CN106629761A - Synthesis method of SSZ-13 molecular sieve - Google Patents
Synthesis method of SSZ-13 molecular sieve Download PDFInfo
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- CN106629761A CN106629761A CN201611187250.6A CN201611187250A CN106629761A CN 106629761 A CN106629761 A CN 106629761A CN 201611187250 A CN201611187250 A CN 201611187250A CN 106629761 A CN106629761 A CN 106629761A
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- C01B39/02—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
- 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 invention provides a synthesis method of an SSZ-13 molecular sieve. A USY molecular sieve or Beta molecular sieve with adsorbed N,N,N-trimethyl-1-adamantanamine cations is used as a structure guide agent to synthesize the SSZ-13 molecular sieve together with an aluminum source, a silicon source, an alkali source, water and mixed seeds, thereby greatly reducing the consumption of the expensive template N,N,N-trimethyl-1-adamantanamine cations in the traditional method, and obviously lowering the cost for synthesizing the SSZ-13 molecular sieve. The method can enhance the crystallization rate of the SSZ-13 molecular sieve and shorten the required crystallization time, and thus, is more beneficial to industrial production. The SSZ-13 molecular sieve synthesized by the method has high crystallinity and favorable hydrothermal stability; and the synthesized SSZ-13 molecular sieve can be used as an MTO (Methanol To Olefins) catalyst and can also be used as an automobile tail gas treatment catalyst support.
Description
Technical field
The invention belongs to Inorganic synthese and field of catalyst preparation, concretely relate to a kind of conjunction of SSZ-13 molecular sieves
Into method.
Background technology
SSZ-13 molecular sieves have good heat stability, can be net as adsorbent or the carrier of catalyst, such as air
Agent, auto-exhaust catalyst etc..While SSZ-13 molecular sieves are also with cation exchange and acid adjustability, therefore for
The catalytic cracking of kinds of reaction such as hydrocarbon compound, be hydrocracked and alkene and aromatic hydrocarbons construction reaction etc. be respectively provided with very
Good catalytic performance.
United States Patent (USP) US 4544538 makes public for the first time a kind of synthetic method of SSZ-13 molecular sieves.The method adopts N, N,
N- trimethyl -1- amantadines (TMAA+) organic cations synthesize SSZ-13 molecular sieves as template.But, N, N, N-
Trimethyl -1- amantadines are expensive, cause to synthesize SSZ-13 molecular sieve high costs, seriously limit SSZ-13 molecular sieves
Commercial Application.
CN 201510583383.4 describes one kind with N, N, N- trimethyl -1- amantadines organic cation and tetrem
The method that base ammonium hydroxide synthesizes SSZ-13 as mixed templates.The method is used as template by adding tetraethyl ammonium hydroxide
Agent, so as to reduce N, the use of N, N- trimethyl -1- amantadine cationes.Although the method can reduce N, N, N- front three
The use of base -1- amantadine cationes synthesizes the synthesis cost of SSZ-13 molecular sieves so as to reduce, but used in the patent
The mole of N, N, N- trimethyl -1- amantadine organic cations and SiO in silicon source2Mole ratio also 0.1 or so,
It is few that the consumption of its N, N, N- trimethyl -1- amantadine organic cations is reduced, and synthesis cost is still higher, is unfavorable for
The industrialization of SSZ-13 molecular sieves.
CN 201310645906.4 discloses a kind of employing choline cation and synthesizes SSZ-13 molecular sieves as template
Method.The method uses choline chloride as template, instead of and adopt in the past N, N, N- trimethyl -1- amantadine (TMAA
+) cation and benzyltrimethylammoncation cation, as the use of template, and synthesize SSZ-13 molecular sieves, although the program
Use relatively inexpensive template, but generated time is but at least more than 4 days, and causing to synthesize cost increases, to SSZ-13
The industrialized production of molecular sieve brings no small obstruction.
Therefore, a kind of synthetic method of SSZ-13 molecular sieves is researched and developed, can greatly reduces N, N, N- trimethyl -1- Buddha's warrior attendants
The consumption of alkanamine organic cation, and generated time can be greatly shortened, so as to reduce production cost just with highly important
Meaning.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of SSZ-13 molecular sieves, of the prior art above-mentioned to overcome
Defect, can greatly reduce N, the consumption of N, N- trimethyl -1- amantadine organic cations, and can greatly shorten synthesis
Time, so as to reduce production cost.
For achieving the above object, the present invention is adopted the following technical scheme that：
A kind of synthetic method of SSZ-13 molecular sieves, comprises the steps：
(1) by USY molecular sieve or Beta molecular sieves and the mixing of N, N, N- trimethyl -1- diamantane (obsolete) Ammonia, stir
Mix, filter, obtain being adsorbed with N, the USY molecular sieve or Beta molecular sieves (mixing of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
Thing A) and containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide；
(2) silicon source is (with Al2O3Meter), silicon source is (with SiO2Meter), alkali source is (with M2O is counted) and water (H2O it is) 1 according to mol ratio:
(10～80):(2.5～40):(100～2400) mix homogeneously, is subsequently adding SAPO-34 molecular sieves with SSZ-13 molecular sieves
Mixing crystal seed, obtains mixture B；
(3) a certain amount of mixture A is added into mixture B, is transferred to after mix homogeneously in autoclave, 120
8～48h of crystallization at～180 DEG C, cooling is filtered, and the crystallization product for obtaining is dried through washing, and roasting obtains SSZ-13 molecules
Sieve；
USY molecular sieve or Beta molecular sieves and N, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide in the step (1)
The mass ratio of solution is 1:(10～50)；
Mixing crystal seed and silicon source are (with SiO in the step (2)2Meter) mass ratio be (0.1～5):100；
The silicon source in a certain amount of mixture A and step (2) in the step (3) is (with SiO2Meter) mass ratio for (5～
20):100。
According to the present invention, the N in the step (1), N, N- trimethyl -1- diamantane (obsolete) Ammonias concentration is 20～
60%.
According to the present invention, the mass ratio of the SAPO-34 molecular sieves in the step (2) and SSZ-13 molecular sieves for (0.1～
10):The silicone content of 1, SAPO-34 molecular sieve is (with SiO2Meter) for 4～12%, SSZ-13 molecular sieves silica alumina ratio be 3.5～60.
According to the present invention, the USY molecular sieve silica alumina ratio in the step (1) is for 9～100, Beta molecular sieve silica alumina ratios
15～150.
According to the present invention, the silicon source in the step (2) is the one kind or many in Ludox, tetraethyl orthosilicate and white carbon
Kind.
According to the present invention, the silicon source in the step (2) is one or two in sodium metaaluminate and aluminum sulfate octadecahydrate.
According to the present invention, the alkali source in the step (2) is one or two in sodium hydroxide and potassium hydroxide.
According to the present invention, the USY molecular sieve or Beta molecular sieves and N, N, N- trimethyl -1- Buddha's warrior attendants in the step (1)
Alkane Ammonia mixes, and 6～10h is stirred at 20～60 DEG C.
According to the present invention, the crystallization product in the step (3) is in atmosphere in 500～600 DEG C of 4～10h of roasting.
According to the present invention, the filtrate L in the step (1) is reused as a follow-up batch or multiple batches of SSZ-13 molecules
Step (1) prepares the raw material of mixture A in sieve synthesis.
Compared with prior art, the synthetic method of SSZ-13 molecular sieves of the invention has advantages below：
1) synthetic method of SSZ-13 molecular sieves of the invention, using N is adsorbed with, N, N- trimethyl -1- amantadines are positive
The USY molecular sieve or Beta molecular sieves of ion synthesizes SSZ-13 molecular sieves as structure directing agent, considerably reduces N, N,
The use of N- trimethyl -1- amantadine cationes, so as to greatly reduce production cost；
2), USY or Beta molecular sieves are depolymerized to sial fragment in high―temperature nuclei system, serve induction SSZ-13 brilliant
The effect of bulk-growth, shortens the induction period of crystal growth, so as to shorten crystallization time so that the industry of SSZ-13 molecular sieves
Metaplasia is produced more easy；
3), the SSZ-13 molecular sieve crystallinities of synthesis are high, with good hydrothermal stability, may be advantageously employed in automobile
The removing of NOx, methanol-to-olefins (MTO) and CO in tail gas2In adsorption separation process.
Description of the drawings
Fig. 1 is XRD spectrum before embodiment 1～14 and the gained sample water Thermal test of comparative example 1.
Fig. 2 is XRD spectrum after embodiment 1～14 and the gained sample water Thermal test of comparative example 1.
Fig. 3 is the XRD spectrum of the gained sample under different crystallization times of comparative example 2, crystallization time is respectively 8,24,48,
72、96h。
Wherein：In Fig. 1 to Fig. 3, abscissa represents 2 θ angles, and vertical coordinate represents molecular sieve feature peak intensity, and SSZ-13 divides
Son sieves characteristic peak positions：9.574°、12.439°、12.989°、14.024°、15.898°、16.190°、17.796°、
20.785°、21.657°、22.094°、22.665°、23.266°、23.453°、24.921°、25.354°、26.110°、
27.857°、28.126°、28.309°、30.916°
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.It should be understood that following examples are merely to illustrate this
Invention is not for restriction the scope of the present invention.
Raw material used in following examples is commercially available.
In the following example, silicon source is one or more in 30% Ludox, tetraethyl orthosilicate and white carbon.But do not limit
In above-mentioned several, silicon source conventional in prior art can be adopted, can be used in mixed way.
Silicon source is one or two in sodium metaaluminate and aluminum sulfate octadecahydrate, but is not limited to above two, as long as can
Al required for Zeolite synthesis is provided2O3Just can replace or be used in mixed way.
Alkali source is one or two in sodium hydroxide and potassium hydroxide, but is not limited to above two, as long as can provide
Alkaline hydroxyl just can be replaced or be used in mixed way.
30% Ludox：(SiO2Mass content 30%, H2O mass contents 70%)
The synthesis of embodiment 1, SSZ-13 molecular sieves
(1) by the N that 10g USY molecular sieves (silica alumina ratio 50) and 100g mass concentrations are 20%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and 6h is stirred at 60 DEG C, then filters, and obtains being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydrogen
The USY molecular sieve (mixture A) of amine-oxides and contain N, the filtrate L 95.7g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) 10.09g potassium hydroxide is dissolved in 48g deionized waters, is uniformly mixing to obtain potassium hydroxide solution, then
To in above-mentioned potassium hydroxide solution add 3.33g aluminum sulfate octadecahydrate, stirring be completely dissolved aluminum sulfate octadecahydrate, then by
The drop Ludox of Deca 60g 30%, after Ludox is added completely into, continues to stir 2h, is subsequently adding 0.12g SAPO-34 molecules
Sieve (silicone content is 4%) and the mixing crystal seed of 0.24g SSZ-13 molecular sieves (silica alumina ratio is 40), obtain final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, then filter, the filter cake Jing deionized waters for obtaining fully is washed
It is placed in after washing in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace, obtains SSZ-13 molecular sieves 1
Sample (1#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:60:18:1000；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 2:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio be 0.5:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 18.49%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
Silicon source is (with SiO2Meter) mole ratio be 0.0046:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 2, SSZ-13 molecular sieves
(1) by the N that 10gBeta (silica alumina ratio 70) molecular sieves and 300g mass concentrations are 60%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and 10h is stirred at 20 DEG C, then filters, and obtains being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydrogen
The Beta molecular sieves (mixture A) of amine-oxides and contain N, the filtrate L 280g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 10.09g is dissolved in 66.4g deionized waters, states then up in potassium hydroxide solution and add
Enter the aluminum sulfate octadecahydrate of 2.85g, stirring is allowed to be completely dissolved, then the dropwise Ludox of Deca 60g 30%, treat that Ludox is complete
After full addition, continue to stir 2h, be subsequently adding 0.12g SAPO-34 molecular sieves (silicone content 12%) and 0.24g SSZ-13 molecules
The mixing crystal seed of sieve (silica alumina ratio is 40), obtains final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, then filter, the filter cake Jing deionized waters for obtaining fully is washed
It is placed in after washing in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace, obtains SSZ-13 molecular sieves 2
Sample (2#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:70:21:1400；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 2:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio be 0.5:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 58%.Then actually used N, the consumption (mole) and silicon of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
SiO in source2Mole ratio be 0.017:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 3, SSZ-13 molecular sieves
(1) by the N that 10gBeta (silica alumina ratio 15) molecular sieves and 100g mass concentrations are 40%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 40 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
The Beta molecular sieves (mixture A) of ammonium and contain N, the filtrate L 93.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) sodium hydroxide of 7.2g is dissolved in 42g deionized waters, then the addition in above-mentioned sodium hydroxide solution again
The aluminum sulfate octadecahydrate of 3.42g, stirring is allowed to be completely dissolved, then dropwise Deca 62g tetraethyl orthosilicate, treats that tetraethyl orthosilicate is complete
After full addition, continue to stir 2h, be subsequently adding 0.12g SAPO-34 molecular sieves (silicone content 8%) and 0.24g SSZ-13 molecules
The mixing crystal seed of sieve (silica alumina ratio is 3.5), obtains final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, then filter, the filter cake Jing deionized waters for obtaining fully is washed
It is placed in after washing in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains SSZ-13 molecular sieves 3
Number sample (3#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:58:17.4:452；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 2:100；The matter of SAPO-34 molecular sieves and SSZ-13 molecular sieves in crystal seed
Amount is than being 0.5:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 37.6%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.0083:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 4, SSZ-13 molecular sieves
(1) by the N that 10g Beta (silica alumina ratio 150) molecular sieves and 500g mass concentrations are 40%, N, N- trimethyl -1- is golden
Just the mixing of alkane Ammonia, stirs 8h at 40 DEG C, then filters, and obtains being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete)
Beta molecular sieves (mixture A) of ammonium hydroxide and containing N, the filtrate L 486g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) sodium hydroxide of 7.2g is dissolved in 84g deionized waters, then the addition in above-mentioned sodium hydroxide solution again
The aluminum sulfate octadecahydrate of 3.42g, stirs 1h and is allowed to be completely dissolved under room temperature, then dropwise Deca 62g tetraethyl orthosilicate, treats positive silicon
After acetoacetic ester is added completely into, continue to stir 2h, be subsequently adding 0.12g SAPO-34 molecular sieves (silicone content 8%) and 0.6g SSZ-
The mixing crystal seed of 13 molecular sieves (silica alumina ratio 60), obtains final product mixture B.
(3) 0.9g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 180 DEG C of baking ovens and keeps 8h, then filter, the filter cake Jing deionized waters for obtaining fully is washed
It is placed in after washing in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains SSZ-13 molecular sieves 4
Number sample (4#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:58:17.4:905；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 5:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 4:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio be 0.2:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 38.7%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.007:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 5, SSZ-13 molecular sieves
(1) by the N that 10gBeta (silica alumina ratio 50) molecular sieves and 500g mass concentrations are 40%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 40 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
Beta molecular sieves (mixture A) of ammonium and containing N, the filtrate L 486g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) sodium hydroxide of 6g is dissolved in 53.33g deionized waters, then again in above-mentioned sodium hydroxide solution plus
Enter the aluminum sulfate octadecahydrate of 19.6g, 1h is stirred under room temperature and is allowed to be completely dissolved, then dropwise Deca 62g tetraethyl orthosilicate, treats just
After silester is added completely into, continue to stir 2h, be subsequently adding 0.12g SAPO-34 molecular sieves (silicone content 5%) and 0.6g
The mixing crystal seed of SSZ-13 molecular sieves (silica alumina ratio is 50), obtains final product mixture B.
(3) 0.9g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 120 DEG C of baking ovens and keeps 48h, then filter, the filter cake Jing deionized waters for obtaining fully is washed
It is placed in after washing in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains SSZ-13 molecular sieves 5
Number sample (5#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:10:2.5:100；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 5:100, mix
Synthetic kind is with silicon source (with SiO2Meter) mass ratio be 4:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio is 0.2:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 38.7%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.007:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 6, SSZ-13 molecular sieves
(1) by the N that 10gBeta (silica alumina ratio 50) molecular sieves and 500g mass concentrations are 40%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 40 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
Beta molecular sieves (mixture A) of ammonium and containing N, the filtrate L 486g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) sodium hydroxide of 12.1g is dissolved in 162.3g deionized waters, then again in above-mentioned sodium hydroxide solution
The aluminum sulfate octadecahydrate of 2.49g is added, 1h is stirred under room temperature and is allowed to be completely dissolved, then dropwise Deca 62g tetraethyl orthosilicate, treats
After tetraethyl orthosilicate is added completely into, continue to stir 2h, be subsequently adding 0.12g SAPO-34 molecular sieves (silicone content 10%) and 0.6g
The mixing crystal seed of SSZ-13 molecular sieves (silica alumina ratio is 6), obtains final product mixture B.
(3) 0.9g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 150 DEG C of baking ovens and keeps 10h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains No. 6 samples of SSZ-13 molecular sieves
Product (6#).
It is computed, each component silicon source is (with Al in embodiment 12O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:80:40:2400；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 5:100, mix
Synthetic kind is with silicon source (with SiO2Meter) mass ratio be 4:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio is 0.2:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 38.7%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.007:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 7, SSZ-13 molecular sieves
(1) by the N that 10gUSY (silica alumina ratio 9) molecular sieves and 100g mass concentrations are 30%, N, N- trimethyl -1- diamantane (obsolete)
Ammonia mixes, and at 60 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
USY molecular sieve (mixture A) and containing N, the filtrate L 94.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 10.09g is dissolved in 84g deionized waters, then again in above-mentioned potassium hydroxide solution plus
Enter the sodium metaaluminate of 0.82g, 1h is stirred under room temperature and is allowed to be completely dissolved, be subsequently adding 18g white carbons, treat that white carbon is added completely into
Afterwards, continue to stir 2h, be subsequently adding 0.0163g SAPO-34 molecular sieves (silicone content 8%) and 0.163g SSZ-13 molecular sieves
The mixing crystal seed of (silica alumina ratio is 14), obtains final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 160 DEG C of baking ovens and keeps 20h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains No. 7 samples of SSZ-13 molecular sieves
Product (7#).
It is computed, each component silicon source is (with Al in embodiment 72O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:60:18:934；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100, mix
Synthetic kind is with silicon source (with SiO2Meter) mass ratio be 1:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio is 0.1:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 27.8%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.0068:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 8, SSZ-13 molecular sieves
(1) by the N that 10gUSY (silica alumina ratio 100) molecular sieves and 100g mass concentrations are 30%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 60 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
The USY molecular sieve (mixture A) of ammonium and containing N, the filtrate L 94.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 10.09g is dissolved in 120g deionized waters, then again in above-mentioned potassium hydroxide solution
The sodium metaaluminate of 0.82g is added, 1h is stirred under room temperature and is allowed to be completely dissolved, then the dropwise Ludox of Deca 60g 30%, treats silicon
After colloidal sol is added completely into, continue to stir 2h, be subsequently adding 0.163g SAPO-34 molecular sieves (silicone content 6%) and 0.0163g
The mixing crystal seed of SSZ-13 molecular sieves (silica alumina ratio is 26), obtains final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 170 DEG C of baking ovens and keeps 20h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 500 DEG C of roasting 10h in Muffle furnace again, obtains No. 8 samples of SSZ-13 molecular sieves
Product (8#).
It is computed, each component silicon source is (with Al in embodiment 82O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:60:18:1800；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 1:100；The matter of SAPO-34 molecular sieves and SSZ-13 molecular sieves in crystal seed
Amount is than being 10:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 27.8%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.0068:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 9, SSZ-13 molecular sieves
(1) by the N that 10gUSY (silica alumina ratio 50) molecular sieves and 100g mass concentrations are 30%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 60 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
The USY molecular sieve (mixture A) of ammonium and containing N, the filtrate L 94.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 10.09g is dissolved in 12g deionized waters, then again in above-mentioned potassium hydroxide solution plus
Enter the sodium metaaluminate of 0.82g, stirring is allowed to be completely dissolved, then the dropwise Ludox of Deca 60g 30%, treat that Ludox adds completely
After entering, continue to stir 2h, be subsequently adding 0.0144g SAPO-34 molecular sieves (silicone content 10%) and 0.0036g SSZ-13 molecules
The mixing crystal seed of sieve (silica alumina ratio is 35), obtains final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains No. 9 samples of SSZ-13 molecular sieves
Product (9#).
It is computed, each component silicon source is (with Al in embodiment 92O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and water
Mol ratio be 1:60:18:600；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100, mix
Synthetic kind is with silicon source (with SiO2Meter) mass ratio be 0.1:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio be 4:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 27.8%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.0068:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 10, SSZ-13 molecular sieves
(1) by the N that 10gUSY (silica alumina ratio 50) molecular sieves and 100g mass concentrations are 30%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 60 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
The USY molecular sieve (mixture A) of ammonium and containing N, the filtrate L 94.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 16.8g is dissolved in 42g deionized waters, then again in above-mentioned potassium hydroxide solution plus
Enter the sodium metaaluminate of 0.82g, stirring is allowed to be completely dissolved, then the dropwise Ludox of Deca 60g 30%, treat that Ludox adds completely
After entering, continue to stir 2h, be subsequently adding 0.3g SAPO-34 molecular sieves (silicone content 9%) and 0.6g SSZ-13 molecular sieve (sial
Than for mixing crystal seed 45), obtaining final product mixture B.
(3) 1.8g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 600 DEG C of roasting 4h in Muffle furnace again, obtains No. 10 samples of SSZ-13 molecular sieves
Product (10#).
It is computed, each component silicon source is (with Al in embodiment 102O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and
The mol ratio of water is 1:60:60:934；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 10:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 5:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in mixing crystal seed
Mass ratio be 0.5:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 27.8%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.0068:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 11, SSZ-13 molecular sieves
(1) by the N that 10gUSY (silica alumina ratio 50) molecular sieves and 100g mass concentrations are 30%, N, N- trimethyl -1- Buddha's warrior attendants
Alkane Ammonia mixes, and at 60 DEG C 8h is stirred, and is then filtered off being adsorbed with N, N, N- trimethyl -1- diamantane (obsolete) hydroxides
The USY molecular sieve (mixture A) of ammonium, and containing N, the filtrate L 94.6g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide.
(2) potassium hydroxide of 8.45g is dissolved in 42g deionized waters, then again in above-mentioned potassium hydroxide solution plus
Enter the sodium metaaluminate of 0.82g, stirring is allowed to be completely dissolved, then the dropwise Ludox of Deca 60g 30%, treat that Ludox adds completely
After entering, continue to stir 2h, be subsequently adding 0.06g SAPO-34 molecular sieves (silicone content 9%) and 0.012g SSZ-13 molecular sieves
The mixing crystal seed of (silica alumina ratio is 56), obtains final product mixture B.
(3) 3.6g mixture A are taken to be added in mixture B, are stirred, be then transferred in have polytetrafluoro liner not
In rust steel autoclave, it is put in 140 DEG C of baking ovens and keeps 13h, filter, the filter cake for obtaining is Jing after deionized water is fully washed
It is placed in 100 DEG C of drying baker and dries 12h, then 550 DEG C of roasting 6h in Muffle furnace again, obtains No. 11 samples of SSZ-13 molecular sieves
Product (11#).
It is computed, each component silicon source is (with Al in embodiment 112O3Meter), silicon source is (with SiO2Meter), alkali source is (with K2O is counted) and
The mol ratio of water is 1:60:30:934；The mixture A that step (3) is used is with silicon source (with SiO2Meter) mass ratio be 20:100,
Mixing crystal seed is with silicon source (with SiO2Meter) mass ratio be 0.4:100；SAPO-34 molecular sieves and SSZ-13 molecular sieves in crystal seed
Mass ratio is 5:1.
Containing N, the N in the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide, N, N- trimethyl -1- diamantane (obsolete) hydrogen-oxygens
The content for changing ammonium is 27.8%.Then actually used N, the consumption (mole) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide with
SiO in silicon source2Mole ratio be 0.014:1.
Containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is repeatable to be used as a follow-up batch or multiple batches of
SSZ-13 Zeolite synthesis in step (1) prepare the raw material of mixture A.
The synthesis of embodiment 12, SSZ-13 molecular sieves
The N that concentration used in embodiment 4 is 40%, N, N- trimethyl -1- diamantane (obsolete) Ammonias are replaced with
Filtrate L resulting in embodiment 4 (N in filtrate, the content of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide for 38.7%), its
His synthesis condition is same as Example 4.
Step (1) in the present embodiment obtains filtrate 479g, is designated as filtrate L1, Jing analysis determine the filtrate in N, N, N- tri-
The content of methyl isophthalic acid-diamantane (obsolete) ammonium hydroxide is 38.2%, finally gives No. 12 samples (12#) of SSZ-13 molecular sieves.
It is computed, actually used N, in the consumption (mole) and silicon source of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
SiO2Mole ratio be 0.0043:1.
The synthesis of embodiment 13, SSZ-13 molecular sieves
Filtrate L used in embodiment 12 is replaced with into filtrate L resulting in embodiment 121, other synthesis conditions
It is identical with embodiment 12.The filtrate 472.6g that step (1) in the present embodiment is obtained, is designated as filtrate L2, Jing analysis determine the filter
The content of N in liquid, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is 37.8%, finally gives No. 13 samples of SSZ-13 molecular sieves
(13#)。
It is computed, actually used N, in the consumption (mole) and silicon source of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
SiO2Mole ratio be 0.0038:1.
The synthesis of embodiment 14, SSZ-13 molecular sieves
By filtrate L used in embodiment 131Replace with filtrate L resulting in embodiment 132, other synthesis conditions
It is identical with embodiment 13.The filtrate 465.3g that step (1) in the present embodiment is obtained, is designated as filtrate L3, Jing analysis determine the filter
The content of N in liquid, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is 37.2%, finally gives No. 14 samples of SSZ-13 molecular sieves
(14#)。
It is computed, actually used N, in the consumption (mole) and silicon source of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
SiO2Mole ratio be 0.0045:1.
Above-mentioned filtrate L3Follow-up synthesis, or the fresh N higher with concentration, N, N- trimethyl -1- Buddha's warrior attendants can also be carried out
The allotment of alkane ammonium hydroxide is used.
Can be seen that compared with conventional synthesis that methods by the result of the test of above-described embodiment 1-14, the synthesis of the present invention
During method synthesis SSZ-13 molecular sieves, template N, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide is significantly reduced, and is greatly reduced
Template cost.
Comparative example 1, using traditional synthetic method synthesis SSZ-13 molecular sieves
The consumption that template is greatly reduced compared with traditional SSZ-13 Zeolite synthesis methods of the invention, in order to compare
The difference of the SSZ-13 molecular sieves obtained by two methods synthesis, the special document according to Wang Yufeng, Li Yuan, Tang Enqi《SSZ-13 point
The synthesis of son sieve and its sign》(《Petroleum refining and chemical industry》02 phase in 2010) provided SSZ-13 molecular sieves classics synthesis side
Method is synthesized, and concrete synthetic method is as follows：
With Ludox, aluminum sulfate octadecahydrate, sodium hydroxide, deionized water as raw material, with N, N, N- front three fund steel alkane hydrogen
Amine-oxides (R) are template, using traditional hydro-thermal method synthesis SSZ-13.By the oxide n (SiO of raw material2):n(A12O3):n
(Na2O):n(R2O):n(H2O)=40:1:16:5:900 mixing, after stirring, at room temperature aging 0.5h, is subsequently poured into band
In politef lining autoclave, crystallization 2～5 days at 155 DEG C.
Reaction pours reactant in beaker into after terminating, and is heated to 70～80 DEG C, adds a certain amount of ammonium chloride and exchanges
2h, vacuumizing filtration, repeated exchanged 3 times.The solid isolated is dried at 120 DEG C, then calcines to remove with temperature programming
Template and moisture in crystal, obtains No. 1 comparative sample of SSZ-13 molecular sieves (contrast sample1#).
Embodiment 15, hydrothermal stability is tested
For SSZ-13 molecular sieves prepared by embodiment 1～14 and the method for comparative example 1, its hydro-thermal is detected as follows
Stability：
(1) carry out before hydrothermal stability test, the XRD spectrum of first detection sample and (BET) specific surface area.
(2) sample is placed in 900 DEG C of tube furnace and is passed to water vapour, the hydro-thermal testing time is 1h, and detects hydro-thermal
XRD spectrum and specific surface area after test.
XRD spectrum before and after hydro-thermal test is respectively as depicted in figs. 1 and 2.Specific surface area data before and after hydro-thermal test is such as
Shown in table 1.
Specific surface area before and after the embodiment 1～14 of table 1 and the gained sample water Thermal test of comparative example 1
From the data of table 1, before hydrothermal stability test, the specific surface of SSZ-13 molecular sieves prepared by embodiment 1-14
Product is 527～566m2/ g, and the specific surface area of No. 1 comparative sample prepared by comparative example 1 is 506m2/ g, hydrothermal stability examination
After testing, the specific surface area of SSZ-13 molecular sieves prepared by embodiment 1-14 is 491～545m2/ g, and prepared by comparative example 1 No. 1
The specific surface area of comparative sample is 430m2/ g, illustrates that the specific surface area of SSZ-13 molecular sieves prepared by the method for comparative example 1 is substantially low
The specific surface area of the SSZ-13 molecular sieves prepared in the present invention.
Meanwhile, the specific surface area retention rate of the SSZ-13 molecular sieves of the synthetic method synthesis of the present invention is more than 90%,
The specific surface area retention rate of No. 1 comparative sample prepared by significantly greater than bigger comparative example 1.
As seen from Figure 1, before hydro-thermal test, SSZ-13 molecular sieves prepared by embodiment 1-14 and comparative example 1 have phase
As XRD spectrum；As seen from Figure 2, after hydro-thermal test, in the XRD spectrum of SSZ-13 molecular sieves prepared by embodiment 1-14
Characteristic peak almost do not reduce, and comparative example 1 prepare SSZ-13 molecular sieves XRD spectrum in characteristic peak substantially reduce.
Comparative example 2
It can be seen from the analytical data of embodiment 12,10g Beta molecular sieves co-adsorption 11.9g N, N, N- in embodiment 4
Trimethyl -1- diamantane (obsolete) ammonium hydroxide, finally takes 0.9g and is adsorbed with N, and the Beta of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide divides
Son sieve is added in reaction system, i.e., 0.45g N, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide are introduced in reaction system.
This comparative example is not adopted in synthesis has adsorbed 0.45g N, the 10g of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
Beta molecular sieves, but 0.45g N are directly added into, N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide makees structure directing agent, other conjunctions
It is same as Example 4 into condition, and respectively in crystallization 8h, 24h, 48h, 72h and 96h sample, sample be denoted as respectively No. 2 it is right
Than sample -8h, No. 2 comparative sample -24h, No. 2 comparative sample -48h, No. 2 comparative sample -72h and No. 2 comparative sample -96h, respectively
The XRD spectrum of No. 2 comparative samples is as shown in Figure 3.
From the XRD spectrum in Fig. 3, when the technical scheme using above-mentioned comparative example 2, crystallization time is 8,24h and 48h
Shi Junwei synthesizes SSZ-13 molecular sieves, when crystallization time is 72 hours, just detects and has synthesized SSZ-13 molecular sieves.Thus may be used
See, using the technical scheme of comparative example 2, at least need crystallization 72 hours (3 days) just to obtain SSZ-13 crystallizations.
The specific embodiment of the present invention has been described in detail above, but it is only used as example, and the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, any equivalent modifications that the invention is carried out and replace
In generation, is also all among scope of the invention.Therefore, the equalization made without departing from the spirit and scope of the invention is converted and repaiied
Change, all should cover within the scope of the invention.
Claims (10)
1. a kind of synthetic method of SSZ-13 molecular sieves, it is characterised in that comprise the steps：
(1) by USY molecular sieve or Beta molecular sieves and the mixing of N, N, N- trimethyl -1- diamantane (obsolete) Ammonia, stirring, mistake
Filter, obtains being adsorbed with N, the USY molecular sieve or Beta molecular sieves (mixture A) of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide
With containing N, the filtrate L of N, N- trimethyl -1- diamantane (obsolete) ammonium hydroxide；
(2) silicon source is (with Al2O3Meter), silicon source is (with SiO2Meter), alkali source is (with M2O is counted) and water (H2O it is) 1 according to mol ratio:(10～
80):(2.5～40):(100～2400) mix homogeneously, is subsequently adding the mix-crystal of SAPO-34 molecular sieves and SSZ-13 molecular sieves
Kind, obtain mixture B；
(3) a certain amount of mixture A is added into mixture B, is transferred to after mix homogeneously in autoclave, 120～180
8～48h of crystallization at DEG C, cooling is filtered, and the crystallization product for obtaining is dried through washing, and roasting obtains SSZ-13 molecular sieves；
USY molecular sieve or Beta molecular sieves and N, N, N- trimethyl -1- diamantane (obsolete) Ammonias in the step (1)
Mass ratio be 1:(10～50)；
Mixing crystal seed and silicon source are (with SiO in the step (2)2Meter) mass ratio be (0.1～5):100；
The silicon source in a certain amount of mixture A and step (2) in the step (3) is (with SiO2Meter) mass ratio be (5～20):
100。
2. synthetic method according to claim 1, it is characterised in that the N in the step (1), N, N- trimethyl -1- are golden
Just alkane Ammonia concentration is 20～60%.
3. synthetic method according to claim 1, it is characterised in that the SAPO-34 molecular sieves in the step (2) with
The mass ratio of SSZ-13 molecular sieves is (0.1～10):The silicone content of 1, SAPO-34 molecular sieve is (with SiO2Meter) it is 4～12%,
The silica alumina ratio of SSZ-13 molecular sieves is 3.5～60.
4. the synthetic method of a kind of SSZ-13 molecular sieves according to claim 1, it is characterised in that in the step (1)
USY molecular sieve silica alumina ratio be 9～100, Beta molecular sieves silica alumina ratio be 15～150.
5. synthetic method according to claim 1, it is characterised in that the silicon source in the step (2) is Ludox, positive silicon
One or more in acetoacetic ester and white carbon.
6. synthetic method according to claim 1, it is characterised in that the silicon source in the step (2) be sodium metaaluminate and
One or two in aluminum sulfate octadecahydrate.
7. synthetic method according to claim 1, it is characterised in that the alkali source in the step (2) be sodium hydroxide and
One or two in potassium hydroxide.
8. synthetic method according to claim 1, it is characterised in that the USY molecular sieve or Beta in the step (1) point
Son sieve and the mixing of N, N, N- trimethyl -1- diamantane (obsolete) Ammonia, stir 6～10h at 20～60 DEG C.
9. synthetic method according to claim 1, it is characterised in that the crystallization product in the step (3) is in atmosphere
In 500～600 DEG C of 4～10h of roasting.
10. the synthetic method according to any one of claim 1-9, it is characterised in that the filtrate L in the step (1)
It is reused as the raw material that step (1) in a follow-up batch or multiple batches of SSZ-13 Zeolite synthesis prepares mixture A.
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| CN111547735A (en) * | 2020-04-30 | 2020-08-18 | 上海工程技术大学 | Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN113698546A (en) * | 2021-08-27 | 2021-11-26 | 中国石油化工股份有限公司 | Method for preparing polyether polycarboxylic acid type high-efficiency water reducing agent from high-boiling residues at bottom of polyethylbenzene tower |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236441A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA by using tetraethyl ammonium hydroxide and N,N,N-trimethyl adamantane ammonium hydroxide mixture as templating agent |
| CN105692647A (en) * | 2016-03-17 | 2016-06-22 | 山东齐鲁华信高科有限公司 | Preparation method of SSZ-13 molecular sieve |
| CN105948070A (en) * | 2016-04-11 | 2016-09-21 | 天津大学 | Method for preparing CHA molecular sieve by taking gangue as silicon-aluminium sources |
-
2016
- 2016-12-20 CN CN201611187250.6A patent/CN106629761B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236441A (en) * | 2015-09-14 | 2016-01-13 | 天津大学 | Method for synthesizing CHA by using tetraethyl ammonium hydroxide and N,N,N-trimethyl adamantane ammonium hydroxide mixture as templating agent |
| CN105692647A (en) * | 2016-03-17 | 2016-06-22 | 山东齐鲁华信高科有限公司 | Preparation method of SSZ-13 molecular sieve |
| CN105948070A (en) * | 2016-04-11 | 2016-09-21 | 天津大学 | Method for preparing CHA molecular sieve by taking gangue as silicon-aluminium sources |
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| CN107758691B (en) * | 2017-12-12 | 2018-08-31 | 太原理工大学 | The preparation method of high silicon CHA types SSZ-13 molecular sieves |
| CN107758691A (en) * | 2017-12-12 | 2018-03-06 | 太原理工大学 | The preparation method of the high molecular sieves of silicon CHA types SSZ 13 |
| CN108059172A (en) * | 2017-12-13 | 2018-05-22 | 山东齐鲁华信高科有限公司 | The preparation method of H-SSZ-13 molecular sieves |
| CN108059172B (en) * | 2017-12-13 | 2020-07-10 | 山东齐鲁华信高科有限公司 | Preparation method of H-SSZ-13 molecular sieve |
| CZ307576B6 (en) * | 2017-12-21 | 2018-12-19 | Unipetrol výzkumně vzdělávací centrum, a.s. | A method of producing SSZ-13 zeolite |
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| CN108190907A (en) * | 2018-02-06 | 2018-06-22 | 四川润和催化新材料股份有限公司 | A kind of SSZ-13 molecular sieves and preparation method thereof |
| CN108383136A (en) * | 2018-05-07 | 2018-08-10 | 太原理工大学 | The preparation method of nucleocapsid SSZ-13@Nano SSZ-13 molecular sieves |
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| CN109110782A (en) * | 2018-10-09 | 2019-01-01 | 山东国瓷功能材料股份有限公司 | A kind of preparation method of SSZ-13 molecular sieve |
| CZ308130B6 (en) * | 2018-11-27 | 2020-01-15 | Unipetrol výzkumně vzdělávací centrum, a.s. | Process for producing zeolite SSZ-13 with mechanochemical activation |
| CN109437221A (en) * | 2018-12-26 | 2019-03-08 | 韩小学 | A kind of method of secondary growth method method preparation pure phase SSZ-13 molecular screen membrane |
| CN109569320A (en) * | 2018-12-26 | 2019-04-05 | 韩小学 | A method of mixing crystal seed method prepares pure phase SSZ-13 molecular screen membrane |
| CN109569320B (en) * | 2018-12-26 | 2020-11-17 | 福州宇卓科技有限公司 | Method for preparing pure-phase SSZ-13 molecular sieve membrane by mixed crystal seed method |
| CN110127720A (en) * | 2019-05-16 | 2019-08-16 | 济南大学 | A kind of method of hetero-seeds auxiliary synthesis SSZ-13 molecular sieve |
| WO2020228369A1 (en) * | 2019-05-16 | 2020-11-19 | 济南大学 | Method for synthesizing ssz-13 molecular sieve under assistance of heterogeneous seed crystal |
| CN110127720B (en) * | 2019-05-16 | 2020-03-31 | 济南大学 | Method for synthesizing SSZ-13 molecular sieve with assistance of heterogeneous crystal seeds |
| CN111056561A (en) * | 2019-12-30 | 2020-04-24 | 卓悦环保新材料（上海）有限公司 | Small-grain SSZ-13 molecular sieve containing hierarchical pores and synthesis method thereof |
| CN111056561B (en) * | 2019-12-30 | 2021-09-07 | 卓悦环保新材料（上海）有限公司 | Small-grain SSZ-13 molecular sieve containing hierarchical pores and synthesis method thereof |
| CN111547735A (en) * | 2020-04-30 | 2020-08-18 | 上海工程技术大学 | Controllable synthesis method of pure silicon and high-silicon CHA molecular sieve |
| CN113698546A (en) * | 2021-08-27 | 2021-11-26 | 中国石油化工股份有限公司 | Method for preparing polyether polycarboxylic acid type high-efficiency water reducing agent from high-boiling residues at bottom of polyethylbenzene tower |
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