KR102224614B1 - Silicoaluminophosphate molecular sieves with CHA topology and their manufacturing method using inorganic structure-directing agent - Google Patents
Silicoaluminophosphate molecular sieves with CHA topology and their manufacturing method using inorganic structure-directing agent Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 title 1
- 230000001939 inductive effect Effects 0.000 claims abstract description 42
- 241000269350 Anura Species 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 40
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- -1 aluminum alkoxide Chemical class 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000001282 organosilanes Chemical class 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000012688 phosphorus precursor Substances 0.000 claims 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical group OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000002441 X-ray diffraction Methods 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 150000001767 cationic compounds Chemical class 0.000 description 7
- 229910001411 inorganic cation Inorganic materials 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000006069 physical mixture Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Classifications
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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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
본 발명은 무기 구조 유도물질을 이용한 CHA형 SAPO 실리코알루미노포스페이트 분자체의 제조 및 이를 이용해서 제조된 무기금속을 포함하는 새로운 CHA형 SAPO 실리코알루미노포스페이트 분자체를 제공한다. The present invention provides a novel CHA-type SAPO silicoaluminophosphate molecular sieve comprising an inorganic metal prepared using the preparation of a CHA-type SAPO silicoaluminophosphate molecular sieve using an inorganic structure-inducing substance and the same.
Description
본 발명은 SAPO 및 그 제조 방법에 관한 것으로서, 보다 상세하게는 무기 금속 성분을 포함하는 CHA형 SAPO 및 그 제조 방법에 관한 것이다.The present invention relates to an SAPO and a method for producing the same, and more particularly, to a CHA-type SAPO containing an inorganic metal component and a method for producing the same.
실리코알루미노포스페이트(SAPO)는 알루미늄, 실리콘과 함께 포스포러스 원자가 골격을 이루는 분자체이다. CHA형 SAPO-34는 산업적으로 응용 범위가 넓어 다양한 합성 방법이 개발되고 있다. Silicoaluminophosphate (SAPO) is a molecular sieve in which phosphorus atoms form a skeleton together with aluminum and silicon. CHA type SAPO-34 has a wide range of industrial applications, and various synthesis methods are being developed.
대한민국 특허 공개 제10-2016-0077109호에서는 제1 유기 구조유도물질을 포함하는 제1 슬러리와 제2 유기구조유도물질을 포함하는 제2 슬러리를 이용하여 실리코알루미노포스페이트 분자체(SAPO-34)를 제조하는 방법을 제공한다.In Korean Patent Publication No. 10-2016-0077109, a silicon aluminophosphate molecular sieve (SAPO-34) using a first slurry containing a first organic structure-inducing material and a second slurry containing a second organic structure-inducing material. It provides a method of manufacturing.
대한민국 특허 공개 제10-2017-0044145호에서는 모노아이소프로판올아민을 사용하여 고순도의 SAPO-34 분자체를 제조하는 방법을 제공한다.Republic of Korea Patent Publication No. 10-2017-0044145 provides a method of preparing a high purity SAPO-34 molecular sieve using monoisopropanolamine.
본 발명에서 해결하고자 하는 과제는 무기 금속 성분을 포함하는 새로운 CHA형 SAPO를 제공하는 것이다.The problem to be solved in the present invention is to provide a new CHA-type SAPO containing an inorganic metal component.
본 발명에서 해결하고자 하는 다른 과제는 무기 금속 성분을 포함하는 새로운 CHA형 SAPO의 제조 방법을 제공하는 것이다.Another problem to be solved in the present invention is to provide a method for producing a new CHA-type SAPO containing an inorganic metal component.
상기와 같은 과제를 해결하기 위해서, 본 발명은 하기와 식 (1)과 같은 몰비 조성을 가지는 CHA구조의 실리코알루미노포스페이트 분자체를 제공한다. In order to solve the above problems, the present invention provides a CHA structure silicoaluminophosphate molecular sieve having a molar ratio composition as shown in the following formula (1).
mM:(SixAlyPz)O2 (1) mM:(Si x Al y P z )O 2 (1)
여기서 "M"은 무기금속성분이며, Here, "M" is an inorganic metal component,
"m"은 (Si x Al y P z )O2 1 몰 당 M의 몰수이며, 0.01≤m≤0.5이며,"m" is the number of moles of M per mole of (Si x Al y P z )O 2, 0.01≤m≤0.5,
x, y, z 는 Si, Al, P 의 몰분율이며, 각각 0.01≤x≤0.98, 0.01≤y≤0.98, 0.01≤z≤0.98로서, x + y + z =1.00이다. x , y , z are the mole fractions of Si, Al, and P, respectively , as 0.01≦x ≦0.98, 0.01≦ y ≦0.98, and 0.01≦ z ≦0.98, where x + y + z =1.00.
본 발명에 있어서, 상기 무기 금속 성분은 적어도 하나 이상의 무기양이온이며, 상기 무기 양이온은 알칼리 금속 양이온, 알칼리 토금속 양이온 및 전이 금속이 될 수 있으며, 두 가지 이상의 금속 양이온의 조합이 가능하다.In the present invention, the inorganic metal component is at least one inorganic cation, and the inorganic cation may be an alkali metal cation, an alkaline earth metal cation, and a transition metal, and a combination of two or more metal cations is possible.
본 발명에 있어서, 상기 알카리 금속은 Li, Na, K, Rb, Cs일 수 있으며, 바람직하게는 Na 또는 K이다.In the present invention, the alkali metal may be Li, Na, K, Rb, Cs, preferably Na or K.
본 발명에 있어서, 상기 알카리 토금속은 Be, Mg, Ca, Sr, Ba일 수 있으며, 바람직하게는 Ca 또는 Sr일 수 있다.In the present invention, the alkaline earth metal may be Be, Mg, Ca, Sr, Ba, preferably Ca or Sr.
본 발명에 있어서, 상기 전이금속은 Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Pd, Ag일 수 있으며, 바람직하게는 Mn일 수 있다.In the present invention, the transition metal may be Ti, Mn, Fe, Co, Ni, Cu, Zn, Zr, Pd, Ag, and preferably Mn.
본 발명에 있어서, 상기 무기 금속 성분은 실리코알루미노포스페이트 분자체의 CHA구조를 유도하기 위해서 사용된 무기구조유도물질일 수 있다. In the present invention, the inorganic metal component may be an inorganic structure-inducing material used to induce the CHA structure of the silicoaluminophosphate molecular sieve.
본 발명의 실시에 있어서, 상기 K-SAPO-CHA는 마름모계 (rhombohedral crystal system)의 R3 공간군에 속하고, 결정 축 단위세포 길이 a 는 대략 10 Å (Angstrom), α= 95 °(degree)일 수 있다.In the practice of the present invention, the K-SAPO-CHA belongs to the R 3 space group of the rhombohedral crystal system, and the crystal axis unit cell length a is approximately 10 Å (Angstrom), α= 95 ° (degree ) Can be.
본 발명의 일 실시에 있어서, 상기 Na-SAPO-CHA는 삼방정계 (trigonal crystal system)의 R--3 공간군에 속하고, 결정 축 단위세포 길이 a 는 대략 10 Å (Angstrom), α= 95 °(degree)일 수 있다.In one embodiment of the present invention, the Na-SAPO-CHA belongs to the R -3 space group of the trigonal crystal system, and the crystal axis unit cell length a is approximately 10 Å (Angstrom), α= 95 It can be in degrees.
본 발명에 있어서, 상기 무기구조유도물질의 몰수 "m"은 (Si x Al y P z )O2 1 몰 당 M의 몰수이며, 바람직하게는 0.2~0.4일 수 있다.In the present invention, the number of moles "m" of the inorganic structure-inducing material is the number of moles of M per 1 mole of (Si x Al y P z )O 2, and preferably 0.2 to 0.4.
본 발명에 있어서, 무기구조유도물질을 포함하는 CHA구조의 실리코알루미노포스페이트 분자체 SAPO는 유기구조유도물질을 더 포함할 수 있다. In the present invention, the CHA structure silicoaluminophosphate molecular sieve SAPO including the inorganic structure-inducing material may further include an organic structure-inducing material.
본 발명의 실시에 있어서, 유기구조유도물질과 무기구조유도물질을 포함하는 CHA구조의 SAPO는 하기와 같은 화학식(2)로 표현될 수 있다. In the practice of the present invention, SAPO having a CHA structure including an organic structure-inducing material and an inorganic structure-inducing material may be represented by the following formula (2).
mM:nR:(SixAlyPz) O2 (2)mM:nR:(SixAlyPz) O2 (2)
여기서 "M"은 무기구조유도물질이며, "R"은 유기구조유도물질이며,Here, "M" is an inorganic structure-inducing material, "R" is an organic structure-inducing material,
"m"은 (Si x Al y P z )O2 1 몰 당 M의 몰수이며, 0.01 ≤ m ≤ 0.5이며,"m" is the number of moles of M per mole of (Si x Al y P z )O 2 , 0.01 ≤ m ≤ 0.5,
"n"은 (Si x Al y P z )O2 1 몰 당 R의 몰수이며, 0.01 ≤ n ≤ 0.3이며,"n" is the number of moles of R per mole of (Si x Al y P z )O 2 , 0.01 ≤ n ≤ 0.3,
x, y, z 는 Si, Al, P 의 몰분율이며, 각각 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98로서, x + y + z = 1.00이다. x , y , z are the mole fractions of Si, Al, and P, respectively, as 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98, and x + y + z = 1.00.
본 발명의 실시에 있어서, 상기 무기 구조유도물질과 함께 사용될 수 있는 유기 구조유도물질(R)은 적어도 하나 이상의 유기 아민(amine), 암모늄(ammonium), 포스포늄(phosphonium) 화합물일 수 있다. In the practice of the present invention, the organic structure-inducing material (R) that can be used together with the inorganic structure-inducing material may be at least one organic amine, ammonium, or phosphonium compound.
본 발명의 바람직한 실시에 있어서, 상기 유기 아민은 예를 들어 diethylamine, triethylamine, morpholine 들일 수 있으며, 상기 암모늄 화합물은 tetraethylammonium hydroxide 일 수 있으며, 상기 포스포늄 화합물은 tetraethylphosphonium 일 수 있다. In a preferred embodiment of the present invention, the organic amine may be, for example, diethylamine, triethylamine, and morpholine, the ammonium compound may be tetraethylammonium hydroxide, and the phosphonium compound may be tetraethylphosphonium.
본 발명은 일 측면에서, 알칼리 금속, 알칼리 토금속, 전이금속 양이온에서 선택되는 적어도 하나의 물질을 무기구조유도물질(M)로 이용하여 CHA형 실리코알루미노포스페이트 분자체인 SAPO를 제조하는 방법을 제공한다. In one aspect, the present invention provides a method for preparing SAPO, a CHA-type silicoaluminophosphate molecular body, using at least one material selected from alkali metal, alkaline earth metal, and transition metal cations as inorganic structure-inducing material (M). .
본 발명에 있어서, 상기 CHA형 SAPO의 제조는 수열 합성법으로 이루어질 수 있다. In the present invention, the preparation of the CHA-type SAPO may be performed by hydrothermal synthesis.
본 발명에 있어서, 상기 CHA형 SAPO 실리코알루미노포스페이트 분자체의 제조를 위한 수열 합성법은 실리카 공급원과, 알루미늄 공급원과, 포스페이트 공급원과, 알칼리 금속, 알칼리 토금속, 전이금속 양이온에서 선택되는 구조유도물질과, 그리고 물을 포함하는 혼합물을 반응시켜 하기 식(3)의 조성을 가지는 합성 화합물을 제조하고, 필요시 시드 결정과 함께, 이를 가열하는 것을 포함할 수 있다.In the present invention, the hydrothermal synthesis method for preparing the CHA-type SAPO silicoaluminophosphate molecular sieve includes a silica source, an aluminum source, a phosphate source, an alkali metal, an alkaline earth metal, and a structure-derived material selected from transition metal cations. , And by reacting a mixture containing water to prepare a synthetic compound having the composition of the following formula (3), and if necessary, it may include heating the same together with the seed crystal.
aM2O:(Si x Al y P z )O2:bH2O (3)aM 2 O:(Si x Al y P z )O 2 :bH 2 O (3)
여기서 "M"은 무기구조유도물질이며, 알칼리 금속 양이온, 알칼리 토금속 양이온 및 전이 금속 양이온으로 이루어진 그룹에서 선택되는 적어도 하나 이상의 무기양이온이며, Here, "M" is an inorganic structure-inducing material, and is at least one inorganic cation selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and a transition metal cation,
"a"는 무기양이온(M)의 구조유도물질로 작용하는데 필요한 양으로서, 최소 0 < a ≤ 3 이며, "a" is an amount required to act as a structure-inducing material of inorganic cation (M), and is at least 0 <a ≤ 3,
"b"는 실리코알루미노포스페이트 분자체의 제조에 필요한 물의 양이며, 0 ≤ a ≤ 500이며, "b" is the amount of water required for the production of the silicoaluminophosphate molecular sieve, 0 ≤ a ≤ 500,
x, y, z는 실리코알루미노포스페이트 합성혼합물을 이루는 Si, Al, P 의 몰분율이며 각각 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98 이다. 이와 같은 표기법은 (Si+Al+P)=(x+y+z)=1.0 몰에 대해 정규화된 것으로, 실제 일반적인 실시예에서 보여지는 합성 화합물 조성은 1.0 몰의 Al2O3 에 대해 정규화된 M2O, P2O5, SiO2, H2O의 몰 수로 표기된다. x , y , z are the mole fractions of Si, Al, and P that make up the silicoaluminophosphate composite mixture, and are 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, and 0.01 ≤ z ≤ 0.98, respectively. This notation is normalized to (Si+Al+P)=( x + y + z ) = 1.0 mol, and the synthetic compound composition shown in the actual general example is normalized to 1.0 mol of Al 2 O 3 . It is expressed as the number of moles of M 2 O, P 2 O 5 , SiO 2 and H 2 O.
본 발명의 실시에 있어서, 알루미늄 (Al) 공급원은 알루미늄이나 알루미늄을 포함하는 전구체 화합물일 수 있으며, 예를 들어, 수도보에마이트 (pseudoboehmite), 염화알루미늄 (aluminium chloride), 알루미늄이소프로폭사이드(aluminium isopropoxide), 알루민산나트륨(sodium aluminate), 수산화알루미늄(aluminium hydroxide), 알루미늄 알콕사이드(aluminium alkoxide), 알루미늄 메탈(aluminium metal), 알루미노실리케이트 제올라이트, 알루미노포스페이트 내지 실리코알루미노포스페이트 제올라이트 등이 가능하다. In the practice of the present invention, the aluminum (Al) source may be aluminum or a precursor compound containing aluminum, for example, pseudoboehmite, aluminum chloride, aluminum isopropoxide ( aluminum isopropoxide), sodium aluminate, aluminum hydroxide, aluminum alkoxide, aluminum metal, aluminosilicate zeolite, aluminophosphate or silicoaluminophosphate zeolite, etc. Do.
본 발명의 실시에 있어서, 실리콘 (Si) 공급원은 실리콘이나 실리콘을 포함하는 전구체 화합물일 수 있으며, 예를 들어, 건식실리카 (fumed silica), 실리카 졸(silica sol), 유기실란(organosilane), 알루미노실리케이트 내지 실리코알루미노포스페이트 제올라이트 등이 가능하다.In the practice of the present invention, the silicon (Si) source may be silicon or a precursor compound containing silicon, for example, fumed silica, silica sol, organosilane, alumina Nosilicate to silicoaluminophosphate zeolite and the like are possible.
본 발명의 실시에 있어서, 포스포러스(P) 전구체 화합물은 인이나 인을 포함하는 전구체 화합물일 수 있으며, 예를 들어 바람직하게는 인산(phosphoric acid)이다.In the practice of the present invention, the phosphorus (P) precursor compound may be phosphorus or a precursor compound containing phosphorus, and, for example, is preferably phosphoric acid.
본 발명에 있어서, 상기 화학식 3의 조성을 갖는 실리코알루미노포스페이트 합성혼합물의 가열 조건은 100~220 ℃ 에서 1~18 일 동안 가열되는 것일 수 있다.In the present invention, the heating condition of the silicoaluminophosphate composite mixture having the composition of Formula 3 may be heated at 100 to 220 °C for 1 to 18 days.
본 발명에 있어서, 상기 시드 결정은 시드 결정이 없을 경우 MER과 같은 다른 구조의 SAPO가 생성되는 경우, 결정 구조를 CHA 구조로 유도하기 위해서 사용될 수 있다. 본 발명의 실시에 있어서, 시드(종자)결정 공급원은 CHA형 실리코알루미노포스페이트 제올라이트일 수 있으며, CHA 및 AFT, AFV, AFX, AVL, ERI, LEV, OFF형 알루미노실리케이트, 알루미노포스페이트, 실리코알루미노포스페이트, 메탈로알루미노포스페이트 제올라이트 등이 가능하다.In the present invention, the seed crystal may be used to induce the crystal structure to the CHA structure when SAPO having a different structure such as MER is generated in the absence of the seed crystal. In the practice of the present invention, the seed (seed) crystal source may be CHA type silicoaluminophosphate zeolite, and CHA and AFT, AFV, AFX, AVL, ERI, LEV, OFF type aluminosilicate, aluminophosphate, silica Aluminophosphate, metalloaluminophosphate zeolite, etc. are possible.
본 발명의 바람직한 실시에 있어서, 상기 화학식 (3)의 조성을 가지는 합성 혼합물은 플라스틱 비커에 물(H2O) 0-500 몰과 알루미늄 공급원 0.01-0.98 몰을 혼합하고 포스포러스 공급원 0.01-0.98 몰과 실리카 공급원 0.01-0.98 몰을 첨가한 후 충분히 교반시킨다. 상기 혼합물에 무기구조유도물질(M2O)로서 적어도 하나 이상의 수산화알칼리금속, 수산화알칼리토금속 또는 수산화전이금속을 0.01-3.00 몰 첨가하여 다시 충분히 교반하여 혼합한다. In a preferred embodiment of the present invention, the synthetic mixture having the composition of formula (3) is mixed with 0-500 mol of water (H 2 O) and 0.01-0.98 mol of aluminum source in a plastic beaker, and 0.01-0.98 mol of phosphorus source and After adding 0.01-0.98 moles of silica source, it is sufficiently stirred. 0.01-3.00 mol of at least one alkali metal hydroxide, alkaline earth hydroxide metal, or transition metal hydroxide is added to the mixture as an inorganic structure-inducing material (M 2 O), followed by sufficiently stirring and mixing.
본 발명에 있어서, 상기 실리코알루미노포스페이트 분자체는 무기 구조 유도물질과 함께 유기 구조 유도물질을 사용하여 제조될 수 있다. 필요시, 상기 혼합물에 유기구조유도물질(R2O)로서 적어도 하나 이상의 유기 아민, 암모늄화합물, 포스포늄 화합물을 0.0-3.0 몰 첨가하여 다시 충분히 교반하여 혼합한다.In the present invention, the silicoaluminophosphate molecular sieve may be prepared using an organic structure-inducing material together with an inorganic structure-inducing material. If necessary, 0.0-3.0 moles of at least one organic amine, ammonium compound, and phosphonium compound are added to the mixture as an organic structure-inducing material (R 2 O), followed by sufficiently stirring and mixing.
본 발명에 있어서, 상기 무기 유도물질과 유기 유도물질을 함께 사용할 경우, 실리코알루미노포스페이트 분자체는 실리카 공급원, 알루미늄 공급원, 포스페이트 공급원, 무기구조유도물질, 유기구조유도물질 및 물을 포함하는 혼합물을 반응시켜 하기 식(4)의 조성을 가지는 합성 화합물을 제조하고, 필요시, 종자결정을 첨가하며, 이를 가열하여 제조될 수 있다.In the present invention, when the inorganic inducing material and the organic inducing material are used together, the silicoaluminophosphate molecular sieve comprises a silica source, an aluminum source, a phosphate source, an inorganic structure inducing material, an organic structure inducing material, and a mixture containing water. By reacting, a synthetic compound having the composition of the following formula (4) is prepared, and if necessary, seed crystals are added, and then it can be prepared by heating.
aM2O:bR2O:(Si x Al y P z )O2:cH2O (4)aM 2 O:bR 2 O:(Si x Al y P z )O 2 :cH 2 O (4)
여기서 "M"은 무기구조유도물질이며, 알칼리 금속 양이온, 알칼리 토금속 양이온 및 전이 금속 양이온으로 이루어진 그룹에서 선택되는 적어도 하나 이상의 무기양이온이며,Here, "M" is an inorganic structure-inducing material, and is at least one inorganic cation selected from the group consisting of an alkali metal cation, an alkaline earth metal cation, and a transition metal cation,
"R"은 유기구조유도물질로서, 유기 아민(amine), 암모늄(ammonium), 포스포늄(phosphonium) 화합물로 이루어진 그룹에서 선택되는 적어도 하나의 물질이며, "R" is an organic structure-inducing material, and is at least one material selected from the group consisting of organic amine, ammonium, and phosphonium compounds,
"a"는 무기양이온(M)의 구조유도물질로 작용하는데 필요한 양으로서, 최소 0<a≤3 이며,"a" is an amount required to act as a structure-inducing material of inorganic cation (M), and is at least 0<a≤3,
"b"는 무기구조유도물질과 함께 선택적으로 사용될 수 있는 유기구조유도물질의 양으로서, 최소 0≤b≤3 이며,"b" is an amount of an organic structure-inducing material that can be selectively used together with an inorganic structure-inducing material, and is at least 0≦b≦3,
"c"는 실리코알루미노포스페이트 분자체의 수열 합성에 필요한 물의 양이며, 0≤c≤500이며,"c" is the amount of water required for hydrothermal synthesis of the silicoaluminophosphate molecular sieve, 0≤c≤500,
x, y, z는 실리코알루미노포스페이트 합성혼합물을 이루는 Si, Al, P 의 몰분율이며 각각 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98 이다. 이와 같은 표기법은 (Si+Al+P)=(x+y+z)=1.0 몰에 대해 정규화된 것으로, 실제 일반적인 실시예에서 보여지는 합성 화합물 조성은 1.0 몰의 Al2O3에 대해 정규화된 M2O, R2O, P2O5, SiO2, H2O의 몰 수로 표기된다. x , y , z are the mole fractions of Si, Al, and P that make up the silicoaluminophosphate composite mixture, and are 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, and 0.01 ≤ z ≤ 0.98, respectively. This notation is normalized to (Si+Al+P)=( x + y + z ) = 1.0 mol, and the synthetic compound composition shown in the actual general example is normalized to 1.0 mol of Al 2 O 3 . It is expressed as the number of moles of M 2 O, R 2 O, P 2 O 5 , SiO 2 , and H 2 O.
본 발명을 통해서 무기구조 유도물질을 사용하여 CHA구조의 SAPO를 제조하는 방법을 제공하였다.Through the present invention, a method of preparing SAPO having a CHA structure using an inorganic structure-derived material was provided.
본 발명에 따라서 제조된 SAPO-CHA는 무기구조유도물질을 세공 내에 포함하는 새로운 SAPO이며, 기존의 유기구조 유도물질을 사용하여 합성된 CHA형 SAPO(SAPO-34)보다 경제적, 친환경적 합성이 가능하다.SAPO-CHA manufactured according to the present invention is a new SAPO containing inorganic structure-inducing material in the pores, and it is more economical and eco-friendly than CHA-type SAPO (SAPO-34) synthesized using an existing organic structure-inducing material. .
또한, 본 발명은 CHA구조의 SAPO대신 다른 형태의 SAPO가 형성되는 조건에서, CHA구조의 SAPO를 형성시킬 수 있는 방안을 제공하였다. In addition, the present invention provides a way to form the SAPO of the CHA structure under the condition that the SAPO of another type is formed instead of the SAPO of the CHA structure.
본 발명은 또한 무기구조유도물질에서 유래되는 무기양이온을 포함하는 새로운 CHA형 SAPO를 제공한다. The present invention also provides a new CHA-type SAPO containing an inorganic cation derived from an inorganic structure-inducing substance.
도 1은 본 발명의 실시예 1에 따라 제조된 실리코알루미노포스페이트 K-SAPO-CHA의 X-선 회절(XRD) 결과이다.
도 2는 본 발명의 실시예 1에 따라 제조된 실리코알루미노포스페이트 K-SAPO-CHA의 주사현미경(SEM) 이미지이다.
도 3은 본 발명의 실시예 2에 따라 제조된 실리코알루미노포스페이트 K-SAPO-CHA의 X-선 회절(XRD) 결과이다.
도 4는 본 발명의 실시예 2에 따라 제조된 실리코알루미노포스페이트 K-SAPO-CHA의 주사현미경(SEM) 이미지이다.
도 5은 본 발명의 실시예 3에 따라 제조된 실리코알루미노포스페이트 Na-SAPO-CHA의 X-선 회절(XRD) 결과이다.
도 6는 본 발명의 실시예 3에 따라 제조된 실리코알루미노포스페이트
Na-SAPO-CHA의 주사현미경(SEM) 이미지이다.1 is an X-ray diffraction (XRD) result of silicoaluminophosphate K-SAPO-CHA prepared according to Example 1 of the present invention.
2 is a scanning microscope (SEM) image of a silicoaluminophosphate K-SAPO-CHA prepared according to Example 1 of the present invention.
3 is an X-ray diffraction (XRD) result of silicoaluminophosphate K-SAPO-CHA prepared according to Example 2 of the present invention.
4 is a scanning microscope (SEM) image of a silicoaluminophosphate K-SAPO-CHA prepared according to Example 2 of the present invention.
5 is an X-ray diffraction (XRD) result of the silicoaluminophosphate Na-SAPO-CHA prepared according to Example 3 of the present invention.
6 is a silicoaluminophosphate prepared according to Example 3 of the present invention.
This is a scanning microscope (SEM) image of Na-SAPO-CHA.
이하, 실시예를 통해서 본 발명을 상세하게 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것이며, 어떠한 경우에도 본 발명을 한정하기 위해서 기재된 것이 아님을 유의하여야 한다.Hereinafter, the present invention will be described in detail through examples. It should be noted that the following examples are intended to illustrate the present invention, and in no case are described to limit the present invention.
실시예 1.Example 1.
K-SAPO-CHA 실리코알루미노포스페이트 분자체의 제조Preparation of K-SAPO-CHA silicoaluminophosphate molecular sieve
플라스틱 비커에 먼저 3.87 g 의 3차 증류수와 0.54 g 의 염화알루미늄을 혼합하여 30분간 교반시킨다. 상기 혼합물에 0.23 g 의 인산(phosphoric acid, 85%) 수용액을 넣고 1시간 교반시킨다. 상기 혼합 용액의 pH가 7-8 이 되도록 수산화포타슘(KOH) 수용액을 넣고 교반시켜 얻은 반응화합물을 건조 후 3.82 g의 3차 증류수와 0.12 g의 건식실리카의 혼합물에 넣고 교반한다. 위 혼합물에 0.25 g 의 수산화포타슘 수용액(45%)을 넣고 교반시켜 하기 화학식 5에 나타낸 반응혼합물의 조성을 얻은 다음, SAPO-34 종자결정을 0.002 g 넣고 충분히 교반한 뒤 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 180 ℃ 에서 5 일 동안 가열한 후, 가열하여 얻은 고체 생성물을 반복 세척하여 상온에서 건조하였다.In a plastic beaker, 3.87 g of tertiary distilled water and 0.54 g of aluminum chloride were first mixed and stirred for 30 minutes. 0.23 g of phosphoric acid (85%) aqueous solution was added to the mixture and stirred for 1 hour. The reaction compound obtained by adding an aqueous potassium hydroxide (KOH) solution and stirring the mixture so that the pH of the mixed solution is 7-8 is dried, and then added to a mixture of 3.82 g of tertiary distilled water and 0.12 g of dry silica and stirred. 0.25 g of potassium hydroxide aqueous solution (45%) was added to the above mixture and stirred to obtain the composition of the reaction mixture shown in the following formula (5), and then 0.002 g of SAPO-34 seed crystals were added and sufficiently stirred, and the obtained reaction mixture was transferred to a Teflon reactor. After putting it in, it was put in a stainless steel container and heated at 180° C. for 5 days, and the solid product obtained by heating was repeatedly washed and dried at room temperature.
본 발명에 따른 K-SAPO-MER 실리코알루미노포스페이트 분자체는 탈수된 상태에서 기본적인 골격 구조가 하기한 화학식 6와 같은 몰비의 산화물 조성으로 이루어지며, 상기 합성을 통해 얻은 고체분말로 X-선 회절 측정시험을 하고 그 결과를 표 1에 나타내었다.The K-SAPO-MER silicoaluminophosphate molecular sieve according to the present invention has a basic skeletal structure in a dehydrated state consisting of an oxide composition in a molar ratio as shown in Formula 6 below, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 1.
[화학식 5][Formula 5]
0.5 K2O : 1.0 Al2O3 : 0.5 P2O5 : 1.0 SiO2 : 110 H2O0.5 K 2 O: 1.0 Al 2 O 3 : 0.5 P 2 O 5 : 1.0 SiO 2 : 110 H 2 O
[화학식 6][Formula 6]
0.23K:(Si0.28Al0.50P0.22)O2 0.23K:(Si 0.28 Al 0.50 P 0.22 )O 2
표 1에서 θ, d, I는 각각 브래그(Bragg)각, 격자간격, 그리고 X선 회절 피크의 강도를 의미한다. 이 분말 X선 회절 패턴을 포함하여 본 발명에서 보고되는 모든 분말 X선 회절 데이터는 표준 X선 회절 방법을 이용하여 측정하였으며, 방사원으로는 구리 Kα선과 40 kV, 30 mA에서 작동하는 X선 튜브를 사용하였다. 수평으로 압축된 분말시료로부터 분당 5도(2θ)의 속도로 측정하였으며, 관찰된 X선 회절 피크의 2θ값과 피크 높이로부터 d와 I를 계산하였다. 상대강도 100I/I0 의 값에 따라 W(약함: 0~20), M(중간: 20~40), S(강함: 40~60), VS(매우 강함: 60~100)로 표현된다.제조된 K-SAPO-CHA를 기존에 보고된 알루미노실리케이트 및 실리코알루미노포스페이트 분자체들의 X-선 회절 패턴들과 비교한 결과, chabazite 구조 패턴임을 확인하였다(도 1). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I 0, it is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared K-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 1). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].
또한, 주사현미경(Scanning Electron Microscope, 약어로 SEM)(도 2)을 측정한 결과, 뭉쳐진 알갱이(grain)의 순수한 결정을 나타내었다. 이는 K-SAPO-CHA가 여러 물질(Physical Mixture)이 섞이지 않은 순수한 물질임을 나타낸다.In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, SEM for abbreviation) (FIG. 2), pure crystals of agglomerated grains were shown. This indicates that K-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).
또한, 이 시료의 조성을 규명하기 위하여 유도결합플라즈마 분석법(Inductive Coupled Plasma, 약어로 ICP)을 통해 원소분석을 수행하여 Si/(Si+Al+P) 과 (Al-P)/(Si+Al+P) 비율이 각각 0.28, 0.28 임을 확인하였다.In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the ratio of P) was 0.28 and 0.28, respectively.
실시예 2Example 2
K-SAPO-CHA 실리코알루미노포스페이트 분자체의 제조Preparation of K-SAPO-CHA silicoaluminophosphate molecular sieve
플라스틱 비커에 먼저 4.47 g 의 3차 증류수와 0.46 g 의 수도보에마이트를 혼합하여 30분간 교반시킨다. 상기 혼합물에 0.75 g의 실리카졸 (Ludox AS-40)과 0.46 g 의 인산(Phosphoric acid, 85%) 수용액을 넣고 1시간 교반시킨다. 상기 용액에 다시 1.12 g의 45% 수산화포타슘(KOH) 수용액을 넣고 충분히 교반시켜 하기 화학식 7에 나타낸 반응혼합물의 조성을 얻은 다음, SAPO-57 종자결정을 0.009 g 넣고 충분히 교반한 뒤 얻은 반응혼합물을 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 200 ℃ 에서 5 일 동안 가열한 후, 가열하여 얻은 고체 생성물을 반복 세척하여 상온에서 건조한다.In a plastic beaker, 4.47 g of tertiary distilled water and 0.46 g of water boehmite were first mixed and stirred for 30 minutes. To the mixture was added 0.75 g of silica sol (Ludox AS-40) and 0.46 g of an aqueous solution of phosphoric acid (85%) and stirred for 1 hour. 1.12 g of 45% potassium hydroxide (KOH) aqueous solution was again added to the solution and sufficiently stirred to obtain the composition of the reaction mixture shown in the following formula (7), and then 0.009 g of SAPO-57 seed crystals were added and sufficiently stirred, and the obtained reaction mixture was Teflon. After being transferred to the reactor, it was placed in a stainless steel container and heated at 200° C. for 5 days, and the solid product obtained by heating was repeatedly washed and dried at room temperature.
본 발명에 따른 K-SAPO-CHA 실리코알루미노포스페이트 분자체는 탈수된 상태에서 기본적인 골격 구조가 하기한 화학식 6와 같은 몰비의 산화물 조성으로 이루어지며, 상기 합성을 통해 얻은 고체분말로 X-선 회절 측정시험을 하고 그 결과를 표 2에 나타내었다.The K-SAPO-CHA silicoaluminophosphate molecular sieve according to the present invention has a basic skeletal structure in a dehydrated state consisting of an oxide composition in a molar ratio as shown in Formula 6 below, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 2.
[화학식 5][Formula 5]
1.3 K2O : 1.0 Al2O3 : 0.5 P2O5 : 1.25 SiO2 : 80 H2O1.3 K 2 O: 1.0 Al 2 O 3 : 0.5 P 2 O 5 : 1.25 SiO 2 : 80 H 2 O
[화학식 6][Formula 6]
0.25K:(Si0.33Al0.46P0.21)O2 0.25K:(Si 0.33 Al 0.46 P 0.21 )O 2
표 1에서 θ, d, I는 각각 브래그(Bragg)각, 격자간격, 그리고 X선 회절 피크의 강도를 의미한다. 이 분말 X선 회절 패턴을 포함하여 본 발명에서 보고되는 모든 분말 X선 회절 데이터는 표준 X선 회절 방법을 이용하여 측정하였으며, 방사원으로는 구리 Kα선과 40 kV, 30 mA에서 작동하는 X선 튜브를 사용하였다. 수평으로 압축된 분말시료로부터 분당 5도(2θ)의 속도로 측정하였으며, 관찰된 X선 회절 피크의 2θ값과 피크 높이로부터 d와 I를 계산하였다. 상대강도 100I/I0 의 값에 따라 W(약함: 0~20), M(중간: 20~40), S(강함: 40~60), VS(매우 강함: 60~100)로 표현된다.제조된 K-SAPO-CHA를 기존에 보고된 알루미노실리케이트 및 실리코알루미노포스페이트 분자체들의 X-선 회절 패턴들과 비교한 결과, chabazite 구조 패턴임을 확인하였다(도 3). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I 0, it is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared K-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 3). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].
또한, 주사현미경(Scanning Electron Microscope, 약어로 SEM)(도 4)을 측정한 결과, 뭉쳐진 알갱이(grain)의 순수한 결정을 나타내었다. 이는 K-SAPO-CHA가 여러 물질(Physical Mixture)이 섞이지 않은 순수한 물질임을 나타낸다.In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, abbreviated SEM) (FIG. 4), pure crystals of aggregated grains were shown. This indicates that K-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).
또한, 이 시료의 조성을 규명하기 위하여 유도결합플라즈마 분석법(Inductive Coupled Plasma, 약어로 ICP)을 통해 원소분석을 수행하여 Si/(Si+Al+P) 과 (Al-P)/(Si+Al+P) 비율이 각각 0.33, 0.25 임을 확인하였다.In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the P) ratio was 0.33 and 0.25, respectively.
<실시예 3><Example 3>
Na-SAPO-CHA 실리코알루미노포스페이트 분자체의 제조Preparation of Na-SAPO-CHA silicoaluminophosphate molecular sieve
플라스틱 비커에 먼저 189.76 g 의 3차 증류수와 26.94 g 의 염화알루미늄을 혼합하여 30 분간 교반시킨다. 상기 혼합물에 20.75 g 의 인산(phosphoric acid, 85%) 수용액을 넣고 1 시간 교반시킨다. 상기 용액 용액의 pH가 7-8 이 되도록 수산화나트륨(NaOH) 수용액을 넣고 교반시켜 얻은 반응화합물 1.28 g을 6.70 g 의 3차 증류수와 1.27 g의 실리카졸(Ludox AS-40)의 혼합물에 넣고 교반한다. 위 혼합물에 0.77 g 의 수산화나트륨 수용액(50%)을 넣고 교반시켜 하기 화학식 7에 나타낸 반응혼합물의 조성을 얻은 다음 테프론 반응기에 옮겨 넣은 후 다시 스테인레스 강철로 만든 용기에 넣어 150 ℃ 에서 7 일 동안 가열한 후, 가열하여 얻은 고체 생성물을 반복 세척하여 상온에서 건조한다.In a plastic beaker, 189.76 g of tertiary distilled water and 26.94 g of aluminum chloride were first mixed and stirred for 30 minutes. 20.75 g of phosphoric acid (85%) aqueous solution was added to the mixture and stirred for 1 hour. 1.28 g of the reaction compound obtained by adding an aqueous sodium hydroxide (NaOH) solution and stirring so that the pH of the solution solution is 7-8 was added to a mixture of 6.70 g of tertiary distilled water and 1.27 g of silica sol (Ludox AS-40) and stirred. do. 0.77 g of sodium hydroxide aqueous solution (50%) was added to the above mixture and stirred to obtain the composition of the reaction mixture shown in the following formula (7), and then transferred to a Teflon reactor and then put into a stainless steel container and heated at 150°C for 7 days. Thereafter, the solid product obtained by heating is repeatedly washed and dried at room temperature.
본 발명에 따른 Na-SAPO-CHA 실리코알루미노포스페이트 분자체는 탈수된 상태에서 기본적인 골격 구조가 하기한 화학식 8와 같은 몰비의 산화물 조성으로 이루어지며, 상기 합성을 통해 얻은 고체분말로 X-선 회절 측정시험을 하고 그 결과를 표 3에 나타내었다.The Na-SAPO-CHA silicoaluminophosphate molecular sieve according to the present invention has a basic skeleton structure of an oxide composition in a molar ratio as shown in Chemical Formula 8 below in a dehydrated state, and X-ray diffraction with the solid powder obtained through the above synthesis. The measurement test was performed and the results are shown in Table 3.
[화학식 7][Formula 7]
1.2 Na2O : 1.0 Al2O3 : 0.9 P2O5 : 1.8 SiO2 : 110 H2O1.2 Na 2 O: 1.0 Al 2 O 3 : 0.9 P 2 O 5 : 1.8 SiO 2 : 110 H 2 O
[화학식 8][Formula 8]
0.27Na:(Si0.34Al0.48P0.18)O2 0.27 Na:(Si 0.34 Al 0.48 P 0.18 )O 2
표 1에서 θ, d, I는 각각 브래그(Bragg)각, 격자간격, 그리고 X선 회절 피크의 강도를 의미한다. 이 분말 X선 회절 패턴을 포함하여 본 발명에서 보고되는 모든 분말 X선 회절 데이터는 표준 X선 회절 방법을 이용하여 측정하였으며, 방사원으로는 구리 Kα선과 40 kV, 30 mA에서 작동하는 X선 튜브를 사용하였다. 수평으로 압축된 분말시료로부터 분당 5도(2θ)의 속도로 측정하였으며, 관찰된 X선 회절 피크의 2θ값과 피크 높이로부터 d와 I를 계산하였다. 상대강도 100I/I0 의 값에 따라 W(약함: 0~20), M(중간: 20~40), S(강함: 40~60), VS(매우 강함: 60~100)로 표현된다.제조된 Na-SAPO-CHA를 기존에 보고된 알루미노실리케이트 및 실리코알루미노포스페이트 분자체들의 X-선 회절 패턴들과 비교한 결과, chabazite 구조 패턴임을 확인하였다(도 5). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].In Table 1, θ, d, and I denote the Bragg angle, the grating interval, 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 a standard X-ray diffraction method, and as a radiation source, a copper Kα ray and an X-ray tube operating at 40 kV and 30 mA were used. Was used. It was measured at a speed of 5 degrees per minute (2θ) from the horizontally compressed powder sample, and d and I were calculated from the 2θ value and the peak height of the observed X-ray diffraction peak. Depending on the value of the relative intensity 100I/I 0, it is expressed as W (weak: 0-20), M (medium: 20-40), S (strong: 40-60), and VS (very strong: 60-100). As a result of comparing the prepared Na-SAPO-CHA with the previously reported X-ray diffraction patterns of aluminosilicate and silicoaluminophosphate molecular sieves, it was confirmed that it was a chabazite structure pattern (FIG. 5). [Collection of Simulated XRD Patterns for Zeolites, Elsevier, 2007], [http://www.iza-structure.org/].
또한, 주사현미경(Scanning Electron Microscope, 약어로 SEM)(도 6)을 측정한 결과, 뭉쳐진 알갱이(grain)의 순수한 결정을 나타내었다. 이는 Na-SAPO-CHA가 여러 물질(Physical Mixture)이 섞이지 않은 순수한 물질임을 나타낸다.In addition, as a result of measuring a scanning microscope (Scanning Electron Microscope, SEM for abbreviation) (FIG. 6), pure crystals of agglomerated grains were shown. This indicates that Na-SAPO-CHA is a pure substance that does not contain several substances (Physical Mixture).
또한, 이 시료의 조성을 규명하기 위하여 유도결합플라즈마 분석법(Inductive Coupled Plasma, 약어로 ICP)을 통해 원소분석을 수행하여 Si/(Si+Al+P) 과 (Al-P)/(Si+Al+P) 비율이 각각 0.34, 0.30 임을 확인하였다.In addition, to determine the composition of this sample, elemental analysis was performed through Inductive Coupled Plasma (ICP) to determine the composition of Si/(Si+Al+P) and (Al-P)/(Si+Al+). It was confirmed that the ratio of P) was 0.34 and 0.30, respectively.
Claims (12)
mM:(SixAlyPz)O2 (1)
여기서 "M"은 무기 구조 유도물질로서, K 및/또는 Na를 포함하며,
"m"은 (Si x Al y P z )O2 1 몰 당 M의 몰수이며, 0.2≤m≤0.4이며,
x, y, z 는 Si, Al, P 의 몰분율이며, 각각 0.01≤x≤0.98, 0.01≤y≤0.98, 0.01≤z≤0.98로서, x + y + z =1.00이며,
여기서, x, y, z 에서 y 가 가장 크며, x > z 임.CHA type silicoaluminophosphate SAPO molecular sieve having a molar ratio composition as shown in the following formula (1).
mM:(Si x Al y P z )O 2 (1)
Here, "M" is an inorganic structure inducing material, and includes K and/or Na,
"m" is the number of moles of M per mole of (Si x Al y P z )O 2, and 0.2≤m≤0.4,
x , y , z are the mole fractions of Si, Al, and P, respectively, as 0.01≤ x ≤0.98, 0.01≤ y ≤0.98, 0.01≤ z ≤0.98, x + y + z =1.00,
Here, y is the largest in x , y , and z , and x > z .
상기 x는 0.28~0.34인 것을 특징으로 하는 CHA형 실리코알루미노포스페이트 SAPO 분자체. The method of claim 1,
The x is 0.28 ~ 0.34, characterized in that the CHA type silicoaluminophosphate SAPO molecular sieve.
상기 수열합성법은 실리카 전구체 화합물, 알루미늄 전구체 화합물, 포스페이트 전구체 화합물, 무기구조유도물질, 및 물을 포함하는 혼합물을 반응시켜 하기 식(3)의 조성을 가지는 합성 화합물을 제조하고, 이를 가열하는 것을 특징으로 하는 CHA형 실리코알루미노포스페이트 SAPO 분자체 제조 방법.
aM2O:(Si x Al y P z )O2:bH2O (3)
여기서 "M"은 무기구조유도물질이며, "a"는 무기구조유도물질이 구조유도물질로 작용하는데 필요한 양으로서, 0<a≤3이며, "b"는 실리코알루미노포스페이트 분자체의 제조에 필요한 물의 양이며, 0≤b≤500이며, x, y, z는 실리코알루미노포스페이트 합성혼합물을 이루는 Si, Al, P 의 몰분율이며 각각 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z ≤ 0.98 임.The method of claim 5,
The hydrothermal synthesis method is characterized in that by reacting a mixture containing a silica precursor compound, an aluminum precursor compound, a phosphate precursor compound, an inorganic structure-inducing material, and water to prepare a synthetic compound having the composition of the following formula (3), and heating it CHA type silicoaluminophosphate SAPO molecular sieve manufacturing method.
aM 2 O:(Si x Al y P z )O 2 :bH 2 O (3)
Here, "M" is an inorganic structure-inducing material, "a" is an amount necessary for the inorganic structure-inducing material to act as a structure-inducing material, 0<a≤3, and "b" is for the manufacture of a silicoaluminophosphate molecular sieve. It is the amount of water required, 0≤b≤500, x , y , z are the mole fractions of Si, Al, and P forming the silicoaluminophosphate composite mixture, respectively 0.01 ≤ x ≤ 0.98, 0.01 ≤ y ≤ 0.98, 0.01 ≤ z Is ≤ 0.98.
알루미늄 (Al) 전구체 화합물은 수도보에마이트(pseudoboehmite), 염화알루미늄 (aluminium chloride), 알루미늄이소프로폭사이드(aluminium isopropoxide), 알루민산나트륨(sodium aluminate), 수산화알루미늄(aluminium hydroxide), 알루미늄 알콕사이드(aluminium alkoxide), 알루미늄 메탈(aluminium metal), 알루미노실리케이트 제올라이트, 알루미노포스페이트 내지 실리코알루미노포스페이트 제올라이트에서 하나 이상 선택되고,
실리콘 (Si) 공급원은 건식실리카 (fumed silica), 실리카 졸(silica sol), 유기실란(organosilane), 알루미노실리케이트 내지 실리코알루미노포스페이트 제올라이트에서 하나 이상 선택되며,
포스포러스(P) 공급원은 인산(phosphoric acid), 알루미노포스페이트 내지 실리코알루미노포스페이트 제올라이트에서 하나 이상 선택되는 것을 특징으로 하는 CHA형 실리코알루미노포스페이트 SAPO 분자체 제조 방법.The method of claim 7,
Aluminum (Al) precursor compounds include pseudoboehmite, aluminum chloride, aluminum isopropoxide, sodium aluminate, aluminum hydroxide, and aluminum alkoxide. aluminum alkoxide), aluminum metal, aluminosilicate zeolite, aluminophosphate to silicoaluminophosphate zeolite,
The silicon (Si) source is one or more selected from fumed silica, silica sol, organosilane, aluminosilicate to silicoaluminophosphate zeolite,
Phosphorus (P) source is phosphoric acid (phosphoric acid), aluminophosphate, CHA type silicoaluminophosphate SAPO molecular sieve production method, characterized in that one or more selected from the silica-aluminophosphate zeolite.
The method of claim 5, further comprising an organic structure-inducing substance.
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