JP2005097177A - Method for purifying propylene oxide - Google Patents
Method for purifying propylene oxide Download PDFInfo
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Abstract
Description
本発明は、プロピレンオキサイドの精製方法に関するものである。更に詳しくは、本発明は、軽沸成分除去工程を含むプロピレンオキサイド方法であって、精製すべきプロピレンオキサイドを含む溶液中に存在する不純物を効率的に除去することができるというという優れた特徴を有するプロピレンオキサイドの精製方法に関するものである。 The present invention relates to a method for purifying propylene oxide. More specifically, the present invention is a propylene oxide method including a light-boiling component removing step, and has an excellent feature that impurities present in a solution containing propylene oxide to be purified can be efficiently removed. The present invention relates to a method for purifying propylene oxide.
プロピレンオキサイドを製造する方法として、触媒存在下、クメンハイドロパーオキサイドとプロピレンを反応させる方法が知られている。かかる反応で得られる反応液中には目的物であるプロピレンオキサイドの他に、不純物として水、炭化水素、メタノール、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、アセトン、ギ酸メチル等の化合物が含まれているのが一般である。よって、反応液から高純度のプロピレンオキサイドを分離・回収するための精製工程が必要となる。 As a method for producing propylene oxide, a method in which cumene hydroperoxide and propylene are reacted in the presence of a catalyst is known. In addition to the target propylene oxide, impurities such as water, hydrocarbons, methanol, formaldehyde, acetaldehyde, propionaldehyde, acetone, and methyl formate are included in the reaction solution obtained by such a reaction. It is common. Therefore, a purification process for separating and recovering high-purity propylene oxide from the reaction solution is required.
プロピレンオキサイドの精製において、炭化水素を抽剤として使用することは公知である。たとえば、特許文献１には、オクタンのようなアルカンが、炭素数６を有する炭化水素不純物の除去に効果的であることが示されている。また、特許文献２には、オクタンのようなアルカンが水の除去に効果的であることが示されている。更に、特許文献３には、プロピレンオキサイド中に含まれるメタノール、プロピオンアルデヒド、アセトン等の不純物の除去にオクタン等の炭化水素が効果的であることが示されている。 It is known to use hydrocarbons as extractants in the purification of propylene oxide. For example, Patent Document 1 shows that an alkane such as octane is effective in removing hydrocarbon impurities having 6 carbon atoms. Patent Document 2 shows that alkanes such as octane are effective in removing water. Further, Patent Document 3 shows that hydrocarbons such as octane are effective in removing impurities such as methanol, propionaldehyde, and acetone contained in propylene oxide.
しかしながら、従来の方法においては、アルデヒド類の除去方法に関しての記載が十分でなく、従来の方法をそのまま実施いた場合には、ホルムアルデヒドやアセトアルデヒド等の沸点の低いアルデヒド類が高濃度で濃縮するストリームにおいては、ポリアセタール類の固形物が析出し、配管の閉塞等により連続的な運転が困難になるという問題があった。 However, in the conventional method, the description regarding the method for removing aldehydes is not sufficient, and when the conventional method is carried out as it is, in a stream in which aldehydes having a low boiling point such as formaldehyde and acetaldehyde are concentrated at a high concentration. However, there was a problem that solid operations such as polyacetals were deposited, and continuous operation became difficult due to blockage of piping.
かかる現状において、本発明が解決しようとする課題は、軽沸成分除去工程を含むプロピレンオキサイド方法であって、精製すべきプロピレンオキサイドを含む溶液中に存在する不純物を効率的に除去することができるというという優れた特徴を有するプロピレンオキサイドの精製方法を提供する点に存するものである。 Under such circumstances, the problem to be solved by the present invention is a propylene oxide method including a light boiling component removing step, which can efficiently remove impurities present in a solution containing propylene oxide to be purified. The present invention resides in providing a method for purifying propylene oxide having such excellent characteristics.
すなわち、本発明は、下記の軽沸成分除去工程を含むプロピレンオキサイドの精製方法であって、軽沸成分除去工程の留出ストリーム中のホルムアルデヒド（ｍｏｌ）／メタノール（ｍｏｌ）比が１以下であるプロピレンオキサイドの精製方法に係わるものである。
軽沸成分除去工程：プロピレンオキサイドに含まれる不純物の中で沸点の低い成分を蒸留により分離する工程
That is, the present invention is a method for purifying propylene oxide including the following light boiling component removal step, wherein the formaldehyde (mol) / methanol (mol) ratio in the distillate stream of the light boiling component removal step is 1 or less. The present invention relates to a method for purifying propylene oxide.
Light boiling component removal step: A step of separating components having low boiling points from impurities contained in propylene oxide by distillation.
本発明により、軽沸成分除去工程を含むプロピレンオキサイド方法であって、精製すべきプロピレンオキサイドを含む溶液中に存在する不純物を効率的に除去することができるというという優れた特徴を有するプロピレンオキサイドの精製方法を提供することができた。 According to the present invention, there is provided a propylene oxide method including a light boiling component removing step, which has an excellent feature that impurities existing in a solution containing propylene oxide to be purified can be efficiently removed. A purification method could be provided.
本発明の精製方法に付される原料液は、軽沸成分を含むプロピレンオキサイドである。 The raw material liquid to be subjected to the purification method of the present invention is propylene oxide containing a light boiling component.
本発明の軽沸成分除去工程は、原料液に含まれる不純物の中で沸点の低い成分を蒸留により分離する工程であり、蒸留の条件としては、除去される軽沸成分が気化しやすい条件を用いることが有利であり、具体的には、蒸留に供給される液の温度や組成によっても変化するが、通常、圧力はゲージ圧で０〜１ＭＰａ、好ましくは０〜０．２ＭＰａ、塔頂温度０〜１００℃である。 The light boiling component removal step of the present invention is a step of separating components having a low boiling point among impurities contained in the raw material liquid by distillation, and the conditions for the distillation are such that the light boiling component to be removed is easily vaporized. It is advantageous to use, and specifically varies depending on the temperature and composition of the liquid supplied to the distillation, but usually the pressure is 0 to 1 MPa in gauge pressure, preferably 0 to 0.2 MPa, the tower top temperature. 0-100 ° C.
本発明で除去される軽沸成分としては、ホルムアルデヒド、アセトアルデヒド、Ｃ１からＣ５の炭化水素等があげられる。過酸化物を酸化剤として用い、プロピレンを酸化して得られた粗プロピレンオキサイド中にはＣ１からＣ９、もしくはそれ以上の炭化水素が含まれるが、Ｃ１からＣ２の炭化水素は通常は過剰量用いられる原料のプロピレンを分離する工程で主に除去し、Ｃ６以上の炭化水素は重沸成分として別途蒸留により除去することが可能である。したがって本発明の軽沸成分除去工程により除去され得る炭化水素はＣ３からＣ５の炭化水素である。 Examples of the light boiling component removed in the present invention include formaldehyde, acetaldehyde, C1 to C5 hydrocarbons, and the like. The crude propylene oxide obtained by oxidizing the propylene with peroxide as an oxidizing agent contains C1 to C9 or higher hydrocarbons, but usually C1 to C2 hydrocarbons are used in excess. The raw material propylene is mainly removed in the process of separating the raw material propylene, and C6 or higher hydrocarbons can be separately removed by distillation as a heavy boiling component. Therefore, the hydrocarbons that can be removed by the light boiling component removal step of the present invention are C3 to C5 hydrocarbons.
本発明において、軽沸成分除去工程における留出ストリーム中のホルムアルデヒド（ｍｏｌ）／メタノール（ｍｏｌ）比が１以下である必要がある。留出ストリーム中のホルムアルデヒド（ｍｏｌ）／メタノール（ｍｏｌ）比を１よりも大きくして該軽沸成分除去工程を実施した場合には、ホルムアルデヒド、アセトアルデヒド等が高濃度で濃縮する部位、例えば、蒸留等塔頂付近、還流ドラム、熱交換器、およびそれらをつなぐ配管、次工程へ繋がる配管、送液ポンプ等でポリアセタール類を容易に生成する。特に、熱交換器、外気温の影響を受けやすい配管およびタンク類、減圧弁の近辺等、他の部位より低温になりやすい部位でポリアセタール類が析出しやすく、配管やポンプ等の閉塞の原因となるため連続的な蒸留塔の運転に大きな支障となる。 In the present invention, the ratio of formaldehyde (mol) / methanol (mol) in the distillate stream in the light boiling component removal step needs to be 1 or less. When the light-boiling component removal step is carried out with the formaldehyde (mol) / methanol (mol) ratio in the distillate stream being greater than 1, a site where formaldehyde, acetaldehyde, etc. are concentrated at a high concentration, for example, distillation Polyacetals are easily generated by using the vicinity of the top of the equal tower, the reflux drum, the heat exchanger, the pipe connecting them, the pipe connected to the next process, the liquid feed pump, and the like. In particular, polyacetals are likely to precipitate at sites that tend to be cooler than other sites, such as heat exchangers, piping and tanks that are susceptible to the outside air temperature, and in the vicinity of pressure reducing valves, which may cause blockage of piping and pumps. Therefore, it becomes a big hindrance to the operation of a continuous distillation tower.
留出ストリーム中のホルムアルデヒド（ｍｏｌ）／メタノール（ｍｏｌ）比は、得られたプロピレンオキサイドの組成によっても大きく変化するが、ホルムアルデヒド（ｍｏｌ）／メタノール（ｍｏｌ）比が１よりも大きかった場合にこれを１以下にする方法としては、軽沸除去工程または本工程に至るまでの蒸留工程における蒸留条件をコントロールしてもよいし、メタノールを新たに追加することにより達成されてもよい。メタノールを新たに追加する部位としては蒸留に供されるプロピレンオキサイド液でもよいし、蒸留塔の中段部、蒸留塔の留出流、熱交換器、還流ドラム、送液ポンプ、およびそれらを繋ぐ配管等があげられ、特にストリームの温度が低下する熱交換器、還流ドラム、およびそれらを繋ぐ配管部位が好ましい。 The formaldehyde (mol) / methanol (mol) ratio in the distillate stream varies greatly depending on the composition of the propylene oxide obtained, but this is the case when the formaldehyde (mol) / methanol (mol) ratio is greater than 1. As a method of reducing the number to 1 or less, the distillation conditions in the light boiling removal step or the distillation step up to this step may be controlled, or may be achieved by newly adding methanol. The part where methanol is newly added may be a propylene oxide solution used for distillation, the middle part of the distillation column, the distillate flow of the distillation column, the heat exchanger, the reflux drum, the feed pump, and the piping connecting them. In particular, a heat exchanger in which the temperature of the stream is lowered, a reflux drum, and a piping portion connecting them are preferable.
本発明の精製方法は軽沸成分除去工程を含むが、本発明はそれにとどまらず、重沸成分除去工程等を組み合わせた複数の蒸留塔によって実施することができるし、不純物の吸着除去工程等を組み合わせて実施することもできる。 The purification method of the present invention includes a light boiling component removal step, but the present invention is not limited to this, and can be carried out by a plurality of distillation towers combined with a heavy boiling component removal step, etc. It can also be implemented in combination.
比較例１〜２および実施例１〜２
ホルムアルデヒドを含むプロピレンオキサイドにメタノールを添加し、２５℃で１８時間静置し、ポリアセタールの析出の有無を観察した。結果を表１に示す．
表中のＰＯはプロピレンオキサイド、ＦＡはホルムアルデヒド、ＭｅＯＨはメタノールを表す。
Comparative Examples 1-2 and Examples 1-2
Methanol was added to propylene oxide containing formaldehyde and allowed to stand at 25 ° C. for 18 hours, and the presence or absence of polyacetal precipitation was observed. The results are shown in Table 1.
In the table, PO represents propylene oxide, FA represents formaldehyde, and MeOH represents methanol.
Claims (3)
軽沸成分除去工程：プロピレンオキサイドに含まれる不純物の中で沸点の低い成分を蒸留により分離する工程 A method for purifying propylene oxide comprising the following light boiling component removal step, wherein the formaldehyde (mol) / methanol (mol) ratio in the distillate stream of the light boiling component removal step is 1 or less.
Light boiling component removal step: A step of separating components having low boiling points from impurities contained in propylene oxide by distillation.
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