WO2006075777A1 - プロピレンオキサイドの製造方法 - Google Patents
プロピレンオキサイドの製造方法 Download PDFInfo
- Publication number
- WO2006075777A1 WO2006075777A1 PCT/JP2006/300666 JP2006300666W WO2006075777A1 WO 2006075777 A1 WO2006075777 A1 WO 2006075777A1 JP 2006300666 W JP2006300666 W JP 2006300666W WO 2006075777 A1 WO2006075777 A1 WO 2006075777A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- propylene
- epoxidation
- supplied
- reaction
- reactor
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
Definitions
- the present invention relates to a method for producing propylene oxide. More specifically, the present invention relates to the production of propylene oxide in which an organic peroxide and propylene are supplied to an epoxidation reactor filled with an epoxidation solid catalyst, and propylene oxide is continuously produced by an epoxidation reaction. Is the method. Background
- the object of the present invention is to supply an organic peroxide and propylene to an epoxidation reactor filled with an epoxidation solid catalyst, and to produce propylene oxide continuously by epoxidation reaction.
- the production method of the present invention which is capable of avoiding a situation in which the catalyst is destroyed due to the pressure loss of the solid catalyst layer that has increased along with the production, and the production amount must be reduced.
- Another object of the present invention is to provide a method for producing propylene oxide having
- the present invention relates to an epoxidation reactor filled with an epoxidation solid catalyst.
- a method for producing propylene oxide in which an organic peroxide and propylene are supplied to the reactor and the propylene oxide is continuously produced by an epoxidation reaction, comprising the following propylene oxide pretreatment step. It is related to the law.
- Propylene pretreatment step A step of treating at least part of propylene supplied to the epoxidation reactor, and removing oxygen-containing organic compounds contained in propylene.
- FIG. 1 is a graph showing the transition (change over time) in the pressure difference between the inlet and outlet of the reactor corresponding to the pressure loss of the solid catalyst layer in Example 1 described later.
- an organic peroxide and propylene are supplied to an epoxidation reactor filled with a solid catalyst for epoxidation, and propylene oxide is continuously produced by an epoxidation reaction.
- a titanium-containing silicon oxide catalyst is used from the viewpoint of obtaining a desired product in a high yield.
- These catalysts are preferably so-called titanium-silicic force catalysts containing titanium chemically bonded to silicon oxide.
- a titanium compound supported on a silica carrier, a compound compounded with silicon oxide by a coprecipitation method or a sol-gel method, or a zeolite compound containing titanium can be used.
- the particle size of the titanium-containing silicon oxide catalyst charged in the epoxidation reactor is not particularly limited, and can be determined as appropriate in consideration of the shape and size of the reactor. 0 mm, more preferably 0.25 to 5 mm. If the particle diameter is too small, the pressure loss of the solid catalyst layer may increase. On the other hand, if it is too large, the yield of propylene oxide may decrease. Examples of organic peroxides include cumene high dropper oxide, ethylbenzen eight dropper oxide, tert-butyl high dropper oxide, etc. Can give.
- the organic peroxide supplied to the epoxidation reactor is synthesized by oxidation of the corresponding hydrocarbon compound (for example, cumene, ethylbenzene, isobutane, etc. in the above organic peroxide, respectively).
- the organic acid generated during the oxidation reaction also acts as a catalyst poison for the epoxidation catalyst. Therefore, as the organic peroxide supplied to the epoxidation reactor, it is preferable to use an organic peroxide from which organic acid has been removed. As a method of removing, for example, it is preferable to contact with an aqueous solution of a compound containing an alkali metal during and / or after the oxidation reaction.
- Examples of the compound containing an alkali metal include sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate and the like, and any of these compounds or a mixed aqueous solution thereof can be used.
- the concentration of the alkali metal in the aqueous solution is preferably 0.05 to 10% by weight. If the concentration is too low, the removal effect of the organic acid may be insufficient. On the other hand, if the concentration is too high, the decomposition reaction of the generated organic peroxide is promoted and the yield decreases. There is. After contact with an aqueous solution of a compound containing an alkali metal, it is usually separated into an oil phase Z aqueous phase, and the organic acid is removed from the oil phase.
- the oil phase after separation from the aqueous phase often contains a trace amount of water. Since this water reduces the yield of the epoxidation reaction and also acts as a catalyst poison, it is preferable to remove it as much as possible.
- the method for removing water include a method of removing using a separation membrane such as coalescer, a method of consuming and removing by a reaction, a method of removing by distillation, and the like. It is preferable to use and remove.
- the solution containing the organic peroxide thus obtained is fed to the epoxidation reactor.
- the epoxidation reaction is carried out in the liquid phase using a solvent.
- the solvent must be liquid under the temperature and pressure during the reaction and be substantially inert to the reactants and products.
- the solvent may consist of substances present in the organic peroxide solution used.
- cumene hydride peroxide is a mixture with its raw material cumene
- ethyl benzene hydroperoxide is a mixture with its raw material ethylbenzene
- tert-butyl hydroperoxide is the raw material.
- the epoxidation reaction temperature is generally 0 to 200 ° C., but a temperature of 25 to 200 ° C. is preferred.
- the pressure may be sufficient to keep the reaction mixture in a liquid state. In general, the pressure is advantageously between 0.1 and 1 OMPa.
- the molar ratio of propylene-no-organic peroxide fed to the epoxidation reactor is 2! ⁇ 50Z 1 is preferred. If the ratio is less than the range, the reaction rate decreases and the efficiency is poor. On the other hand, if the ratio is more than the range, the excess of unreacted propylene is recycled from the epoxidation reaction solution. Separation ⁇ Recovering process requires a lot of energy.
- the liquid linear velocity of the reaction liquid (mixture) in the fixed bed continuous method of the present invention varies depending on the composition of the mixture and the particle size of the solid catalyst, but is generally preferably 0.1 to 3 c / sec. . If the liquid line speed falls below that range, drift may occur in the solid catalyst layer in the reactor, while if it exceeds this range, the pressure loss in the solid catalyst layer may increase.
- Distillation can be used as a method for separating and recovering unreacted propylene.
- Distillation usually uses conditions where propylene is easily vaporized from the reaction solution.
- the distillation conditions vary depending on the temperature and composition of the reaction solution supplied to the distillation process, but usually the pressure is 0 to 5 MPa in gauge pressure, preferably 0 to 3 MPa, and the top temperature is 50 to 1 50 ° C, tower bottom temperature 5 0-20 0 ° C, preferably 8 0-2 0 0 ° C I can give you.
- a method of distilling propylene in stages using a plurality of distillation columns may be used.
- the unreacted propylene separated and recovered in this way can be mixed with newly supplied propylene and supplied to the epoxidation reactor.
- the solid catalyst layer of the epoxidation reactor The problem of increased pressure loss occurred.
- the organic peroxide supplied to the epoxidation reactor is in contact with an aqueous solution of a compound containing an alkali metal, and the propylene supplied to the epoxidation reactor is unreacted after the epoxidation reaction.
- the increase in pressure loss of the solid catalyst layer of the epoxidation reactor was particularly remarkable.
- the said subject was able to be solved by performing the following pre-processing process to propylene.
- the propylene pretreatment step is a step of treating at least a part of propylene supplied to the epoxidation reactor, and is a step of removing oxygenated organic compounds contained in propylene.
- oxygen-containing organic compounds examples include formaldehyde, acetoaldehyde, formic acid, methanol and the like.
- Oxygenated organic compounds are often generated in the epoxidation reactor.
- the oxygenated organic compound generated in the epoxidation reactor is contained in unreacted propylene separated and recovered from the mixed solution after the epoxidation reaction, and as the propylene is recycled and supplied to the epoxidation reactor, Supplied into the epoxidation reactor.
- Examples of the method for removing the oxygen-containing organic compound contained in propylene include a method of removing by washing with water, a method of removing by distillation, and a method of removing by adsorbent. Among them, the method of washing propylene with water is preferable because the oxygen-containing organic compound contained in propylene can be efficiently removed. Specific examples of washing propylene with water are as follows: It is.
- the propylene supplied to the epoxidation reactor is usually a mixture of unreacted propylene separated and recovered from the mixed solution after the epoxidation reaction and newly supplied propylene.
- Examples of the method for washing propylene with water include a method for washing gaseous propylene with water, a method for bringing liquid propylene into contact with water, and the like.
- propylene supplied to the epoxidation reactor is usually in liquid form, contact efficiency, volume necessary for contact, etc., a method of contacting liquid propylene with water is preferable.
- the liquid propylene is washed by contacting part or all of it with water before being fed to the epoxidation reactor.
- a method of contact with water a method of simply cutting water into the pipe to mix and contact in the pipe, or a method of increasing the contact efficiency with a mixer or the like can be used.
- the mixer include a stirrer / mixer comprising a stirrer and a container, but a pipe-scaled one such as a static mixer can also be used if the contact efficiency is sufficient.
- the contact condition any condition may be used as long as it is sufficiently washed.
- Preferred examples include a propylene water weight ratio of 0.1 to 200, a contact temperature of 4 to 120, The contact time can be increased to 1 to 180 seconds (excluding static and separation time). Propylene mixed and contacted with water is separated into an oil phase and an aqueous phase by standing.
- the standing and separation time is 1 to 300 minutes, and the temperature is 4 to 120 ° C.
- the oxygenated organic compound concentration in the propylene after washing, standing and separation is preferably 20 ppm by weight or less, more preferably 30 ppm by weight or less as the concentration of each oxygenated organic compound. is there. Washing, standing and separation conditions are selected so that such propylene is obtained. Since the separated aqueous phase contains oxygen-containing organic compounds, it is discarded out of the system or used in other processes if possible. Some of them may be recycled and used again for propylene washing.
- the separated oil phase may be supplied to the epoxidation reactor as it is, but the remaining water reduces the yield of the epoxidation reaction and also acts as a catalyst poison. Therefore, it is preferable to remove as much as possible.
- the method of removing water include a method of removing using a separation membrane such as coalescer, a method of consuming and removing by a reaction, a method of removing by adsorption with an adsorbent, a method of removing by distillation, and the like. .
- propylene oxide can be efficiently produced from an organic peroxide and propylene.
- the Ti-containing silicon oxide catalyst prepared according to Example 1 of Japanese Patent Laid-Open No. 2 004-1 9 53 7 9 is screened to a particle size of 0.25 to 0.5 mm and fixed by SUS.
- a bed flow reactor was charged.
- 2 A solution containing 5% by weight cumene high dropper oxide and propylene (formaldehyde concentration less than 10 wt p pm) obtained in the following propylene pretreatment step were used under the conditions of a weight ratio of 1: 1 and liquid linear velocity of 2 cm / sec.
- the epoxidation reaction was carried out by feeding continuously, and simultaneously the pressure changes at the inlet and outlet of the reactor were observed.
- the reaction temperature was 80, and the reaction pressure was 4.2 MPa as a gauge pressure on the outlet side of the reactor.
- Figure 1 shows the change over time in the pressure difference between the inlet and outlet of the reactor corresponding to the pressure loss of the solid catalyst layer in this experiment.
- propylene (contains 50 wt-pm formaldehyde) 30 g / hr, 30 g / hr water, 7 cm long Propylene was washed with water by feeding it (contact time: about 5 seconds). At this time, the contact temperature was room temperature, the system pressure was 2 MPa, liquid propylene and water were brought into contact with each other, washed with water, and then allowed to stand to separate into propylene and an aqueous phase. The formaldehyde concentration in the resulting propylene is 10 weight! ) It was less than pm.
- a method for producing propylene oxide comprising supplying an organic peroxide and propylene to an epoxidation reactor filled with a solid catalyst, and continuously producing propylene oxide by an epoxidation reaction.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06700853A EP1837334A4 (en) | 2005-01-14 | 2006-01-12 | PROCESS FOR PRODUCING PROPYLENE OXIDE |
CN2006800022625A CN101103010B (zh) | 2005-01-14 | 2006-01-12 | 1,2-环氧丙烷的制备方法 |
US11/813,293 US20090209771A1 (en) | 2005-01-14 | 2006-01-12 | Method for producing propylene oxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005007343 | 2005-01-14 | ||
JP2005-007343 | 2005-01-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006075777A1 true WO2006075777A1 (ja) | 2006-07-20 |
Family
ID=36677791
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2006/300666 WO2006075777A1 (ja) | 2005-01-14 | 2006-01-12 | プロピレンオキサイドの製造方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20090209771A1 (ja) |
EP (1) | EP1837334A4 (ja) |
KR (1) | KR20070094657A (ja) |
CN (1) | CN101103010B (ja) |
WO (1) | WO2006075777A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1931649A1 (en) * | 2005-08-25 | 2008-06-18 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104230855B (zh) * | 2013-06-17 | 2016-07-13 | 中国石油化工股份有限公司 | 过氧化氢异丙苯与丙烯环氧化的方法 |
CN105367520B (zh) * | 2014-08-27 | 2018-02-13 | 中国石油化工股份有限公司 | 制备环氧丙烷的方法 |
CN114082383B (zh) * | 2021-12-27 | 2023-08-08 | 红宝丽集团泰兴化学有限公司 | 环氧化反应稳定性的提升方法及提升装置 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430106A (en) * | 1977-08-05 | 1979-03-06 | Halcon Res & Dev | Method of purifying propylene oxide |
JP2001031662A (ja) * | 1999-07-14 | 2001-02-06 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081953A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081955A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081954A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003238547A (ja) * | 2002-02-15 | 2003-08-27 | Sumitomo Chem Co Ltd | プロピレンオキサイドの精製方法 |
JP2005089379A (ja) * | 2003-09-18 | 2005-04-07 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの精製方法 |
JP2005089405A (ja) * | 2003-09-19 | 2005-04-07 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの製造方法 |
JP2005097208A (ja) * | 2003-09-26 | 2005-04-14 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4367342A (en) * | 1969-04-02 | 1983-01-04 | Shell Oil Company | Olefin epoxidation |
US3580819A (en) * | 1969-04-21 | 1971-05-25 | Shell Oil Co | Recovery of propylene and propylene oxide by selective separation with plural stage distillation,propylene oxide absorption and subsequent distillation |
FR2264012B1 (ja) * | 1974-03-13 | 1976-12-17 | Rhone Poulenc Ind | |
US5274138A (en) * | 1993-01-21 | 1993-12-28 | Texaco Chemical Company | Epoxidation process for manufacture of olefin oxide and alcohol |
US5675066A (en) * | 1995-09-05 | 1997-10-07 | Pioneer Hi-Bred International, Inc. | Inbred maize line PH06N |
US5723637A (en) * | 1995-12-06 | 1998-03-03 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
EP1074548B1 (en) * | 1999-08-06 | 2006-01-11 | Repsol Quimica S.A. | A method for continuous production of propylene oxide and other alkene oxides |
WO2001032561A1 (en) * | 1999-11-02 | 2001-05-10 | Shell Internationale Research Maatschappij B.V. | Process for the purification of industrial waste water from a propylene oxide production process |
US6844454B2 (en) * | 2002-04-12 | 2005-01-18 | Shell Oil Company | Process |
WO2004083196A1 (en) * | 2003-03-18 | 2004-09-30 | Dow Global Technologies Inc. | Purification of propylene oxide resulting from epoxidation of propylene with hydrogen peroxide |
-
2006
- 2006-01-12 US US11/813,293 patent/US20090209771A1/en not_active Abandoned
- 2006-01-12 CN CN2006800022625A patent/CN101103010B/zh not_active Expired - Fee Related
- 2006-01-12 WO PCT/JP2006/300666 patent/WO2006075777A1/ja active Application Filing
- 2006-01-12 EP EP06700853A patent/EP1837334A4/en not_active Withdrawn
- 2006-01-12 KR KR1020077018371A patent/KR20070094657A/ko not_active Application Discontinuation
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5430106A (en) * | 1977-08-05 | 1979-03-06 | Halcon Res & Dev | Method of purifying propylene oxide |
JP2001031662A (ja) * | 1999-07-14 | 2001-02-06 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081953A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081955A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003081954A (ja) * | 2001-09-12 | 2003-03-19 | Sumitomo Chem Co Ltd | プロピレンオキサイドの製造方法 |
JP2003238547A (ja) * | 2002-02-15 | 2003-08-27 | Sumitomo Chem Co Ltd | プロピレンオキサイドの精製方法 |
JP2005089379A (ja) * | 2003-09-18 | 2005-04-07 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの精製方法 |
JP2005089405A (ja) * | 2003-09-19 | 2005-04-07 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの製造方法 |
JP2005097208A (ja) * | 2003-09-26 | 2005-04-14 | Sumitomo Chemical Co Ltd | プロピレンオキサイドの製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1837334A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1931649A1 (en) * | 2005-08-25 | 2008-06-18 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
EP1931649A4 (en) * | 2005-08-25 | 2010-04-21 | Sumitomo Chemical Co | PROCESS FOR PRODUCTION OF PROPYLENE OXIDE |
US8481764B2 (en) | 2005-08-25 | 2013-07-09 | Sumitomo Chemical Company, Limited | Process for producing propylene oxide |
Also Published As
Publication number | Publication date |
---|---|
EP1837334A4 (en) | 2010-08-11 |
EP1837334A1 (en) | 2007-09-26 |
CN101103010B (zh) | 2011-07-27 |
US20090209771A1 (en) | 2009-08-20 |
CN101103010A (zh) | 2008-01-09 |
KR20070094657A (ko) | 2007-09-20 |
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