KR20060037500A - Synthesis method of imidazole-heteropolyate and production method of propylene oxide using same - Google Patents
Synthesis method of imidazole-heteropolyate and production method of propylene oxide using same Download PDFInfo
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- KR20060037500A KR20060037500A KR1020040086449A KR20040086449A KR20060037500A KR 20060037500 A KR20060037500 A KR 20060037500A KR 1020040086449 A KR1020040086449 A KR 1020040086449A KR 20040086449 A KR20040086449 A KR 20040086449A KR 20060037500 A KR20060037500 A KR 20060037500A
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- imidazole
- heteropoly acid
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- heteropolyacid
- propylene oxide
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 9
- 238000001308 synthesis method Methods 0.000 title description 2
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 43
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
본 발명은 이미다졸-헤테로폴리산 염을 제공한다. 또한, 이미다졸-헤테로폴리산 염을 이용한 프로필렌 옥사이드 합성 방법을 제공한다.
The present invention provides imidazole-heteropoly acid salts. Also provided is a method for synthesizing propylene oxide using imidazole-heteropolyacid salts.
헤테로폴리산, 이미다졸, 이미다졸-헤테로폴리산 염, 프로필렌 옥사이드Heteropolyacids, imidazoles, imidazole-heteropoly acid salts, propylene oxide
Description
프로필렌 옥사이드는 폴리우레탄 수지, 코팅, 접착제 등을 생산하는 화학 중간체로서 다양하게 사용된다. 또한, 프로필렌 옥사이드는 프로필렌글리콜 (섬유유리-강화 플라스틱), 계면활성제, 화장품, 제약제품, 포장물질, 염료, 수력학적 유체, 기름 및 에멀젼 등으로 변활될 수 있다. 현재 세계적으로 년간 약 5,000,000 톤 정도가 생산되고 있으며, 수요에 비하여 그 생산이 매우 부족한 실정이다. 기존의 PO 제조 공정은 Chlorohydrin process와 Peroxidation process에 의해 제조되지만, 이들은 모두 2단계 반응을 거치는 간접적인 제조방법이며, 유해성 높은 산화제를 이용하고, 발생하는 부생성물이 많은 문제점들로 인하여 이들의 대체 공정에 대한 관심이 집중되어 왔다. Propylene oxide is used in a variety of chemical intermediates to produce polyurethane resins, coatings, adhesives and the like. Propylene oxide can also be converted to propylene glycol (fiberglass-reinforced plastics), surfactants, cosmetics, pharmaceuticals, packaging materials, dyes, hydraulic fluids, oils, emulsions, and the like. Currently, about 5,000,000 tons are produced annually in the world, and their production is very low compared to demand. Conventional PO manufacturing processes are produced by the Chlorohydrin process and the peroxidation process, but they are all indirect manufacturing methods that go through a two-step reaction.They are alternative processes due to the use of hazardous oxidizers and many byproducts. Attention has been focused on.
미국특허 4,474,979 및 일본특허 095,772 등은 클로로하이드린을 이용한 프로필렌 옥사이드의 생산 공정을 개시하고 있다. 이 공정은 전세계 프로필렌 옥사이 드 생산량의 55% 이상을 점유하고 있으며, CaCl2가 부산물로 나온다. U.S. Patent 4,474,979, Japanese Patent 095,772 and the like disclose a process for producing propylene oxide using chlorohydrin. The process accounts for more than 55% of the world's propylene oxide production, with CaCl 2 as a byproduct.
그러나, 이 공정의 문제점은 다량의 염소 가스를 사용한다는 것인데, 염소 가스는 고가(高價)임과 동시에 유독하며, 부식성이 매우 강한 기체이기 때문에 공정 전체가 매우 위험하다. 또한 부산물로 염소계 유기물을 내놓을 수 있기 때문에 환경적으로 매우 부담스러운 공정이다. However, the problem with this process is that it uses a large amount of chlorine gas, which is very dangerous and highly toxic and highly corrosive gas, making the whole process very dangerous. In addition, it is an environmentally burdensome process because chlorine-based organics can be produced as a by-product.
Peroxidation process는 유기 과산화물을 사용하는 공정으로, 부산물이 PO 자체보다 더 많이 생산되며, 반응물이 매우 비싸다는 문제점이 있다. 그러므로 부산물인 phenylethanol이 어느 정도 가치를 가지느냐에 따라서 공정의 경제성이 결정된다. The peroxidation process is a process using organic peroxides, and more by-products are produced than PO itself, and the reactants are very expensive. Therefore, the economic value of the process depends on the value of the by-product phenylethanol.
이러한 문제점을 해결하기 위해 미국특허 4,410,501와 4,833,260 등에는 TS-1 촉매를 사용한 프로필렌 옥사이드 합성 공정이 개시되어 있다. 이 공정은 Titanium silicate를 촉매로 사용하고, 과산화수소 생산 공정을 병합시킨 것으로 높은 PO 수율을 얻을 수 있는 것으로 보고 되고 있다. In order to solve this problem, US Pat. Nos. 4,410,501 and 4,833,260 disclose a process for synthesizing propylene oxide using a TS-1 catalyst. This process is a combination of Titanium silicate as a catalyst and hydrogen peroxide production process has been reported to achieve high PO yield.
이 공정과 관련하여 미국 특허 6,635,793과 6,670,491 등에서는 TS-1 촉매를 비롯하여 다양한 귀금속 및 산화물계 촉매의 제조방법과 프로필렌 옥사이드 생산 공정이 개시되어 있으며, 일본 특허 117,101 등에서도 유사한 종류의 촉매를 제공하고 있다. 따라서, 프로필렌 옥사이드 합성 반응에는 오랫동안 TS-1 촉매가 가장 좋은 촉매로 알려져 있다. 그러나, 아직까지 TS-1을 대체할 만한 새로운 촉매가 보고되고 있지 않다. In connection with this process, US Pat. Nos. 6,635,793 and 6,670,491 disclose a process for producing various noble metals and oxide catalysts, including TS-1 catalysts, and a process for producing propylene oxide, and Japanese Patent 117,101, etc., to provide similar catalysts. . Therefore, TS-1 catalyst has long been known as the best catalyst for the propylene oxide synthesis reaction. However, no new catalyst has yet been reported to replace TS-1.
이에 본 발명은 현재까지 문헌상으로 전혀 보고된 바가 없는 이미다졸-헤테로폴리산 염을 프로필렌 옥사이드 합성 촉매로서 제공하고자 한다.
Accordingly, the present invention seeks to provide an imidazole-heteropolyacid salt, which has not been reported in the literature at all, as a propylene oxide synthesis catalyst.
본 발명이 이루고자 하는 기술적 과제는 이미다졸-헤테로폴리산 염을 제공하고자 하는 것이다. The technical problem to be achieved by the present invention is to provide an imidazole-heteropoly acid salt.
또한, 본 발명이 이루고자 하는 다른 기술적 과제는 상기 이미다졸-헤테로폴리산 염을 이용한 프로필렌 옥사이드 합성 방법을 제공하는 것이다.
In addition, another technical problem to be achieved by the present invention is to provide a propylene oxide synthesis method using the imidazole-heteropoly acid salt.
본 발명은 이미다졸-헤테로폴리산 염을 제공한다. The present invention provides imidazole-heteropoly acid salts.
상기 목적을 위하여 본 발명에 따르면,According to the present invention for this purpose,
(A) 다음의 구조를 갖는 이미다졸 군으로부터 선택된 하나 혹은 그 이상의 이미다졸을 준비하는 단계(A) preparing one or more imidazoles selected from the group of imidazoles having the structure
(R1, R2, R3, R4는 수소(H) 혹은 탄화수소류)
(R1, R2, R3, R4 are hydrogen (H) or hydrocarbons)
(B) 상기의 이미다졸을 증류수에 용해시키는 단계
(B) dissolving the imidazole in distilled water
(C) 다음의 구조를 갖는 헤테로폴리산으로 이루어진 군에서 선택된 하나 혹은 그 이상의 물질을 준비하는 단계(C) preparing one or more materials selected from the group consisting of heteropolyacids having the structure
Hm[XxYyOz]nH2O H m [ X x Y y O z ] n H 2 O
(X: B, Al, Ga, Si, Ge, Sn, P, As, Sb, Te, I, 제 1, 2, 3 그룹 전이 금속, Y: 제 1, 2, 3 그룹 전이 금속)
(X: B, Al, Ga, Si, Ge, Sn, P, As, Sb, Te, I, 1st, 2, 3 group transition metal, Y: 1st, 2, 3 group transition metal)
(D) 상기의 헤테로폴리산을 증류수에 용해시키는 단계
(D) dissolving the heteropolyacid in distilled water
(E) 상기의 헤테로폴리산 수용액에 (B) 단계에서 준비한 이미다졸 수용액을 헤테로폴리산과 이미다졸의 몰 비율이 1 : 0.1에서 1 : 3의 비율로 혼합시키는 단계
(E) mixing the aqueous solution of imidazole prepared in step (B) with the aqueous solution of heteropoly acid and imidazole in a ratio of 1: 0.1 to 1: 3
(F) 상기의 헤테로폴리산과 이미다졸 혼합용액을 상온에서 12시간 이상 교반하여 헤테로폴리산-이미다졸 염을 형성시키는 단계
(F) stirring the heteropolyacid and imidazole mixed solution at room temperature for 12 hours or more to form a heteropolyacid-imidazole salt
(G) 상기의 이미다졸-헤테로폴리산 염을 감압여과 및 원심분리하여 고형분만을 분리해내는 단계
(G) separating the solids only by filtration and centrifugation of the imidazole-heteropoly acid salt
(H) 상기의 이미다졸-헤테로폴리산 염을 증류수에 장시간 교반하여 세척해주는 단계
(H) a step of washing by stirring the imidazole-heteropoly acid salt in distilled water for a long time
(I) (G)와 (H) 단계를 반복하여 잔류하는 이미다졸을 완전히 제거하는 단계
(I) repeating steps (G) and (H) to completely remove residual imidazole
(J) 상기의 헤테로폴리산-이미다졸 염을 80℃에서 12시간 이상 건조하는 단계를 포함하는 것을 특징으로 하는 이미다졸-헤테로폴리산 염의 제조방법이 제공된다.
(J) A method for preparing an imidazole-heteropoly acid salt comprising the step of drying the heteropolyacid-imidazole salt at least 12 hours at 80 ° C is provided.
한편, 본 발명은 상기의 이미다졸-헤테로폴리산 염 외에도 이미다졸-헤테로폴리산 염을 사용한 프로필렌 옥사이드 합성 공정이 제공된다. Meanwhile, the present invention provides a propylene oxide synthesis process using an imidazole-heteropoly acid salt in addition to the imidazole-heteropoly acid salt.
상기 목적을 위하여 본 발명에 따르면,According to the present invention for this purpose,
(A) 고압 반응기에 이미다졸-헤테로폴리산 염을 넣는 단계
(A) adding imidazole-heteropoly acid salt to a high pressure reactor
(B) 일정량의 과산화수소수를 반응기로 직접 도입하거나, 과산화수소수를 생산할 수 있는 특정 공정을 반응기와 연결하여 과산화수소수를 반응기로 도입하는 단계
(B) introducing hydrogen peroxide water into the reactor by introducing a certain amount of hydrogen peroxide water directly into the reactor, or by connecting a specific process capable of producing hydrogen peroxide water to the reactor;
(C) 일정량의 프로필렌 기체를 반응기로 도입하는 단계
(C) introducing an amount of propylene gas into the reactor
(D) 압력범위 0.1 - 1 MPa 과 온도범위 40-100℃에서 반응기를 운전하여 프로필렌 옥사이드를 합성하는 단계를 포함하는 것을 특징으로 하는 이미다졸-헤테로폴리산염을 사용한 프로필렌 옥사이드 합성 공정이 제공된다. (D) A propylene oxide synthesis process is provided using an imidazole-heteropolyacid comprising the step of synthesizing propylene oxide by operating a reactor at a pressure range of 0.1-1 MPa and a temperature range of 40-100 ° C.
본 발명에서는 이미다졸-헤테로폴리산염을 제조하였으며, 이를 프로필렌 옥사이드 합성 공정에 응용하였다. 이하 실시예에 의해 본 발명의 이미다졸-헤테로폴리산 염을 제조하고, 프로필렌 옥사이드 합성 과정을 구체적으로 설명하되, 본 발명이 반드시 이에 한정된 것은 아니다. In the present invention, imidazole-heteropolyacid was prepared and applied to the propylene oxide synthesis process. Hereinafter, the imidazole-heteropolyacid salt of the present invention is prepared by the following examples, and the propylene oxide synthesis process will be described in detail, but the present invention is not necessarily limited thereto.
<실시예 1><Example 1>
이미다졸-헤테로폴리산 염의 합성Synthesis of Imidazole-Heteropoly Acid Salt
5M의 이미다졸 (C3N2H4) 수용액을 0.1M 헤테로폴리산 (H3PW12O40) 수용액에 3:1(몰비) 비율로 첨가하여 24시간 반응시켜 침전물을 얻고, 이를 원심분리하고, 세척하였다. 얻어진 분말을 80℃에서 충분히 건조한 뒤 사용하였다.
5M aqueous solution of imidazole (C3N2H4) was added to a 0.1M aqueous solution of heteropolyacid (H3PW12O40) in a 3: 1 (molar ratio) ratio to react for 24 hours to obtain a precipitate, which was centrifuged and washed. The obtained powder was used after drying sufficiently at 80 ° C.
<비교예 1>Comparative Example 1
TS-1 촉매의 합성Synthesis of TS-1 Catalyst
테트라에톡시 실리케이트 (Si(C2H5)4) 45g과 테트라프로필 암모늄하이드록사이드 (C3H7)3NOH) 용액 53g을 교반시키면서 혼합하였고, 별도의 용기에 티타늄 부톡사이드 (Ti(C4H9)4) 1.612g을 이소프로필 알콜 60g으로 희석한 다음 희석액을 상기 혼합물에 교반하면서 서서히 떨어뜨렸다. 15분 동안 교반을 해주면서 혼합물이 맑은 용액이 되는지를 확인한다. 이 맑은 용액에 테트라프로필 암모늄하이드록사이드 17g을 더 넣어서 다시 수분 동안 교반한 후 80℃로 승온시켜 4시간 동안 미반응 알콜을 제거한다. 70g의 물이 추가로 첨가되어 약 100 시간 동안의 결정화 시간을 갖는다. 전체적인 조성비는 Ti : Si : H2O : TPA+ : IPA = 0.2 : 1 : 25 : 0.32 : 0.77 으로 고정하였다. 최종적으로 얻어진 TS-1 용액은 원심분리기를 통해 고체의 형태로 얻고, 이를 다시 650℃에서 열처리하여 사용하였다.
45 g of tetraethoxy silicate (Si (C2H5) 4) and 53 g of tetrapropyl ammonium hydroxide (C3H7) 3NOH) solution were mixed with stirring, and 1.612 g of titanium butoxide (Ti (C4H9) 4) was separated in a separate vessel. Dilution with 60 g of propyl alcohol was followed by dropwise dilution with stirring to the mixture. Stir for 15 minutes to see if the mixture is a clear solution. 17 g of tetrapropyl ammonium hydroxide was further added to the clear solution, stirred for several minutes, and then heated to 80 ° C. to remove unreacted alcohol for 4 hours. An additional 70 g of water has a crystallization time of about 100 hours. The overall composition ratio was fixed to Ti: Si: H 2 O: TPA +: IPA = 0.2: 1: 25: 0.32: 0.77. The finally obtained TS-1 solution was obtained in the form of a solid through a centrifuge, which was then used by heat treatment at 650 ° C.
<실시예 2><Example 2>
프로필렌 옥사이드의 합성 반응Synthesis Reaction of Propylene Oxide
온도와 압력이 조절되는 반응기에 촉매 30mg, H2O2(30%) 0.2ml를 넣고, 반응기의 압력이 0.4 MPa이 되도록 프로필렌 가스를 충전한다. 60℃를 유지하고, 3시간동안 반응하였다. 반응이 끝난 후에는 GC-Mass를 통해 프로필렌의 소모량의 소모량과 프로필렌 옥사이드의 생성량, 모모메틸에테르의 생성량, 프로필렌글리콜의 생성량을 측정하여 선택도와 전환율을 계산하였다. 30 mg of catalyst and 0.2 ml of H 2 O 2 (30%) were added to a reactor in which temperature and pressure were controlled, and propylene gas was charged so that the pressure of the reactor was 0.4 MPa. The reaction was maintained at 60 ° C. for 3 hours. After the reaction, the selectivity and conversion rate were calculated by measuring the consumption of propylene, the production of propylene oxide, the production of momomethyl ether, and the production of propylene glycol through GC-Mass.
표 1은 <실시예 1>의 이미다졸-헤테로폴리산 염과 <비교예 2>의 TS-1 촉매의 프로필렌 전환율과 프로필렌 옥사이드 선택도이다. 이미다졸-헤테로폴리산 염의 프로필렌 옥사이드 선택도가 TS-1 촉매보다 높은 것을 확인할 수 있다.
Table 1 shows propylene conversion and propylene oxide selectivity of the imidazole-heteropolyacid salt of <Example 1> and the TS-1 catalyst of <Comparative Example 2>. It can be seen that the propylene oxide selectivity of the imidazole-heteropoly acid salt is higher than the TS-1 catalyst.
본 발명에서는 이미다졸-헤테로폴리산 염을 제조하였으며, 이를 프로필렌 옥사이드 합성 공정에 응용하였다.In the present invention, the imidazole-heteropoly acid salt was prepared and applied to the propylene oxide synthesis process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103357434A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Synthesizing method of heteropolyacid imidazolium salt catalyst |
| CN103360594A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Method for preparing polytetramethylene ether glycol by using imidazole polyoxometalate catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103357434A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Synthesizing method of heteropolyacid imidazolium salt catalyst |
| CN103360594A (en) * | 2013-07-18 | 2013-10-23 | 吕涛 | Method for preparing polytetramethylene ether glycol by using imidazole polyoxometalate catalyst |
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