CN104891527A - Method for synthesizing mordenite - Google Patents
Method for synthesizing mordenite Download PDFInfo
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- CN104891527A CN104891527A CN201510282947.0A CN201510282947A CN104891527A CN 104891527 A CN104891527 A CN 104891527A CN 201510282947 A CN201510282947 A CN 201510282947A CN 104891527 A CN104891527 A CN 104891527A
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- sio
- piperazine
- tetraethyl
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Abstract
The invention relates to the field of catalytic material synthesis and particularly relates to a method for synthesizing mordenite by adopting N, N, N', N'-tetraethyl piperazine double-quaternary ammonium hydroxide as a structure-directing agent. The method comprises the following steps: uniformly mixing a silicon source, an aluminum source, inorganic base and the structure-directing agent N, N, N', N'-tetraethyl piperazine double-quaternary ammonium hydroxide R with water to obtain a reaction mixture; performing hydrothermal crystallization on the reaction mixture for 20-150 hours at 120-200 DEG C; cooling to room temperature; and filtering, washing and drying to obtain mordenite. According to the method for synthesizing mordenite, provided by the invention, the silica-alumina ratio range of gel in synthesis is wide and can change between 10 and 150, and the synthesized mordenite can obtain a relatively wide silica-alumina ratio; and particularly, by adopting the method provided by the invention, the mordenite of which the silica-alumina ratio is greater than 60 can be synthesized in relatively short time, and seed crystals are not needed in the preparation process.
Description
Technical field
The present invention relates to catalytic material synthesis field, specifically one take the two quaternary ammonium hydroxide of N, N, N', N'-tetraethyl-piperazine as the method for the synthesizing flokite of structure directing agent.
Background technology
Mordenite is a class supersiliceous zeolite, belong to orthorhombic structure, have two-dimensional channel structure, octatomic ring (0.34nm × 0.48nm and the 0.26nm × 0.57nm) duct of the twelve-ring main aperture road being 0.67nm × 0.70nm by port size and two distortions is formed.This zeolite can be used as the catalyzer of many important catalyzed reactions, as hydrocracking, hydroisomerizing, alkylation, reformation, dewaxing, is especially used as the catalyzer of synthesizing dimethylamine.
Mordenite divides natural and synthesis two classes.Natural mordenite zeolite purity is not high enough, pore structure cannot regulate, the mordenite structure of synthetic is adjustable, catalytic performance is excellent, 1948, Barrer sodium carbonate is mineralizer, make mixing silicic acid gel and sodium aluminate aqueous solution hydrothermal crystallizing at 265 ~ 295 DEG C, synthesize mordenite first.At present mainly with water glass or silicon sol for silicon source adopts without amine hydrothermal method synthesizing flokite, the mordenite silica alumina ratio usually synthesized is close with natural mordenite zeolite, can only synthesize the mordenite of silica alumina ratio 9 ~ 11.The silica alumina ratio improving mordenite effectively can strengthen its thermostability and solid acid character, and then improve its performance in catalyzed reaction, the method that raising silica alumina ratio often adopts has acid extraction, roasting-acid extraction, high-temperature vapor process-acid extraction and complex compound dealuminzation etc., not only operating process is long, and often produces lattice imperfection and non-skeleton fragment to some extent while de-framework aluminum.
In order to solve Problems existing in aforesaid method, it is raw material that US 3677973 discloses with water glass, aluminium salt, sulfuric acid, ammoniacal liquor etc., the high silicon alumino silica gel that silica alumina ratio is 15 ~ 30 is obtained through plastic, washing, drying, then hydro-oxidation sodium crystallization synthesizing flokite, but prepare high silicon alumino silica gel process complexity, long flow path, more equipment need be used.EP 0040104 discloses and than the mordenite being 17.4 ~ 25.8, but wherein there is significant quantity stray crystal with water glass, aluminium salt crystallization synthesizing Si-Al under sodium-chlor exists.It is raw material that CN 1050011A discloses with water glass, aluminium salt or aluminate etc., synthesizes the mordenite of silica alumina ratio 15 ~ 30, but need the amount adding crystal seed close to 10% of final product under liquefied ammonia or liquefied ammonia-sodium-chlor exist.
Under the condition adding Organic structure directing agent, significantly can improve the silica alumina ratio of direct synthetic product mordenite.US 4205052 discloses and makes structure directing agent synthesizing flokite with ethylpyridine, US 4390457 discloses and makes structure directing agent synthesizing flokite with diamino-pyridine, US 4585640 discloses and makes structure directing agent synthesizing flokite by methyl violet, US 5173282 discloses and makes structure directing agent synthesizing flokite with 1-aminomethyl-hexalin, EP 80615 discloses and makes structure directing agent synthesizing flokite with bromination diethyl piperidines, CN 1147479A discloses with oxygen-containing organic compound, as oxyamine, hydroxylated diamines, structure directing agent synthesizing flokite made by sodium-chlor-trolamine, CN 1328961A discloses with hexamethylene imine, 1, 4-phenodiazine suberane, heptamethylene imines, suberane amine, hexamethylene alkanamine makes knots structure directed agents synthesizing flokite.Prepare the structure directing agent that mordenite adopts and also have tetraethyl-ammonium salt, Tributylamine, triethylamine, Diisopropylamine, isobutylamine, diisobutylamine, tert-Octylamine, neo-pentyl amine, 1,2-diamino-cyclohexane etc.During with aforesaid method synthesizing flokite, total shortcoming to add crystal seed, when the silica alumina ratio that feeds intake is more than 30, easily generates other stray crystal phase.
Summary of the invention
The present invention aim to provide a kind of with the two quaternary ammonium hydroxide of N, N, N', N'-tetraethyl-piperazine for structure directing agent, without the need to adding crystal seed, not easily generate stray crystal, crystallization time is short and have the method for the synthesizing flokite of wider silica alumina ratio.
The present invention is achieved by the following technical solutions: a kind of method of synthesizing flokite, the steps include: silicon source, aluminium source, mineral alkali and structure directing agent N, N, N', the two quaternary ammonium hydroxide of N'-tetraethyl-piperazine and water mix preparation feedback mixture, and reaction mixture hydrothermal crystallizing 20 ~ 150 hours at 120 ~ 200 DEG C, is then cooled to room temperature, filtration, washing, drying, obtain mordenite;
The mol ratio of described reaction mixture is SiO
2/ Al
2o
3=10 ~ 150, H
2o/SiO
2=10 ~ 60, OH
-/ SiO
2=0.1 ~ 2.0, M/SiO
2=0.05 ~ 1.0, R/SiO
2=0.025 ~ 0.5, wherein M represents basic metal, R representative structure directed agents N, the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine.
As preferred technical scheme, the mol ratio of described reaction mixture is SiO
2/ Al
2o
3=15 ~ 90, H
2o/SiO
2=15 ~ 45, OH
-/ SiO
2=0.2 ~ 1.0, M/SiO
2=0.1 ~ 0.5, R/SiO
2=0.05 ~ 0.25.
As preferred technical scheme, the temperature of described hydrothermal crystallizing is 140 ~ 180 DEG C.
As preferred technical scheme, the time of described hydrothermal crystallizing is 40 ~ 120 hours.
As preferred technical scheme, described silicon is in a steady stream from silicon sol, silica gel, water glass or white carbon black.Described aluminium is in a steady stream from sodium aluminate, Tai-Ace S 150, aluminium hydroxide or aluminum isopropylate.Described mineral alkali is derived from sodium hydroxide or potassium hydroxide.
As preferred technical scheme, described structure directing agent N, N, the preparation method of the two quaternary ammonium hydroxide R of N', N'-tetraethyl-piperazine is: by N, N – diethyl piperazine dissolved in acetone, add excessive monobromethane, stirred at ambient temperature, after 10 ~ 22 hours, refluxes 1 ~ 3 hour, cooled and filtered goes out solid, through acetone, washed with diethylether, and vacuum-drying, obtain dibrominated N, N, N', N'-tetraethyl-piperazine; Dissolve dibrominated N in deionized water again, N, N', N'-tetraethyl-piperazine, adds excessive silver suboxide, at room temperature stirs and spends the night, filter after stirring, and obtains the aqueous solution containing the two quaternary ammonium hydroxide of N, N, N', N'-tetraethyl-piperazine.
The basic metal of alkali metal source in step of the present invention in mineral alkali, or mineral alkali and silicon source are or/and basic metal in aluminium source.
The method principal character compared with prior art of a kind of synthesizing flokite provided by the present invention is that the method makes structure directing agent synthesizing flokite with the two quaternary ammonium hydroxide of N, N, N', N'-tetraethyl-piperazine.Gel silica alumina ratio wide ranges in synthesis, can change between 10 ~ 150, and the mordenite of synthesis can have wider silica alumina ratio, especially employing the inventive method can synthesize the mordenite that silica alumina ratio is greater than 60 within a short period of time, and does not need in preparation process to add crystal seed.
Accompanying drawing explanation
X-ray diffraction (XRD) figure of the mordenite of Fig. 1 synthesized by the embodiment of the present invention 1.
X-ray diffraction (XRD) figure of the mordenite of Fig. 2 synthesized by the embodiment of the present invention 2.
X-ray diffraction (XRD) figure of the mordenite of Fig. 3 synthesized by the embodiment of the present invention 3.
Embodiment
Below by specific embodiment, the present invention will be further described, but do not limit application of the present invention.
Embodiment 1
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
By 14.22g (0.10 mole) N, N – diethyl piperazine dissolved at 100 milliliters of acetone, add excessive monobromethane (32.69g, 0.3 mole), stirred at ambient temperature is after 15 hours, and reflux 1 hour, cooled and filtered goes out solid, acetone, washed with diethylether, vacuum-drying, obtains 33.12g (0.092 mole) dibrominated N, N, N', N'-tetraethyl-piperazine.Its chemical structure is confirmed through NMR spectrum, IR spectrum and ultimate analysis.In 300g deionized water, dissolve 33.12g (0.092 mole) dibrominated N again, N, N', N'-tetraethyl-piperazine, add excessive silver suboxide (Ag
2o) 27.71g (0.12 mole), at room temperature stirs this mixture and spends the night.After stirring, filtering mixt, obtains N, the two quaternary ammonium hydroxide aqueous solution of N, N', N'-tetraethyl-piperazine, then 50 DEG C of rotary evaporations 2 hours, passes through 0.1molL
-1hCI measures the concentration of this solution, and in final solution, the two quaternary ammonium hydroxide concentration of N, N, N', N'-tetraethyl-piperazine is 1.36 × 10
-3mol/g.
The preparation of II, mordenite
By 0.804g sodium aluminate (Na
2o 34.3wt%, Al
2o
342.3wt%), 0.445g sodium hydroxide, 7.36g N, the two quaternary ammonium alkali solution (1.36 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 30.98g water, be stirred to dissolving, under then stirring, instillation 10.01g silicon sol solution (SiO
240wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=20, H
2o/SiO
2=35, OH
-/ SiO
2=0.6, Na/SiO
2=0.3, R/SiO
2=0.15.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 145 DEG C, crystallization was taken out after 72 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 1.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 16.8.
Embodiment 2
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
By 17.04g (0.12 mole) N, N – diethyl piperazine dissolved at 90 milliliters of acetone, add excessive monobromethane (38.14g, 0.35 mole), stirred at ambient temperature is after 10 hours, and reflux 2 hours, cooled and filtered goes out solid, acetone, washed with diethylether, vacuum-drying, obtains 40.17g (0.112 mole) dibrominated N, N, N', N'-tetraethyl-piperazine.Its chemical structure is confirmed through NMR spectrum, IR spectrum and ultimate analysis.In 400g deionized water, dissolve 40.17g (0.112 mole) dibrominated N again, N, N', N'-tetraethyl-piperazine, add excessive silver suboxide (Ag
2o) 34.65g (0.15 mole), at room temperature stirs this mixture and spends the night.After stirring, filtering mixt, obtains N, the two quaternary ammonium hydroxide aqueous solution of N, N', N'-tetraethyl-piperazine, then 60 DEG C of rotary evaporations 2.5 hours, passes through 0.1molL
-1hCI measures the concentration of this solution, and in final solution, the two quaternary ammonium hydroxide concentration of N, N, N', N'-tetraethyl-piperazine is 1.52 × 10
-3mol/g.
The preparation of II, mordenite
By 0.669g sodium aluminate (Na
2o 34.3wt%, Al
2o
342.3wt%), 0.637g sodium hydroxide, the two quaternary ammonium alkali solution (1.52 × 10 of 9.87gN, N, N', N'-tetraethyl-piperazine
-3mol/g), add in 31.14g water, be stirred to dissolving, under then stirring, instillation 12.5g silicon sol solution (SiO
240wt%), add rear continuation stirring and make it to mix for 30 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=30, H
2o/SiO
2=30, OH
-/ SiO
2=0.64, Na/SiO
2=0.28, R/SiO
2=0.18.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 150 DEG C, crystallization was taken out after 80 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 2.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 26.2.
Embodiment 3
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
By 25.56g (0.18 mole) N, N – diethyl piperazine dissolved at 150 milliliters of acetone, add excessive monobromethane (54.48g, 0.5 mole), stirred at ambient temperature is after 22 hours, and reflux 1.5 hours, cooled and filtered goes out solid, acetone, washed with diethylether, vacuum-drying, obtains 58.32g (0.162 mole) dibrominated N, N, N', N'-tetraethyl-piperazine.Its chemical structure is confirmed through NMR spectrum, IR spectrum and ultimate analysis.In 600g deionized water, dissolve 58.32g (0.162 mole) dibrominated N again, N, N', N'-tetraethyl-piperazine, add excessive silver suboxide (Ag
2o) 46.18g (0.2 mole), at room temperature stirs this mixture and spends the night.After stirring, filtering mixt, obtains N, the two quaternary ammonium hydroxide aqueous solution of N, N', N'-tetraethyl-piperazine, then 60 DEG C of rotary evaporations 2 hours, passes through 0.1molL
-1hCI measures the concentration of this solution, and in final solution, the two quaternary ammonium hydroxide concentration of N, N, N', N'-tetraethyl-piperazine is 1.45 × 10
-3mol/g.
The preparation of II, mordenite
By 0.603g sodium aluminate (Na
2o 34.3wt%, Al
2o
342.3wt%), 0.734g sodium hydroxide, the two quaternary ammonium alkali solution (1.45 × 10 of 12.43gN, N, N', N'-tetraethyl-piperazine
-3mol/g), add in 27.78g water, be stirred to dissolving, under then stirring, instillation 15.02g silicon sol solution (SiO
240wt%), add rear continuation stirring and make it to mix for 30 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=40, H
2o/SiO
2=25, OH
-/ SiO
2=0.61, Na/SiO
2=0.25, R/SiO
2=0.18.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 150 DEG C, crystallization was taken out after 60 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample is shown in accompanying drawing 3.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 34.2.
Embodiment 4
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
By 31.31g (0.22 mole) N, N – diethyl piperazine dissolved at 200 milliliters of acetone, add excessive monobromethane (76.28g, 0.7 mole), stirred at ambient temperature is after 18 hours, and reflux 3 hours, cooled and filtered goes out solid, acetone, washed with diethylether, vacuum-drying, obtains 72.36g (0.201 mole) dibrominated N, N, N', N'-tetraethyl-piperazine.Its chemical structure is confirmed through NMR spectrum, IR spectrum and ultimate analysis.In 800g deionized water, dissolve 72.36g (0.201 mole) dibrominated N again, N, N', N'-tetraethyl-piperazine, add excessive silver suboxide (Ag
2o) 57.73g (0.25 mole), at room temperature stirs this mixture and spends the night.After stirring, filtering mixt, obtains N, the two quaternary ammonium hydroxide aqueous solution of N, N', N'-tetraethyl-piperazine, then 50 DEG C of rotary evaporations 3 hours, passes through 0.1molL
-1hCI measures the concentration of this solution, and in final solution, the two quaternary ammonium hydroxide concentration of N, N, N', N'-tetraethyl-piperazine is 1.64 × 10
-3mol/g.
The preparation of II, mordenite
By 0.603g sodium aluminate (Na
2o 34.3wt%, Al
2o
342.3wt%), 0.534g sodium hydroxide, the two quaternary ammonium alkali solution (1.64 × 10 of 9.15gN, N, N', N'-tetraethyl-piperazine
-3mol/g), add in 48.36g water, be stirred to dissolving, under then stirring, slowly add 6.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 30 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=40, H
2o/SiO
2=30, OH
-/ SiO
2=0.5, Na/SiO
2=0.2, R/SiO
2=0.15.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 150 DEG C, crystallization was taken out after 70 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 35.6.
Embodiment 5
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 1.
The preparation of II, mordenite
By 1.11g Tai-Ace S 150 (Al
2(SO
4)
318H
2o), 0.80g sodium hydroxide, 16.18g N, the two quaternary ammonium alkali solution (1.36 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 60.97g water, be stirred to dissolving, under then stirring, slowly add 6.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=60, H
2o/SiO
2=40, OH
-/ SiO
2=0.64, Na/SiO
2=0.2, R/SiO
2=0.22.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 170 DEG C, crystallization was taken out after 90 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 49.8.
Embodiment 6
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 1.
The preparation of II, mordenite
By 0.84g Tai-Ace S 150 (Al
2(SO
4)
318H
2o), 0.88g sodium hydroxide, 14.71g N, the two quaternary ammonium alkali solution (1.36 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 43.97g water, be stirred to dissolving, under then stirring, slowly add 6.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=80, H
2o/SiO
2=30, OH
-/ SiO
2=0.62, Na/SiO
2=0.22, R/SiO
2=0.2.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 160 DEG C, crystallization was taken out after 100 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 62.7.
Embodiment 7
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 1.
The preparation of II, mordenite
By 6.66g Tai-Ace S 150 (Al
2(SO
4)
318H
2o), 2.00g sodium hydroxide, 18.38g N, the two quaternary ammonium alkali solution (1.36 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 14.47g water, be stirred to dissolving, under then stirring, slowly add 6.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=10, H
2o/SiO
2=15, OH
-/ SiO
2=1.0, Na/SiO
2=0.5, R/SiO
2=0.25.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 120 DEG C, crystallization was taken out after 40 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 8.7.
Embodiment 8
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 1.
The preparation of II, mordenite
By 2.24g aluminum isopropylate, 4.68g potassium hydroxide, 30.88g N, the two quaternary ammonium alkali solution (1.36 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 46.63g water, be stirred to dissolving, under then stirring, slowly add 5.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=15, H
2o/SiO
2=45, OH
-/ SiO
2=2.0, K/SiO
2=1.0, R/SiO
2=0.5.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 140 DEG C, crystallization was taken out after 120 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 11.5.
Embodiment 9
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 2.
The preparation of II, mordenite
By 0.37g aluminum isopropylate, 0.17g sodium hydroxide, 1.38g N, the two quaternary ammonium alkali solution (1.52 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 89.11g water, be stirred to dissolving, under then stirring, slowly add 5.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 30 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=90, H
2o/SiO
2=60, OH
-/ SiO
2=0.1, Na/SiO
2=0.05, R/SiO
2=0.025.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 180 DEG C, crystallization was taken out after 150 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 64.5.
Embodiment 10
I, structure directing agent N, the preparation of the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine
With embodiment 2.
The preparation of II, mordenite
By 0.22g aluminum isopropylate, 0.334g sodium hydroxide, 2.76g N, the two quaternary ammonium alkali solution (1.52 × 10 of N, N', N'-tetraethyl-piperazine
-3mol/g), add in 13.25g water, be stirred to dissolving, under then stirring, slowly add 5.01g white carbon black (SiO
299.9wt%), add rear continuation stirring and make it to mix for 40 minutes, the composition (ratio) of reaction mixture is SiO
2/ Al
2o
3=150, H
2o/SiO
2=10, OH
-/ SiO
2=0.2, Na/SiO
2=0.1, R/SiO
2=0.05.Then above-mentioned reaction mixture is sealed in band teflon-lined 100ml stainless steel autoclave, at 200 DEG C, crystallization was taken out after 20 hours, reactor drops to room temperature rapidly, filter out solid product, and with deionized water wash to neutral, 100 DEG C of dried overnight, obtain product, verify as the crystal phase structure of mordenite through X-ray diffraction (XRD), X-ray diffraction (XRD) figure of sample and accompanying drawing 3 similar, therefore no longer list.Fluorometry measures the SiO of above-mentioned product
2/ Al
2o
3be 61.4.
Claims (8)
1. a method for synthesizing flokite, is characterized in that, the steps include:
By silicon source, aluminium source, mineral alkali and structure directing agent N, N, N', the two quaternary ammonium hydroxide of N'-tetraethyl-piperazine and water mix preparation feedback mixture, reaction mixture hydrothermal crystallizing 20 ~ 150 hours at 120 ~ 200 DEG C, then be cooled to room temperature, filtration, washing, drying, obtain mordenite;
The mol ratio of described reaction mixture is SiO
2/ Al
2o
3=10 ~ 150, H
2o/ SiO
2=10 ~ 60, OH
-/ SiO
2=0.1 ~ 2.0, M/SiO
2=0.05 ~ 1.0, R/SiO
2=0.025 ~ 0.5, wherein M represents basic metal, R representative structure directed agents N, the two quaternary ammonium hydroxide of N, N', N'-tetraethyl-piperazine.
2. the method for synthesizing flokite according to claim 1, is characterized in that, the mol ratio of described reaction mixture is SiO
2/ Al
2o
3=15 ~ 90, H
2o/ SiO
2=15 ~ 45, OH
-/ SiO
2=0.2 ~ 1.0, M/SiO
2=0.1 ~ 0.5, R/SiO
2=0.05 ~ 0.25.
3. the method for synthesizing flokite according to claim 1, is characterized in that, the temperature of described hydrothermal crystallizing is 140 ~ 180 DEG C.
4. the method for synthesizing flokite according to claim 1, is characterized in that, the time of described hydrothermal crystallizing is 40 ~ 120 hours.
5. the method for synthesizing flokite according to claim 1, is characterized in that, described silicon is in a steady stream from silicon sol, silica gel, water glass or white carbon black.
6. the method for synthesizing flokite according to claim 1, is characterized in that, described aluminium is in a steady stream from sodium aluminate, Tai-Ace S 150, aluminium hydroxide or aluminum isopropylate.
7. the method for synthesizing flokite according to claim 1, is characterized in that, described mineral alkali is derived from sodium hydroxide or potassium hydroxide.
8. the method for the synthesizing flokite according to claim any described in claim 1 to 7, is characterized in that, described structure directing agent N, the preparation method of the two quaternary ammonium hydroxide R of N, N', N'-tetraethyl-piperazine is: by N, in acetone, add excessive monobromethane, stirred at ambient temperature is after 10 ~ 22 hours for N – diethyl piperazine dissolved, reflux 1 ~ 3 hour, cooled and filtered goes out solid, through acetone, washed with diethylether, vacuum-drying, obtains dibrominated N, N, N', N'-tetraethyl-piperazine; Dissolve dibrominated N in deionized water again, N, N', N'-tetraethyl-piperazine, adds excessive silver suboxide, at room temperature stirs and spends the night, filter after stirring, and obtains the aqueous solution containing the two quaternary ammonium hydroxide of N, N, N', N'-tetraethyl-piperazine.
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| CN111099634B (en) * | 2018-10-25 | 2021-06-22 | 中国石油化工股份有限公司 | SCM-21 metal phosphoaluminate and preparation method thereof |
| CN114364637A (en) * | 2019-08-27 | 2022-04-15 | 埃克森美孚研究工程公司 | Zeolite synthesis using bis-quaternary ammonium structure directing agents |
| CN114364637B (en) * | 2019-08-27 | 2024-03-19 | 埃克森美孚科技工程公司 | Zeolite synthesis using dual quaternary ammonium structure directing agents |
| CN114516642A (en) * | 2020-11-18 | 2022-05-20 | 中国科学院大连化学物理研究所 | MOR molecular sieve, and preparation method and application thereof |
| CN114644344A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Mordenite and preparation method thereof |
| CN114644344B (en) * | 2020-12-18 | 2024-03-12 | 中国石油化工股份有限公司 | Mordenite and preparation method thereof |
| CN113603109A (en) * | 2021-08-05 | 2021-11-05 | 肯特催化材料股份有限公司 | Preparation method of mordenite and mordenite with high silica-alumina ratio prepared by preparation method |
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