CN102659134A - Method for preparing mordenite molecular sieve - Google Patents
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- CN102659134A CN102659134A CN2012101391342A CN201210139134A CN102659134A CN 102659134 A CN102659134 A CN 102659134A CN 2012101391342 A CN2012101391342 A CN 2012101391342A CN 201210139134 A CN201210139134 A CN 201210139134A CN 102659134 A CN102659134 A CN 102659134A
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Abstract
The invention relates to a method for preparing a mordenite molecular sieve. The method comprises the following steps of: dissolving an aluminum source in a sodium hydroxide solution, adding silicon sources, stirring at room temperature by strong magnetic force, and dispersing for a period of time; mixing the silicon sources which are dispersed uniformly and an aluminum source solution to form glue, adding a zeolite molecular sieve containing a five-membered ring as a crystal seed, stirring and mixing uniformly by the strong magnetic force at room temperature, and transferring the mixture into a reaction crystallization kettle, and performing crystallization reaction at the temperature of between 150 and 170 DEG C for 0.5 to 3 days; and performing suction filtration, washing and drying conventionally to obtain the mordenite molecular sieve. According to the method, an expensive organic amine template agent is not used as a structure guiding agent, and the zeolite molecular sieve which is wide in using, low in cost and readily available and contains the five-membered ring is used as the crystal seed to synthesize the mordenite molecular sieve with a high silica-alumina ratio directly, so the prepared mordenite molecular sieve has the advantages of high crystallinity and purity, controllable granular sizes and appearance, high yield, convenience for industrial production and the like.
Description
Technical field
The present invention relates to the synthetic of zeolite molecular sieve, particularly a kind of compound method of mordenite molecular sieve.Specifically contain the method for pentacyclic zeolite molecular sieve not using organic ammonium to add under as the structure directing agent condition as crystal seed synthesizing flokite molecular sieve.
Background technology
Micro porous molecular sieve has uniform pore passage structure, proper acidic and good hydrothermal stability, has become important petrochemical complex catalytic material.H-mordenite with the straight tubular of one dimension twelve-ring duct (aperture 0.695 nm * 0.581 nm) has shown excellent catalytic performance in toluene disproportionation, alkylation, C8 aromatics isomerization and toluene selective disproportionation reaction.But the synthetic lower (SiO of the common silica alumina ratio of mordenite molecular sieve that obtains of traditional method
2/ Al
2O
3Between the mol ratio 5～10, have mordenite than low silica-alumina ratio), and particle size big (﹥ 1.0 μ m).Lower silica alumina ratio obviously reduces the acid resistance of mordenite and hydrothermal stability, and oarse-grained in addition mordenite is unfavorable for diffusion and the mass transfer that macromolecular reaction is participated in, and has reduced the reaction efficiency of catalyzer.
Current synthesizing high-silicon aluminum ratio (SiO
2/ Al
2O
3Greater than 10, being called mordenite with high silicon aluminum ratio) synthesis strategy of mordenite mainly includes machine template guiding method and two kinds of ways of hydro-thermal aftertreatment dealuminzation.In the organic formwork agent synthesis strategy; Tetraethyl ammonium hydroxide or its halo derivatives salt are the most frequently used structure directing agent (Chinese patent CN 1666956A); Other organic substance also can be used as the organic formwork agent synthesizing high silicon content mordenite like pyoktanin blue 2-B and Methylene blue pigment molecule (U.S. Pat P4585640), 1-aminomethyl-hexalin (U.S. Pat P5173282), benzyl trimethyl amine (a day disclosure is speciallyyed permit clear 58-88118), bromination diethylammonium croak pyridine (European patent 080615 (1983)), AS (Chinese patent CN 1230518A), polyvalent alcohol (Chinese patent CN 1843915A), trolamine (Chinese patent CN 1147479A) and starch (Chinese patent CN1891627A).Although the synthetic mordenite that obtains has higher silica alumina ratio (SiO
2/ Al
2O
3Mol ratio is greater than 20), but because organic formwork agent costs an arm and a leg and the template removal very easily causes environmental pollution, limited its large-scale commercial prodn.At present; The synthesis strategy that the preparation high silicon mordenite is the most commonly used is with the direct concentrated nitric acid reflow treatment of non-amine method synthetic mordenite; Or with mordenite through steam treatment to remove the aluminium in the framework of molecular sieve; But this synthesis strategy preparation condition is harsh and comparatively complicated, has greatly improved the synthetic cost of mordenite, and environment has been caused a large amount of pollutions.
Therefore organic-free template method synthesizing high silicon content mordenite has caused attention widely.Chinese patent CN 1050011A reported use cheap water glass as silicon source mordenite the most crystal seed prepare the compound method of mordenite with high silicon aluminum ratio, high silica alumina ratio can reach 25, but synthetic particle size is greater than 1.0 μ m.In Chinese patent CN 1837046A, use mordenites such as Xing Shujian utilize the way of segmentation crystallization to prepare nano level mordenite molecular sieve as crystal seed, but synthesis step is loaded down with trivial details relatively.Beatriz etc. through directly regulating the method for synthetic parameters, have synthesized nanometer needle-like mordenite molecular sieve under no template condition, the width of basic crystal grain is 63 nm, and length is 240nm, but crystallization time is longer, need 2～3 days usually.Liu Xiyao etc. disclose a kind of synthesis strategy of organic-free template synthesizing high silicon content mordenite in Chinese patent CN 1093513C, the mol ratio of sial reaches 60, and particulate pattern and size are not appeared in the newspapers.This synthesis strategy uses the F ion as mineralizer in addition, cause equipment corrosion and environmental pollution serious, and crystallization time is longer.Recently; Li Xiaofeng etc. utilize the synthesis strategy of solid phase in-situ crystallization to prepare to have novel pattern microcrystal mordenites; Different fully with the grain morphology that hydrothermal method is synthetic regular; 10～30 μ m ellipsoid particulate shape characteristics that sample has the unequigranular irregular strip crystal grain of 100～500 nm and formed by its accumulation, and exist abundant secondary to pile up the hole.The result of document and Chinese patent investigation shows: have the synthetic of low-cost and eco-friendly mordenite simultaneously and do not appear in the newspapers as yet.
Summary of the invention
The object of the present invention is to provide a kind of method of non-amine method synthesizing flokite molecular sieve, need not add organic amine,, carry out crystallization at a certain temperature and obtain mordenite to contain pentacyclic zeolite molecular sieve as crystal seed.This method has that synthesis material is cheap and easy to get, production cost is low, output is high, technological operation is simple, advantages of environment protection.Institute of the present invention synthetic nano mordenite molecular sieve has higher silica alumina ratio, crystallization time weak point, percent crystallinity and purity height and output advantages of higher.
The objective of the invention is to realize like this:
A kind of preparation method of mordenite molecular sieve, this method comprises following concrete steps:
(1) with deionized water, sodium hydroxide and aluminium source uniform mixing, the room temperature lower magnetic force is stirred to clear liquid, then the silicon source is joined the strong magnetic agitation of this solution for continuous 1～3 hour, and the mole of its reaction mass consists of SiO
2: Al
2O
3=10～100, Na
2O: SiO
2=0.18～0.33, H
2O: SiO
2=20～80;
(2) join in the above-mentioned mixing solutions as crystal seed to contain pentacyclic zeolite molecular sieve; At room temperature continue to stir 0.5～3 hour; The pH value 11.0～13.0 of reaction mixture; 150～170 ℃ of crystallizations 0.5～3 day, the add-on of its crystal seed was 0.1～10 % of reaction mass gross weight then;
(3) the direct suction filtration separation of solid product, water washing were dried 24 hours down, are got high silica alumina ratio microcrystal mordenites molecular sieve for 100 ℃ to neutral after crystallization finished; Wherein:
Said pentacyclic zeolite molecular sieve is Silicate-1 zeolite molecular sieve, ZSM-5 zeolite molecular sieve, ZSM-11 zeolite molecular sieve and ZSM-35 zeolite molecular sieve, and the crystal seed add-on is 0.5～8.0 % of reactant feed mixture total weight amount;
Said silicon source is a kind of in WHITE CARBON BLACK (silica gel of being fuming), silicon sol solution, Qingdao silica gel, column chromatography silica gel, pulverous silica gel G or the water glass;
Said aluminium source is a kind of in aluminum nitrate, sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, white lake or the pseudo-boehmite.
According to method disclosed by the invention, can add the kind of crystal seed and the pattern of silica alumina ratio, particle diameter and the crystal grain of amount, basicity, the water yield, silicon source and aluminium source, crystallization mode (dynamically, static state), crystallization temperature and time adjusting mordenite through regulating synthetic system.
Utilize its phase structure of X-ray diffraction technical Analysis, grain size and percent crystallinity, with its pattern of SEM scanning electron microscope observation and grain size.Do not use in the building-up process of the present invention poisonous, valency is high and the organic amine structure directing agent that environment had pollution; But adopt wide material sources, cheap contain pentacyclic zeolite molecular sieve as crystal seed; Through the modulation synthesis condition, the microcrystal mordenites of direct synthesizing high-silicon aluminum ratio.This compound method obtains mordenite and has novel crystal morphology; Different fully with the grain morphology that conventional hydrothermal method is synthetic regular; The 6 μ m spheroidal particle that finally obtain for there being the unequigranular needle-like crystal accumulation of 3～6 μ m to form; And exist abundant secondary to pile up the hole, have bigger surface-area and pore volume.
High silica alumina ratio nano mordenite molecular sieve compound method of the present invention compared with prior art has following characteristics: do not use expensive organic amine template, use wide material sources, cheap and easy to get contain pentacyclic zeolite molecular sieve as crystal seed.The introducing of crystal seed has promoted the formation of mordenite structure, plays a part to make " template ", " directed agents ", impels the formation of high silicon mordenite, and is unfavorable for the formation of stray crystals such as quartzy phase, ZSM-5; On the other hand, the adding of crystal seed makes reaction mixture help the rapid formation of a large amount of mordenite nucleus from the gel state state that reaches capacity rapidly, has shortened crystallization time greatly, helps synthetic mordenite than close grain or nanocrystal simultaneously.Use compound method of the present invention, greatly reduce the synthetic cost of mordenite, pollution on the environment is few relatively, is particularly suitable for industrial mass production.
Description of drawings
Fig. 1 is the X-ray powder diffraction collection of illustrative plates of synthesizing flokite molecular sieve of the present invention;
Fig. 2 is ESEM (SEM) figure of synthesizing flokite molecular sieve of the present invention;
Fig. 3 is ESEM (SEM) figure of synthesizing flokite molecular sieve of the present invention;
Fig. 4 is ESEM (SEM) figure of synthesizing flokite molecular sieve of the present invention.
Embodiment
Through embodiment the present invention is described further below, its purpose only is better to understand research contents of the present invention and unrestricted protection scope of the present invention.
Embodiment 1
9.50 g NaOH are joined contain 190 ml deionized waters, stir to clarify solution, 4.8 g sodium metaaluminates are joined in the above-mentioned solution, room temperature continues to be stirred to solid all dissolves, and adds 200 ml water then, continues to stir 15 minutes.The 29.1 g silica gel of being fuming is joined in the above-mentioned mixing solutions; Continued strong magnetic agitation 1 hour; Then 1.7g ZSM-5 zeolite molecular sieve is joined in the reaction system as crystal seed, add continued and stirred 0.5 hour, at last mixture is put into the stainless steel crystallizing kettle of teflon lined; Airtight back crystallization 24 hours in 170 ℃ of baking ovens must solid product after conventional suction filtration, washing, drying; The mole of the initial colloidal sol of this mixture consists of: SiO
2: Al
2O
3=20, Na
2O: SiO
2=0.25, H
2O: SiO
2=45.
Solid product is a mordenite through x-ray analysis, its SiO
2: Al
2O
3Mol ratio is 13.5; The 6 μ m spheroidal particle that finally obtain have the unequigranular needle-like crystal accumulation of 3～6 μ m to form; X-ray diffraction characterizes (XRD) like Fig. 1, and Fig. 2, Fig. 3 and Fig. 4 are ESEM (SEM) characterization result of institute's synthesizing flokite different amplification.
Embodiment 2
Except that replace ZSM-5 zeolite molecular sieve among the embodiment 1 as the crystal seed with the Silicate-1 zeolite molecular sieve, other preparation condition is all identical with embodiment 1.The x-ray diffraction pattern of product has the characteristic of Fig. 1, proves mordenite molecular sieve.
Embodiment 3
Except that replace ZSM-5 zeolite molecular sieve among the embodiment 1 as the crystal seed with the ZSM-11 zeolite molecular sieve, other preparation condition is all identical with embodiment 1.The x-ray diffraction pattern of product has the characteristic of Fig. 1, proves mordenite molecular sieve.
Embodiment 4
Except that replace ZSM-5 zeolite molecular sieve among the embodiment 1 as the crystal seed with the ZSM-35 zeolite molecular sieve, other preparation condition is all identical with embodiment 1.The x-ray diffraction pattern of product has the characteristic of Fig. 1, proves mordenite molecular sieve.
Embodiment 5
Except that replace sodium metaaluminate among the embodiment 1 as the aluminium source with aluminum nitrate, other preparation condition is all identical with embodiment 1, is had abundant mesoporous high purity mordenite molecular sieve equally.The x-ray diffraction pattern of product has the characteristic of Fig. 1, proves mordenite molecular sieve.
Embodiment 6
Except that replace the silica gel of being fuming among the embodiment 1 as the silicon source with silicon sol solution, other preparation condition is all identical with embodiment 1.The x-ray diffraction pattern of product has the characteristic of Fig. 1, proves mordenite molecular sieve.
Claims (1)
1. the preparation method of a mordenite molecular sieve is characterized in that this method comprises following concrete steps:
(1) with deionized water, sodium hydroxide and aluminium source uniform mixing, the room temperature lower magnetic force is stirred to clear liquid, then the silicon source is joined the strong magnetic agitation of this solution for continuous 1～3 hour, and the mole of its reaction mass consists of SiO
2: Al
2O
3=10～100, Na
2O: SiO
2=0.18～0.33, H
2O: SiO
2=20～80;
(2) join in the above-mentioned mixing solutions as crystal seed to contain pentacyclic zeolite molecular sieve; At room temperature continue to stir 0.5～3 hour; The pH value 11.0～13.0 of reaction mixture; 150～170 ℃ of crystallizations 0.5～3 day, the add-on of its crystal seed was 0.1～10 % of reaction mass gross weight then;
(3) the direct suction filtration separation of solid product, water washing were dried 24 hours down, are got mordenite molecular sieve for 100 ℃ to neutral after crystallization finished; Wherein:
Said pentacyclic zeolite molecular sieve is Silicate-1 zeolite molecular sieve, ZSM-5 zeolite molecular sieve, ZSM-11 zeolite molecular sieve and ZSM-35 zeolite molecular sieve;
Said silicon source is a kind of in WHITE CARBON BLACK, silicon sol solution, Qingdao silica gel, column chromatography silica gel, pulverous silica gel G or the water glass;
Said aluminium source is a kind of in aluminum nitrate, sodium metaaluminate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, white lake or the pseudo-boehmite.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601213A (en) * | 2013-12-06 | 2014-02-26 | 天津大学 | Preparation method for low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve |
| WO2015021610A1 (en) * | 2013-08-14 | 2015-02-19 | 中国科学院大连化学物理研究所 | Zsm-35 molecular sieve and synthesis method for me-zsm-35 |
| CN108217680A (en) * | 2016-12-09 | 2018-06-29 | 中国科学院大连化学物理研究所 | The method of synthesizing flokite MOR molecular sieves, and products thereof and application |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
| CN111573691A (en) * | 2020-05-25 | 2020-08-25 | 天津大学 | Flower-shaped mordenite and preparation method and application thereof |
| RU2744166C1 (en) * | 2019-12-09 | 2021-03-03 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Type mor zeolite and a method for production thereof |
| CN112850743A (en) * | 2019-11-26 | 2021-05-28 | 中国科学院大连化学物理研究所 | Green synthesis method for regulating morphology of mordenite molecular sieve |
| CN113491998A (en) * | 2021-07-09 | 2021-10-12 | 武汉工程大学 | Method for synthesizing ZSM-5 adsorbent by aid of seed crystals |
| CN113979447A (en) * | 2021-11-17 | 2022-01-28 | 常州大学 | Preparation method of efficient acid-resistant mordenite molecular sieve |
| CN114291823A (en) * | 2021-12-29 | 2022-04-08 | 延长中科（大连）能源科技股份有限公司 | Preparation method of mordenite molecular sieve |
| CN115231586A (en) * | 2022-07-06 | 2022-10-25 | 安阳工学院 | ZSM-5 molecular sieve with adjustable Coffin morphology and synthetic method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1145278A (en) * | 1996-06-28 | 1997-03-19 | 太原工业大学 | Synthesis of hypersilicon zeolit and hetero-atom isomorphism substituted derivative |
| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1648047A (en) * | 2004-12-16 | 2005-08-03 | 复旦大学 | Non-crystal inorganic structure guide agent for synthesizing nano/submicrometer high silicon ZSM-5 zeolite and its preparing process |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN102060308A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
-
2012
- 2012-05-08 CN CN 201210139134 patent/CN102659134B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1145278A (en) * | 1996-06-28 | 1997-03-19 | 太原工业大学 | Synthesis of hypersilicon zeolit and hetero-atom isomorphism substituted derivative |
| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN1648047A (en) * | 2004-12-16 | 2005-08-03 | 复旦大学 | Non-crystal inorganic structure guide agent for synthesizing nano/submicrometer high silicon ZSM-5 zeolite and its preparing process |
| CN1837046A (en) * | 2006-04-24 | 2006-09-27 | 南开大学 | Process for synthesis of nano mordenite molecular sieve |
| CN102060308A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Synthesis method of nano fibrous mordenite |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015021610A1 (en) * | 2013-08-14 | 2015-02-19 | 中国科学院大连化学物理研究所 | Zsm-35 molecular sieve and synthesis method for me-zsm-35 |
| CN103601213A (en) * | 2013-12-06 | 2014-02-26 | 天津大学 | Preparation method for low silicon-aluminum ratio nanosheet flower cluster-like mordenite molecular sieve |
| CN108217680A (en) * | 2016-12-09 | 2018-06-29 | 中国科学院大连化学物理研究所 | The method of synthesizing flokite MOR molecular sieves, and products thereof and application |
| CN108217680B (en) * | 2016-12-09 | 2021-05-25 | 延长中科（大连）能源科技股份有限公司 | Method for synthesizing mordenite MOR molecular sieve, product and application thereof |
| CN109485064A (en) * | 2018-12-10 | 2019-03-19 | 卓悦环保新材料（上海）有限公司 | The method of useless MTP catalyst preparation modenite and the application of useless MTP catalyst |
| CN112850743B (en) * | 2019-11-26 | 2023-01-13 | 中国科学院大连化学物理研究所 | Green synthesis method for regulating morphology of mordenite molecular sieve |
| CN112850743A (en) * | 2019-11-26 | 2021-05-28 | 中国科学院大连化学物理研究所 | Green synthesis method for regulating morphology of mordenite molecular sieve |
| RU2744166C1 (en) * | 2019-12-09 | 2021-03-03 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Type mor zeolite and a method for production thereof |
| CN111573691B (en) * | 2020-05-25 | 2022-12-09 | 天津大学 | Flower-shaped mordenite and preparation method and application thereof |
| CN111573691A (en) * | 2020-05-25 | 2020-08-25 | 天津大学 | Flower-shaped mordenite and preparation method and application thereof |
| CN113491998A (en) * | 2021-07-09 | 2021-10-12 | 武汉工程大学 | Method for synthesizing ZSM-5 adsorbent by aid of seed crystals |
| CN113979447A (en) * | 2021-11-17 | 2022-01-28 | 常州大学 | Preparation method of efficient acid-resistant mordenite molecular sieve |
| CN114291823A (en) * | 2021-12-29 | 2022-04-08 | 延长中科（大连）能源科技股份有限公司 | Preparation method of mordenite molecular sieve |
| CN114291823B (en) * | 2021-12-29 | 2023-10-20 | 延长中科（大连）能源科技股份有限公司 | Preparation method of mordenite molecular sieve |
| CN115231586A (en) * | 2022-07-06 | 2022-10-25 | 安阳工学院 | ZSM-5 molecular sieve with adjustable Coffin morphology and synthetic method thereof |
| CN115231586B (en) * | 2022-07-06 | 2023-10-20 | 安阳工学院 | ZSM-5 molecular sieve with adjustable crystal face and Coffin morphology and synthesis method thereof |
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