CN109279623A - A method of it with micropore aluminium phosphite NKX-12 is silicon source synthesizing high-silicon aluminium than modenite - Google Patents
A method of it with micropore aluminium phosphite NKX-12 is silicon source synthesizing high-silicon aluminium than modenite Download PDFInfo
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- CN109279623A CN109279623A CN201811186279.1A CN201811186279A CN109279623A CN 109279623 A CN109279623 A CN 109279623A CN 201811186279 A CN201811186279 A CN 201811186279A CN 109279623 A CN109279623 A CN 109279623A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
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Abstract
A method of it with micropore aluminium phosphite NKX-12 is silicon source synthesizing high-silicon aluminium than modenite, its main feature is that a kind of the use of micropore aluminium phosphite NKX-12 containing structure terminal hydroxy group (Al-OH) being silicon source, using tlc silica gel or silica solution or precipitated silica as silicon source, according to mol ratio Na2O∶Al2O3∶SiO2∶H2O=4~6: in 1~1.2: 30: 250~324 mixtures formed, it is uniformly mixing to obtain synthesized gel rubber, is then transferred in stainless steel kettle, hydrothermal crystallizing 1~5 day under 170~190 DEG C and self-generated pressure, molecular sieve post-processing approach routinely is cooling, washing, it is dry, collect product.
Description
Technical field
The present invention relates to a kind of method without using organic formwork agent synthesizing high-silicon aluminium than modenite, be specifically exactly with
One kind containing structure terminal hydroxy group (Al-OH) micropore aluminium phosphite NKX-12 be silicon source, tlc silica gel or silica solution or
Precipitated silica is silicon source, does not add organic formwork agent and prepares mordenite with high silicon aluminum ratio.
Technical background
Mordenite structure is unique, altogether between the connected five-membered ring pair in side by four-membered ring connection chaining, with eight between chain
Member ring couples to form straight barrel type twelve-ring main aperture road, and special structure makes modenite be likely to become straight chain alkane isomerization
Catalyst.However, conventional modenite group becomes Na8(H2O)24[Al8Si40O96], silica alumina ratio (SiO2/Al2O3Molar ratio) only
It is 10, keeps modenite weaker as the acidity of alkane isomerization catalyst, need relatively high reaction temperature, and reacted
Catalytic performance, such as C easily are influenced because water vapor acting dealuminzation destroys structural intergrity in journey5/C6Alkane isomerization reacts just
Need (the SiO of high silica alumina ratio2/Al2O3>=20) modenite.
Synthesizing high-silicon aluminium ratio (SiO2/Al2O3>=20) modenite is usually required using organic formwork agent, still, meeting in this way
Increase the modenite product cost of preparation, and in preparation, pollution is generated in product last handling process, therefore, without using having
Machine template synthesizing high-silicon aluminium has a extensive future than the method for modenite.
CN1050011A disclose one kind under conditions of not adding organic formwork agent using waterglass as silicon source, aluminum sulfate or
Aluminum nitrate is the method for silicon source hydrothermal synthesis mordenite with high silicon aluminum ratio, but joined ammonium hydroxide during the experiment, this is not
It effectively reduces cost and also creates environmental pollution.
Document Zeolites 1991,11,745 and master thesis " mesoporous mordenite under the conditions of no organic formwork
Synthesis and characterization " it reports and is boiled using sodium metaaluminate as silicon source synthesizing high-silicon aluminium than mercerising without using organic formwork agent
The method of stone, but sodium metaaluminate makes the silica alumina ratio of synthetic product be difficult to stability contorting as silicon source, brings to actual use
Difficulty.
Document Acta Phys.-Chim.Sin., 2006,22 (2), 198 have reported industrial waterglass and aluminum sulfate as former
Expect, hydrothermal crystallizing synthesizing high silicon content mordenite under the conditions of 170 DEG C in the presence of sodium fluoride；CN 1257831A discloses a kind of synthesis
The method of high silicon mordenite.But fluorine ion is all introduced in both methods.
Document Acta Petrolei Sinica (Petroleum Processing Setcion) 2006,10,217 is reported
A kind of method without using organic formwork agent synthesizing high silicon content mordenite, but this method and process is complicated, need hydrogen-oxygen
Silica solution is added dropwise after being dissolved in water for change sodium and aluminum sulfate solution is mixed to get colloidal sol, then the crystalline substance being dispersed in water wherein is being added
Kind, it is agitated, at room temperature aging, be dried to obtain sial dry glue, continue crystallization synthesizing high silicon content mordenite, and the required sial that feeds intake
It is higher than very, cause raw material using insufficient and waste.
Summary of the invention
A kind of method for using micropore aluminium phosphite NKX-12 as silicon source synthesizing high-silicon aluminium than modenite of the present invention, makes
Micropore aluminium phosphite NKX-12 and preparation method have been disclosed in file CN103204484B, used in the present invention
In the structure of NKX-12, all aluminium atoms be all with six oxygen atom ligands, wherein thering is 3/7 to belong to terminal hydroxy group (Al-OH), in height
Reaction that can effectively between fcc raw material reactant in silica alumina ratio modenite synthesis process, promotes mordenite with high silicon aluminum ratio
Crystallization process.Therefore, it is characteristic of the invention that containing structure aluminum-oxygen terminal hydroxy group (Al-OH) micropore phosphorous acid using a kind of
Aluminium NKX-12 is silicon source, using tlc silica gel or silica solution or precipitated silica as silicon source, does not use organic formwork agent,
The direct synthesizing high silicon content mordenite of hydro-thermal method is taken under suitable crystallization temperature, crystallization time.This method silicon source application range
Extensively, environmental protection, economy, the high silicon mordenite product silica alumina ratio of synthesis is stable, application prospect is extensive.
Preparation method of the invention includes the following steps:
Respectively by silicon source and water, after silicon source, sodium hydroxide and water mix in proportion, obtain two kinds of mixtures are fallen
Together, 30~60 minutes are stirred at room temperature into homogeneous gel: later, mixture being transferred to polytetrafluoroethyllining lining
It in stainless steel cauldron, is placed in 170~190 DEG C of constant temperature oven and stands crystallization 1~5 day, take out reaction kettle, it is rapid with cold water
It is cooled to room temperature, products therefrom is washed with distilled water to separation, drying after neutrality, finally obtains target product.
Silicon source is in the present invention with SiO2Meter, silicon source is with Al2O3Meter, sodium hydroxide is with Na2O meter.Reaction raw materials rub according to following
That stoichiometry: Na2O∶Al2O3∶SiO2∶H2O=4~6: 1~1.2: 30: 250~324.
Silicon source described in the method for the present invention is tlc silica gel (100wt.%SiO2) or silica solution (40wt.%
SiO2, 1.285 grams per milliliters) or precipitated silica (89.28wt.%SiO2), the silicon source is micropore aluminium phosphite NKX-
12, the sodium hydroxide is prepared sodium hydroxide solution (6 mol/L).
The hydro-thermal method is the hydrothermal crystallizing under 170~190 DEG C of self-generated pressures.
Present invention is characterized in that under conditions of not adding organic formwork agent, it is molten with tlc silica gel or silicon respectively
Glue or precipitated silica are as silicon source, NKX-12 direct synthesizing high silicon content mordenite under alkaline medium as silicon source.It is this
Method environmental protection environmental protection, economy, the mordenite with high silicon aluminum ratio application prospect of synthesis are extensive.
Detailed description of the invention
Fig. 1 is the x-ray diffractogram of powder (XRD) of product modenite described in the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
3.087 grams of tlc silica gels are added in 5 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.676 gram of NKX-12 to be dissolved in 2.57 milliliters of sodium hydroxide solutions, adds 2.43 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 30 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 170 DEG C of constant temperature oven and is stood crystallization 4 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Embodiment 2
3.087 grams of tlc silica gels are added in 4 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.603 gram of NKX-12 to be dissolved in 2.86 milliliters of sodium hydroxide solutions, adds 1.78 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 30 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 175 DEG C of constant temperature oven and is stood crystallization 3 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Embodiment 3
3.087 grams of tlc silica gels are added in 5 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.676 gram of NKX-12 to be dissolved in 3.43 milliliters of sodium hydroxide solutions, adds 1.57 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 60 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 180 DEG C of constant temperature oven and is stood crystallization 5 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Embodiment 4
6 milliliters of silica solution are mixed with 1 milliliter of distilled water, at room temperature stirring a period of time, referred to as solution A；Weigh 0.603
Gram NKX-12 is dissolved in 2.28 milliliters of sodium hydroxide solutions, adds 0.73 milliliter of distilled water after complete reaction, referred to as molten
Liquid B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 45 minutes.Later, mixture is transferred to and is had
In the stainless steel cauldron of polytetrafluoroethyllining lining, it is placed in 175 DEG C of constant temperature oven and stands crystallization 2 days.Finally, taking out reaction
Kettle is rapidly cooled to room temperature with cold water, takes out separation after product is washed to neutrality, drying, finally obtains modenite product.
Embodiment 5
6 milliliters of silica solution are mixed with 1.37 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution A；It weighs
0.563 gram of NKX-12 is dissolved in 2.57 milliliters of sodium hydroxide solutions, adds 1.43 milliliters of distilled water after complete reaction, is claimed
For solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 60 minutes.Later, mixture is transferred to
In stainless steel cauldron with polytetrafluoroethyllining lining, it is placed in 190 DEG C of constant temperature oven and stands crystallization 1 day.Finally, taking out
Reaction kettle is rapidly cooled to room temperature with cold water, takes out separation after product is washed to neutrality, drying, finally obtains modenite production
Object.
Embodiment 6
3.457 grams of precipitated silicas are added in 5 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.603 gram of NKX-12 to be dissolved in 2.57 milliliters of sodium hydroxide solutions, adds 2.43 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 45 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 170 DEG C of constant temperature oven and is stood crystallization 4 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Embodiment 7
3.457 grams of precipitated silicas are added in 5 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.563 gram of NKX-12 to be dissolved in 2.28 milliliters of sodium hydroxide solutions, adds 2.72 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 30 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 180 DEG C of constant temperature oven and is stood crystallization 3 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Embodiment 8
3.087 grams of tlc silica gels are added in 4 milliliters of distilled water, at room temperature stirring a period of time, referred to as solution
A；It weighs 0.676 gram of NKX-12 to be dissolved in 2.57 milliliters of sodium hydroxide solutions, adds 1.15 milliliters of steamings after complete reaction
Distilled water, referred to as solution B；Solution B is poured into solution A, continues stirring and forms uniform mixture in 60 minutes.Later, it will mix
Object is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, is placed in 170 DEG C of constant temperature oven and is stood crystallization 3 days.
Finally, taking out reaction kettle, it is rapidly cooled to room temperature with cold water, separation after product is washed to neutrality, drying is taken out, finally obtains silk
Geolyte product.
Claims (4)
- It with micropore aluminium phosphite NKX-12 is method of the silicon source synthesizing high-silicon aluminium than modenite 1. a kind of, it is characterized in that using One kind is silicon source containing structure aluminum-oxygen terminal hydroxy group (Al-OH) micropore aluminium phosphite NKX-12, by itself and silicon source, inorganic base hydrogen Sodium oxide molybdena and water are according to molar ratio Na2O∶Al2O3∶SiO2∶H2O=4~6: 1~1.2: 30: 250~324 form mixture, stirring 30~60 minutes, uniform mixture is formed, is then transferred in stainless steel kettle, the hydro-thermal under 170~190 DEG C and self-generated pressure Crystallization 1~5 day, molecular sieve post-processing approach routinely was cooling, washs, dry, collected product.
- 2. it is described in accordance with the claim 1 it is a kind of with micropore aluminium phosphite NKX-12 be silicon source synthesizing high-silicon aluminium than modenite Method, it is characterised in that all aluminium atoms in the structure of used micropore aluminium phosphite NKX-12 are all and six oxygen atoms Coordination, wherein thering is 3/7 to belong to terminal hydroxy group (Al-OH).
- 3. it is described in accordance with the claim 1 it is a kind of with micropore aluminium phosphite NKX-12 be silicon source synthesizing high-silicon aluminium than modenite Method, the silicon source are tlc silica gel (100wt.%SiO2) or silica solution (40wt.%SiO2, 1.285 grams/milli Rise) or precipitated silica (89.28wt.%SiO2)。
- 4. it is described in accordance with the claim 1 it is a kind of with micropore aluminium phosphite NKX-12 be silicon source synthesizing high-silicon aluminium than modenite Method, the sodium hydroxide are the sodium hydroxide solutions that concentration is 6 mol/Ls.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790283A (en) * | 2019-12-10 | 2020-02-14 | 天津神能科技有限公司 | Synthesis method of mordenite with high silicon-aluminum ratio |
| CN112646368A (en) * | 2020-12-01 | 2021-04-13 | 聚石化学(苏州)有限公司 | Flame-retardant reinforced polyamide composite material and preparation method and application thereof |
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| EP0464249A1 (en) * | 1990-07-05 | 1992-01-08 | VAW Aluminium AG | Process for the manufacture of crystalline molecular sieves with large pores |
| US5171556A (en) * | 1989-09-22 | 1992-12-15 | Institut Francais Du Petrole | Beta type zeolite and its preparation process |
| US5254327A (en) * | 1992-04-03 | 1993-10-19 | Intevep, S.A. | Zeolitic catalyst of MFI type, its preparation and use |
| CN102190316A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous mordenite |
| CN102602957A (en) * | 2012-04-13 | 2012-07-25 | 华东师范大学 | Preparation method for mordenite with high Si/Al ratio and small crystal particle |
| CN103253682A (en) * | 2013-05-20 | 2013-08-21 | 南开大学 | Method for synthesizing beta molecular sieve by using crystalline-state aluminum phosphate as aluminum source |
| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
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2018
- 2018-10-12 CN CN201811186279.1A patent/CN109279623A/en active Pending
Patent Citations (7)
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|---|---|---|---|---|
| US5171556A (en) * | 1989-09-22 | 1992-12-15 | Institut Francais Du Petrole | Beta type zeolite and its preparation process |
| EP0464249A1 (en) * | 1990-07-05 | 1992-01-08 | VAW Aluminium AG | Process for the manufacture of crystalline molecular sieves with large pores |
| US5254327A (en) * | 1992-04-03 | 1993-10-19 | Intevep, S.A. | Zeolitic catalyst of MFI type, its preparation and use |
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| CN106044792A (en) * | 2016-05-31 | 2016-10-26 | 南开大学 | SAPO-34 molecular-sieve preparing method simultaneously using crystal microporous aluminum phosphite NKX-6 as phosphorus source and aluminum source |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790283A (en) * | 2019-12-10 | 2020-02-14 | 天津神能科技有限公司 | Synthesis method of mordenite with high silicon-aluminum ratio |
| CN112646368A (en) * | 2020-12-01 | 2021-04-13 | 聚石化学(苏州)有限公司 | Flame-retardant reinforced polyamide composite material and preparation method and application thereof |
| CN112646368B (en) * | 2020-12-01 | 2022-12-20 | 聚石化学(苏州)有限公司 | Flame-retardant reinforced polyamide composite material and preparation method and application thereof |
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