization 48 hours, take out, quenching, to crystallization product into
Row is separated by solid-liquid separation, washing, and dry and roasting obtains Na-SSZ-13 molecular sieve 1#.
Then ammonium exchange is carried out to it, with 1mol/L ammonium chloride solution with the ratio of solid-to-liquid ratio 1:10 to above-mentioned Na-SSZ-
13 molecular sieves are separated by solid-liquid separation later in 90 DEG C of progress 2h exchanges, are washed, dry, obtain just exchanging NH4- SSZ-13 molecule
Sieve 1#.
Weigh 76.8gCu (NO3)2•H2O is dissolved in 1000 mL deionized waters, and copper nitrate aqueous solution is made, and weighs on 100 g
State gained NH in step4- SSZ-13 type Si-Al molecular sieve, is added in above-mentioned copper nitrate solution, with nitric acid by said mixture
PH value is adjusted between 4.5 ~ 5.0, and said mixture is then placed in 60 DEG C of stirring 6h, drying is filtered, finally in 550 ~ 600 DEG C
4h is roasted in air atmosphere, obtains Cu-SSZ-13 molecular sieve 1#.
The SiO of gained Cu-SSZ-13 molecular sieve 1#2/Al2O3=19.8, copper content is Cu=2.30wt%, boron content B2O3=
0.94wt%, acid amount are 0.88 mmol/g.
2 Cu-SSZ-13 molecular sieve 2# of embodiment
By the N of 161.0 grams of 25wt%, N, N- trimethyl hydroxide amantadine is added in 269.4 grams of deionized waters, is uniformly mixed,
3.6 grams of sodium hydroxides, stirring to abundant dissolution is added thereto again, then by 25.0 grams of sodium metaaluminates, is sufficiently mixed, then thereto
2.4 grams of boric acid are added, 100.0 grams of solid silicones are finally added thereto, 2h is sufficiently stirred.It is poly- that said mixture is transferred to band
In the stainless steel cauldron of tetrafluoroethene liner, be placed in 160 DEG C of baking ovens crystallization 60 hours, take out, quenching, to crystallization product into
Row is separated by solid-liquid separation, washing, and dry and roasting obtains Na-SSZ-13 molecular sieve 2#.
Then ammonium exchange is carried out to it, with 1mol/L ammonium chloride solution with the ratio of solid-to-liquid ratio 1:10 to above-mentioned Na-SSZ-
13 molecular sieves are separated by solid-liquid separation later in 90 DEG C of progress 2h exchanges, are washed, dry, obtain just exchanging NH4- SSZ-13 molecule
Sieve 2#.
Weigh 63.5g Cu (CH3COO)2•H2The molten 1000 mL deionized water of O, is made acetic acid copper liquor, weighs 100g
Gained NH in above-mentioned steps4- SSZ-13 type Si-Al molecular sieve, is added in above-mentioned copper acetate solution, with nitric acid by said mixture
PH value be adjusted between 4.5 ~ 5.0, said mixture is then placed in 80 DEG C of stirring 3h, drying is filtered, finally in 550 ~ 600
4h is roasted in DEG C air atmosphere, obtains Cu-SSZ-13 molecular sieve 2#.
The SiO of gained Cu-SSZ-13 molecular sieve 2#2/Al2O3=14.6, copper content is Cu=3.02wt%, boron content B2O3=
0.82wt%, acid amount are 0.96 mmol/g.
3 Cu-SSZ-13 molecular sieve 3# of embodiment
By the N of 136.0 grams of 25wt%, N, N- trimethyl hydroxide amantadine solution is added in 20.0 grams of deionized waters, and mixing is equal
It is even, then 7.0 grams of sodium hydroxides are added thereto, stirring to abundant dissolution, then by 7.2 grams of boehmites, be sufficiently mixed, then to
1.6 grams of boric acid are wherein added, the silica solution that 320.0 grams of solid contents are 30% is finally added thereto, 2h is sufficiently stirred.It will be above-mentioned
Mixture is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 170 DEG C of baking ovens crystallization 60 hours, is taken out,
Quenching is separated by solid-liquid separation crystallization product, washing, and dry and roasting obtains Na-SSZ-13 molecular sieve 3#.
Then ammonium exchange is carried out to it, with 1mol/L ammonium chloride solution with the ratio of solid-to-liquid ratio 1:10 to above-mentioned Na-SSZ-
13 molecular sieve 3# are separated by solid-liquid separation later in 90 DEG C of progress 2h exchanges, are washed, dry, obtain just exchanging NH4- SSZ-13 points
Son sieve 3#.
Weigh 78.9g CuSO4•5H2O is dissolved in 1000 mL deionized waters, and copper sulfate solution is made, and weighs 100 g
NH4- SSZ-13 type Si-Al molecular sieve, is added in above-mentioned copper-bath, and the pH value of said mixture is adjusted to 4.5 with nitric acid
Between ~ 5.0, said mixture is then placed in 80 DEG C of stirring 3h, drying is filtered, is finally roasted in 550 ~ 600 DEG C of air atmospheres
4h is burnt, Cu-SSZ-13 molecular sieve 3# is obtained.
The SiO of gained Cu-SSZ-13 molecular sieve 3#2/Al2O3=27.2, copper content is Cu=1.95wt%, boron content B2O3=
0.53wt%, acid amount are 0.65mmol/g.
The characterization of 4 Cu-SSZ-13 molecular sieve 1-3# of embodiment
XRD diagram 1 line as shown in figure 1 of Cu-SSZ-13 molecular sieve 1# prepared by embodiment 1, Cu-SSZ- prepared by embodiment 2
2 lines of the XRD diagram of 13 molecular sieve 2# as shown in figure 1, the XRD diagram of Cu-SSZ-13 molecular sieve 3# prepared by embodiment 3 is as shown in figure 1
3 lines, the XRD peak data of Cu-SSZ-13 molecular sieve 1-3# prepared by embodiment 1-3 is as shown in table 1.
As shown in Table 1, its XRD result of Cu-SSZ-13 molecular sieve 1-3# prepared by embodiment 1-3 meets CHA skeleton structure
Characteristic peak, do not find the characteristic peak for belonging to the oxide of copper；With SiO2/ (Al2O3+B2O3) increase, characteristic peak
The position 2theta is gradually reduced.
1 Cu-SSZ-13 molecular sieve D1# of comparative example
It is synthesized according to process described in embodiment 1 and just exchanges NH4- SSZ-13 molecular sieve D1#, wherein the additional amount of aluminium hydroxide from
12.4 grams are changed into 20.2 grams, and other conditions are constant.
NH is just exchanged to above-mentioned gained using liquid-phase ion exchange according to process described in embodiment 14- SSZ-13 molecular sieve
Cu is introduced in D1#, experiment condition and condition described in embodiment 1 are completely the same.
The SiO of gained Cu-SSZ-13 molecular sieve D1#2/Al2O3=10.8, copper content is Cu=2.18wt%, boron content B2O3
=0.89wt%, acid amount are 1.07mmol/g.
2 Cu-SSZ-13 molecular sieve D2# of comparative example
It is synthesized according to process described in embodiment 1 and just exchanges NH4The additional amount of-SSZ-13 molecular sieve D2#, boric acid become 0 from 5.8 grams
Gram, other conditions are constant.
NH is just exchanged to above-mentioned gained using liquid-phase ion exchange according to process described in embodiment 14- SSZ-13 molecular sieve
Cu is introduced in D2#, experiment condition and condition described in embodiment 1 are completely the same.
The SiO of gained Cu-SSZ-13 molecular sieve D2#2/Al2O3=19.4, copper content is Cu=2.23wt%, boron content B2O3
=0wt%, acid amount are 0.46 mmol/g.
3 Cu-SSZ-13 molecular sieve D3# of comparative example
It is synthesized according to process described in embodiment 1 and just exchanges NH4Condition described in-SSZ-13 molecular sieve 1#, experiment condition and embodiment 1
It is completely the same.
Weigh 127.0g Cu (CH3COO)2•H2O is dissolved in 1000 mL deionized waters, and acetic acid copper liquor is made, weighs 100
Synthesis gained NH in g above-mentioned steps4- SSZ-13 type Si-Al molecular sieve, is added in above-mentioned copper acetate solution, then by above-mentioned mixing
Object is placed in 60 DEG C of stirring 6h, filters drying, finally roasts 4h in 550 ~ 600 DEG C of air atmospheres, obtain Cu-SSZ-13 molecular sieve
D3#。
The SiO of gained Cu-SSZ-13 molecular sieve D3#2/Al2O3=19.2, copper content is Cu=3.24wt%, boron content B2O3
=0.92wt%, acid amount are 0.56 mmol/g.
4 Cu-MFI molecular sieve D4# of comparative example
The tetrapropyl oxyammonia of 260.0 grams of 25wt% is added in 237.0 grams of deionized waters, is uniformly mixed, then partially by 13.5 grams
Sodium aluminate is added, and is sufficiently mixed, then 5.8 grams of boric acid are added thereto, 100.0 grams of solid silicones is finally added thereto, sufficiently
Stir 2h.Said mixture is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, crystallization in 170 DEG C of baking ovens is placed in
It 72 hours, takes out, quenching is separated by solid-liquid separation crystallization product, washs, and dry and roasting obtains Na-MFI molecular sieve.
Then ammonium exchange is carried out to it, with 1mol/L ammonium chloride solution with the ratio of solid-to-liquid ratio 1:10 to above-mentioned Na-MFI points
Son sieve is separated by solid-liquid separation later in 90 DEG C of progress 2h exchanges, is washed, dry, obtains NH4- MFI molecular sieve；
Weigh 63.5gCu (CH3COO)2•H2O is dissolved in 1000 mL deionized waters, and acetic acid copper liquor is made, and weighs 100g NH4-
MFI type Si-Al molecular sieve is added in above-mentioned copper acetate solution, with nitric acid by the pH value of said mixture be adjusted to 4.5 ~ 5.0 it
Between, said mixture is then placed in 80 DEG C of stirring 3h, drying is filtered, finally roasts 4h in 550 ~ 600 DEG C of air atmospheres, obtain
To Cu-MFI molecular sieve D4#.
The SiO of gained Cu-MFI molecular sieve D4#2/Al2O3=27.9, copper content is Cu=2.28wt%, boron content B2O3=
0.86wt%, acid amount are 0.49 mmol/g.
The characterization of 5 Cu-SSZ-13 molecular sieve D1-D3# of comparative example
The XRD diagram of Cu-SSZ-13 molecular sieve D1# prepared by comparative example 1 such as 1 line in Fig. 2, Cu-SSZ- prepared by comparative example 2
The XRD diagram of 13 molecular sieve D2# such as 2 lines in Fig. 2, XRD diagram such as Fig. 2 of Cu-SSZ-13 molecular sieve D3# prepared by comparative example 3
In 3 lines, the XRD peak data of Cu-SSZ-13 molecular sieve D1-3# prepared by comparative example 1-3 is as shown in table 2.
As shown in Table 2, its XRD result of Cu-SSZ-13 molecular sieve D1-3# prepared by comparative example 1-3 meets CHA skeleton structure
Characteristic peak, do not find the characteristic peak for belonging to the oxide of copper；The wherein SiO of molecular sieve D1#2/ (Al2O3+B2O3) minimum, phase
Answer the 2theta angle value of ground characteristic peak maximum, the SiO of D2#2/ (Al2O3+B2O3) highest, the angle 2theta of corresponding characteristic peak
Angle value is minimum.
The characterization of 6 Cu-MFI molecular sieve D4# of comparative example
XRD diagram such as Fig. 3 of Cu-SSZ-13 molecular sieve D4# prepared by comparative example 4, the XRD peak data of Cu-SSZ-13 molecular sieve D4#
As shown in table 3.
As shown in Table 3, its XRD result of Cu-MFI molecular sieve D4# prepared by comparative example 4 meets MFI skeleton structure
Characteristic peak does not find the characteristic peak for belonging to the oxide of copper.
Embodiment 5 Cu-SSZ-13 molecular sieve catalyst 1-3#, Cu-SSZ-13 molecular sieve catalyst D1-D3#, Cu-MFI
The preparation of molecular sieve catalyst D4#
Obtained Cu-SSZ-13 molecular sieve 1-3#, Cu-SSZ-13 molecular sieve D1-D3#, Cu-MFI molecular sieve D4# is carried out respectively
Be ground up, sieved, take 80 ~ 100 mesh granular sizes as catalyst sample, be denoted as respectively Cu-SSZ-13 molecular sieve catalyst 1-3#,
Cu-SSZ-13 molecular sieve catalyst D1-D3#, Cu-MFI molecular sieve catalyst D4#.
Embodiment 6 Cu-SSZ-13 molecular sieve catalyst 1-3#, Cu-SSZ-13 molecular sieve catalyst D1-D3#, Cu-MFI
The catalytic performance of molecular sieve catalyst D4# is tested
To Cu-SSZ-13 molecular sieve catalyst 1-3#, Cu-SSZ-13 molecular sieve catalyst D1-D3#, Cu-MFI molecular sieve catalytic
The NH of agent D4#3- SCR catalytic performance is tested, and test temperature is 100-550 DEG C, normal pressure, reaction velocity 35000h-1, NH3It is dense
Degree is 500ppm, NO concentration 500ppm, 5%O2, N2As Balance Air.Cu-SSZ-13 molecular sieve catalyst 1-3#, Cu-SSZ-13
The NH of molecular sieve catalyst D1-D3#, Cu-MFI molecular sieve catalyst D4#3Conversion ratio in-SCR reaction under the different temperatures of NO
Test result is as shown in table 4.
As shown in Table 4, Cu-SSZ-13 the molecular sieve D1#, silica alumina ratio SiO prepared according to comparative example 12/Al2O3It is obvious for 10.8
Lower than the Cu-SSZ-13 molecular sieve 1# prepared according to embodiment 1；Its acid amount is 1.07mol/g, is higher than Cu-SSZ-13 molecular sieve
1#；Cu-SSZ-13 molecular sieve catalyst D1# is 200oThe conversion ratio of NO is substantially less than Cu-SSZ-13 molecular sieve catalyst when C
1#。
As shown in Table 4, the Cu-SSZ-13 molecular sieve D2# prepared according to comparative example 2, not boracic；Its silica alumina ratio SiO2/
Al2O3It is suitable with the Cu-SSZ-13 molecular sieve 1# prepared according to embodiment 1；Its acid amount is 0.46mol/g, substantially less than Cu-
SSZ-13 molecular sieve 1#；Cu-SSZ-13 molecular sieve catalyst D2# is 200oThe conversion ratio of NO is substantially less than Cu-SSZ-13 points when C
Sub- sieve catalyst 1#.
As shown in Table 4, Cu-SSZ-13 the molecular sieve D3#, silica alumina ratio SiO prepared according to comparative example 32/Al2O3With basis
Cu-SSZ-13 molecular sieve 1# prepared by embodiment 1 is suitable；Its boron content and the Cu-SSZ-13 molecular sieve prepared according to embodiment 1
1# is suitable；Its Cu content is 3.24wt%, hence it is evident that is higher than Cu-SSZ-13 molecular sieve 1#；Cu-SSZ-13 molecular sieve catalyst D2# In
200oC and 550oThe conversion ratio of NO is substantially less than Cu-SSZ-13 molecular sieve catalyst 1# when C.
As shown in Table 4, the Cu-MFI molecular sieve D4# prepared according to comparative example 4, skeleton structure are that MFI is different from according to reality
Apply the Cu-SSZ-13 molecular sieve 1# of the preparation of example 1；Cu-MFI molecular sieve catalyst D4# is 200oC and 550oThe conversion ratio of NO is aobvious when C
It writes and is lower than Cu-SSZ-13 molecular sieve 1#.
The above, only embodiments herein, the protection scope of the application is not by these specific embodiments
Limitation, but determined by following claims.To those skilled in the art, the application can have various
Change and variation.All any modification, equivalent replacement, improvement and so within the technical idea and principle of the application, should all
Comprising within the scope of protection of this application.
Claims (22)
1. one kind Cu-CHA containing copper zeolite, which is characterized in that it includes the Cu of element silicon, aluminium element and 1.65-3.05wt%
The zeolite including CHA skeleton structure, further include the boron of 0.5-1.5wt% in the Cu-CHA molecular sieve, the Cu-CHA points
Son sieve acid amount is 0.25-0.98mmol/g.
2. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the Cu in the Cu-CHA molecular sieve contains
Amount is 1.95-3.02wt%, and the acid amount of the Cu-CHA molecular sieve is 0.65-0.96mmol/g.
3. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the boron atom is located at the skeleton of zeolite
On.
4. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the dioxy in the Cu-CHA molecular sieve
SiClx and the molar ratio of aluminium oxide are 13-28.
5. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the Cu-CHA molecular sieve also includes not
It is less than 1000ppm with the content of the metal of Copper Ion Exchange, the metal of non-ion exchange；
The metal of the non-ion exchange is selected from least one of alkali metal.
6. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the crystal grain of the Cu-CHA molecular sieve is big
Small is 0.2 ~ 3 μm.
7. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the specific surface of the Cu-CHA molecular sieve
Product is not less than 500 m2/g。
8. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the total pore volume of the Cu-CHA molecular sieve
Not less than 0.25 cm3/g。
9. Cu-CHA containing copper zeolite according to claim 1, which is characterized in that the test method of the acid amount is ammonia
Temperature Programmed Desorption.
10. the preparation method of the Cu-CHA of any of claims 1-9 containing copper zeolite, which is characterized in that it includes
Following step:
1) providing has the aluminosilicate zeolite of CHA skeleton structure as CHA molecular sieve；
2) the CHA molecular sieve is subjected to NH4 +Or H+Exchange system, which obtains, just exchanges CHA molecular sieve；
3) using liquid-phase ion exchange by copper source introduce it is described just exchange CHA molecular sieve, dry, roasting obtains described
Cu-CHA molecular sieve.
11. preparation method according to claim 10, which is characterized in that the copper content in the Cu-CHA molecular sieve is
1.65-3.05wt%.
12. preparation method according to claim 10, which is characterized in that the preparation method of the CHA molecular sieve includes:
1) silicon source, silicon source, boron source, template, alkali and deionized water are mixed to get just mixed object；
2) object just will be mixed at autogenous pressures made from step 1), in 150 ~ 200 DEG C of 12 ~ 96 h of crystallization to get the CHA molecule
Sieve；
Wherein, the Al in the just mixed object2O3、SiO2、B2O3, template, OH-And H2The molar ratio of O are as follows: 1:18-32:0.8-
1.7:1.8-3.8:2.4-6.5:200-380；
The template is selected from N, N, at least one of N- trimethyl hydroxide amantadine, benzyl trimethyl amine and choline.
13. preparation method according to claim 10, which is characterized in that the CHA molecular sieve is SSZ-13 molecular sieve.
14. preparation method according to claim 10, which is characterized in that copper source is selected from copper acetate, copper nitrate and sulphur
At least one of sour copper.
15. preparation method according to claim 10, which is characterized in that the temperature of the ion exchange in solution is 20 ~ 90
℃。
16. preparation method according to claim 10, which is characterized in that the time of the ion exchange in solution is 0.5 ~ 24
h。
17. a kind of catalyst, which is characterized in that including Cu-CHA molecular sieve；
The Cu-CHA molecular sieve is selected from Cu-CHA molecular sieve of any of claims 1-9, and according to claim
At least one of the Cu-CHA molecular sieve that any one of 10-16 the method is prepared.
18. catalyst according to claim 17, which is characterized in that it includes that the Cu-CHA molecular sieve is deposited on institute
It states on honeycomb substrates, the honeycomb substrates are selected from wall flow substrate or flow through substrate.
19. catalyst according to claim 17, which is characterized in that it further includes binder, and the binder is dioxy
Change zirconium base binder.
20. application of the catalyst in ammine selectivity catalytic reduction described in any one of claim 17-19.
21. a kind of waste gas processing method, including making catalysis described in any one of exhaust gas containing NOx combustion and claim 17-19
Agent contact.
22. a kind of emission-control equipment, which is characterized in that it includes the catalyst described in any one of claim 17-19,
Middle exhaust gas is transported to the position in exhaust device downstream from diesel engine, and reducing agent is added herein, and contains added reduction
The waste gas stream of agent is transported to catalyst described in claim 17-19.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911034501.0A CN110523432A (en) | 2019-10-29 | 2019-10-29 | Cu-CHA containing copper zeolite and its catalyst, application |
| PCT/CN2019/120867 WO2021082140A1 (en) | 2019-10-29 | 2019-11-26 | Cu-cha copper-containing molecular sieve, and catalyst and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911034501.0A CN110523432A (en) | 2019-10-29 | 2019-10-29 | Cu-CHA containing copper zeolite and its catalyst, application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110523432A true CN110523432A (en) | 2019-12-03 |
Family
ID=68672130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911034501.0A Pending CN110523432A (en) | 2019-10-29 | 2019-10-29 | Cu-CHA containing copper zeolite and its catalyst, application |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110523432A (en) |
| WO (1) | WO2021082140A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110665538A (en) * | 2019-12-06 | 2020-01-10 | 山东国瓷功能材料股份有限公司 | Modified CHA type molecular sieve and preparation method and application thereof |
| CN112495426A (en) * | 2021-01-29 | 2021-03-16 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230382745A1 (en) * | 2022-05-31 | 2023-11-30 | Chevron U.S.A. Inc. | Molecular sieve ssz-113 with high acidity, its synthesis and use |
| WO2023235697A1 (en) * | 2022-05-31 | 2023-12-07 | Chevron U.S.A. Inc. | Molecular sieve ssz-121 with high acidity, its synthesis and use |
| US20230382748A1 (en) * | 2022-05-31 | 2023-11-30 | Chevron U.S.A. Inc. | MOLECULAR SIEVE SSZ-117x WITH HIGH ACIDITY |
| CN115791860A (en) * | 2022-12-05 | 2023-03-14 | 山东国瓷功能材料股份有限公司 | Method for measuring copper and aluminum element contents, copper-aluminum ratio and silicon-aluminum ratio in molecular sieve |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098743A (en) * | 2004-11-30 | 2008-01-02 | 切夫里昂美国公司 | Boron-containing molecular sieve cha |
| CN104128200A (en) * | 2014-07-22 | 2014-11-05 | 清华大学苏州汽车研究院（吴江） | Copper-based SCR catalyst and preparation method thereof |
| CN105314648A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum molecular sieves, and preparation methods and applications thereof |
| WO2016177924A1 (en) * | 2015-05-05 | 2016-11-10 | Consejo Superior De Investigaciones Cientificas (Csic) | Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis |
| CN109867294A (en) * | 2019-03-19 | 2019-06-11 | 南开大学 | Cupric CHA type zeolite, its manufacturing method and purposes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101319715B1 (en) * | 2004-11-30 | 2013-10-17 | 셰브런 유.에스.에이.인크. | Boron-Containing Moleculear Sieve CHA |
| US7998423B2 (en) * | 2007-02-27 | 2011-08-16 | Basf Corporation | SCR on low thermal mass filter substrates |
| US8883119B2 (en) * | 2009-11-24 | 2014-11-11 | Basf Se | Process for the preparation of zeolites having CHA structure |
| CN107282096B (en) * | 2016-04-01 | 2020-09-25 | 中触媒新材料股份有限公司 | SSZ-13 molecular sieve catalyst and preparation method and application thereof |
| CN110215931A (en) * | 2019-06-18 | 2019-09-10 | 安徽艾可蓝环保股份有限公司 | Cupric molecular screen material and preparation method thereof and catalyst |
-
2019
- 2019-10-29 CN CN201911034501.0A patent/CN110523432A/en active Pending
- 2019-11-26 WO PCT/CN2019/120867 patent/WO2021082140A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098743A (en) * | 2004-11-30 | 2008-01-02 | 切夫里昂美国公司 | Boron-containing molecular sieve cha |
| CN104128200A (en) * | 2014-07-22 | 2014-11-05 | 清华大学苏州汽车研究院（吴江） | Copper-based SCR catalyst and preparation method thereof |
| CN105314648A (en) * | 2014-07-29 | 2016-02-10 | 孙红 | CHA-type silicon-aluminum molecular sieves, and preparation methods and applications thereof |
| WO2016177924A1 (en) * | 2015-05-05 | 2016-11-10 | Consejo Superior De Investigaciones Cientificas (Csic) | Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis |
| CN109867294A (en) * | 2019-03-19 | 2019-06-11 | 南开大学 | Cupric CHA type zeolite, its manufacturing method and purposes |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110665538A (en) * | 2019-12-06 | 2020-01-10 | 山东国瓷功能材料股份有限公司 | Modified CHA type molecular sieve and preparation method and application thereof |
| CN112495426A (en) * | 2021-01-29 | 2021-03-16 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
| CN113198524A (en) * | 2021-01-29 | 2021-08-03 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
| CN113198524B (en) * | 2021-01-29 | 2022-06-10 | 山东国瓷功能材料股份有限公司 | Copper molecular sieve catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021082140A1 (en) | 2021-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110523432A (en) | Cu-CHA containing copper zeolite and its catalyst, application | |
| US9242241B2 (en) | Copper containing levyne molecular sieve for selective reduction of NOx | |
| WO2011073390A2 (en) | Process for preparation of copper containing molecular sieves with the cha structure, catalysts, systems and methods | |
| WO2008038422A1 (en) | β-TYPE ZEOLITE FOR SCR CATALYST AND METHOD FOR CONVERTING NITROGEN OXIDE USING THE ZEOLITE | |
| EP2340103A1 (en) | Transition metal-containing aluminosilicate zeolite | |
| MX2012007059A (en) | High silica chabazite for selective catalytic reduction, methods of making using same. | |
| CN110407221B (en) | Preparation method of chabazite molecular sieve and preparation method of SCR catalyst | |
| CN112055613A (en) | Aluminum-rich zeolite material containing rare earth elements | |
| CN109590021B (en) | Sandwich-structured ammonia leakage catalyst and preparation method and application thereof | |
| CN110961144A (en) | Symbiotic composite molecular sieve with CHA/LEV topological structure, preparation method thereof and SCR application thereof | |
| CN111013648A (en) | Symbiotic composite molecular sieve with CHA/KFI structure, preparation method thereof and SCR application thereof | |
| JP6171255B2 (en) | NOx selective reduction catalyst, method for producing the same, and NOx purification method using the same | |
| CN111001437A (en) | AEI/AFX structure symbiotic composite molecular sieve, preparation method and SCR application thereof | |
| JP2018094478A (en) | Scr catalyst system | |
| CN113856749A (en) | Samarium-based CHA molecular sieve catalyst and application thereof | |
| CN110139831A (en) | Molecular sieve SSZ-108, its synthesis and purposes | |
| CN110961146A (en) | Symbiotic composite molecular sieve with CHA/RTH topological structure, preparation method thereof and SCR application thereof | |
| CN110665538A (en) | Modified CHA type molecular sieve and preparation method and application thereof | |
| JPH08173761A (en) | Method for removing nitrogen oxide | |
| JPH11221470A (en) | Catalyst for reducing nitrogen oxide and reduction of nitrogen oxide | |
| CN110589851B (en) | SAPO-34 molecular sieve, copper-based SAPO-34 denitration catalyst, preparation method and application thereof, and denitration method | |
| JP7104298B2 (en) | New zeolite and hydrocarbon adsorbent containing it | |
| JP2021161022A (en) | Zeolite composition having yfi structure, hydrocarbon adsorbent, and hydrocarbon adsorption method | |
| CN111530498A (en) | Catalyst for synergistic purification of multiple pollutants in adipic acid device, preparation and application | |
| US20230312357A1 (en) | Process for preparing zeolite material having an afx framework structure and zeolite material as prepared |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191203 |
|
| RJ01 | Rejection of invention patent application after publication |