KR20030082022A - The zeolites TNU-9 and TNU-10 and their manufacturing process - Google Patents
The zeolites TNU-9 and TNU-10 and their manufacturing process Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004809 Teflon Substances 0.000 claims description 6
- 229920006362 Teflon® Polymers 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- JWEOXDHEGNGCEP-UHFFFAOYSA-N [Br-].[Br-].CCCC.C[NH+]1CCCC1.C[NH+]1CCCC1 Chemical compound [Br-].[Br-].CCCC.C[NH+]1CCCC1.C[NH+]1CCCC1 JWEOXDHEGNGCEP-UHFFFAOYSA-N 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 239000011973 solid acid Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000001939 inductive effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010428 baryte Substances 0.000 description 2
- 229910052601 baryte Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- -1 alkyl ammonium ions Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SBXORXZXXUXJIE-UHFFFAOYSA-N butane 1-methylpyrrolidine Chemical compound CCCC.CN1CCCC1 SBXORXZXXUXJIE-UHFFFAOYSA-N 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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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
- 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
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
본 발명은 새로운 골격구조 또는 조성을 갖는 제올라이트들인 TNU-9와 TNU-10 및 그 제조방법에 관한 것으로, 보다 상세하게는 지금까지 알려진 제올라이트와는 전혀 다른 새로운 구조와 조성을 갖는 TNU-9 제올라이트와 천연 제올라이트의 일종인 배러라이트(Barrerite)와 동일한 구조를 갖고 있으나 골격내 SiO2/Al2O3비가 더 큰 TNU-10 제올라이트를 제조하여, 독특한 형상 선택성을 갖는 고체산 촉매 또는 특정 분자에 대한 분리제로 사용할 수 있는 새로운 제올라이트 및 그 제조방법을 제공하는데 그 목적이 있으며, 상기와 같은 목적을 달성하기 위한 본 발명은, 기본적인 골격구조의 조성이 하기한 화학식 1과 같은 몰비의 산화물들로 이루어져 있으며, 최소 400 m2/g 이상의 높은 표면적과 함께 500℃ 이상의 고온에서도 그 골격구조를 유지하는 높은 열적 안정성을 가지며 최소 4.5 Å보다 큰 크기의 균일한 세공을 그 내부에 포함하고 있어 정밀화학, 석유화학공업 등에서 이온교환제, 분리제, 촉매 또는 촉매 지지체로 사용될 수 있는 물리화학적 성질을 갖고 있는 것을 특징으로 하는 제올라이트들을 제공함으로써 달성할 수 있다.The present invention relates to TNU-9 and TNU-10, which are zeolites having a new skeleton structure or composition, and a method for preparing the same. More specifically, the present invention relates to TNU-9 zeolite and natural zeolite having a completely different structure and composition from those known to date. TNU-10 zeolite having the same structure as Barrerite, but having a higher SiO 2 / Al 2 O 3 ratio in the skeleton, is used as a solid acid catalyst having unique shape selectivity or as a separation agent for a specific molecule. It is an object of the present invention to provide a new zeolite and a method for producing the same, and the present invention for achieving the above object, the composition of the basic skeleton structure is composed of oxides of the molar ratio of the formula (1) below, at least 400 High thermal stability that maintains its framework even at high temperatures above 500 ° C with high surface areas of more than m 2 / g It is qualitative and contains uniform pores with a size of at least 4.5 최소 inside, and has physicochemical properties that can be used as an ion exchanger, separator, catalyst or catalyst support in fine chemicals and petrochemical industries. It can be achieved by providing zeolites.
＜화학식 1＞<Formula 1>
1.0 Al2O3: 10.0-200.0 SiO2 1.0 Al 2 O 3 : 10.0-200.0 SiO 2
Description
본 발명은 새로운 골격구조와 조성을 갖는 제올라이트 및 그 제조방법에 관한 것으로, 보다 상세하게는 지금까지 알려진 제올라이트와는 전혀 다른 새로운 구조와 조성을 갖는 TNU-9 제올라이트와 천연 제올라이트의 일종인 배러라이트(Barrerite)와 동일한 구조를 갖고 있으나 골격조성이 다른 TNU-10 제올라이트 및 그 제조방법에 관한 것이다.The present invention relates to a zeolite having a new skeleton structure and composition, and to a method of manufacturing the same. The present invention relates to a TNU-10 zeolite having the same structure as the other but having a different skeleton composition, and a method for preparing the same.
현재 제올라이트를 포함하는 분자체는 정밀화학, 석유화학 등의 다양한 분야에서 이온교환제, 분리제, 촉매 또는 촉매지지체로 광범위하게 사용되고 있다[Kirk Othmer Encyclo. Chem. Technol., 1995, 16권, 888페이지]. 제올라이트와 분자체의 내부에는 골격구조에 따라 0.1 Å 이하의 오차범위 내에서 크기가 균일한 세공이 존재한다. 따라서, 이들 물질은 무정형의 산화물에서는 관찰되지 않는 독특한 형상 선택성을 가지고 있어 정밀화학, 석유화학공업 등에서 이온교환제, 분리제, 촉매 또는 촉매지지체로 적용됨으로써 기존 화학공정의 획기적 개선은 물론 상업적으로 매우 중요한 수많은 새로운 공정의 개발을 가능케 하였다[Molecular Transport andReaction in Zeolites, VCH, 1994]. 이와 같은 제올라이트의 상업적 성공은 세공의 크기와 모양이 기존의 물질과 다른 제올라이트들이 지난 수십년 동안 계속해서 발견되어 수많은 석유화학, 정밀화학 공정에 다양하게 적용됨으로써 기술혁신의 견인차 역할을 해왔기 때문이라 할 수 있다.Currently, molecular sieves including zeolites are widely used as ion exchangers, separators, catalysts or catalyst supports in various fields such as fine chemistry and petrochemicals [Kirk Othmer Encyclo. Chem. Technol., 1995, Vol. 16, p. 888]. Inside the zeolite and the molecular sieve, there are pores with a uniform size within an error range of 0.1 Å or less depending on the framework structure. Therefore, these materials have unique shape selectivity not found in amorphous oxides, and thus are applied as ion exchangers, separators, catalysts, or catalyst supports in fine chemicals, petrochemical industries, etc. It has enabled the development of many important new processes [Molecular Transport and Reaction in Zeolites, VCH, 1994]. Zeolite's commercial success is due to the fact that zeolites with different pore sizes and shapes have been discovered over the last few decades and have been applied to numerous petrochemical and fine chemical processes, and have been the driving force behind technological innovation. can do.
이에 본 발명자는 지금까지 알려진 제올라이트들과 전혀 다른 골격구조 또는 조성을 갖는 제올라이트들을 제조하기 위한 연구를 거듭하여 두 종의 새로운 제올라이트 두 종을 발견하기에 이르렀다.Accordingly, the present inventors have repeatedly studied to prepare zeolites having a skeleton structure or composition completely different from those of the known zeolites, and found two new zeolite species.
본 발명은 지금까지 알려진 제올라이트들과 전혀 다른 골격구조 또는 조성을 갖는 제올라이트들을 제조하여 정밀화학, 석유화학공업 등에서 이온교환제, 분리제, 촉매 또는 촉매지지체로서 새로운 물성을 갖는 제올라이트들 및 그 제조방법을 제공하는데 그 목적이 있다.The present invention provides a zeolite having a new physical property as an ion exchanger, separator, catalyst or catalyst support in fine chemicals, petrochemical industry, etc. The purpose is to provide.
상기와 같은 목적을 달성하기 위한 본 발명은, 기본적인 골격구조의 조성이 하기한 화학식 1과 같은 몰 비의 산화물로 이루어져 있으며, 최소 400 m2/g 이상의 높은 표면적과 함께 500℃ 이상의 고온에서도 그 골격구조를 유지하는 높은 열적 안정성을 가지며 최소 4.5 Å보다 큰 크기의 균일한 세공을 그 내부에 포함하고 있는 것을 특징으로 하는 제올라이트들을 제공함으로써 달성할 수 있다.The present invention for achieving the above object, the composition of the basic skeleton structure is composed of the oxide of the molar ratio as shown in the following formula (1), with a high surface area of at least 400 m 2 / g or more of the skeleton at a high temperature of 500 ℃ or more It can be achieved by providing zeolites having a high thermal stability to maintain the structure and containing therein uniform pores of a size larger than at least 4.5 mm 3.
[화학식 1][Formula 1]
1.0 Al2O3: 10.0-200.0 SiO2 1.0 Al 2 O 3 : 10.0-200.0 SiO 2
본 발명에 개시된 두 종의 제올라이트들을 지금부터 각각 TNU-9(Taejon University Number 9)와 TNU-10(Taejon University Number 10)으로 명명한다. TNU-9의 경우 이 제올라이트와 동일한 골격구조를 갖는 제올라이트들은 아직까지 문헌에 명시된 바가 없으며 TNU-10은 그 골격이 천연 제올라이트의 일종인 배러라이트(Barrerite)와 동일하나 배러라이트를 인위적으로 합성한 예는 전혀 보고된 바가 없다[Atlas of Zeolite Structure Types, Butterworth, 1992].The two zeolites disclosed in the present invention are now named TNU-9 (Taejon University Number 9) and TNU-10 (Taejon University Number 10), respectively. In the case of TNU-9, zeolites having the same skeleton structure as this zeolite have not been specified in the literature so far, and TNU-10 is an example in which the skeleton is the same as that of barrerite, which is a kind of natural zeolite, but artificially synthesized the barrite. Has not been reported at all [Atlas of Zeolite Structure Types, Butterworth, 1992].
본 발명에 의한 TNU-9와 TNU-10 제올라이트들은 diquaternary ammonium salt인 1,4-bis(N-methylpyrrolidinium)butane(이하 MPB라 칭함) dibromide를 포함하는 반응혼합물내 SiO2/Al2O3및 NaOH/SiO2비를 조절한 후 수열결정화를 통하여 제조할 수 있다. 일반적으로 제올라이트의 합성은 무기 양이온, 유기 양이온 또는 이 두가지 양이온을 동시에 알루미노실리케이트 겔에 첨가하여 열처리하는 소위 수열결정화 방법을 통하여 이루어지며, 현재까지 60여 종 이상의 새로운 골격구조를 갖는 제올라이트들이 이와 같은 합성방법으로 발견되어 왔다[Handbook of Molecular Sieves, Van Nostrand Reinhold, 1992]. 최근 본 발명자는 제올라이트의 합성에서 유기구조유도분자로 첨가되는 알킬 아민 또는 알킬 암모늄이온의 분자배좌 (molecular conformation)는 반응혼합물내 여러 무기성분간의 몰비, 특히 SiO2/Al2O3및 NaOH/SiO2비에 따라 크게 달라질 수 있으며, 따라서 유기구조유도분자의 conformation을 적절히 조절함으로써 새로운 제올라이트를 합성할 수 있음을 전문 잡지에 제시한 바 있다 [J. Phys. Chem., 2001, 105권, 9994페이지]. 한편, 본 발명에서 유기구조유도분자로 사용된 MPB는 층상 실리케이트 물질의 일종인 MCM-47의 합성에 사용된 예가 미국 특허 5, 068, 096호에 소개되어 있으나, 이 유기구조유도분자를 이용한 제올라이트의 합성은 지금까지 보호된 바가 없다.TNU-9 and TNU-10 zeolites according to the present invention are SiO 2 / Al 2 O 3 and NaOH / SiO in a reaction mixture containing 1,4-bis ( N- methylpyrrolidinium) butane (hereinafter referred to as MPB) dibromide, which is a diquaternary ammonium salt. After adjusting the ratio 2 may be prepared by hydrothermal crystallization. In general, the synthesis of zeolites is accomplished through a so-called hydrothermal crystallization method in which an inorganic cation, an organic cation, or both cations are simultaneously added to an aluminosilicate gel and heat treated. Synthetic methods have been found (Handbook of Molecular Sieves, Van Nostrand Reinhold, 1992). Recently, the inventors have found that the molecular conformation of alkyl amines or alkyl ammonium ions, which are added as organic structure-inducing molecules in the synthesis of zeolites, is a molar ratio between various inorganic components in the reaction mixture, in particular SiO 2 / Al 2 O 3 and NaOH / SiO. 2 , which can vary greatly depending on the ratio, suggests in the journal that new zeolites can be synthesized by appropriately adjusting the conformation of organic structure-derived molecules [J. Phys. Chem., 2001, Vol. 105, p. 9994]. On the other hand, MPB used as the organic structure-inducing molecule in the present invention is an example used in the synthesis of MCM-47, a kind of layered silicate material is introduced in US Patent No. 5, 068, 096, zeolite using this organic structure-inducing molecule Has never been protected.
상기 화학식 1과 같은 골격구조와 조성을 갖는 TNU-9와 TNU-10 제올라이트들을 제조하기 위한 본 발명은, 비이커에 질산 알루미늄(Al(NO3)3ㆍ9H20) 1몰에 대하여 1가의 수산화나트륨(NaOH)의 수용액을 20내지 32몰의 비율이 되도록 첨가하여 녹인 후 실리카 졸 또는 무정형의 실리카를 산화알루미늄 1몰에 대하여 30내지 120몰비로 5분내지 10분에 걸쳐 천천히 가하여 1시간 교반시킨다. 마지막으로 3내지 6몰의 MPB를 첨가한 다음 다시 상온에서 24시간 교반시킨다. 여기에서 유기구조유도분자로 사용된 MPB는 acetone을 용매로 사용, 3몰의 1-methylpyrrolidine과 1몰의 1,4-dibromobutane을 반응시켜 합성하였다. 이렇게 얻은 반응혼합물의 조성은 화학식 2와 같다.The present invention for preparing TNU-9 and TNU-10 zeolites having a skeleton structure and composition as shown in Formula 1, monovalent sodium hydroxide per 1 mole of aluminum nitrate (Al (NO 3 ) 3 ㆍ 9H 2 0) in a beaker An aqueous solution of (NaOH) is added to a ratio of 20 to 32 moles to dissolve, and then a silica sol or amorphous silica is slowly added over a period of 5 to 10 minutes at a molar ratio of 30 to 120 moles per 1 mole of aluminum oxide and stirred for 1 hour. Finally add 3 to 6 moles of MPB and then stir again at room temperature for 24 hours. The MPB used as the organic structural guide molecule was synthesized by reacting 3 moles of 1-methylpyrrolidine with 1 mole of 1,4-dibromobutane using acetone as a solvent. The composition of the reaction mixture thus obtained is shown in Chemical Formula 2.
[화학식 2][Formula 2]
4.0-6.0 MPB:.x Na2O : 1.0 Al2O3: 30.0-120.0 SiO2: 600-1500 H2O4.0-6.0 MPB: .x Na 2 O: 1.0 Al 2 O 3 : 30.0-120.0 SiO 2 : 600-1500 H 2 O
여기서 x는 TNU-9와 TNU-10의 경우에 각각 10-12와 14-16이다. 위에 서술된 순서와 시약을 사용하여 얻은 반응혼합물을 테프론 반응기에 옮기고 다시 스테인레스 강철로 만든 용기에 넣어 140-180℃에서 3-21 일 동안 가열하는 것을 특징으로 하는 TNU-9와 TNU-10 제올라이트들의 제조방법을 제공한다. 특히, 반응혼합물이 화학식3과 같은 조성을 가질 때 160℃에서 14 일 동안 가열하면 순수한 TNU-9와 TNU-10의 합성이 용이하다.Where x is 10-12 and 14-16 for TNU-9 and TNU-10, respectively. The reaction mixtures obtained using the procedure and reagents described above were transferred to a Teflon reactor and placed in a stainless steel container and heated at 140-180 ° C. for 3-21 days to prepare the TNU-9 and TNU-10 zeolites. It provides a manufacturing method. In particular, when the reaction mixture has a composition as shown in Formula 3, heating at 160 ° C. for 14 days facilitates the synthesis of pure TNU-9 and TNU-10.
[화학식 3][Formula 3]
4.5 MPB:.x Na2O : 0.75-0.25 Al2O3: 30.0 SiO2: 1200 H2O4.5 MPB: .x Na 2 O: 0.75-0.25 Al 2 O 3 : 30.0 SiO 2 : 1200 H 2 O
여기서 x는 TNU-9와 TNU-10의 경우에 각각 11과 15이다.Where x is 11 and 15 for TNU-9 and TNU-10, respectively.
상기의 제조방법에 의한 TNU-9 제올라이트를 X-선 회절 측정시험을 하면 표 1에 나타난 결과를 얻을 수 있다.X-ray diffraction measurement test of the TNU-9 zeolite according to the above production method can obtain the results shown in Table 1.
[표 1]TABLE 1
표 1 에서 , θ, d, I는 각각 브래그(Bragg)각, 격자간격, 그리고 x-선 회절 피크 의 강도를 의미한다. 이 분말 X-선 회절 패턴을 포함하여 본 발명에서 보고되는 모든 분말 X-선 회절 데이터는 표준 X-선 회절 방법을 이용하여 측정하였으며, 방사원으로는 구리 Kα선과 30kV, 40mA에서 작동하는 X-선 튜브를 사용하였다. 수평으로 압축된 문말시료로부터 분당 2도(2θ)의 속도로 측정하였으며, 관찰된 X-선회절 피크의 2θ값과 피크 높이로부터 d와 I를 계산하였다.In Table 1, θ, d, and I represent the Bragg angle, the lattice spacing, and the intensity of the x-ray diffraction peak, respectively. All powder X-ray diffraction data reported in the present invention, including this powder X-ray diffraction pattern, were measured using standard X-ray diffraction methods. As a radiation source, X-rays operated at 30 kV, 40 mA with copper Kα rays. A tube was used. From the horizontally compressed text sample, it was measured at a rate of 2 degrees per minute (2θ), and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peaks.
상기한 결과에 따라 지금부터 골격구조가 화학식 1과 같은 조성으로 이루어져 있으며, 적어도 표 1에 주어진 격자간격들을 포함하는 X-선 회절 패턴을 갖는 제올라이트를 TNU-9로 규정한다.According to the above results, the zeolite having a X-ray diffraction pattern including a lattice interval given in Table 1 and having a skeleton structure of the formula 1 is now defined as TNU-9.
또한 모든 TNU-9 물질에 대한 일반적인 X-선 회절 패턴은 표 2에 기록된 격자 간격들의 범위 내에 포함하는 것으로 규정한다.In addition, the general X-ray diffraction pattern for all TNU-9 materials is defined to fall within the range of grating intervals reported in Table 2.
[표 2]TABLE 2
또한 본 발명은 상기의 제조방법에 의한 TNU-10 제올라이트를 X-선 회절 측정시험을 하면 표 3에 나타난 결과를 얻을 수 있다.In addition, the present invention can obtain the results shown in Table 3 by X-ray diffraction measurement test of TNU-10 zeolite according to the above production method.
[표 3]TABLE 3
상기한 결과에 따라 지금부터 골격구조가 화학식 1과 같은 조성으로 이루어져 있으며, 적어도 표3에 주어진 격자간격들을 포함하는 X-선 회절 패턴을 갖는 제올라이트를 TNU-10으로 규정한다.According to the above results, the zeolite having the X-ray diffraction pattern including the lattice spacings of which the skeleton structure has the same composition as the formula (1) and at least given in Table 3 is defined as TNU-10.
또한 모든 TNU-10 물질에 대한 일반적인 X-선 회절 패턴은 표 4에 기록된 격자 간격들의 범위 내에 포함하는 것으로 규정한다.In addition, a general X-ray diffraction pattern for all TNU-10 materials is defined to fall within the range of grating intervals reported in Table 4.
[표 4]TABLE 4
이하, 본 발명을 대표적인 몇 가지 실시 예를 들어 TNU-9와 TNU-10 제올라이트들의 제조방법의 상세한 이해를 위하여 설명하나, 이는 단지 그 실시 양태를 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described for a detailed understanding of several exemplary embodiments, for example, the preparation method of TNU-9 and TNU-10 zeolites, which are only intended to illustrate the embodiments and to limit the scope of the present invention. It is not.
＜실시예 1＞<Example 1>
TNU-9 제올라이트의 제조Preparation of TNU-9 Zeolite
플라스틱 비커에 먼저 1.96g의 50 중량 % 수산화나트륨(NaOH) 수용액과 0.64g의 질산 알루미늄(Al(NO3)3ㆍ9H2O)을 22.48g의 물에 넣어 5분간 교반한 다음, 2.0g의 무정형 실리카(Degussa, Aerosil 200)를 천천히 첨가하여 30분 교반하고, 1.97g의 MPB를 가하여 하기한 화학식 4에 나타낸 반응혼합물을 얻은 다음, 상기에서 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든용기에 넣어 160℃에서 14 일 동안 분당 100회씩 회전시켜가며 가열한 다음, 얻어진 고체 생성물을 물로 반복 세척하여 상온에서 건조하였다.In a plastic beaker, first, 1.96 g of 50 wt% aqueous sodium hydroxide (NaOH) solution and 0.64 g of aluminum nitrate (Al (NO 3 ) 3 ㆍ 9H 2 O) were added to 22.48 g of water and stirred for 5 minutes, followed by 2.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 1.97 g of MPB to obtain a reaction mixture represented by the following formula (4), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was put in a container made of heated to rotate 100 times per minute at 160 ℃ for 14 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.
[화학식 4][Formula 4]
4.5 MPB:.11.0 Na2O : 0.75 Al2O3: 30.0 SiO2: 1200 H2O4.5 MPB: .11.0 Na 2 O: 0.75 Al 2 O 3 : 30.0 SiO 2 : 1200 H 2 O
상기 실시예 1에서 얻은 고체분말로 X-선 회절 측정시험을 하고 그 결과를 표 5에 나타내었다.X-ray diffraction measurement test was carried out with the solid powder obtained in Example 1, and the results are shown in Table 5.
[표 5]TABLE 5
＜실시예 2＞<Example 2>
TNU-9 제올라이트의 제조Preparation of TNU-9 Zeolite
플라스틱 비커에 먼저 5.87g의 50 중량 % 수산화나트륨(NaOH) 수용액과 1.28g의 질산 알루미늄(Al(NO3)3ㆍ9H2O)을 67.72g의 물에 넣어 5분간 교반한 다음, 6.0g의 무정형 실리카(Degussa, Aerosil 200)를 천천히 첨가하여 30분 교반하고, 5.91g의 MPB를 가하여 하기한 화학식 5에 나타낸 반응혼합물을 얻은 다음, 상기에서 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 160℃에서 14 일 동안 분당 100회씩 회전시켜 가며 가열한 다음, 얻어진 고체 생성물을 물로 반복 세척하여 상온에서 건조하였다.In a plastic beaker, first, 5.87 g of 50% by weight aqueous sodium hydroxide (NaOH) solution and 1.28 g of aluminum nitrate (Al (NO 3 ) 3 ㆍ 9H 2 O) were added to 67.72 g of water and stirred for 5 minutes, followed by 6.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 5.91 g of MPB to obtain a reaction mixture represented by Formula 5 below, transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 14 days and then, the obtained solid product was repeatedly washed with water and dried at room temperature.
[화학식 5][Formula 5]
4.5 MPB:.11.0 Na2O : 0.5 Al2O3: 30.0 SiO2: 1200 H2O4.5 MPB: .11.0 Na 2 O: 0.5 Al 2 O 3 : 30.0 SiO 2 : 1200 H 2 O
상기 실시예 2에서 얻은 고체생성물의 분말로 X-선 회절 측정시험을 한 결과 표 5에 주어진 X-선 데이터와 동일하였으며 다른 상은 관찰되지 않았다.X-ray diffraction measurement test with the powder of the solid product obtained in Example 2 was the same as the X-ray data given in Table 5, no other phase was observed.
상기 실시예 2에서 얻은 시료의 일부분을 550℃의 공기 하에서 12시간 소성한 후 다시 X-선 회절 패턴을 측정하였을 때 소성된 시료는 실시예 1의 경우와 근본적으로 동일한 X-선 패턴을 나타내는 것으로 관찰되었으며, 이 시료의 조성을 규명하기 위하여 원소분석을 수행, 얻은 결과를 화학식 6에 나타내었다.When a portion of the sample obtained in Example 2 was fired for 12 hours under air at 550 ° C., and the X-ray diffraction pattern was measured again, the fired sample exhibited essentially the same X-ray pattern as in Example 1. It was observed, and the results obtained by performing elemental analysis to identify the composition of this sample are shown in the formula (6).
[화학식 6][Formula 6]
0.28 Na2O : 1.0 Al2O3: 25.3 SiO2 0.28 Na 2 O: 1.0 Al 2 O 3 : 25.3 SiO 2
상기 실시예 2에서 얻은 시료의 일부분을 550℃의 공기 하에서 12시간 소성하여 1.0몰 질산 암모늄 용액에 넣어 80℃에서 6시간 가열한 후 다시 500℃의 공기하에서 8시간 소성하여 질소 흡착 시험을 한 결과 TNU-9제올라이트는 약 500 m2/g의 BET표면적을 갖는 것으로 관찰되었다.A part of the sample obtained in Example 2 was calcined under air at 550 ° C. for 12 hours, put in a 1.0 molar ammonium nitrate solution, heated at 80 ° C. for 6 hours, and calcined again at 500 ° C. for 8 hours for nitrogen adsorption test. TNU-9 zeolite was observed to have a BET surface area of about 500 m 2 / g.
＜실시예 3＞<Example 3>
TNU-10 제올라이트의 제조Preparation of TNU-10 Zeolite
플라스틱 비커에 먼저 3.69g의 50 중량 % 수산화나트륨(NaOH) 수용액과 0.29g의 질산 알루미늄(Al(NO3)3ㆍ9H2O)을 30.80g의 물에 넣어 5분간 교반한 다음, 2.77g의 무정형 실리카(Degussa, Aerosil 200)를 천천히 첨가하여 30분 교반하고, 2.73g의 MPB를 가하여 하기한 화학식 7에 나타낸 반응혼합물을 얻은 다음, 상기에서 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 160℃에서 12 일 동안 분당 100회씩 회전시켜가며 가열한 다음, 얻어진 고체 생성물을 물로 반복 세척하여 상온에서 건조하였다.In a plastic beaker, 3.69 g of 50% by weight aqueous sodium hydroxide (NaOH) solution and 0.29 g of aluminum nitrate (Al (NO 3 ) 3 ㆍ 9H 2 O) were added to 30.80 g of water and stirred for 5 minutes, followed by 2.77 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 2.73 g of MPB to obtain a reaction mixture represented by the following formula (7), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 12 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.
[화학식 7][Formula 7]
4.5 MPB:.15.0 Na2O : 0.25 Al2O3: 30.0 SiO2: 1200 H2O4.5 MPB: .15.0 Na 2 O: 0.25 Al 2 O 3 : 30.0 SiO 2 : 1200 H 2 O
상기 실시예 3에서 얻은 고체분말로 X-선 회절 측정시험을 하고 그 결과를 표 6에 나타내었다.X-ray diffraction measurement test was carried out with the solid powder obtained in Example 3, and the results are shown in Table 6.
[표 6]TABLE 6
기존에 보고된 제올라이트들의 X-선 회절 패턴들과 비교하였을 때 TNU-10은 천연제올라이트의 일종인 배러라이트와 동일한 구조를 갖고 있는 것으로 확인되었다[Collection of Simulated XRD Patterns fro Zeolites, Elsevier, 1996].Compared with the previously reported X-ray diffraction patterns of zeolites, TNU-10 was found to have the same structure as barite, a kind of natural zeolite [Collection of Simulated XRD Patterns fro Zeolites, Elsevier, 1996].
＜실시예 4＞<Example 4>
TNU-10 제올라이트의 제조Preparation of TNU-10 Zeolite
플라스틱 비커에 먼저 2.67g의 50 중량 % 수산화나트륨(NaOH) 수용액과 0.43g의 질산 알루미늄(Al(NO3)3ㆍ9H2O)을 22.22g의 물에 넣어 5분간 교반한 다음, 2.0g의 무정형 실리카(Degussa, Aerosil 200)를 천천히 첨가하여 30분 교반하고,1.97g의 MPB를 가하여 하기한 화학식 8에 나타낸 반응혼합물을 얻은 다음, 상기에서 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 160℃에서 14 일 동안 분당 100회씩 회전시켜가며 가열한 다음, 얻어진 고체 생성물을 물로 반복 세척하여 상온에서 건조하였다.In a plastic beaker, 2.67 g of 50 wt% aqueous sodium hydroxide (NaOH) solution and 0.43 g of aluminum nitrate (Al (NO 3 ) 3 ㆍ 9H 2 O) were added to 22.22 g of water and stirred for 5 minutes, followed by 2.0 g of Slowly add amorphous silica (Degussa, Aerosil 200) and stir for 30 minutes, add 1.97 g of MPB to obtain a reaction mixture represented by the following formula (8), transfer the reaction mixture obtained above to a Teflon reactor, and then again stainless steel It was heated in a container made of a rotating 100 times per minute at 160 ℃ for 14 days, and then the obtained solid product was repeatedly washed with water and dried at room temperature.
[화학식 8][Formula 8]
4.5 MPB:.15.0 Na2O : 0.50 Al2O3: 30.0 SiO2: 1200 H2O4.5 MPB: .15.0 Na 2 O: 0.50 Al 2 O 3 : 30.0 SiO 2 : 1200 H 2 O
상기 실시예 4에서 얻은 고체생성물의 분말로 X-선 회절 측정시험을 한 결과 실시예 3에 주어진 X-선 데이터와 동일하였으며 다른 상은 관찰되지 않았다.As a result of X-ray diffraction measurement test with the powder of the solid product obtained in Example 4, it was the same as the X-ray data given in Example 3, and no other phase was observed.
상기 실시예 4에서 얻은 시료의 일부분을 550℃의 공기 하에서 12시간 소성한 후 다시 X-선 회절 패턴을 측정하였을 때 소성된 시료는 표 6의 경우와 근본적으로 동일한 X-선 패턴을 나타내는 것으로 관찰되었으며, 이 시료의 조성을 규명하기 위하여 원소분석을 수행, 얻은 결과를 화학식 9에 나타내었다.When a portion of the sample obtained in Example 4 was fired for 12 hours under air at 550 ° C., and the X-ray diffraction pattern was measured again, the fired sample showed the same X-ray pattern as in Table 6. In order to identify the composition of the sample, elemental analysis was performed to show the results of the general formula (9).
[화학식 9][Formula 9]
0.40 Na2O : 1.0 Al2O3: 13.0 SiO2 0.40 Na 2 O: 1.0 Al 2 O 3 : 13.0 SiO 2
본 발명의 TNU-10과 동일한 구조를 갖고 있는 천연제올라이트의 일종인 배러라이트의 골격내 SiO2/Al2O3비(6.8)에 비해 TNU-10의 SiO2/Al2O3비(13.0)가 더 높은 것으로 확인되었다.Within the framework of the Barre light kind of natural zeolite which has the same structure and TNU-10 of the present invention, SiO 2 / Al 2 O 3 of TNU-10 compared to the ratio (6.8) SiO 2 / Al 2 O 3 ratio (13.0) Was found to be higher.
상기 실시예에서 얻은 시료의 일부분을 550℃의 공기 하에서 12시간 소성하여 1.0몰 질산 암모늄 용액에 넣어 80℃에서 6시간 가열한 후 다시 500℃의 공기하에서 8시간 소성하여 질소 흡착 시험을 한 결과 TNU-10 제올라이트는 약 440 m2/g의 BET표면적을 갖는 것으로 관찰되었다.A portion of the sample obtained in the above example was calcined under air at 550 ° C. for 12 hours, put in a 1.0 mol ammonium nitrate solution, heated at 80 ° C. for 6 hours, and calcined again at 500 ° C. for 8 hours under nitrogen adsorption test. The -10 zeolite was observed to have a BET surface area of about 440 m 2 / g.
상기에서 살펴본 바와 같이 본 발명은, 지금까지 알려진 제올라이트와는 전혀 다른 새로운 구조와 조성을 갖는 TNU-9 제올라이트와 천연 제올라이트의 일종인 배러라이트와 동일한 구조를 갖고 있으나 골격내 SiO2/Al2O3비가 더 큰 TNU-10 제올라이트를 제조하여, 독특한 형상 선택성을 갖는 고체산 촉매 또는 특정 분자에 대한 분리제로 사용할 수 있는 새로운 제올라이트 및 그 제조방법을 제공하는 유용한 발명인 것이다.As described above, the present invention has the same structure as that of TNU-9 zeolite having a new structure and composition different from the known zeolites, and a barite which is a kind of natural zeolite, but the SiO 2 / Al 2 O 3 ratio in the skeleton It is a useful invention to make larger TNU-10 zeolites and to provide new zeolites and methods for their preparation that can be used as solid acid catalysts with unique shape selectivity or as a separator for certain molecules.
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| EP0295019A1 (en) * | 1987-06-08 | 1988-12-14 | Mobil Oil Corporation | Treatment of aluminosilicate zeolites |
| FR2634140B1 (en) * | 1988-07-12 | 1990-09-14 | Inst Francais Du Petrole | GALLIUM-CONTAINING ALUMINOSILICATE TYPE CATALYST AND ITS USE IN FLAVORING C2-C4 LIGHT GASES |
| FR2651221B1 (en) * | 1989-08-30 | 1991-11-08 | Elf Aquitaine | NOVEL ZEOLITE FROM THE MAZZITE FAMILY, ITS SYNTHESIS PROCESS AND ITS USE AS A CATALYST. |
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