CN103224242B - Low cost method for rapidly synthesizing ITQ-13 molecular sieve - Google Patents

Low cost method for rapidly synthesizing ITQ-13 molecular sieve Download PDF

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CN103224242B
CN103224242B CN201310134763.0A CN201310134763A CN103224242B CN 103224242 B CN103224242 B CN 103224242B CN 201310134763 A CN201310134763 A CN 201310134763A CN 103224242 B CN103224242 B CN 103224242B
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itq
molecular sieve
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CN103224242A (en
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李晓峰
贾妙娟
潘瑞丽
徐丹
张燕挺
窦涛
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Taiyuan Dacheng Huanneng Chemical Technology Co Ltd
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Taiyuan University of Technology
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Abstract

The invention relates to a low cost method for rapidly synthesizing an ITQ-13 molecular sieve. The method comprises the steps of dissolving a template in deionized water; adding a promoter, an alkali source, germanium dioxide, an aluminium source and crystal seeds; adding a silicon source and a fluorine source successively when the above materials are dissolved; stirring to form a uniform gel; crystallizing for 0.5-8 days under self-generated pressure and at a crystallization temperature of 100-220 DEG C; shock cooling with cold water; fully washing a crystallization product with the deionized water; and drying to obtain molecular sieve raw powder. The synthetic method has the advantages of simpleness, rapidity, easiness and low cost.

Description

A kind of method of low cost Fast back-projection algorithm ITQ-13 molecular sieve
Technical field
The invention belongs to a kind of method of synthesis of molecular sieve, specifically a kind of method of low cost Fast back-projection algorithm ITQ-13 molecular sieve.
Background technology
ITQ-13 molecular sieve, be within 2002, invented by Mobil company a kind ofly there is nonatomic ring and ten-ring simultaneously intersect the novel three-dimensional poromerics in duct.Nonatomic ring straight hole road and a set of ten-ring straight hole road intersect vertically and define another set of sinusoidal ten-ring duct, very close with the duct type of ZSM-5.Unique structure creates unique type of selecting selectivity, makes to demonstrate good catalytic performance in the reactions such as its isomerization at catalytic cracking, aromizing, dimethylbenzene, toluene disproportionation, methanol-to-olefins, alkylation, lubricating oil dewaxing, modifying lubricating oil.
The synthetic method of the ITQ-13 of current bibliographical information is few, and comparatively similar.General with hydroxide hexamethonium C6 for template, using silicon sol, silica gel, tetraethoxy etc. as silicon source, using germanium oxide as germanium source, the ITQ-13 molecular sieve synthesized in fluorine-containing system.It is long to there is crystallization time in traditional method, often reaches more than 10 days even several weeks; Synthesis cost is high, and template used dose of hydroxide hexamethonium C6 carries out ion-exchange via C6 and obtain, and template preparation cost is high; In addition, be generally pure silicon or high silicon structure by the ITQ-13 molecular sieve product of traditional method synthesis, the trivalent element such as boron, aluminium is difficult to directly introduce and causes that it is no acidic or acidity is more weak, and does not have catalytic activity.
US6,471,941 B1 disclose and make template with hydroxide hexamethonium C6, the method of pure silicon or silicon borosilicate molecular sieve is synthesized under hydrofluoric existence, and by aluminium isomorphous substitution boron aftertreatment preparation containing aluminium ITQ-13 molecular sieve, degree of crystallinity is not high, and can not directly synthesize containing aluminium ITQ-13 molecular sieve.Subsequently, a lot of researcher has also carried out much research to the synthetic method of ITQ-13, but is do template to synthesize with hydroxide hexamethonium C6 substantially, and degree of crystallinity is not high, is not easy aluminium, consuming time longer.USP6,723,300 and US App.20040087822 disclose and use silica gel as the method for silicon source water heat transfer total silicon ITQ-13.
The process of synthesis ITQ-13 is all generally obtain hydroxide hexamethonium C6 by carrying out ion-exchange containing the cationic halogen of hexamethonium C6 and hydroxide radical, and this process makes the preparation process of ITQ-13 complicated, and adds the synthesis cost of ITQ-13.CN 101274767 discloses and a kind ofly makes template with hydroxide hexamethonium C6, take white carbon black as the method that Al-ITQ-13 is directly synthesized in silicon source, and product degree of crystallinity is lower.Xiaolong Liu etc. (Microporous and Mesoporous Materials 156 (2012) 257 – 261) disclose a kind of method at xerogel synthesis ITQ-13 molecular sieve, hydroxide hexamethonium C6 is template, and synthesis cycle is at least 5 weeks, the time is longer.
Summary of the invention
The object of this invention is to provide a kind of low cost, prepare the method for ITQ-13 molecular sieve fast.
The concrete steps of preparation method of the present invention are:
(1) template is dissolved in deionized water, then adds promotor, alkali source, germanium dioxide, aluminium source, crystal seed, after it dissolves, add silicon source, fluorine source successively, stir and form uniform gel; Wherein silicon source is with SiO 2meter, each molar ratio of material consists of: template/SiO 2=0.3-3.6; SiO 2/ OH -=1-8, preferred 2-6; When using organic bases as template, alkali source addition is 0; GeO 2/ SiO 2=0-0.5, preferred 0.001-0.4; SiO 2/ Al 2o 3=20-3000, preferably 30-3000; F -/ SiO 2=0.3-3; The addition of promotor is the 0-10wt ﹪ of sieve and silica-sesquioxide total amount, is preferably 0.001wt ﹪-5 wt ﹪ of sieve and silica-sesquioxide; The add-on of crystal seed accounts for the 0-25wt% of material total amount, preferred 0.1wt ﹪-2wt ﹪.
(2) by prepared gel, at temperature 100-220 DEG C, preferably 120 DEG C-220 DEG C, carry out crystallization under autogenous pressure, crystallization time is 0.5 day-8 days, preferably 0.5 day-5 days; With cold water quenching, crystallization product fully washs after drying through deionized water and obtains molecular screen primary powder.
Described template is containing the cationic halogen of hexamethonium C6 or hydroxide hexamethonium C6, containing the cationic halogen of hexamethonium C6 specifically C6 or Chloor-hexaviet.
Described alkali source can be the mineral alkali such as sodium hydroxide or potassium hydroxide;
Described aluminium source can be ANN aluminium nitrate nonahydrate, aluminum isopropylate, sodium metaaluminate or Tai-Ace S 150;
Described silicon source can be silicon sol, white carbon black, gas-phase silica or tetraethoxy;
Described fluorine source can be Neutral ammonium fluoride or hydrofluoric acid;
Described promotor can be the nitrate such as iron nitrate, zinc nitrate, cupric nitrate, SODIUMNITRATE or magnesium nitrate.Be preferably iron nitrate or magnesium nitrate.
Effect of the present invention is:
1, the present invention be directed to traditional method crystallization time long, the present invention introduces promotor, and Molecular regulator sieve nucleation and growth speed, significantly shortens crystallization time.
2, the present invention synthesizes ITQ-13 molecular sieve containing in accelerator gel system, and to contain the cationic haloid of hexamethonium C6 for template, it is alkali source that sodium hydroxide replaces hydroxide hexamethonium C6 organic bases, also significantly reduces synthesis cost.
3, the present invention is by optimum synthesis gel proportioning, in conjunction with promotor nucleation, growth regulating effect, in synthetic system, directly introduces boron source, aluminium source, directly synthesizes the ITQ-13 molecular sieve that degree of crystallinity is higher, have acidity; The ITQ-13 molecular sieve finished product prepared has good degree of crystallinity and purity, and has larger specific surface area, and silica alumina ratio scope is very large, the potential value that this molecular sieve is applied for multiclass solid acid catalysis.
4, synthetic method of the present invention simply, easy, cheap fast, and shorten preparation and the production time of gel, which reduces loss unnecessary in process of production, reduce production cost.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 product A;
Fig. 2 is the XRD figure of the embodiment of the present invention 2 product B;
Fig. 3 is the XRD figure of the embodiment of the present invention 3 product C;
Fig. 4 is the XRD figure of the embodiment of the present invention 4 product D;
Fig. 5 is the XRD figure of the embodiment of the present invention 5 product E;
Fig. 6 is the XRD figure of the embodiment of the present invention 6 product F;
Fig. 7 is the XRD figure of the embodiment of the present invention 7 product G;
Fig. 8 is the XRD figure of the embodiment of the present invention 8 product H;
Fig. 9 is the XRD figure of the embodiment of the present invention 9 product I;
Figure 10 is the XRD figure of the embodiment of the present invention 10 product J;
Figure 11 is the XRD figure of the embodiment of the present invention 11 product K;
Figure 12 is the XRD figure of the embodiment of the present invention 12 product L;
Figure 13 is the XRD figure of the embodiment of the present invention 13 product M;
Figure 14 is the XRD figure of the embodiment of the present invention 14 product N;
Figure 15 is the XRD figure of the embodiment of the present invention 15 product O.
Embodiment
Embodiment 1:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, adds the promotor (0.3wt%) of 4ml, 0.4gNaOH, 0.05gGeO wherein 2, 0.2g NaAlO 2, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtains product A for 100 DEG C.The XRD of product A is shown in accompanying drawing 1, and as can be seen from the figure product A has the characteristic peak of ITQ-13, and degree of crystallinity is very high.
Embodiment 2:
First, the C6 taking 2g is dissolved in the deionized water of 6ml, adds the promotor of 0.01g, 0.35gNaOH, 0.15g GeO wherein 2, 0.30g NaAlO 2, add the silicon sol (30wt%) of 6.86ml after mixing, under stirring, add the Neutral ammonium fluoride of 0.7g, continue to stir until form uniform SiGe gel, be then transferred in tetrafluoroethylene reactor, 175 DEG C of static reactions 3 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.044GeO 2: 0.036Al 2o 3: SiO 2: 0.17R(C6): 0.55NH 4f: 18H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtains product B for 100 DEG C.The XRD of product B is shown in accompanying drawing 2, and as can be seen from the figure product B has the characteristic peak of ITQ-13, and degree of crystallinity is very high, does not have stray crystal.
Embodiment 3:
First, the C6 taking 2g is dissolved in the deionized water of 4ml, adds the promotor of 0.01g, the GeO of 0.35gNaOH, 0.15g wherein 2, 0.30g NaAlO 2, 0.1g crystal seed, add the silicon sol of 6.86ml after mixing, under stirring, add the Neutral ammonium fluoride of 0.8g, continue to stir until form uniform SiGe gel, be then transferred in tetrafluoroethylene reactor, 200 DEG C of static reactions 2 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.044GeO 2: 0.036Al 2o 3: SiO 2: 0.17R(C6): 0.63NH 4f: 15H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtains product C for 100 DEG C.The XRD of product C is shown in accompanying drawing 3, and as can be seen from the figure product C has the characteristic peak of ITQ-13, and degree of crystallinity is very high, does not have stray crystal.
Embodiment 4:
First, the C6 taking 3g is dissolved in the deionized water of 6ml, adds the NaAlO of 0.20g wherein 2, 0.35gNaOH, 0.15g GeO 2, 0.1g crystal seed, add the silicon sol of 6.86ml after mixing, under stirring, add the Neutral ammonium fluoride of 0.7g, continue to stir until form uniform gel, be then transferred in tetrafluoroethylene reactor, 175 DEG C of dynamic responses 5 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.024Al 2o 3: SiO 2: 0.25R(C6): 0.55NH 4f: 18H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtains product D for 100 DEG C.The XRD of product D is shown in accompanying drawing 4, and as can be seen from the figure product D has the characteristic peak of ITQ-13.
Embodiment 5:
First, the C6 taking 3g is dissolved in the deionized water of 6ml, adds the NaAlO of 0.20g wherein 2, 0.35gNaOH, 0.15g GeO 2, 0.1g crystal seed, add 2.14g gas-phase silica after mixing, under stirring, add the Neutral ammonium fluoride of 0.7g, continue to stir until form uniform gel, be then transferred in tetrafluoroethylene reactor, 175 DEG C of dynamic responses 5 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.024Al 2o 3: SiO 2: 0.25R(C6): 0.55NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product E for 100 DEG C.The XRD of product E is shown in accompanying drawing 5, and as can be seen from the figure product E has the characteristic peak of ITQ-13.
Embodiment 6:
First, the C6 taking 2g is dissolved in the deionized water of 6ml, adds the promotor of 0.01g, the NaAlO of 0.4gNaOH, 0.25g wherein 2, 0.15g GeO 2, 0.1g crystal seed, add the white carbon black of 2.4g after mixing, under stirring, add the Neutral ammonium fluoride of 0.7g, continue to stir until form uniform SiGe gel, be then transferred in tetrafluoroethylene reactor, 175 DEG C of static reactions 3 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.039GeO 2: 0.027Al 2o 3: SiO 2: 0.15R(C6): 0.49NH 4f: 9H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product F for 100 DEG C.The XRD of product F is shown in accompanying drawing 6, and as can be seen from the figure product F has the characteristic peak of ITQ-13, and degree of crystallinity is very high, does not have stray crystal.
Embodiment 7:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.4gNaOH, 0.10g 2, 0.2g NaAlO 2, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 5 days under 160 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product G for 100 DEG C.The XRD of product G is shown in accompanying drawing 7, and as can be seen from the figure product G has the characteristic peak of ITQ-13, but containing certain amorphous substance.
Embodiment 8:
First, the C6 taking 1g is dissolved in the deionized water of 6ml, adds the promotor of 0.01g, the NaAlO of 0.4gNaOH, 0.25g wherein 2, 0.15g GeO 2, add the silicon sol of 8.24ml after mixing, under stirring, add the Neutral ammonium fluoride of 0.7g, continue to stir until form uniform SiGe gel, be then transferred in tetrafluoroethylene reactor, 180 DEG C of static reactions 3 days.The mol ratio of reaction raw materials is 0.27NaOH: 0.039GeO 2: 0.027Al 2o 3: SiO 2: 0.075R(C6): 0.49NH 4f: 9H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product H for 100 DEG C.The XRD figure of product H is shown in Fig. 8, and as can be seen from the figure product H has the characteristic peak of ITQ-13, and well-crystallized.
Embodiment 9:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.4gNaOH, 0.05g 2, 0.2g NaAlO 2, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 1 day under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product I for 100 DEG C.The XRD figure of product I is shown in Fig. 9, and as can be seen from the figure product I has the characteristic peak of ITQ-13, containing certain amorphous substance.
Embodiment 10:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.4gNaOH, 0.10g 2, 0.2g NaAlO 2, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 7 days under 130 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product J for 100 DEG C.The XRD figure of product J is by Figure 10, and as can be seen from the figure product J has the characteristic peak of ITQ-13, containing a certain amount of amorphous substance.
Embodiment 11:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.4gNaOH, 0.10g 2, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product K for 100 DEG C.The XRD figure of product K is shown in Figure 11, and as can be seen from the figure product K has the characteristic peak of ITQ-13, does not have stray crystal, well-crystallized.
Embodiment 12:
First, the Chloor-hexaviet solid taking 1.51g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.4gNaOH, 0.05g 2, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: SiO 2: 0.17 R(Chloor-hexaviet): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product L for 100 DEG C.The XRD figure of product L is shown in Figure 13, and as can be seen from the figure product L has the characteristic peak of ITQ-13.
Embodiment 13:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add the GeO of 0.56gKOH, 0.05g 2, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.60ml hydrofluoric acid (40wt%), continue to stir until form uniform SiGe gel, be then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: SiO 2: 0.17 R(C6): 0.59HF: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product M for 100 DEG C.The XRD figure of product M is shown in Figure 13, and as can be seen from the figure product M has the characteristic peak of ITQ-13.
Embodiment 14:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add 0.4gNaOH, 0.05gGeO 2, 0.603g ANN aluminium nitrate nonahydrate, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product N for 100 DEG C.The XRD figure of product N is shown in Figure 14, and as can be seen from the figure product N has the characteristic peak of ITQ-13.
Embodiment 15:
First, the C6 solid taking 2g is dissolved in the deionized water of 2ml, and then the promotor (0.3wt%) adding 4ml wherein add 0.4gNaOH, 0.05gGeO 2, 0.50g aluminum isopropylate, 0.1g crystal seed, mix and slowly add 2.14g white carbon black afterwards, under agitation add 0.75gNH 4f, continues to stir until form uniform SiGe gel, is then transferred in stainless steel cauldron, static crystallization 2 days under 180 DEG C of conditions.The mol ratio of reaction raw materials is 0.30NaOH: 0.015GeO 2: 0.024Al 2o 3: SiO 2: 0.17 R(C6): 0.59NH 4f: 10H 2o.Question response still is cooled to room temperature, by product suction filtration, is washed with water to neutrality, dries and obtain product O for 100 DEG C.The XRD figure of product O is shown in Figure 15, and as can be seen from the figure product O has the characteristic peak of ITQ-13.

Claims (6)

1. a method for low cost Fast back-projection algorithm ITQ-13 molecular sieve, is characterized in that comprising the steps:
(1) template is dissolved in deionized water, then adds promotor, alkali source, germanium dioxide, aluminium source, crystal seed, after it dissolves, add silicon source, fluorine source successively, stir and form uniform gel; Wherein silicon source is with SiO 2meter, each molar ratio of material consists of: template/SiO 2=0.3-3.6; SiO 2/ OH -=2-6; GeO 2/ SiO 2=0.001-0.4; SiO 2/ Al 2o 3=30-3000; F -/ SiO 2=0.3-3; The addition of promotor is 0.001wt ﹪-5 wt ﹪ of sieve and silica-sesquioxide total amount; The add-on of crystal seed accounts for the 0.1wt ﹪-2wt ﹪ of material total amount;
(2) by prepared gel, at crystallization temperature 100-220 DEG C, carry out crystallization under autogenous pressure, crystallization time is 0.5 day-8 days; With cold water quenching, crystallization product fully washs after drying through deionized water and obtains molecular screen primary powder;
Described template is for containing the cationic halogen of hexamethonium C6;
Described silicon source is silicon sol, gas-phase silica or tetraethoxy; Aluminium source is sodium metaaluminate or Tai-Ace S 150;
Described promotor is iron nitrate, zinc nitrate, cupric nitrate, SODIUMNITRATE or magnesium nitrate.
2. the method for a kind of low cost Fast back-projection algorithm ITQ-13 molecular sieve as claimed in claim 1, is characterized in that described is C6 or Chloor-hexaviet containing the cationic halogen of hexamethonium C6.
3. the method for a kind of low cost Fast back-projection algorithm ITQ-13 molecular sieve as claimed in claim 1, is characterized in that described alkali source is sodium hydroxide or potassium hydroxide mineral alkali.
4. the method for a kind of low cost Fast back-projection algorithm ITQ-13 molecular sieve as claimed in claim 1, is characterized in that described fluorine source is Neutral ammonium fluoride or hydrofluoric acid.
5. the method for a kind of low cost Fast back-projection algorithm ITQ-13 molecular sieve as claimed in claim 1, is characterized in that described promotor is iron nitrate or magnesium nitrate.
6. the method for a kind of low cost Fast back-projection algorithm ITQ-13 molecular sieve as claimed in claim 1, it is characterized in that crystallization temperature 120 DEG C-220 DEG C in described step (2), crystallization time is 0.5 day-5 days.
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CN106542546B (en) * 2015-09-16 2019-04-05 中国石油大学(北京) Little crystal grain multi-stage porous ITH structure Si-Al molecular sieve and the preparation method and application thereof
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CN106698456B (en) * 2017-01-06 2018-09-21 浙江大学 The method of the line style polyquaternary amine alkali organic formwork agent one-step synthesis method molecular sieves of ITQ-13 containing aluminium
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