CN110467200A - A kind of Cu-SSZ-39 molecular sieve and its preparation method and application - Google Patents
A kind of Cu-SSZ-39 molecular sieve and its preparation method and application Download PDFInfo
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The present invention relates to a kind of Cu-SSZ-39 molecular sieves and its preparation method and application；Using ZSM-5 molecular sieve as silicon source and silicon source in the preparation process of the Cu-SSZ-39 molecular sieve, it is mixed with nitrogenous organic formwork agent, water, copper source, tetraethylenepentamine and alkali source, it is reacted, crystallization, roasting, the Cu-SSZ-39 molecular sieve is obtained, the Cu-SSZ-39 molecular sieve is prepared through a step hydro-thermal reaction using above-mentioned raw materials in the method for the invention, with good NH3- SCR catalytic activity and nitrogen selective, while having hydrothermal stability well and the ability of resistance to high-speed, and the raw material ZSM-5 molecular sieve of its preparation process is from a wealth of sources, cost is relatively low, to have certain economic benefit and environmental benefit.
Description
Technical field
The present invention relates to catalysis material fields more particularly to a kind of Cu-SSZ-39 molecular sieve and its preparation method and application.
Background technique
Nitrogen oxides is a kind of important pollutant in atmosphere, in the shape of the atmosphere pollution phenomenon such as gray haze, photochemical fog
Play the part of important role in.The source of nitrogen oxides is divided into natural source and artificial source, wherein artificial discharge is mainly divided into
Stationary source and moving source, the latter is because discharge amount is big and dispersion, difficulty of governance are larger.In stationary source and moving source denitration technology
In, ammonia SCR technology is occupied an leading position.
In NH3In SCR technology, WO3Or MoO3The V of load2O5-TiO2Catalyst was once used as stationary source, moving source denitration master
Catalyst to be used.It is increasingly harsh with discharge standard, in the exhaust gas from diesel vehicle after-treatment system for meeting six standard of state,
Particulate matter trap (Diesel Particulate Filter, DPF) is preposition in selective catalytic reduction (Selective
Catalytic Reduction, SCR) after-treatment system.The regeneration of DPF can generate the environment of high temperature, high humidity, and SCR is catalyzed
More stringent requirements are proposed for the high-temperature hydrothermal stability of agent.Traditional catalytic component based on vanadium is exposed in hot and humid environment living for a long time
Property can decline to a great extent, therefore develop while to have both high activity, the catalyst of high-temperature hydrothermal stability feature particularly necessary.
In recent years, small pore molecular sieve catalyst is since its excellent activity, selectivity and hydrothermal stability are gradually by section
Grind the favor with industrial circle.Wherein, the Cu-SSZ-13 molecular sieve with CHA configuration is in small pore molecular sieve catalyst
Typical Representative.
CN104709917A and CN103157505A discloses Cu-SSZ-13 molecular sieve catalyst in preparation, modification and answers
With the technology in field.Although Cu-SSZ-13 has excellent hydrothermal stability compared to traditional catalytic component based on vanadium, grind
Study carefully display, for Cu-SSZ-13 molecular sieve after 850 DEG C of hydrothermal agings, inactivation is serious.Cu-SSZ-13 molecule is considered simultaneously
The problems such as synthesis cost is higher is sieved, it is still necessary to exploitation novel molecular sieve catalyst.
CN108097301A discloses the preparation method and purposes of the Cu-SSZ-39 molecular sieve with AEI configuration.But it is selected
With Na-SSZ-39 is obtained first, by pernitric acid ammonium and two step exchange system of copper nitrate for the method for Cu-SSZ-39, process is complicated,
Time, economic cost are higher.Meanwhile during preparing Na-SSZ-39, it is to turn brilliant raw material which, which selects high silicon Y molecular sieve,
And the last handling process by the complexity such as dealumination complement silicon is needed in the synthesis process of high silicon Y molecular sieve, economic benefit and environment
Benefit is to be improved.
Therefore, a kind of method for preparing Cu-SSZ-39 molecular sieve of simplicity is developed, and is used for stationary source, moving source
Denitration field has important practical significance.
Summary of the invention
The purpose of the present invention is to provide a kind of Cu-SSZ-39 molecular sieves and its preparation method and application；The Cu-SSZ-
Using ZSM-5 molecular sieve as silicon source and silicon source in the preparation process of 39 molecular sieves, by itself and nitrogenous organic formwork agent, water, copper
Source, tetraethylenepentamine (Tetraethylenepentamine, TEPA) and alkali source mixing, are reacted, crystallization, roast, obtain
The Cu- is prepared through a step hydro-thermal reaction using above-mentioned raw materials in the Cu-SSZ-39 molecular sieve, the method for the invention
SSZ-39 molecular sieve, with good NH3- SCR catalytic activity and nitrogen selective, at the same have hydrothermal stability well and
The ability of resistance to high-speed, and the raw material ZSM-5 molecular sieve of its preparation process is from a wealth of sources, cost is relatively low, to have certain
Economic benefit and environmental benefit.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of Cu-SSZ-39 molecular sieve, the method includes by ZSM-
5 molecular sieves, nitrogenous organic formwork agent, water, copper source, TEPA and alkali source mixing, obtain silica-alumina gel, crystallization roasts later, obtains
The Cu-SSZ-39 molecular sieve；
The mass ratio of the ZSM-5 molecular sieve and nitrogenous organic formwork agent is 1:0.2-0.4, such as 1:0.21,1:0.23,
1:0.25,1:0.28,1:0.3,1:0.35 or 1:0.38 etc..
Preferably, the mass ratio of the ZSM-5 molecular sieve and alkali source is 1:0.05-0.3, such as 1:0.06,1:0.09,1:
0.12,1:0.15,1:0.18,1:0.2,1:0.23,1:0.25 or 1:0.27 etc..
Using ZSM-5 molecular sieve, as brilliant material is turned, Cu-SSZ- is prepared through one step hydro thermal method in the method for the invention
39 molecular sieves, so as to avoid using Y molecular sieve as silicon source and silicon source during, post processing cost is high, generation pollutant
The problems such as matter, while the process that Cu is supported on to SSZ-39 is eliminated, further simplify preparation method.
The method of the invention, as brilliant material is turned, is the silicoaluminophosphate molecular with MFI configuration using ZSM-5 molecular sieve
Sieve has extensive silica alumina ratio, can be used as silicon source, silicon source with AEI configuration molecular sieve.Because of the AEI molecular sieve silicon of stable state
Aluminium is relatively more fixed, therefore the molecular sieve with suitable silica alumina ratio is most important as brilliant material is turned.Simultaneously ZSM-5 molecular sieve with contain
After nitrogen organic formwork machine combines, stability energy is higher than the combination of AEI molecular sieve and itrogenous organic substance template machine, therefore from energy
From the perspective of, ZSM-5 can be used as turn brilliant material of AEI synthesis.
The Cu-SSZ-39 molecular sieve is for AEI configuration.
The method of the invention makes the Cu- being prepared by adjusting raw material proportioning, crystallization condition and roasting condition
Catalyst of the SSZ-39 molecular sieve as ammonia selective catalyst reduction of nitrogen oxides, with wide temperature window, especially
The ability of its anti-high-speed, 400,000h-1Under air speed, still it is able to maintain within the scope of 250 DEG C -550 DEG C to nitrogen oxides 70%
Above removal rate is highly suitable for the environment of the high-speeds such as exhaust gas from diesel vehicle post-processing, and it is selected with excellent nitrogen
Property, (150 DEG C -550 DEG C) keep 90% or more nitrogen selective in entire Range of measuring temp.
The method of the invention makes the Cu- being prepared by adjusting raw material proportioning, crystallization condition and roasting condition
SSZ-39 molecular sieve is for excellent hydrothermal stability, compared to fresh Cu-SSZ-39 molecular sieve, by the Cu-SSZ-39
After molecular sieve carries out hydrothermal aging processing 16h under the conditions of 750 DEG C, nitrogen oxides within the temperature range of 250 DEG C -550 DEG C
Decline≤5% of removal rate, at the same nitrogen selective within the scope of entire temperature test (150 DEG C -550 DEG C) decline≤5%,
To illustrate that Cu-SSZ-39 molecular sieve of the present invention has excellent hydrothermal stability.
Preferably, the method that ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and alkali source are mixed
Including mixing in water ZSM-5 molecular sieve and nitrogenous organic formwork agent, copper source and TEPA are added, it is mixed that alkali source is added later
It closes.
Preferably, the nitrogenous organic formwork agent includes N, N- dimethyl-N, N- bicyclic nonane, 2,2,6,6- tetramethyls-
N, N- lupetidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N- methyl-N ethyl piperidines, 2- ethyl-N, N- bis-
Methyl piperidine, 3,5- dimethyl-N, N- lupetidine, 2,6- dimethyl-N, N- lupetidine, 2,5- dimethyl-N, N-
Diethyl pyrroles, N- methyl-N ethyl -2- ethyl piperidine, N- methyl-N ethyl-lupetidine, N- ethyl-N- third
Base-lupetidine, N, N- diethyl -2- ethyl piperidine, 2,6- dimethyl -5- nitrogen spiral shell-[4.5]-decane or N, N-
In diethyl -2,6- lupetidine any one or at least two combination, the combination examples include N, N- bis-
The combination of methyl-N, N- bicyclic nonane and 2,2,6,6- tetramethyl-N, N- lupetidine, N- cyclooctane base-pyridine and 2,2,
Combination, 2- ethyl-N, N- lupetidine and 3,5- dimethyl-N, the N- diformazan of 6,6- tetramethyl-N- methyl-N ethyl piperidines
The combination of phenylpiperidines, the combination of 2,6- dimethyl-N, N- lupetidine and 2,5- dimethyl-N, N- diethyl pyrroles, N- first
Base-N- ethyl -2- ethyl piperidine and the combination of N- methyl-N ethyl-lupetidine, N- ethyl-N- propyl -2,6- two
Methyl piperidine and N, the combination of N- diethyl -2- ethyl piperidine or 2,6- dimethyl -5- nitrogen spiral shell-[4.5]-decane and N, N- bis-
Ethyl-lupetidine combination etc.；Preferably N, N- diethyl-lupetidine and/or 3,5- dimethyl-N,
N- lupetidine.
The present invention uses template of the above-mentioned nitrogenous organic formwork agent as crystallization, on the one hand common trait is
It contains nitrogen-containing heterocycle, and relative molecular weight is moderate, and structure directing and duct filling can be played in sieve synthesis procedure
Effect；On the other hand, which is dissolved in electrically charged after water, and charge filling effect is played in sieve synthesis procedure.
Preferably, the nitrogenous organic formwork agent is prepared by the following method, which comprises before template
Body, iodoethane, saleratus and solvent mixing are driven, is reacted, is separated, ion exchange obtains the nitrogenous organic formwork agent.
The preparation process of nitrogenous organic formwork agent of the present invention using template presoma, iodoethane, saleratus and
Solvent hybrid reaction obtains the iodide of the nitrogenous organic formwork agent later, by the iodide of the nitrogenous organic formwork agent
After separating, the nitrogenous organic formwork agent is obtained through ion exchange.
Template presoma of the present invention and nitrogenous organic formwork agent contain pyridine structure, and presoma passes through substitution reaction
Nitrogenous organic formwork agent needed for available.
Preferably, the solvent is methanol.
Preferably, the reaction is to carry out back flow reaction under agitation.
Preferably, the temperature of the back flow reaction is 45-60 DEG C, such as 48 DEG C, 50 DEG C, 53 DEG C, 55 DEG C or 58 DEG C etc..
Preferably, the time of the back flow reaction be 3-7 days, such as 3.5 days, 4 days, 4.5 days, 5 days, 5.5 days, 6 days or
6.5 days etc..
Preferably, the isolated method includes that rotary evaporation removes solvent and iodoethane, and chloroform is added, is separated by solid-liquid separation,
Mixed solution is obtained, removes chloroform later, is recrystallized.
In separating step of the present invention, rotary evaporation removes solvent and unreacted iodoethane, and chloroform is added later, molten
Organic matter therein is solved, solid is separated off, removes chloroform therein later, is then recrystallized to give nitrogenous organic formwork
The salt compounded of iodine of agent.
Preferably, the method for removing chloroform includes rotary evaporation.
Preferably, the solvent used that recrystallizes is ethyl alcohol and/or ether.
Recrystallization process of the present invention selects the mixed liquor of ethyl alcohol and ether, and recrystallization effect is best, wherein ethyl alcohol
Effect be dissolution raw material, the effect of ether is recrystallization.
Preferably, the method for the ion exchange includes being dispersed in water recrystallized product, later with hydrogen-oxygen type sun from
Subtree rouge carries out ion exchange, obtains the nitrogenous organic formwork agent.
Preferably, the nitrogenous organic formwork agent is N, N- diethyl -2,6- lupetidine, before the template used
Drive body is cis- lupetidine.
Preferably, nitrogenous organic formwork agent is 3,5- dimethyl-N, N- lupetidine, the template presoma used
For 3,5- lupetidine.
Preferably, the mass ratio of the template presoma and solvent is 1:(2-5), such as 1:2.5,1:3,1:3.5,1:
4 or 1:4.5 etc..
Preferably, the mass ratio of the template presoma and iodoethane be 1:(3-7), such as 1:3.5,1:4,1:4.5,
1:5,1:5.5,1:6 or 1:6.5 etc..
Preferably, the mass ratio of the template presoma and saleratus is 1:(1-3), such as 1:1.5,1:2 or 1:
2.5 waiting.
The template presoma, iodoethane, saleratus and solvent mass ratio be 1:(3-7): (1-3): (2-5),
Such as 1:3.5:2.5:2.5,1:5:2:3 or 1:6.5:1.5:4.5 etc., preferably 1:(5-5.15): (1.8-2): (3.4-
3.75)。
Preferably, the silica alumina ratio of the ZSM-5 molecular sieve be 5-30, such as 6,7,8,9,10,11,12,13,14,15,
16,17,18,19,20,21,22,23,24,25,26,27,28,29 or 30 etc., preferably 10-15.
It is the ZSM-5 molecular sieve of 5-30 as brilliant material is turned that the method for the invention, which uses silica alumina ratio, and it is suitable to can provide
The silicon source and silicon source of content, as silica alumina ratio < 5, aluminium content is excessively high, and silicone content is insufficient, can not synthesize stable AEI configuration point
Son sieve, as silica alumina ratio > 30, silicone content is excessively high, and skeleton stability is excessively high, and ZSM-5 molecular sieve structure is difficult to decompose.
Preferably, copper source includes any one in copper sulphate, copper acetate, copper nitrate or copper chloride or at least two
Combination, the combination examples include the combination of copper sulphate and copper acetate, the combination of copper nitrate and copper chloride or copper acetate
With the combination of copper nitrate etc., preferably copper sulphate.
Preferably, the alkali source include sodium hydroxide, potassium hydroxide, in ammonium hydroxide or carbonic acid sodium any one or at least two
The combination of kind, the combination examples include the combination of sodium hydroxide and potassium hydroxide, the combination of ammonium hydroxide and sodium carbonate or hydrogen
Sodium oxide molybdena and the combination of ammonium hydroxide etc., preferably sodium hydroxide.
Preferably, the mass ratio of the ZSM-5 molecular sieve and nitrogenous organic formwork agent is 1:0.25-0.35, such as 1:
0.27,1:0.29,1:0.31 or 1:0.33 etc..
Preferably, the mass ratio of the ZSM-5 molecular sieve and water is 1:2-6, for example, 1:3,1:3.5,1:4,1:4.5,1:
5 or 1:5.5 etc., preferably 1:3-5.
Preferably, the ZSM-5 molecular sieve and the mass ratio of copper source are 1:0.01-0.2, such as 1:0.02,1:
0.05,1:0.06,1:0.08,1:0.1,1:0.12,1:0.15 or 1:0.18 etc., preferably 1:0.02-0.15.
Preferably, the ZSM-5 molecular sieve and TEPA mass ratio are 1:0.02-0.15, such as 1:0.03,1:0.05,1:
0.07,1:0.09,1:0.12 or 1:0.14 etc..
Preferably, the mass ratio of the ZSM-5 molecular sieve and alkali source be 1:0.14-0.2, such as 1:0.15,1:0.17 or
1:0.19 waiting.Preferably, the mass ratio of the ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and alkali source is 1:
(0.2-0.4): (2-6): (0.01-0.2): (0.02-0.15): (0.05-0.3), preferably 1:(0.25-0.35): (3-5):
(0.02-0.15): (0.05-0.12) (0.14-0.2).
Preferably, the crystallization is dynamic crystallization.
Preferably, the method for the crystallization includes that silica-alumina gel is carried out hydro-thermal process.
Preferably, the time of the hydro-thermal process is 2-8 days, such as 3 days, 4 days, 5 days, 6 days or 7 days etc..
Preferably, the temperature of the hydro-thermal process is 120-170 DEG C, such as 130 DEG C, 140 DEG C, 150 DEG C or 160 DEG C etc..
The temperature of hydro-thermal reaction is controlled during crystallization of the present invention at 120-170 DEG C, advantageously forms crystallization
Well, the Cu-SSZ-39 molecular sieve with AEI configuration with high purity, when crystallization temperature is lower than 120 DEG C, energy is not enough to convert
ZSM-5 molecular sieve be AEI molecular sieve, when crystallization temperature be higher than 170 DEG C, will form the miscellaneous phase containing other molecular sieves.
Preferably, after the crystallization, before roasting, further include being separated by solid-liquid separation crystallization product, dry later.
Preferably, the method for the separation of solid and liquid includes filtering or centrifugation.
Preferably, the temperature of the drying is 90-150 DEG C, such as 95 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140
DEG C or 145 DEG C etc..
Preferably, the time of the drying be 12-24h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h,
21h, 22h or 23h etc..
Preferably, the temperature of the roasting be 600-750 DEG C, such as 620 DEG C, 640 DEG C, 660 DEG C, 680 DEG C, 700 DEG C,
720 DEG C or 740 DEG C etc..
The method of the invention controls maturing temperature within the above range, is conducive to the template removal in product,
So that the Cu-SSZ-39 molecular sieve is as ammonia Selective Catalytic Reduction of NOxDuring show higher catalysis
Activity.
Preferably, the time of the roasting is 5-12h, such as 6h, 7h, 8h, 9h, 10h or 11h etc..
As currently preferred technical solution, the described method comprises the following steps:
(1) ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and sodium hydroxide are mixed, stirring obtains
Silica-alumina gel；The nitrogenous organic formwork agent includes N, N- dimethyl-N, N- bicyclic nonane, 2,2,6,6- tetramethyl-N, N- bis-
Methyl piperidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N- methyl-N ethyl piperidines, 2- ethyl-N, N- dimethyl piperazine
Pyridine, 3,5- dimethyl-N, N- lupetidine, 2,6- dimethyl-N, N- lupetidine, 2,5- dimethyl-N, N- diethyl
Pyrroles, N- methyl-N ethyl -2- ethyl piperidine, N- methyl-N ethyl-lupetidine, N- ethyl-N- propyl -2,6-
Lupetidine, N, N- diethyl -2- ethyl piperidine, 2,6- dimethyl -5- nitrogen spiral shell-[4.5]-decane or N, N- diethyl -
In lupetidine any one or at least two combination；
The nitrogenous organic formwork agent is prepared by the following method, and the described method comprises the following steps:
(a) template presoma, iodoethane, saleratus and methanol are mixed, back flow reaction 3- is carried out at 45-60 DEG C
7 days；
(b) by the product evaporation of solvent and iodoethane of the back flow reaction of step (a), chloroform, solid-liquid point are added later
From solid is removed, mixed solution is obtained；
(c) mixed solution for obtaining step (b) carries out rotary evaporation and removes chloroform, is tied again with ethyl alcohol and ether
It is brilliant；
(d) product recrystallized step (c) is soluble in water to carry out ion exchange with hydrogen-oxygen type resin cation, obtains institute
State nitrogenous organic formwork agent；
(2) by the product of step (1) 120-170 DEG C at a temperature of carry out hydro-thermal process 2-8 days；
(3) product of step (2) is separated by solid-liquid separation, dry 12-24h at 90-150 DEG C；
(4) product of step (3) is roasted into 5-12h at 600-750 DEG C, obtains the Cu-SSZ-39 molecular sieve.
Second aspect, the present invention provides a kind of Cu-SSZ-39 molecular sieve that method is prepared as described in relation to the first aspect,
In the Cu-SSZ-39 molecular sieve mass percentage of Cu element be 0.5-10wt.%, such as 1wt.%, 3wt.%,
5wt.%, 7wt.% or 9wt.% etc., preferably 1-3wt.%.
Preferably, the silica alumina ratio of the Cu-SSZ-39 molecular sieve is 5-25, such as 6,8,10,15,20 or 23 etc., preferably
For 6-12.
The third aspect, the purposes for the Cu-SSZ-39 molecular sieve that the present invention provides a kind of as described in second aspect are described
Removing of the Cu-SSZ-39 molecular sieve for stationary source flue gas and/or moving source nitrogen oxide in tail gas.
Compared with the existing technology, the invention has the following advantages:
(1) preparation method of Cu-SSZ-39 molecular sieve of the present invention is using ZSM-5 as silicon source and silicon source, a step water
Cu-SSZ-39 molecular sieve is prepared in thermal method, so as to avoid using Y molecular sieve as silicon source and silicon source during, post-process
It is with high costs, generate the problems such as polluter, meanwhile, eliminate Cu load and (such as nitric acid Copper Ion Exchange be supported on SSZ-
39, process need to be using copper nitrate, ammonium nitrate etc.) process, further simplify preparation process；
(2) the method for the invention makes the Cu- being prepared by adjusting raw material proportioning, crystallization condition and roasting condition
Catalyst of the SSZ-39 molecular sieve as ammonia selective catalyst reduction of nitrogen oxides, with wide temperature window, and especially
Suitable for the removal of nitrogen oxide under high-speed, 400,000h-1Under air speed, within the temperature range of 250 DEG C -550 DEG C,
With the removal rate to 70% or more nitrogen oxides, it is highly suitable for the environment of the high-speeds such as exhaust gas from diesel vehicle post-processing, meanwhile,
Its selectivity for being also equipped with high nitrogen, (150 DEG C -550 DEG C) keep 90% or more nitrogen in entire Range of measuring temp
Gas selectivity；
(3) the method for the invention makes the Cu- being prepared by adjusting raw material proportioning, crystallization condition and roasting condition
SSZ-39 molecular sieve has excellent hydrothermal stability, compared to fresh Cu-SSZ-39 molecular sieve, by the Cu-SSZ-39
Molecular sieve under the conditions of 750 DEG C hydrothermal aging processing 16h after, the nitrogen oxide removal efficiency in 250 DEG C of -550 DEG C of temperature ranges
Decline≤5%；Simultaneously nitrogen selective within the scope of entire temperature test (150 DEG C -550 DEG C) decline≤5%, to say
Bright Cu-SSZ-39 molecular sieve of the present invention has excellent hydrothermal stability, is suitable in exhaust gas from diesel vehicle after-treatment system；
(4) for the method for the invention using ZSM-5 as brilliant material is turned, cost is relatively low, has certain economic benefit.
Detailed description of the invention
Fig. 1 is the XRD diagram of the fresh Cu-SSZ-39 arrived prepared by the embodiment of the present invention 1；
Fig. 2 is nitrogen oxidation of the fresh Cu-SSZ-39 molecular sieve that is prepared of the embodiment of the present invention 1 under different air speeds
Object removal rate curve；
Fig. 3 is nitrogen choosing of the fresh Cu-SSZ-39 molecular sieve that is prepared of the embodiment of the present invention 1 under different air speeds
Selecting property；
Fig. 4 be the fresh Cu-SSZ-39 molecular sieve that is prepared of the embodiment of the present invention 1 after hydrothermal aging is handled not
With the nitrogen oxide removal efficiency curve under air speed；
Fig. 5 be the fresh Cu-SSZ-39 molecular sieve that is prepared of the embodiment of the present invention 1 after hydrothermal aging is handled not
With the nitrogen selective under air speed.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The nitrogenous organic formwork agent that the present embodiment uses is N, N- diethyl -2,6- lupetidine, preparation method packet
Include following steps:
(a) by 35g cis- 2,6- lupetidine, 180g iodoethane, 70g saleratus and the mixing of 120g methanol, at 50 DEG C
Under be stirred back flow reaction 4 days；
(b) the product rotary evaporation of the back flow reaction of step (a) is removed into liquid, chloroform dissolution is added later, suction filtration removes
Solid is removed, mixed solution is obtained；
(c) mixed solution for obtaining step (b) carries out rotary evaporation and removes chloroform, and ethyl alcohol is added later and ether carries out
Recrystallization, obtains N, N- diethyl-cis- 2,6- lupetidine salt compounded of iodine powder；
(d) product recrystallized step (c) is soluble in water to carry out ion exchange with hydrogen-oxygen type resin cation, obtains institute
Nitrogenous organic formwork agent is stated, the nitrogenous organic formwork agent is N, N- diethyl -2,6- lupetidine.
The preparation method of Cu-SSZ-39 molecular sieve in the present embodiment:
(1) the above-mentioned nitrogenous organic formwork agent of 0.9g is added in 12g deionized water, 3g ZSM-5 molecular sieve is added later
(silica alumina ratio 12) stirs 1h, 0.18g copper sulphate, 0.15g TEPA is added later, stirs 1h, and 0.6g sodium hydroxide is added, stirs
It mixes overnight, obtains silica-alumina gel；
(2) product of step (1) is placed in reaction kettle, 150 DEG C at a temperature of carry out hydro-thermal process 3 days；
(3) product of step (2) is separated by solid-liquid separation, dry 10h at 100 DEG C；
(4) product of step (3) is roasted into 6h at 700 DEG C, obtains the Cu-SSZ-39 molecular sieve.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
The X-ray diffraction curve for the Cu-SSZ-39 molecular sieve that the present embodiment is prepared is as shown in Figure 1, its diffraction peak
Setting is AEI configuration zeolites characteristic peak, it can thus be seen that the present embodiment products therefrom is the Cu- with AEI configuration
SSZ-39 molecular sieve.
In order to verify catalyst described in the present embodiment in the ability of anti-high-speed, the air speed that test process is set separately is
100,000h-1、200,000h-1And 400,000h-1, it is denoted as condition A, condition B and condition C respectively；Its removal to nitrogen oxides
Test results are shown in figure 2 for rate, and test process is to the selectivity of nitrogen as shown in figure 3, can be seen that in conjunction with Fig. 2 and Fig. 3
The removal rate of nitrogen oxides is all larger than 80% in 250 DEG C of -550 DEG C of temperature ranges, while the selectivity of nitrogen is at 150 DEG C -550
95% is all larger than within the scope of DEG C, it can be seen that, the Cu-SSZ-39 molecular sieve catalyst that the method for the invention is prepared has
Good active, selective and anti-high-speed ability.
The Cu-SSZ-39 molecular sieve that the present embodiment is prepared carries out hydrothermal aging processing, tests different air speeds later
Under, the removal rate to nitrogen oxides and the selectivity to nitrogen, test result is as shown in Figure 4 and Figure 5, can in conjunction with Fig. 4 and Fig. 5
To find out, the Cu-SSZ-39 molecular sieve is kept in 250 DEG C of -550 DEG C of temperature ranges to nitrogen after hydrothermal aging is handled
The removal rate of 80% or more oxide keeps 90% or more nitrogen selective in 150 DEG C of -550 DEG C of temperature ranges, thus may be used
See, the Cu-SSZ-39 molecular sieve catalyst which provides has good hydrothermal stability.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, the raw material in step (a) replaces with cis- 2, the 6- dimethyl piperazine of 40g
Pyridine, 200g iodoethane, 80g saleratus and 150g methanol, other conditions are identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, at 250 DEG C -500
75% or more is held in the removal rate of nitrogen oxides in DEG C temperature range, nitrogen selective is in 150 DEG C of -550 DEG C of temperature models
95% or more is held in enclosing.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of the present embodiment synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 3
The present embodiment the difference from embodiment 1 is that, by the replacement of the quality such as cis- 2,6- lupetidine in step (a)
For cis- 3,5- lupetidine, the silica alumina ratio of the ZSM-5 molecular sieve used is 12, other conditions complete phase compared with Example 1
Together.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 250 DEG C-
80% or more is held in the removal rate of nitrogen oxides in 550 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
95% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 4
The present embodiment the difference from embodiment 1 is that, 3g ZSM-5 molecular sieve is replaced with into 3.5g ZSM-5 in step (1)
Molecular sieve, other conditions are identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 250 DEG C-
70% or more is held in the removal rate of nitrogen oxides in 550 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
90% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 5
The present embodiment the difference from embodiment 1 is that, sulfuric acid copper content in step (1) is replaced with into 0.21g, TEPA content
0.18g is replaced with, other conditions are identical compared with Example 1.
The mass percentage of Cu element is 2.5% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 200 DEG C-
80% or more is held in the removal rate of nitrogen oxides in 450 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
90% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 6
The present embodiment the difference from embodiment 1 is that, the additional amount of sodium hydroxide in step (1) is replaced with into 0.5g,
His condition is identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 200 DEG C-
80% or more is held in the removal rate of nitrogen oxides in 500 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
90% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 7
The present embodiment the difference from embodiment 1 is that, the condition of hydro-thermal process in step (2) is replaced with 140 DEG C and is lauched
Heat treatment 5 days, other conditions are identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 200 DEG C-
80% or more is held in the removal rate of nitrogen oxides in 550 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
95% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 8
The present embodiment the difference from embodiment 1 is that, temperature dry in step (3) is replaced with 120 DEG C, other conditions
It is identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 200 DEG C-
90% or more is held in the removal rate of nitrogen oxides in 550 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
95% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Embodiment 9
The present embodiment the difference from embodiment 1 is that, the temperature roasted in step (4) is replaced with 600 DEG C, other conditions
It is identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by the present embodiment.
Cu-SSZ-39 molecular sieve is prepared in the present embodiment, under test condition of the present invention, 200 DEG C-
90% or more is held in the removal rate of nitrogen oxides in 550 DEG C of temperature ranges, nitrogen selective is in 150 DEG C of -550 DEG C of temperature
95% or more is held in range.It can be seen that the Cu-SSZ-39 molecular sieve catalyst of this example synthesis is with excellent
NH3SCR activity and nitrogen selective.
Comparative example 1
Raw material in embodiment 1 in step (a) is replaced with the cis- lupetidine of 40g, 20g iodine second by this comparative example
Alkane, 15g saleratus and 500g methanol, other conditions are identical compared with Example 1.
This comparative example can not synthesize to obtain Cu-SSZ-39 molecular sieve, it can be seen that this comparative example condition is unable to reach this hair
Bright requirement.
Comparative example 2
This comparative example the difference from embodiment 1 is that, the quality of the ZSM-5 molecular sieve in step (1) is replaced with by 3g
10g, other conditions are identical compared with Example 1.
This comparative example can not synthesize to obtain Cu-SSZ-39 molecular sieve, it can be seen that this comparative example condition is unable to reach this hair
Bright requirement.
Comparative example 3
This comparative example the difference from embodiment 1 is that, the quality of NaOH in step (1) is replaced with into 5g, other conditions with
Embodiment 1 is compared to identical.
This comparative example can not synthesize to obtain Cu-SSZ-39 molecular sieve, it can be seen that this comparative example condition is unable to reach this hair
Bright requirement.
Comparative example 4
This comparative example the difference from embodiment 1 is that, the condition of hydro-thermal process in step (2) is replaced with into 140 DEG C of hydro-thermals
12h is handled, other conditions are identical compared with Example 1.
This comparative example can not synthesize to obtain Cu-SSZ-39 molecular sieve, it can be seen that this comparative example condition is unable to reach this hair
Bright requirement.
Comparative example 5
This comparative example the difference from embodiment 1 is that, the condition roasted in step (4) is replaced with and roasts 4h at 400 DEG C,
Other conditions are identical compared with Example 1.
The mass percentage of Cu element is 2.1% in Cu-SSZ-39 molecular sieve obtained by this comparative example.
Molecular sieve obtained by this comparative example removes nitrogen oxides in 250 DEG C of -550 DEG C of temperature ranges as catalyst
Except rate is held in 50% or less.It can be seen that the Cu-SSZ-39 molecular sieve catalyst catalytic performance decline of this comparative example synthesis
Obviously, reason may is that maturing temperature is too low, cause the template in catalyst that can not remove by roasting, to influence
The activity of catalyst.
Performance test methods:
The Cu-SSZ-39 molecular screen primary powder that embodiment 1-9 and comparative example 5 are prepared carries out tabletting, grinding, sieving,
20-40 mesh particulate samples are taken to test for nitrogen oxide removal efficiency and nitrogen selective；
Nitrogen oxide removal efficiency test, test condition are as follows: [NO]=[NH3]=500ppm, [O2]=[H2O]=
5%, N2As Balance Air, range of reaction temperature is 150 DEG C -550 DEG C, and each thermotonus stops 1h to reacting balance.Reaction
Object NH3, NO and byproduct of reaction NO2、N2O concentration is measured by infrared Thermo IS10；It is outer unless otherwise specified, to each reality
The air speed for applying the test process of catalyst in example and comparative example is 400,000h-1；
The condition of hydrothermal aging processing: containing 10% H2O, air is as carrier gas, and air velocity: 200mL/min, hydro-thermal are old
The temperature for changing processing is 750 DEG C, and the time of hydrothermal aging processing is 16h.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of Cu-SSZ-39 molecular sieve, which is characterized in that the method includes by ZSM-5 molecular sieve, nitrogenous
Organic formwork agent, water, copper source, tetraethylenepentamine and alkali source mixing, obtain silica-alumina gel, and crystallization roasts later, obtain described
Cu-SSZ-39 molecular sieve；
The mass ratio of the ZSM-5 molecular sieve and nitrogenous organic formwork agent is 1:0.2-0.4；
The mass ratio of the ZSM-5 molecular sieve and alkali source is 1:0.05-0.3.
2. the method as described in claim 1, which is characterized in that described by ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper
The method in source, tetraethylenepentamine and alkali source mixing include ZSM-5 molecular sieve and nitrogenous organic formwork agent are mixed in water, then plus
Enter copper source and tetraethylenepentamine, alkali source mixing is added later；
Preferably, the nitrogenous organic formwork agent includes N, N- dimethyl-N, N- bicyclic nonane, 2,2,6,6- tetramethyl-N, N-
Lupetidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N- methyl-N ethyl piperidines, 2- ethyl-N, N- dimethyl
Piperidines, 3,5- dimethyl-N, N- lupetidine, 2,6- dimethyl-N, N- lupetidine, 2,5- dimethyl-N, N- diethyl
Base pyrroles, N- methyl-N ethyl -2- ethyl piperidine, N- methyl-N ethyl-lupetidine, propyl -2 N- ethyl-N-,
6- lupetidine, N, N- diethyl -2- ethyl piperidine, 2,6- dimethyl -5- nitrogen spiral shell-[4.5]-decane or N, N- diethyl
In base -2,6- lupetidine any one or at least two combination, preferably N, N- diethyl -2,6- lupetidine
And/or 3,5- dimethyl-N, N- lupetidine；
Preferably, the nitrogenous organic formwork agent is prepared by the following method, which comprises by template forerunner
Body, iodoethane, saleratus and solvent mixing, are reacted, are separated, ion exchange obtains the nitrogenous organic formwork agent；
Preferably, the solvent is methanol；
Preferably, the reaction is to carry out back flow reaction under agitation；
Preferably, the temperature of the back flow reaction is 45-60 DEG C；
Preferably, the time of the back flow reaction is 3-7 days；
Preferably, the isolated method includes that rotary evaporation removes solvent and iodoethane, and chloroform is added, is separated by solid-liquid separation, obtains
Mixed solution removes chloroform later, recrystallization；
Preferably, the method for removing chloroform includes rotary evaporation；
Preferably, the solvent used that recrystallizes is ethyl alcohol and/or ether；
Preferably, the method for the ion exchange includes being dispersed in water recrystallized product, later with hydrogen-oxygen type cation tree
Rouge carries out ion exchange, obtains the nitrogenous organic formwork agent.
3. method according to claim 2, which is characterized in that the nitrogenous organic formwork agent is N, N- diethyl -2,6- bis-
Methyl piperidine, the template presoma used is cis- 2,6- lupetidine；
Preferably, nitrogenous organic formwork agent is 3,5- dimethyl-N, N- lupetidine, the template presoma used for 3,
5- lupetidine；
Preferably, the mass ratio of the template presoma and solvent is 1:(2-5)；
Preferably, the mass ratio of the template presoma and iodoethane is 1:(3-7)；
Preferably, the mass ratio of the template presoma and saleratus is 1:(1-3)；
Preferably, the mass ratio of the template presoma, iodoethane, saleratus and solvent is 1:(3-7): (1-3): (2-
5), preferably 1:(5-5.15): (1.8-2): (3.4-3.75).
4. the method according to claim 1, which is characterized in that the silica alumina ratio of the ZSM-5 molecular sieve is 5-30,
Preferably 10-15；
Preferably, copper source include in copper sulphate, copper nitrate, copper acetate or copper chloride any one or at least two group
It closes, preferably copper sulphate；
Preferably, the alkali source include sodium hydroxide, potassium hydroxide, in ammonium hydroxide or carbonic acid sodium any one or at least two
Combination, preferably sodium hydroxide；
Preferably, the mass ratio of the ZSM-5 molecular sieve and nitrogenous organic formwork agent is 1:0.25-0.35；Preferably, described
The mass ratio of ZSM-5 molecular sieve and water is 1:2-6；
Preferably, the ZSM-5 molecular sieve and the mass ratio of copper source are 1:0.01-0.2；
Preferably, the ZSM-5 molecular sieve and the mass ratio of tetraethylenepentamine are 1:0.02-0.15；
Preferably, the mass ratio of the ZSM-5 molecular sieve and alkali source is 1:0.14-0.2；
Preferably, the mass ratio of the ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper source, tetraethylenepentamine and alkali source is
1:(0.2-0.4): (2-6): (0.01-0.2): (0.02-0.15): (0.05-0.3), preferably 1:(0.25-0.35): (3-
5): (0.02-0.15): (0.05-0.12) (0.14-0.2).
5. method according to any of claims 1-4, which is characterized in that the crystallization is dynamic crystallization；
Preferably, the method for the crystallization includes that silica-alumina gel is carried out hydro-thermal process；
Preferably, the time of the hydro-thermal process is 2-8 days；
Preferably, the temperature of the hydro-thermal process is 120-170 DEG C.
6. the method according to claim 1 to 5, which is characterized in that after the crystallization, before roasting, further include by
Crystallization product is separated by solid-liquid separation, and is dried later；
Preferably, the method for the separation of solid and liquid includes filtering or centrifugation；
Preferably, the temperature of the drying is 90-150 DEG C；
Preferably, the time of the drying is 12-24h.
7. as the method according to claim 1 to 6, which is characterized in that the temperature of the roasting is 600-750 DEG C；
Preferably, the time of the roasting is 5-12h.
8. the method according to claim 1 to 7, which is characterized in that the described method comprises the following steps:
(1) ZSM-5 molecular sieve, nitrogenous organic formwork agent, water, copper source, tetraethylenepentamine and sodium hydroxide are mixed, stirring obtains
To silica-alumina gel；The nitrogenous organic formwork agent includes N, N- dimethyl-N, N- bicyclic nonane, 2,2,6,6- tetramethyl-N, N-
Lupetidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N- methyl-N ethyl piperidines, 2- ethyl-N, N- dimethyl
Piperidines, 3,5- dimethyl-N, N- lupetidine, 2,6- dimethyl-N, N- lupetidine, 2,5- dimethyl-N, N- diethyl
Base pyrroles, N- methyl-N ethyl -2- ethyl piperidine, N- methyl-N ethyl-lupetidine, propyl -2 N- ethyl-N-,
6- lupetidine, N, N- diethyl -2- ethyl piperidine, 2,6- dimethyl -5- nitrogen spiral shell-[4.5]-decane or N, N- diethyl
In base-lupetidine any one or at least two combination；
The nitrogenous organic formwork agent is prepared by the following method, and the described method comprises the following steps:
(a) template presoma, iodoethane, saleratus and methanol are mixed, is carried out back flow reaction 3-7 days at 45-60 DEG C；
(b) by the product evaporation of solvent and iodoethane of the back flow reaction of step (a), chloroform is added later, separation of solid and liquid is removed
Solid is removed, mixed solution is obtained；
(c) mixed solution for obtaining step (b) carries out rotary evaporation and removes chloroform, is recrystallized with ethyl alcohol and ether；
(d) product recrystallized step (c) is soluble in water to carry out ion exchange with hydrogen-oxygen type resin cation, obtains described contain
Nitrogen organic formwork agent；
(2) by the product of step (1) 120-170 DEG C at a temperature of carry out hydro-thermal process 2-8 days；
(3) product of step (2) is separated by solid-liquid separation, dry 12-24h at 90-150 DEG C；
(4) product of step (3) is roasted into 5-12h at 600-750 DEG C, obtains the Cu-SSZ-39 molecular sieve.
9. a kind of Cu-SSZ-39 molecular sieve being prepared such as any one of claim 1-8 the method, which is characterized in that institute
The mass percentage for stating Cu element in Cu-SSZ-39 molecular sieve is 0.5-10wt.%, preferably 1-3wt.%；
Preferably, the silica alumina ratio of the Cu-SSZ-39 molecular sieve is 5-25, preferably 6-12.
10. a kind of purposes of Cu-SSZ-39 molecular sieve as claimed in claim 9, which is characterized in that the Cu-SSZ-39 points
Removing of the son sieve for stationary source flue gas and/or moving source nitrogen oxide in tail gas.
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