JP6045890B2 - MCM-22 type zeolite having novel crystal structure and aromatic hydrocarbon purification catalyst comprising said zeolite - Google Patents
MCM-22 type zeolite having novel crystal structure and aromatic hydrocarbon purification catalyst comprising said zeolite Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 88
- 239000010457 zeolite Substances 0.000 title claims description 79
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 75
- 239000003054 catalyst Substances 0.000 title claims description 44
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 19
- 238000000746 purification Methods 0.000 title claims description 14
- 239000013078 crystal Substances 0.000 title description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000003795 desorption Methods 0.000 claims description 12
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000523 sample Substances 0.000 description 19
- 229910004298 SiO 2 Inorganic materials 0.000 description 18
- 238000001027 hydrothermal synthesis Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- -1 xylene olefins Chemical class 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 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 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000007670 refining Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000705939 Shortia uniflora Species 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
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Description
本発明は、新規な結晶構造を有するＭＣＭ−２２型ゼオライトに関するものであり、より詳細には、芳香族炭化水素精製触媒として好適に使用されるＭＣＭ−２２型ゼオライトに関する。 The present invention relates to an MCM-22 type zeolite having a novel crystal structure, and more particularly to an MCM-22 type zeolite suitably used as an aromatic hydrocarbon purification catalyst.
ベンゼン、トルエン、キシレン（Ｃ8 芳香族）等の芳香族炭化水素からオレフィン、ジオレフィン等の不飽和化合物を除去する目的で、従来から精製処理が行われている。この精製処理は、ＢＴＸ等の芳香族炭化水素中に含まれる不飽和化合物を、芳香族炭化水素へのアルキル化によって多環芳香族化合物に変えたり、また重合により二量体乃至三量体としたりすることによって高分子量化し、高沸点留分として除去するというものである。この重合に際しては、トルエンやキシレン等のアルキル芳香族化合物の不均化反応や異性化反応を引き起こすことも知られている。 Benzene, toluene, xylene olefins from aromatic hydrocarbons (C 8 aromatics), etc., for the purpose of removing unsaturated compounds diolefins such purification process is conventional. In this purification treatment, an unsaturated compound contained in an aromatic hydrocarbon such as BTX is changed to a polycyclic aromatic compound by alkylation to an aromatic hydrocarbon, or is converted into a dimer or trimer by polymerization. To increase the molecular weight and remove it as a high-boiling fraction. In this polymerization, it is also known to cause a disproportionation reaction or an isomerization reaction of an alkyl aromatic compound such as toluene or xylene.
上記の精製処理には、不飽和化合物の芳香族アルキル化触媒や重合触媒として作用し且つ不均化等の副反応が少ないという観点から、各種のゼオライトが使用されており、特にＭＣＭ−２２と称される合成ゼオライトが芳香族炭化水素の精製処理用の触媒として最も高性能品であると認識されている（例えば特許文献１参照）。 In the above purification treatment, various zeolites are used from the viewpoint of acting as an aromatic alkylation catalyst or polymerization catalyst for unsaturated compounds and having few side reactions such as disproportionation, and particularly with MCM-22. Synthetic zeolite called is recognized as the most high-performance product as a catalyst for refining aromatic hydrocarbons (see, for example, Patent Document 1).
また、高結晶性のＭＣＭ−２２型ゼオライトの製造方法としては、ＳｉＯ２源とＡｌ２Ｏ３源とを、アルカリ及びテンプレートであるヘキサメチレンイミンの存在下で水熱反応せしめ、反応物を焼成してヘキサメチレンイミンを除去する方法が知られている（特許文献２参照）。 In addition, as a method for producing a highly crystalline MCM-22 type zeolite, SiO 2 source and Al 2 O 3 source are hydrothermally reacted in the presence of alkali and template hexamethyleneimine, and the reaction product is calcined. A method of removing hexamethyleneimine is known (see Patent Document 2).
ところで、炭化水素系精製触媒として使用されるＭＣＭ−２２型ゼオライトにおいても、未だ改良の余地があり、特に触媒寿命が短いという問題がある。特に、ＭＣＭ−２２型ゼオライトは、他の鉱物系の触媒に比してコスト高であり、従って、触媒寿命が短いということが工業的には致命的であり、その触媒寿命の延長が望まれている。 By the way, the MCM-22 type zeolite used as the hydrocarbon purification catalyst still has room for improvement, and there is a problem that the catalyst life is particularly short. In particular, MCM-22 type zeolite is expensive compared to other mineral-based catalysts, and therefore it is industrially fatal that the catalyst life is short, and it is desired to extend the catalyst life. ing.
従って本発明の目的は、炭化水素系精製触媒としての触媒寿命が大幅に延長された新規なＭＣＭ−２２型ゼオライトを提供することにある。 Accordingly, an object of the present invention is to provide a novel MCM-22 type zeolite having a greatly extended catalyst life as a hydrocarbon purification catalyst.
本発明者等は、結晶性の高いＭＣＭ−２２型の製造方法について多くの実験を行った結果、ゼオライト骨格合成時の反応条件やその後の熱履歴を調整することにより、ｃ軸方向の結晶成長が抑制され且つ特定の環境に在る４配位Ａｌが一定のレベルで存在している新規な結晶構造のＭＣＭ−２２型ゼオライトが得られ、しかも、かかるＭＣＭ−２２型ゼオライトは、炭化水素系精製触媒としての触媒寿命が、従来公知のＭＣＭ−２２型ゼオライトに比して著しく延長していることを見出し、本発明を完成させるに至った。 As a result of conducting many experiments on the production method of the highly crystalline MCM-22 type, the present inventors have adjusted the reaction conditions during the synthesis of the zeolite skeleton and the subsequent thermal history to thereby grow the crystal in the c-axis direction. Is obtained, and MCM-22 type zeolite having a novel crystal structure in which tetracoordinate Al existing in a specific environment is present at a certain level is obtained. It has been found that the catalyst life as a refining catalyst is remarkably extended as compared with conventionally known MCM-22 type zeolite, and the present invention has been completed.
即ち、本発明によれば、ＸＲＤで測定される（１０１）面のピーク強度Ｐ１と（１０２）面のピーク強度Ｐ２との比（Ｐ１／Ｐ２）が０．１０〜０．６０の範囲にあると共に、２７Ａｌ−固体ＮＭＲで５９．５±２．０に観測される４配位Ａｌのピーク強度比Ｉｑ４が０．１４〜０．７０の範囲にあることを特徴とするＭＣＭ−２２型ゼオライトが提供される。このＭＣＭ−２２型ゼオライトは好適には、アンモニアＴＰＤ法により測定されるアンモニア脱離量が、吸着エンタルピーが１３０〜１５０ｋＪ／ｍｏｌの範囲において、１．０５〜２．５０ｍｏｌ／ｋｇである。
本発明によれば、また、上記のＭＣＭ−２２型ゼオライトからなる芳香族炭化水素精製触媒が提供される。
That is, according to the present invention, the ratio (P 1 / P 2 ) between the peak intensity P 1 of the (101) plane and the peak intensity P 2 of the (102) plane measured by XRD is 0.10 to 0.60. MCM, characterized in that the peak intensity ratio Iq4 of tetracoordinated Al observed in 59.5 ± 2.0 by 27 Al-solid NMR is in the range of 0.14 to 0.70. A −22 type zeolite is provided. This MCM-22 type zeolite preferably has an ammonia desorption amount measured by an ammonia TPD method of 1.05 to 2.50 mol / kg when the adsorption enthalpy is in the range of 130 to 150 kJ / mol.
According to the present invention, there is also provided an aromatic hydrocarbon refining catalyst comprising the above MCM-22 type zeolite.
ゼオライトは、規則的な管状細孔（チャンネル）と空洞（キャビティ）とを有する陰イオン性の骨格と、この陰イオンを相殺する陽イオンとの組み合わせからなるアルカリ（またはアルカリ土類金属）含有含水アルミノケイ酸塩であり、ＳｉＯ４或いはＡｌＯ４の四面体が３次元網目状に連なった基本骨格の結晶構造を有している。このようなゼオライトは、この基本骨格により形成される細孔のパターンに応じて種々の構造コードが与えられている。ＭＣＭ−２２型ゼオライトは、ＭＷＷ型に属するものであり、下記式；
Ｍ＋ Ｘ・［ＡｌＸＳｉ７２−ＸＯ１４４］
Ｍ＋はＮａ等のカチオンであり、
ｘは、０＜ｘ＜６．５を満足する数である、
で表される組成の結晶骨格を有しており、Ａｌ或いはＳｉの一部はＴｉで同型置換されていてもよい。
Zeolite has an alkali (or alkaline earth metal) -containing water content composed of a combination of an anionic skeleton having regular tubular pores (channels) and cavities (cavities) and a cation that counteracts the anions. It is an aluminosilicate and has a basic skeletal crystal structure in which SiO 4 or AlO 4 tetrahedrons are linked in a three-dimensional network. Such zeolites are given various structural codes according to the pattern of pores formed by this basic skeleton. MCM-22 type zeolite belongs to the MWW type and has the following formula:
M + X · [Al X Si 72-X O 144]
M + is a cation such as Na;
x is a number satisfying 0 <x <6.5.
And a part of Al or Si may be isomorphously substituted with Ti.
本発明のＭＣＭ−２２型ゼオライトは、ＭＷＷ型に属する基本骨格を有していながら、Ｘ線回折（ＸＲＤ）により測定される（１０１）面のピーク強度Ｐ１と（１０２）面のピーク強度Ｐ２との比（Ｐ１／Ｐ２）が０．１０〜０．６０の範囲にある。即ち、このゼオライトは、（１０２）面に比して（１０１）面の成長が抑制されていることを示している。
さらに、本発明のＭＣＭ−２２型ゼオライトは、ＮＭＲで５９．５±２．０ｐｐｍにピークを示す４配位Ａｌのピーク強度比Ｉｑ４がかなり高いレベルにあり、特定の環境に在るＡｌＯ４四面体の連鎖を多く含んでいる。
Although the MCM-22 type zeolite of the present invention has a basic skeleton belonging to the MWW type, the peak intensity P 1 of the (101) plane and the peak intensity P of the (102) plane measured by X-ray diffraction (XRD). the ratio between the 2 (P 1 / P 2) is in the range of from 0.10 to 0.60. That is, this zeolite shows that the growth of the (101) plane is suppressed as compared to the (102) plane.
Furthermore, the MCM-22 type zeolite of the present invention has a 4-coordinated Al peak intensity ratio Iq4 that shows a peak at 59.5 ± 2.0 ppm by NMR at a considerably high level, and the AlO 4 tetrahedral surface in a specific environment. Contains many body chains.
上記のような構造を有する本発明のＭＣＭ−２２型ゼオライトは、後述する実施例に示されているように、芳香族炭化水素精製触媒として著しく延長された触媒寿命を有している。即ち、このような触媒寿命の延長は、実験的に確認されたものであり、理論的解明には至っていないが、その延長は驚くべきほどに顕著である。例えば、上記のＸＲＤによるピーク強度比（Ｐ１／Ｐ２）やＮＭＲによる４配位Ａｌのピーク強度比Ｉｑ４が上述した範囲外である比較例１〜３のＭＣＭ−２２型ゼオライトは、その触媒寿命（詳細な実験方法は実施例参照）は２２０〜２４０時間程度であるが、実施例１〜４の本発明のＭＣＭ−２２型ゼオライトでの触媒寿命は４００時間以上であり、触媒寿命が著しく向上していることが判る。 The MCM-22 type zeolite of the present invention having the structure as described above has a significantly extended catalyst life as an aromatic hydrocarbon refining catalyst, as shown in the Examples described later. That is, such an extension of the catalyst life has been experimentally confirmed and has not yet been theoretically elucidated, but the extension is surprisingly remarkable. For example, the MCM-22 type zeolites of Comparative Examples 1 to 3 in which the peak intensity ratio (P 1 / P 2 ) by XRD and the peak intensity ratio Iq4 of 4-coordinated Al by NMR are outside the above-described range are the catalysts. The lifetime (refer to the examples for detailed experimental methods) is about 220 to 240 hours, but the catalyst lifetimes of the MCM-22 type zeolites of the present invention of Examples 1 to 4 are 400 hours or more, and the catalyst lifetime is remarkably high. It turns out that it is improving.
また、本発明のＭＣＭ−２２型ゼオライトは、好ましくはアンモニアＴＰＤ法により測定されるアンモニア脱離量が、吸着エンタルピーが１３０〜１５０ｋＪ／ｍｏｌの範囲で１．０５〜２．５０ｍｏｌ／ｋｇである。アンモニア脱離量がこのような高い値を示すことにより、触媒活性に関し、従来公知のＭＣＭ−２２型ゼオライトと同等以上のレベルにあることを示している。 The MCM-22 type zeolite of the present invention preferably has an ammonia desorption amount measured by an ammonia TPD method of 1.05 to 2.50 mol / kg when the adsorption enthalpy is in the range of 130 to 150 kJ / mol. When the ammonia desorption amount shows such a high value, it indicates that the catalyst activity is at a level equal to or higher than that of conventionally known MCM-22 type zeolite.
上述の通り、本発明によれば良好な触媒活性を示すとともに触媒寿命が著しく延長された、炭化水素系精製触媒として極めて有用なＭＣＭ−２２型ゼオライトが得られる。 As described above, according to the present invention, it is possible to obtain MCM-22 type zeolite which is very useful as a hydrocarbon purification catalyst, which exhibits good catalytic activity and has a significantly extended catalyst life.
＜ＭＣＭ−２２型ゼオライトの製造＞
本発明のＭＣＭ−２２型ゼオライトは、ＳｉＯ２源・Ａｌ２Ｏ３源・アルカリ及びテンプレートであるヘキサメチレンイミンを脱イオン水と混合し、この混合物をオートクレーブ中で水熱反応せしめ、得られた反応物を焼成してヘキサメチレンイミンを除去するというプロセスを経て合成される。
<Manufacture of MCM-22 type zeolite>
The MCM-22 type zeolite of the present invention was obtained by mixing SiO 2 source / Al 2 O 3 source / alkali and hexamethyleneimine as a template with deionized water and hydrothermally reacting the mixture in an autoclave. It is synthesized through a process of removing the hexamethyleneimine by baking the reaction product.
上記のプロセスを経て合成されるという点では、従来公知のＭＣＭ−２２型ゼオライトと同様であるが、本発明では、ＸＲＤで測定される（１０１）面のピーク強度Ｐ１と（１０２）面のピーク強度Ｐ２との比（Ｐ１／Ｐ２）を０．１０〜０．６０の範囲とし、且つ２７Ａｌ−固体ＮＭＲで５９．５±２．０ｐｐｍ（以下、６０ｐｐｍ付近と略す）に観測される４配位Ａｌのピーク強度比Ｉｑ４が０．１４〜０．７０の範囲とするために、水熱反応時の反応条件や、水熱反応後の熱履歴に関して、従来公知の製造方法にはみられない設定をすることが重要である。以下、これらを考慮して、本発明のＭＣＭ−２２型ゼオライトを製造する方法について説明する。 It is the same as the conventionally known MCM-22 type zeolite in that it is synthesized through the above process, but in the present invention, the peak intensity P 1 of the (101) plane and the (102) plane measured by XRD are used. The ratio (P 1 / P 2 ) with the peak intensity P 2 is in the range of 0.10 to 0.60, and observation is made at 59.5 ± 2.0 ppm (hereinafter, abbreviated as 60 ppm) by 27 Al-solid NMR. In order to set the peak intensity ratio Iq4 of tetracoordinated Al to be in the range of 0.14 to 0.70, regarding the reaction conditions during the hydrothermal reaction and the thermal history after the hydrothermal reaction, a conventionally known production method is used. It is important to make settings that are not visible. Hereinafter, in consideration of these, the method for producing the MCM-22 type zeolite of the present invention will be described.
まず、原料として用いるＳｉＯ２源としては、ケイ酸ソーダに代表されるケイ酸アルカリや二酸化ケイ素（シリカ）を使用することができるが、特に反応を均一且つ迅速に進行させるため、微細なシリカ、例えばコロイダルシリカが好適に使用される。
また、Ａｌ２Ｏ３源としては、反応を迅速に進行させるため、アルミン酸ナトリウム（ＮａＡｌＯ２）等のアルミン酸アルカリが好適に使用される。
ＳｉＯ２源とＡｌ２Ｏ３源との量比は、ＭＷＷ型構造の骨格を形成し得るように設定され、例えば、ＳｉＯ２とＡｌ２Ｏ３とのモル比（ＳｉＯ２／Ａｌ２Ｏ３）で１５〜５０、好ましくは２８〜４５の範囲に設定される。
First, as the SiO 2 source used as a raw material, alkali silicate represented by sodium silicate and silicon dioxide (silica) can be used, but in order to make the reaction proceed uniformly and rapidly, fine silica, For example, colloidal silica is preferably used.
Further, as the Al 2 O 3 source, alkali aluminate such as sodium aluminate (NaAlO 2 ) is preferably used in order to allow the reaction to proceed rapidly.
The quantity ratio between the SiO 2 source and the Al 2 O 3 source is set so as to form a skeleton having an MWW type structure. For example, the molar ratio between SiO 2 and Al 2 O 3 (SiO 2 / Al 2 O 3 ) In the range of 15-50, preferably 28-45.
テンプレートとして使用されるヘキサメチレンイミン（以下、ＨＭＩと略すことがある）は、通常、ＳｉＯ２１モル当り０．２〜１．０モルの範囲とするのがよい。このようなテンプレートを使用することで、後述する水熱反応により、ＭＣＭ−２２型ゼオライトの結晶の基本骨格が形成される。 Hexamethyleneimine (hereinafter sometimes abbreviated as HMI) used as a template is usually in the range of 0.2 to 1.0 mole per mole of SiO 2 . By using such a template, a basic skeleton of crystals of MCM-22 type zeolite is formed by a hydrothermal reaction described later.
また、アルカリとしては、Ｎａ、Ｋ、Ｌｉに代表されるアルカリ金属の水酸化物が使用され、通常、ＳｉＯ２１モル当り０．１〜０．２モルの範囲に設定される。
As the alkali, Na, K, alkali metal hydroxide typified by Li is used, it is typically in the range of
上述したＳｉＯ２源、Ａｌ２Ｏ３源、ＨＭＩ及びアルカリは脱イオン水に混合されて水熱反応に供されるが、この水分量は、通常、ＳｉＯ２１００質量部当り６００〜２０００質量部である。 The above-mentioned SiO 2 source, Al 2 O 3 source, HMI and alkali are mixed with deionized water and subjected to a hydrothermal reaction. The amount of water is usually 600 to 2000 parts by mass per 100 parts by mass of SiO 2. It is.
尚、水熱反応を速やかに進行せしめ、比較的低い温度で結晶化させるために、ＮａＣｌ等の鉱化剤を使用することもできる。このような鉱化剤は、通常、ＳｉＯ２１モル当り０．００１〜０．１モルの量で使用される。
A mineralizer such as NaCl can also be used in order to allow the hydrothermal reaction to proceed rapidly and to crystallize at a relatively low temperature. Such mineralizing agent is generally used in an amount of
水熱反応は、オートクレーブ中で行われるが、この水熱反応はある程度以上の強撹拌下で行うことが必要である。この撹拌が弱すぎると、ＸＲＤによるピーク強度比（Ｐ１／Ｐ２）が前述した範囲を超えてしまう。即ち、（１０１）面の成長が（１０２）面の成長度合いに近くなってしまい、また、特定の環境に在るＡｌＯ４の四面体の成長も不十分となり、ＮＭＲによる４配位Ａｌのピーク強度比Ｉｑ４が低い値となってしまい、この結果、芳香族炭化水素精製触媒としての触媒寿命を延長することができなくなってしまう。ＭＣＭ−２２型ゼオライトの結晶構造を形成するための反応時間はかなり長く、このため、撹拌条件が結晶の成長に大きな影響を及ぼすものと思われる。
尚、具体的な撹拌条件は、水熱反応に供する液量等によって異なるため、予めラボ実験を行って、目的とする液量に応じて回転数などの撹拌条件を設定することが必要である。
The hydrothermal reaction is performed in an autoclave, but this hydrothermal reaction needs to be performed with a certain degree of strong stirring. If this stirring is too weak, the peak intensity ratio (P 1 / P 2 ) by XRD exceeds the range described above. That is, the growth of the (101) plane is close to the degree of growth of the (102) plane, and the growth of the tetrahedron of AlO 4 in a specific environment is insufficient, and the peak of tetracoordinated Al by NMR. The intensity ratio Iq4 becomes a low value, and as a result, the catalyst life as an aromatic hydrocarbon purification catalyst cannot be extended. The reaction time for forming the crystal structure of the MCM-22 type zeolite is considerably long, and it is considered that the stirring conditions have a great influence on the crystal growth.
Since specific stirring conditions vary depending on the amount of liquid used for the hydrothermal reaction, it is necessary to conduct a laboratory experiment in advance and set the stirring conditions such as the number of rotations according to the target liquid volume. .
さらに、本発明のＭＣＭ−２２型ゼオライトを製造するためには、反応温度及び反応時間も適宜の範囲に設定することが必要である。
例えば水熱反応の温度は、比較的低温領域とすることが必要であり、具体的には１００〜２００℃、特に１２０〜１５８℃の範囲とするのがよい。この反応温度が高いと、（１０１）面の成長が促進されてしまい、やはり、ＸＲＤによるピーク強度比（Ｐ１／Ｐ２）が前述した範囲を超えてしまう。
また、反応時間は、反応温度や液量などによって多少異なり、厳密に規定することはできないが、通常は４８〜１６８時間、好ましくは７２〜１６８時間程度とする。即ち、反応時間が長くなるほど、（１０１）面が成長し、ＸＲＤによるピーク強度比（Ｐ１／Ｐ２）が前述した範囲を超えてしまうこととなる。また、反応時間が短すぎると、当然のことながらゼオライトの基本骨格が十分に形成されない。
Furthermore, in order to produce the MCM-22 type zeolite of the present invention, it is necessary to set the reaction temperature and the reaction time within appropriate ranges.
For example, the temperature of the hydrothermal reaction needs to be in a relatively low temperature range, and specifically, it may be in the range of 100 to 200 ° C., particularly 120 to 158 ° C. When this reaction temperature is high, the growth of the (101) plane is promoted, and the peak intensity ratio (P 1 / P 2 ) by XRD exceeds the aforementioned range.
The reaction time varies somewhat depending on the reaction temperature, liquid volume, etc., and cannot be strictly defined, but is usually 48 to 168 hours, preferably about 72 to 168 hours. That is, as the reaction time becomes longer, the (101) plane grows, and the peak intensity ratio (P 1 / P 2 ) by XRD exceeds the above-described range. If the reaction time is too short, it is natural that the basic framework of zeolite is not sufficiently formed.
水熱反応後は、室温まで冷却した後、オートクレーブ中から反応生成物を取り出し、常法により、ろ過、脱イオン水による洗浄を行い、適宜、乾燥を行った後、焼成を行うことにより、テンプレートとして使用されたＨＭＩを分解除去し、これにより、反応に使用されたアルカリ金属の種類に応じて、例えばＮａ型、Ｋ型などのＭＣＭ−２２型ゼオライトを得ることができる。 After the hydrothermal reaction, after cooling to room temperature, the reaction product is taken out from the autoclave, filtered, washed with deionized water by a conventional method, appropriately dried, and then baked to obtain a template. As a result, HMI used as a catalyst can be decomposed and removed to obtain MCM-22 type zeolite such as Na type and K type according to the kind of alkali metal used in the reaction.
上記のようにしてＭＣＭ−２２型ゼオライトを得ることができるが、特に本発明のＭＣＭ−２２型ゼオライトを製造する場合には、高温での熱履歴を避けることが必要であり、具体的には、７００℃よりも低い温度で、テンプレート除去のための焼成を行うことが必要である。即ち、水熱反応による生成物が７００℃以上の温度に加熱されると、結晶中のＡｌＯ４の四面体の構造破壊が生じ、４配位Ａｌのピーク強度比Ｉｑ４が低い値となり、また、結晶中の（１０１）面の成長が促進されてしまい、ＸＲＤによるピーク強度比（Ｐ１／Ｐ２）が前述した範囲を超えてしまうこともあり、目的とする触媒寿命の向上が実現できなくなってしまう。 Although the MCM-22 type zeolite can be obtained as described above, it is necessary to avoid the heat history at high temperature, particularly when the MCM-22 type zeolite of the present invention is produced. It is necessary to perform baking for removing the template at a temperature lower than 700 ° C. That is, when the product of the hydrothermal reaction is heated to a temperature of 700 ° C. or higher, AlO 4 tetrahedron structural breakage in the crystal occurs, and the peak intensity ratio Iq4 of tetracoordinate Al becomes a low value, The growth of the (101) plane in the crystal is promoted, and the peak intensity ratio (P 1 / P 2 ) by XRD may exceed the aforementioned range, so that the target catalyst life cannot be improved. End up.
＜ＭＣＭ−２２型ゼオライトの特性及び用途＞
上記のようにして得られる本発明のＭＣＭ−２２型ゼオライトは、結晶中の（１０１）面の成長が抑制されており、ＸＲＤで測定される（１０１）面のピーク強度Ｐ１と（１０２）面のピーク強度Ｐ２との比（Ｐ１／Ｐ２）が０．１０〜０．６０の範囲にある。また、特定の環境に在るＡｌＯ４の四面体も一定レベル以上の割合で存在しており、２７Ａｌ−固体ＮＭＲで６０ｐｐｍ付近に観測される４配位Ａｌのピーク強度比Ｉｑ４が０．１４〜０．７０の範囲にある。
このようなＸＲＤによるピーク強度比（Ｐ１／Ｐ２）とＮＭＲによるピーク強度比Ｉｑ４を有しているため、後述する実施例にも示されているように、芳香族炭化水素中に含まれるオレフィンやジオレフィンなどの不飽和炭化水素を、蒸留により分離可能な重合体の形態に転換せしめる芳香族炭化水素精製触媒としての触媒寿命が大幅に延長されたものとなっている。
<Characteristics and use of MCM-22 type zeolite>
In the MCM-22 type zeolite of the present invention obtained as described above, the growth of the (101) plane in the crystal is suppressed, and the peak intensity P 1 of the (101) plane measured by XRD and (102) the ratio of the peak intensity P 2 faces (P 1 / P 2) is in the range of 0.10 to 0.60. Further, AlO 4 tetrahedrons present in a specific environment are also present at a certain level or higher, and the peak intensity ratio Iq4 of tetracoordinated Al observed at around 60 ppm by 27 Al-solid NMR is 0.14. It is in the range of ~ 0.70.
Since it has such a peak intensity ratio (P 1 / P 2 ) by XRD and a peak intensity ratio Iq4 by NMR, it is contained in aromatic hydrocarbons as shown in Examples described later. The catalyst life as an aromatic hydrocarbon refining catalyst that converts unsaturated hydrocarbons such as olefins and diolefins into a polymer form separable by distillation is greatly extended.
また、このような本発明のＭＣＭ−２２型ゼオライトは、好ましくはアンモニアＴＰＤ法により測定されるアンモニア脱離量が、吸着エンタルピーが１３０〜１５０ｋＪ／ｍｏｌの範囲で１．０５〜２．５０ｍｏｌ／ｋｇ、と高い値を示す。 Further, the MCM-22 type zeolite of the present invention preferably has an ammonia desorption amount measured by an ammonia TPD method of 1.05 to 2.50 mol / kg when the adsorption enthalpy is in the range of 130 to 150 kJ / mol. , And a high value.
アンモニアＴＰＤ法において、吸着熱は固体酸強度に、アンモニア脱離量は固体酸量に関係付けられる。即ち、アンモニアＴＰＤ法は、後述する実施例に記載されているように、塩基プローブ分子であるアンモニアを試料の固体に吸着させ、温度を連続的に上昇させることによって脱離するアンモニアの量及び温度を同時測定するというものである。弱い酸点に吸着しているアンモニアが低温で脱離し（吸着熱が低い範囲での脱離に相当）、強い酸点に吸着しているアンモニアが高温で脱離する（吸着熱が高い範囲での脱離に相当）こととなる。従来、ＢＴＸ等の芳香族炭化水素の精製処理において、オレフィンやジオレフィンなどの不飽和炭化水素化合物のアルキル化や重合といった反応は、触媒中に単純に酸強度の高い固体酸の量が多いほど促進されるものと考えられてきた。しかしながら、このような反応に寄与する固体酸は、吸着エンタルピーとして１３０〜１５０ｋＪ／ｍｏｌの範囲に対応する酸強度のものに限られ、これ以外の酸強度の範囲にある固体酸は、副反応を促進し、触媒寿命を低下させてしまう。従って、触媒性能の評価では、このような吸着エンタルピーの範囲でのアンモニア脱離量が重要なパラメータとなる。 In the ammonia TPD method, the heat of adsorption is related to the solid acid strength, and the ammonia desorption amount is related to the solid acid amount. That is, in the ammonia TPD method, as described in the examples described later, the amount and temperature of ammonia desorbed by adsorbing ammonia, which is a base probe molecule, to a solid sample and continuously increasing the temperature. Are measured simultaneously. Ammonia adsorbed on weak acid sites desorbs at low temperatures (equivalent to desorption in a low adsorption heat range), and ammonia adsorbed on strong acid sites desorbs at high temperatures (in a high adsorption heat range). Is equivalent to detachment). Conventionally, in the purification treatment of aromatic hydrocarbons such as BTX, reactions such as alkylation and polymerization of unsaturated hydrocarbon compounds such as olefins and diolefins are performed simply by increasing the amount of solid acid having high acid strength in the catalyst. It has been thought to be promoted. However, solid acids that contribute to such reactions are limited to those with acid strengths corresponding to the range of 130 to 150 kJ / mol as adsorption enthalpies, and solid acids with other acid strengths range from side reactions. Promotes and reduces catalyst life. Therefore, in the evaluation of the catalyst performance, the amount of ammonia desorption within such an adsorption enthalpy range is an important parameter.
本発明のＭＣＭ−２２型ゼオライトは、上記の通りアンモニア脱離量が高い値であることで、触媒寿命が延長されたばかりか、触媒活性の点でも、従来公知のものと同等以上のレベルにあることを示している。 The MCM-22 type zeolite of the present invention has a high ammonia desorption amount as described above, so that not only the catalyst life is extended, but also in terms of catalyst activity, it is at or above the level of conventionally known ones. It is shown that.
尚、上記のような触媒活性や触媒寿命は、ゼオライト充填層を通過させた後蒸留により高沸点留分を除去した芳香族炭化水素について、オレフィン分の含有量の指標となる臭素指数を求めることにより評価することができる。 For the catalytic activity and catalyst life as described above, the bromine index, which is an index of the olefin content, is obtained for aromatic hydrocarbons that have been passed through the zeolite packed bed and then removed by high-boiling fraction by distillation. Can be evaluated.
このように、本発明のＭＣＭ−２２型ゼオライトは、ＢＴＸなどの芳香族炭化水素の精製触媒として優れた特性を有しており、その使用形態に応じて、粒度調整して使用に供される。
例えば、芳香族炭化水素の精製処理をバッチで行う場合には、その粒径は一般に２０〜４０μｍ、特に２５〜３５μｍのメジアン径の粉末に調整され、固定床で用いる場合は、一般に粒径が、０．２５〜１．０ｍｍの範囲の粒状物の形態に調整される。粒子形状は、球状、顆粒状、立方体状、タブレット状、円柱状、不定形状等の何れの形状であってもよい。
As described above, the MCM-22 type zeolite of the present invention has excellent characteristics as a purification catalyst for aromatic hydrocarbons such as BTX, and is used after adjusting the particle size according to the use form. .
For example, when the purification process of aromatic hydrocarbons is performed in batches, the particle size is generally adjusted to 20 to 40 μm, particularly 25 to 35 μm median diameter powder, and when used in a fixed bed, the particle size is generally , Adjusted to a granular form in the range of 0.25 to 1.0 mm. The particle shape may be any shape such as a spherical shape, a granular shape, a cubic shape, a tablet shape, a cylindrical shape, and an indefinite shape.
また、上述した本発明のＭＣＭ−２２型ゼオライトは、Ｎａ型等のアルカリイオン型に限定されるものではなく、例えばアルカリイオンをアンモニウムイオンやカルシウム等のアルカリ土類金属のイオンにイオン交換した形態で使用に供することもできるし、また、プロトン型（Ｈ＋）にイオン交換して使用することもできる。このイオン交換は、イオン交換するイオンを含む塩（例えば硝酸アンモニウム）や硫酸等を用いての中和処理によっても行うことができる。
尚、例えば、本発明のＭＣＭ−２２型ゼオライトを硝酸アンモニウム水溶液等で処理してアンモニウム型に変化させた後、これを焼成することによってもプロトン型にイオン交換することができるが、このような焼成を行う場合にも、前述した理由により、７００℃以上の高温での焼成は避けなければならない。
Further, the above-described MCM-22 type zeolite of the present invention is not limited to the alkali ion type such as Na type, and for example, the form in which alkali ions are ion-exchanged with ions of alkaline earth metals such as ammonium ions and calcium. It can also be used for use, or can be used after ion-exchanged to the proton form (H + ). This ion exchange can also be performed by a neutralization treatment using a salt (for example, ammonium nitrate) or sulfuric acid containing ions to be ion exchanged.
In addition, for example, the MCM-22 type zeolite of the present invention can be changed to the ammonium type by treating it with an aqueous ammonium nitrate solution and the like, and then calcinated to be ion-exchanged to the proton type. Even in the case of performing baking, firing at a high temperature of 700 ° C. or more must be avoided for the above-described reason.
本発明のＭＣＭ−２２型ゼオライトは、芳香族炭化水素の精製触媒として好適に使用することができるが、勿論、オレフィンの重合触媒としても使用することができるし、公知のＭＣＭ−２２型ゼオライトと同様の用途に使用することができる。 The MCM-22 type zeolite of the present invention can be suitably used as a purification catalyst for aromatic hydrocarbons, but of course can also be used as a polymerization catalyst for olefins. It can be used for similar applications.
本発明を次の実験例で説明する。
尚、以下の実験例での各種物性の測定は、以下の方法により行った。
The invention is illustrated by the following experimental example.
The various physical properties in the following experimental examples were measured by the following methods.
（１）化学組成
Ｓｉ、ＡｌとＮａの各元素は、加圧成型機で作成したペレットについて、(株)リガク製RIX2100を用いてXRF測定を行った。
H2Oについては、セイコーインスツル（株）製ＥＸＳＴＡＲ６０００を用い、１１０〜１０００℃の質量減少量として測定した。測定条件は、昇温速度１０℃／分、空気流速２００ｃｍ３／分とした。
これらの測定結果からSiO2/Al2O3(SAR)、Na2O/SiO2、H2O/SiO2のモル比を算出した。
(1) Chemical composition Each element of Si, Al, and Na was subjected to XRF measurement using a RIX2100 manufactured by Rigaku Corporation on pellets produced by a pressure molding machine.
The H 2 O, using Seiko Instruments Co. EXSTAR6000, was measured as weight loss of 110 to 1,000 ° C.. The measurement conditions were a heating rate of 10 ° C./min and an air flow rate of 200 cm 3 / min.
From these measurement results, the molar ratio of SiO 2 / Al 2 O 3 (SAR), Na 2 O / SiO 2 , and H 2 O / SiO 2 was calculated.
（２）比表面積
Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＴｒｉＳｔａｒ３０００を用いて測定を行った。比表面積は比圧が０．０５から０．２５の吸着枝側窒素吸着等温線からＢＥＴ法で解析した。
(2) Specific surface area It measured using TriStar3000 made from Micromeritics. The specific surface area was analyzed by the BET method from the adsorption side nitrogen adsorption isotherm having a specific pressure of 0.05 to 0.25.
（３）ＸＲＤによるピーク強度比（Ｐ１／Ｐ２）
試料1gを、食塩水で飽和させたデシケータ中で調湿させた。NBS法（“Standard X-ray diffraction powder patterns”, NBS Monograph,25(1971).）で試料をホルダーに充填し、測定角度2θが3〜15[deg]の範囲でＸＲＤ測定を行った。その際の測定条件は、電圧40[V]電流40[mA]、D Slit & S Slit：2/3、V Slit：10[mm]、R Slit 0.3[mm]、Step：0.02[deg]であった。各試料について、2θ=8°付近の(101)と2θ=10°付近の(102)の回折ピーク面積強度Ｐ１とＰ２をそれぞれ求め、その試料の強度比（Ｐ１／Ｐ２）を決定した。
(3) Peak intensity ratio by XRD (P 1 / P 2 )
A 1 g sample was conditioned in a desiccator saturated with saline. A sample was filled in a holder by the NBS method (“Standard X-ray diffraction powder patterns”, NBS Monograph, 25 (1971).), And XRD measurement was performed in a measurement angle 2θ of 3 to 15 [deg]. The measurement conditions at that time are as follows: voltage 40 [V] current 40 [mA], D Slit & S Slit: 2/3, V Slit: 10 [mm], R Slit 0.3 [mm], Step: 0.02 [deg] there were. For each sample, the diffraction peak area intensities P 1 and P 2 of (101) near 2θ = 8 ° and (102) near 2θ = 10 ° are obtained, and the intensity ratio (P 1 / P 2 ) of the sample is obtained. Were determined.
（４）ＮＭＲによる４配位Ａｌのピーク強度比（Ｉｑ４）
各試料の２７Ａｌ−ＭＡＳＮＭＲの測定は、日本電子（株）製JEOL CMX400型のＮＭＲ装置を用い、食塩水で飽和させたデシケータ中で調湿させた試料をセルに充填し秤量してから、下記の条件で測定を行った。
観測周波数104.170MHz、パルス遅延1sec、パルス幅4μsec（２７Ａｌ 10゜パルス）
試料回転数 10 kHz、化学シフト基準硫酸アルミニウム飽和水溶液（外部基準：0.0ppm）。
得られた四配位アルミニウムのスペクトルを解析ソフトのDeltaで波形分離し、66、60、および53ｐｐｍ付近のピークに分割した。触媒学会の参照触媒JRC-Z-HY5.6における６０ｐｐｍ付近ピークの質量あたり面積に対する各試料の60ｐｐｍ付近ピークの質量あたり面積の比を、その試料のＩｑ４とした。
(4) Peak intensity ratio of tetracoordinated Al by NMR (Iq4)
The measurement of 27 Al-MAS NMR of each sample was carried out by using a JEOL CMX400 type NMR device manufactured by JEOL Ltd., filling a cell with a sample conditioned in a desiccator saturated with saline, and weighing it. Measurement was performed under the following conditions.
Observation frequency 104.170MHz,
Sample rotation speed 10 kHz, chemical shift standard saturated aqueous solution of aluminum sulfate (external standard: 0.0 ppm).
The spectrum of the resulting tetracoordinated aluminum was separated into waveforms by analysis software Delta and divided into peaks around 66, 60, and 53 ppm. The ratio of the area per mass of the peak near 60 ppm of each sample to the area per mass of the peak near 60 ppm in the reference catalyst JRC-Z-HY5.6 of the Catalysis Society was defined as Iq4 of the sample.
（５）アンモニア脱離量（アンモニアＴＰＤ法）
試料約０．１ｇを日本ベル製ＴＰＤ−ＡＴ−１型昇温脱離装置の石英セル（内径１０ｍｍ）にセットし、Ｏ２（６０ｃｍ３ｍｉｎ−１、１ａｔｍ）流通下、７７３Ｋまで１０Ｋｍｉｎ−１で昇温し、到達温度で１ｈｒ保った。その後Ｏ２を流通させたまま３７３Ｋまで放冷した後に真空脱気し、１００ＴｏｒｒのＮＨ３を導入して３０ｍｉｎ間吸着させ、その後３０ｍｉｎ間脱気した後に水蒸気処理を行った。水蒸気処理としては、１００℃で約２５Ｔｏｒｒの蒸気圧の水蒸気を導入、そのまま３０ｍｉｎ保ち、３０ｍｉｎ脱気、再び３０ｍｉｎ水蒸気導入、再び３０ｍｉｎ脱気の順に繰り返した。その後Ｈｅ ０．０４１ｍｍｏｌｓ−１を減圧（１００Ｔｏｒｒ、１３．３ｋＰａ）に保ちながら流通させ、１００℃で３０ｍｉｎ保った後に試料床を１０Ｋｍｉｎ−１で１０７３Ｋまで昇温し、出口気体を質量分析計（ＡＮＥＬＶＡ Ｍ−ＱＡ １００Ｆ）で分析した。Ｗ／Ｆは１３ｋｇｓ／ｍ３である。
測定に際しては質量数（ｍ／ｅ）１６のマススペクトルを記録した。終了後に１ｍｏｌ％−ＮＨ３／Ｈｅ標準ガスをさらにヘリウムで希釈してＮＨ３濃度０、０．１、０．２、０．３、０．４ｍｏｌ％，合計流量が０．０４１ｍｍｏｌｓ−１となるようにして検出器に流通させ、スペクトルを記録し、アンモニアの検量線を作成して検出器強度を補正した。
得られたＴＰＤスペクトルから酸強度分布（Ｃｗ／ΔＨ）への変換は、鳥取大学大学院工学研究科／工学部研究報告，４０，２３（２００９）に従って行った。得られた酸強度分布から、吸着エンタルピー（ΔＨ）が１３０〜１５０ｋＪ／ｍｏｌの範囲におけるアンモニア脱離量（Ｃｗ）を算出した。
(5) Ammonia desorption amount (ammonia TPD method)
About 0.1 g of a sample was set in a quartz cell (inner diameter: 10 mm) of a TPD-AT-1 type thermal desorption apparatus manufactured by Nippon Bell, and 10 Kmin − up to 773 K under O 2 (60 cm 3 min −1 , 1 atm) flow. The temperature was raised at 1 and kept at the ultimate temperature for 1 hr. Thereafter, the mixture was allowed to cool to 373 K while O 2 was circulated, then vacuum degassed, 100 Torr NH 3 was introduced and adsorbed for 30 min, and then degassed for 30 min, followed by steam treatment. As the water vapor treatment, water vapor having a vapor pressure of about 25 Torr was introduced at 100 ° C., maintained for 30 minutes as it was, repeated for 30 minutes, degassing again for 30 minutes, and degassing again for 30 minutes . Thereafter, He 0.041 mmols −1 was circulated while maintaining a reduced pressure (100 Torr, 13.3 kPa), and after maintaining at 100 ° C. for 30 min, the sample bed was heated to 1073 K at 10 Kmin −1 , and the outlet gas was changed to a mass spectrometer (ANELVA). M-QA 100F). W / F is 13 kgs / m 3 .
During the measurement, a mass spectrum having a mass number (m / e) 16 was recorded. After completion, the 1 mol% -NH 3 / He standard gas is further diluted with helium, and the NH 3 concentration becomes 0, 0.1, 0.2, 0.3, 0.4 mol%, and the total flow rate becomes 0.041 mmols −1. The spectrum was recorded, and a calibration curve of ammonia was prepared to correct the detector intensity.
Conversion from the obtained TPD spectrum to acid strength distribution (Cw / ΔH) was performed according to Tottori University Graduate School of Engineering / Faculty of Engineering Research Report, 40, 23 (2009). From the obtained acid strength distribution, the ammonia desorption amount (Cw) in the range of adsorption enthalpy (ΔH) of 130 to 150 kJ / mol was calculated.
（６）触媒寿命（通油試験）
芳香族炭化水素成分の測定は、JIS K2536-3に準拠し、島津製作所(株)製ガスクロマトグラフGC-2010を用いて測定した。また、臭素指数（Br-Index、以下、BIと略記)は、平沼産業（株）製電量滴定式BR-7で測定した。
供試油の成分を表１に示す。なお、供試油のBI(BI0)は646であった。
(6) Catalyst life (oil passage test)
The aromatic hydrocarbon component was measured using a gas chromatograph GC-2010 manufactured by Shimadzu Corporation in accordance with JIS K2536-3. The bromine index (Br-Index, hereinafter abbreviated as BI) was measured by the coulometric titration BR-7 manufactured by Hiranuma Sangyo Co., Ltd.
Table 1 shows the components of the test oil. The sample oil BI (BI 0 ) was 646.
以下の各実験例につき、採用したＳｉＯ２／Ａｌ２Ｏ３仕込みモル比、ＮａＣｌ／ＳｉＯ２モル比、水熱反応条件（撹拌速度、反応時間及び反応温度）、ＨＭＩ除去のための焼成温度、ＮＨ４型からＨ型に変換するための焼成温度を表２に示した。また、得られた各サンプルにつき、各種物性、及び芳香族炭化水素精製触媒としての評価（触媒寿命Ts）を表３に示した。 For each of the following experimental examples, the employed SiO 2 / Al 2 O 3 charged molar ratio, NaCl / SiO 2 molar ratio, hydrothermal reaction conditions (stirring speed, reaction time and reaction temperature), firing temperature for HMI removal, Table 2 shows the firing temperature for converting the NH 4 type to the H type. Table 3 shows various physical properties and evaluations (catalyst lifetime Ts) as aromatic hydrocarbon refining catalysts for each sample obtained.
＜比較例１＞
（１）ゼオライト合成工程
23.08g（SiO2換算で9.23g）のコロイダルシリカ（ＬｕｄｏｘＨＳ−４０）、及び７．６１ｇのヘキサメチレンイミン（ＨＭＩ）を、プラスチックビーカー中で混合撹拌してＡ液を調製した。一方、0.27ｇのＮａＡｌＯ２（Ａｌ２Ｏ３換算で0.17ｇ）、０．６０ｇのNaOH、及び０．４８ｇのＮａＣｌを別のプラスチックビーカーで１２４．２ｇの脱イオン水に溶解させてＢ液を調製した。Ｂ液を撹拌しつつ、Ａ液をプラスチックの滴下漏斗で３０分かけてＢ液に滴下した。その後、３０分撹拌を継続した。
<Comparative Example 1>
(1) Zeolite synthesis process
Liquid A was prepared by mixing and stirring 23.08 g (9.23 g in terms of SiO 2 ) of colloidal silica (Ludox HS-40) and 7.61 g of hexamethyleneimine (HMI) in a plastic beaker. On the other hand, 0.27 g of NaAlO 2 (0.17 g in terms of Al 2 O 3 ), 0.60 g of NaOH, and 0.48 g of NaCl were dissolved in 124.2 g of deionized water in another plastic beaker, and the solution B was dissolved. Prepared. While stirring the B liquid, the A liquid was dropped into the B liquid with a plastic dropping funnel over 30 minutes. Thereafter, stirring was continued for 30 minutes.
得られた混合液を２個のポリテトラフルオロエチレン容器に等量ずつ入れて専用ステンレス製オートクレーブにセットした。次いで、タンブリング回転用シャフトを備えた水熱合成用オーブンのシャフトに、このオートクレーブを取り付け、１５０℃、１５ｒｐｍで８４時間、水熱合成を行った。この後、室温まで冷却後、オートクレーブの内容物を取り出し、吸引ろ過、および脱イオン水での洗浄を３回繰り返した。得られたケーキを１００℃で３時間乾燥させた。 An equal amount of the obtained mixed solution was put into two polytetrafluoroethylene containers and set in a dedicated stainless steel autoclave. Next, the autoclave was attached to the shaft of a hydrothermal synthesis oven equipped with a tumbling rotation shaft, and hydrothermal synthesis was performed at 150 ° C. and 15 rpm for 84 hours. Thereafter, after cooling to room temperature, the contents of the autoclave were taken out, suction filtration, and washing with deionized water were repeated three times. The obtained cake was dried at 100 ° C. for 3 hours.
次いで、マッフル炉（昇温速度２℃／ｍｉｎ）を用い、上記の乾燥物を５８０℃で３時間焼成してＨＭＩを除去してＮａ型のＭＣＭ−２２ゼオライトを得た。
Next, using a muffle furnace (
（２）イオン交換工程
上記のようにして得られたＮａ型のＭＣＭ−２２ゼオライト７．２ｇを、１０．８ｇの０．５Ｎ硝酸アンモニウムと共に、２７０ｍｌの脱イオン水が入れられた１０００ｍｌの三角フラスコに加え、撹拌子で撹拌しながら７５℃で２４時間イオン交換した。撹拌終了後、吸引ろ過、脱イオン水による洗浄を２回行い、１００℃の乾燥機中で２時間乾燥させてＮＨ４型のＭＣＭ−２２ゼオライトを得た。
上記のＮＨ４型のＭＣＭ−２２ゼオライトを、マッフル炉（昇温速度２℃／分）にて５４０℃で４時間焼成することで、Ｈ型のＭＣＭ−２２ゼオライト（Ｈ−１）を得た。
(2) Ion Exchange Step 7.2 g of Na-type MCM-22 zeolite obtained as described above was placed in a 1000 ml Erlenmeyer flask containing 270 ml of deionized water together with 10.8 g of 0.5N ammonium nitrate. In addition, ion exchange was performed at 75 ° C. for 24 hours while stirring with a stirring bar. After completion of the stirring, suction filtration and washing with deionized water were performed twice, followed by drying in a dryer at 100 ° C. for 2 hours to obtain NH 4 type MCM-22 zeolite.
The NH 4 type MCM-22 zeolite (H-1) was obtained by calcining the NH 4 type MCM-22 zeolite in a muffle furnace (
＜比較例２＞
（１）ゼオライト合成工程
１７５ｇ（SiO2換算で70g）のコロイダルシリカと５９．０ｇのＨＭＩを混合してＡ液を調製し、５．０７ｇのＮａＯＨと、６．２８ｇのＮａＡｌＯ２（Ａｌ２Ｏ３換算で３．８９ｇ）、１．３７ｇのＮａＣｌ、を９４５ｇの脱イオン水に混合してＢ液を調製した。上記のＢ液を攪拌しつつ、Ａ液をプラスチックの滴下漏斗で３０分かけてＢ液に滴下し、その後３０分攪拌を継続した。得られた混合液を、内容量１．５Ｌの耐圧硝子工業（株）社製オートクレープに入れ、１５０℃、６０ｒｐｍで８５時間水熱合成を行った。室温まで冷却後、オートクレープの内容物を取り出し、吸引ろ過、および脱イオン水での洗浄をｐＨが１１以下になるまでに繰り返した。得られたケーキを１１０℃で３時間かけて乾燥させた後、マッフル炉（昇温速度２℃／分）を用い７００℃で４時間焼成し、ＨＭＩを除去してＮａ型のＭＣＭ−２２ゼオライトを得た。
<Comparative example 2>
(1) Zeolite synthesis step 175 g (70 g in terms of SiO 2 ) of colloidal silica and 59.0 g of HMI are mixed to prepare solution A. 5.07 g of NaOH and 6.28 g of NaAlO 2 (Al 2 O The liquid B was prepared by mixing 3.89 g in terms of 3 ) and 1.37 g of NaCl with 945 g of deionized water. While stirring the above-mentioned B liquid, A liquid was dripped at the B liquid with the plastic dropping funnel over 30 minutes, and stirring was continued for 30 minutes after that. The obtained mixed solution was put into an autoclave manufactured by Pressure Glass Industrial Co., Ltd. having an internal volume of 1.5 L, and hydrothermal synthesis was performed at 150 ° C. and 60 rpm for 85 hours. After cooling to room temperature, the contents of the autoclave were taken out, suction filtration, and washing with deionized water were repeated until the pH was 11 or less. The cake obtained was dried at 110 ° C. for 3 hours and then calcined at 700 ° C. for 4 hours using a muffle furnace (
（２）イオン交換工程
次いで、得られた乾燥ケークを粗砕してから水に分散し、固形分１％の懸濁液を得た。この懸濁液にゼオライトと同質量の硝酸アンモニウムを加え、攪拌しながら８０℃で４時間イオン交換した。ｐＨが６から７程度になるまで水洗し、１１０℃で乾燥した。得られた乾燥ケーキを粗砕してから、５８０℃で４時間焼成して、Ｈ型のＭＣＭ−２２ゼオライト（Ｈ−２）を得た。
(2) Ion Exchange Step Next, the obtained dried cake was crushed and then dispersed in water to obtain a suspension having a solid content of 1%. Ammonium nitrate of the same mass as the zeolite was added to this suspension, and ion exchange was performed at 80 ° C. for 4 hours with stirring. It was washed with water until the pH reached about 6 to 7, and dried at 110 ° C. The obtained dried cake was roughly crushed and then calcined at 580 ° C. for 4 hours to obtain H-type MCM-22 zeolite (H-2).
＜比較例３＞
水熱合成を１５８時間行った以外は、比較例２のゼオライト合成工程およびイオン交換工程と同様にして、Ｈ型のＭＣＭ−２２ゼオライト（Ｈ−３）を得た。
<Comparative Example 3>
H-type MCM-22 zeolite (H-3) was obtained in the same manner as the zeolite synthesis step and ion exchange step of Comparative Example 2 except that hydrothermal synthesis was performed for 158 hours.
＜実施例１＞
水熱合成を１３８時間行い、ＨＭＩの除去のための焼成温度を５８０℃とした以外は、比較例２のゼオライト合成工程と同様にして、Ｎａ型のＭＣＭ−２２ゼオライト（Ｊ−１）を得た。
<Example 1>
Na-type MCM-22 zeolite (J-1) was obtained in the same manner as the zeolite synthesis step of Comparative Example 2 except that hydrothermal synthesis was performed for 138 hours and the calcination temperature for removing HMI was 580 ° C. It was.
＜実施例２＞
実施例１で得られたＮａ型のＭＣＭ−２２ゼオライト（Ｊ−１）を水に分散し、固形分１％の懸濁液を得た。この懸濁液にゼオライトと同量の硝酸アンモニウムを加え、攪拌しながら８０℃で４時間イオン交換した。ｐＨが６から７程度になるまで水洗し、１１０℃で乾燥し、得られた乾燥ケーキを粗砕してから、５４０℃で４時間焼成してＨ型のＭＣＭ−２２ゼオライト（Ｊ−２）を得た。
尚、得られたＨ型のＭＣＭ−２２ゼオライト（Ｊ−２）のＸＲＤチャートを図１に示した。
<Example 2>
The Na-type MCM-22 zeolite (J-1) obtained in Example 1 was dispersed in water to obtain a suspension having a solid content of 1%. The same amount of ammonium nitrate as the zeolite was added to this suspension, and ion exchange was performed at 80 ° C. for 4 hours with stirring. Washed with water until the pH reached about 6 to 7, dried at 110 ° C., coarsely crushed the dried cake, and calcined at 540 ° C. for 4 hours to form H-type MCM-22 zeolite (J-2) Got.
An XRD chart of the obtained H-type MCM-22 zeolite (J-2) is shown in FIG.
＜実施例３＞
ＨＭＩを４１．３ｇ、ＮａＯＨを４．９２ｇ、ＮａＡｌＯ２を４．６４ｇ（Ａｌ２Ｏ３換算で２．８８ｇ）、鉱化剤としてのＮａＣｌを不使用、水熱合成時間を１３７時間、ＨＭＩ除去のための焼成温度を５８０℃、とした以外は、比較例２のゼオライト合成工程と同様にして、Ｎａ型のＭＣＭ−２２ゼオライト（Ｊ−３）を得た。
<Example 3>
41.3 g of HMI, 4.92 g of NaOH, 4.64 g of NaAlO 2 (2.88 g in terms of Al 2 O 3 ), no NaCl as a mineralizer, hydrothermal synthesis time of 137 hours, removal of HMI Na-type MCM-22 zeolite (J-3) was obtained in the same manner as the zeolite synthesis step of Comparative Example 2 except that the calcination temperature for was 580 ° C.
＜実施例４＞
実施例３で得られたＮａ型のＭＣＭ−２２ゼオライト（Ｊ−３）を粗砕してから水に分散し、固形分１％の懸濁液を得た。この懸濁液にゼオライトと同量の硝酸アンモニウムを加え、攪拌しながら８０℃で４時間イオン交換した。ｐＨが６から７程度になるまで水洗し、１１０℃で乾燥した。得られた乾燥ケーキを粗砕してから、５４０℃で４時間焼成して、Ｈ型のＭＣＭ−２２ゼオライト（Ｊ−４）を得た。
<Example 4>
The Na-type MCM-22 zeolite (J-3) obtained in Example 3 was roughly crushed and then dispersed in water to obtain a suspension having a solid content of 1%. The same amount of ammonium nitrate as the zeolite was added to this suspension, and ion exchange was performed at 80 ° C. for 4 hours with stirring. It was washed with water until the pH reached about 6 to 7, and dried at 110 ° C. The obtained dried cake was roughly crushed and then calcined at 540 ° C. for 4 hours to obtain H-type MCM-22 zeolite (J-4).
＜比較例４＞
ＨＭＩ除去の焼成温度を７００℃とした以外は実施例３と同様にしてＮａ型のＭＣＭ−２２ゼオライトを合成した。次いで（Ｊ−３）に代えてこのＮａ型ＭＣＭ−２２ゼオライトを用いた以外は実施例４と同様にして、Ｈ型のＭＣＭ−２２ゼオライト（Ｈ−４）を得た。
<Comparative example 4>
Na-type MCM-22 zeolite was synthesized in the same manner as in Example 3 except that the calcination temperature for removing HMI was 700 ° C. Next, an H-type MCM-22 zeolite (H-4) was obtained in the same manner as in Example 4 except that this Na-type MCM-22 zeolite was used instead of (J-3).
＜実施例５＞
実施例３で得られたＮａ型のＭＣＭ−２２ゼオライト（Ｊ−３）を粗砕してから５質量％の硫酸水に分散し、攪拌しながら室温で３時間中和処理した。ｐＨが４から５程度になるまで水洗し、１１０℃で乾燥した。得られた乾燥ケーキを粗砕して、Ｈ型のＭＣＭ−２２ゼオライト（Ｊ−５）を得た。
<Example 5>
The Na-type MCM-22 zeolite (J-3) obtained in Example 3 was roughly crushed and then dispersed in 5% by mass sulfuric acid, and neutralized at room temperature for 3 hours with stirring. It was washed with water until the pH reached about 4 to 5, and dried at 110 ° C. The obtained dried cake was roughly crushed to obtain H-type MCM-22 zeolite (J-5).
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