CN1843915A - Method for synthesizing high-silicon mordenite in the absence of amine - Google Patents
Method for synthesizing high-silicon mordenite in the absence of amine Download PDFInfo
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- CN1843915A CN1843915A CN 200610050623 CN200610050623A CN1843915A CN 1843915 A CN1843915 A CN 1843915A CN 200610050623 CN200610050623 CN 200610050623 CN 200610050623 A CN200610050623 A CN 200610050623A CN 1843915 A CN1843915 A CN 1843915A
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- mordenite
- sio
- crystallization
- amine
- silicon
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Abstract
The invention discloses a method for preparing high silica mordenite without amine. The method employs silicon, alumina and deionized water as raw amaterial, and employs polyatomic alcohol as addictive; proceeds thermal crystallization in steeless autoclave interlined with politef, the crystallization temperature is 120-200 Deg. C and time is 12-240 hours; sucts, washes and dried the mixture got after crystallization and gets high silia mordenite with molar proportion of SiO2/Al2O3 is 15-30:1. The invention employs pentaerythrite which is cheap, abundant and environment-friendly to replace the organic amine which is dear and environment-pollutant, and uses no inorganic acid or alkali corrosive to device. The pentaerythrite is helpful for generation of high silica mordenite and for reducing crystallization time. The invention is characterized by low production cost, high output, simple process and environment-friendly.
Description
Technical field
The invention belongs to synthesis method of zeolite molecular sieve, especially relate to a kind of no amine method for preparing high silica mordenite.
Background technology
Mordenite can be used as sorbent material and is used for gas or liquid separation; Simultaneously also can be used as a kind of good catalyzer, be used for catalytic processs such as catalytic cracking, alkylation, isomerization, disproportionation and transalkylation, reformation, dewaxing pour point depression, methyl alcohol amination.
Natural or early stage synthetic mordenite, its SiO
2/ Al
2O
3Mol ratio is usually about 10.But, for some reaction, for example, toluene disproportionation and transalkylation reaction, high silicon (SiO
2/ Al
2O
3Mol ratio＞10) mordenite presents higher catalytic activity, selectivity and stability.
The preparation high silicon mordenite generally has two approach at present: the one, and with low silicon (SiO
2/ Al
2O
3Mol ratio≤10) mordenite is a starting raw material, handle through one or more dealumination process, as acid extraction, roasting-acid extraction, high-temperature vapor processing-acid extraction and complex compound dealuminzation etc., produce high silicon mordenite, its shortcoming is a complex operation, time-consuming, and when taking off framework aluminum, often produce lattice imperfection and non-skeleton fragment to some extent, cause the identical SiO of gained
2/ Al
2O
3The mordenite of mol ratio is showing evident difference aspect physicochemical property and the catalytic activity.The 2nd, adopting organic amine is " template " or " structure directing agent ", directly synthesizing high silicon content mordenite.The organic amine of having reported in existing document or patent mainly contains 5 classes: (1) straight chain or cyclic alkyl amine, as benzyl trimethyl amine, tetraethyl-ammonium salt, Tributylamine, triethylamine, Diisopropylamine, isobutylamine, diisobutylamine, tert-Octylamine, neopentyl amine, hexahydroaniline, cycloheptylamine, 1,2-diamino hexahydroaniline, 2-or 4-methyl cyclohexylamine, tetramethyl-ethyl diamines, R
4N
+-spiralization compound etc.; (2) oxygen-containing organic compound, as oxyamine, hydroxyl diamines, sodium-chlor-trolamine, contain 1 or 2 Sauerstoffatom saturated cyclic amines, with ether (particularly cyclic ethers class), thanomin, the saturated low-carbon alcohol of IV family metal complex; (3) nitrogen-containing heterocycle compound is as piperidines, bromination diethyl piperidines, ethylpyridine, 2-aminopyridine, methyl violet etc.; (4) alkylsulfonate; (5) ionene of nitrogenous positive ion or its ionomer etc.The shortcoming of using the organic amine synthesizing high silicon content mordenite is that organic amine source difficulty, price are high, also may cause environmental pollution simultaneously.
Adopt the shortcoming that organic amine brought in order to overcome, some documents or patent report use non-amine method, promptly do not use organic amine to be additive, prepare the example of high silicon mordenite.
In US3677973 (1972), proposed a kind of with aqueous ammonia to replace organic amine method for preparing high silica mordenite.Make SiO with raw materials such as water glass, aluminium salt, sulfuric acid, ammoniacal liquor through becoming glue, washing, drying
2/ Al
2O
3Mol ratio is 15～30 high silicon pure aluminium silicate, then the synthetic SiO that obtains of hydro-oxidation sodium crystallization
2/ Al
2O
3Mol ratio is 15～30 high silicon mordenite, and the shortcoming of this method is the high silicon alumino silica gel process complexity of preparation, long flow path, needs more equipment.
In EP0040104 (1981) and JP58088119 (1983), reported raw materials such as water glass, Tai-Ace S 150, sulfuric acid in the presence of sodium-chlor, crystallization is synthesized SiO
2/ Al
2O
3Mol ratio is the method for 17.4～25.8 high silicon mordenite, but XRD detects and shows the stray crystal that wherein exists significant quantity.
(Zeolites, 1989 (6): 30), with raw materials such as amorphous silica gel, aluminium salt, alkali, crystallization can obtain SiO under certain condition according to Itabashi etc.
2/ Al
2O
3Mol ratio is about 15 mordenite, but the silica alumina ratio that feeds intake must be very high.
In Chinese patent CN1050011 (1991) and CN1490245 (2004), method for preparing high silica mordenite in the presence of liquefied ammonia or liquefied ammonia-sodium-chlor has been proposed, need to add crystal seed simultaneously.
In Chinese patent CN1201758 (1998), a kind of method of molding synthesizing flokite has been proposed, promptly earlier with silicon source, aluminium source, sodium source and water according to SiO
2/ Al
2O
3Mol ratio is 15～50, Na
2O/SiO
2Mol ratio is 0～1.0 mixing, is shaped, and is placed in the basic solution Na of control solution through roasting
2O/SiO
2Mol ratio is 10～50, and heating crystallization adds crystal seed amount 1%～10%, the highest SiO of gained mordenite
2/ Al
2O
3Mol ratio is 50.
In Chinese patent CN1230518 (1999), proposed a kind of with anion surfactant replacement organic amine method for preparing high silica mordenite.In Chinese patent CN1198404 (1998) and CN1257831 (2000), the fluorine-containing system method for preparing high silica mordenite of a kind of employing has been proposed.In Chinese patent CN1243100 (2000), a kind of full-inorganic system method for preparing high silica mordenite has been proposed.In Chinese patent CN1463921 (2003), having proposed with the hexanolactam is the template method for preparing high silica mordenite.
In Chinese patent CN1673081 (2005), provide vapor phase rotation crystalline substance (vapor phase transmission method, i.e. VPT) in a kind of full-inorganic system to prepare the method for high silicon mordenite.This method is that the mixture of the oxide source that will contain alkali metal source, trivalent element, tetradic oxide source, water composition is made gel, obtain dried glue through dehydration, carry out autogiration crystal reaction at water vapour in mutually, after cooling, washing, suction filtration, oven dry, obtain SiO
2/ Al
2O
3Mol ratio is 20～40 mordenite.
From the patent of above-mentioned introduction or document as can be seen, present non-amine method synthesizing high silicon content mordenite, though do not use poisonous and expensive organic amine, but employed additive such as inorganic ammonia, anion surfactant, hexanolactam, fluorochemical etc., also exist such as environment had pollution, cost an arm and a leg, problems such as quality product is low, complex process; And most of the needs used mineral acid or mineral alkali, causes problems such as environmental pollution, equipment corrosion easily.
Summary of the invention
The object of the present invention is to provide a kind of no amine method for preparing high silica mordenite, need not add organic amine, mineral acid and mineral alkali, only in the presence of polyvalent alcohol, make silicon source and aluminium source carry out crystallization at a certain temperature and obtain high silicon mordenite.This method has that production cost is low, output is high, technological operation is simple, advantages of environment protection.
The objective of the invention is to be achieved through the following technical solutions: with silicon source, aluminium source and deionized water is raw material, is additive with the polyvalent alcohol, and the mol ratio of each component is in the reactant: Na
2O/Al
2O
3=3～15: 1, SiO
2/ Al
2O
3=15～75: 1, H
2O/Al
2O
3=390～2000: 1, polyvalent alcohol/Al
2O
3=0.1～10: 1, hydrothermal crystallizing in the stainless steel cauldron of teflon lined, crystallization temperature are 120～200 ℃, and crystallization time is 12～240 hours, and the mixture after the crystallization obtains SiO after suction filtration, washing, drying
2/ Al
2O
3Mol ratio is 15～30: 1 high silicon mordenite.
Described silicon source is water glass and SiO 2 powder, water glass and silica gel or water glass and silicon sol.
Described polyvalent alcohol is a tetramethylolmethane.
Described aluminium source is aluminium salt or aluminate.
Described aluminium salt is aluminum nitrate, Tai-Ace S 150 or aluminum chloride, and described aluminate is a sodium aluminate.
The present invention compares the beneficial effect that has with background technology:
Adopt low price in the synthesizing high silicon content mordenite, abundant, the eco-friendly tetramethylolmethane in source replaces costing an arm and a leg, environment being had the organic amine of pollution is additive, does not use mineral acid or the mineral alkali that equipment is had corrosive nature simultaneously.In synthetic system, add the generation that tetramethylolmethane helps high silicon mordenite, can effectively shorten crystallization time simultaneously.The present invention has that production cost is low, output is high, technological operation is simple, advantages of environment protection.
Embodiment
Embodiment 1
9.3923 gram Al
2(SO
4)
318H
2O is dissolved in the 179.71 gram water, under agitation adds 20.34 gram silica gel (chemical pure), 24.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 19.18 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 72 hours in 170 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 16.7: 1.
Embodiment 2
3.004 gram aluminum nitrate (chemical pure) is dissolved in the 184.71 gram water, under agitation adds 20.34 grams two
Silicon oxide powder (chemical pure), 24.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 5.7538 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 96 hours in 160 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 18.5: 1.
Embodiment 3
7.0169 gram sodium aluminate (Al
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) be dissolved in the 186.46 gram water, under agitation add 22.04 gram SiO 2 powders (chemical pure), 16.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 1.9179 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 24 hours in 180 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 14.5: 1.
Embodiment 4
3.5084 gram sodium aluminate (Al
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) be dissolved in the 185.37 gram water, under agitation add 21.19 gram silica gel (chemical pure), 20.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 5.7538 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 48 hours in 180 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 18.2: 1.
Embodiment 5
1.4034 gram sodium aluminate (Al
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) be dissolved in the 189.81 gram water, under agitation add 20.68 gram SiO 2 powders (chemical pure), 22.44 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 1.9179 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 72 hours in 180 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 30.1: 1.
Embodiment 6
3.5085 gram sodium aluminate (Al
2O
341.0wt%, Na
2O24.9wt%, H
2O34.1wt%) be dissolved in the 135.94 gram water, under agitation add 70.63 gram silicon sol (SiO
230wt%, H
2O70wt%), 20.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 0.1918 the gram tetramethylolmethane (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 72 hours in 170 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 25.2: 1.
Embodiment 7
1.8827 gram aluminum chloride (chemical pure) is dissolved in the 184.71 gram water, under agitation adds 20.34 gram silica gel (chemical pure), 24.04 gram water glass (SiO
221.15wt%, Na
2O21.82wt%, H
2O57.03wt%) and 9.5897 the gram tetramethylolmethanes (chemical pure), adding the back continues to stir 0.5 hour, then mixture is put into the stainless steel crystallizing kettle of teflon lined, airtight back crystallization 240 hours in 160 ℃ of baking ovens, after the suction filtration of routine, washing, drying solid product.
Solid product is a mordenite through the X-diffraction analysis, its SiO
2/ Al
2O
3Mol ratio is 17.4: 1.
Embodiment in the above-mentioned embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (5)
1. do not have the amine method for preparing high silica mordenite, it is characterized in that: with silicon source, aluminium source and deionized water is raw material, is additive with the polyvalent alcohol, and the mol ratio of each component is in the reactant: Na
2O/Al
2O
3=3～15: 1, SiO
2/ Al
2O
3=15～75: 1, H
2O/Al
2O
3=390～2000: 1, polyvalent alcohol/Al
2O
3=0.1～10: 1, hydrothermal crystallizing in the stainless steel cauldron of teflon lined, crystallization temperature are 120～200 ℃, and crystallization time is 12～240 hours, and the mixture after the crystallization obtains SiO after suction filtration, washing, drying
2/ Al
2O
3Mol ratio is 15～30: 1 high silicon mordenite.
2. no amine method for preparing high silica mordenite according to claim 1 is characterized in that described silicon source is water glass and SiO 2 powder, water glass and silica gel or water glass and silicon sol.
3. no amine method for preparing high silica mordenite according to claim 1 is characterized in that described polyvalent alcohol is a tetramethylolmethane.
4. no amine method for preparing high silica mordenite according to claim 1 is characterized in that described aluminium source is aluminium salt or aluminate.
5. no amine method for preparing high silica mordenite according to claim 4 is characterized in that described aluminium salt is aluminum nitrate, Tai-Ace S 150 or aluminum chloride, and described aluminate is a sodium aluminate.
Priority Applications (1)
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|---|---|---|---|
| CNB2006100506235A CN100436320C (en) | 2006-05-08 | 2006-05-08 | Method for synthesizing high-silicon mordenite in the absence of amine |
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|---|---|---|---|
| CNB2006100506235A CN100436320C (en) | 2006-05-08 | 2006-05-08 | Method for synthesizing high-silicon mordenite in the absence of amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1843915A true CN1843915A (en) | 2006-10-11 |
| CN100436320C CN100436320C (en) | 2008-11-26 |
Family
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602958A (en) * | 2012-04-13 | 2012-07-25 | 华东师范大学 | Preparation method of mesoporous mordenite |
| CN105174284A (en) * | 2015-09-29 | 2015-12-23 | 山东大学 | Efficient two-silicon-source amine-free synthesis method for morphology-controllable large-size mordenite |
| CN107758688A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The nanometer aggregation plate-like modenite of different compactness |
| CN107758685A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Nanometer aggregation piece shape modenite |
| CN108383134B (en) * | 2018-02-08 | 2021-05-04 | 西安建筑科技大学 | Method for synthesizing solid waste multistage pore block mordenite |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4527229B2 (en) * | 2000-02-28 | 2010-08-18 | 日本碍子株式会社 | Mordenite zeolite membrane and method for producing the same |
| CN1202995C (en) * | 2002-06-05 | 2005-05-25 | 中国科学院大连化学物理研究所 | Process for synthesizing high silicon content mordenite |
| CN1212269C (en) * | 2002-10-16 | 2005-07-27 | 中国石油化工股份有限公司 | High silicon mordenite and preparing method thereof |
| JP4882202B2 (en) * | 2004-02-09 | 2012-02-22 | 東ソー株式会社 | Method for synthesizing high silica mordenite |
| JP4639713B2 (en) * | 2004-09-17 | 2011-02-23 | 東ソー株式会社 | Method for synthesizing high purity high silica mordenite |
| CN1666956A (en) * | 2005-02-04 | 2005-09-14 | 华东理工大学 | Method for synthesizing nanometer size mordenite |
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2006
- 2006-05-08 CN CNB2006100506235A patent/CN100436320C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102602958A (en) * | 2012-04-13 | 2012-07-25 | 华东师范大学 | Preparation method of mesoporous mordenite |
| CN102602958B (en) * | 2012-04-13 | 2013-09-18 | 华东师范大学 | Preparation method of mesoporous mordenite |
| CN105174284A (en) * | 2015-09-29 | 2015-12-23 | 山东大学 | Efficient two-silicon-source amine-free synthesis method for morphology-controllable large-size mordenite |
| CN107758688A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The nanometer aggregation plate-like modenite of different compactness |
| CN107758685A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | Nanometer aggregation piece shape modenite |
| CN107758688B (en) * | 2016-08-23 | 2020-08-07 | 中国石油化工股份有限公司 | Nano-aggregated disk-shaped mordenite with different compactness |
| CN107758685B (en) * | 2016-08-23 | 2020-09-04 | 中国石油化工股份有限公司 | Nano aggregated sheet mordenite |
| CN108383134B (en) * | 2018-02-08 | 2021-05-04 | 西安建筑科技大学 | Method for synthesizing solid waste multistage pore block mordenite |
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| Publication number | Publication date |
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| CN100436320C (en) | 2008-11-26 |
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