CN109867294A - Cupric CHA type zeolite, its manufacturing method and purposes - Google Patents
Cupric CHA type zeolite, its manufacturing method and purposes Download PDFInfo
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- CN109867294A CN109867294A CN201910209822.3A CN201910209822A CN109867294A CN 109867294 A CN109867294 A CN 109867294A CN 201910209822 A CN201910209822 A CN 201910209822A CN 109867294 A CN109867294 A CN 109867294A
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Abstract
The present invention relates to a kind of cupric CHA type zeolites, and skeletal atom further includes silicon and aluminium, wherein the molar ratio of silicon and aluminium be more than or equal to 5 and less than 7.5, and the molar ratio of copper and aluminium be more than or equal to 0.2 and be less than or equal to 0.5.In addition, the invention further relates to the preparation method of this cupric CHA type zeolite, the denitrating catalyst comprising this cupric CHA type zeolite, and the purification of nitrogen oxides system comprising the denitrating catalyst.
Description
Technical field
The present invention relates to denitration fields, more particularly, to a kind of cupric CHA type zeolite and its preparation method and application.
Background technique
Oxynitrides (NOx) there is strong and stimulating and corrosivity, it is extremely harmful to human health.Nitrogen oxidation in atmosphere
It closes object to be also easy to interact with other hazardous compounds, generates the nuisances such as sulfate, nitrate.Thus oxynitrides is made
Four big air pollutants are listed as a kind of environment harmful gas and sulfur oxide, ammonia and volatile organic matter.At present for
Industrial waste gas and engine exhaust gas containing oxynitrides, mainly using urea or ammonia as reducing agent, to nitrogen oxidation
It closes object and carries out selective catalytic reduction (SCR), generate harmless nitrogen.
Patent document US7601662B2 and JP2013095653 propose a kind of cupric that silicon/al mole ratio is 7.5 or more
CHA type zeolite is as SCR catalyst, and this catalyst has very excellent low-temperature catalytic activity, especially at 200 DEG C or less
Temperature range in, catalyzed conversion NOxEfficiency be conventional vanadium tungsten titanium oxide catalyst 2 times or more.However, this contain
Copper CHA type zeolite is faced with the technical problems such as manufacturing cost height, poor, the hydrothermal stability difference of sulfur resistance.In addition, as have compared with
The catalysis oxidation ability of the catalyst of high low-temperature catalytic activity, this cupric CHA type zeolite is stronger, then causes in high-temperature region
Ammonia of the interior catalysis oxidation as SCR reducing agent, thus in the temperature range of high temperature section, especially 500 DEG C or more, denitration
Performance sharply declines.It is 7.5 below that patent document WO2010054034A2 and CN102215960B, which report silicon/al mole ratio,
CHA type zeolite, but this same high-temperature hydrothermal stability of CHA type zeolite is lower, is not able to satisfy moving source tail gas denitration catalyst
The requirement of agent.
The present inventor proposes a kind of novel copper-containing CHA type zeolite, which exists by a large amount of research
All there is good SCR denitration performance, to solve this in the high-temperature region of 200 DEG C of low-temperature spaces below and 500 DEG C or more
Some technical problems that field has been deposited.
Summary of the invention
In the first aspect of the present invention, a kind of cupric CHA type zeolite is provided, skeletal atom further includes silicon and aluminium,
In, the molar ratio of silicon and aluminium is more than or equal to 5 and less than 7.5, and the molar ratio of copper and aluminium is more than or equal to 0.2 and to be less than etc.
In 0.5.
In one embodiment, the crystal grain of the cupric CHA type zeolite is less than or equal to 1 μm, is preferably smaller than equal to 0.8 μ
M, more preferably less than or equal to 0.6 μm.In yet another embodiment, the crystal grain of the cupric CHA type zeolite is more than or equal to 50nm,
Preferably greater than or equal to 100nm.In another embodiment, the BET specific surface area of the cupric CHA type zeolite is 550m2/g
More than, preferably 600m2/ g or more.
In yet another embodiment, the cupric CHA type zeolite also include selected from titanium, zirconium, vanadium, chromium, manganese, iron, cobalt,
One of zinc, gallium, germanium, arsenic, tin and boron or various other elements, and the molal quantity of the other elements accounts in the zeolite
Nonoxygen element total mole number 40% hereinafter, it is preferred that 30% or less, more preferable 20% or less.In further embodiment
In, the cupric CHA type zeolite also includes selected from one of alkali metal, alkaline-earth metal, rare earth metal and transition metal or more
Kind cation.
In the second aspect of the present invention, a kind of method for preparing above-mentioned cupric CHA type zeolite, the method packet are provided
It includes: (a) copper source being dissolved in phosphoric acid solution, to obtain cupric gel；(b) to by silicon source, silicon source, inorganic base, organic formwork
In the mixture that agent and water are constituted, the cupric gel that step (a) is obtained is added, to obtain just gel；(c) make the initial set
Glue undergoes hydrothermal synthesis reaction, and obtains reaction product through being separated by solid-liquid separation；(d) reaction product that removal step (c) obtains has
Machine template obtains the zeolite of cupric alkali metal containing；(e) the cupric alkali metal containing zeolite obtained with copper ion displacement step (d)
In alkali metal ion, obtain cupric CHA type zeolite through dry and roasting.
In one embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 1~5.?
In another embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 1.5~4.At another
In embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 2~3.
In one embodiment, in step (b), silicon source, silicon source, inorganic base, organic formwork agent, water, copper, phosphorus rub
You are than being 1SiO2: 0.067~0.1Al2O3: 0.05~0.6OH-: 0.02~0.4 template: 15~80 water: 0.01~0.1Cu:
0.01~0.5P.In another embodiment, in step (b), it is molten that the silicon source is selected from fumed silica, silica
One of glue, colloidal silicon dioxide, waterglass, silester and methyl silicate are a variety of.In yet another embodiment,
In step (b), the silicon source is a kind of or more in fumed silica, silicon dioxide gel and colloidal silicon dioxide
Kind.
In one embodiment, in step (b), source of aluminium be selected from boehmite, aluminium isopropoxide, aluminium alkoxide,
One of aluminium hydroxide, alumina sol and sodium aluminate are a variety of.In another embodiment, in step (b), institute
It states silicon source and is selected from one of boehmite, aluminium hydroxide and sodium aluminate or a variety of.
In one embodiment, in step (b), the organic formwork agent, which is that CHA easy to form is zeolite structured, to be contained
Nitrogen organic compound and/or the organic compounds containing nitrogen that complex compound can be generated with copper.In another embodiment, exist
In step (b), the organic formwork agent is quaternary ammonium salt.In yet another embodiment, in step (b), the organic formwork
Agent be selected from N, N, N- trimethyl adamantane ammonium, benzyltrimethylammon.um, copper-tetraethylenepentamine complex compound, tetraethyl ammonium hydroxide with
And one of tetrapropylammonium hydroxide or a variety of.
In one embodiment, in step (b), the inorganic base is monoacidic base metal inorganic alkali or combinations thereof.?
In another embodiment, in step (b), the inorganic base in lithium hydroxide, sodium hydroxide or potassium hydroxide one
Kind is several.
In one embodiment, in step (c), the reaction temperature of hydrothermal synthesis reaction is 100~200 DEG C, synthesis
Time is 12~96 hours.In another embodiment, in step (c), the reaction temperature of hydrothermal synthesis reaction is 120~
180 DEG C, generated time is 18~72 hours.In yet another embodiment, in step (c), the reaction of hydrothermal synthesis reaction
Temperature is 150~180 DEG C, and generated time is 24~48 hours.
In one embodiment, in step (d), by dry and roast the reaction product that the step (c) obtains
To remove organic formwork agent.In another embodiment, in step (d), when drying temperature is 40~120 DEG C and dries
Between be 12~48 hours, maturing temperature is 300~800 DEG C and calcining time is 0.5~24 hour.In another embodiment
In, in step (d), drying temperature is 80~100 DEG C and drying time is 18~36 hours, and maturing temperature is 400~700
DEG C and calcining time be 1~12 hour.
In one embodiment, in step (e), by ion-exchange directly by the cupric alkali metal containing zeolite
In alkali metal ion be replaced into copper ion.In another embodiment, in step (e), first by ion-exchange
Alkali metal ion in the cupric alkali metal containing zeolite is replaced into the ion other than copper, then will be described by ion-exchange
Ion exchange other than copper is copper ion.In yet another embodiment, in step (e), first will by ion-exchange
Alkali metal ion in the cupric alkali metal containing zeolite is replaced into ammonium ion, then is replaced into ammonium ion by ion-exchange
Copper ion.In another embodiment, in step (e), the ion-exchange 0~100 DEG C at a temperature of carry out 0.5
~96 hours, then the product through ion exchange is separated, and 40~120 DEG C dry 12~36 hours, at 300~800 DEG C
Roasting 1~5 hour obtains cupric CHA type zeolite.
In the third aspect of the present invention, a kind of purification of nitrogen oxides catalyst converter is provided, wherein set in the catalyst converter
It is equipped with containing cupric CHA type zeolite as described herein or the cupric CHA type zeolite being prepared according to method described herein
Denitrating catalyst.
In the fourth aspect of the present invention, a kind of purification of nitrogen oxides system is provided, wherein be provided in the system
Purification of nitrogen oxides catalyst converter as described herein.
In the fifth aspect of the invention, cupric CHA type zeolite as described herein is provided in terms of purifying nitrogen oxides
Purposes.One embodiment of the invention provides cupric CHA type zeolite and is used as denitration in purification of nitrogen oxides catalyst converter
The purposes of catalyst.
The inventors found that influence of the silicon/al mole ratio to SCR denitration performance contained by the skeleton of CHA type zeolite
It is larger, it had both determined the solid acid amount of zeolite, and had also determined the quantity by ion exchange site, and the latter directly affects zeolite
The copper species of portative high dispersion state quantity.Cupric CHA type zeolite disclosed by the invention is in low-temperature space and high-temperature region
Good catalytic activity is all had, this is because zeolite of the invention is due to further defining copper/al mole ratio, thus had both been contained
There is the quantity of the copper species of enough high dispersion states, also contains enough bronsted acid points.
Detailed description of the invention
There is provided herein attached drawings, so that those skilled in the art more fully understand embodiment illustrated herein, still
These attached drawings are not intended to be limiting the scope of the present invention.
Fig. 1 is the XRD diagram according to the cupric zeolite 1,2,3,4 of embodiment of the present invention；
Fig. 2 is to be schemed according to the SEM of the cupric zeolite 1 of one embodiment of the invention；
Fig. 3 is to be schemed according to the SEM of the cupric zeolite 2 of one embodiment of the invention；
Fig. 4 is to be schemed according to the SEM of the cupric zeolite 3 of one embodiment of the invention；
Fig. 5 is to be schemed according to the SEM of the cupric zeolite 4 of one embodiment of the invention.
Specific embodiment
Hereinafter, by by specific embodiment come the content that the present invention is further explained.However, cited is specific
Embodiment for illustration purposes only, and is not intended to limit the scope of the invention.It will be appreciated by those skilled in the art that following
The particular technique feature gone out given in any embodiment can be used for other embodiments, as long as it is without departing substantially from master of the invention
Purport.
Cupric CHA type zeolite
Zeolite of the invention refers to that International Zeolite Association (International Zeolite Association) is (following
Abbreviation IZA) as defined in zeolite.Zeolite is usually by skeletal atom tetrahedron (such as SiO4 tetrahedron, AlO4 tetrahedron or PO4
Tetrahedron) each vertex oxygen atom by share be coupled made of rule mesh-like structure, and usually by oxygen element it
Outer Elements Atom is known as non-oxygen atom or T atom.The basic unit of mesh-like structure first is that the connection of N number of TO4 tetrahedron and
At ring-type, call it as N member ring (N is generally 3 or more positive integer, such as 3 member rings, 6 member rings, 8 member rings etc.).Of the invention
In one embodiment, the cupric CHA type zeolite is the CHA type zeolite of IZA defined, and the structure of this zeolite can pass through
X-ray diffraction method (XRD) determines.
In the present invention, cupric CHA type zeolite refers at least containing aerobic, aluminium, silicon as the atom for constituting skeleton structure
Zeolite, and a part of in skeletal atom can be replaced the element other than one or more aforementioned 3 kinds of elements, wherein
Copper position present in zeolite and its specific chemical valence state are not particularly limited, that is, copper can reside in the bone of zeolite
At frame, it can also exist on except the skeleton of zeolite.From the perspective of catalytic activity, copper is preferably in except skeleton and is in
Ionic valence condition.
In one embodiment, the skeletal atom of cupric CHA type zeolite includes silicon and aluminium, wherein mole of silicon and aluminium
Than more than or equal to 5 and less than 7.5, to be greater than 5 and less than 7.5, and the molar ratio of copper and aluminium is more than or equal to 0.2 and small
In being equal to 0.5, it is greater than 0.2 and less than 0.5.Studied, be found to have the cupric CHA type zeolite of features described above low temperature with
And high-temperature region all has excellent denitration catalyst activity.
While not wishing to be bound by any theory, it is believed that cupric CHA type zeolite of the present invention in low temperature and
High-temperature region all has excellent catalytic activity, can be attributed to the suitable molar ratio of copper in zeolite, element silicon, aluminium element
Example, and specific zeolite configuration.
It is generally believed that the presence of aluminosilicate zeolite middle skeleton aluminium leads to bronsted acid site and ion in zeolite
The formation in site is exchanged, content determines the acid amount of zeolite and the number that ion outside skeleton can be imported by ion exchange form
Amount.Range of the molar ratio of silicon and aluminium 5 to 7.5, it is ensured that cupric CHA type zeolite can introduce enough copper ions, together
When retain certain solid acid.In this CHA type zeolite, the ratio of copper ion also determines the low-temperature catalyzed of such zeolite
Denitration performance, and retaining certain solid acid can make such zeolite remain to the energy for retaining absorption ammonia in high temperature section
Power, to also have good catalytic denitration performance in high temperature section.
However, the molar ratio of silicon and aluminium 5 hereinafter, copper and aluminium molar ratio 0.5 or more, will lead to catalyst bone
Frame aluminium is too many and copper content is excessively high, and then the high-temperature hydrothermal stability of cupric CHA type zeolite is caused to reduce, and is unfavorable for actually making
With.
In one embodiment, the crystal grain of the cupric CHA type zeolite is less than or equal to 1 μm.In another embodiment
In, the crystal grain of the cupric CHA type zeolite is less than or equal to 0.6 μm.In yet another embodiment, the cupric CHA type zeolite
Crystal grain be less than or equal to 0.5 μm.For CHA type zeolite of the invention, the size of crystal grain can influence zeolite denitration performance,
The diffusion path of reactant can be greatly reduced in lesser crystal grain, improve the catalytic efficiency of zeolite.Inventors have found that for this hair
For bright cupric CHA type zeolite, usual 50nm or more and 1 μm of crystal grain below can guarantee reaction gas in zeolite interior
Good diffusion performance, and then come into full contact with the active site in zeolite.Therefore, in one embodiment, described to contain
The crystal grain of copper CHA type zeolite is more than or equal to 50nm.In another embodiment, the crystal grain of the cupric CHA type zeolite is greater than
Equal to 100nm.
In one embodiment, the BET specific surface area of the cupric CHA type zeolite is 550m2/ g or more.At another
In embodiment, the BET specific surface area of the cupric CHA type zeolite is 600m2/ g or more.
In one embodiment, the cupric CHA type zeolite also include selected from titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, zinc,
One of gallium, germanium, arsenic, tin and boron or various other elements.In another embodiment, the molal quantity of these other elements
The 40% of the total mole number of the nonoxygen element in the zeolite is accounted for hereinafter, it is preferred that 30% or less, more preferable 20% or less.At one
In embodiment, the cupric CHA type zeolite also includes in alkali metal, alkaline-earth metal, rare earth metal and transition metal
One or more cations.
Cupric CHA type zeolite of the present invention can efficiently solve cupric zeolite temperature window existing in the prior art
The relatively narrow problem of mouth, it is not only high in 200 DEG C of low-temperature range catalytic activity below, also have in 500 DEG C or more of high temperature section
Excellent catalytic performance is urged so as to be efficiently used for the selectivity of the catalytic purification of nitrogen oxides, especially nitrogen oxides
Change reduction.
The preparation of cupric CHA type zeolite
Cupric CHA type zeolite of the invention can be prepared using hydrothermal synthesis method, wherein by the way that raw material and water to be configured to
First gel (being also referred to as aqueous gel sometimes below), is then placed in reaction vessel and carries out hydrothermal synthesis reaction, to synthesize mesh
Mark zeolite.
In one embodiment, the method for preparing cupric CHA type zeolite includes: that copper source is dissolved in phosphoric acid solution by (a)
In, to obtain cupric gel；(b) into the mixture being made of silicon source, silicon source, inorganic base, organic formwork agent and water, step is added
Suddenly the cupric gel that (a) is obtained, to obtain just gel；(c) make the just gel experience hydrothermal synthesis reaction, and through solid-liquid
Isolated reaction product；(d) organic formwork agent for the reaction product that removal step (c) obtains, obtains cupric alkali metal containing
Zeolite；(e) alkali metal ion in cupric alkali metal containing zeolite obtained with copper ion displacement step (d), through dry and roasting
Obtain the cupric CHA type zeolite.
In one embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 1~5.?
In another embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 1.5~4.At another
In embodiment, in step (a), the molar ratio of phosphorus and copper in the cupric gel is 2~3.
Copper source of the invention is not particularly limited, and can make copper source commonly used in the art.Mantoquita, such as copper can be used
Nitrate, sulfate, acetate, hydrochloride etc., Cu oxide, such as copper oxide etc. also can be used.In step (a),
Copper source can be made more fully to be dissolved in phosphoric acid solution by modes such as heating.
In one embodiment, in step (b), silicon source, silicon source, inorganic base, organic formwork agent, water, copper, phosphorus rub
You are than being 1SiO2: 0.067~0.1Al2O3: 0.05~0.6OH-: 0.02~0.4 template: 15~80 water: 0.01~0.1Cu:
0.01~0.5P, but not limited to this.The element of the zeolite obtained by hydro-thermal reaction form it is related to the composition in first gel, because
The composition of this adjustable aqueous gel obtains the zeolite with expectation composition.
Silicon source of the invention is not particularly limited, and can make silicon source commonly used in the art.In one embodiment, institute
Fumed silica, silicon dioxide gel, colloidal silicon dioxide, waterglass, silester and silicic acid can be selected from by stating silicon source
One of methyl esters is a variety of.In yet another embodiment, the silicon source can be molten selected from fumed silica, silica
It is one or more in glue and colloidal silicon dioxide.
Silicon source of the invention is not particularly limited, and can make silicon source commonly used in the art.In one embodiment, institute
State silicon source can selected from boehmite, aluminium isopropoxide, aluminium alkoxide (such as three aluminium ethylates), aluminium hydroxide, alumina sol with
And one of sodium aluminate or a variety of.In another embodiment, source of aluminium can be selected from boehmite, aluminium hydroxide
And one of sodium aluminate or a variety of.
In general, synthesis is zeolite structured related with template that is selecting.In one embodiment, template can be with
It is organic template agent, such as the organic formwork agent of CHA structure easy to form, it is possible thereby to which making the zeolite of preparation has CHA
Structure.In one embodiment, in step (b), the organic formwork agent is that zeolite structured nitrogenous of CHA easy to form has
Machine compound and/or the organic compounds containing nitrogen that complex compound can be generated with copper.In another embodiment, in step
(b) in, the organic formwork agent is quaternary ammonium salt.In another embodiment, in step (b), the organic formwork agent choosing
From N, N, one of N- trimethyl adamantane ammonium, benzyltrimethylammon.um, copper-tetraethylenepentamine complex compound or a variety of.The present invention
Organic formwork agent be also possible to other kinds of quaternary ammonium salt, such as tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl
Ammonium hydroxide, dimethyl diethyl ammonium hydroxide, methyl triethylammonium hydroxide, trimethylethyl ammonium hydroxide etc., preferably
Tetraethyl ammonium hydroxide and/or tetrapropylammonium hydroxide.
Inorganic base of the invention is not particularly limited, and can make inorganic base commonly used in the art.In an embodiment
In, in step (b), the inorganic base is monoacidic base metal inorganic alkali or combinations thereof.In another embodiment, in step
(b) in, the inorganic base is selected from one or more of lithium hydroxide, sodium hydroxide or potassium hydroxide.
In step (b), the order by merging of various raw materials and water and unlimited especially system, those skilled in the art can basis
The condition used is suitably selected, such as can first be mixed water and inorganic base, silicon source, silicon source and organic formwork agent, then
It mixes, can also first mix water with cupric gel etc. before being mixed with template with cupric gel.
In one embodiment, used silicon source, silicon source, inorganic base, copper source, phosphorus source, the molar ratio of template, water
It can be 1SiO2: 0.067~0.1Al2O3: 0.05~0.6AOH:0.01~0.1Cu:0.005~0.25P2O5: 0.02~
0.4R:15~80H2(monovalence alkali metal ion is indicated O with " A "；Template is indicated with " R "), preferably 1SiO2: 0.07~
0.09Al2O3: 0.05~0.4AOH:0.02~0.05Cu:0.02~0.15P2O5: 0.05~0.2R:40~60H2O；Work as zeolite
When being intended to comprising other backbone elements, the molar ratio of silicon source and other backbone elements can be 1:0.01~0.4, preferably 1:
0.03~0.3.In the present invention, the mole dosage for calculating the above-mentioned silicon source of molar ratio, silicon source, copper source and phosphorus source is respectively
Refer to that element silicon in raw material, aluminium element, copper and P elements conversion are the mole of oxide.
In one embodiment, in step (c), the reaction temperature of hydrothermal synthesis reaction is 100~200 DEG C, synthesis
Time is 12~96 hours.In another embodiment, in step (c), the reaction temperature of hydrothermal synthesis reaction is 120~
180 DEG C, generated time is 18~72 hours.In yet another embodiment, in step (c), the reaction of hydrothermal synthesis reaction
Temperature is 150~180 DEG C, and generated time is 24~48 hours.In step (c), the combination of reaction temperature and generated time can
With according to the knowledge conventional selection of those skilled in the art, as long as product can be made to be fully crystallized.
During above-mentioned hydrothermal synthesis reaction, too long soaking time is also unnecessary, also will increase time cost on the contrary,
And lower holding temperature equally may require that relatively long soaking time.The present inventor obtains through overtesting, above-mentioned
Reaction temperature and generated time in range can both guarantee the structure of the CHA type zeolite finally obtained, can also save production
Cost.In addition, heating rate in reaction vessel is 10~40 DEG C/h, such as 15,20 or 30 DEG C/h, it is preferred to heat up
Rate is 15~20 DEG C/h, and heating rate is too fast to be easy to cause non-uniform temperature in the reaction vessel of sealing, and then leads to original
Material reaction is uneven；Heating rate is too low, increases time cost.
In one embodiment, in step (c), product obtained is separated by solid-liquid separation, separation method not by
It is special to limit, such as can be separated by the methods of filtering, centrifugation, stratification.Resulting solid can also be through water
After washing, separate again.
In one embodiment, in step (d), by dry and roast the reaction product that the step (c) obtains
To remove organic formwork agent.In another embodiment, in step (d), when drying temperature is 40~120 DEG C and dries
Between be 12~48 hours, maturing temperature is 300~800 DEG C and calcining time is 0.5~24 hour.In another embodiment
In, in step (d), drying temperature is 80~100 DEG C and drying time is 18~36 hours, and maturing temperature is 400~700
DEG C and calcining time be 1~12 hour.
Zeolite comprising organic formwork agent usually can by under the inert gas atmosphere containing a small amount of air or oxygen or
Person roasts under inert gas atmosphere, to remove organic formwork agent.It is of course also possible to using ethanol water, contain HCl
The extractant of ether etc. extracted, to remove organic formwork agent.In the present invention, it is preferred to be removed in zeolite by roasting
Organic formwork agent.Roasting apparatus in the present invention is not particularly limited, can be common using Muffle furnace, tunnel oven or rotary kiln etc.
Industrial Stoves.Considered from quantity-produced convenience, it is preferable to use rotary kiln.In this regard, maturing temperature referred to above is equal
It is the temperature in kiln.
In one embodiment, in step (e), by ion-exchange directly by the cupric alkali metal containing zeolite
In alkali metal ion be replaced into copper ion.In another embodiment, in step (e), first by ion-exchange
Alkali metal ion in the cupric alkali metal containing zeolite is replaced into the ion other than copper, then will be described by ion-exchange
Ion exchange other than copper is copper ion.In yet another embodiment, in step (e), first will by ion-exchange
Alkali metal ion in the cupric alkali metal containing zeolite is replaced into ammonium ion, then is replaced into ammonium ion by ion-exchange
Copper ion.
In this regard, the cupric alkali metal containing zeolite can be dispersed in inorganic ammonium salt solution or acid solution, 0~
Ion exchange 0.5~96 hour at a temperature of 100 DEG C.Hereafter, product can be separated, separation method is not limited particularly
It is fixed, such as can be separated by the methods of filtering, centrifugation, stratification, resulting zeolite is cupric CHA of the invention
Type zeolite.
In a preferred embodiment, the product through ion exchange can be separated, and at 40~120 DEG C dry 12
~36 hours, 300~800 DEG C roast 1~5 hour, obtain cupric CHA type zeolite.In another preferred embodiment,
Product through ion exchange can be separated, and 18~24 hours dry, small in 400~600 DEG C of roastings 2~4 at 80~100 DEG C
When, obtain cupric CHA type zeolite.In still another preferred embodiment, the product through ion exchange can be separated, and
80~100 DEG C of dryings 18~24 hours roast 2~3 hours at 500 DEG C, obtain cupric CHA type zeolite.
It in a further embodiment, can be by the material for cupric the CHA type zeolite and copper ions that step (e) obtains
It contacts again, the method exchanged by solid or liquid ions obtains the cupric CHA type zeolite with more high copper content.At this
In the embodiment of sample, the method for the present invention includes steps (f): the cupric CHA type zeolite and copper-containing solution that step (e) is obtained
Ion exchange is mixed and carries out, subsequent separation of solid and liquid, drying are simultaneously sintered, and obtain cupric CHA type zeolite.Implement as one
In scheme, the copper-containing solution is copper salt solution, such as the solution of copper nitrate, copper sulphate, copper acetate, hydrochloric acid copper.At another
In such embodiment, in step (f), drying temperature is 40~120 DEG C and drying time is 12~48 hours, roasting
Temperature is 300~800 DEG C and calcining time is 0.5~5 hour.In yet another embodiment, dry in step (f)
Temperature is 80~100 DEG C and drying time is 18~36 hours, maturing temperature be 400~700 DEG C and calcining time be 1~
3 hours.
In this regard, the alkali metal ion in removal cupric CHA type zeolite is conducive to the method by ion exchange, further mention
High copper content is conducive to the high-temperature hydrothermal stability for improving the copper zeolite of type containing CHA.
The purposes of cupric CHA type zeolite
Cupric CHA type zeolite of the invention can also can mix directly with powdered use with adhesive, be made containing
It is used after the mixture of zeolite.The inorganic adhesives such as adhesive used typically silica, aluminium oxide, zirconium oxide or
The polysiloxane-based organic adhesion agent of person.The dosage of adhesive is not particularly limited, and in terms of the mixture being finally made, usually may be used
Think 1~20 weight %, from the aspect of fabrication strength, preferably 2~15 weight %.
Cupric CHA type zeolite of the invention or the mixture containing the zeolite it is also pelletized or forming after use.Be granulated or
The method of forming is not particularly limited, and can be carried out using various well known methods.In general, making cupric CHA type of the invention
Zeolite mixture forming, uses, the shape of formed body can be a variety of as formed body.
For example, when cupric CHA type zeolite of the invention is used as the purification of nitrogen oxides in the exhaust gas of means of transports such as automobile
When with catalyst, can be coating process or forming process using the method for the zeolite, using by molded zeolite as honeycombed catalyst.It applies
Deposited method usually mixes zeolite with inorganic adhesives such as silica, aluminium oxide or zirconium oxides, and production is slurried, then is coated on
By the surface of the honeycombs of the inorganic matters such as cordierite production, it is subsequently dried, fires.Forming process is usually by zeolite and dioxy
The inorfils such as the inorganic adhesives such as SiClx, aluminium oxide or alumina fibre, glass fibre are kneaded, and pass through extrusion molding or compression method
It is configured to honeycomb, and dries, fire in turn.
When cupric CHA type zeolite of the invention is as catalyst, zeolite by with the exhaust gas contact containing nitrogen oxides come
Purify nitrogen oxides.It can include nitric oxide, nitrogen dioxide, one with the nitrogen oxides of cupric CHA type Zeolite-purification of the invention
Nitrous oxide etc..In the present invention, purification nitrogen oxides is that nitrogen oxides is instigated to react on a catalyst, is converted to nitrogen and oxygen
Gas etc..
In this regard, nitrogen oxides can directly react, it can also be for the purpose for improving purification efficiency, cupric of the invention
CHA type zeolite is used in conjunction with reducing agent.Simultaneously use reducing agent when, can make oxynitrides purification reaction be easier into
Row, ammonia, urea, organic amine, carbon monoxide, hydrocarbon, hydrogen etc. can be used for reducing agent, it is preferable to use ammonia, urea.
When using cupric CHA type zeolite of the invention as catalyst, it can purify from diesel car, gasoline automobile, consolidate
Fixed pattern power generation ship, agricultural machinery, construction implement, motorcycle, the various gasoline and diesel engines of aircraft, boiler, combustion gas wheel
Nitrogen oxides contained by the various exhaust gas being discharged in machine etc..
Embodiment
Below, further description is carried out to the present invention by specific embodiment, but the present invention is not limited in
Following embodiment.In the examples below, chemical reagent used is that chemistry is pure if not otherwise specified.
X-ray diffraction (XRD) measurement
X-ray diffraction measure instrument is the x-ray powder diffraction instrument measurement device (Ulitma IV) of Rigaku manufacture.
Component analysis method
Pass through the content of each component in inductively coupled plasma spectroscopic assay zeolite.Inductively coupled plasma spectrum (ICP)
Measurement uses PerkinElmer Optima 8x00, wherein obtaining concentration gradient absorption curve after standard sample is diluted.Tool
Body, it will be diluted with water after sample hydrofluoric acid dissolution, the concentration of each element in sample then measured by absorbing peak intensity.
Specific area measuring
The instrument of test: the high-performance specific surface and micropore diameter analysis of scientific and technological (Beijing) the Co., Ltd manufacture of Bei Shide instrument
Instrument (3H-2000) is measured.
The evaluation method of catalyst activity
After the zeolite punch forming of preparation, break into pieces, whole grain.The zeolite (1ml) that whole grain is crossed is filled into atmospheric fixed bed
In flow type reaction tube.With 1500ml/min (space velocity SV=100000/ hours), make the gas containing composition shown in table 1
It circulates on catalyst layer, while catalyst layer is heated.Respectively at different temperature, according to NO concentration at the outlet, by
The value of following formula removes deactivation to evaluate the nitrogen oxides of catalyst.
(NO purifying rate)={ (entrance NO concentration)-(NO concentration at the outlet) }/(entrance NO concentration)
[table 1]
| Gas component | Concentration |
| NO | 500ppm |
| NH3 | 500ppm |
| O2 | 14vol% |
| H2O | 5vol% |
| N2 | Remaining ingredient |
The preparation of cupric gel 1
690g phosphoric acid (85 weight % of concentration) is added in 690g water, 240g copper oxide is then added, reacts 2 at 80 DEG C
Hour, obtain cupric gel 1.
The preparation of cupric gel 2
1035g phosphoric acid (85 weight % of concentration) is added in 690g water, 240g copper oxide is then added, is reacted at 80 DEG C
2 hours, obtain cupric gel 2.
Embodiment 1
13g sodium hydroxide is added into 450g water, 25% N of 135g, N, N- trimethyl adamantane is added in stirring and dissolving
Ammonium (TMADA) aqueous solution is added 10g aluminium hydroxide, then adds the silica of the 40 weight % of 120g after mixing
After being stirred to react 4 hours, 26g cupric gel 1 is added in colloidal sol (silica solution), continues stirring 2 hours, is sufficiently had after reaction
There is the first gel mixture of consisting of: 1SiO2: 0.07Al2O3: 0.2Na2O:0.06Cu:0.06P2O5: 0.2TMADA:
50H2O。
Gel mixture is put into autoclave, after 2 hours are warming up to 160 DEG C, isothermal reaction 48 hours, carries out water
Thermal synthesis reaction.After reaction, it is cooled to room temperature, after filtering, products therefrom are washed three times with deionized water, 100 DEG C of dryings
After 24 hours, the cupric zeolite containing organic formwork agent is obtained.Cupric zeolite containing organic formwork agent is put into Muffle furnace, 550
DEG C roasting 6 hours, obtain the cupric zeolite for eliminating template.
By 30g chloride leach in 200g water, the cupric zeolite for eliminating template is added, stirs 8 hours at room temperature,
Filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, the cupric for obtaining removal sodium ion boils
Stone.Then the cupric zeolite for removing sodium ion is added in 200g saturated acetic acid copper liquor, is stirred 8 hours at room temperature, mistake
Filter, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder roasts 2 hours through 500 DEG C
Afterwards, cupric zeolite 1 is obtained.
Test results are shown in figure 1 by the XRD of cupric zeolite 1, it was demonstrated that it is CHA type zeolite.Flying-spot microscope (SEM) test
As a result as shown in Fig. 2, rectangular crystal grain is respectively less than 0.6 μm.Elemental Composition analysis the result shows that, the molar ratio of silicon and aluminium is 7.3；
The molar ratio of copper and aluminium is 0.32.BET specific surface area measurement result is 610m2/g。
Embodiment 2
13g sodium hydroxide is added into 450g water, 25% N of 135g, N, N- trimethyl adamantane is added in stirring and dissolving
Ammonium (TMADA) aqueous solution is added 10g aluminium hydroxide, then adds the silica of the 40 weight % of 120g after mixing
After being stirred to react 4 hours, 26g cupric gel 2 is added in colloidal sol (silica solution), continues stirring 2 hours, is sufficiently had after reaction
There is the first gel mixture of consisting of: 1SiO2: 0.07Al2O3: 0.2Na2O:0.06Cu:0.09P2O5: 0.2TMADA:
50H2O。
Gel mixture is put into autoclave, after 2 hours are warming up to 160 DEG C, isothermal reaction 48 hours, carries out water
Thermal synthesis reaction.After reaction, it is cooled to room temperature, after filtering, products therefrom are washed three times with deionized water, 100 DEG C of dryings
After 24 hours, the cupric zeolite containing organic formwork agent is obtained.Cupric zeolite containing organic formwork agent is put into Muffle furnace, 550
DEG C roasting 6 hours, obtain the cupric zeolite for eliminating template.
By 30g chloride leach in 200g water, the cupric zeolite for eliminating template is added, stirs 8 hours at room temperature,
Filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, the cupric for obtaining removal sodium ion boils
Stone.Then the cupric zeolite for removing sodium ion is added in 200g saturated acetic acid copper liquor, is stirred 8 hours at room temperature, mistake
Filter, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder roasts 2 hours through 500 DEG C
Afterwards, cupric zeolite 2 is obtained.
Test results are shown in figure 1 by the XRD of cupric zeolite 2, it was demonstrated that it is CHA type zeolite.Its flying-spot microscope (SEM) is surveyed
Test result is as shown in figure 3, rectangular crystal grain is respectively less than 0.6 μm.Elemental Composition analysis the result shows that, the molar ratio of silicon and aluminium is
7.1；The molar ratio of copper and aluminium is 0.35.BET specific surface area measurement result is 595m2/g。
Embodiment 3
Sodium hydroxide 13g is added into 450g water, 25% N of 135g, N, N- trimethyl adamantane is added in stirring and dissolving
Ammonium (TMADA) aqueous solution is added 13g aluminium hydroxide, then adds the silica of the 40 weight % of 120g after mixing
After being stirred to react 4 hours, 30g cupric gel 1 is added in colloidal sol, is continued stirring 2 hours, sufficiently is obtained having with the following group after reaction
At first gel mixture: 1SiO2: 0.09Al2O3: 0.2Na2O:0.06Cu:0.06P2O5: 0.2TMADA:50H2O。
Gel mixture is put into autoclave, after 2 hours are warming up to 160 DEG C, isothermal reaction 48 hours, carries out water
Thermal synthesis reaction.After reaction, it is cooled to room temperature, after filtering, products therefrom are washed three times with deionized water, 100 DEG C of dryings
After 24 hours, the cupric zeolite containing organic formwork agent is obtained.Cupric zeolite containing organic formwork agent is put into Muffle furnace, 550
DEG C then obtain eliminating the cupric zeolite of template after roasting 6 hours.
By 30g chloride leach in 200g water, the cupric zeolite for eliminating template is added, stirs 8 hours at room temperature,
Filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, the cupric for obtaining removal sodium ion boils
Stone.Then the cupric zeolite for removing sodium ion is added in 200g saturated acetic acid copper liquor, is stirred 8 hours at room temperature, mistake
Filter, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder roasts 2 hours through 500 DEG C
Afterwards, cupric zeolite 3 is obtained.
Test results are shown in figure 1 by the XRD of cupric zeolite 3, it was demonstrated that it is CHA type zeolite.Its flying-spot microscope (SEM) is surveyed
Test result is as shown in figure 4, rectangular crystal grain is respectively less than 0.5 μm.Elemental Composition analysis the result shows that, the molar ratio of silicon and aluminium is
5.5；The molar ratio of copper and aluminium is 0.41.BET specific surface area measurement result is 582m2/g。
Embodiment 4
13g sodium hydroxide is added in 450g water, 25% N of 135g, N, N- trimethyl adamantane ammonium is added in stirring and dissolving
(TMADA) 13g aluminium hydroxide is added after mixing in aqueous solution, and the 40 weight % silica for then adding 120g are molten
After being stirred to react 4 hours, 26g cupric gel 2 is added in glue, is continued stirring 2 hours, is sufficiently obtained after reaction with consisting of
First gel mixture: 1SiO2: 0.09Al2O3: 0.2Na2O:0.06Cu:0.09P2O5: 0.2TMADA:50H2O。
Gel mixture is put into autoclave, after 2 hours are warming up to 160 DEG C, isothermal reaction 48 hours, carries out water
Thermal synthesis reaction.After reaction, it is cooled to room temperature, after filtering, products therefrom are washed three times with deionized water, 100 DEG C of dryings
After 24 hours, the cupric zeolite containing organic formwork agent is obtained.Cupric zeolite containing organic formwork agent is put into Muffle furnace, 550
DEG C roasting 6 hours, obtain the cupric zeolite for eliminating template.
By 30g chloride leach in 200g water, the cupric zeolite for eliminating template is added, stirs 8 hours at room temperature,
Filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, the cupric for obtaining removal sodium ion boils
Stone.Then the cupric zeolite for removing sodium ion is added in 200g saturated acetic acid copper liquor, is stirred 8 hours at room temperature, mistake
Filter, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder roasts 2 hours through 500 DEG C
Afterwards, cupric zeolite 4 is obtained.
Test results are shown in figure 1 by the XRD of cupric zeolite 4, it was demonstrated that it is CHA type zeolite.Flying-spot microscope (SEM) test
As a result as shown in figure 5, rectangular crystal grain is respectively less than 0.5 μm.Elemental Composition analysis the result shows that, the molar ratio of silicon and aluminium is 5.7；
The molar ratio of copper and aluminium is 0.43.BET specific surface area measurement result is 564m2/g。
Comparative example 1
6.6g sodium hydroxide is added into 450g water, 25% N of 135g, N, N- trimethyl Buddha's warrior attendant is added in stirring and dissolving
Alkane ammonium (TMADA) aqueous solution is added 5g aluminium hydroxide, then adds the titanium dioxide of the 40 weight % of 125g after mixing
Silica solution after being stirred to react 4 hours, obtains the first gel mixture with consisting of: 1SiO2:: 0.03Al2O3:
0.2Na2O:0.2TMADA:50H2O,
Gel mixture is put into autoclave, after 2 hours are warming up to 160 DEG C, isothermal reaction 48 hours, carries out water
Thermal synthesis reaction.Be cooled to room temperature, filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours
Afterwards, the Wessalith CS containing organic formwork agent is obtained.Zeolite containing organic formwork agent is put into Muffle furnace, after 550 DEG C roast 6 hours
Then obtain eliminating the Wessalith CS of template.
By 30g chloride leach in 200g water, the Wessalith CS for eliminating template is added, stirs 8 hours at room temperature, mistake
Filter, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, obtain the Wessalith CS for removing sodium ion.So
The Wessalith CS for removing sodium ion is added in 200g saturated acetic acid copper liquor afterwards, is stirred 8 hours at room temperature, filtering, gained produce
After object is washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder is contained after 500 DEG C roast 2 hours
Copper zeolite 5.
The XRD test result of cupric zeolite 5 is shown, is CHA type zeolite.Elemental Composition analysis the result shows that, silicon with
The molar ratio of aluminium is 14.3；The molar ratio of copper and aluminium is 0.45.BET specific surface area measurement result is 620m2/g。
Comparative example 2
The CHA type zeolite B containing potassium ion is synthesized according to the method for patent document CN102215960B embodiment 1.
By 30g chloride leach in 200g water, the CHA type zeolite B containing potassium ion is added, stirs 8 hours at room temperature,
Filtering, after products therefrom washed three times with deionized water, 100 DEG C drying 24 hours, obtain the zeolite B for removing potassium ion.
Then the zeolite B for removing potassium ion is added in 200g saturated acetic acid copper liquor, is stirred 8 hours at room temperature, filtering, gained
After product is washed three times with deionized water, 100 DEG C drying 24 hours.Gained powder obtains after 500 DEG C roast 2 hours
Cupric zeolite 6.
Elemental Composition analysis the result shows that, the molar ratio of silicon and aluminium is 2.8；The molar ratio of copper and aluminium is 0.12.BET ratio
Surface area test result is 485m2/g。
According to the evaluation method of catalyst activity described above, the catalytic activity of cupric zeolite 1-6, acquired results are tested
As shown in the following Table 2.
[table 2]
Therefore using cupric CHA type zeolite of the invention, not only urged in 200 DEG C of low-temperature ranges below with height
Change activity, also has excellent catalytic properties, be suitable for use as SCR denitration cleaning catalyst in 500 DEG C or more of high temperature section.
Although describing a specific embodiment of the invention above with reference to specific embodiment, but it is to be understood that ability
Field technique personnel can make a variety of adjustment and change to it, as long as it is without prejudice to the scope and spirit of the present invention.
Claims (10)
1. cupric CHA type zeolite, skeletal atom further includes silicon and aluminium, wherein the molar ratio of silicon and aluminium is more than or equal to 5 and small
In 7.5, and the molar ratio of copper and aluminium is more than or equal to 0.2 and to be less than or equal to 0.5.
2. cupric CHA type zeolite as described in claim 1, wherein the crystal grain of the zeolite is less than or equal to 1 μm, preferably smaller than
Equal to 0.8 μm, more preferably less than or equal to 0.6 μm, and the crystal grain of the zeolite is more than or equal to 50nm, preferably greater than or equal to
100nm。
3. cupric CHA type zeolite as described in claim 1, wherein the BET specific surface area of the zeolite is 550m2/ g or more,
It is preferred that 600m2/ g or more.
4. cupric CHA type zeolite as claimed any one in claims 1 to 3, wherein the zeolite also include selected from titanium, zirconium,
One of vanadium, chromium, manganese, iron, cobalt, zinc, gallium, germanium, arsenic, tin and boron or various other elements, and the other elements are rubbed
Your number accounts for the 40% of the total mole number of the nonoxygen element in the zeolite hereinafter, it is preferred that 30% or less, more preferable 20% or less；
And/or the zeolite also include selected from one of alkali metal, alkaline-earth metal, rare earth metal and transition metal or it is a variety of sun from
Son.
5. the method for preparing cupric CHA type zeolite described in any one of Claims 1-4, which comprises
(a) copper source is dissolved in phosphoric acid solution, to obtain cupric gel；
(b) into the mixture being made of silicon source, silicon source, inorganic base, organic formwork agent and water, the institute that step (a) is obtained is added
Cupric gel is stated, to obtain just gel；
(c) make the just gel experience hydrothermal synthesis reaction, and obtain reaction product through being separated by solid-liquid separation；
(d) organic formwork agent for the reaction product that removal step (c) obtains, obtains the zeolite of cupric alkali metal containing；
(e) alkali metal ion in cupric alkali metal containing zeolite obtained with copper ion displacement step (d), is obtained through dry and roasting
Obtain cupric CHA type zeolite.
6. method as claimed in claim 5, wherein
In step (a), the molar ratio of phosphorus and copper in the cupric gel is 1~5；
In step (b), silicon source, silicon source, inorganic base, organic formwork agent, water, copper, phosphorus molar ratio be 1:0.067~0.1:
0.05~0.6:0.02~0.4:15~80:0.01~0.1:0.01~0.5；
In step (c), the reaction temperature of hydrothermal synthesis reaction is 100~200 DEG C, and generated time is 12~96 hours；
In step (d), organic formwork agent is removed by drying and roasting the reaction product that the step (c) obtains；
In step (e), directly the alkali metal ion in the cupric alkali metal containing zeolite is replaced by ion-exchange
Copper ion, or the alkali metal ion in the cupric alkali metal containing zeolite is replaced into other than copper first by ion-exchange
Ion, then by ion-exchange by the ion exchange other than the copper be copper ion.
7. method as claimed in claim 6, wherein
In step (a), the molar ratio of phosphorus and copper in the cupric gel is 1.5~4；
In step (b), the silicon source is selected from fumed silica, silicon dioxide gel, colloidal silicon dioxide, waterglass, silicon
One of acetoacetic ester and methyl silicate are a variety of,
Source of aluminium is in boehmite, aluminium isopropoxide, aluminium alkoxide, aluminium hydroxide, alumina sol and sodium aluminate
It is one or more,
The organic formwork agent is the zeolite structured organic compounds containing nitrogen of CHA easy to form and/or can generate with copper
The organic compounds containing nitrogen of complex compound, preferably quaternary ammonium salt,
The inorganic base is monoacidic base metal inorganic alkali or combinations thereof,
In step (c), the reaction temperature of hydrothermal synthesis reaction is 120~180 DEG C, and generated time is 18~72 hours；
In step (d), drying temperature is 40~120 DEG C and drying time is 12~48 hours, maturing temperature be 300~
800 DEG C and calcining time are 0.5~24 hour；
In step (e), directly the alkali metal ion in the cupric alkali metal containing zeolite is replaced by ion-exchange
Copper ion, or by ion-exchange first by the alkali metal ion in the cupric alkali metal containing zeolite be replaced into ammonium from
Son, then ammonium ion is replaced by copper ion by ion-exchange.
8. method as claimed in claim 6, wherein
In step (a), the molar ratio of phosphorus and copper in the cupric gel is 2~3；
In step (b), the silicon source it is a kind of in fumed silica, silicon dioxide gel and colloidal silicon dioxide or
It is a variety of,
Source of aluminium is selected from one of boehmite, aluminium hydroxide and sodium aluminate or a variety of,
The organic formwork agent be selected from N, N, N- trimethyl adamantane ammonium, benzyltrimethylammon.um, copper-tetraethylenepentamine complex compound,
One of tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide are a variety of,
The inorganic base is selected from one or more of lithium hydroxide, sodium hydroxide or potassium hydroxide,
In step (c), the reaction temperature of hydrothermal synthesis reaction is 150~180 DEG C, and generated time is 24~48 hours；
In step (d), drying temperature is 80~100 DEG C and drying time is 18~36 hours, maturing temperature be 400~
700 DEG C and calcining time are 1~12 hour；
In step (e), the ion-exchange 0~100 DEG C at a temperature of carry out 0.5~96 hour, then will be through ion
The product of exchange separates, and dries 12~36 hours at 40~120 DEG C, roasts 1~5 hour at 300~800 DEG C, obtains cupric
CHA type zeolite.
9. purification of nitrogen oxides catalyst converter, wherein be provided in the catalyst converter containing any one of claims 1 to 4 institute
The cupric CHA type boiling that the cupric CHA type zeolite stated or the method according to any one of claim 5 to 8 are prepared
The denitrating catalyst of stone.
10. purification of nitrogen oxides system, wherein be provided with purification of nitrogen oxides as claimed in claim 9 in the system and use
Catalyst converter.
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| CN111871452A (en) * | 2020-08-10 | 2020-11-03 | 中触媒新材料股份有限公司 | CHA-type molecular sieve and catalyst for diesel vehicle exhaust purification, and preparation method and application thereof |
| CN111871455A (en) * | 2020-08-10 | 2020-11-03 | 中触媒新材料股份有限公司 | Preparation method and application of CHA-type aluminum-silicon molecular sieve and SCR (Selective catalytic reduction) catalyst |
| CN111871450A (en) * | 2020-08-10 | 2020-11-03 | 中触媒新材料股份有限公司 | CHA structure molecular sieve and preparation method and application of tail gas denitration catalyst thereof |
| CN111960433A (en) * | 2020-08-10 | 2020-11-20 | 中触媒新材料股份有限公司 | CHA type molecular sieve synthesized by using bicyclic group-containing quaternary ammonium onium template agent, and preparation and application of catalyst |
| CN111871453A (en) * | 2020-08-10 | 2020-11-03 | 中触媒新材料股份有限公司 | CHA structure molecular sieve, synthesis method, nitrogen oxide selective reduction catalyst and application |
| CN111871454A (en) * | 2020-08-10 | 2020-11-03 | 中触媒新材料股份有限公司 | CHA zeolite molecular sieve for purifying nitrogen oxides and preparation method and application of catalyst thereof |
| CN113149027A (en) * | 2021-05-08 | 2021-07-23 | 浙江大学 | Method for synthesizing Co-SSZ-13 zeolite molecular sieve by one step by using cobalt-amine complex as template agent |
| CN114713041A (en) * | 2022-04-14 | 2022-07-08 | 南京工业大学 | Method for in-situ preparation of Si-CHA molecular sieve membrane |
| CN114804146A (en) * | 2022-04-14 | 2022-07-29 | 南京工业大学 | Preparation method of all-silicon CHA molecular sieve membrane |
| CN114713041B (en) * | 2022-04-14 | 2023-09-29 | 南京工业大学 | Method for preparing Si-CHA molecular sieve membrane in situ |
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