JP2021142504A - Catalyst for production of olefin - Google Patents
Catalyst for production of olefin Download PDFInfo
- Publication number
- JP2021142504A JP2021142504A JP2020043800A JP2020043800A JP2021142504A JP 2021142504 A JP2021142504 A JP 2021142504A JP 2020043800 A JP2020043800 A JP 2020043800A JP 2020043800 A JP2020043800 A JP 2020043800A JP 2021142504 A JP2021142504 A JP 2021142504A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- olefin
- catalyst
- acid
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 82
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000010457 zeolite Substances 0.000 claims abstract description 117
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 114
- 239000011148 porous material Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 25
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 15
- 239000005977 Ethylene Substances 0.000 abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 14
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 68
- ZTNANFDSJRRZRJ-UHFFFAOYSA-N 2,4-dimethylquinoline Chemical compound C1=CC=CC2=NC(C)=CC(C)=C21 ZTNANFDSJRRZRJ-UHFFFAOYSA-N 0.000 description 44
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 239000007789 gas Substances 0.000 description 25
- 238000010521 absorption reaction Methods 0.000 description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 15
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- -1 ethylene, propylene Chemical group 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- QMMOXUPEWRXHJS-HYXAFXHYSA-N (z)-pent-2-ene Chemical compound CC\C=C/C QMMOXUPEWRXHJS-HYXAFXHYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
本発明は、外表面に特定量のブレンステッド酸点を有する１０員環細孔ゼオライトである新規なゼオライトを含むオレフィン製造用触媒に関するものであり、更に詳細には、特定の平均粒子径、外表面に微量のブレンステッド酸点を有する１０員環細孔ゼオライトを含んでなることにより、エチレン、プロピレン等に代表されるオレフィンを製造効率良く製造することができるオレフィン製造用触媒に関するものである。 The present invention relates to a catalyst for producing an olefin containing a novel zeolite which is a 10-membered ring-pore zeolite having a specific amount of blended acid points on the outer surface, and more specifically, a specific average particle size, outer surface. The present invention relates to a catalyst for producing an olefin, which can efficiently produce an olefin typified by ethylene, propylene or the like by containing a 10-membered ring-pore zeolite having a trace amount of blended acid spots on the surface.
エチレン、プロピレン等（以下、総称してオレフィンと表記する場合がある。）は、多くの場合、石油精製により得られた原料油（例えば、ナフサなど）を、熱分解反応装置にて分解し、得られた熱分解生成物からオレフィンを蒸留によって分離精製することで得られる。これらによるオレフィンの製造では、オレフィン以外の熱分解生成物として、芳香族炭化水素等の副生物が含まれる。そのため、オレフィン製造の際の生産量は他の副生物の生産量を見合って調整がなされ、おのずと生産量に制限を受けるものであった。 Ethylene, propylene, etc. (hereinafter, may be collectively referred to as olefins) are often obtained by decomposing raw material oil (for example, naphtha) obtained by petroleum refining with a pyrolysis reaction device. It is obtained by separating and purifying an olefin from the obtained pyrolysis product by distillation. In the production of olefins by these, by-products such as aromatic hydrocarbons are included as thermal decomposition products other than olefins. Therefore, the production amount at the time of olefin production was adjusted in proportion to the production amount of other by-products, and the production amount was naturally limited.
ゼオライトは、石油化学触媒、内燃機関等の排ガス浄化触媒、吸着剤等の用途として工業的に幅広く用いられる。そして、工業的使用の際には、耐久性、取り扱い性の向上を目的として、バインダー（例えば、シリカ、粘土鉱物など）を混合し、所定の形状に成形され、高温焼成により焼結を行うことでゼオライトとバインダーとを複合化したゼオライト成形体として用いられてきた。 Zeolites are widely used industrially as petrochemical catalysts, exhaust gas purification catalysts for internal combustion engines, adsorbents, and the like. Then, in industrial use, for the purpose of improving durability and handleability, a binder (for example, silica, clay mineral, etc.) is mixed, formed into a predetermined shape, and sintered by high-temperature firing. It has been used as a zeolite molded body in which a zeolite and a binder are combined.
また、中細孔ゼオライト、ゼオライト複合体は、芳香族化合物相当のサイズの細孔を利用した高選択性触媒として用いられている。そのようなゼオライトで代表的なＭＦＩ型ゼオライトを触媒として用いた例として、トルエンの不均化、キシレンの異性化などが提案されている。これらの反応は主に、ゼオライトのミクロ細孔の特徴を利用したものである。中細孔ゼオライトのミクロ細孔は、入口径がおよそ０．５ｎｍであり、この細孔径に近接した分子径を持つ分子の有効な反応場となると考えられている。 Further, medium-pore zeolite and zeolite complex are used as highly selective catalysts utilizing pores having a size equivalent to that of an aromatic compound. Disproportionation of toluene, isomerization of xylene, and the like have been proposed as examples of using MFI-type zeolite, which is a typical example of such zeolite, as a catalyst. These reactions mainly utilize the characteristics of the micropores of zeolite. The micropores of the medium-pore zeolite have an inlet diameter of about 0.5 nm, and are considered to be an effective reaction field for molecules having a molecular diameter close to the pore diameter.
そして、脂肪族または脂環式炭化水素原料を、中細孔径ゼオライトを主に含んだ触媒と約４００℃〜約８００℃程度の温度で接触させることにより、オレフィンを製造する方法（例えば、特許文献１，２参照。）が提案されている。これら製造法には、熱分解によるオレフィンの製造法と比較して、比較的低温での反応でオレフィンが製造できるという利点がある。その一方で、その生産効率、選択性という点でまだまだ課題を有するものであった。 Then, a method for producing an olefin by contacting an aliphatic or alicyclic hydrocarbon raw material with a catalyst mainly containing medium pore size zeolite at a temperature of about 400 ° C. to about 800 ° C. (for example, Patent Document). 1 and 2) have been proposed. Compared with the method for producing an olefin by thermal decomposition, these production methods have an advantage that the olefin can be produced by a reaction at a relatively low temperature. On the other hand, there are still problems in terms of production efficiency and selectivity.
また、ゼオライトを触媒とした反応においては、ゼオライト表面（外表面）の酸点における反応も知られており、この反応は一般的には非選択的反応と考えられている。これらの非選択的反応はしばしば、生成物収量の低下、生成物選択率の低下、コーク析出による触媒の失活、等を誘発し、望ましくないものと判断されている。 Further, in a zeolite-catalyzed reaction, a reaction at an acid point on the zeolite surface (outer surface) is also known, and this reaction is generally considered to be a non-selective reaction. These non-selective reactions often induce a decrease in product yield, a decrease in product selectivity, catalyst inactivation due to cork precipitation, etc., and are judged to be undesirable.
このような非選択的反応を抑制する方法として、外表面の酸点の一部を除去または不活性化したゼオライトが提案されている。例えば、嵩高い試剤で表面のアルミニウムを抽出する、または表面を被覆する方法が提案され、具体的には、ＭＦＩ構造を有するゼオライトをシリケートで被覆し、ｐ−キシレンを選択的に製造する方法（例えば、特許文献３参照。）、嵩高いジアルキルアミン試剤でゼオライトの表面酸点を被覆する方法（例えば、特許文献４，５参照。）、等が提案されている。 As a method for suppressing such a non-selective reaction, a zeolite in which a part of the acid spots on the outer surface is removed or inactivated has been proposed. For example, a method of extracting aluminum on the surface with a bulky reagent or coating the surface has been proposed. Specifically, a method of coating a zeolite having an MFI structure with a silicate to selectively produce p-xylene (a method of selectively producing p-xylene. For example, Patent Document 3), a method of coating the surface acid spot of zeolite with a bulky dialkylamine reagent (see, for example, Patent Documents 4 and 5), and the like have been proposed.
しかし、特許文献１，２に提案のオレフィンの製造方法においては、より長時間触媒性能を安定的に維持することが望まれ、コーキング析出による触媒失活を軽減することのできるオレフィンの製造方法が望まれている。また、特許文献３に提案の方法については、ゼオライトをシリケートで被覆する際に複数回の水熱合成が必要という課題を有する上に、ｐ−キシレンを選択的に製造するものであり、オレフィンの選択的、効率的な製造という点では何ら考慮のなされていないものである。さらに、特許文献４，５に提案された方法においては、アミンによる表面酸点の被覆を提案するものであり、高温下ではアミンの脱離もしくは分解が発生しやすいため、高温下での使用を前提とするオレフィン製造用触媒としての安定性に課題を有するものであった。 However, in the olefin production method proposed in Patent Documents 1 and 2, it is desired to maintain stable catalytic performance for a longer period of time, and an olefin production method capable of reducing catalyst deactivation due to caulking precipitation is available. It is desired. Further, the method proposed in Patent Document 3 has a problem that hydrothermal synthesis is required a plurality of times when the zeolite is coated with a silicate, and p-xylene is selectively produced. No consideration is given to selective and efficient manufacturing. Further, the methods proposed in Patent Documents 4 and 5 propose coating of surface acid spots with amines, and since amines are likely to be desorbed or decomposed at high temperatures, they should be used at high temperatures. There was a problem in stability as a prerequisite catalyst for olefin production.
そこで、本発明者らは、上記の課題を解決するため鋭意検討を行った結果、特定の平均粒子径、及び外表面ブレンステッド酸量を有する新規な１０員環細孔ゼオライトを用いたオレフィン製造用触媒が、非芳香族炭化水素を原料とした際にエチレン、プロピレン等に代表されるオレフィンを効率よく製造することが可能となることを見出し、本発明を完成するに至った。 Therefore, as a result of diligent studies to solve the above problems, the present inventors have produced olefins using a novel 10-membered ring-pore zeolite having a specific average particle size and an outer surface blended acid amount. We have found that when a catalyst for use is made from a non-aromatic hydrocarbon as a raw material, it is possible to efficiently produce an olefin typified by ethylene, propylene and the like, and have completed the present invention.
即ち、本発明は、下記（ｉ）〜（ｉｉｉ）の特性を満足するゼオライトを含むことを特徴とするオレフィン製造用触媒に関するものである。
（ｉ）平均粒子径が１００ｎｍ以下。
（ｉｉ）１０員環細孔ゼオライト。
（ｉｉｉ）外表面のブレンステッド酸量が０．０１〜１０．０μｍｏｌ／ｇ。
That is, the present invention relates to a catalyst for producing an olefin, which comprises a zeolite satisfying the following characteristics (i) to (iii).
(I) The average particle size is 100 nm or less.
(Ii) 10-membered ring pore zeolite.
(Iii) The amount of Bronsted acid on the outer surface is 0.01 to 10.0 μmol / g.
以下に、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の新規なオレフィン製造用触媒は、（ｉ）平均粒子径（以下、ＰＤと記す場合もある。）がＰＤ≦１００ｎｍ、（ｉｉ）１０員環細孔ゼオライト、（ｉｉｉ）外表面のブレンステッド酸点が０．０１〜１０．０μｍｏｌ／ｇ、のいずれの要件をも満足するゼオライトを含むものである。 The novel catalyst for producing an olefin of the present invention has (i) an average particle size (hereinafter, also referred to as PD) of PD ≦ 100 nm, (ii) 10-membered ring-pore zeolite, and (iii) bren on the outer surface. It contains a zeolite that satisfies any of the requirements of 0.01 to 10.0 μmol / g in terms of steady acidity.
本発明の新規なオレフィン製造用触媒は、（ｉ）ＰＤ≦１００ｎｍのものであり、特に熱安定性にも優れるオレフィン製造用触媒となることから、５ｎｍ≦ＰＤ≦１００ｎｍであることが望ましい。ここで、ＰＤが１００ｎｍを越えるものである場合、炭化水素のオレフィン転化反応用の触媒とした場合、その反応効率に劣るものとなる。 The novel catalyst for olefin production of the present invention has (i) PD ≦ 100 nm, and is particularly excellent in thermal stability. Therefore, it is desirable that the catalyst for olefin production is 5 nm ≦ PD ≦ 100 nm. Here, when PD exceeds 100 nm, the reaction efficiency is inferior when it is used as a catalyst for the olefin conversion reaction of hydrocarbons.
なお、本発明におけるＰＤは、その測定方法に制限はなく、例えば走査型電子顕微鏡（ＳＥＭ）や透過型電子顕微鏡（ＴＥＭ）の写真から任意の粒子を１００個以上選んで、その平均直径を求める方法、ゼオライトの外表面積から以下の式（１）を用いて算出する方法、等の任意の方法を挙げることができる。
ＰＤ＝６／Ｓ×（１／（２．２９×１０６）＋０．１８×１０−６） （１）
（ここで、Ｓは外表面積（ｍ２／ｇ）を示すものである。）
なお、式（１）における外表面積（Ｓ（ｍ２／ｇ））は、液体窒素温度における一般的な窒素吸着法を用い、ｔ−ｐｌｏｔ法から求めることができる。例えば、ｔを吸着量の厚みとするときに、ｔについて０．６〜１ｎｍの範囲の測定点を直線近似し、得られた回帰直線の傾きからゼオライトの外表面積を求めるものである。
The measurement method of PD in the present invention is not limited. For example, 100 or more arbitrary particles are selected from photographs of a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the average diameter thereof is obtained. Any method can be mentioned, such as a method, a method of calculating from the outer surface surface of zeolite using the following formula (1), and the like.
PD = 6 / S × (1 / (2.29 × 10 6 ) + 0.18 × 10-6 ) (1)
(Here, S indicates the outer surface area (m 2 / g).)
The outer surface area (S (m 2 / g)) in the formula (1) can be obtained from the t-prot method using a general nitrogen adsorption method at a liquid nitrogen temperature. For example, when t is the thickness of the adsorption amount, the measurement points in the range of 0.6 to 1 nm are linearly approximated with respect to t, and the outer surface surface of the zeolite is obtained from the slope of the obtained regression line.
そして、中でも簡便な測定が可能であることから、ＳＥＭ又はＴＥＭによる方法が好ましい。 And, above all, the method by SEM or TEM is preferable because simple measurement is possible.
本発明の新規なオレフィン製造用触媒に含まれるゼオライトは、（ｉｉ）１０員環細孔ゼオライトであり、骨格構造が１０員環構造を有し、細孔を有するゼオライトであれば如何なるものでも良く、該１０員環細孔構造を有するゼオライトとしては、具体的にはＡＥＬ、ＥＵＯ、ＦＥＲ、ＨＥＵ、ＭＥＵ、ＭＥＬ、ＭＦＩ、ＮＥＳ型等のゼオライトを挙げることができ、特にオレフィン製造用触媒として期待されるものとなることからＭＦＩ型またはＭＥＬ型であることが好ましい。そして、例えばＭＦＩ型としては、国際ゼオライト学会で定義される構造コードＭＦＩに属するアルミノシリケート化合物を挙げることができる。 The zeolite contained in the novel catalyst for producing an olefin of the present invention is (ii) a 10-membered ring-pore zeolite, and any zeolite having a skeleton structure having a 10-membered ring structure and pores may be used. Specific examples of the zeolite having the 10-membered ring pore structure include zeolites of AEL, EUO, FER, HEU, MEU, MEL, MFI, NES type and the like, and are particularly expected as catalysts for olefin production. It is preferably MFI type or MEL type because it will be used. And, for example, as the MFI type, an aluminosilicate compound belonging to the structure code MFI defined by the International Zeolite Society can be mentioned.
本発明の新規なオレフィン製造用触媒に含まれるゼオライトは、（ｉｉｉ）外表面のブレンステッド酸量（以下、Ｂ酸量と記す場合がある。）が０．０１〜１０．０μｍｏｌ／ｇであり、特定の範囲内の外表面Ｂ酸量を有することでオレフィン製造用触媒とした際に特に優れた触媒性能を示すものとなる。ここで、外表面Ｂ酸量が０．０１μｍｏｌ／ｇ未満である場合、オレフィン製造用触媒とした際の生産効率、選択性の触媒性能に劣るものとなる。一方、１０.０μｍｏｌ／ｇよりも大きい場合、触媒表面における副反応、コーキングが生じやすく、触媒性能が悪化したものとなる。そして、本発明の新規なオレフィン製造用触媒においては、オレフィンの製造効率、選択性に優れる触媒となることから、Ｂ酸量が０．０１〜１．０ｍｍｏｌ／ｇであるものが好ましい。 The zeolite contained in the novel catalyst for producing an olefin of the present invention has a (iii) outer surface Bronsted acid amount (hereinafter, may be referred to as B acid amount) of 0.01 to 10.0 μmol / g. By having the amount of B acid on the outer surface within a specific range, it exhibits particularly excellent catalytic performance when used as a catalyst for olefin production. Here, when the amount of B acid on the outer surface is less than 0.01 μmol / g, the production efficiency and selectivity of the catalyst performance when used as a catalyst for olefin production are inferior. On the other hand, if it is larger than 10.0 μmol / g, side reactions and caulking on the catalyst surface are likely to occur, and the catalyst performance is deteriorated. The novel catalyst for olefin production of the present invention preferably has a B acid content of 0.01 to 1.0 mmol / g because it is a catalyst having excellent olefin production efficiency and selectivity.
ここで、ゼオライトのＢ酸量とは、ゼオライトに存在する酸性ＯＨ基を示すものである。通常、ゼオライトは、その外表面及び（ミクロ）細孔内にＢ酸点を有するものである。そして、外表面にＢ酸点をわずかしか有さないものとは、そのＢ酸点はそのほとんどが（ミクロ）細孔内に存在することを意味するものである。 Here, the amount of B acid in the zeolite indicates an acidic OH group present in the zeolite. Zeolites usually have B acid points on their outer surface and in (micro) pores. And, having only a few B acid points on the outer surface means that most of the B acid points are present in the (micro) pores.
本発明の新規なオレフィン製造用触媒を構成するゼオライトにおける外表面のＢ酸量の確認方法としては、その確認を行うことが可能であれば如何なる方法をも用いることが可能であり、例えばＢ酸点に対する吸着性を有する２，４−ジメチルキノリンの吸着により確認することが可能である。２，４−ジメチルキノリンは、ゼオライト（細孔内を含む）に存在するＢ酸点（酸性ＯＨ基）との吸着性質を有している。しかし、ＭＦＩ型のようにゼオライトの（ミクロ）細孔径が２，４−ジメチルキノリン分子より小さい場合、（ミクロ）細孔内に侵入することができず、（ミクロ）細孔内のＢ酸点と吸着することは出来ない。つまり、ゼオライトの外表面のＢ酸点のみと吸着するものとなる。よって、ＭＦＩ型ゼオライトの外表面のＢ酸点への２，４−ジメチルキノリンの吸着量を求めることで、外表面のＢ酸量を定量することができる。 As a method for confirming the amount of B acid on the outer surface of the zeolite constituting the novel catalyst for producing an olefin of the present invention, any method can be used as long as the confirmation can be performed, for example, B acid. It can be confirmed by adsorption of 2,4-dimethylquinoline, which has adsorptivity to points. 2,4-Dimethylquinoline has an adsorptive property with the B acid point (acidic OH group) present in zeolite (including in the pores). However, when the (micro) pore diameter of the zeolite is smaller than the 2,4-dimethylquinoline molecule as in the MFI type, it cannot penetrate into the (micro) pores and the B acid point in the (micro) pores. Cannot be adsorbed. That is, it adsorbs only the B acid point on the outer surface of the zeolite. Therefore, the amount of B acid on the outer surface can be quantified by determining the amount of 2,4-dimethylquinoline adsorbed on the B acid point on the outer surface of the MFI-type zeolite.
より具体的な方法としては、ゼオライトの前処理として４００℃で２時間の脱気・脱水処理を行ったゼオライトの１５０℃における赤外吸収スペクトル測定を行う。そして、脱気・脱水処理を行ったゼオライトに２，４−ジメチルキノリンガスを導入して３０分間吸着させ、１５０℃での排気により余剰２，４−ジメチルキノリンを除き、２，４−ジメチルキノリン吸着ゼオライトの調製を行い１５０℃における赤外吸収スペクトル測定を行う。つまり、２，４−ジメチルキノリン吸着前後の赤外吸収の差スペクトルにおいて、３６００〜３６５０ｃｍ−１の範囲で赤外線吸収の差（減少）を定量することで、外表面のＢ酸量を得ることができる。なお、２，４−ジメチルキノリンはゼオライト表面のシラノール部位にも吸着するが、シラノールのＯ−Ｈ伸縮振動に由来する吸収は、３７００〜３８００ｃｍ−１に観測される。一方、ゼオライトの外表面のＢ酸点のＯ−Ｈ伸縮振動に由来する吸収は、３６００〜３６５０ｃｍ−１に観測され、２，４−ジメチルキノリンを吸着してＢ酸点のＯ−Ｈ伸縮振動に由来する吸収３６００〜３６５０ｃｍ−１の範囲に赤外吸収スペクトルの減少がみられることは、２，４−ジメチルキノリンがゼオライトの外表面のＢ酸点に吸着したことを示す。 As a more specific method, infrared absorption spectrum measurement at 150 ° C. of zeolite which has been degassed and dehydrated at 400 ° C. for 2 hours as a pretreatment of zeolite is performed. Then, 2,4-dimethylquinoline gas is introduced into the degassed / dehydrated zeolite and adsorbed for 30 minutes, and excess 2,4-dimethylquinoline is removed by exhaust at 150 ° C. to remove 2,4-dimethylquinoline. The adsorbed zeolite is prepared and the infrared absorption spectrum is measured at 150 ° C. That is, the amount of B acid on the outer surface can be obtained by quantifying the difference (decrease) in infrared absorption in the range of 3600 to 3650 cm -1 in the infrared absorption difference spectrum before and after adsorption of 2,4-dimethylquinoline. can. Although 2,4-dimethylquinoline is also adsorbed on the silanol site on the zeolite surface, absorption derived from the oh expansion and contraction vibration of silanol is observed at 3700 to 3800 cm -1. On the other hand, the absorption derived from the OH expansion and contraction vibration of the B acid point on the outer surface of the zeolite was observed at 3600 to 3650 cm -1 , adsorbing 2,4-dimethylquinoline and the OH expansion and contraction vibration of the B acid point. The decrease in the infrared absorption spectrum in the range of absorption 3600 to 3650 cm -1 derived from the above indicates that 2,4-dimethylquinoline was adsorbed on the B acid point on the outer surface of the zeolite.
また、本発明の新規なオレフィン製造用触媒を構成するゼオライトのＢ酸量（外表面及び（ミクロ）細孔内に存在するＢ酸点）の測定方法としては、その測定を行うことが可能であれば如何なる方法をも用いることが可能であり、例えばＢ酸点に対する吸着性を有するピリジンの吸着により確認することが可能である。ピリジンは、ゼオライト（細孔内を含む）に存在するＢ酸点（酸性ＯＨ基）との吸着性質を有しており、ゼオライトの（ミクロ）細孔径がピリジンより大きい場合、（ミクロ）細孔内にも侵入することができ、外表面及び（ミクロ）細孔内のＢ酸点とも吸着出来る。よって、ＭＦＩ型ゼオライトの細孔内に存在するＢ酸点も含め、ゼオライトに存在するＢ酸量を定量することができる。 Further, as a method for measuring the amount of B acid (B acid point existing on the outer surface and in the (micro) pores) of the zeolite constituting the novel catalyst for olefin production of the present invention, it is possible to measure the amount. Any method can be used if there is any, and it can be confirmed by, for example, adsorption of pyridine having an adsorptivity to the B acid point. Pyridine has an adsorption property with the B acid point (acidic OH group) existing in the zeolite (including in the pores), and when the (micro) pore diameter of the zeolite is larger than the pyridine, the (micro) pores It can also penetrate inside and can adsorb both the outer surface and the B acid points in the (micro) pores. Therefore, the amount of B acid present in the zeolite can be quantified, including the B acid point existing in the pores of the MFI type zeolite.
より具体的な方法としては、ゼオライトの前処理として４００℃で２時間の脱気・脱水処理を行ったゼオライトの１５０℃における赤外吸収スペクトル測定を行う。そして、脱気・脱水処理を行ったゼオライトにピリジンガスを導入して１０分間吸着させ、１５０℃での排気により余剰ピリジンを除き、ピリジン吸着ゼオライトの調製を行い１５０℃における赤外吸収スペクトル測定を行う。つまり、ピリジン吸着前後の赤外吸収の差スペクトルにおいて、１５１５〜１５６５ｃｍ−１の範囲で赤外線吸収の差（減少）を定量することで、細孔内も含めたＢ酸量を得ることができる。 As a more specific method, infrared absorption spectrum measurement at 150 ° C. of zeolite which has been degassed and dehydrated at 400 ° C. for 2 hours as a pretreatment of zeolite is performed. Then, pyridine gas is introduced into the degassed / dehydrated zeolite and adsorbed for 10 minutes, excess pyridine is removed by exhaust at 150 ° C., pyridine-adsorbed zeolite is prepared, and infrared absorption spectrum measurement at 150 ° C. is performed. conduct. That is, in the infrared absorption difference spectrum before and after pyridine adsorption, the amount of B acid including the inside of the pores can be obtained by quantifying the difference (decrease) in infrared absorption in the range of 1515 to 1565 cm -1.
そして、本発明における新規なオレフィン製造用触媒は、オレフィンの製造効率、選択性に優れる触媒となることから、外表面に僅かなＢ酸点を有し、Ｂ酸点のほとんどが（ミクロ）細孔内に存在するゼオライトであることが好ましく、その外表面に存在するＢ酸点は、全Ｂ酸点の１〜１０％のものであることが好ましい。なお、外表面のＢ酸点の割合は、上述したゼオライトの外表面のＢ酸量を、ゼオライト（細孔内を含む）に存在するＢ酸量の割合として求められる。 Since the novel catalyst for olefin production in the present invention is a catalyst having excellent olefin production efficiency and selectivity, it has a slight B acid point on the outer surface and most of the B acid points are (micro) fine. The zeolite is preferably present in the pores, and the B acid point present on the outer surface thereof is preferably 1 to 10% of the total B acid point. The ratio of the B acid point on the outer surface is determined by using the amount of B acid on the outer surface of the above-mentioned zeolite as the ratio of the amount of B acid present in the zeolite (including the inside of the pores).
本発明の新規なオレフィン製造用触媒に含まれるゼオライトの製造方法としては、上記（ｉ）〜（ｉｉｉ）に記載の特性を満足するゼオライトの製造が可能であれば如何なる方法をも用いることは可能である。そして、外表面に特定量の微量のＢ酸点を有するゼオライト、つまり、ゼオライト表面のＢ酸点の選択的な除去方法としては、（ｉ）〜（ｉｉ）の特性を満足するゼオライトを製造する際の焼成処理（熱処理）の一部又は全部を水熱（スチーム）処理とし、該焼成処理の前後にイオン交換処理を付加する方法を挙げることができる。 As a method for producing a zeolite contained in the novel catalyst for producing an olefin of the present invention, any method can be used as long as it is possible to produce a zeolite satisfying the characteristics described in (i) to (iii) above. Is. Then, a zeolite having a specific amount of a small amount of B acid point on the outer surface, that is, a zeolite satisfying the characteristics of (i) to (ii) is produced as a method for selectively removing the B acid point on the zeolite surface. Examples thereof include a method in which a part or all of the firing treatment (heat treatment) is a hydrothermal (steam) treatment, and an ion exchange treatment is added before and after the firing treatment.
そして、（ｉ）〜（ｉｉ）の特性を満足するゼオライトの合成方法としては、一般的な公知の方法を用いることにより、ＰＤ≦１００ｎｍ、１０員環細孔の骨格構造を有するゼオライトとすることができる。具体的にはカチオンとしてアルカリ金属及び／又はアルカリ土類金属を含む化合物、有機構造指向剤とアルミノシリケートゲルとを混合し、得られた結晶物を焼成することにより製造することができる。その際のアルカリ金属、アルカリ土類金属を含む化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム等を挙げることでき、中でも水酸化ナトリウムが好ましい。有機構造指向剤としては、例えばテトラプロピルアンモニウム水酸化物、テトラブチルアンモニウム水酸化物、テトラエチルアンモニウム水酸化物等を挙げることができる。また、アルミノシリケートゲルとしては、例えば不定形アルミノシリケートゲル等を挙げることができる。 Then, as a method for synthesizing the zeolite satisfying the characteristics (i) to (ii), a generally known method is used to obtain a zeolite having a skeleton structure of PD ≦ 100 nm and 10-membered ring pores. Can be done. Specifically, it can be produced by mixing a compound containing an alkali metal and / or an alkaline earth metal as a cation, an organic structure-directing agent and an aluminosilicate gel, and calcining the obtained crystal product. Examples of the compound containing an alkali metal and an alkaline earth metal at that time include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like, and sodium hydroxide is particularly preferable. Examples of the organic structure-directing agent include tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and tetraethylammonium hydroxide. Moreover, as an aluminosilicate gel, for example, an amorphous aluminosilicate gel and the like can be mentioned.
さらに、(ｉ)〜（ｉｉｉ）の特性を満足するゼオライトとする際には、上記により得られた結晶物を焼成する前にイオン交換を行い、焼成の際の一部又は全部を水熱処理とし、その後、更にイオン交換を行う方法、上記により得られた結晶物を焼成した後にイオン交換を行いプロトン型ゼオライトとし、その後に水熱雰囲気下で焼成を行う方法、等により製造することが可能となる。 Further, in order to obtain zeolite satisfying the characteristics of (i) to (iii), ion exchange is performed before firing the crystals obtained as described above, and a part or all of the firing is subjected to hydrothermal treatment. After that, it can be produced by a method of further ion exchange, a method of calcining the crystal obtained as described above, then ion exchange to obtain a proton-type zeolite, and then calcining in a hydrothermal atmosphere. Become.
その際の焼成条件としては、処理温度としては３００〜９００℃が好ましく、特に４００〜７００℃であることが好ましい。処理時間は、工業的には好ましくは５分〜２５時間である。雰囲気としては、例えば窒素、空気、酸素、アルゴン、その他不活性ガスのうち一つもしくは二つ以上の組み合わせのガスをも挙げることができる。そして、該焼成工程の一部又は全部を水熱（スチーム）処理を行うことにより、Ｂ酸点のアルミニウムが脱離される。水熱処理の処理温度としては４００〜７５０℃が好ましく、特に５００〜６５０℃が好ましい。また、水蒸気濃度は５〜１００％が好ましく、特に１０〜８０％であることが好ましい。 As the firing conditions at that time, the treatment temperature is preferably 300 to 900 ° C, particularly preferably 400 to 700 ° C. The treatment time is industrially preferably 5 minutes to 25 hours. The atmosphere may also include, for example, nitrogen, air, oxygen, argon, or any other combination of one or more of the inert gases. Then, by performing a hydrothermal (steam) treatment on a part or all of the firing step, the aluminum at the B acid point is desorbed. The treatment temperature of the hydrothermal treatment is preferably 400 to 750 ° C, particularly preferably 500 to 650 ° C. The water vapor concentration is preferably 5 to 100%, particularly preferably 10 to 80%.
また、イオン交換は、焼成工程の前後に行うものであり、複数回のイオン交換に分割して行ってもよい。また、イオン交換は、塩化アンモニウム、塩酸、硝酸等の酸を用いたイオン交換が挙げられ、塩酸、硝酸によるものが好ましい。また、イオン交換は水での洗浄で代用することもできる。 Further, the ion exchange is performed before and after the firing step, and may be divided into a plurality of times of ion exchange. Further, the ion exchange includes ion exchange using an acid such as ammonium chloride, hydrochloric acid and nitric acid, and those using hydrochloric acid and nitric acid are preferable. In addition, ion exchange can be replaced by washing with water.
本発明の新規なオレフィン製造用触媒は、オレフィンの製造時、例えば脂肪族炭化水素からオレフィンを製造する際の生産性、選択性に優れる触媒としての作用を有し、該ゼオライトを含むオレフィン製造用触媒として優れた性能を発揮するものとなる。 The novel catalyst for producing an olefin of the present invention has an action as a catalyst having excellent productivity and selectivity during the production of an olefin, for example, when producing an olefin from an aliphatic hydrocarbon, and is used for producing an olefin containing the zeolite. It exhibits excellent performance as a catalyst.
そして、オレフィン製造用触媒とする際には、その取り扱い性、触媒性能に優れる触媒となることから成形体としての形状付与を行うことが好ましい。形状付与を行う際には如何なる方法により成形してもよく、例えば、ゼオライト粉末をそのまま圧縮成形等により所定形状に成形し成形体とする方法、所定割合のバインダーをゼオライトに混合し、場合によっては更なる添加剤等を所定割合で混合し、その混合物を所定形状に成形し成形体とする方法、さらには焼結を付随し成形体とする方法などを挙げることが出来る。そして、本発明の新規なオレフィン製造用触媒は、成形体としての成形性に優れることはもとより、高い圧壊強度を示しその取り扱い性、触媒寿命にも優れるものとなることから、該ゼオライト及びバインダーとからなる成形体であることが好ましく、より良好な触媒性能を示すものとなることから該ゼオライト及びシリカとからなる成形体であることがより好ましい。その際のシリカとしては、シリカと称される範疇に属するものであれば如何なるものであってもよく、特定の結晶構造を有するもの、また、非結晶性のものであってもよい。さらに、シリカの粒子径や凝集径等に関しても如何なる制限もない。また、該ゼオライトとシリカの配合割合は任意であり、中でも特に優れた触媒性能、取り扱い性、触媒寿命を示すオレフィン製造用触媒となることから、該ゼオライト：シリカ＝５０〜９５：５０〜５（重量割合）であることが好ましく、特に６０〜９０：４０〜１０であることが好ましい。 When the catalyst for olefin production is used, it is preferable to give the shape as a molded product because the catalyst is excellent in handleability and catalytic performance. When the shape is imparted, it may be molded by any method. For example, a method in which zeolite powder is directly molded into a predetermined shape by compression molding or the like to form a molded product, a predetermined ratio of binder is mixed with zeolite, and in some cases, the zeolite is mixed. Examples thereof include a method in which further additives and the like are mixed at a predetermined ratio and the mixture is molded into a predetermined shape to form a molded product, and a method in which sintering is accompanied to form a molded product. The novel catalyst for olefin production of the present invention is not only excellent in moldability as a molded product, but also exhibits high crushing strength and is excellent in handleability and catalyst life. Therefore, the zeolite and the binder are used together. A molded product made of the same material is preferable, and a molded product made of the zeolite and silica is more preferable because it exhibits better catalytic performance. The silica at that time may be any silica as long as it belongs to the category called silica, and may have a specific crystal structure or may be amorphous. Furthermore, there are no restrictions on the particle size, aggregation diameter, etc. of silica. Further, the mixing ratio of the zeolite and silica is arbitrary, and the zeolite: silica = 50 to 95: 50 to 5 ( Weight ratio), and particularly preferably 60 to 90:40 to 10.
該オレフィン製造用触媒は、その形状が如何なるものであってもよく、例えば円柱形状、円筒形状、三角柱形状，四角柱形状，五角柱形状，六角柱形状等の多角柱形状、中空多角柱形状、球形状等を挙げることができ、中でも、連続生産性に優れ、かつ圧壊強度の高い触媒となることから円柱形状、円筒形状であることが好ましい。また、その直径，幅，長さ等のサイズ、嵩密度，真密度等の密度としては充填効率等を考慮し任意に選択可能であり、特にオレフィンを有効に製造することが可能となる触媒となることから、径１〜１０ｍｍの円柱形状又は厚さ０．５〜５．０ｍｍの円筒形状を有するものであることが好ましい。さらに、該オレフィン製造用触媒は、更に担持、イオン交換、物理混合、蒸着等の処理により、任意の金属種を導入したものであっても良い。 The shape of the olefin production catalyst may be any shape, for example, a polygonal prism shape such as a cylindrical shape, a cylindrical shape, a triangular prism shape, a square prism shape, a pentagonal prism shape, a hexagonal prism shape, or a hollow polygonal prism shape. A spherical shape and the like can be mentioned. Among them, a cylindrical shape and a cylindrical shape are preferable because the catalyst has excellent continuous productivity and high crushing strength. Further, the size such as diameter, width and length, bulk density, density such as true density can be arbitrarily selected in consideration of filling efficiency, etc., and in particular, a catalyst capable of effectively producing an olefin. Therefore, it is preferable that the cylinder has a cylindrical shape having a diameter of 1 to 10 mm or a cylindrical shape having a thickness of 0.5 to 5.0 mm. Further, the catalyst for producing an olefin may be one in which any metal species is introduced by further treatments such as loading, ion exchange, physical mixing, and vapor deposition.
該オレフィン製造用触媒は、例えば炭素数４〜６の非芳香族炭化水素を原料として接触することにより、特に効率よくオレフィンを製造することを可能とするものである。より高効率にオレフィンを製造するために、脂肪族または脂環式原料は好ましくは２０質量パーセント以上、より好ましくは５０質量パーセント以上、さらに好ましくは７０質量パーセントの炭素数４〜６の非芳香族炭化水素を含むことが好ましい。その際の炭素数４〜６の非芳香族炭化水素としてはその範疇に属するものであれば如何なるものを挙げることができ、例えば飽和脂肪族炭化水素、不飽和脂肪族炭化水素、脂環式炭化水素、それらの混合物等を挙げることができ、より具体的には、ｎ−ブタン、イソブタン、１−ブテン、２−ブテン、イソブテン、ブタジエン、シクロブテン、シクロブタン、ｎ−ペンタン、１−ペンタン、２−ペンタン、１−ペンテン、２−ペンテン、３−ペンテン、ｎ−ヘキサン、１−ヘキサン、２−ヘキサン、１−ヘキセン、２−ヘキセン、３−ヘキセン、ヘキサジエン、シクロヘキサン及びそれらの混合物等を挙げることができる。また、場合によっては原料中に含まれる炭素数４〜６の非芳香族炭化水素以外の原料成分としては、炭素成分を含んだ化合物であれば如何なるものであってよく、例えば、炭素数１〜３の炭化水素、炭素数７〜１５の炭化水素、含酸素化合物（アルコール、エーテル、カルボン酸、ケトン等）、および含窒素化合物（アミン等）が挙げられ、オレフィンを効率よく製造する観点から、炭素数１〜３の炭化水素または炭素数７〜１０の炭化水素であることが好ましい。また、得られるオレフィンとしては、オレフィンの範疇に属するものであればよく、例えばエチレン、プロピレン、ブテン、ヘキセン等を挙げることができ、特にその製造効率に優れることからエチレン及び／又はプロピレンであることが好ましく、さらにエチレン及びプロピレンを同時に効率よく製造するものであることが好ましい。 The catalyst for producing an olefin can produce an olefin particularly efficiently by contacting it with, for example, a non-aromatic hydrocarbon having 4 to 6 carbon atoms as a raw material. In order to produce olefins with higher efficiency, the aliphatic or alicyclic raw material is preferably 20% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass of non-aromatic compounds having 4 to 6 carbon atoms. It preferably contains hydrocarbons. At that time, any non-aromatic hydrocarbon having 4 to 6 carbon atoms can be mentioned as long as it belongs to the category, for example, saturated aliphatic hydrocarbon, unsaturated aliphatic hydrocarbon, alicyclic hydrocarbon. Hydrogen, mixtures thereof and the like can be mentioned, and more specifically, n-butane, isobutane, 1-butene, 2-butene, isobutene, butadiene, cyclobutane, cyclobutane, n-pentane, 1-pentane, 2- Examples include pentane, 1-pentene, 2-pentene, 3-pentene, n-hexane, 1-hexane, 2-hexane, 1-hexene, 2-hexene, 3-hexene, hexadiene, cyclohexane and mixtures thereof. can. In some cases, the raw material component other than the non-aromatic hydrocarbon having 4 to 6 carbon atoms contained in the raw material may be any compound containing a carbon component, for example, 1 to 1 carbon number. Examples thereof include hydrocarbons of 3, hydrocarbons having 7 to 15 carbon atoms, oxygen-containing compounds (alcohol, ether, carboxylic acid, ketone, etc.), and nitrogen-containing compounds (amine, etc.), from the viewpoint of efficiently producing olefins. It is preferably a hydrocarbon having 1 to 3 carbon atoms or a hydrocarbon having 7 to 10 carbon atoms. Further, the obtained olefin may be any one belonging to the category of olefin, and examples thereof include ethylene, propylene, butene, hexene and the like, and ethylene and / or propylene because of their excellent production efficiency. It is preferable that ethylene and propylene are efficiently produced at the same time.
そして、該オレフィン製造用触媒を用いたオレフィンの製造において、その反応温度は特に制限されるものではなく、オレフィンの製造が可能であればよく、中でも、副生成物の生成を抑制し、必要以上の耐熱反応装置を要しないオレフィンの効率的な製造方法となることから４００〜８００℃の範囲が望ましく、特に４００〜５５０℃の範囲が望ましい。また、反応圧力にも制限はなく、例えば０．０５ＭＰａ〜５ＭＰａ程度の圧力範囲で運転が可能である。そして、該オレフィン製造用触媒に対する反応原料の供給は、該触媒体積に対し原料ガスの体積の比として特に制限されるものではなく、例えば１ｈ−１〜５００００ｈ−１程度の空間速度を挙げることができる。炭化水素を原料ガスとして供給する際には、特定の炭化水素の単一ガス、混合ガス、およびこれらを窒素等の不活性ガス、水素、一酸化炭素、二酸化炭素から選ばれる単一または混合ガスにより希釈したものとして用いることもできる。 The reaction temperature of the olefin using the olefin production catalyst is not particularly limited as long as the olefin can be produced, and above all, the production of by-products is suppressed and more than necessary. The temperature range of 400 to 800 ° C. is desirable, and the range of 400 to 550 ° C. is particularly desirable, because it is an efficient method for producing an olefin that does not require a heat-resistant reaction device. Further, the reaction pressure is not limited, and the operation can be performed in a pressure range of, for example, about 0.05 MPa to 5 MPa. The supply of the reaction raw material to the catalyst for producing the olefin is not particularly limited as the ratio of the volume of the raw material gas to the catalyst volume, and for example, a space velocity of about 1h -1 to 50,000h -1 can be mentioned. can. When supplying a hydrocarbon as a raw material gas, a single gas of a specific hydrocarbon, a mixed gas, and a single or mixed gas selected from an inert gas such as nitrogen, hydrogen, carbon monoxide, and carbon dioxide. It can also be used as diluted with.
オレフィンを製造する際の反応形式としては制限なく、例えば固定床、輸送床、流動床、移動床、多管式反応器のみならず連続流式および間欠流式並びにスイング式反応器、等を用いることができる。 The reaction type for producing the olefin is not limited, and for example, a fixed bed, a transport bed, a fluidized bed, a moving bed, a multi-tube reactor, a continuous flow type, an intermittent flow type, a swing type reactor, and the like are used. be able to.
本発明の特定の平均粒子径、外表面に微量のＢ酸量を有する１０員環細孔ゼオライトを含む新規なオレフィン製造用触媒は、優れた生産効率、選択性でオレフィンを製造することが可能となり、その工業的な有用性が期待されるものである。 A novel catalyst for producing an olefin containing a 10-membered ring-pore zeolite having a specific average particle size and a trace amount of B acid on the outer surface of the present invention can produce an olefin with excellent production efficiency and selectivity. Therefore, its industrial usefulness is expected.
以下に、本発明を実施例により具体的に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
なお、実施例および比較例に用いた１０員環細孔ゼオライトは、特許６０７０３３６号に基づき調製を行った。また、ゼオライト及びオレフィン製造用触媒は、以下の方法により測定した。 The 10-membered ring-pore zeolite used in Examples and Comparative Examples was prepared based on Japanese Patent No. 60070336. The catalyst for producing zeolite and olefin was measured by the following method.
〜平均粒子径の測定〜
平均粒子径は、透過型電子顕微鏡（以下、ＴＥＭと記す場合がある。）及び走査型電子顕微鏡（以下、ＳＥＭと記す場合がある。）により測定を行った。ＴＥＭは、透過型電子顕微鏡（日本電子株式会社製、（商品名）ＪＥＭ−２１００、加速電圧２００ｋＶ、観察倍率３万倍）を用い、乳鉢で軽く粉砕した試料をアセトン中に超音波分散し、プラスチック支持膜上に滴下し自然乾燥させたものを検鏡用試料とし、写真を撮影した。写真中の各一次粒子について、最長径とその中点において直角方向の径の平均を測定し、合計３００個の粒子の平均を平均粒子径とした。
ＳＥＭは、走査型電子顕微鏡（株式会社キーエンス製、（商品名）ＶＥ−９８００、加速電圧２０ｋＶ、観察倍率２０００倍）を用い、乳鉢で軽く粉砕した試料を試料台に乗せ、金蒸着させたものを検鏡用試料とし、写真を撮影した。写真中の粒子一辺の長さを１５０個計測し、その平均値を平均結晶径とした。
~ Measurement of average particle size ~
The average particle size was measured with a transmission electron microscope (hereinafter, may be referred to as TEM) and a scanning electron microscope (hereinafter, may be referred to as SEM). For TEM, a transmission electron microscope (manufactured by JEOL Ltd., (trade name) JEM-2100, acceleration voltage 200 kV, observation magnification 30,000 times) was used, and a sample lightly crushed in a dairy pot was ultrasonically dispersed in acetone. A sample was taken as a sample for a microscope, which was dropped on a plastic support film and naturally dried. For each primary particle in the photograph, the average of the diameters in the direction perpendicular to the longest diameter and its midpoint was measured, and the average of a total of 300 particles was taken as the average particle diameter.
The SEM is a scanning electron microscope (manufactured by KEYENCE CORPORATION, (trade name) VE-9800, acceleration voltage 20 kV, observation magnification 2000 times), and a sample lightly crushed in a dairy pot is placed on a sample table and vapor-deposited with gold. Was used as a sample for a microscope, and a photograph was taken. The length of one side of 150 particles in the photograph was measured, and the average value was taken as the average crystal diameter.
〜２，４−ジメチルキノリン吸着赤外吸収分光測定〜
２，４−ジメチルキノリン吸着赤外吸収分光測定は、特願２０１９-１２８０４７号公報にと同様の方法により測定した。
~ 2,4-Dimethylquinoline adsorption infrared absorption spectroscopy ~
The 2,4-dimethylquinoline adsorption infrared absorption spectroscopy was measured by the same method as in Japanese Patent Application No. 2019-128047.
赤外吸収分光の測定は、ＦＴ−ＩＲ測定装置（（商品名）ＦＴ／ＩＲ−６７００，日本分光株式会社製）を用いて、透過法により測定を行った。ＭＣＴ検出器を使用し、積算回数２５６回にてスペクトルを得た。試料は直径１３ｍｍのディスクに成形した後、石英製真空脱気セル内のディスクホルダーに設置することで、赤外光路上に垂直に設置した。試料の前処理として、真空排気下、１０℃／分で４００℃まで昇温し、２時間保持した。１５０℃に冷却後、２，４−ジメチルキノリン吸着前の赤外吸収スペクトルを測定した。２，４−ジメチルキノリンガスを導入し、３０分間吸着させ、１５０℃で１時間真空排気した後、２，４−ジメチルキノリン吸着後の赤外吸収スペクトルを測定した。２，４−ジメチルキノリン吸着後の赤外吸収スペクトルと吸着前のスペクトルの差をとり、吸着による赤外吸収の変化を測定した。この差スペクトルのうち３６００ｃｍ−１付近のピークがブレンステッド酸に吸着した２，４−ジメチルキノリンの吸収スペクトルのピークであり、この面積強度を求めた後、ランベルト−ベア（Ｌａｍｂｅｒ−ｂｅｒｒ）の法則により下記の式（２）よりＢ酸量を求めた。
Ｂ酸量（μｍｏｌ／ｍｇ）＝Ａ・Ｓ／（Ｗ・ε） 式（２）
（ここで、Ａ；対象のピークのピーク面積強度（ｃｍ−１）、Ｓ；サンプル断面積（ｃｍ２）、Ｗ；サンプル重量（ｍｇ）、ε；積分吸光係数であり、３．７ｃｍ・μｍｏｌ−１、のそれぞれを示す。）
〜ピリジン吸着赤外吸収分光測定〜
上記の２，４−ジメチルキノリン吸着赤外吸収分光測定において、ピリジンガスを導入し、１０分間吸着させた点のみを変更し、同一の装置、同一の手法で測定した。
The infrared absorption spectroscopy was measured by a transmission method using an FT-IR measuring device ((trade name) FT / IR-6700, manufactured by Nippon Spectroscopy Co., Ltd.). A spectrum was obtained after 256 integrations using an MCT detector. The sample was formed into a disc having a diameter of 13 mm and then placed in a disc holder in a quartz vacuum degassing cell, so that the sample was placed vertically on the infrared optical path. As a pretreatment of the sample, the temperature was raised to 400 ° C. at 10 ° C./min under vacuum exhaust and held for 2 hours. After cooling to 150 ° C., the infrared absorption spectrum before adsorption of 2,4-dimethylquinoline was measured. 2,4-Dimethylquinoline gas was introduced, adsorbed for 30 minutes, evacuated at 150 ° C. for 1 hour, and then the infrared absorption spectrum after adsorbing 2,4-dimethylquinoline was measured. The difference between the infrared absorption spectrum after adsorption of 2,4-dimethylquinoline and the spectrum before adsorption was taken, and the change in infrared absorption due to adsorption was measured. Of this difference spectrum, the peak near 3600 cm -1 is the peak of the absorption spectrum of 2,4-dimethylquinoline adsorbed on Bronsted acid, and after determining this area intensity, Lamber-berr's law The amount of B acid was calculated from the following formula (2).
Amount of B acid (μmol / mg) = A · S / (W · ε) Equation (2)
(Here, A; peak area intensity of the target peak (cm -1 ), S; sample cross-sectional area (cm 2 ), W; sample weight (mg), ε; integral extinction coefficient, 3.7 cm · μmol. -1 and each are shown.)
~ Pyridine adsorption infrared absorption spectroscopy measurement ~
In the above 2,4-dimethylquinoline adsorption infrared absorption spectroscopic measurement, only the point where pyridine gas was introduced and adsorbed for 10 minutes was changed, and the measurement was carried out by the same apparatus and the same method.
ただし、差スペクトルにおける１５４５ｃｍ−１付近のピークをブレンステッド酸に吸着したピリジンの吸収スペクトルのピークとして用い、積分吸光係数を１．６７ｃｍ・μｍｏｌ−１をして、上記の式（２）よりＢ酸量を求めた。 However, the peak near 1545 cm -1 in the difference spectrum was used as the peak in the absorption spectrum of the pyridine adsorbed on Bronsted acid, the integrated absorption coefficient was 1.67 cm · μmol -1 , and B was obtained from the above equation (2). The amount of acid was determined.
〜成形体最側面から成形体の中心(成形体断面の中心)又は成形体内筒の側面への最短距離の測定〜
無作為に選択した３０個の成形体粒子について、ノギスを用い測定を行い、その平均を測定値とした。
-Measurement of the shortest distance from the outermost side of the molded body to the center of the molded body (center of the cross section of the molded body) or the side surface of the molded body cylinder-
30 randomly selected molded particles were measured using calipers, and the average was used as the measured value.
〜粉末Ｘ線回折の測定〜
Ｘ線回折測定装置（スペクトリス社製、（商品名）Ｘ’ｐｅｒｔ ＰＲＯ ＭＰＤ）を用い、管電圧４５ｋＶ、管電流４０ｍＡとしてＣｕＫα１を用いて、大気中において測定した。０．０４〜５度の範囲を０．０８度／ステップ、２００秒／ステップで分析した。また、ダイレクトビームの吸収率で補正したバックグラウンドを除去している。
~ Measurement of powder X-ray diffraction ~
It was measured in the atmosphere using an X-ray diffraction measuring device (manufactured by Spectris, (trade name) X'pert PRO MPD), using CuKα1 as a tube voltage of 45 kV and a tube current of 40 mA. The range of 0.04 to 5 degrees was analyzed at 0.08 degrees / step and 200 seconds / step. In addition, the background corrected by the absorption rate of the direct beam is removed.
ピークの有無の確認を目視で行うことにより結晶構造の同定を行った。他の方法として、ピークサーチプログラムを利用してもよい。ピークサーチプログラムは、一般的なプログラムが利用できる。例えば、横軸が２θ（度）、縦軸が強度（ａ．ｕ．）の測定結果をＳＡＶＩＴＳＫＹ＆ＧＯＬＡＹの式とＳｌｉｄｉｎｇ Ｐｏｌｙｎｏｍｉａｌフィルターで平滑化した後、２次微分を行ったときに、３点以上連続する負の値がある場合、ピークが存在すると判断できる。 The crystal structure was identified by visually confirming the presence or absence of peaks. As another method, a peak search program may be used. As the peak search program, a general program can be used. For example, when the measurement results of 2θ (degrees) on the horizontal axis and intensity (a.u.) on the vertical axis are smoothed by the SAVITSKY & GOLAY equation and the Sliding Polynomial filter, and then the second derivative is performed, three or more points are continuous. If there is a negative value, it can be determined that a peak exists.
〜オレフィン製造装置及びその製造方法〜
実施例、比較例により得られた触媒により、以下の方法によりオレフィンの製造を行い、オレフィン製造用触媒としての性能評価を行った。
-Olefin production equipment and its production method-
Using the catalysts obtained in Examples and Comparative Examples, olefins were produced by the following methods, and their performance as catalysts for olefin production was evaluated.
ステンレス製反応管（内径１６ｍｍ、長さ６００ｍｍ）を有する固定床気相流通式反応装置を用いた。ステンレス製反応管の中段に、成形体を充填し、乾燥空気流通下での加熱前処理を行ったのち、原料ガスをフィードした。そして、加熱はセラミック製管状炉を用い、触媒（成形体）層の温度を制御した。反応出口ガスおよび反応液を採取し、ガスクロマトグラフを用い、ガス成分および液成分を個別に分析した。ガス成分は、ＴＣＤ検出器を備え、充填剤（Ｗａｔｅｒｓ社製、（商品名）ＰｏｒａｐａｋＱまたはＧＬサイエンス社製、（商品名）ＭＳ−５Ａ）を有するガスクロマトグラフ（島津製作所製、（商品名）ＧＣ−１７００）を用いて分析した。液成分は、ＦＩＤ検出器を備え、分離カラムとしてキャピラリーカラム（ＧＬサイエンス社製、（商品名）ＴＣ−１）を有するガスクロマトグラフ（島津製作所製、（商品名）ＧＣ−２０１５）を用いて分析した。 A fixed-bed gas-phase flow reactor having a stainless steel reaction tube (inner diameter 16 mm, length 600 mm) was used. The middle stage of the stainless steel reaction tube was filled with a molded product, pretreated by heating under a dry air flow, and then the raw material gas was fed. Then, a ceramic tube furnace was used for heating, and the temperature of the catalyst (mold) layer was controlled. The reaction outlet gas and the reaction solution were collected, and the gas component and the liquid component were analyzed individually using a gas chromatograph. The gas component is a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC) equipped with a TCD detector and having a filler (manufactured by Waters, (trade name) PolapakQ or GL Sciences, (trade name) MS-5A). -1700) was used for analysis. The liquid components were analyzed using a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-2015) equipped with a FID detector and having a capillary column (manufactured by GL Sciences, Inc. (trade name) TC-1) as a separation column. ..
反応条件は下記のように設定した。 The reaction conditions were set as follows.
（オレフィン製造条件）
触媒重量：３．８ｇ。
流通ガス：原料ガス５０ｍｏｌ％＋窒素５０ｍｏｌ％の混合ガス。
反応温度：５００℃。
(Olefin production conditions)
Catalyst weight: 3.8 g.
Distribution gas: A mixed gas of 50 mol% of raw material gas + 50 mol% of nitrogen.
Reaction temperature: 500 ° C.
（前処理条件）
触媒温度：５００℃。
流通ガス：空気１００Ｎｍｌ／分。
処理時間；１時間。
(Pretreatment conditions)
Catalyst temperature: 500 ° C.
Flowing gas: Air 100 Nml / min.
Processing time; 1 hour.
実施例１
テトラプロピルアンモニウム（以降、ＴＰＡと略記する場合がある。）水酸化物と水酸化ナトリウムの水溶液に不定形アルミノシリケートゲルを添加して懸濁させた。得られた懸濁液にＭＦＩ型ゼオライトを種晶として加え原料組成物とした。その際の種晶の添加量は、原料組成物中のＡｌ２Ｏ３とＳｉＯ２の重量に対して、０．７重量％とした。また、副生したエタノールは蒸発させて除いた。
Example 1
Atypical aluminosilicate gel was added to an aqueous solution of tetrapropylammonium (hereinafter sometimes abbreviated as TPA) hydroxide and sodium hydroxide and suspended. MFI-type zeolite was added as a seed crystal to the obtained suspension to prepare a raw material composition. The amount of the seed crystal added at that time was 0.7% by weight with respect to the weight of Al 2 O 3 and SiO 2 in the raw material composition. In addition, the by-produced ethanol was removed by evaporation.
該原料組成物の組成は以下のとおりである。
ＳｉＯ２／Ａｌ２Ｏ３モル比＝４８、ＴＰＡ／Ｓｉモル比＝０．０５、Ｎａ／Ｓｉモル比＝０．１６、ＯＨ／Ｓｉモル比＝０．２１、Ｈ２Ｏ／Ｓｉモル比＝１０。
The composition of the raw material composition is as follows.
SiO 2 / Al 2 O 3 molar ratio = 48, TPA / Si molar ratio = 0.05, Na / Si molar ratio = 0.16, OH / Si molar ratio = 0.21, H 2 O / Si molar ratio = 10.
得られた原料組成物をステンレス製オートクレーブに密閉し、１１５℃で攪拌しながら４日間結晶化させ、スラリー状混合液を得た。結晶化後のスラリー状混合液を遠心沈降機で固液分離した後、十分量の純水で固体粒子を洗浄し、１１０℃で乾燥して乾燥粉末を得た。 The obtained raw material composition was sealed in a stainless steel autoclave and crystallized for 4 days with stirring at 115 ° C. to obtain a slurry-like mixture. The slurry-like mixture after crystallization was solid-liquid separated by a centrifugal settler, and then the solid particles were washed with a sufficient amount of pure water and dried at 110 ° C. to obtain a dry powder.
得られた乾燥粉末を１ｍｏｌ／Ｌの常温の塩酸中に分散し、ろ過した後に、十分量の純水で固体粒子を洗浄し、再度ろ過後、１００℃で１晩乾燥させた。空気下、５５０℃で１時間焼成後、６００℃、３０％の水蒸気で２時間処理した。 The obtained dry powder was dispersed in hydrochloric acid at room temperature of 1 mol / L, filtered, and then the solid particles were washed with a sufficient amount of pure water, filtered again, and dried at 100 ° C. overnight. After firing at 550 ° C. for 1 hour under air, it was treated with 30% steam at 600 ° C. for 2 hours.
得られた粉末を１ｍｏｌ／Ｌの常温の塩酸中に分散し、ろ過した後に、十分量の純水で固体粒子を洗浄し、再度ろ過後、ゼオライトを得た。 The obtained powder was dispersed in hydrochloric acid at room temperature of 1 mol / L, filtered, and then the solid particles were washed with a sufficient amount of pure water and filtered again to obtain zeolite.
得られたゼオライトの物性を表１に示す。得られたゼオライトは、ＭＦＩ型ゼオライトの骨格構造を有する１０員環細孔ゼオライトであり、ＴＥＭを用いて測定した平均粒子径２４ｎｍであった。 The physical characteristics of the obtained zeolite are shown in Table 1. The obtained zeolite was a 10-membered ring-pore zeolite having a skeleton structure of an MFI-type zeolite, and had an average particle size of 24 nm measured using a TEM.
得られたゼオライトに２，４−ジメチルキノリンを吸着させた前後の赤外吸収の差スペクトルの３６００ｃｍ−１のゼオライトＢ酸点のＯＨに由来するピークの減少から求めた外表面のＢ酸量は２．７μｍｏｌ／ｇであった。また、得られたゼオライトにピリジンを吸着させた前後の赤外吸収の差スペクトルの１５４５ｃｍ−１のゼオライトＢ酸点に吸着したピリジンに由来するピークの増加から求めたＢ酸量は０．１５ｍｍｏｌ／ｇ、外表面Ｂ酸率は１．８％であった。 The amount of B acid on the outer surface obtained from the decrease in the peak derived from the OH of the zeolite B acid point of 3600 cm -1 in the difference spectrum of infrared absorption before and after adsorbing 2,4-dimethylquinoline on the obtained zeolite is It was 2.7 μmol / g. The amount of B acid determined from the increase in the peak derived from pyridine adsorbed on the zeolite B acid point of 1545 cm -1 in the difference spectrum of infrared absorption before and after adsorbing pyridine on the obtained zeolite was 0.15 mmol /. g, the outer surface B acid ratio was 1.8%.
得られたゼオライト１００重量部に対して、シリカ（日産化学工業社製、（商品名）スノーテックスＮ−３０Ｇ）２５重量部、セルロース５重量部、純水５５重量部を加え混練した。そして、混練物を直径３．０ｍｍ、長さ２．０〜９．０ｍｍ（平均長さ６．６ｍｍ）の円柱状の成形体とした。これを１００℃で１晩乾燥した。乾燥後の成形体を、空気流通下、６００℃で２時間焼成して成形体を得た。 To 100 parts by weight of the obtained zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 5 parts by weight of cellulose, and 55 parts by weight of pure water were added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 3.0 mm and a length of 2.0 to 9.0 mm (average length of 6.6 mm). This was dried at 100 ° C. overnight. The dried molded product was fired at 600 ° C. for 2 hours under air flow to obtain a molded product.
得られた成形体をオレフィン製造用触媒として、上記した条件にてオレフィンの製造を行い、評価を行った。原料ガスの流通量は、イソブタン２Ｎｍｌ／分、ノルマルブタン５Ｎｍｌ／分、トランス−２−ブテン９Ｎｍｌ／分、１−ブテン１６Ｎｍｌ／分、イソブテン３Ｎｍｌ／分、プロパン５Ｎｍｌ／分とした。反応時間に対するＣ４成分転化率、エチレン収率、プロピレン収率をそれぞれ表２〜４に示す。反応時間１０分〜７８５０分の間、Ｃ４成分転化率、エチレン収率、プロピレン収率はいずれも高い値が安定的に得られ、エチレンとプロピレンを高い効率で同時生産することが可能であった。 Using the obtained molded product as a catalyst for olefin production, olefins were produced under the above conditions and evaluated. The flow rate of the raw material gas was isobutane 2N ml / min, normal butene 5Nml / min, trans-2-butene 9Nml / min, 1-butene 16Nml / min, isobutene 3Nml / min, and propane 5Nml / min. Tables 2 to 4 show the C4 component conversion rate, ethylene yield, and propylene yield with respect to the reaction time, respectively. During the reaction time of 10 minutes to 7850 minutes, high values of C4 component conversion rate, ethylene yield, and propylene yield were all stably obtained, and it was possible to simultaneously produce ethylene and propylene with high efficiency. ..
実施例２
オートクレーブによるゼオライトの結晶化、洗浄、乾燥操作までを実施例１と同様に行った。得られた乾燥粉末を１ｍｏｌ／Ｌの常温の塩酸中に分散し、ろ過した後に、十分量の純水で固体粒子を洗浄し、再度ろ過後、１００℃で１晩乾燥させた。空気下、５５０℃で１時間焼成後、６００℃、４５％の水蒸気で３時間処理した。
Example 2
Crystallization, washing, and drying of zeolite by autoclave were carried out in the same manner as in Example 1. The obtained dry powder was dispersed in hydrochloric acid at room temperature of 1 mol / L, filtered, and then the solid particles were washed with a sufficient amount of pure water, filtered again, and dried at 100 ° C. overnight. After firing in air at 550 ° C. for 1 hour, it was treated with 600 ° C. and 45% steam for 3 hours.
得られた粉末を１ｍｏｌ／Ｌの４０℃の塩酸中に分散し、ろ過した後に、十分量の純水で固体粒子を洗浄し、再度ろ過後、１００℃で１晩乾燥させ、ゼオライトを得た。 The obtained powder was dispersed in 1 mol / L of hydrochloric acid at 40 ° C., filtered, and then the solid particles were washed with a sufficient amount of pure water, filtered again, and dried at 100 ° C. overnight to obtain zeolite. ..
得られたゼオライトの測定結果を表１に示す。得られたゼオライトは、ＭＦＩ型ゼオライトの骨格構造を有する１０員環細孔ゼオライトであり、ＴＥＭを用いて測定した平均粒子径２０ｎｍであった。 The measurement results of the obtained zeolite are shown in Table 1. The obtained zeolite was a 10-membered ring-pore zeolite having a skeleton structure of an MFI-type zeolite, and had an average particle size of 20 nm measured using a TEM.
得られたゼオライトに２，４−ジメチルキノリンを吸着させた前後の赤外吸収の差スペクトルの３６００ｃｍ−１のゼオライトＢ酸点のＯＨに由来するピークの減少から求めた外表面のＢ酸量は３．０μｍｏｌ／ｇであった。また、得られたゼオライトにピリジンを吸着させた前後の赤外吸収の差スペクトルの１５４５ｃｍ−１のゼオライトＢ酸点に吸着したピリジンに由来するピークの増加から求めたＢ酸量は０．１３ｍｍｏｌ／ｇ、外表面Ｂ酸率は２．３％であった。 The amount of B acid on the outer surface obtained from the decrease in the peak derived from the OH of the zeolite B acid point of 3600 cm -1 in the difference spectrum of infrared absorption before and after adsorbing 2,4-dimethylquinoline on the obtained zeolite is It was 3.0 μmol / g. The amount of B acid determined from the increase in the peak derived from pyridine adsorbed on the zeolite B acid point of 1545 cm -1 in the difference spectrum of infrared absorption before and after adsorbing pyridine on the obtained zeolite was 0.13 mmol /. g, the outer surface B acid ratio was 2.3%.
得られたゼオライト１００重量部に対して、シリカ（日産化学工業社製、（商品名）スノーテックスＮ−３０Ｇ）２５重量部、セルロース５重量部、純水５５重量部を加え混練した。そして、混練物を直径３．０ｍｍ、長さ２．０〜９．０ｍｍ（平均長さ６．４ｍｍ）の円柱状の成形体とした。これを１００℃で１晩乾燥した。乾燥後の成形体を、空気流通下、６００℃で２時間焼成して成形体を得た。 To 100 parts by weight of the obtained zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 5 parts by weight of cellulose, and 55 parts by weight of pure water were added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 3.0 mm and a length of 2.0 to 9.0 mm (average length of 6.4 mm). This was dried at 100 ° C. overnight. The dried molded product was fired at 600 ° C. for 2 hours under air flow to obtain a molded product.
得られた成形体をオレフィン製造用触媒として、上記した条件にてオレフィンの製造を行い、評価を行った。原料ガスの流通量は、イソブタン２Ｎｍｌ／分、ノルマルブタン５Ｎｍｌ／分、トランス−２−ブテン９Ｎｍｌ／分、１−ブテン１６Ｎｍｌ／分、イソブテン３Ｎｍｌ／分、プロパン５Ｎｍｌ／分とした。反応時間に対するＣ４成分転化率、エチレン収率、プロピレン収率をそれぞれ表２〜４に示す。反応時間１０分〜７８５０分の間、Ｃ４成分転化率、エチレン収率、プロピレン収率はいずれも高い値が安定的に得られ、エチレンとプロピレンを高い効率で同時生産することが可能であった。 Using the obtained molded product as a catalyst for olefin production, olefins were produced under the above conditions and evaluated. The flow rate of the raw material gas was isobutane 2N ml / min, normal butene 5Nml / min, trans-2-butene 9Nml / min, 1-butene 16Nml / min, isobutene 3Nml / min, and propane 5Nml / min. Tables 2 to 4 show the C4 component conversion rate, ethylene yield, and propylene yield with respect to the reaction time, respectively. During the reaction time of 10 minutes to 7850 minutes, high values of C4 component conversion rate, ethylene yield, and propylene yield were all stably obtained, and it was possible to simultaneously produce ethylene and propylene with high efficiency. ..
比較例１
オートクレーブによるゼオライトの結晶化、洗浄、乾燥操作までを実施例１と同様に行った。
Comparative Example 1
Crystallization, washing, and drying of zeolite by autoclave were carried out in the same manner as in Example 1.
得られた乾燥粉末を、空気下、５５０℃で焼成後、得られた粉末を常温の１ｍｏｌ／Ｌの塩酸中に分散し、ろ過した後に、十分量の純水で固体粒子を洗浄し、再度ろ過後、１００℃で１晩乾燥させ、ゼオライトを得た。 The obtained dry powder is fired in air at 550 ° C., the obtained powder is dispersed in 1 mol / L hydrochloric acid at room temperature, filtered, and then the solid particles are washed with a sufficient amount of pure water and again. After filtration, it was dried at 100 ° C. overnight to obtain zeolite.
得られたゼオライトの評価結果を表１に示す。得られたゼオライトは、ＭＦＩ型ゼオライトの骨格構造を有し、ＴＥＭを用いて測定した平均粒子径は２６ｎｍであった。 The evaluation results of the obtained zeolite are shown in Table 1. The obtained zeolite had a skeleton structure of MFI-type zeolite, and the average particle size measured using TEM was 26 nm.
得られたゼオライトに２，４−ジメチルキノリンを吸着させた前後の赤外吸収の差スペクトルの３６００ｃｍ−１のゼオライトＢ酸点のＯＨに由来するピークの減少から求めた外表面のＢ酸量は１７．４μｍｏｌ／ｇであった。また、得られたゼオライトにピリジンを吸着させた前後の赤外吸収の差スペクトルの１５４５ｃｍ−１のゼオライトＢ酸点に吸着したピリジンに由来するピークの増加から求めたＢ酸量は０．１５ｍｍｏｌ／ｇ、外表面Ｂ酸率は１１．６％であった。 The amount of B acid on the outer surface obtained from the decrease in the peak derived from the OH of the zeolite B acid point of 3600 cm -1 in the difference spectrum of infrared absorption before and after adsorbing 2,4-dimethylquinoline on the obtained zeolite is It was 17.4 μmol / g. The amount of B acid determined from the increase in the peak derived from pyridine adsorbed on the zeolite B acid point of 1545 cm -1 in the difference spectrum of infrared absorption before and after adsorbing pyridine on the obtained zeolite was 0.15 mmol /. g, the outer surface B acid ratio was 11.6%.
得られたゼオライト１００重量部に対して、シリカ（日産化学工業社製、（商品名）スノーテックスＮ−３０Ｇ）２５重量部、セルロース５重量部、純水５５重量部を加え混練した。そして、混練物を直径３．０ｍｍ、長さ２．０〜９．０ｍｍ（平均長さ６．４ｍｍ）の円柱状の成形体とした。これを１００℃で１晩乾燥した。乾燥後の成形体を、空気流通下、６００℃で２時間焼成して成形体を得た。 To 100 parts by weight of the obtained zeolite, 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd., (trade name) Snowtex N-30G), 5 parts by weight of cellulose, and 55 parts by weight of pure water were added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 3.0 mm and a length of 2.0 to 9.0 mm (average length of 6.4 mm). This was dried at 100 ° C. overnight. The dried molded product was fired at 600 ° C. for 2 hours under air flow to obtain a molded product.
得られた成形体を触媒として、上記した条件にてオレフィンの製造を行い、評価を行った。原料ガスの流通量は、イソブタン２Ｎｍｌ／分、ノルマルブタン５Ｎｍｌ／分、トランス−２−ブテン９Ｎｍｌ／分、１−ブテン１６Ｎｍｌ／分、イソブテン３Ｎｍｌ／分、プロパン５Ｎｍｌ／分とした。反応時間に対するＣ４成分転化率、エチレン収率、プロピレン収率をそれぞれ表２〜４に示す。Ｃ４成分転化率の経時的な低下が顕著である上、反応時間１０分におけるエチレン収率およびプロピレン収率が顕著に低く、エチレンとプロピレンを効率的に同時生産できるとは言い難かった。反応時間７８５０分での反応を試みたが、２９０分を経過した時点で反応系が不安定となったため、製造を停止した。 Using the obtained molded product as a catalyst, olefins were produced under the above conditions and evaluated. The flow rate of the raw material gas was isobutane 2N ml / min, normal butene 5Nml / min, trans-2-butene 9Nml / min, 1-butene 16Nml / min, isobutene 3Nml / min, and propane 5Nml / min. Tables 2 to 4 show the C4 component conversion rate, ethylene yield, and propylene yield with respect to the reaction time, respectively. The C4 component conversion rate decreased remarkably with time, and the ethylene yield and the propylene yield at the reaction time of 10 minutes were remarkably low, so it was difficult to say that ethylene and propylene could be efficiently produced at the same time. An attempt was made to react with a reaction time of 7850 minutes, but the reaction system became unstable after 290 minutes, and the production was stopped.
比較例２
プロトン型ＭＦＩ型ゼオライト粉末（東ソー株式会社製、商品名：ＨＳＺ−８４０ＨＯＡ；ＳＥＭ観察による平均粒子径２１１０ｎｍ、Ｂ酸量は０．２７ｍｍｏｌ／ｇ、外表面のＢ酸量は１７．５μｍｏｌ／ｇ、外表面Ｂ酸率は６．４％。）１００重量部に対して、シリカ（日産化学工業社製、（商品名）スノーテックスＮ−３０Ｇ）２５重量部、セルロース５重量部、純水５５重量部を加え混練した。そして、混練物を直径３．０ｍｍ、長さ２．０〜９．０ｍｍ（平均長さ６．５ｍｍ）の円柱状の成形体とした。これを１００℃で１晩乾燥した。乾燥後の成形体を、空気流通下、６００℃で２時間焼成して成形体を得た。
Comparative Example 2
Proton type MFI type zeolite powder (manufactured by Tosoh Corporation, trade name: HSZ-840HOA; average particle size 2110 nm as observed by SEM, B acid amount is 0.27 mmol / g, B acid amount on the outer surface is 17.5 μmol / g, The outer surface B acid ratio is 6.4%.) 25 parts by weight of silica (manufactured by Nissan Chemical Industries, Ltd. (trade name) Snowtex N-30G), 5 parts by weight of cellulose, 55 weight of pure water with respect to 100 parts by weight. Part was added and kneaded. Then, the kneaded product was made into a columnar molded body having a diameter of 3.0 mm and a length of 2.0 to 9.0 mm (average length of 6.5 mm). This was dried at 100 ° C. overnight. The dried molded product was fired at 600 ° C. for 2 hours under air flow to obtain a molded product.
得られた成形体を触媒として、上記した条件にてオレフィンの製造を行い、評価を行った。原料ガスの流通量は、イソブタン２Ｎｍｌ／分、ノルマルブタン５Ｎｍｌ／分、トランス−２−ブテン９Ｎｍｌ／分、１−ブテン１６Ｎｍｌ／分、イソブテン３Ｎｍｌ／分、プロパン５Ｎｍｌ／分とした。反応時間に対するＣ４成分転化率、エチレン収率、プロピレン収率をそれぞれ表２〜４に示す。反応時間１０分〜７８５０分の間でＣ４成分転化率の経時的な低下が顕著である上、エチレン収率が顕著に低く、生成バランスに劣りエチレンとプロピレンを効率的に同時生産できるとは言い難かった。 Using the obtained molded product as a catalyst, olefins were produced under the above conditions and evaluated. The flow rate of the raw material gas was isobutane 2N ml / min, normal butene 5Nml / min, trans-2-butene 9Nml / min, 1-butene 16Nml / min, isobutene 3Nml / min, and propane 5Nml / min. Tables 2 to 4 show the C4 component conversion rate, ethylene yield, and propylene yield with respect to the reaction time, respectively. It is said that the C4 component conversion rate decreases remarkably over time between the reaction time of 10 minutes and 7850 minutes, the ethylene yield is remarkably low, the production balance is poor, and ethylene and propylene can be efficiently produced simultaneously. It was difficult.
本発明の外表面に微量のＢ酸量を有する微結晶中細孔ゼオライトを含む新規なオレフィン製造用触媒は、例えば非芳香族炭化水素原料の転化・異性化反応、特に低級オレフィンの製造の際に特異的な安定性・効率を発現し、その触媒としての産業的価値は極めて高いものである。 The novel catalyst for producing an olefin containing a microcrystalline medium-pore zeolite having a trace amount of B acid on the outer surface of the present invention is, for example, during a conversion / isomerization reaction of a non-aromatic hydrocarbon raw material, particularly in the production of a lower olefin. It exhibits stability and efficiency peculiar to zeolite, and its industrial value as a catalyst is extremely high.
Claims (7)
（ｉ）平均粒子径が１００ｎｍ以下。
（ｉｉ）１０員環細孔ゼオライト。
（ｉｉｉ）外表面のブレンステッド酸量が０．０１〜１０．０μｍｏｌ／ｇ。 A catalyst for producing an olefin, which comprises a zeolite that satisfies the following characteristics (i) to (iii).
(I) The average particle size is 100 nm or less.
(Ii) 10-membered ring pore zeolite.
(Iii) The amount of Bronsted acid on the outer surface is 0.01 to 10.0 μmol / g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020043800A JP2021142504A (en) | 2020-03-13 | 2020-03-13 | Catalyst for production of olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020043800A JP2021142504A (en) | 2020-03-13 | 2020-03-13 | Catalyst for production of olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021142504A true JP2021142504A (en) | 2021-09-24 |
Family
ID=77765759
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020043800A Pending JP2021142504A (en) | 2020-03-13 | 2020-03-13 | Catalyst for production of olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021142504A (en) |
-
2020
- 2020-03-13 JP JP2020043800A patent/JP2021142504A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Álvaro-Muñoz et al. | Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reaction | |
| JP5354976B2 (en) | Catalyst for producing light olefins and method for producing light olefins | |
| US6517611B1 (en) | Olefin separations employing CTS molecular sieves | |
| KR20190105086A (en) | Dual Catalytic Processes and Systems for Propylene Production | |
| Ma et al. | Selective synthesis of gasoline from syngas in near-critical phase | |
| Parkhomchuk et al. | Catalytic cracking of n-hexane in the presence of zeolite ZSM-5 micro-and nanocrystals | |
| JP6862966B2 (en) | Metal-containing zeolite | |
| JP6733501B2 (en) | Aromatic compound production catalyst and method for producing aromatic compound | |
| JP2018145085A (en) | Zeolite and method for producing the same | |
| JP6780369B2 (en) | Aromatic compound production catalyst and method for producing aromatic compounds | |
| WO2021006188A1 (en) | Novel zeolite, and catalyst for use in production of aromatic hydrocarbon which comprises same | |
| JP6953711B2 (en) | Metal-containing MFI-type zeolite and catalyst for producing aromatic compounds | |
| JP2021142504A (en) | Catalyst for production of olefin | |
| JP2021059484A (en) | Novel silver-containing zeolite and zeolite-containing catalyst for producing aromatic hydrocarbons | |
| JP7452205B2 (en) | alcohol conversion catalyst | |
| JP2018154538A (en) | Silver-containing zeolite | |
| JP5023639B2 (en) | Propylene production method | |
| JP2022098620A (en) | Alkaline earth metal-containing mfi-type zeolite and catalyst for producing hydrocarbon | |
| JP7396052B2 (en) | Catalyst for producing aromatic compounds | |
| JP2023055086A (en) | Metal-containing mfi type zeolite and catalyst for hydrocarbon compound production containing the same | |
| JP2022110633A (en) | Metal-containing mfi type zeolite and catalyst for producing hydrocarbon | |
| JP2022187571A (en) | Simultaneous production method of lower aliphatic hydrocarbon and aromatic hydrocarbon | |
| JP2022172510A (en) | Silver-alkaline earth metal-containing mfi-type zeolite and catalyst for producing hydrocarbon | |
| JP2022175167A (en) | Conversion catalyst for thermal decomposition product of hydrocarbon-based plastic and production method of lower hydrocarbon using the same | |
| JP2023055080A (en) | Mfi type zeolite and catalyst for hydrocarbon production containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230215 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20230831 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231003 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20231128 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240206 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240405 |