阅读说明：本技术 一种Cu-SSZ-39分子筛及其制备方法和用途 (A kind of Cu-SSZ-39 molecular sieve and its preparation method and application ) 是由 贺泓 杜金鹏 单玉龙 余运波 石晓燕 于 2019-09-20 设计创作，主要内容包括：本发明涉及一种Cu-SSZ-39分子筛及其制备方法和用途；所述Cu-SSZ-39分子筛的制备过程中采用beta分子筛作为硅源和铝源,将其与含氮有机模板剂、水、铜源、四乙烯五胺和碱源混合,晶化,焙烧,得到所述Cu-SSZ-39分子筛,本发明所述方法采用上述原料经一步水热反应制备得到所述Cu-SSZ-39分子筛,其具有良好的NH<Sub>3</Sub>-SCR催化活性和氮气选择性,同时具有水热稳定性良好和耐高空速的能力,且其制备过程的原料beta分子筛来源广泛,成本较低,从而具备一定的经济效益和环境效益。(The present invention relates to a kind of Cu-SSZ-39 molecular sieves and its preparation method and application；Using beta 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, crystallization, roasting, obtain the Cu-SSZ-39 molecular sieve, 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 NH 3 - SCR catalytic activity and nitrogen selective, while having hydrothermal stability well and the ability of resistance to high-speed, and the raw material beta molecular sieve of its preparation process is from a wealth of sources, cost is relatively low, to have certain economic benefit and environmental benefit.)

1. a kind of preparation method of Cu-SSZ-39 molecular sieve, which is characterized in that the method includes by beta 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 beta molecular sieve and alkali source is 1:0.05-1:0.3.

2. the method as described in claim 1, which is characterized in that described by beta molecular sieve, nitrogenous organic formwork agent, water, copper The method in source, tetraethylenepentamine and alkali source mixing include beta 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- diethyl -2,6- lupetidine, 2,6- dimethyl -5- nitrogen Spiral shell-[4.5]-decane, N, N- diethyl -2- ethyl piperidine, N- ethyl-N- propyl-lupetidine, N- methyl-N- second Base-lupetidine, N- methyl-N ethyl -2- ethyl piperidine, 2,5- dimethyl-N, N- diethyl pyrroles, 2,6- diformazan Base-N, N- lupetidine, 3,5- dimethyl-N, N- lupetidine, 2- ethyl-N, N- lupetidine, 2,2,6,6- tetra- Methyl-N-methyl-N-ethylpiperidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N, N- lupetidine or N, N- bis- In methyl-N, N- bicyclic nonane 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 isolated method includes that reaction product is removed solvent and iodoethane through rotary evaporation, and chloroform is added, Gu Liquid separation, obtains mixed solution, removes chloroform later, recrystallizes；

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:(5-6): (1.5-2): (3-3.75)；

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.

4. the method according to claim 1, which is characterized in that the silica alumina ratio of the beta 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 beta molecular sieve and nitrogenous organic formwork agent is 1:0.2-1:0.4, preferably 1:0.25- 1:0.35；

Preferably, the mass ratio of the beta molecular sieve and water is 1:2-1:6, preferably 1:3-1:5；

Preferably, the beta molecular sieve and the mass ratio of copper source are 1:0.01-1:0.2, preferably 1:0.02-1: 0.15；

Preferably, the beta molecular sieve and tetraethylenepentamine mass ratio are as follows: 1:0.02-1:0.15, preferably 1:0.05-1: 0.12；

Preferably, the mass ratio of the beta molecular sieve and alkali source is 1:0.14-1:0.2；

Preferably, the mass ratio of the beta 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 36-96h；

Preferably, the temperature of the hydro-thermal process is 110-150 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 80-120 DEG C；Preferably 90-100 DEG C；

Preferably, the time of the drying is 10-36h, preferably 12-20h.

7. as the method according to claim 1 to 6, which is characterized in that the temperature of the roasting is 550-700 DEG C, preferably It is 600-650 DEG C；

Preferably, the time of the roasting is 4-10h, preferably 6-8h.

8. the method according to claim 1 to 7, which is characterized in that the described method comprises the following steps:

(1) beta molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and sodium hydroxide are mixed, it is solidifying to obtain sial for stirring Glue；The nitrogenous organic formwork agent includes N, N- diethyl-lupetidine, 2,6- dimethyl -5- nitrogen spiral shell-[4.5] - Decane, N, N- diethyl -2- ethyl piperidine, N- ethyl-N- propyl-lupetidine, N- methyl-N ethyl -2,6- two Methyl piperidine, N- methyl-N ethyl -2- ethyl piperidine, 2,5- dimethyl-N, N- diethyl pyrroles, 2,6- dimethyl-N, N- bis- Methyl piperidine, 3,5- dimethyl-N, N- lupetidine, 2- ethyl-N, N- lupetidine, 2,2,6,6- tetramethyl-N- first Base-N-ethylpiperidine, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N, N- lupetidine or N, N- dimethyl-N, N- In bicyclic nonane 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) 110-150 DEG C at a temperature of carry out hydro-thermal process 36-96h；

(3) product of step (2) is separated by solid-liquid separation, dry 10-36h at 80-120 DEG C；

(4) product of step (3) is roasted into 4-10h at 550-700 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 1-10wt.%, preferably 2-5wt.%；

Preferably, the Cu-SSZ-39 molecular sieve has AEI configuration；

Preferably, the specific surface area of the Cu-SSZ-39 molecular sieve is 350-800m²/g；

Preferably, the silica alumina ratio of the Cu-SSZ-39 molecular sieve is 3-30, preferably 5-12.

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.

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, and photochemical fog, acid rain and gray haze etc. can be caused a series of Environmental problem is mainly derived from the burning and exhausting of mobile source tail-gas and stationary source fossil fuel.NH₃Selective catalytic reduction nitrogen Oxide technique (NH₃- Selective Catalytic Reduction, NH₃- SCR) be widely used in mobile source tail-gas and The purification of stationary source nitrogen oxides in effluent.It is with NOx conversion efficiency height, N₂Height is selectively produced, environment is not produced The advantages that raw secondary pollution.

V₂O₅-WO₃(MoO₃)-TiO₂Catalyst and the molecular sieve type of metal ion (such as: copper, iron) load are (such as: ZSM-5 points Son sieve, beta molecular sieve) catalyst can be used as NH₃SCR catalyst, but there are temperature operating windows narrow, high temperature N₂Selectivity The disadvantages of difference, thermal stability is poor.Especially in the exhaust gas from diesel vehicle after-treatment system for meeting six standard of state, China, SCR system is needed It wants preposition grain catcher (Diesel Particulate Filter, DPF), downstream SCR can be catalyzed during dpf regeneration Agent is placed in hot and humid environment, therefore SCR catalyst should also have excellent hydrothermal stability.

In recent years, the Cu base small pore molecular sieve (Cu-SSZ-13) for being configured as representing with CHA is since it is in NH₃- SCR reaction In have excellent NH₃SCR activity and hydrothermal stability receive the extensive concern of academia and industry.Such as CN107115888A and CN109364989A etc. disclose the preparation about CHA configuration molecular sieve catalyst, modification and NH₃The application in the field-SCR.But still have using CHA as the molecular sieve of configuration at present expensive, hydrothermal stability is to be improved The problem of.Cu-SSZ-13 molecular sieve catalyst with CHA configuration is after 850 DEG C of hydrothermal aging processing, NH₃- SCR is living Property is substantially reduced.

CN108097301A discloses the preparation method and purposes of a kind of Cu-SSZ-39 molecular sieve, and carrier uses high silicon Y Molecular sieve as turning a brilliant material, however at present conventional method can not synthesizing high-silicon (silica alumina ratio is greater than 6) Y molecular sieve, preparation is logical Often need the last handling process of the complexity such as dealumination complement silicon under hydrothermal condition.The loss of many and diverse synthesis process, a large amount of crystallinity The problem of environmental pollution generated with the process makes Y molecular sieve as brilliant material is turned and is restricted, therefore develops other molecular sieves It is of great significance by the transgranular preparation method for being converted into SSZ-39 molecular sieve.Meanwhile the SSZ-39 of conventional synthesis method preparation Carrier needs just obtain after ammonium ion and Cu ion exchange to can be used for NH₃The Cu-SSZ-39 catalyst of-SCR reaction, should Process is complicated for operation, waste of energy.

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 beta 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, crystallization, roasting obtain the Cu- SSZ-39 molecular sieve, the method for the invention are prepared the Cu-SSZ-39 points through a step hydro-thermal reaction using above-mentioned raw materials Son sieve, with good NH₃- SCR catalytic activity and nitrogen selective, while having hydrothermal stability well and resistance to high-speed Ability, and the raw material beta molecular sieve of its preparation process is from a wealth of sources, and cost is relatively low, thus 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 beta Molecular sieve, 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 beta molecular sieve and alkali source be 1:0.05-1:0.3, such as 1:0.07,1:0.09,1:0.13, 1:0.15,1:0.19,1:0.21,1:0.25 or 1:0.29 etc..

Using beta 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 Cu-SSZ-39 molecular sieve is for AEI configuration.

Cu-SSZ-39 molecular sieve of the present invention be using SSZ-39 molecular sieve as the transition metal based catalysts of carrier, Have AEI configuration, is the 3 D pore canal molecular sieve with four-membered ring, hexatomic ring and octatomic ring for basic component units, rises along a The channel diameter that three axis, b axis, c-axis directions are spread is respectively 0.38nm, 0.38nm, 0.36nm, and specific cellular structure is determined It has been determined in NH₃There is good application prospect in the field-SCR.

The method of the invention is the Si-Al molecular sieve with BEA configuration using beta molecular sieve as carrier, is had wide General silica alumina ratio can be used as silicon source, silicon source with AEI configuration molecular sieve.Because the AEI molecular sieve sial of stable state is more solid It is fixed, therefore the molecular sieve with suitable silica alumina ratio is most important as brilliant material is turned.Beta molecular sieve and nitrogenous organic mould simultaneously After trigger combines, stability energy is higher than the combination of AEI molecular sieve and itrogenous organic substance template machine, therefore comes from the angle of energy Say that it can be used as turn brilliant material of AEI synthesis.

The present invention is by limiting specific raw material proportioning, crystallization condition and maturing temperature, so that the method is prepared Catalyst of the Cu-SSZ-39 molecular sieve as ammonia selective catalyst reduction of nitrogen oxides, with wide temperature window, especially It is 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 -500 DEG C to nitrogen oxides 70% or more removal rate is highly suitable for the environment of the high-speeds such as exhaust gas from diesel vehicle post-processing, and it is with excellent nitrogen Selectivity, keeps 90% or more nitrogen selective within the temperature range of 200 DEG C -550 DEG C.

The present invention is by limiting specific raw material proportioning, crystallization condition and maturing temperature, so that the method is prepared Cu-SSZ-39 molecular sieve for excellent hydrothermal stability, compared to fresh Cu-SSZ-39 molecular sieve, by the Cu- After SSZ-39 molecular sieve carries out hydrothermal aging processing 16h under the conditions of 750 DEG C, nitrogen within the temperature range of 250 DEG C -500 DEG C Decline≤5% of oxide removal efficiency, while decline≤2% of nitrogen selective within the temperature range of 200 DEG C -550 DEG C, from And illustrating Cu-SSZ-39 molecular sieve of the present invention has excellent hydrothermal stability.

Preferably, the method packet that beta molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and alkali source are mixed It includes and mixes beta molecular sieve and nitrogenous organic formwork agent in water, add copper source and TEPA, alkali source mixing is added later.

Preferably, the nitrogenous organic formwork agent includes N, N- diethyl -2,6- lupetidine, 2,6- dimethyl -5- Nitrogen spiral shell-[4.5]-decane, N, N- diethyl -2- ethyl piperidine, N- ethyl-N- propyl-lupetidine, N- methyl - N- ethyl-lupetidine, N- methyl-N ethyl -2- ethyl piperidine, 2,5- dimethyl-N, N- diethyl pyrroles, 2,6- Dimethyl-N, N- lupetidine, 3,5- dimethyl-N, N- lupetidine, 2- ethyl-N, N- lupetidine, 2,2,6, 6- tetramethyl-N- methyl-N ethyl piperidines, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N, N- lupetidine or N, In N- dimethyl-N, N- bicyclic nonane any one or at least two combination, the combination examples include N, N- bis- Ethyl -2,6- lupetidine and 2, the combination of 6- dimethyl -5- nitrogen spiral shell-[4.5]-decane, N, N- diethyl -2- ethyl piperazine Pyridine and the combination of N- ethyl-N- propyl-lupetidine, N- methyl-N ethyl-lupetidine and N- methyl- Combination, 2,5- dimethyl-N, N- diethyl pyrroles and 2,6- dimethyl-N, the N- lupetidine of N- ethyl -2- ethyl piperidine Combination, the combination of 3,5- dimethyl-N, N- lupetidine and 2- ethyl-N, N- lupetidine, 2,2,6,6- tetramethyl- N- methyl-N ethyl piperidines and the combination of N- cyclooctane base-pyridine or 2,2,6,6- tetramethyl-N, N- lupetidine and N, N- The combination etc. of dimethyl-N, N- bicyclic nonane；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, it is characterised in that this type organic Contain cyclic structure and molecular size is moderate, structure directing is played in Cu-SSZ-39 sieve synthesis procedure and filling is made With；In addition, this type organic is electrically charged in aqueous solution, charge filling is played in Cu-SSZ-39 sieve synthesis procedure Effect.

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 is that nitrogenous organic formwork agent synthesizes necessary precursor substance, both contains piperidines Structure, but substituent group is different, and template presoma passes through the available required nitrogenous organic formwork agent of substitution reaction.Preferably, The solvent is methanol.

Preferably, the reaction is to carry out back flow reaction under agitation.

Preferably, the isolated method includes that reaction product rotary evaporation is removed solvent and iodoethane, and chloroform is added, It is separated by solid-liquid separation, obtains mixed solution, remove chloroform later, recrystallize.

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 ether.

Recrystallization process of the present invention is selected in the mixed liquor of ethyl alcohol and ether, and recrystallization effect is best, wherein second The effect of alcohol is dissolution raw material, and 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.

Preferably, the mass ratio of the template presoma, iodoethane, saleratus and solvent is 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:(5-6): (1.5-2): (3- 3.75)。

Preferably, the temperature of the back flow reaction is 45-60 DEG C, such as 48 DEG C, 50 DEG C, 52 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 silica alumina ratio of the beta molecular sieve is 5-30, such as 6,8,10,12,15 or 18 etc., preferably 10- 15。

The silica alumina ratio of the beta molecular sieve used in the method for the invention can provide the silicon source of appropriate level for 5-30 And silicon source, as silica alumina ratio < 5, aluminium content is excessively high, and silicone content is insufficient, can not synthesize stable AEI configuration molecular sieve, work as sial When than > 30, silicone content is excessively high, and skeleton stability is excessively high, and beta molecular sieve structure is difficult to decompose.

The cupric ammine complex that copper source of the present invention, TEPA can be formed in aqueous solution, can be with nitrogenous organic formwork Agent is the template of the crystallization of raw material collectively as beta molecular sieve, so that it is promoted to be converted into Cu-SSZ-39 molecular sieve, Cu element exists in the form of ionic state Cu in its gained Cu-SSZ-39 molecular sieve, and high degree of dispersion, so that catalysis reaction Has excellent catalytic activity.

Preferably, copper source includes copper sulphate, copper nitrate, copper acetate, copper chloride, preferably copper sulphate.

Preferably, the alkali source includes sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, preferably sodium hydroxide.

Preferably, the mass ratio of the beta molecular sieve and nitrogenous organic formwork agent is 1:0.2-1:0.4, such as: 1: 0.22,1:0.25,1:0.3,1:0.35 or 1:0.38, preferably 1:0.25-1:0.35.

Preferably, the mass ratio of the beta molecular sieve and water is 1:2-1:6, such as: 1:2,1:3,1:4,1:5 or 1:6, Preferably 1:3-1:5.

Preferably, the beta molecular sieve and the mass ratio of copper source are 1:0.01-1:0.2, such as: 1:0.01,1: 0.05,1:0.1,1:0.15 or 1:0.2, preferably 1:0.02-1:0.15.

Preferably, the beta molecular sieve and TEPA mass ratio are as follows: 1:0.02-1:0.15, such as: 1:0.02,1:0.05, 1:0.1 or 1:0.15, preferably 1:0.05-1:0.12.

Preferably, the mass ratio of the beta molecular sieve and alkali source be 1:0.14-1:0.2, such as 1:0.15,1:0.17 or 1:0.19 waiting.

Preferably, the mass ratio of the beta 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 36-96h, such as 40h, 50h, 60h, 70h, 80h or 90h etc..

Preferably, the temperature of the hydro-thermal process is 110-150 DEG C, such as 120 DEG C, 130 DEG C, 140 DEG C or 145 DEG C etc..

The temperature of hydro-thermal reaction is controlled during crystallization of the present invention at 110-150 DEG C, is conducive to AEI structure The formation of type molecular sieve, when temperature < 110 DEG C, the conversion of the not enough beta molecular sieves of energy；It is unfavorable when 150 DEG C of crystallization temperature > In the growth of AEI configuration molecular sieve, it is more to generate miscellaneous phase.

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 80-120 DEG C, such as 90 DEG C, 100 DEG C, 110 DEG C or 115 DEG C etc., preferably 90-100℃。

Preferably, the time of the drying be 10-36h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 25h or 30h etc., preferably 12-20h.

Preferably, the temperature of the roasting is 550-700 DEG C, such as 570 DEG C, 600 DEG C, 640 DEG C, 660 DEG C or 680 DEG C Deng preferably 600-650 DEG C.

Preferably, the time of the roasting is 4-10h, such as 6h, 7h, 8h or 9h etc., preferably 6-8h.

As currently preferred technical solution, the described method comprises the following steps:

(1) beta molecular sieve, nitrogenous organic formwork agent, water, copper source, TEPA and sodium hydroxide are mixed, stirring obtains silicon Alumina gel；The nitrogenous organic formwork agent includes N, N- diethyl-lupetidine, 2,6- dimethyl -5- nitrogen spiral shell - [4.5]-decane, N, N- diethyl -2- ethyl piperidine, N- ethyl-N- propyl-lupetidine, N- methyl-N ethyl - Lupetidine, N- methyl-N ethyl -2- ethyl piperidine, 2,5- dimethyl-N, N- diethyl pyrroles, 2,6- dimethyl - N, N- lupetidine, 3,5- dimethyl-N, N- lupetidine, 2- ethyl-N, N- lupetidine, 2,2,6,6- tetramethyl Base-N- methyl-N ethyl piperidines, N- cyclooctane base-pyridine, 2,2,6,6- tetramethyl-N, N- lupetidine or N, N- diformazan In base-N, N- bicyclic nonane 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) 110-150 DEG C at a temperature of carry out hydro-thermal process 36-96h；

(3) product of step (2) is separated by solid-liquid separation, dry 10-36h at 80-120 DEG C；

(4) product of step (3) is roasted into 4-10h at 550-700 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 1-10wt.%, such as 1.5wt.%, 3wt.%, 5wt.%, 7wt.% or 9wt.% etc., preferably 2-5wt.%.

Preferably, the Cu-SSZ-39 molecular sieve has AEI configuration.

Preferably, the specific surface area of the Cu-SSZ-39 molecular sieve is 350-800m²/ g, such as 400m²/g、450m²/g、 500m²/g、550m²/g、600m²/g、700m²/ g or 750m²/ g etc..

Preferably, the silica alumina ratio of the Cu-SSZ-39 molecular sieve is 3-30, such as 5,8,10,15,20 or 27 etc., preferably For 5-12.

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 process of Cu-SSZ-39 molecular sieve of the present invention is used as using beta molecular sieve turns a brilliant material, by it With nitrogenous organic formwork agent, water, copper source, TEPA and alkali source hybrid reaction, one-step method obtains Cu-SSZ-39 molecule of the present invention Sieve, preparation process is simple, and yield is high, and advantages of nontoxic raw materials is harmless, will not cause damages to human and environment；

(2) the method for the invention to be prepared by adjusting specific raw material proportioning, crystallization and roasting condition Catalyst of the Cu-SSZ-39 molecular sieve as ammonia selective catalyst reduction of nitrogen oxides is removed with high nitrogen oxides Rate and nitrogen selective, and the removal of nitrogen oxide being particularly suitable under high-speed, 400,000h^-1Under air speed, 250 Within the temperature range of DEG C -500 DEG C, there is the removal rate to 70% or more nitrogen oxides, meanwhile, it is also equipped with high nitrogen Selectivity, keeps 90% or more nitrogen selective within the temperature range of 200 DEG C -550 DEG C；

(3) the method for the invention to be prepared by adjusting specific raw material proportioning, crystallization and roasting condition Cu-SSZ-39 molecular sieve has excellent hydrothermal stability, compared to fresh Cu-SSZ-39 molecular sieve, by the Cu-SSZ- 39 molecular sieves are under the conditions of 750 DEG C after hydrothermal aging processing 16h, and nitrogen oxides removes in 250 DEG C of -500 DEG C of temperature ranges Decline≤5% of rate；Decline≤2% of nitrogen selective within the temperature range of 200 DEG C -550 DEG C simultaneously, to illustrate this hair The bright Cu-SSZ-39 molecular sieve has excellent hydrothermal stability, is suitable in exhaust gas from diesel vehicle after-treatment system；

(4) being used as using beta molecular sieve for the method for the invention turns a brilliant material, and cost is relatively low, has certain warp Ji benefit.

Detailed description of the invention

Fig. 1 is the XRD diagram of the fresh Cu-SSZ-39 molecular sieve arrived prepared by present example 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.