ES2172063T3 - Procedimiento para la descomposicion de hidroperoxido de cumeno. - Google Patents
Procedimiento para la descomposicion de hidroperoxido de cumeno.Info
- Publication number
- ES2172063T3 ES2172063T3 ES98112218T ES98112218T ES2172063T3 ES 2172063 T3 ES2172063 T3 ES 2172063T3 ES 98112218 T ES98112218 T ES 98112218T ES 98112218 T ES98112218 T ES 98112218T ES 2172063 T3 ES2172063 T3 ES 2172063T3
- Authority
- ES
- Spain
- Prior art keywords
- decomposition
- procedure
- cumen hydroperoxide
- cumen
- hydroperoxide
- 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.)
- Expired - Lifetime
Links
- 238000000354 decomposition reaction Methods 0.000 title abstract 3
- 238000000034 method Methods 0.000 title abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical group CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/517—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of peroxy-compounds to >C = O groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/40—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals
- C07C15/42—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic
- C07C15/44—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts substituted by unsaturated carbon radicals monocyclic the hydrocarbon substituent containing a carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
LA INVENCION SE REFIERE A UN METODO PARA MEJORAR LA DESCOMPOSICION DE CHP EN FENOL Y ACETONA, EL CUAL COMPRENDE LA PRESENCIA DE AGUA ADICIONAL EN EL REACTOR DE DESCOMPOSICION DE CHP.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/944,688 US5254751A (en) | 1992-09-14 | 1992-09-14 | Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| ES2172063T3 true ES2172063T3 (es) | 2002-09-16 |
Family
ID=25481882
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES93307016T Expired - Lifetime ES2127253T5 (es) | 1992-09-14 | 1993-09-06 | Procedimiento para la produccion de fenol, acetona y alfa-metilestireno. |
| ES96202123T Expired - Lifetime ES2148669T3 (es) | 1992-09-14 | 1993-09-06 | Procedimiento para la descomposicion de hidroperoxido de cumeno. |
| ES98112218T Expired - Lifetime ES2172063T3 (es) | 1992-09-14 | 1993-09-06 | Procedimiento para la descomposicion de hidroperoxido de cumeno. |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ES93307016T Expired - Lifetime ES2127253T5 (es) | 1992-09-14 | 1993-09-06 | Procedimiento para la produccion de fenol, acetona y alfa-metilestireno. |
| ES96202123T Expired - Lifetime ES2148669T3 (es) | 1992-09-14 | 1993-09-06 | Procedimiento para la descomposicion de hidroperoxido de cumeno. |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5254751A (es) |
| EP (4) | EP0589588B2 (es) |
| JP (3) | JP3268082B2 (es) |
| KR (1) | KR0161540B1 (es) |
| CN (3) | CN1071293C (es) |
| CA (1) | CA2105187A1 (es) |
| DE (4) | DE69331564T2 (es) |
| ES (3) | ES2127253T5 (es) |
Families Citing this family (61)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166752B2 (en) * | 1989-01-17 | 2007-01-23 | Sunoco, Inc. (R&M) | Decomposition of cumene oxidation product |
| US5371305A (en) * | 1992-12-31 | 1994-12-06 | Hercules Incorporated | Process for producing phenol from cumene |
| RU2108318C1 (ru) * | 1994-03-01 | 1998-04-10 | Закошанский Владимир Михайлович | СПОСОБ ПОЛУЧЕНИЯ ФЕНОЛА, АЦЕТОНА И α МЕТИЛСТИРОЛА |
| JP3711504B2 (ja) * | 1994-03-01 | 2005-11-02 | ゼネラル・エレクトリック・カンパニイ | 工業用クメンヒドロペルオキシドのフェノール、アセトン及びα−メチルスチレンへの酸分解方法 |
| US5457244A (en) * | 1994-10-04 | 1995-10-10 | General Electric Company | Phenol tar waste reduction process |
| TW318174B (es) * | 1994-11-04 | 1997-10-21 | Gen Electric | |
| CA2161995A1 (en) * | 1994-11-23 | 1996-05-24 | Arkady S. Dyckman | Method of phenol tar desalting |
| US5510543A (en) * | 1994-12-09 | 1996-04-23 | General Electric Company | Removal and neutralization of acid catalyst from products of cumene hydroperoxide cleavage |
| US5463136A (en) * | 1994-12-22 | 1995-10-31 | Shell Oil Company | Cumene hydroperoxide cleavage process |
| JP3769050B2 (ja) * | 1995-07-07 | 2006-04-19 | 三井化学株式会社 | フェノールの製造方法 |
| US5672774A (en) * | 1995-10-24 | 1997-09-30 | General Electric Company | Phenol tar processing method |
| US5962751A (en) * | 1996-04-26 | 1999-10-05 | General Electric Company | Phenol tar desalting method |
| RU2125038C1 (ru) * | 1996-09-24 | 1999-01-20 | Закошанский Владимир Михайлович | Безотходный экономичный способ получения фенола и ацетона |
| RU2141938C1 (ru) | 1996-12-15 | 1999-11-27 | ООО "Илла Интернешнл", Лтд. | Энергосберегающий и высокоселективный способ получения фенола и ацетона (процесс иф-96) |
| RU2114816C1 (ru) * | 1997-02-13 | 1998-07-10 | Открытое акционерное общество "Казаньоргсинтез" | Способ разложения гидроперекиси кумола кислотным катализатором на фенол и ацетон |
| RU2142932C1 (ru) * | 1997-11-03 | 1999-12-20 | Закошанский Владимир Михайлович | Высокоселективный способ получения фенола и ацетона (процесс фан-98) |
| WO2000014042A1 (en) * | 1998-09-04 | 2000-03-16 | Illa International L.L.C. | High selective method of phenol and acetone production |
| DE19858770A1 (de) * | 1998-12-18 | 2000-06-21 | Phenolchemie Gmbh & Co Kg | Verfahren zur Herstellung von Phenol und Aceton durch säurekatalysierte Spaltung von Cumolhydroperoxid |
| DE19911024B4 (de) * | 1999-03-12 | 2005-09-08 | Phenolchemie Gmbh & Co. Kg | Verfahren zum Anfahren von Schlaufenreaktorsystemen, in denen zumindest eine exotherme Reaktion durchgeführt werden soll |
| US6201157B1 (en) * | 2000-01-10 | 2001-03-13 | Sunoco, Inc. (R&M) | Method for production of phenol and acetone by decomposition of cumene hydroperoxide |
| DE10021482A1 (de) * | 2000-05-03 | 2001-11-08 | Phenolchemie Gmbh & Co Kg | Verfahren zur thermischen Nachbehandlung von Spaltprodukt aus der säurekatalysierten Spaltung von Cumolhydroperoxid |
| RU2179167C1 (ru) * | 2000-09-29 | 2002-02-10 | Открытое акционерное общество "Всероссийский научно-исследовательский институт органического синтеза" | СПОСОБ ПОЛУЧЕНИЯ ФЕНОЛА, АЦЕТОНА И α-МЕТИЛСТИРОЛА |
| DE10051581A1 (de) * | 2000-10-18 | 2002-06-20 | Phenolchemie Gmbh & Co Kg | Verfahren zur Spaltung von Alkylarylhydroperoxiden |
| DE10111889A1 (de) * | 2001-03-13 | 2002-10-02 | Phenolchemie Gmbh & Co Kg | Verfahren zur säurekatalysierten Spaltung von Cumolhydroperoxid |
| RU2231045C2 (ru) * | 2002-05-20 | 2004-06-20 | Общество с ограниченной ответственностью "Еврохим-СпбТрейдинг" | Способ измерения концентрации гидропероксидов алкилароматических углеводородов в жидких промышленных потоках |
| US7282613B2 (en) * | 2003-02-14 | 2007-10-16 | Shell Oil Company | Process for producing phenol and methyl ethyl ketone |
| US7141703B2 (en) * | 2003-02-14 | 2006-11-28 | Shell Oil Company | Process for producing phenol and ketone using neutralizing base |
| US7312365B2 (en) * | 2003-02-14 | 2007-12-25 | Shell Oil Company | Process for low temperature cleavage of an oxidation mixture comprising hydroperoxides |
| US7626060B2 (en) * | 2003-07-11 | 2009-12-01 | INEOS Phenol GmbH & Co., KG | Process for the preparation of phenolic compounds, for separating phenol from cleavage product mixtures, and an apparatus |
| KR20070002039A (ko) * | 2004-03-31 | 2007-01-04 | 제너럴 일렉트릭 캄파니 | 페놀의 제조방법 |
| US7141701B1 (en) * | 2005-08-19 | 2006-11-28 | Uop Llc | Decomposition of cumene hydroperoxide |
| US7141700B1 (en) * | 2005-08-19 | 2006-11-28 | Uop Llc | Decomposition of cumene hydroperoxide |
| WO2007137021A2 (en) * | 2006-05-16 | 2007-11-29 | Shell Oil Company | Catalysts comprising a combination of oxidized metals and a method for cleaving phenylalkyl hydroperoxides using the catalysts |
| US20100063329A1 (en) * | 2006-05-16 | 2010-03-11 | John Charles Saukaitis | Method for decomposing di(phenylalkyl)peroxides to produce hydroxybenzenes and phenylalkenes using solid catalysts |
| US7888537B2 (en) * | 2006-12-29 | 2011-02-15 | Uop Llc | Solid acid catalyst and process for decomposition of cumene hydroperoxide |
| US8445730B2 (en) | 2008-10-10 | 2013-05-21 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US8592634B2 (en) | 2009-02-26 | 2013-11-26 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| WO2012145030A1 (en) | 2011-04-19 | 2012-10-26 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US20110306800A1 (en) * | 2010-06-09 | 2011-12-15 | Scott Roy Keenan | Method for the decomposition of cumene hydroperoxide |
| CN105646156B (zh) | 2010-09-14 | 2018-07-13 | 埃克森美孚化学专利公司 | 用于制备苯酚的方法 |
| CN103052618B (zh) | 2010-09-14 | 2015-08-05 | 埃克森美孚化学专利公司 | 生产苯酚的方法 |
| WO2012036826A2 (en) | 2010-09-14 | 2012-03-22 | Exxonmobil Chemical Patents Inc. | Processes for producing phenol |
| US8921610B2 (en) | 2010-09-14 | 2014-12-30 | Exxonmobil Chemical Patents Inc. | Oxidation of alkylbenzenes |
| WO2012067711A1 (en) | 2010-11-16 | 2012-05-24 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US9388102B2 (en) | 2011-04-19 | 2016-07-12 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| EP2699347B1 (en) | 2011-04-19 | 2016-10-05 | ExxonMobil Chemical Patents Inc. | Process for producing phenol |
| WO2012145032A2 (en) | 2011-04-19 | 2012-10-26 | Exxonmobil Chemical Patents Inc. | Method for producing phenol and/or cyclohexanone |
| US9469589B2 (en) | 2011-06-30 | 2016-10-18 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and/or cyclohexanone |
| US8697917B2 (en) * | 2011-09-19 | 2014-04-15 | Kellogg Brown & Root Llc | Methods and systems for co-producing a low-methanol content acetone |
| WO2013043271A1 (en) | 2011-09-23 | 2013-03-28 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US9067870B2 (en) | 2011-09-23 | 2015-06-30 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| WO2013052217A2 (en) | 2011-10-07 | 2013-04-11 | Exxonmobil Chemical Patents Inc. | Mixed metal oxide catalysts and use thereof |
| US8865957B2 (en) | 2012-03-09 | 2014-10-21 | Honeywell Intenational Inc. | Method for producing alpha-methyl styrene from cumene |
| WO2014209577A1 (en) | 2013-06-28 | 2014-12-31 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and/or cyclohexanone |
| WO2015161466A1 (en) | 2014-04-23 | 2015-10-29 | Dow Global Technologies Llc | Neutralization of acidic catalysts in production of phenol |
| CN104151144A (zh) * | 2014-07-16 | 2014-11-19 | 常州大学 | 一种过氧化氢异丙苯分解制苯酚/丙酮的方法 |
| RU2565764C1 (ru) | 2014-08-08 | 2015-10-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Способ получения фенола и ацетона |
| KR102040059B1 (ko) | 2016-11-14 | 2019-11-05 | 주식회사 엘지화학 | 페놀의 정제 방법 |
| CN110818536A (zh) * | 2019-11-13 | 2020-02-21 | 中国石油化工股份有限公司 | 一种采用微反应器装置催化分解过氧化氢异丙苯的方法 |
| CN114426463B (zh) * | 2020-10-13 | 2024-05-28 | 中国石油化工股份有限公司 | 制备间苯二酚的方法 |
| US11858874B2 (en) | 2020-12-21 | 2024-01-02 | Lg Chem, Ltd. | Method for preparing alpha-methylstyrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA482145A (en) | 1952-04-01 | Harold Hall Reginald | Decomposition of organic peroxides | |
| DE976951C (de) * | 1947-02-13 | 1964-08-06 | The Distillers Comp. Ltd., Edinburgh (Grossbritannien) | Verfahren zur Herstellung von Phenolen durch unvollständige Oxydation von Benzolderivaten |
| IT486308A (es) * | 1949-12-30 | |||
| US2668180A (en) * | 1950-07-01 | 1954-02-02 | Hercules Powder Co Ltd | Preparation of aryldialkyl peroxides |
| US2757209A (en) * | 1951-04-26 | 1956-07-31 | Allied Chem & Dye Corp | Recovery of phenol and alphamethylstyrene from cumene oxidation reaction mixtures |
| US2761877A (en) | 1951-05-17 | 1956-09-04 | Rhone Poulenc Sa | Production of phenols and carbonyl compounds |
| FR1109297A (fr) * | 1953-07-30 | 1956-01-24 | California Research Corp | Procédé de fabrication de l'acétone |
| US2904592A (en) † | 1953-07-30 | 1959-09-15 | California Research Corp | Production of acetone |
| GB864486A (en) * | 1957-05-27 | 1961-04-06 | It Resine Soc | Process for manufacturing phenol and acetone from cumene hydro-peroxide |
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| GB1202687A (en) * | 1968-03-28 | 1970-08-19 | Sir Soc Italiana Resine Spa | Process for preparing phenol and acetone |
| US4207264A (en) | 1969-10-29 | 1980-06-10 | The Goodyear Tire & Rubber Company | Rearrangement of aralkyl hydroperoxides to form phenols and carbonyl compounds |
| US3927124A (en) | 1970-03-05 | 1975-12-16 | Goodyear Tire & Rubber | Process for the neutralization of alkyl aromatic hydroperoxide rearrangement reaction products |
| US3899538A (en) | 1970-12-14 | 1975-08-12 | Sun Ventures Inc | Acid-catalyzed decomposition of aliphatic hydroperoxides |
| US4016213A (en) * | 1971-05-03 | 1977-04-05 | Allied Chemical Corporation | Recovery of phenol, acetone and dimethyl phenyl carbinol from cumene oxidation product |
| SU537066A1 (ru) * | 1974-01-25 | 1976-11-30 | Казанский Ордена Октябрьской Революции Завод Органического Синтеза | Способ получени фенола и ацетона |
| GB1499666A (en) | 1974-05-06 | 1978-02-01 | Burmah Oil Trading Ltd | Production of phenols |
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| JPS5289609A (en) | 1976-01-21 | 1977-07-27 | Sumitomo Chem Co Ltd | Prpduction of aromatic hydroxides and alifatic ketones |
| US4297518A (en) | 1977-11-18 | 1981-10-27 | Gulf Research & Development Company | Decomposition of cumene hydroperoxide with a homogeneous catalyst |
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| SU721395A1 (ru) | 1977-12-01 | 1980-03-15 | Омское специальное конструкторское бюро Научно-производственного объединения "Нефтехимавтоматика" | Способ автоматического регулировани процессом разложени гидроперекиси изопропилбензола |
| DD149857A3 (de) | 1978-05-26 | 1981-08-05 | Bernd Haase | Verfahren zur herstellung von phenol-und aceton aus cumolhydroperoxid |
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| SU1131865A1 (ru) | 1983-07-07 | 1984-12-30 | Предприятие П/Я А-1748 | Способ получени фенола и ацетона |
| IT1187662B (it) | 1985-04-23 | 1987-12-23 | Enichem Sintesi | Catalizzatore per la decomposizione selettiva del cumilidroperossido e procedimento utilizzante lo stesso |
| JPH0251408A (ja) * | 1988-08-12 | 1990-02-21 | Toshiba Tungaloy Co Ltd | 炭化タングステンを過飽和に含有してなる固溶体組成物及びその製造方法 |
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| US4870217A (en) | 1988-10-24 | 1989-09-26 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| US4898987A (en) | 1989-03-17 | 1990-02-06 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| US4898995A (en) | 1988-10-24 | 1990-02-06 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| US4876397A (en) | 1988-10-24 | 1989-10-24 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| US5015786A (en) | 1988-11-28 | 1991-05-14 | Mitsui Petrochemical Industries Inc. | Preparation of cumene through alkylation of an aromatic compound and preparation of phenol through cumene |
| EP0492807A3 (en) | 1990-12-27 | 1992-08-12 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| US5245090A (en) | 1992-09-11 | 1993-09-14 | Aristech Chemical Corporation | Two-stage cleavage of cumene hydroperoxide |
-
1992
- 1992-09-14 US US07/944,688 patent/US5254751A/en not_active Ceased
-
1993
- 1993-08-19 CA CA002105187A patent/CA2105187A1/en not_active Abandoned
- 1993-09-06 DE DE69331564T patent/DE69331564T2/de not_active Expired - Lifetime
- 1993-09-06 ES ES93307016T patent/ES2127253T5/es not_active Expired - Lifetime
- 1993-09-06 ES ES96202123T patent/ES2148669T3/es not_active Expired - Lifetime
- 1993-09-06 DE DE69329300T patent/DE69329300T2/de not_active Expired - Lifetime
- 1993-09-06 EP EP93307016A patent/EP0589588B2/en not_active Expired - Lifetime
- 1993-09-06 EP EP01112781A patent/EP1142855B1/en not_active Expired - Lifetime
- 1993-09-06 EP EP96202123A patent/EP0738698B1/en not_active Expired - Lifetime
- 1993-09-06 EP EP98112218A patent/EP0873983B1/en not_active Expired - Lifetime
- 1993-09-06 DE DE69323140T patent/DE69323140T3/de not_active Expired - Lifetime
- 1993-09-06 DE DE69333863T patent/DE69333863T2/de not_active Expired - Lifetime
- 1993-09-06 ES ES98112218T patent/ES2172063T3/es not_active Expired - Lifetime
- 1993-09-11 CN CN93117275A patent/CN1071293C/zh not_active Expired - Lifetime
- 1993-09-13 KR KR1019930018372A patent/KR0161540B1/ko not_active Expired - Lifetime
- 1993-09-14 JP JP22882993A patent/JP3268082B2/ja not_active Expired - Fee Related
-
1995
- 1995-10-19 US US08/545,092 patent/USRE40668E1/en not_active Expired - Lifetime
-
1997
- 1997-11-25 JP JP32255697A patent/JP3281587B2/ja not_active Expired - Fee Related
-
1999
- 1999-04-30 CN CN99105393A patent/CN1101371C/zh not_active Expired - Lifetime
- 1999-04-30 CN CN99105392A patent/CN1088051C/zh not_active Expired - Lifetime
-
2001
- 2001-10-24 JP JP2001325724A patent/JP3797914B2/ja not_active Expired - Fee Related
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