CN101746774A - Tin-containing L zeolite and preparation method thereof - Google Patents

Tin-containing L zeolite and preparation method thereof Download PDF

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CN101746774A
CN101746774A CN 200810227649 CN200810227649A CN101746774A CN 101746774 A CN101746774 A CN 101746774A CN 200810227649 CN200810227649 CN 200810227649 CN 200810227649 A CN200810227649 A CN 200810227649A CN 101746774 A CN101746774 A CN 101746774A
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molecular sieve
tin
zeolite
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aluminium
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CN101746774B (en
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王嘉欣
马爱增
张大庆
陈志祥
臧高山
张玉红
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides tin-containing L zeolite. The chemical composition of the zeolite is (0.9-1.3)M.(0.01-0.3) SnO2.Al2O3.(5-7) SiO2, wherein M in a formula is K2O or a mixture of K2O and Na2O. The zeolite supporting noble metal is used for alkane aromatization reaction, and has good aromatization activity and stability.

Description

A kind of tin-containing L zeolite and preparation method thereof
Technical field
The present invention is a kind of heteroatomic Si-Al molecular sieve and preparation method thereof that contains, and specifically, is a kind of heteroatomic L molecular sieve and preparation method thereof that contains.
Background technology
L type molecular sieve (international molecular sieve association code: LTL) be a kind of synthetic molecular sieve that nineteen sixty-five Union Carbide company develops, find equivalents as yet so far at occurring in nature.The L molecular sieve is a kind of large pore molecular sieve of alkalescence, its crystal is cylindric, has the one-dimensional tunnel structure that parallels with cylinder axis, pile up on the C direction of principal axis by alternative hexagonal prism cage and cancrinite cage and to form, press the hexagonal axis rotation again and produce the twelve-ring duct, its aperture is 0.71nm, and kinetic diameter is 0.81nm.The typical chemical constitution molecular formula of L molecular sieve is as follows:
(0.9～1.3)M 2/nO:Al 2O 3:xSiO 2:yH 2O
M is a metal ion in the formula, and topmost metal ion is K +, also can be replaced, but in the general L zeolite 90% above K be arranged by other alkali or alkaline-earth metal ions +Be not easy to be exchanged.N is the valence mumber of M, x=5～7, y=0～9.
From Bernard (Proc.5th Int.Conf.on Zeolites, Wiley, New York, 1980,68) find that PtKL has had than since traditional dual-function catalyst much higher activity and selectivity the aromizing of normal hexane, the L molecular sieve that carries platinum obtains extensive concern as the normal paraffin dehydrogenation cyclization catalyst.Subsequently, Chevron company has applied for that with EXXON many relevant PtKL molecular sieve catalysts are used for the patent of dehydrogenation reaction and reforming reaction, and has realized the industrial applications of this catalyzer.
Hetero-atom molecular-sieve is synthetic to be the important means of Si-Al molecular sieve modification.After heteroatoms with property enters framework of molecular sieve, because the different structure and the character that might change molecular sieve of heteroatomic radius, electric charge and coordination environment, thereby acid-basicity, stability, absorption property and catalytic performance to molecular sieve exert an influence, for molecular sieve catalyst provides more wide Application Areas.Relevant SnS-1, SnS-2, SnZSM-5, SnZSM-12, SnAPO-5, stanniferous molecular sieves such as Sn β, SnMCM-41 all have bibliographical information.
Under the high severity reaction conditions of high-temperature low-pressure, Pt-Sn/Al 2O 3Dual metal reforming catalyst has good alkane aromatization selectivity and stable preferably.Add a spot of tin in the catalyzer, can effectively suppress the hydrogenolysis activity at catalytic reforming reaction initial stage.
USP5736478 discloses alkane dehydrogenating catalyst, by dipping tin and platinum is carried on the L molecular sieve, makes the PtSn/KL catalyzer, and this catalyzer has excellent catalytic performance to dehydrogenation of isobutane.But tin-containing L zeolite, and tin is not seen relevant report so far to PtKL catalyst system alkane aromatization Effect on Performance.
Summary of the invention
The purpose of this invention is to provide a kind of tin-containing L zeolite and preparation method thereof, the catalyzer that makes behind this molecular sieve carried platinum has alkane aromatization activity, selectivity and good activity stability preferably.
Tin-containing L zeolite provided by the invention, its chemical constitution is: (0.9～1.3) M (0.01～0.3) SnO 2Al 2O 3(5～7) SiO 2, M is Na in the formula 2O or Na 2O and K 2The mixture of O.
The present invention will contain the synthesis reaction mixture of silicon source, aluminium source, Xi Yuan and alkaline aqueous solution, add or not add directed agents, obtain tin-containing L zeolite through hydrothermal crystallizing, this molecular sieve purity height, degree of crystallinity height, and crystal is right cylinder, and grain-size is controlled.The catalyzer that makes behind this molecular sieve carried platinum is used for the straight-chain paraffin aromatization, has high reaction activity and high and arenes selectivity, and activity stability is significantly improved than the catalyzer that sial L molecular sieve makes.
Description of drawings
Fig. 1 is the XRD spectra of synthetic tin-containing L zeolite of the present invention.
Embodiment
The present invention will contain silicon source, aluminium source, Xi Yuan and alkaline aqueous solution and be mixed and made into reaction mixture, adding or not adding under the situation of directed agents, obtain tin-containing L zeolite through hydrothermal crystallizing.This molecular sieve purity height, degree of crystallinity height, crystal are that right cylinder, grain-size are controlled, the SiO of molecular sieve 2/ SnO 2Atomic ratio can be by changing the synthesis condition regulation and control.The catalyzer that makes with this molecular sieve carried platinum has higher aromatization activity and arenes selectivity, and activity stability is better.
Described tin-containing L zeolite SiO 2/ SnO 2Mol ratio can regulate preferred SiO 2/ SnO 2Mol ratio be 18～200, more preferably 20～150.
The preparation method of molecular sieve provided by the invention comprises that your ratio of Jiang Xiyuan, aluminium source, silicon source, mineral alkali and hydromassage is (0.01～0.8) SnO 2: Al 2O 3: (5～20) SiO 2: (0.5～4.0) mineral alkali: (60～300) H 2The ratio thorough mixing of O forms reaction mixture gel, behind 100～200 ℃ of hydrothermal crystallizings, with solids washing, drying.In the described reaction mixture gel, the tin that contains in the tin source compound is with SnO 2Meter, the aluminium that contains in the aluminum source compound is with Al 2O 3Meter, the silicon that contains in the silicon source compound is with SiO 2Meter.
The mol ratio of contained each material is preferably (0.05～0.5) SnO in the above-mentioned reaction mixture gel 2: Al 2O 3: (7～15) SiO 2: (1～3.0) mineral alkali: (100～200) H 2O.
In the inventive method, to the raw material addition sequence of synthetic tin-containing L zeolite and have no special requirements, preferred order of addition(of ingredients) is: Jiang Xiyuan joins in the alkaliferous aluminium colloidal sol, mixes the formation reaction mixture gel with the silicon source again, perhaps Xi Yuan joined in the silicon source, mix the formation reaction mixture gel with alkaliferous aluminium colloidal sol again, in reaction mixture gel, add or do not add directed agents, carry out hydrothermal crystallizing then, again with solids washing, drying.
Among the present invention, can add or not add directed agents when synthesizing tin-containing L zeolite, the prescription characteristics of directed agents are that silica alumina ratio is high and alkali silicon ratio is high, for system provides oversaturated nucleation condition.Concrete synthetic method is: your ratio of aluminium source, silicon source, mineral alkali and hydromassage is (5～15) K 2O: Al 2O 3: (10～25) SiO 2: (230～500) H 2The ratio thorough mixing of O, order of addition(of ingredients) is preferably the aluminium source is dissolved in the alkaline solution, and then this alkaline solution is joined in the silicon sol lentamente, stirs to form white gels, obtain translucent colloidal sol in 24～72 hours in 25～35 ℃ of ageings again, be crystallization director.The dosage of directed agents is with Al 2O 3Be benchmark calculating, the i.e. Al that contains in the directed agents of Jia Ruing 2O 3With Al in the molecular sieve synthesis material mixture (not comprising directed agents) 2O 3Mol ratio be 1～5%, preferred 2～3%.Directed agents can directly join in the reaction mixture gel, also can join in aluminium colloidal sol or the silicon sol.
Described hydrothermal crystallizing temperature is 100～200 ℃, preferred 110～170 ℃, and the time is 1～10 day, preferred 2～5 days.After the crystallization, crystallization product is drying to obtain tin-containing L zeolite of the present invention, preferred 80～120 ℃ of drying temperature, preferred 8～14 hours of time.
The preferred stannate of Xi Yuan described in the aforesaid method, crystallization tin tetrachloride or their mixture, the preferred aluminium hydroxide in described aluminium source, sodium metaaluminate or their mixture, the preferred silicon sol in silicon source, the preferred potassium hydroxide of mineral alkali, sodium hydroxide or their mixture.The preferred sodium stannate of described stannate.SiO in the described silicon sol 2Content be 20～45 quality %, preferred 25～40 quality %.
Tin-containing L zeolite of the present invention also can roasting after drying, and maturing temperature is 300～650 ℃, preferred 350～450 ℃.
Tin-containing L zeolite provided by the invention also can be through the K in alkali or the alkaline-earth metal ions exchange duct +, method is to exchange with the salts solution and the described tin-containing L zeolite that contain alkali or alkaline-earth metal ions, dry then, roasting.Preferred 100～120 ℃ of drying temperature after the exchange, preferred 10～15 hours of time.Preferred 450～650 ℃ of maturing temperature, preferred 2～4 hours of time.
Tin-containing L zeolite of the present invention can directly be used as catalyst component, make catalyzer again after being preferably load active component, the preferred pickling process of the method for load active component, promptly with the solution impregnation molecular sieve that contains active ingredient, liquid/solid volume during dipping is than preferred 2～6: 1, and gained solid drying, roasting promptly get catalyzer after will flooding.
Further specify the present invention below by example, but the present invention is not limited to this.
In the example, the crystalline phase of synthesis of molecular sieve and relative crystallinity all adopt the X-ray powder diffraction analysis, and chemical constitution is by x-ray fluorescence spectrometry.
Example 1
The used directed agents of preparation the present invention.
The mixture mole consists of 8K according to feeding intake 2OAl 2O 314SiO 2320H 2The prescription of O is with 4.35gAl (OH) 3(Chinese Aluminium Co., Ltd produces, trade mark H-WF-10, down with), join 106ml and contain in the solution of 30gKOH (purity 82%, down with), heating for dissolving obtains aluminium colloidal sol.Stir down aluminium colloidal sol to be joined in the 65mL silicon sol that is preheated to 50 ℃ and (contain 30%SiO 2, the pH value is 9, down together), stir and formed white gels in 0.5 hour, white gels was obtained translucent colloidal sol in 72 hours in 30 ℃ of ageings, be crystallization director.
Example 2
Prepare tin-containing L zeolite of the present invention.
With 4.35gAl (OH) 3Join 50mL and contain in the solution of 12.9gKOH, heating for dissolving obtains aluminium colloidal sol, with 1.94gSnCl 45H 2O is dissolved in the 20mL distilled water, mixes with aluminium colloidal sol to form mixing solutions again, stirs down mixing solutions is joined in the silicon sol of 78.3mL, stirs and forms white gels in 0.5 hour, and its mole consists of: 0.1SnO 21.7K 2OAl 2O 38.47SiO 2136H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get the former powder SL-1 of tin-containing L zeolite, its X-ray powder diffraction analysis of spectra is seen Fig. 1, and relative crystallinity is 112%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.97K 2O0.05SnO 2Al 2O 35.90SiO 2
Example 3
Method by example 2 prepares tin-containing L zeolite, and different is that crystallization time is 2 days, and the degree of crystallinity that obtains the former powder SL-2 of tin-containing L zeolite is 95%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.91K 2O0.05SnO 2Al 2O 35.85SiO 2
Example 4
Method by example 2 prepares tin-containing L zeolite, and different is that crystallization time is 1 day, and the degree of crystallinity that obtains the former powder SL-3 of tin-containing L zeolite is 86%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.93K 2O0.04SnO 2Al 2O 35.80SiO 2
Example 5
This example adds the synthetic tin-containing L zeolite of directed agents.
With 4.35gAl (OH) 3Join 50mL and contain in the solution of 12.9gKOH, heating for dissolving obtains aluminium colloidal sol; 20mL is contained 1.94gSnCl 45H 2The solution of O mixes with aluminium colloidal sol and obtains solution G; Under agitation the directed agents with G and 1 preparation of 6.52g example joins in the 78.3mL silicon sol, stirs to form white gels in 0.5 hour, and the mole of molecular sieve synthetic mixture consists of: 0.1SnO 21.7K 2OAl 2O 38.47SiO 2136H 2O (not comprising directed agents, down together), Al in the directed agents 2O 3With Al in the molecular sieve synthetic mixture 2O 3Mol ratio be 3%.
Above-mentioned white gels is moved in the reactor in 150 ℃ of crystallization 1 day, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 100 ℃ of dryings 10 hours, get the former powder SL-4 of tin-containing L zeolite, its relative crystallinity is 103%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.96K 2O0.06SnO 2Al 2O 36.22SiO 2
Example 6
Method by example 5 prepares tin-containing L zeolite, and different is that the tin source compound that adds is 4.41gNa 2SnO 33H 2O drops into the molecular sieve synthetic mixture mole that obtains behind each raw material and consists of: 0.3SnO 21.7K 2O0.3Na 2OAl 2O 38.47SiO 2136H 2O, Al in the directed agents 2O 3With Al in the molecular sieve synthetic mixture 2O 3Mol ratio be 3%.The relative crystallinity of the former powder SL-5 of tin-containing L zeolite that makes through hydrothermal crystallizing, washing, drying is 107%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.90K 2O0.08Na 2O0.12SnO 2Al 2O 36.31SiO 2
Example 7
Method by example 2 prepares tin-containing L zeolite, and different is that the tin source compound that adds is 7.35gNa 2SnO 33H 2O, the reactant gel mole that obtains consists of: 0.5SnO 21.7K 2O0.5Na 2OAl 2O 38.47SiO 2136H 2O, the relative crystallinity of the former powder SL-6 of tin-containing L zeolite that makes through hydrothermal crystallizing, washing, drying is 98%, anhydrous chemical constitution (in oxide mol ratio) is: 0.97K 2O0.11Na 2O0.28SnO 2Al 2O 35.85SiO 2
Example 8
With 15.6g Al (OH) 3Join 100mL and contain in the solution of 28.6gKOH, heating for dissolving obtains aluminium colloidal sol, with 7.32gSnCl 45H 2O is dissolved in the 53mL distilled water, mixes with aluminium colloidal sol to form mixing solutions again, stirs down mixing solutions is joined in the silicon sol of 166.7mL, stirs and forms white gels in 0.5 hour, and its mole consists of 0.2SnO 22.1K 2OAl 2O 310SiO 2150H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get the former powder SL-7 of tin-containing L zeolite, its relative crystallinity is 97%, and anhydrous chemical constitution (in oxide mol ratio) is: 1.12K 2O0.09SnO 2Al 2O 35.93SiO 2
Example 9
Method by example 8 prepares tin-containing L zeolite, and different is that the mineral alkali that adds is the aqueous solution that 100mL contains 34.1gKOH, and the reaction mixture gel mole that obtains consists of: 0.2SnO 22.5K 2OAl 2O 310SiO 2165H 2O, the relative crystallinity that makes the former powder SL-8 of tin-containing L zeolite after hydrothermal crystallizing, washing, drying is 95%, anhydrous chemical constitution (in oxide mol ratio) is: 1.19K 2O0.11SnO 2Al 2O 35.71SiO 2
Example 10
With 15.6gAl (OH) 3Join 200mL and contain in the solution of 38.2gKOH, heating for dissolving obtains aluminium colloidal sol, with 7.32gSnCl 45H 2O is dissolved in the 50mL distilled water, mixes with aluminium colloidal sol to form mixing solutions again, stirs down mixing solutions is joined in the silicon sol of 233.4mL, stirs and forms white gels in 0.5 hour, and its mole consists of 0.2SnO 22.8K 2OAl 2O 314SiO 2230H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get the former powder SL-9 of tin-containing L zeolite, its relative crystallinity is 90%, and anhydrous chemical constitution (in oxide mol ratio) is: 1.21K 2O0.10SnO 2Al 2O 35.97SiO 2
Example 11
With 4.35gAl (OH) 3Join 50mL and contain in the solution of 12.9gKOH, heating for dissolving obtains aluminium colloidal sol, with 1.94gSnCl 45H 2O is dissolved in the 20mL distilled water, mixes with aluminium colloidal sol to form mixing solutions again, and the silicon sol with 78.3mL under stirring joins in the above-mentioned mixing solutions, stirs to form white gels in 0.5 hour, and its mole consists of: 0.1SnO 21.7K 2OAl 2O 38.47SiO 2136H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get the former powder SL-10 of tin-containing L zeolite, its relative crystallinity is 110%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.98K 2O0.05SnO 2Al 2O 35.92SiO 2
Example 12
With 4.35gAl (OH) 3Join 50mL and contain in the solution of 12.9gKOH, heating for dissolving obtains aluminium colloidal sol; With 1.94gSnCl 45H 2O is dissolved in the 20mL distilled water, mixes with the silicon sol of 78.3mL to form mixing solutions again, stirs down aluminium colloidal sol is joined in the above-mentioned mixing solutions, stirs and forms white gels in 0.5 hour, and its mole consists of: 0.1SnO 21.7K 2OAl 2O 38.47SiO 2136H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get the former powder SL-11 of tin-containing L zeolite, its relative crystallinity is 108%, and anhydrous chemical constitution (in oxide mol ratio) is: 0.97K 2O0.06SnO 2Al 2O 35.91SiO 2
Comparative Examples 1
The preparation method and the composition of sial L molecular sieve.
With 21.8gAl (OH) 3Join 175mL and contain in the solution of 32.3gKOH, heating for dissolving obtains aluminium colloidal sol, stirs down aluminium colloidal sol is joined in the silicon sol of 195.8mL, stirs to form white gels in 0.5 hour, and its mole consists of: 1.7K 2OAl 2O 38.47SiO 2136H 2O.Above-mentioned white gels was moved in the reactor 150 ℃ of crystallization 3 days, be cooled to 40 ℃ then rapidly, product through centrifugation, wash to liquid phase PH valve be 10～11, the gained solid was in 120 ℃ of dryings 10 hours, get sial L molecular screen primary powder, its relative crystallinity is 110%, and anhydrous chemical constitution (in oxide mol ratio) is: 1.01K 2OAl 2O 35.93SiO 2
Getting 5g sial L molecular sieve is carrier, is the Pt (NH of 16mg/mL with concentration 3) 2Cl 2Solution supersaturation dipping, liquid during dipping/solid volume ratio is 4: 1, dipping back solid is in 120 ℃ of dryings 12 hours, 350 ℃ of roastings 4 hours, making Pt content is the catalyzer M of 1.0 quality %.
Comparative Examples 2
Getting above-mentioned sial L molecular sieve 10g, is the SnCl of 10 quality % with concentration 4Solution is 30 ℃ of dippings 24 hours, will flood afterwards solid in 120 ℃ of dryings 12 hours, and 350 ℃ of roastings 4 hours make the sial L molecular sieve carrier Sn/L that contains 1.0 quality %Sn.
Getting 5g carrier S n/L, is the Pt (NH of 16mg/mL with concentration 3) 2Cl 2Solution supersaturation dipping, liquid during dipping/solid volume ratio is 4: 1, and dipping back solid is in 120 ℃ of dryings 12 hours, and the catalyst n that Pt content is 1.0 quality % is made in 350 ℃ of roastings 4 hours.
Example 13～25
This example is estimated the aromatization activity and the stability of tin-containing L zeolite.
The tin-containing L zeolite 5g that gets the present invention's preparation is respectively the Pt (NH of 16mg/mL with concentration as carrier 3) 2Cl 2Solution supersaturation dipping, liquid during dipping/solid volume ratio is 4: 1, and dipping back solid is in 120 ℃ of dryings 12 hours, and the catalyzer that Pt content is 1.0 quality % is made in 350 ℃ of roastings 4 hours, and each example catalyst numbering and used molecular sieve carrier see Table 1.
Filling 2mL catalyzer is that raw material carries out aromatization with the normal hexane on high-pressure micro-device, and temperature of reaction is that 500 ℃, pressure are 1.0MPa, and the feeding liquid hourly space velocity is 3h-1, and hydrogen/hydrocarbon volume ratio 1200: 1 the results are shown in Table 1.
As shown in Table 1, behind the molecular sieve carried Sn of sial L, normal hexane aromizing performance obviously reduces; And the tin-containing L zeolite of the inventive method preparation be the catalyzer of carrier than being the catalyzer of carrier with sial L molecular sieve, have suitable initial conversion and product yield, but activity stability is better.
Table 1
Figure G2008102276491D0000081
In the table 1, BTX is respectively benzene, toluene and dimethylbenzene

Claims (10)

1. tin-containing L zeolite, its chemical constitution is: (0.9～1.3) M (0.01～0.3) SnO 2Al 2O 3(5～7) SiO 2, M is K in the formula 2O or K 2O and Na 2The mixture of O.
2. according to the described molecular sieve of claim 1, it is characterized in that SiO in the described molecular sieve 2With SnO 2Mol ratio be 18～200.
3. the preparation method of the described molecular sieve of claim 1 comprises that your ratio of Jiang Xiyuan, aluminium source, silicon source, mineral alkali and hydromassage is (0.01～0.8) SnO 2: Al 2O 3: (5～20) SiO 2: (0.5～4.0) mineral alkali: (60～300) H 2The ratio thorough mixing of O forms reaction mixture gel, behind the hydrothermal crystallizing, with solids washing, drying.
4. in accordance with the method for claim 3, it is characterized in that your ratio of Jiang Xiyuan, aluminium source, silicon source, mineral alkali and hydromassage is (0.05～0.5) SnO 2: Al 2O 3: (7～15) SiO 2: (1～3.0) mineral alkali: (100～200) H 2The mixed of O.
5. in accordance with the method for claim 3, the order of addition(of ingredients) that it is characterized in that synthetic described molecular sieve is: Jiang Xiyuan joins in the alkaliferous aluminium colloidal sol, mixes the formation reaction mixture gel with the silicon source again, perhaps Xi Yuan joined in the silicon source, mix the formation reaction mixture gel with alkaliferous aluminium colloidal sol again, behind 100～200 ℃ of hydrothermal crystallizings, with solids washing, drying.
6. according to claim 3 or 5 described methods, it is characterized in that in reaction mixture, adding directed agents, described directed agents consist of (5～15) K 2O: Al 2O 3: (10～25) SiO 2: (230～500) H 2O, add Al in the directed agents 2O 3With Al in the molecular sieve synthesis material mixture 2O 3Mol ratio be 1～5%.
7. in accordance with the method for claim 3, it is characterized in that described hydrothermal crystallizing temperature is 100～200 ℃, the time is 1～10 day.
8. in accordance with the method for claim 7, it is characterized in that described Xi Yuan is selected from stannate, crystallization tin tetrachloride or their mixture, described aluminium source is selected from aluminium hydroxide, sodium metaaluminate or their mixture, the silicon source is selected from silicon sol, and mineral alkali is selected from potassium hydroxide, sodium hydroxide or their mixture.
9. in accordance with the method for claim 8, it is characterized in that described stannate is a sodium stannate.
10. in accordance with the method for claim 8, it is characterized in that SiO in the described silicon sol 2Content be 20～45 quality %.
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CN104107716B (en) * 2013-04-18 2016-04-13 中国科学院大连化学物理研究所 For catalyst and the Synthesis and applications thereof of C6 ~ C8 n-alkane aromatisation
CN104556110B (en) * 2013-10-29 2017-01-25 中国石油化工股份有限公司 Tin-silicon molecular sieve as well as synthesis method and application thereof
CN105271294A (en) * 2014-06-24 2016-01-27 中国石油化工股份有限公司 Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method
CN105271294B (en) * 2014-06-24 2017-05-24 中国石油化工股份有限公司 Tin-silicon molecular sieve and synthetic method and application thereof, and phenol hydroxylation method
CN106367116B (en) * 2015-07-23 2019-02-22 中国石油化工股份有限公司 A method of light aromatics is prepared using reforming raffinate oil
CN106367112B (en) * 2015-07-23 2019-02-22 中国石油化工股份有限公司 A method of using reforming raffinate oil production aromatic hydrocarbons and improving by-product octane number
CN108190905A (en) * 2017-12-04 2018-06-22 中国科学院宁波材料技术与工程研究所 The preparation method and applications of KL molecular sieve catalysts
CN110550640A (en) * 2018-06-04 2019-12-10 中国石油化工股份有限公司 Germanium-containing L-type molecular sieve and preparation method thereof
CN112551538A (en) * 2020-12-23 2021-03-26 中触媒新材料股份有限公司 Synthesis method of nanoscale Sn-Beta
CN113683098A (en) * 2021-09-01 2021-11-23 奥斯催化材料（大连)有限公司 Method for dynamically synthesizing GaKL molecular sieve and application

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