WO2015078592A1 - Procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine - Google Patents

Procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine Download PDF

Info

Publication number
WO2015078592A1
WO2015078592A1 PCT/EP2014/003188 EP2014003188W WO2015078592A1 WO 2015078592 A1 WO2015078592 A1 WO 2015078592A1 EP 2014003188 W EP2014003188 W EP 2014003188W WO 2015078592 A1 WO2015078592 A1 WO 2015078592A1
Authority
WO
WIPO (PCT)
Prior art keywords
epichlorohydrin
epoxy
hexene
hexadiene
ech
Prior art date
Application number
PCT/EP2014/003188
Other languages
English (en)
Inventor
Jimmy Antonius Van Rijn
Joachim Lienke
Original Assignee
Hexion Research Belgium S.A.
Momentive Specialty Chemicals Inc.,
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from EP13075078.9A external-priority patent/EP2878597A1/fr
Application filed by Hexion Research Belgium S.A., Momentive Specialty Chemicals Inc., filed Critical Hexion Research Belgium S.A.
Publication of WO2015078592A1 publication Critical patent/WO2015078592A1/fr

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
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids

Definitions

  • This invention concerns a process to remove 1 , 2-epoxy-5-hexene from epichlorohydrin which is produced by oxidation of
  • unpurified allyl chloride comprising at least 1 , 5-hexadiene as impurity .
  • TCP trichloropropane
  • the CN , 102417490 provides a process for
  • ECH containing 1 , 2-epoxy-5-hexene contaminant 1 , 2-epoxy-5-hexene is treated with excess chlorine or bromine at a temperature in the range of 5 to 30°C.
  • the 1 , 2-epoxy-5-hexene was then converted into a product with a significantly higher boiling temperature. Next, remaining halogen was removed by flushing with nitrogen.
  • reaction is carried out in a separate reactor, where the halogen is added to the ECH. Therefore, an extra reactor setup is required, increasing capital costs. Also chlorinated organic compounds are produced, which are generally harmful for the environment and do not have direct application.
  • the reaction is carried out at temperatures that require active cooling of the ECH, even below ambient temperatures.
  • the reaction temperature according to this reference is 0-30°C, preferably 0-15°C, more preferably 0-5°C.
  • the current inventors set out to solve the problem arising from allyl chloride containing 1 , 5-hexadiene impurity by an
  • the current invention provides a process for removing 1 , 2-epo.xy-5-hexene and 1,5 hexadiene from ECH by:
  • ECH 1, 5-hexadiene, 1 , 2-epoxy-5-hexene with hydrogen peroxide and a transition metal complex containing compound as catalyst.
  • the current invention allows to employ allyl chloride
  • the product of the contaminant is ' 1,2,5,6- diepoxyhexane , also known as 1 , 5-hexadiene diepoxide.
  • This has a boiling point of.l88°C (62°C at a reduced pressure of 30 ⁇ mm Hg) . Its boiling point is therefore' significantly different from ECH, which facilitates the separation of the product ' .
  • the 1 , 2 , 5 , 6-diepoxyhexane may be used, for instance in resin compositions. The ' latter is a significant advantage over other processes, like chlorination, where the products formed are considered useless.
  • Step (a) is preferably carried out by contacting the organic phase of a mixture comprising at least allyl chloride,
  • the preferred oxidant for the reaction is hydrogen peroxide.
  • Other oxidants may be used, i.e. as precursor to the hydrogen
  • Hydrogen peroxide has strong oxidizing properties. It is typically used in an aqueous solution.
  • the oxidation catalyst is preferably chosen from transition metal catalysts active in oxidation or epoxidations with hydrogen peroxide as the oxidant.
  • Typical catalysts contain transition metals like manganese, tungsten, titanium,
  • molybdenum molybdenum, rhenium, silver, vanadium and iron.
  • the oxidation is conducted with a homogenous catalyst, such as manganese or tungsten.
  • a homogenous catalyst such as manganese or tungsten.
  • suitable catalysts that have a favourable solubility in either water or the organic phase, desired reactivity towards epoxidation and stability against
  • One preferable class " of catalyst comprises manganese complexes incorporating cycling nitrogen containing compounds, the manganese catalyst preferably contains a tertiary substituted nitrogen ligand.
  • Another preferable class of catalysts comprises tungsten salts or their acids in the presence of phosphates. Also
  • phosphotungstate salts or their acids can be used. These compounds are used in the absence of organic ligands, but in the presence of a phase transfer agent.
  • the oxidant is preferably added to the aqueous reaction medium at a rate about equal to the reaction rate of the catalytic oxidation.
  • the catalytic oxidation may be performed in a batch process, in a continuous process or in a semi-continuous process.
  • step (a) is performed in a common stirred tank reactor provided with a means of stirring.
  • the catalyst, aqueous reaction medium ' and reactants may be added, in batch, or the reactants may be added over a period of time. If hydrogen peroxide is added during the reaction, then it is added to either the (stirred) organic phase comprising the crude ECH or the (stirred) aqueous reaction medium.
  • various recycling streams may be used to control the reaction conditions and to optimize the production rate.
  • a settler may be added to optimize " the gravitational separation of the organic phase containing the ECH .
  • a membrane unit may be used to recycle the. agueous reaction medium with reduced loss of catalyst.
  • step (a) the product comprising crude ECH which is subjected to rectification steps (b) and (c) . Rectification conditions, such as distillation and fractional distillation, are known in the art .
  • unreacted allyl chloride (for recycle purposes) and light ends such as 1 , 5-hexadiene , chloropropanes , and
  • chloropropenes and the like are removed as part of step (b) in one or more stages from the crude ECH first.
  • a typical ECH composition (crude after reaction) is as follow:
  • the crude ECH is subjected to distillation, preferably in a perforated-plate column, bubble-cap plate column and/or packed column. This may be a single column or a series of columns.
  • the column is preferably equipped with an evaporation or heating device (or an evaporation or heating area or zone) located at or near the bottom of the column (or below the first plate) . It is furnished with means to introduce an inlet stream at a point intermediate between the bottom and the top of the column; means to withdraw a lower-boiling stream at or near the top of the column, and means to withdraw a hi.gher-boiling stream at or near the bottom of the column and possibly means to withdraw a product stream at- an intermediate point on the column .
  • an evaporation or heating device or an evaporation or heating area or zone located at or near the bottom of the column (or below the first plate) . It is furnished with means to introduce an inlet stream at a point intermediate between the bottom and the top of the column; means to withdraw a lower-boiling stream at or near the top of the column, and means to withdraw a hi.gher-boiling stream at or near the bottom of the column and possibly means to withdraw a product
  • a lower-boiling stream is continuously drawn off at the head of the column and a higher-boiling ' stream is
  • the TCP was not detectable in the crude ECH. Further
  • the 1 , 2-epoxy-5-hexene in the ECH is converted into a higher boiling product, this is achieved by epoxidizing the mono-epoxide into the corresponding diepoxide.
  • this contaminant can effectively be removed.
  • this may lead to the production of 1,2,5,6- diepoxyhexane that can be cleanly separated and form an
  • reaction conditions during epoxidation of crude ECH are such that on molar basis at least 45% of the contaminant 1 , 5-hexadiene is converted into 1,2,5,6- diepoxyhexane and thus can be collected during distillation in the fraction that has a higher boiling point than ECH.
  • Desired reaction conditions according to this inventio are those in which the rate of the consecutive reactions are such that formation of 1 , 2 , 5 , 6-diepoxyhexane from 1, 2-epoxy-5-hexene. is at least 0.50 that of the formation of 1 , 2-epoxy-5-hexene from 1 , 5-hexadiene .
  • Somebody ordinary skilled in the. art ca derive those conditions from theoretical considerations as ' for example explained in Chemical Reactor Development, Dirk Thoenes or by variation of reactor types and reaction conditions such as phase ratio or residence time.
  • 2-epoxy-5-hexene can lead to reduced peroxide yields defined as the molar ratio of ECH produced over hydrogen peroxide charged. It can also lead to a reduction in turn over numbers defined as molar ratio of ECH produced over catalyst charged. Without being bound to any specific theory it is fair to assume that a high conversion of 1 , 2-epoxy-5-hexene to 1,2,5,6- diepoxyhexane is coupled to relatively low concentrations of allyl chloride in the reaction media which results in side, reactions of the epoxidation becoming more favourable, such as decomposition of peroxide and decomposition of ECH .
  • this invention might be best practised when the removal of 1 , 2-epoxy-5-hexene is high, while the decrease in Yield and TON is small to nihil.
  • the present invention of removal of 1 , 2-epoxy-5-hexene via epoxidation can be combined with other techniques known in the , art. This includes "bleeding" a fraction of the allyl chloride recycle stream removing low boiling side products of the allyl chloride productions that will accumulate or chlorination of - remaining 1 , 2-epoxy-5-hexene in epichlorohydrin .
  • the flows of the components are 0.24 mol per hour of hydrogen peroxide, 9.0 micromol per hour of catalyst, 2.5 millimol per hour of oxalic acid and 0.79 mol per hour of crude ECH. pH is maintained between pH 3.2 and 4.0. Temperature 1 . is set at 15 °C and the reaction volume is controlled at about 200 ml.
  • the catalyst used is a [Mn 2 ( ⁇ - 0) 3(1,4, 7-trimethyl-l , 4 , 7-triazacyclononane ⁇ 2 ] 2+ salt.
  • the starting allyl chloride contains 0.4 wt% 1 , 5-hexadiene as starting feedstock to produce the crude ECH. This results in a steady state yield of ECH based on the peroxide added of 72 % ⁇ and a diepoxide/monoepoxide (DO/BO) ratio of 1.
  • the allyl chloride contains 1.2 wt% 1,5- hexadiene as starting feedstock to produce the crude ECH. This results in a steady state yield based on the peroxide added of 69 %, and a DO/BO ratio of.1.
  • the product of the organic phase of examples 1-7 are further purified by distillation according to a method as given above in the description.
  • the crude composition of the organic phase has an average composition as given of the table below:
  • Additional distillation can be performed to remove light (allyl chloride) and heavy boiling components further (DO).
  • the ECH obtained had the following composition, as was determined by gas chromatography.
  • the EGH-.purity obtained by the process has given in the above examples is superior to 99.10 weight % and free, of

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

L'invention concerne un procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine qui est produite par oxydation de chlorure d'allyle non purifié comprenant au moins 1,5-hexadiène en tant qu'impureté.
PCT/EP2014/003188 2013-11-28 2014-11-25 Procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine WO2015078592A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP13075078.9A EP2878597A1 (fr) 2013-11-28 2013-11-28 Procédé pour l'élimination de 1,2-époxy-5-hexène de l'épichlorhydrine
EP13075078.9 2013-11-28
EP13005597 2013-12-02
EP13005597.3 2013-12-02
EP14075044 2014-07-11
EP14075044.9 2014-07-11

Publications (1)

Publication Number Publication Date
WO2015078592A1 true WO2015078592A1 (fr) 2015-06-04

Family

ID=51987119

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/003188 WO2015078592A1 (fr) 2013-11-28 2014-11-25 Procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine

Country Status (2)

Country Link
TW (1) TW201522320A (fr)
WO (1) WO2015078592A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970683A (zh) * 2017-12-28 2019-07-05 中国石油化工股份有限公司 环氧氯丙烷的分离方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110183305A (zh) * 2019-06-04 2019-08-30 山东凯泰科技股份有限公司 一种直接氧化法生产环氧氯丙烷的原料氯丙烯预处理工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010012360A1 (fr) * 2008-08-01 2010-02-04 Hexion Specialty Chemicals Research Belgium S.A. Procédé de fabrication d’épichlorhydrine du glycérol utilisant du peroxyde d’hydrogène et un complexe de manganèse
CN102417490A (zh) * 2011-10-20 2012-04-18 江苏瑞祥化工有限公司 含烯烃杂质的环氧氯丙烷的提纯方法
WO2012175182A1 (fr) * 2011-06-22 2012-12-27 Momentive Specialty Chemicals Research Belgium Sa Appareil et procédés pour préserver l'activité catalytique dans un procédé d'époxydation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010012360A1 (fr) * 2008-08-01 2010-02-04 Hexion Specialty Chemicals Research Belgium S.A. Procédé de fabrication d’épichlorhydrine du glycérol utilisant du peroxyde d’hydrogène et un complexe de manganèse
WO2012175182A1 (fr) * 2011-06-22 2012-12-27 Momentive Specialty Chemicals Research Belgium Sa Appareil et procédés pour préserver l'activité catalytique dans un procédé d'époxydation
CN102417490A (zh) * 2011-10-20 2012-04-18 江苏瑞祥化工有限公司 含烯烃杂质的环氧氯丙烷的提纯方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109970683A (zh) * 2017-12-28 2019-07-05 中国石油化工股份有限公司 环氧氯丙烷的分离方法
CN109970683B (zh) * 2017-12-28 2020-09-22 中国石油化工股份有限公司 环氧氯丙烷的分离方法

Also Published As

Publication number Publication date
TW201522320A (zh) 2015-06-16

Similar Documents

Publication Publication Date Title
JP4705373B2 (ja) 粗製プロペンオキサイドの精製方法
KR100367135B1 (ko) 통합된에폭시화방법
KR100321509B1 (ko) 에폭사이드를 제조하는 통합 방법
KR102655920B1 (ko) 프로펜의 에폭시화 방법
JP2013079259A (ja) 過酸化物化合物を用いたオキシランの製造方法
JP2004506627A (ja) 酸化オレフィン類の一体化製造方法
EP2321292A2 (fr) Procédé de fabrication d'époxydes
EP1359148A1 (fr) Procédé d' époxydation des oléfines
KR20080096774A (ko) 직접 에폭시화 공정
JPS6346752B2 (fr)
WO2010024839A1 (fr) Procédé de fabrication d'oxyde de propylène
KR20030009354A (ko) 올레핀의 에폭시화 방법
JP5047444B2 (ja) エポキシドの一体化製法
JP2004238388A (ja) 有機化合物を選択的に酸化するための一体的な方法
US7687647B2 (en) Propylene oxide process
US6723861B2 (en) Method for producing oxirane
JP2006008544A (ja) プロピレンオキサイドの精製方法
JP5615797B2 (ja) エピクロロヒドリンの製造方法
WO2015078592A1 (fr) Procédé d'extraction de 1,2-époxy-5-hexène à partir de l'épichlorohydrine
EP1419146A1 (fr) Procede d'epoxydation d'olefines
TW200303865A (en) Process for purification of propylene oxide
JP7018880B2 (ja) プロピレンオキサイドの製造方法
WO2003024901A1 (fr) Procede de fabrication de cumene
EP2878597A1 (fr) Procédé pour l'élimination de 1,2-époxy-5-hexène de l'épichlorhydrine
JP2009007294A (ja) プロピレンオキサイドの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14803053

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14803053

Country of ref document: EP

Kind code of ref document: A1