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WO2011070879A1 - Procédé de production de zéolithe de type ddr - Google Patents

Procédé de production de zéolithe de type ddr Download PDF

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Publication number
WO2011070879A1
WO2011070879A1 PCT/JP2010/069726 JP2010069726W WO2011070879A1 WO 2011070879 A1 WO2011070879 A1 WO 2011070879A1 JP 2010069726 W JP2010069726 W JP 2010069726W WO 2011070879 A1 WO2011070879 A1 WO 2011070879A1
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WIPO (PCT)
Prior art keywords
type zeolite
raw material
ddr type
material solution
ddr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/069726
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English (en)
Japanese (ja)
Inventor
哲哉 内川
健二 谷島
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NGK Insulators Ltd
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NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Priority to CN201080053919.7A priority Critical patent/CN102639441B/zh
Priority to JP2011545152A priority patent/JP5695576B2/ja
Priority to EP10835801.1A priority patent/EP2511234B1/fr
Publication of WO2011070879A1 publication Critical patent/WO2011070879A1/fr
Priority to US13/457,838 priority patent/US8545802B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent

Definitions

  • the present invention relates to a method for producing a DDR type zeolite that can be used for a catalyst, a catalyst carrier, an adsorbent, a gas separation membrane, a pervaporation membrane, and the like.
  • DDR Deca-Dodecasil 3R
  • the pore diameter of the DDR type zeolite is 4.4 ⁇ 3.6 angstrom, which is relatively small among the pore diameters of various zeolites.
  • DDR type zeolite has unique adsorption characteristics for low molecular gases in addition to small pore diameters. Therefore, DDR type zeolite is applied as an adsorbent for separating only a specific low molecular gas.
  • DDR type zeolite can be used as a molecular sieve membrane for low molecular gas by forming into a film.
  • DDR type zeolite In the production method of DDR type zeolite, 1-adamantanamine is used as a structure-directing agent, colloidal silica, ethylenediamine, and water are used as raw materials, and seed crystals of DDR type zeolite are added to these raw materials for hydrothermal synthesis. Thus, a method for crystal growth of DDR type zeolite is known. In this production method, an all-silica DDR type zeolite containing no aluminum can be produced (Patent Documents 1 and 2).
  • the problem of the present invention is that it can be carried out with a material having a low impact on the environment, the hydrothermal synthesis time is short and constant stirring of the raw material solution is not required, and the production cost is low. It is to provide a method for producing a DDR type zeolite.
  • the present inventors have found a method for synthesizing a DDR type zeolite using 1-adamantanamine hydrochloride, and have completed the present invention. That is, according to this invention, the manufacturing method of the DDR type zeolite shown below is provided.
  • a crystal growth step for producing a DDR type zeolite.
  • the raw material solution preparing step includes the step of preparing the raw material solution containing the silica (SiO 2 ) using silica sol, and the pH adjusting step of adjusting the pH of the raw material solution [1]. Or the manufacturing method of the DDR type zeolite as described in [2].
  • silica SiO 2
  • sodium hydroxide NaOH
  • the DDR type zeolite is crystal-grown on the support by immersing the support in the raw material solution in which the DDR type zeolite powder is dispersed.
  • the support on which the DDR type zeolite powder is adhered is immersed in the raw material solution to bring the raw material solution into contact with the DDR type zeolite powder.
  • the manufacturing method of the DDR type zeolite in any one of.
  • the method for producing DDR type zeolite of the present invention requires a short hydrothermal synthesis time and does not require constant stirring of the raw material solution. Moreover, the manufacturing method of the DDR type zeolite of the present invention can be carried out without using ethylenediamine, which is pointed out to affect the environment. In addition, the production method of the DDR type zeolite of the present invention can reduce the production cost by using 1-adamantanamine hydrochloride, which has a large circulation amount and is inexpensive.
  • FIG. 1 is a diagram showing an X-ray diffraction pattern of a powdery DDR type zeolite of Example 1.
  • FIG. 4 is a diagram showing an X-ray diffraction pattern of a powdered DDR type zeolite of Example 2.
  • FIG. 4 is a diagram showing an X-ray diffraction pattern of a support made of alumina after hydrothermal synthesis of Example 3.
  • the method for producing a DDR type zeolite of the present invention comprises a raw material solution preparation step for preparing a raw material solution containing 1-adamantanamine hydrochloride, silica (SiO 2 ) and water, and the raw material solution and the DDR type zeolite powder are in contact with each other. And a crystal growth step of growing the DDR type zeolite by using the DDR type zeolite powder as a seed crystal.
  • the above raw material solution contains 1-adamantanamine hydrochloride, SiO 2 and water, and the molar ratio of 1-adamantanamine hydrochloride / SiO 2 is 0.002 to 0.5 and water / SiO 2 .
  • the molar ratio is 10 to 500.
  • 1-adamantanamine acts as a so-called structure-directing agent, which serves as a template for forming the crystal structure of the DDR type zeolite when the DDR type zeolite grows.
  • 1-adamantanamine is hardly soluble in water. Therefore, the method for producing a DDR type zeolite of the present invention uses 1-adamantanamine hydrochloride having high solubility in the raw material solution. Even if 1-adamantanamine is dissolved in the raw material solution in the form of hydrochloride, it can function as a structure-directing agent in the crystal growth of DDR type zeolite.
  • a sufficient amount of structure directing agent can be dissolved in the raw material solution by using 1-adamantanamine hydrochloride instead of 1-adamantanamine. ing.
  • the crystal growth of the DDR type zeolite proceeds efficiently in the crystal growth step.
  • zeolite crystals are produced with very little mixed phase with crystal phases other than the DDR type.
  • Raw material solution preparation process In the raw material solution preparation step, a raw material solution containing 1-adamantanamine hydrochloride, silica (SiO 2 ), and water is prepared.
  • the raw material solution is prepared so that the molar ratio of 1-adamantanamine hydrochloride / SiO 2 is 0.002 to 0.5.
  • the 1-adamantanamine hydrochloride / SiO 2 molar ratio is 0.002 or more, there is no shortage of the amount of the structure-directing agent dissolved in the raw material solution. As a result, the rate of crystal growth of the DDR type zeolite Will not drop.
  • the 1-adamantanamine hydrochloride / SiO 2 molar ratio is up to 0.5, the amount of 1-adamantanamine hydrochloride is sufficient to maintain the crystal growth rate of the DDR type zeolite.
  • 1-adamantanamine hydrochloride / SiO 2 is 0.5 or less
  • 1-adamantanamine hydrochloride can be kept to the minimum necessary amount, and 1-adamantanamine hydrochloride can be saved. Therefore, it is preferable from the viewpoint of manufacturing cost.
  • the raw material solution is prepared so that the molar ratio of water / SiO 2 is 10 to 500. This numerical range is suitable for crystal growth of DDR type zeolite.
  • silica (SiO 2 ) can be contained in the raw material solution by using silica sol as the raw material.
  • the silica sol may be one prepared by dissolving fine powdered silica in water, or commercially available colloidal silica.
  • Silica sol tends to gel even if the pH is too high or conversely too low.
  • the raw material solution adjustment step when preparing the raw material solution using silica sol, it is preferable to perform a pH adjustment step of adjusting the pH of the raw material solution in order to prevent the silica sol from gelling.
  • a specific example of the pH adjustment step is the addition of a hydroxide solution.
  • the raw material solution it is preferable to prepare the raw material solution so that the molar ratio of sodium hydroxide (NaOH) to NaOH / 1-adamantanamine hydrochloride is 1.0 or less by the above pH adjustment step or the like. This makes it difficult for the raw material solution to be in an excessively high pH state or an excessively low pH state, and as a result, the raw material solution has a very low tendency to gel.
  • NaOH sodium hydroxide
  • the DDR type zeolite powder that becomes a seed crystal can be dispersed in the raw material solution in advance.
  • the method for producing a DDR type zeolite of the present invention 1-adamantanamine hydrochloride that is easily dissolved in water is used. Therefore, the method for producing a DDR type zeolite of the present invention can be carried out without using an additive (for example, ethylenediamine) for dissolving 1-adamantanamine in the raw material solution.
  • an additive for example, ethylenediamine
  • Crystal growth process In the crystal growth step, the DDR type zeolite is crystal-grown using the DDR type zeolite powder as a seed crystal by hydrothermal synthesis in which the raw material solution and the DDR type zeolite powder are in contact with each other.
  • the temperature of the raw material solution is usually 100 to 170 ° C., and more preferably 120 to 170 ° C. from the viewpoint of increasing the crystal growth rate.
  • the hydrothermal synthesis time is usually 8 to 120 hours, and preferably 12 to 24 hours from the viewpoint of reducing the production cost.
  • Embodiments in which the raw material solution does not contain ethylenediamine In the method for producing a DDR type zeolite of the present invention, ethylenediamine is used to dissolve 1-adamantanamine in the raw material solution by containing 1-adamantanamine in the raw material solution in the form of a hydrochloride that is easily dissolved in water. There is no need. Therefore, in the manufacturing method of the DDR type zeolite of the present invention, an embodiment in which ethylenediamine is not included in the raw material solution can be applied.
  • This embodiment has less influence on the environment because it does not use ethylenediamine, which is a PRTR system target substance.
  • Embodiment in which DDR type zeolite powder is dispersed in a raw material solution can be carried out by dispersing DRR-type zeolite powder to be seed crystals in the raw material solution. In this embodiment, as a result of crystal growth, a powdery DDR type zeolite can be produced.
  • the DDR type zeolite in the crystal growth step, can be grown on the support by immersing the support in the raw material solution in which the DDR type zeolite powder is dispersed. In this embodiment, a DDR type zeolite crystal particle adhered to the support can be produced.
  • the DDR type zeolite powder may or may not adhere to the support before being immersed in the raw material solution.
  • Embodiment using a support to which a DDR type zeolite powder is attached The crystal growth step can also be carried out by immersing the support on which the DDR type zeolite powder is adhered in the raw material solution. In this embodiment, as a result of crystal growth, a DDR type zeolite membrane is formed on the support. In this embodiment, the raw material solution may or may not contain the DDR type zeolite powder.
  • Examples 1 and 2 (Raw material solution preparation process) An aqueous 1-adamantanamine hydrochloride solution was prepared by adding 0.81 g of water and 1-adamantanamine hydrochloride (manufactured by Idemitsu Kosan Co., Ltd.) to a 100 ml wide-mouth bottle made of fluororesin and mixing them. At this time, 1-adamantanamine hydrochloride was completely dissolved in water by stirring using a stirrer. To this 1-adamantanamine hydrochloride aqueous solution, a 10% by mass aqueous sodium hydroxide solution was added and mixed with a stirrer.
  • silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd., solid content concentration: 30% by mass) was added to this liquid and stirred using a shaker to obtain a raw material solution.
  • Table 1 shows the molar ratio of 1-adamantanamine hydrochloride / SiO 2 in the raw material solutions of Examples 1 and 2, water / SiO 2 molar ratio, and the molar ratio of NaOH / 1-adamantanamine hydrochloride in the raw material solutions.
  • a DDR type zeolite seed crystal dispersion was prepared by dispersing DDR type zeolite powder composed of particles having a particle size of 5 ⁇ m or less in water at a solid content concentration of 0.34% by mass. 0.8 g of this DDR type zeolite seed crystal dispersion was added to a wide-mouth bottle containing the raw material solution, and lightly stirred. Then, this raw material solution was transferred to a stainless steel pressure resistant vessel with a fluororesin inner cylinder having an internal volume of 100 ml, and hydrothermal synthesis was performed at 160 ° C. for 16 hours. During the hydrothermal synthesis, the liquid was not stirred.
  • Example 1 the powdery DDR type zeolite obtained in Example 1 is referred to as the powdery DDR type zeolite of Example 1. The same applies to Example 2.
  • DDR type zeolite 2 is an X-ray analysis result of the powdered DDR type zeolite of Example 2.
  • the “diffraction peak of DDR type zeolite” in X-ray diffraction refers to No. corresponding to Deca-dodecyl 3R shown in International Center for Diffraction Data (ICDD) and “Powder Diffraction File”. It is a diffraction peak described in 38-651 or 41-571.
  • Example 3 (Raw material solution preparation process) An aqueous 1-adamantanamine hydrochloride solution was prepared by adding 61 ml of water and 0.71 g of 1-adamantanamine hydrochloride (manufactured by Daicel Chemical Industries) into a 100 ml wide-mouth bottle made of fluororesin. At this time, 1-adamantanamine hydrochloride was completely dissolved in water by stirring using a stirrer. To this 1-adamantanamine hydrochloride aqueous solution, silica sol (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd., solid content concentration: 30% by mass) was added.
  • silica sol trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd., solid content concentration: 30% by mass
  • Table 1 shows the molar ratio of 1-adamantanamine hydrochloride / SiO 2 and the molar ratio of water / SiO 2 in the raw material solution of Example 3.
  • the graph shown in FIG. 3 is an X-ray analysis result obtained by measuring an alumina support after hydrothermal synthesis of Example 3 using an X-ray diffractometer.
  • the diffraction peak of alumina corundum which is a component of the support (FIG. 3, the peak indicated by cross (x)
  • the diffraction peak of DDR-type zeolite FIG. 3, the peak indicated by circle ( ⁇ )
  • halo was detected.
  • Example 3 the DDR type zeolite crystals were formed on the alumina support after the hydrothermal synthesis of Example 3 on the alumina support.
  • the DDR type zeolite could be crystal-grown even if the raw material solution did not contain sodium hydroxide (NaOH).
  • the present invention can be used as a method for producing a DDR type zeolite that can be used for a catalyst, a catalyst carrier, an adsorbent, a gas separation membrane, a pervaporation membrane, and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

La présente invention concerne un procédé de production de zéolithe de type DDR, ledit procédé comprenant : une étape d'élaboration d'une solution de produits bruts permettant d'obtenir une solution de produits bruts comprenant du chlorhydrate de 1-adamantaneamine, de la silice (SiO2) et de l'eau dans un rapport molaire tel que le rapport molaire du chlorhydrate de 1-adamantaneamine sur SiO2 (chlorhydrate de 1-adamantaneamine/SiO2) est compris entre 0,002 et 0,5, et le rapport molaire de l'eau sur SiO2 (eau/SiO2) est compris entre 10 et 500 ; et une étape de croissance cristalline consistant en le chauffage de la solution de produits bruts et d'une poudre de zéolithe de type DDR tout en mettant les deux substances en contact l'une avec l'autre pour faire croître des cristaux de la zéolithe de type DDR en utilisant la poudre de zéolithe de type DDR au titre d'amorce cristalline. Le procédé de production d'une zéolithe de type DDR peut être mis en oeuvre avec des substances ayant un faible impact sur l'environnement, ne nécessite qu'une durée de synthèse hydrothermique plus courte, ne nécessite pas d'agitation continue de la solution de produit brut et peut être mis en oeuvre de façon économique.
PCT/JP2010/069726 2009-12-10 2010-11-05 Procédé de production de zéolithe de type ddr Ceased WO2011070879A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201080053919.7A CN102639441B (zh) 2009-12-10 2010-11-05 Ddr型沸石的制造方法
JP2011545152A JP5695576B2 (ja) 2009-12-10 2010-11-05 Ｄｄｒ型ゼオライトの製造方法
EP10835801.1A EP2511234B1 (fr) 2009-12-10 2010-11-05 Procédé de production de zéolithe de type ddr
US13/457,838 US8545802B2 (en) 2009-12-10 2012-04-27 Process for production of DDR-type zeolite

Applications Claiming Priority (2)

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JP2009-280294 2009-12-10
JP2009280294 2009-12-10

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US13/457,838 Continuation US8545802B2 (en) 2009-12-10 2012-04-27 Process for production of DDR-type zeolite

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EP (1) EP2511234B1 (fr)
JP (1) JP5695576B2 (fr)
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WO (1) WO2011070879A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014157323A1 (fr) * 2013-03-29 2014-10-02 日本碍子株式会社 Procédé de production de cristaux de zéolite du type ddr et procédé de production de film de zéolite du type ddr

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106955600B (zh) * 2017-04-08 2018-09-18 谢丽萍 一种片式分子筛膜的制备方法
WO2019187640A1 (fr) * 2018-03-30 2019-10-03 日本碍子株式会社 Corps composite de membrane en zéolite, procédé de production de corps composite de membrane en zéolite, et procédé de séparation

Citations (4)

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JPS6340718A (ja) * 1986-07-31 1988-02-22 アンスティテュー・フランセ・デュ・ペトロール ゼオライトＮｕ−３の製造方法
JP2003159518A (ja) * 2001-09-17 2003-06-03 Ngk Insulators Ltd Ｄｄｒ型ゼオライト膜の製造方法
JP2004083375A (ja) 2002-08-29 2004-03-18 Ngk Insulators Ltd Ｄｄｒ型ゼオライトの製造方法
JP2005067991A (ja) 2003-08-28 2005-03-17 Ngk Insulators Ltd Ｄｄｒ型ゼオライトの製造方法

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MXPA04002508A (es) * 2001-09-17 2004-05-31 Ngk Insulators Ltd Metodo para preparar membrana de zeolita tipo ddr, membrana de zeolita tipo ddr y membrana de zeolita tipo ddr compuesta y metodo para preparar las mismas.
JP4204273B2 (ja) * 2002-08-09 2009-01-07 日本碍子株式会社 Ｄｄｒ型ゼオライト膜複合体及びその製造方法
EP1995215B1 (fr) * 2006-03-14 2014-10-22 NGK Insulators, Ltd. Procede de fabrication d'une membrane en zeolithe de type ddr
WO2009113715A1 (fr) * 2008-03-12 2009-09-17 日本碍子株式会社 Procédé de fabrication d'une structure pourvue d'une membrane à zéolite de type ddr

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JPS6340718A (ja) * 1986-07-31 1988-02-22 アンスティテュー・フランセ・デュ・ペトロール ゼオライトＮｕ−３の製造方法
JP2003159518A (ja) * 2001-09-17 2003-06-03 Ngk Insulators Ltd Ｄｄｒ型ゼオライト膜の製造方法
JP2004083375A (ja) 2002-08-29 2004-03-18 Ngk Insulators Ltd Ｄｄｒ型ゼオライトの製造方法
JP2005067991A (ja) 2003-08-28 2005-03-17 Ngk Insulators Ltd Ｄｄｒ型ゼオライトの製造方法

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DEN EXTER M J ET AL.: "Separation of Permanent Gases on the All-Silica 8-Ring Clathrasil DD3R", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 84, 1994, pages 1159 - 1166, XP008156441 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014157323A1 (fr) * 2013-03-29 2014-10-02 日本碍子株式会社 Procédé de production de cristaux de zéolite du type ddr et procédé de production de film de zéolite du type ddr
JPWO2014157323A1 (ja) * 2013-03-29 2017-02-16 日本碍子株式会社 Ｄｄｒ型ゼオライト結晶の製造方法及びｄｄｒ型ゼオライト膜の製造方法
US10093547B2 (en) 2013-03-29 2018-10-09 Ngk Insulators, Ltd. Method for producing DDR type zeolite crystals and method for producing DDR type zeolite membrane

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Publication number Publication date
EP2511234A4 (fr) 2015-08-05
EP2511234B1 (fr) 2017-12-20
JPWO2011070879A1 (ja) 2013-04-22
EP2511234A1 (fr) 2012-10-17
US20120213696A1 (en) 2012-08-23
US8545802B2 (en) 2013-10-01
JP5695576B2 (ja) 2015-04-08
CN102639441B (zh) 2014-10-22
CN102639441A (zh) 2012-08-15

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