KR900009149B1 - Catalyst based on silicon titanium and gallium - Google Patents
Catalyst based on silicon titanium and gallium Download PDFInfo
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- KR900009149B1 KR900009149B1 KR1019900013293A KR900013293A KR900009149B1 KR 900009149 B1 KR900009149 B1 KR 900009149B1 KR 1019900013293 A KR1019900013293 A KR 1019900013293A KR 900013293 A KR900013293 A KR 900013293A KR 900009149 B1 KR900009149 B1 KR 900009149B1
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- 239000003054 catalyst Substances 0.000 title claims description 13
- 229910052733 gallium Inorganic materials 0.000 title claims description 11
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims description 10
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical group CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- -1 nitrogenous organic bases Chemical class 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N methyl heptene Natural products CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002258 gallium Chemical class 0.000 description 2
- 229940044658 gallium nitrate Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- CSZZMFWKAQEMPB-UHFFFAOYSA-N 1-methoxybutan-2-ol Chemical compound CCC(O)COC CSZZMFWKAQEMPB-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- HSANASOQSCIDJG-UHFFFAOYSA-N OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 HSANASOQSCIDJG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007479 molecular analysis Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
내용 없음.No content.
Description
제1도는 본 발명의 물질에 대한 I.R. 스펙트럼.Figure 1 shows the I.R. spectrum.
제2도는 ZSM-5의 I.R 스펙트럼.2 is the I.R spectrum of ZSM-5.
제3도는 실시예 1, 3, 4 내지 7의 갈륨-티탄-실리카라이트의 I.R. 스펙트럼.3 shows I.R. of gallium-titanium-silicalite of Examples 1, 3, 4-7. spectrum.
제4도는 실시예 7에서 수득한 생성물의 SiO2/TiO2비와 SiO2/Ga2O3비의 관계를 나타내는 도표.4 is a graph showing the relationship between the SiO 2 / TiO 2 ratio and the SiO 2 / Ga 2 O 3 ratio of the product obtained in Example 7.
제6도는 실시예 7의 갈륨과 지얼라이트 치환량과의 관계.6 is a relationship between gallium and zeolite replacement amounts in Example 7.
본 발명은 지얼라이트 성질의 다공성 결정체 구조로 된 실리콘, 티탄 및 갈륨산화물을 포함하는 합성물질과 이것의 제조방법에 관한 것이다. 이러한 물질은 미국특허 제3,702,886호에서 발표된 지올라이트 ZSM-5와 구조적으로 유사하며, M1n/O, SiO2, Al2O3즉 산화금속, 실리카와 알루미나(여기서 M=원자가의 양이온)를 사용하여 소성 무수물 형태로 구성한다.The present invention relates to a composite material comprising silicon, titanium and gallium oxide having a zeolite porous crystal structure and a method for producing the same. This material is structurally similar to the zeolite ZSM-5 published in U.S. Patent No. 3,702,886, with M 1n / O, SiO 2 , Al 2 O 3 ie metal oxides, silica and alumina (where M = Valent cations) in the form of calcined anhydride.
지얼라이트 ZSM-5와 구조적으로 상호 관련하는 다른 합성물질은 미국특허 제4,061,724호에 발표된 것같이 SiO2에 의해서 소성 무수물 형태로 구성되고 또한 BE-886,812에서 발표된 것같이 SiO2와 TiO2를 사용하여 소성 무수물 형태로 구성하는 것으로 공지되어 있다.Other composites that are structurally interrelated with the Zeolite ZSM-5 are composed of calcined anhydride by SiO 2 as disclosed in US Pat. No. 4,061,724 and also contain SiO 2 and TiO 2 as disclosed in BE-886,812. It is known to construct in the form of calcined anhydrides.
금번 발견한 것은 티탄-갈륨-실리카라이트라고 부르는 신균의 합성 지얼라이트가 실리카라이트(silicalite)와 유사하고, 이것을 분자체로 사용하거나 이온-교환물질로 사용하고 또는 아래의 반응에서 촉매로서 사용할 수가 있다. 크래킹, 선택형성, 수소화 및 탈수소화, 올리고머화, 알킬화, 이성화, 산소함유 유기화합물로부터의 탈수작업, H2O2을 이용한 유기기질의 선택적 산화 및 히드록시화(예컨대 올레핀, 디올레핀,알코올의 산화, 방향족등의 히드록시화).The findings of this time are the new synthetic geolites called titanium-gallium-silicalite, which are similar to silicalite and can be used as molecular sieves or as ion-exchange materials or as catalysts in the reactions below. . Cracking, selective formation, hydrogenation and dehydrogenation, oligomerization, alkylation, isomerization, dehydration from oxygen-containing organic compounds, selective oxidation and hydroxylation of organic substrates using H 2 O 2 (eg olefins, diolefins, alcohols) Hydroxylation of oxidation, aromatics, etc.).
실리콘, 티탄 및 갈륨의 산화물을 포함하는 본 발명의 지얼라이트 성질을 갖춘 합성 결정형 다공성 물질 은 소성 무수물 형태일때 아래의 실험식으로 나타낸다 :The synthetic crystalline porous material of the present invention, including oxides of silicon, titanium and gallium, is represented by the following empirical formula when in the form of calcined anhydride:
pHGaO2·qTiO2·SiO2 pHGaO 2 · qTiO 2 · SiO 2
여기서는 0보다 크고 0.050과 같거나 이보다 작은 값이며,는 0보다 크고 0.025와 같거나 이보다 작은 값이며 ; HGaO2의 H+는 양이온으로 대체할 수 있다.here Is a value greater than 0 and less than or equal to 0.050. Is a value greater than 0 and less than or equal to 0.025; H + of HGaO 2 can be replaced with a cation.
양이온 형태로부터 또다른 양이온 형태로의 전이는 선행기술에서 공지된 통상적인 치환방법에 따라 실행된다.The transition from the cationic form to another cationic form is carried out according to conventional substitution methods known in the prior art.
본 발명의 합성물질은 X-선으로 시험할때 결정체를 나타낸다.The synthetic material of the present invention exhibits crystals when tested by X-rays.
이러한 시험은 CuK-알파 방사선을 사용하는 전자펄스(pulse), 계산시스템이 장치된 분말-회절계로 실시한다. 강도를 계산하기 위해 피크의 높이를 측정하고 가장 강한 피크에 대한 백분율로 나타낸다.This test is carried out with a powder-diffraction system equipped with an electronic pulse, calculation system using CuK-alpha radiation. To calculate the intensity, the height of the peak is measured and expressed as a percentage of the strongest peak.
소성 무수생성물에 대한 주 반사량은의 아래의 값을 특징으로 한다(여기서는 내측평면 거리임) :The main reflectance for the calcined anhydrous product is It is characterized by the following values of Is the inner plane distance):
(여기서 vs는 매우강함 ; s=강함 ; m=중간 ; mw=중간약함).(Where vs is very strong; s = strong; m = medium; mw = medium).
이러한 회절 스펙트럼은 ZSM-5의 그것과 본질적으로 유사하고 따라서 본 발표문헌의 서두에서 거론한 ZSM-5와 구조적으로 상호관계하는 다른 지얼라이트와도 유사하다.This diffraction spectrum is essentially similar to that of ZSM-5 and thus similar to other Zeolites that are structurally interrelated with ZSM-5 discussed at the beginning of this document.
본 발명의 물질은 다음의(여기서는 파장값)의 가장 대표적인 값을 특징으로 하는 I.R. 스펙트럼을 보여준다) .The material of the present invention is (here Shows the IR spectrum characterized by the most representative value of wavelength).
wn(㎝-1) 상대강도wn (㎝ -1 ) relative strength
1220-1230 w1220-1230 w
1080-1110 s1080-1110 s
965- 975 mw965- 975 mw
795- 805 mw795- 805 mw
550- 560 m550- 560 m
450- 470 ms450-470 ms
(여기서 s=강함 ; ms=중간-강함 ; m=중간 ; mw=중간-약함 ; w=약함).Where s = strong; ms = medium-strong; m = medium; mw = medium-weak; w = weak.
제1도에서는 I.R. 스펙트럼을 발표하여 여기서 가로좌표에는 파장을 ㎝-1로서, 세로좌표는 투과율(%)을 나타낸다.In Fig. 1, the IR spectrum is released, where the abscissa represents the wavelength in cm −1 , and the ordinate represents the transmittance (%).
이러한 I.R. 스펙트럼은 BE-886, 812에 발표된 지얼라이트의 그것과 유사하고 제 2도에 표시된 ZSM- 5(또는 유사한 구조물)와는 현저한 차이가 있다.Such I.R. The spectra are similar to those of Zeolite published in BE-886, 812 and differ markedly from ZSM-5 (or similar structures) shown in FIG.
스펙트럼에서 관찰할 수 있는 것은 BE-886, 812의 티탄-실리카라이트와 티탄-갈륨-딜리카라이트의 특징이 되는 965-975㎝-1에서의 밴드가 없다는 것이다. 요약하면, 여기서 발표한 물질은 실험식과 1.R 스펙트럼 두가지 모두에 기인하여 미국특허 제3,702,586 호의 ZSM-5와는 상이하고 실험식 때문에 BE-886, 812의 지얼라이트와도 상이하다.What can be observed in the spectra is that there is no band at 965-975 cm −1 , which is characteristic of the titanium-silicalite and titanium-gallium-dicalite of BE-886,812. In summary, the material presented here differs from ZSM-5 in US Pat. No. 3,702,586 due to both the empirical formula and the 1.R spectrum, and also the zeolite of BE-886, 812 because of the empirical formula.
사실, 미국특허 제3,702,886호의 ZSM-5는 산소함유 유기화합물로부터의 탈수, 크랙킹, 선택적형성, 수소화 및 탈수소화, 올리고머화, 알킬화, 이성화와 같은 반응에서 촉매로 사용할 수 있지만, 유기질과 H2O2와의 반응(페놀을 디페놀로 만드는 히드록시화 올레핀의 산화등)에서는 비활성을 나타내고 한편, BE-886, 812의 지얼라이트는 첫번째 반응에서는 비활성이고 최종 반응에서는 활성이며 ; 반면에 여기서 발표한 지얼 라이트는 위에 거론한 모든 반응에서 활성이다.In fact, ZSM-5 of US Pat. No. 3,702,886 can be used as a catalyst in reactions such as dehydration, cracking, selective formation, hydrogenation and dehydrogenation, oligomerization, alkylation, and isomerization from oxygen-containing organic compounds, but with organic matter and H 2 O Reaction with 2 (oxidation of hydroxylated olefins to make phenol diphenols) is inactive, while Zeolites BE-886, 812 are inactive in the first reaction and active in the final reaction; On the other hand, the Zeolites presented here are active in all the reactions discussed above.
본 발명의 두번째 목적은 위에 발표한 합성 결정형 다공성 물질을 얻는 제조방법이다.A second object of the present invention is a preparation method for obtaining the synthetic crystalline porous material disclosed above.
이러한 방법은 수성환경과 최소한 실온 내지 200℃의 온도에서 실리콘 유도체, 티탄유도체, 갈륨 유도체 및 질소질 유기염기를 반응시키는 것을 특징으로 하며 이때 반응물의 SiO2/Ga2O2몰비는 100 이상이고, 특히 150 내지 600의 범위이며, 반응물의 SiO2/TiO2몰비는 5 이상이고, 특히 15 내지 25의 범위이며, 반응물의 H2O/SiO2몰비는 10 내지 100의 범위이고 특히 30 내지 50의 범위이며, 하나나 그이상의 알칼리-및 또는 알칼리-토금속 염 및/또는 수산화물이 있을 경우 반응물의 M/SiO2몰비(여기서 M는 알칼리 및/또는 알칼리-토금속 양이온)는 0.1 이하이고, 특히 0.01 이하이거나 또는 0과 같다.This method is characterized by reacting silicon derivatives, titanium derivatives, gallium derivatives and nitrogenous organic bases in an aqueous environment and at least from room temperature to 200 ° C., wherein the reactant SiO 2 / Ga 2 O 2 molar ratio is at least 100, in particular The molar ratio of SiO 2 / TiO 2 of the reactants is at least 5, in particular in the range of 15 to 25, and the molar ratio of H 2 O / SiO 2 in the reactants is in the range of 10 to 100 and in particular in the range of 30 to 50. When there is one or more alkali- and / or alkaline-earth metal salts and / or hydroxides, the M / SiO 2 molar ratio of the reactants, where M is an alkali and / or alkaline-earth metal cation, is 0.1 or less, in particular 0.01 or less Or equal to zero.
이 물질의 실험식에서, 갈륨은 HGaO2의 형태로 나타내어 이 물질이 H+형태인 것을 강조한다. 각종 반응물간의 비율을 거론할때, 갈륨의 경우 Ga2O3형태가 이용되며 이것이 더욱 유용하다.In the empirical formula of this material, gallium is represented in the form of HGaO 2 , emphasizing that the material is in H + form. When discussing the ratio between the various reactants, the Ga 2 O 3 form is used for gallium, which is more useful.
실리콘 유도체는 실리카겔, 실리카졸 및 알킬규산염중에서 선택하며, 이중에 테트라에틸규산염이 가장 바람직하고, 티탄유도체는 예컨대 할로겐화 티탄처럼, 티안산염과 또한 예컨대 알킬-티탄산, 특히 테트라에 틸-티탄산과 같은 유기티탄산 유도체중에서 선택하고 ; 갈륨유도체는 예컨대 할로겐화 갈륨, 질산갈륨 및 수산화갈륨과 같은 그의 염에서 선택한다.The silicone derivative is selected from silica gel, silica sol and alkyl silicates, of which tetraethyl silicate is most preferred, and titanium derivatives are organic such as, for example, titanium halides, and also organic such as alkyl-titanic acids, in particular tetraethyl-titanic acid, for example titanium halides. Selected from titanic acid derivatives; Gallium derivatives are selected from, for example, salts thereof such as gallium halides, gallium nitrate and gallium hydroxide.
질소계 유기염기로 수산화 알킬암모늄, 특히 수산화 테트라프로필-암모늄이 있다.Nitrogen-based organic bases include alkylammonium hydroxides, in particular tetrapropyl-ammonium hydroxide.
수산화 테트라프로필-암모늄을 사용하는 경우, 반응물의 TPA+/SiO2비(여기서 TPA른 테트라프로필- 암모늄)는 0.1 내지 1, 특히 0.2 내지 0.4의 범위이다. 이 반응물은 100 내지 200℃ 범위의 온도에서 조작하여 반응시킨다. pH9 내지 14의 범위, 특히 pH10 내지 12의 범위에서 1시간 내지 5일의 시간동안 반응시킨다.When using tetrapropyl-ammonium hydroxide, the TPA + / SiO 2 ratio of the reactants, where TPA is tetrapropyl-ammonium, ranges from 0.1 to 1, in particular from 0.2 to 0.4. This reactant is reacted by operation at a temperature in the range of 100 to 200 ° C. The reaction is carried out for a period of 1 hour to 5 days in the range of
본 발명을 실행한 또다른 구체예에 따르면 티탄-갈륨-실리카라이트는 무정형 올리코머 실리카와 결합된 형태로서 무정형의 올리고머 실리카/티탄-갈륨-실리카라이트의 몰비를 0.05 내지 0.2의 범위로 하고, 여기서 티탄-갈륨-실리카라이트 결정체는 Si-O-Si의 가교에 의해서 결합되고 또한 미세구형의 실리카가 들어있는 티탄-갈륨-실리카라이트 결정체는 5 내지 1000㎛ 크기의 직경으로 되어있다. 결합제를 포함한 촉매의 제조방법은 테트라알킬-균산염, 특히 수산화 테트라알킬암모늄의 수용액에서 테트라에틸-오르토균 산염의 가수분해로 수득되는 수산화 테트라알킬-암모늄과 실리카 수용액을 사용하는데 근거한다.According to another embodiment of the present invention, titanium-gallium-silicalite is in combination with amorphous oligomeric silica and has a molar ratio of amorphous oligomeric silica / titanium-gallium-silicalite in the range of 0.05 to 0.2. Titanium-gallium-silicalite crystals are bonded by crosslinking of Si-O-Si, and titanium-gallium-silicalite crystals containing microspherical silica have a diameter of 5 to 1000 µm. The process for the preparation of catalysts comprising binders is based on the use of aqueous tetraalkyl-ammonium hydroxides and aqueous silica solutions obtained by hydrolysis of tetraethyl-ortho-acid salts in aqueous solutions of tetraalkyl-acid salts, in particular tetraalkylammonium hydroxide.
테트라알킬-암모늄부분에 있는 알킬기는 1 내지 5 범위의 탄소원자를 포함한다.The alkyl group in the tetraalkyl-ammonium moiety contains carbon atoms in the range of 1-5.
가수분해는 실온 내지 200℃ 온도와 0.2 패지 10시간에서 액체상태로 실시한다.Hydrolysis is carried out in a liquid state at room temperature to 200 ° C. and 0.2 hours for 10 hours.
이러한 용액에서, 실리카는 올리고머 형태로서 예컨대>10과 같은 충분히 높은 pH값으로 존재한다. 매우 미세한 결정체가 있는 결정형의 티탄-갈륨-실리카라이트를 이 용액에 분산시킬때 결정체 표면은 매질의 알칼리성 때문에 부분적으로 부식되고 ; 이러한 상태는 용액속의 결정체의 표면과 올리고머 규산염 사이에 안정한 화학결합이 형성될때 도움을 준다. 분무 건조기로 이 현탁액을 급속히 건조하면, 물이 제거되고 동시에 올리고머에 가교결합이 생겨서 삼차원 격자로 형성된 미세구가 생기고 여기서 지얼라이트 결정체는 Si-O-Si-가교에 의해서 정밀하게 결합한다.In such solutions, the silica is in oligomeric form, for example It is present at a sufficiently high pH value such as> 10. When dispersing the crystalline titanium-gallium-silicalite with very fine crystals in this solution, the crystal surface is partially corroded due to the alkalinity of the medium; This condition helps when a stable chemical bond is formed between the surface of the crystal in the solution and the oligomeric silicate. Rapid drying of this suspension with a spray drier removes water and at the same time crosslinks to the oligomer, resulting in microspheres formed into three-dimensional lattice, where the zeolite crystals are precisely bound by Si-O-Si-crosslinking.
사용하기전에, 미세구를 불활성 매질(H2, N2등)하에서 먼저 소성하고 다음에 150 내지 700℃ 특히, 500 내지 600℃ 온도에서 산화시킨다.Prior to use, the microspheres are first calcined under an inert medium (H 2 , N 2, etc.) and then oxidized at a temperature between 150 and 700 ° C., in particular between 500 and 600 ° C.
분무시킬 현탁액의 전체고체(SiO2, 티탄-갈륨-실리카라이트, TAA-OH)의 최적농도는 10 내지 40중량%이다. 이 현탁액의 고체농도와 분무기의 크기를 다르게 하면 수득하는 입자의 평균직경을 변화시킬 수가 있다. 이와같이 촉매 미세구의 직경을 5 내지 1000㎛ 범위내에서 변경하여 특정한 사용에 가장 적합한 크기로 선택한다.The optimal concentration of the total solids (SiO 2 , titanium-gallium-silicalite, TAA-OH) of the suspension to be sprayed is 10 to 40% by weight. By varying the solid concentration of this suspension and the size of the nebulizer, the average diameter of the resulting particles can be varied. As such, the diameter of the catalyst microspheres is varied within the range of 5 to 1000 μm to select the size that is most suitable for the specific use.
본 발명을 보다 잘 설명하기 위하여, 제조방법 및 응용 실시예를 다음같이 발표하였으나 본 발명이 이것에 제한되는 것은 아니다.In order to better explain the present invention, the production method and application examples are disclosed as follows, but the present invention is not limited thereto.
[실시예 1]Example 1
6.1g의 Ga(NO3)3·8H3O를 70g의 C2H5OH에 용해시키고 이렇게 얻는 용액을 약하게 교반하면서 22.7g의 테트라에틸-티탄산염과 416g의 테트라에틸-균산염으로 구성된 용액에 첨가한다.A solution consisting of 22.7 g of tetraethyl-titanate and 416 g of tetraethyl-mycotic acid, dissolving 6.1 g of Ga (NO 3 ) 3 .8H 3 O in 70 g of C 2 H 5 OH and gently stirring the resulting solution. Add to
이렇게 수득한 투명한 알코올성 용액을 14%의 수산화 테트라프로괼-암모늄으로된 수용액 870g에 알맞게 교반하면서 첨가한다. 이 혼합물을 단일상의 맑은 용액을 얻을때까지 가열하면서 계속 교반한다. 또한 이 혼합물을 다시 시간동안 교반하면서 700g의 탈염수를 첨가한다. 여기에서 수득한 혼합물을 교반중인 스테인리스강 압력솥에 넣고 자생 압력하에서 최고 170℃의 온도까지 가열한다. 이러한 조건을 15시간동안 유지한후 압력솥을 냉각시키고 반응 혼합물을 배출한다. 수득한 현탁액은 원심분리하고 고체는 재-분산 및 원심분리하여 세척하고 120℃에서 건조한 다음에 550℃에서 4시간동안 소성한다.The clear alcoholic solution thus obtained is added with moderate stirring to 870 g of an aqueous solution of 14% tetrapropione-ammonium hydroxide. The mixture is kept stirring while heating until a clear solution of single phase is obtained. In addition, 700 g of demineralized water is added while stirring the mixture again for an hour. The mixture obtained here is placed in a stirring stainless steel pressure cooker and heated to a temperature of up to 170 ° C. under autogenous pressure. After maintaining this condition for 15 hours, the autoclave is cooled and the reaction mixture is drained. The resulting suspension is centrifuged and the solid is washed by re-dispersion and centrifugation, dried at 120 ° C. and calcined at 550 ° C. for 4 hours.
수득된 생성물은 공지된 방법에 따라 양성자형태로 치환시킨다.The product obtained is substituted in proton form according to known methods.
화학 분석에서 무수물 생성물이 아래의 조성으로 된 것을 알 수 있다 : SiO2/Ga2O3=195.5, SiO2/TiO2= 54.2.Chemical analysis shows that the anhydride product is of the composition: SiO 2 / Ga 2 O 3 = 195.5, SiO 2 / TiO 2 = 54.2.
분말 X-선 회절 분석결과는 이 생성물이 결정체이고 ZSM-5 형태의 구조로 된 것을 보여준다. 이것의 I.R. 스펙트럼은 제3도에 표시한다.Powder X-ray diffraction analysis shows that this product is crystalline and has a ZSM-5 form structure. I.R. of this. The spectrum is shown in FIG.
[실시예 2-6]Example 2-6
실시예 1과 같은 방식으로 다섯가지를 제조하였는데 여기서 반응 혼합물의 분자조성과 수득된 생성물의 분자조성을 표 1에 기록한 것같은 화학 분석결과를 보여준다 .Five kinds were prepared in the same manner as in Example 1, in which the molecular analysis of the reaction mixture and the molecular composition of the obtained product are shown in Table 1 as shown in Table 1.
실시예 3 및 6에서 결정화 시간과 온도를 변경하였다. 특히 실시예 3에서는 190℃에서 3시간동안 결정화 반응을 실시하였고 실시예 6에서는 100℃에서 5일간 실시하였다.The crystallization time and temperature were changed in Examples 3 and 6. In particular, in Example 3, the crystallization reaction was performed at 190 ° C. for 3 hours, and in Example 6, it was performed at 100 ° C. for 5 days.
실시예 2에서 발표된 것같이 기술한 조건에서 제조한 반응 혼합물은 결정화하지 않았으며 다만 젤리형 농도로 된 무정형 생성물로서 남아있었다.The reaction mixture prepared under the conditions described as disclosed in Example 2 did not crystallize but remained as an amorphous product in a jellyous concentration.
실시예 3 내지 6에서 취한 생성물은 결정체이고 X-선 회절 분석에서 ZSM-5형 구조인 것을 보여준다.The products taken in Examples 3-6 are crystalline and show to be ZSM-5 type structures in X-ray diffraction analysis.
이의 I.R. 스펙트럼은 제 3도에 나타난다.I.R. The spectrum is shown in FIG.
[실시예 7]Example 7
실시예 1과 같은 방식으로 반응 혼합물을 제조하며 이것의 몰비는 다음과 같다 : SiO2/TiO2=20 ; SiO2/Ga2O3=200 ; TPA/SiO2=0.3 ; H2O/SiO2=40.A reaction mixture was prepared in the same manner as in Example 1 and the molar ratio thereof was as follows: SiO 2 / TiO 2 = 20; SiO 2 / Ga 2 O 3 = 200; TPA / SiO 2 = 0.3; H 2 O / SiO 2 = 40.
유일한 차이는 질산갈륨을 14%의 수산화 테트라프로필-암모늄 용액에 직접 용해시키고 에틸알코올에서는 용해시키지 않는 것이다. 이 반응 혼합물을 압력솥에 넣고 자생 압력하의 170℃ 온도에서 15시간동안 방치한다. 배출된 생성물을 원심분리하고 재-분산 및 원심분리로 두번 세척하고 다시 이것을 120℃에서 1시간동안 건조한후 공지중에서 550℃로 4시간동안 소성한다.The only difference is that gallium nitrate is directly dissolved in 14% tetrapropyl-ammonium hydroxide solution and not in ethyl alcohol. The reaction mixture is placed in an autoclave and left for 15 hours at 170 ° C. under autogenous pressure. The discharged product is centrifuged, washed twice by re-dispersion and centrifugation, which is then dried at 120 ° C. for 1 hour and then calcined at 550 ° C. for 4 hours in known batches.
소성 무수물 형태로 수득된 생성물은 다음과 같은 화학조성으로 되어있다 : SiO2/TiO2=38.2 ; SiO2/Ga2O3=140.The product obtained in the form of calcined anhydride has the following chemical composition: SiO 2 / TiO 2 = 38.2; SiO 2 / Ga 2 O 3 = 140.
분말 X-선 회절 분석에서 결정체 구조의 ZSM-5 형태와 미량의 결정체 TiO2(아나타스형)가 있음을 알수 있다.In powder X-ray diffraction analysis, it can be seen that there is a ZSM-5 form of crystal structure and a small amount of crystal TiO 2 (anatas type).
제3도에서 I.R. 스펙트럼은 실시예 1 및 3 내지 7의 갈륨-티탄-실리카라이트를 나타낸다.In Figure 3 I.R. The spectrum shows the gallium-titanium-silicalite of Examples 1 and 3-7.
제4도에서, 수득된 생성물은 200 이상의 SiO2/Ga2O3비에 대하여 SiO2/TiO2비가 40-50정도에서 안정될 때까지 SiO2/Ga2O3비의 증가에 따라서 감소한다는 것을 알수가 있다.In FIG. 4, the obtained product decreases with increasing SiO 2 / Ga 2 O 3 ratio until the SiO 2 / TiO 2 ratio stabilizes at about 40-50 with respect to the SiO 2 / Ga 2 O 3 ratio of 200 or more. I can see that.
제5도는, 상대 강도 비율이 I.R. 스펙트럼에서 구조적 티탄에 기여하는 970㎝-1(I1)에서의 결합띠와 또한 550㎝-1에서의 결합띠 사이에서 어떻게 변하는지 보여준다.5 shows how the relative intensity ratio varies between the bond band at 970 cm −1 (I 1 ) and also at 550 cm −1 , which contributes to the structural titanium in the IR spectrum.
이러한 강도 비율은 SiO2/Ga2O3비가 증가하면 커지고 이 사실은 결정체 격자속의 티탄이 갈륨의 감소에 따라서 실제로 감소한다는 것을 보여준다.This strength ratio increases as the SiO 2 / Ga 2 O 3 ratio increases and this fact shows that the titanium in the crystal lattice actually decreases as the gallium decreases.
제6도는 화학 분석에서 나타난 갈륨값의 증가에 따라서 수득한 지얼라이트의 치환량에 증가하는 것을 보여준다 ; 이것은 화학 분석에서 발견된 갈륨이 실제로 구조적인 갈륨인 것을 나타낸다.FIG. 6 shows that the substitution amount of zeolite obtained is increased with increasing gallium value shown in chemical analysis; This indicates that the gallium found in chemical analysis is actually structural gallium.
[실시예 8]Example 8
이 실시예에서, 결합제가 있는 실시예 1의 촉매를 제조한다.In this example, the catalyst of Example 1 with a binder is prepared.
100g의 Ga(NO3)3·8H2O 1,050의 C2H5OH에 용해시키고 이렇게 수득한 용액을 가볍게 교반하면서 340.5g의 테트라에틸-터탄산염과 6,240g의 테트라에틸-규산염으로 구성된 용액에 첨가한다.Dissolved in 100 g of Ga (NO 3 ) 3 8 H 2 O 1,050 C 2 H 5 OH and the solution so obtained was stirred in a solution consisting of 340.5 g of tetraethyl-tercarbonate and 6,240 g of tetraethyl-silicate with gentle stirring. Add.
이렇게 수득한 투명한 알코올성 용액을 적당히 교반하면서 14% 수산화 테트라프로필-암모늄 수용액의 13,000g에 첨가한다. 이 혼합물을 계속 교반하면서 한편으로 단일상의 맑은 용액을 얻을때까지 가열도 한다. 또한 10,500g의 탈염수를 첨가하고 이 혼합물을 한시간동안 계속 교반한다. 수득되는 혼합물을 교반중인 스테인리스강 압력솥에 주입하고 자생압력하에서 최고 170℃까지 가열한다. 이 조건을 15시간동안 유지 하고 다음에 압력솥을 냉각하고 반응 혼합물을 배출한다. 수득한 현탁액을 원심분리하고 고체는 재-분산 및 원심분리하여 세척한다.The clear alcoholic solution thus obtained is added to 13,000 g of 14% aqueous tetrapropyl-ammonium hydroxide solution with moderate stirring. The mixture is kept stirring while heating until a clear solution of single phase is obtained. Also 10,500 g of demineralized water is added and the mixture is kept stirring for an hour. The resulting mixture is poured into a stirring stainless steel autoclave and heated up to 170 ° C. under autogenous pressure. Maintain this condition for 15 hours, then cool the autoclave and drain the reaction mixture. The suspension obtained is centrifuged and the solid is washed by re-dispersion and centrifugation.
550g의 테트라에틸-규산염을 590g의 수산화 테트라프로필-암모늄 12% 수용액에 교반하면서 첨가하고 수득되는 혼합물을 대략 60℃에서 1시간동안 교반하고 다음에 2400g의 탈염수를 첨가하고 다음에 용액을 다시 한시간동안 교반하고 한편으로 대략 25℃까지 냉각시킨다.550 g of tetraethyl-silicate is added to 590 g of 12% aqueous solution of tetrapropyl ammonium hydroxide with stirring and the resulting mixture is stirred at approximately 60 ° C. for 1 hour, then 2400 g of demineralized water is added, and the solution is then added for another hour. Stir and cool to approximately 25 ° C on the one hand.
이렇게 수득한 투명한 용액에 대해 위에서 발표한 것같은 2050g의 세척한 원심분리 케이크를 조심스럽게 분산시킨다. 이 원심분리 케이크는 대략 70중량%의 지얼라이트를 포함한다.Carefully disperse the 2050 g washed centrifuge cake as disclosed above for the clear solution thus obtained. This centrifugal cake contains approximately 70% zeolite by weight.
그결과로 나온 우유같은 현탁액을 분무-건조기(NIRO-ATOMIZER ; disk-atomized ; 입구공기온도 300℃ ; 출구 공기온도 120℃ ; 챔버직경 1.5m), 조밀한 미세구를 수득하고, 이것은 20㎛에 근접하는 평균 직경으로 되어있다.The resulting milky suspension is spray-dried (NIRO-ATOMIZER; disk-atomized;
분무한 쟁성물을 N2대에서 550℃로 가열하고 ; 이 대를 N2로부터 점차적으로 공기로 바꾼다 ; 또한 이 생성물을 추가로 공기에서 550℃로 2시간동안 유지한다.The sprayed competitor is heated to 550 ° C. in the N 2 band; Gradually change this zone from N 2 to air; This product is further maintained at 550 ° C. for 2 hours in air.
수득된 고체는 아래의 조성과 몰비를 가진다 : SiO2/Ga2O3=217 ; SiO2/TiO2=60.The obtained solid has the following composition and molar ratio: SiO 2 / Ga 2 O 3 = 217; SiO 2 / TiO 2 = 60.
[실시예 9]Example 9
실시예 4에 따른 4g의 촉매와 60㎖빈의 1-옥탄을 유지된 압력솥에 주입하고 교반하면서 5시간동안 200℃로 가열한다. 냉각후, 현탁액을 여과하고 생성물을 가스-크로마토그래피와 질량분석으로 분석하였다.4 g of catalyst according to Example 4 and 60 ml of 1-octane in 1 ml octane are injected into a maintained pressure cooker and heated to 200 ° C. for 5 hours with stirring. After cooling, the suspension was filtered and the product analyzed by gas chromatography and mass spectrometry.
1-옥텐전환율 : 18%1-octene conversion: 18%
이량체에 대한 선택율 95%95% selectivity for dimers
삼량체에 대한 선택성 : 5%Selectivity to trimers: 5%
[실시예 10]Example 10
기계식 교반기와 온도 조절 시스템이 장치된 1리터 용량의 강 압력솥에 373g의 메탄올, 실시예 8에 따른 촉매 4g, 5.0g의 벤젠(가스-크로마토그래피 분석용 내부표준으로서) 및 45g의 1-부텐을 주입한다. 온도를 22℃의 기준치에 맞춘뒤에, 이 현탁액에 33%(w/v)의 과산화수소 20㎖를 강하게 교반하면서 첨가한다. 이 반응은 분석용 시료를 취하여 여과해서 관찰한다. 과산화수소는 요오드 적정으로 측정하고 반응 생성물은 Porcpak PS로 충전된 1.8m 길이의 칼럼이 설치된 GLC에서 측정한다. 45분후의 상황은 아래와 같다 :In a 1 liter steel autoclave equipped with a mechanical stirrer and temperature control system, 373 g of methanol, 4 g of catalyst according to Example 8, 5.0 g of benzene (as internal standard for gas-chromatographic analysis) and 45 g of 1-butene Inject. After adjusting the temperature to the reference value of 22 ° C, 20 ml of 33% (w / v) hydrogen peroxide was added to this suspension with vigorous stirring. This reaction is observed by taking a sample for analysis and filtering. Hydrogen peroxide is measured by iodine titration and the reaction product is measured in GLC equipped with a 1.8 m long column filled with Porcpak PS. After 45 minutes, the situation is as follows:
전환된 H2O285%Converted H 2 O 2 85%
1,2-에폭시부탄 : 0.0326몰1,2-epoxybutane: 0.0326 moles
1-메톡시-2-히드록시부탄 : 0.0795몰1-methoxy-2-hydroxybutane: 0.0795 mol
2-메톡디-1-히드록시부탄 : 0.0517몰2-Methodi-1-hydroxybutane: 0.0517 mol
[실시예 11]Example 11
용량의 1리터이고 기계식 교반기 온도 조절 시스템 및 일정 압력 조절 시스템이 장치된 압력솥에 193g의 메탄올과 실시예 4에 따른 촉매 4.0g을 주입한다. 압력솥과 연결된 용기에 32%(w/w)의 H2O211.2g를 주입한다. 온도를 22℃의 기준치로 조정하고, 교반하면서 프로필렌을 넣어 300KPa까지 압력을 올린후(이 압 력은 전체 반응시간중에 일정하게 유지한다). 압력솥의 이 현탁액에 과산화수소를 일시에 모두 첨가한다.193 g of methanol and 4.0 g of the catalyst according to example 4 are injected into a pressure cooker of 1 liter of capacity and equipped with a mechanical stirrer temperature control system and a constant pressure control system. Add 11.2 g of 32% (w / w) H 2 O 2 to the vessel connected to the autoclave. Adjust the temperature to the reference value of 22 ° C, add propylene while stirring and raise the pressure to 300 KPa (this pressure is kept constant during the entire reaction time). Hydrogen peroxide is added all at once to this suspension of the pressure cooker.
이 반응은 현탁액의 시료를 취하여 여과 및 분석해서 관찰한다. 과산화수소는 요오드 적정으로 측정하고 반응 생성물은 Poropak PS.로 채워진 1.8미터 길이의 칼럼에서 가스-크로마토그래피로 측정하다. 45분후의 상황은 아래와 같다 :This reaction is observed by taking a sample of the suspension, filtering and analyzing. Hydrogen peroxide is measured by iodine titration and the reaction product is measured by gas-chromatography on a 1.8 meter long column filled with Poropak PS. After 45 minutes, the situation is as follows:
전환된 H2O288%Converted H 2 O 2 88%
산화프로필렌 6.02×10-3몰Propylene Oxide 6.02 × 10 -3 Mole
1-메톡시 -2-히드록시 프로판 : 52.0×10-3몰1-methoxy-2-hydroxy propane: 52.0 × 10 -3 moles
2-메톡시 -1-히드록시 프로판 : 34.6×10-3몰2-methoxy-1-hydroxy propane: 34.6 × 10 -3 moles
[실시예 12]Example 12
250cc 용량의 작은 유리 플라스크에 페놀, 99.8g ; 물 24.2g ; 아세톤 18.5g 또한 촉매를 실시예 5에서와 같이 차례대로 주입한다.99.8 g of phenol in a 250 cc small glass flask; Water 24.2 g; 18.5 g of acetone. The catalyst is also injected in sequence as in Example 5.
이 반응 혼합물을 교반하면서 100℃로 가열하고 환류시키고 다음에 같은 조건에서 45분 이내에 60% w/ w의 H2O215.4g를 점적해서 첨가한다.The reaction mixture is heated to 100 ° C. with stirring and refluxed, and then 15.4 g of H 2 O 2 at 60% w / w is added dropwise within 45 minutes under the same conditions.
첨가시작 60분후에 모든 H2O2는 전환되었으며, 반응 생성물은 가스 크로마토그래피로 분석하였다.After 60 minutes of addition all H 2 O 2 was converted and the reaction product was analyzed by gas chromatography.
H2O2의 잔유량은 피치와 O2로 전환된다. 수득한 디페놀에서 오르토/파라의 비는 1.26이다.The residual amount of H 2 O 2 is converted to pitch and O 2 . The ratio of ortho / para in the diphenol obtained is 1.26.
[표 1]TABLE 1
Claims (7)
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KR1019900013293A KR900009149B1 (en) | 1986-08-04 | 1990-08-28 | Catalyst based on silicon titanium and gallium |
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KR2019860011690U KR890008385Y1 (en) | 1986-08-04 | 1986-08-04 | Circuit for sensing on-use of branched telephone |
IT8622070A IT1213363B (en) | 1986-10-22 | 1986-10-22 | SYNTHETIC MATERIAL POROUS CRYSTALLINE CONTAINING SILICON OXIDES TITANIUM AND GALLIUM. |
IT22070A/86 | 1987-11-06 | ||
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