JP2001172228A - Method for producing hydroxyalkyl (meth)acrylate - Google Patents
Method for producing hydroxyalkyl (meth)acrylateInfo
- Publication number
- JP2001172228A JP2001172228A JP2000032340A JP2000032340A JP2001172228A JP 2001172228 A JP2001172228 A JP 2001172228A JP 2000032340 A JP2000032340 A JP 2000032340A JP 2000032340 A JP2000032340 A JP 2000032340A JP 2001172228 A JP2001172228 A JP 2001172228A
- Authority
- JP
- Japan
- Prior art keywords
- absorption
- meth
- alkylene oxide
- tower
- acrylate
- 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.)
- Granted
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 42
- 125000002768 hydroxyalkyl group Chemical group 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 238000010521 absorption reaction Methods 0.000 claims abstract description 135
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000002904 solvent Substances 0.000 claims abstract description 41
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 57
- 238000001816 cooling Methods 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 22
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003957 anion exchange resin Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、（メタ）アクリル
酸とアルキレンオキシドを反応させてヒドロキシアルキ
ル（メタ）アクリレートを製造する方法に関する。The present invention relates to a method for producing hydroxyalkyl (meth) acrylate by reacting (meth) acrylic acid with an alkylene oxide.
【０００２】[0002]
【従来の技術】（メタ）アクリル酸とアルキレンオキシ
ドを反応させてヒドロキシアルキル（メタ）アクリレー
トを製造するプロセスにおいて、副生成物の生成を抑
え、反応率を極力高くするため、アルキレンオキシドを
（メタ）アクリル酸よりも過剰モル量反応器に供給する
ことが知られている（特公昭４１−１３０１９号公報、
特公昭４３−１８８９０号公報等）。この場合、反応終
了時の反応液中に未反応のアルキレンオキシドが残存す
るため、分離した後、廃棄または回収再利用する必要が
ある。2. Description of the Related Art In a process for producing hydroxyalkyl (meth) acrylate by reacting (meth) acrylic acid with an alkylene oxide, in order to suppress the generation of by-products and to maximize the reaction rate, the alkylene oxide is converted to a (meth) acrylate. ) It is known that a molar amount of acrylic acid is supplied to a reactor (JP-B-41-13019,
JP-B-43-18890). In this case, since unreacted alkylene oxide remains in the reaction solution at the end of the reaction, it is necessary to separate, discard or collect and reuse it.
【０００３】また、反応液から分離したアルキレンオキ
シドを冷却、凝縮して回収再利用する場合にも、冷却に
多大なエネルギーを要するので経済的に不利であった。
そこで、特開平１０−３３０３２０号公報には、未反応
のエチレンオキシドを原料である（メタ）アクリル酸に
吸収させ、このエチレンオキシドを含む（メタ）アクリ
ル酸を付加反応に再利用することにより、未反応のエチ
レンオキシドを有効に利用できることが開示されている
が、回収効率の点では十分満足できるレベルとはいえな
い。Also, when cooling and condensing the alkylene oxide separated from the reaction solution to recover and reuse it, a large amount of energy is required for cooling, which is economically disadvantageous.
Therefore, Japanese Unexamined Patent Publication No. 10-330320 discloses that unreacted ethylene oxide is absorbed by (meth) acrylic acid as a raw material, and (meth) acrylic acid containing this ethylene oxide is reused in an addition reaction to thereby provide unreacted ethylene oxide. It is disclosed that ethylene oxide can be effectively used, but it cannot be said that the level of recovery efficiency is sufficiently satisfactory.
【０００４】[0004]
【発明が解決しようとする課題】したがって本発明が解
決しようとする課題は、（メタ）アクリル酸とアルキレ
ンオキシドを反応させてヒドロキシアルキル（メタ）ア
クリレートを製造する方法において、未反応アルキレン
オキシドを経済的、且つ、効率良く回収再利用できる方
法を提供することである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing hydroxyalkyl (meth) acrylate by reacting (meth) acrylic acid with alkylene oxide to reduce unreacted alkylene oxide. It is an object of the present invention to provide a method which can be efficiently and efficiently recovered and reused.
【０００５】[0005]
【課題を解決するための手段】本発明者は上記課題を解
決すべく鋭意検討した。その結果、アルキレンオキシド
の吸収効率は、吸収溶剤の温度が低いほど高くなること
に着目し、（１）吸収溶剤の凝固点が低いほど冷却温度
を低くできること、（２）アルキレンオキシド蒸気の吸
収により溶剤温度が上昇してしまうので、その吸収に伴
う溶剤温度の上昇を抑えることができれば、吸収効率も
向上すること、を考えた。そして、上記（１）の点よ
り、凝固点が（メタ）アクリル酸（凝固点：約１５℃）
に比べて非常に低いヒドロキシアルキル（メタ）アクリ
レート（凝固点：約−７０℃）を吸収溶剤に用いれば、
かなりの低温まで冷却でき、しかも、高効率で回収再利
用できることを見いだした。また、上記（２）の点よ
り、吸収工程の吸収後液の一部あるいは吸収工程途中の
吸収液の一部または全量を抜き出して冷却し、吸収工程
に再供給すれば、吸収溶剤の温度上昇を効率的に抑えら
れることを見いだした。本発明はこのようにして完成さ
れた。Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, focusing on the fact that the absorption efficiency of the alkylene oxide increases as the temperature of the absorption solvent decreases, (1) the cooling temperature can be reduced as the freezing point of the absorption solvent decreases, and (2) the solvent absorption by absorption of the alkylene oxide vapor. Since the temperature rises, it has been considered that if the rise in the solvent temperature due to the absorption can be suppressed, the absorption efficiency also improves. And, from the above point (1), the freezing point is (meth) acrylic acid (freezing point: about 15 ° C.)
If a very low hydroxyalkyl (meth) acrylate (freezing point: about -70 ° C) is used as the absorbing solvent,
It has been found that it can be cooled down to a very low temperature and that it can be recovered and reused with high efficiency. From the point of the above (2), if a part of the liquid after absorption in the absorption step or a part or the whole amount of the absorption liquid in the middle of the absorption step is extracted, cooled and supplied again to the absorption step, the temperature of the absorbing solvent rises. Was found to be efficiently controlled. The present invention has been completed in this manner.
【０００６】すなわち、本発明に係るヒドロキシアルキ
ル（メタ）アクリレートの製造方法は、（メタ）アクリ
ル酸とアルキレンオキシドを反応させ、反応液中の未反
応アルキレンオキシドを放散させて溶剤に吸収させる工
程を含む、ヒドロキシアルキル（メタ）アクリレートを
製造する方法において、前記吸収溶剤としてヒドロキシ
アルキル（メタ）アクリレート溶液を用いることを特徴
とする。また、本発明に係る別のヒドロキシアルキル
（メタ）アクリレートの製造方法は、（メタ）アクリル
酸とアルキレンオキシドを反応させ、反応液中の未反応
アルキレンオキシドを放散させて溶剤に吸収させる工程
を含む、ヒドロキシアルキル（メタ）アクリレートを製
造する方法において、前記吸収工程の吸収後液の一部を
冷却後、吸収工程に再供給することを特徴とする。That is, the method for producing a hydroxyalkyl (meth) acrylate according to the present invention comprises a step of reacting (meth) acrylic acid with an alkylene oxide, and dispersing unreacted alkylene oxide in the reaction solution to absorb it in a solvent. In the method for producing hydroxyalkyl (meth) acrylate, a hydroxyalkyl (meth) acrylate solution is used as the absorbing solvent. Further, another method for producing a hydroxyalkyl (meth) acrylate according to the present invention includes a step of reacting (meth) acrylic acid with an alkylene oxide, dispersing unreacted alkylene oxide in the reaction solution, and absorbing the unreacted alkylene oxide in a solvent. And a method for producing hydroxyalkyl (meth) acrylate, characterized in that a part of the liquid after absorption in the absorption step is cooled and then re-supplied to the absorption step.
【０００７】また、本発明に係る別のヒドロキシアルキ
ル（メタ）アクリレートの製造方法は、（メタ）アクリ
ル酸とアルキレンオキシドを反応させ、反応液中の未反
応アルキレンオキシドを放散させて溶剤に吸収させる工
程を含む、ヒドロキシアルキル（メタ）アクリレートを
製造する方法において、前記吸収工程途中の吸収液の一
部または全量を抜き出し、冷却後、吸収工程に再供給す
ることを特徴とする。In another method for producing hydroxyalkyl (meth) acrylate according to the present invention, (meth) acrylic acid is reacted with an alkylene oxide, and the unreacted alkylene oxide in the reaction solution is diffused and absorbed in a solvent. In the method for producing a hydroxyalkyl (meth) acrylate including a step, a part or the entire amount of the absorbing liquid in the course of the absorption step is withdrawn, cooled, and then supplied again to the absorption step.
【０００８】[0008]
【発明の実施の形態】以下本発明を詳細に説明する。初
めに、本発明に係る特徴的な製造方法を好ましく適用す
ることができるヒドロキシアルキル（メタ）アクリレー
トの製造プロセスの概略を説明する。まず、（メタ）ア
クリル酸とアルキレンオキシドとを、触媒の存在下で付
加反応させる。この付加反応は反応率が１００％に満た
ないことが多く、反応終了時の反応液中には未反応の
（メタ）アクリル酸やアルキレンオキシド等が残存する
場合が一般的である。そこで、上記の反応液は、これら
未反応原料等を反応液中から除去するための工程へと導
かれる。そして、続く最終段階として、蒸留等による精
製が行われて、目的のヒドロキシアルキル（メタ）アク
リレートが得られる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, an outline of a process for producing a hydroxyalkyl (meth) acrylate to which the characteristic production method according to the present invention can be preferably applied will be described. First, an addition reaction is performed between (meth) acrylic acid and an alkylene oxide in the presence of a catalyst. This addition reaction often has a reaction rate of less than 100%, and generally unreacted (meth) acrylic acid, alkylene oxide, or the like remains in the reaction solution at the end of the reaction. Then, the above-mentioned reaction liquid is led to a step for removing these unreacted raw materials and the like from the reaction liquid. Then, as a subsequent final step, purification by distillation or the like is performed to obtain a target hydroxyalkyl (meth) acrylate.
【０００９】本発明を実施するにあたり、上記（メタ）
アクリル酸とアルキレンオキシドとの反応における原料
の仕込み量は、（メタ）アクリル酸１モルに対して、ア
ルキレンオキシドが１．０〜２．０モルが好ましい範囲
であり、より好ましくは１．１〜１．７モル、さらに好
ましくは１．２〜１．５モルである。アルキレンオキシ
ドの仕込み量が１．０モル未満の場合には、反応率が低
下し、副生成物が増加するので好ましくない。また、ア
ルキレンオキシドの仕込み量が２モルを超えると、経済
的に好ましくない。本発明を実施するにあたり、上記
（メタ）アクリル酸とアルキレンオキシドとの反応に使
用する触媒は、特に限定されず、例えば公知の付加反応
用の均一触媒あるいは不均一触媒を用いることができ
る。また、反応液には、ハイドロキノン、ハイドロキノ
ンモノメチルエーテル、フェノチアジン等の重合防止剤
を必要により添加してもよい。In carrying out the present invention, the above (meth)
The amount of the raw materials charged in the reaction between acrylic acid and alkylene oxide is preferably in the range of 1.0 to 2.0 mol, more preferably 1.1 to 2.0 mol, per mol of (meth) acrylic acid. It is 1.7 mol, more preferably 1.2 to 1.5 mol. If the charged amount of the alkylene oxide is less than 1.0 mol, the reaction rate is decreased and the amount of by-products is increased, which is not preferable. On the other hand, if the charged amount of the alkylene oxide exceeds 2 mol, it is economically undesirable. In carrying out the present invention, the catalyst used for the reaction between the (meth) acrylic acid and the alkylene oxide is not particularly limited, and for example, a known homogeneous or heterogeneous catalyst for an addition reaction can be used. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and phenothiazine may be added to the reaction solution as needed.
【００１０】本発明に係るヒドロキシアルキル（メタ）
アクリレートの製造方法は、上述の一連の製造プロセス
中において、（メタ）アクリル酸とアルキレンオキサイ
ドとの反応後、未反応のアルキレンオキシドを反応液中
から除去する工程、特に、未反応のアルキレンオキシド
を放散させた後に溶剤に吸収させる吸収工程に特徴を有
するものである。以下に、本発明に係る特徴的な製造方
法を説明する。（メタ）アクリル酸とアルキレンオキシ
ドとの付加反応により得られた反応液中には、目的物で
あるヒドロキシアルキル（メタ）アクリレートと共に、
通常、未反応のアルキレンオキシドが含まれている。こ
の反応後液を、好ましくは反応後の温度を保ったまま
で、放散装置に供給する。放散装置に供給する際の温度
は、理論的には放散効率の向上のために高いほどよい
が、アルキレンオキシド含有液の再加熱は爆発の危険性
を伴うので、反応後液は、上記のように反応後の温度を
保ったままで、放散装置に供給するのが好ましい形態で
ある。また、反応後液の温度は、反応収率向上および副
生成物抑制などをも目的として制限されるものであり、
好ましくは４０〜１３０℃、より好ましくは５０〜９０
℃である。上記放散装置としては特に限定されないが、
放散効率向上のためには、充填塔や泡鐘塔、多孔板塔な
どの棚段塔が好ましい。The hydroxyalkyl (meth) according to the present invention
The method for producing acrylate is a step of removing unreacted alkylene oxide from the reaction solution after the reaction between (meth) acrylic acid and alkylene oxide in the above-described series of production processes, and in particular, removing unreacted alkylene oxide. It has a feature in an absorption step of absorbing the solvent after the emission. Hereinafter, a characteristic manufacturing method according to the present invention will be described. In the reaction solution obtained by the addition reaction of the (meth) acrylic acid and the alkylene oxide, along with the hydroxyalkyl (meth) acrylate as the target substance,
Usually, unreacted alkylene oxide is contained. The post-reaction liquid is supplied to the diffusion device, preferably while maintaining the temperature after the reaction. Although the temperature at the time of supplying to the diffusion device is theoretically preferably higher to improve the radiation efficiency, reheating of the alkylene oxide-containing liquid involves an explosion risk. In a preferred embodiment, the solution is supplied to the diffusion device while maintaining the temperature after the reaction. In addition, the temperature of the solution after the reaction is limited for the purpose of improving the reaction yield and suppressing by-products,
Preferably 40 to 130 ° C, more preferably 50 to 90.
° C. Although there is no particular limitation on the dispersing device,
In order to improve the radiation efficiency, a plate tower such as a packed tower, a bubble bell tower, or a perforated plate tower is preferable.
【００１１】放散装置に供給されたアルキレンオキシド
含有の反応後液は、減圧気化あるいは不活性ガスによっ
て未反応アルキレンオキシドが放散され、吸収溶剤が存
在する吸収装置へと導かれる。特に、アルキレンオキシ
ドの断熱圧縮による温度上昇が引き起こす爆発の危険性
が回避でき、安全な製造プロセスを提供できる点で、不
活性ガスを用いることが好ましい。放散装置から放散さ
れたアルキレンオキシドは、続く吸収装置に供給され、
吸収装置内の溶剤に吸収される。吸収装置としては特に
限定されないが、吸収効率向上のために、充填塔や泡鐘
塔、多孔板塔などの棚段塔が好ましい。The unreacted alkylene oxide-containing reaction liquid supplied to the stripping device is vaporized under reduced pressure or unreacted alkylene oxide is diffused by an inert gas, and is led to an absorbing device in which an absorbing solvent is present. In particular, it is preferable to use an inert gas because it can avoid the danger of explosion caused by temperature rise due to adiabatic compression of alkylene oxide and can provide a safe manufacturing process. Alkylene oxide released from the diffusion device is supplied to a subsequent absorption device,
Absorbed by the solvent in the absorber. The absorber is not particularly limited, but a tray tower such as a packed tower, a bubble bell tower, or a perforated plate tower is preferable for improving the absorption efficiency.
【００１２】本発明の製造方法の一つにおいては、未反
応アルキレンオキシドの吸収溶剤として、ヒドロキシア
ルキル（メタ）アクリレート溶液を用いることを特徴と
する。ヒドロキシアルキル（メタ）アクリレートは、
（メタ）アクリル酸に比べて、アルキレンオキシドの吸
収能力に優れているので、吸収溶剤として優れている。
また、吸収させる際の吸収温度は低温であるほど吸収効
率が良いが、例えば、（メタ）アクリル酸は凝固点が約
１５℃と高いために、吸収温度を実質２０℃以下に設定
することはできない。しかし、ヒドロキシアルキル（メ
タ）アクリレートは凝固点が約−７０℃と低いので、吸
収温度を２０℃以下、あるいはさらにかなりの低温にま
で下げることができる。本発明において吸収溶剤として
用いるヒドロキシアルキル（メタ）アクリレート溶液中
に含まれるヒドロキシアルキル（メタ）アクリレートの
他成分との割合は特に限定されず、吸収温度を下げるこ
とのみを目的とするならばヒドロキシアルキル（メタ）
アクリレートの割合は高いほうが好ましい。また、本発
明において吸収溶剤として用いるヒドロキシアルキル
（メタ）アクリレート溶液中に含まれるヒドロキシアル
キル（メタ）アクリレートの他成分の種類については特
に限定されるものではなく、（メタ）アクリル酸、水、
ベンゼン、トルエン、キシレン等のいずれでもよい。One of the production methods of the present invention is characterized in that a hydroxyalkyl (meth) acrylate solution is used as a solvent for absorbing unreacted alkylene oxide. Hydroxyalkyl (meth) acrylate is
Compared to (meth) acrylic acid, it has an excellent ability to absorb alkylene oxide, and is therefore excellent as an absorbing solvent.
The lower the absorption temperature at the time of absorption, the better the absorption efficiency. For example, since (meth) acrylic acid has a high freezing point of about 15 ° C., the absorption temperature cannot be set to substantially 20 ° C. or less. . However, since hydroxyalkyl (meth) acrylate has a low freezing point of about -70 ° C, the absorption temperature can be reduced to 20 ° C or less, or even much lower. The ratio of the hydroxyalkyl (meth) acrylate contained in the hydroxyalkyl (meth) acrylate solution used as the absorbing solvent in the present invention to other components is not particularly limited. (Meta)
A higher acrylate ratio is preferred. Further, the type of other components of the hydroxyalkyl (meth) acrylate contained in the hydroxyalkyl (meth) acrylate solution used as the absorbing solvent in the present invention is not particularly limited, and (meth) acrylic acid, water,
Any of benzene, toluene, xylene and the like may be used.
【００１３】本発明において吸収溶剤として用いるヒド
ロキシアルキル（メタ）アクリレート溶液は、アルキレ
ンオキシドを吸収後、適宜必要に応じて（メタ）アクリ
ル酸やアルキレンオキシドが加えられて、再び、ヒドロ
キシアルキル（メタ）アクリレート製造の原料として循
環再利用してもよいし、アルキレンオキシドを溶剤と分
離し、他のアルキレンオキシド誘導体製造プロセスの原
料としてもよい。本発明の別の製造方法は、吸収工程の
吸収後液の一部を冷却後、吸収工程に再供給することを
特徴とする。アルキレンオキシド蒸気を溶剤に吸収させ
ると、アルキレンオキシドの蒸発潜熱の為に溶剤温度が
上昇してしまうので、吸収効率が低下する。そこで、吸
収工程の吸収後液の一部を冷却後、吸収工程に再供給す
ることにより、溶剤の温度上昇を抑制することができ、
吸収効率の向上が可能となる。The hydroxyalkyl (meth) acrylate solution used as an absorption solvent in the present invention is prepared by absorbing an alkylene oxide, adding (meth) acrylic acid or an alkylene oxide as needed, and then re-adding the hydroxyalkyl (meth) acrylate. It may be recycled and reused as a raw material for acrylate production, or the alkylene oxide may be separated from a solvent and used as a raw material for another alkylene oxide derivative production process. Another manufacturing method of the present invention is characterized in that a part of the liquid after absorption in the absorption step is cooled and then supplied again to the absorption step. When the alkylene oxide vapor is absorbed by the solvent, the solvent temperature rises due to the latent heat of vaporization of the alkylene oxide, and the absorption efficiency decreases. Therefore, after cooling part of the liquid after absorption in the absorption step, by re-supplying the liquid to the absorption step, it is possible to suppress the temperature rise of the solvent,
It is possible to improve the absorption efficiency.
【００１４】具体的には、吸収工程において用いる吸収
塔が１本の場合には、例えば、図１、図２に示すよう
に、吸収塔底からの吸収後液（アルキレンオキシドの吸
収により温度が上昇している）の一部を冷却器に通し、
液温を下げたものを再び吸収塔内に供給する。また、吸
収工程において用いる吸収塔が複数の場合には、例え
ば、図３（２本の場合）に示すように、最も底部に位置
する吸収塔からの吸収後液（アルキレンオキシドの吸収
により温度が上昇している）の一部を冷却器に通し、液
温を下げたものを再び吸収塔内に供給する。この場合、
再供給する吸収塔は図３のように最も底部に位置する吸
収塔でもよいし、それ以外の吸収塔でもよい。Specifically, when one absorption tower is used in the absorption step, for example, as shown in FIG. 1 and FIG. 2, the liquid after absorption from the bottom of the absorption tower (the temperature is reduced by the absorption of alkylene oxide). Through the cooler,
The solution whose temperature has been lowered is supplied again into the absorption tower. In the case where a plurality of absorption towers are used in the absorption step, for example, as shown in FIG. 3 (two cases), the liquid after absorption from the absorption tower located at the bottom (the temperature is reduced due to the absorption of alkylene oxide). A part of the solution (which is rising) is passed through a cooler, and the solution whose temperature is lowered is supplied again into the absorption tower. in this case,
The resupplying absorption tower may be the absorption tower located at the bottom as shown in FIG. 3 or may be another absorption tower.
【００１５】吸収溶剤としては、ヒドロキシアルキル
（メタ）アクリレート溶液、（メタ）アクリル酸、水、
ベンゼン、トルエン、キシレン等が挙げられるが、アル
キレンオキシドの吸収能力が優れているという点ではヒ
ドロキシアルキル（メタ）アクリレートの方が好まし
い。吸収塔に再供給される吸収後液量は、吸収溶剤量
（図１〜３のライン１６）に対して多ければ多いほど吸
収効率が向上するが、多すぎるとポンプ容量、冷却熱量
も増大し、多大なエネルギーを必要とするため、経済的
に不利となる。したがって、現実的には、吸収塔に再供
給される吸収後液量は、好ましくは吸収溶剤量の１００
倍以下、より好ましくは５０倍以下、特に好ましくは１
０倍以下である。As the absorbing solvent, hydroxyalkyl (meth) acrylate solution, (meth) acrylic acid, water,
Benzene, toluene, xylene and the like can be mentioned, but hydroxyalkyl (meth) acrylate is more preferable in that it has an excellent ability to absorb alkylene oxide. As the amount of liquid after absorption re-supplied to the absorption tower increases with the amount of the absorbing solvent (line 16 in FIGS. 1 to 3), the absorption efficiency improves, but if it is too large, the pump capacity and the amount of cooling heat also increase. Requires a great deal of energy, which is economically disadvantageous. Therefore, in practice, the amount of the liquid after absorption re-supplied to the absorption tower is preferably 100% of the amount of the absorbing solvent.
Times or less, more preferably 50 times or less, particularly preferably 1 time
It is 0 or less.
【００１６】この製造方法においては、冷却器を用いた
冷却により、再供給する液温は、好ましくは０〜４０
℃、より好ましくは５〜３０℃、特に好ましくは１０〜
２０℃である。４０℃よりも高いと、吸収溶剤の温度上
昇を十分に抑えることができないため好ましくない。ま
た、０℃よりも低いと、冷却に要するコストが多大にな
るので経済上好ましくない。また、この冷却器の形式
は、特に限定されるものではなく、例えば、多管式熱交
換器、スパイラル式熱交換器、プレート式熱交換器、二
重管式熱交換器等が挙げられる。本発明の別の製造方法
は、吸収工程途中の吸収液の一部または全量を抜き出
し、冷却後、吸収工程に再供給することを特徴とする。In this production method, the temperature of the resupplied liquid is preferably from 0 to 40 by cooling using a cooler.
° C, more preferably 5 to 30 ° C, particularly preferably 10 to
20 ° C. If the temperature is higher than 40 ° C., it is not preferable because the temperature rise of the absorbing solvent cannot be sufficiently suppressed. On the other hand, when the temperature is lower than 0 ° C., the cost required for cooling becomes large, which is not economically preferable. The type of the cooler is not particularly limited, and examples thereof include a multi-tube heat exchanger, a spiral heat exchanger, a plate heat exchanger, and a double-tube heat exchanger. Another manufacturing method of the present invention is characterized in that a part or the whole amount of the absorbing liquid in the middle of the absorption step is extracted, cooled, and then supplied again to the absorption step.
【００１７】先に説明したように、アルキレンオキシド
蒸気を溶剤に吸収させると、アルキレンオキシドの蒸発
潜熱の為に溶剤温度が上昇してしまうので、吸収効率が
低下する。そこで、吸収工程途中の吸収液の一部または
全量を抜き出し、冷却後、吸収工程に再供給することに
より、溶剤の温度上昇を抑制することができ、吸収効率
の向上が可能となる。具体的には、吸収工程において用
いる吸収塔が１本の場合には、例えば、図４に示すよう
に、吸収塔の途中から抜き出した吸収液の一部（アルキ
レンオキシドの吸収により温度が上昇している）を冷却
器に通し、液温を下げたものを再び吸収塔内に供給す
る。また、吸収工程において用いる吸収塔が複数の場合
には、例えば、図５（２本の場合）に示すように、最上
部に位置する吸収塔の塔底部から抜き出した吸収液の一
部または全量（アルキレンオキシドの吸収により温度が
上昇している）を冷却器に通し、液温を下げたものを再
び吸収塔内に供給する。この場合、抜き出す吸収塔はい
ずれの塔でもよいし、再供給する吸収塔は図５のように
最も底部に位置する吸収塔でもよいし、それ以外の吸収
塔でもよい。As described above, when the alkylene oxide vapor is absorbed into the solvent, the solvent temperature rises due to the latent heat of vaporization of the alkylene oxide, and the absorption efficiency decreases. Therefore, by extracting a part or the whole amount of the absorbing liquid in the middle of the absorption step, and cooling and re-supplying the absorption liquid to the absorption step, it is possible to suppress a rise in the temperature of the solvent and improve the absorption efficiency. Specifically, when one absorption tower is used in the absorption step, for example, as shown in FIG. 4, a part of the absorption liquid extracted from the middle of the absorption tower (the temperature rises due to the absorption of alkylene oxide). Is passed through a cooler, and the solution whose temperature is lowered is supplied again into the absorption tower. When there are a plurality of absorption towers used in the absorption step, for example, as shown in FIG. 5 (two cases), a part or the whole amount of the absorption liquid extracted from the bottom of the absorption tower located at the top (The temperature has increased due to the absorption of the alkylene oxide) is passed through a cooler, and the solution whose temperature has been lowered is supplied again into the absorption tower. In this case, any of the absorption towers to be extracted may be used, and the absorption tower to be re-supplied may be the absorption tower located at the bottom as shown in FIG. 5, or may be another absorption tower.
【００１８】吸収溶剤としては、ヒドロキシアルキル
（メタ）アクリレート溶液、（メタ）アクリル酸、水、
ベンゼン、トルエン、キシレン等が挙げられるが、アル
キレンオキシドの吸収能力が優れているという点ではヒ
ドロキシアルキル（メタ）アクリレートの方が好まし
い。吸収塔の途中から抜き出した液を、抜き出し口より
も上部に再供給する場合（図６）、その供給液量は、最
上部に位置する吸収塔の塔頂部に新たに供給される吸収
溶剤量（図４〜６のライン１６）に対して多ければ多い
ほど吸収効率が向上するが、多すぎるとポンプ容量、冷
却熱量も増大し、多大なエネルギーを必要とするため、
経済的に不利となる。したがって、現実的には、吸収塔
に再供給される吸収後液量は、好ましくは吸収溶剤量の
１００倍以下、より好ましくは５０倍以下、特に好まし
くは１０倍以下である。As the absorbing solvent, hydroxyalkyl (meth) acrylate solution, (meth) acrylic acid, water,
Benzene, toluene, xylene and the like can be mentioned, but hydroxyalkyl (meth) acrylate is more preferable in that it has an excellent ability to absorb alkylene oxide. When the liquid withdrawn from the middle of the absorption tower is resupplied above the outlet (FIG. 6), the amount of the supplied liquid is determined by the amount of absorbing solvent newly supplied to the top of the uppermost absorption tower. (Line 16 in FIGS. 4 to 6), the more it is, the higher the absorption efficiency is, but if it is too much, the pump capacity and the amount of cooling heat also increase, and a large amount of energy is required.
Economically disadvantageous. Therefore, in practice, the amount of the liquid after absorption resupplied to the absorption tower is preferably 100 times or less, more preferably 50 times or less, and particularly preferably 10 times or less, the amount of the absorbing solvent.
【００１９】この製造方法においては、冷却器を用いた
冷却により、再供給する液温は、好ましくは０〜４０
℃、より好ましくは５〜３０℃、特に好ましくは１０〜
２０℃である。４０℃よりも高いと、吸収溶剤の温度上
昇を十分に抑えることができないため好ましくない。ま
た、０℃よりも低いと、冷却に要するコストが多大にな
るので経済上好ましくない。また、この冷却器の形式
は、特に限定されるものではなく、例えば、多管式熱交
換器、スパイラル式熱交換器、プレート式熱交換器、二
重管式熱交換器等が挙げられる。放散、吸収の操作圧力
は、放散に対しては操作圧力が低いほど放散効率が高
く、吸収に対しては操作圧力が高いほど吸収効率が高く
なる。従って、吸収の操作圧力を放散の操作圧力よりも
かなり高くすればするほど、理論的には、放散効率と吸
収効率の双方ともに向上することになる。しかしなが
ら、吸収の操作圧力が放散の操作圧力よりもかなり高く
する場合には、アルキレンオキシド含有の放散ガスをコ
ンプレッサー等で断熱圧縮することになり、温度上昇に
よって爆発の危険が生じる。そこで、放散効率と吸収効
率をともに実用的レベルに保つようにした場合、安全で
あり、且つ、効率良く、アルキレンオキシドを放散・吸
収できるためには、反応液中の未反応アルキレンオキシ
ドを放散させる工程と、放散させた未反応アルキレンオ
キシドを吸収する工程との操作圧の差が１０００ｈＰａ
以下であることが好ましい。また、不活性ガスを循環再
使用する場合、吸収装置から排出されるガスを放散装置
に戻すために昇圧する必要があるが、このときにも、安
全性の面から、放散の操作圧力と吸収の操作圧力の差を
１０００ｈＰａ以下にすることが好ましい。In this manufacturing method, the temperature of the resupplied liquid is preferably from 0 to 40 by cooling using a cooler.
° C, more preferably 5 to 30 ° C, particularly preferably 10 to
20 ° C. If the temperature is higher than 40 ° C., it is not preferable because the temperature rise of the absorbing solvent cannot be sufficiently suppressed. On the other hand, when the temperature is lower than 0 ° C., the cost required for cooling becomes large, which is not economically preferable. The type of the cooler is not particularly limited, and examples thereof include a multi-tube heat exchanger, a spiral heat exchanger, a plate heat exchanger, and a double-tube heat exchanger. Regarding the operating pressure for radiation and absorption, the lower the operating pressure is for radiation, the higher the radiation efficiency is, and the higher the operating pressure is for absorption, the higher the absorption efficiency is. Thus, the greater the operating pressure for absorption is significantly higher than the operating pressure for dissipation, theoretically both the emission efficiency and the absorption efficiency will be improved. However, if the operating pressure for absorption is significantly higher than the operating pressure for emission, the aerated gas containing alkylene oxide will be adiabatically compressed by a compressor or the like, and the temperature rise will cause a risk of explosion. Therefore, when the emission efficiency and the absorption efficiency are both kept at a practical level, the unreacted alkylene oxide in the reaction solution is emitted in order to safely and efficiently emit and absorb the alkylene oxide. The difference in operating pressure between the step and the step of absorbing the released unreacted alkylene oxide is 1000 hPa
The following is preferred. In addition, when the inert gas is circulated and reused, it is necessary to increase the pressure in order to return the gas discharged from the absorption device to the emission device. It is preferable that the difference between the operating pressures is 1000 hPa or less.
【００２０】[0020]
【実施例】以下に本発明を具体的に説明するが、本発明
はこれらの実施例に限定されるものではない。以下にヒ
ドロキシエチルアクリレートの反応を例にして本発明を
説明する。 ［実施例１］撹拌翼を有するオートクレーブに触媒とし
てアニオン交換樹脂（三菱化学（株）製ＤＩＡＩＯＮ
ＰＡ３１６）を水膨潤状態で４８０ｍｌ仕込み、エチレ
ンオキシド２２９ｇ／ｈ、アクリル酸２８８ｇ／ｈを連
続的に供給し（エチレンオキシド/ アクリル酸モル比
１．３）、反応温度７０℃、滞留時間４．１ｈで反応を
行った。反応時の圧力は約４２００ｈＰａであった。オ
ートクレーブ出口の反応後液を分析した結果、未反応ア
クリル酸５．６重量％、未反応エチレンオキシド１３．
４重量％、アクリル酸の転化率は９０．０％、エチレン
オキシドの転化率は６９．８％であった。この反応後液
からアニオン交換樹脂を分離した後、反応後液を操作圧
力が１０５３ｈＰａである塔径３２ｍｍ、高さ３０ｃｍ
の放散塔に塔頂から供給し、塔底から酸素濃度３モル％
に調製した窒素ガス７２ｇ／ｈを供給して放散を行っ
た。放散後の塔頂ガスを操作圧力が１０１３ｈＰａであ
る塔径３２ｍｍ、高さ２０ｃｍの吸収塔に塔底から供給
し、塔頂から吸収液としてヒドロキシエチルアクリレー
ト２８８ｇ／ｈを供給した。吸収液は１０℃で供給し
た。塔底からの吸収液を分析した結果、エチレンオキシ
ドは１５．６重量％であった。これは未反応エチレンオ
キシド回収効率７６．７％に相当する。EXAMPLES The present invention will be described in detail below, but the present invention is not limited to these examples. Hereinafter, the present invention will be described by taking the reaction of hydroxyethyl acrylate as an example. [Example 1] An anion exchange resin (DIAION manufactured by Mitsubishi Chemical Corporation) was used as a catalyst in an autoclave having a stirring blade.
PA 316) was charged in a water-swollen state (480 ml), 229 g / h of ethylene oxide and 288 g / h of acrylic acid were continuously supplied (ethylene oxide / acrylic acid molar ratio: 1.3), and the reaction was carried out at a reaction temperature of 70 ° C. and a residence time of 4.1 h. Was done. The pressure during the reaction was about 4200 hPa. As a result of analyzing the solution after the reaction at the outlet of the autoclave, 5.6% by weight of unreacted acrylic acid and 13.2% of unreacted ethylene oxide were obtained.
4% by weight, the conversion of acrylic acid was 90.0%, and the conversion of ethylene oxide was 69.8%. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction was converted into a liquid having a tower diameter of 32 mm and a height of 30 cm at an operating pressure of 1053 hPa.
Is supplied from the top to the stripper, and the oxygen concentration is 3 mol% from the bottom.
72 g / h of nitrogen gas prepared above was supplied to perform emission. The top gas after the dispersion was supplied from the bottom of the absorption tower having an operation pressure of 1013 hPa and having a tower diameter of 32 mm and a height of 20 cm, and 288 g / h of hydroxyethyl acrylate was supplied as an absorbing solution from the top of the tower. The absorbing solution was supplied at 10 ° C. As a result of analyzing the absorption liquid from the bottom of the tower, ethylene oxide was found to be 15.6% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 76.7%.
【００２１】［実施例２］ヒドロキシエチルアクリレー
トの反応を実施例１と同じ条件で連続的に行った。この
反応後液からアニオン交換樹脂を分離した後、反応後液
を操作圧力が１０５３ｈＰａである塔径３２ｍｍ、高さ
３０ｃｍの放散塔に塔頂から供給し、塔底から酸素濃度
３モル％に調製した窒素ガス７２ｇ／ｈを供給して放散
を行った。放散後の塔頂ガスを操作圧力が１０１３ｈＰ
ａである塔径３２ｍｍ、高さ２０ｃｍの吸収塔に塔底か
ら供給し、塔頂から吸収液としてヒドロキシエチルアク
リレート２８８ｇ／ｈを供給した。吸収液は２０℃で供
給した。塔底からの吸収液を分析した結果、エチレンオ
キシドは１４．２重量％であった。これは未反応エチレ
ンオキシド回収効率６９．０％に相当する。Example 2 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The operating pressure of the top gas after emission is 1013 hP
The solution was supplied from the bottom to the absorption tower having a diameter of 32 mm and a height of 20 cm, and 288 g / h of hydroxyethyl acrylate was supplied as an absorbing solution from the top of the tower. The absorbing solution was supplied at 20 ° C. As a result of analyzing the absorption liquid from the bottom of the column, ethylene oxide was 14.2% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 69.0%.
【００２２】［実施例３］ヒドロキシエチルアクリレー
トの反応を実施例１と同じ条件で連続的に行った。この
反応後液からアニオン交換樹脂を分離した後、反応後液
を操作圧力が１０５３ｈＰａである塔径３２ｍｍ、高さ
３０ｃｍの放散塔に塔頂から供給し、塔底から酸素濃度
３モル％に調製した窒素ガス７２ｇ／ｈを供給して放散
を行った。放散後の塔頂ガスを操作圧力が１０１３ｈＰ
ａである塔径３２ｍｍ、高さ２０ｃｍの吸収塔に塔底か
ら供給し、塔頂から吸収液としてヒドロキシエチルアク
リレート２８８ｇ／ｈを供給した。吸収液は１０℃で供
給した。また、吸収塔底液の一部を１４４ｇ／ｈｒで、
１０℃まで冷却後、塔頂から１０ｃｍのところに再度供
給した。塔底からの吸収液を分析した結果、エチレンオ
キシドは１６．８重量％であった。これは未反応エチレ
ンオキシド回収効率８４．２％に相当する。 ［実施例４］ヒドロキシエチルアクリレートの反応を実
施例１と同じ条件で連続的に行った。この反応後液から
アニオン交換樹脂を分離した後、反応後液を操作圧力が
１０５３ｈＰａである塔径３２ｍｍ、高さ３０ｃｍの放
散塔に塔頂から供給し、塔底から酸素濃度３モル％に調
製した窒素ガス７２ｇ／ｈを供給して放散を行った。放
散後の塔頂ガスを操作圧力が１０１３ｈＰａである塔径
３２ｍｍ、高さ２０ｃｍ、塔頂から１０ｃｍのところに
チムニートレイを持つ吸収塔に塔底から供給し、塔頂か
ら吸収液としてヒドロキシエチルアクリレート２８８ｇ
／ｈを供給した。吸収液は１０℃で供給した。チムニー
トレイにて吸収塔内液を１４４ｇ／ｈｒで塔外に一部抜
き出し、１０℃まで冷却後、塔頂から１０ｃｍのところ
に再度供給した。塔底からの吸収液を分析した結果、エ
チレンオキシドは１６．９重量％であった。これは未反
応エチレンオキシド回収効率８４．４％に相当する。Example 3 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The operating pressure of the top gas after emission is 1013 hP
The solution was supplied from the bottom to the absorption tower having a diameter of 32 mm and a height of 20 cm, and 288 g / h of hydroxyethyl acrylate was supplied as an absorbing solution from the top of the tower. The absorbing solution was supplied at 10 ° C. In addition, a part of the bottom liquid of the absorption tower was 144 g / hr,
After cooling to 10 ° C., it was fed again at a position 10 cm from the top of the tower. As a result of analyzing the absorbing solution from the bottom of the column, ethylene oxide was found to be 16.8% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 84.2%. Example 4 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The overhead gas after the emission is supplied from the bottom to an absorption tower having a chimney tray at a tower diameter of 32 mm, a height of 20 cm and a height of 10 cm from the top at an operating pressure of 1013 hPa, and hydroxyethyl acrylate is used as an absorbing solution from the top. 288g
/ H. The absorbing solution was supplied at 10 ° C. A part of the liquid in the absorption tower was withdrawn by a chimney tray at a rate of 144 g / hr to the outside of the tower, cooled to 10 ° C., and supplied again to a position 10 cm from the top of the tower. As a result of analyzing the absorption liquid from the bottom of the tower, ethylene oxide was found to be 16.9% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 84.4%.
【００２３】［実施例５］ヒドロキシエチルアクリレー
トの反応を実施例１と同じ条件で連続的に行った。この
反応後液からアニオン交換樹脂を分離した後、反応後液
を操作圧力が１０５３ｈＰａである塔径３２ｍｍ、高さ
３０ｃｍの放散塔に塔頂から供給し、塔底から酸素濃度
３モル％に調製した窒素ガス７２ｇ／ｈを供給して放散
を行った。放散後の塔頂ガスを操作圧力が１０１３ｈＰ
ａである塔径３２ｍｍ、高さ２０ｃｍの吸収塔に塔底か
ら供給し、塔頂から吸収液としてアクリル酸２８８ｇ／
ｈを供給した。吸収液は２０℃で供給した。また、吸収
塔底液１４４ｇ／ｈを２０℃まで冷却後、吸収塔の上か
ら１０ｃｍのところに供給した。塔底からの吸収液を分
析した結果、エチレンオキシドは１４．８重量％であっ
た。これは未反応エチレンオキシド回収効率７２．５％
に相当する。Example 5 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The operating pressure of the top gas after emission is 1013 hP
a) is supplied from the bottom of the column to an absorption tower having a tower diameter of 32 mm and a height of 20 cm, and 288 g of acrylic acid /
h. The absorbing solution was supplied at 20 ° C. After 144 g / h of the bottom liquid of the absorption tower was cooled to 20 ° C., it was supplied to a position 10 cm from the top of the absorption tower. As a result of analyzing the absorption liquid from the bottom of the column, ethylene oxide was found to be 14.8% by weight. This is the efficiency of recovery of unreacted ethylene oxide 72.5%
Is equivalent to
【００２４】［実施例６］ヒドロキシエチルアクリレー
トの反応を実施例１と同じ条件で連続的に行った。この
反応後液からアニオン交換樹脂を分離した後、反応後液
を操作圧力が１０５３ｈＰａである塔径３２ｍｍ、高さ
３０ｃｍの放散塔に塔頂から供給し、塔底から酸素濃度
３モル％に調製した窒素ガス７２ｇ／ｈを供給して放散
を行った。放散後の塔頂ガスを操作圧力が１０１３ｈＰ
ａである塔径３２ｍｍ、高さ２０ｃｍ、塔頂から１０ｃ
ｍのところにチムニートレイを持つ吸収塔に塔底から供
給し、塔頂から吸収液としてアクリル酸２８８ｇ／ｈを
供給した。吸収液は２０℃で供給した。チムニートレイ
にて吸収塔内液を１４４ｇ／ｈｒで塔外に一部抜き出
し、２０℃まで冷却後、塔頂から１０ｃｍのところに再
度供給した。塔底からの吸収液を分析した結果、エチレ
ンオキシドは１４．９重量％であった。これは未反応エ
チレンオキシド回収効率７２．７％に相当する。Example 6 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The operating pressure of the top gas after emission is 1013 hP
a, tower diameter 32 mm, height 20 cm, 10 c from the top of the tower
m, was supplied from the bottom to an absorption tower having a chimney tray, and 288 g / h of acrylic acid was supplied from the top as an absorbing solution. The absorbing solution was supplied at 20 ° C. A part of the liquid in the absorption tower was withdrawn by a chimney tray at a rate of 144 g / hr to the outside of the tower, cooled to 20 ° C., and supplied again to a position 10 cm from the top of the tower. As a result of analyzing the absorption liquid from the bottom of the column, ethylene oxide was found to be 14.9% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 72.7%.
【００２５】［比較例１］ヒドロキシエチルアクリレー
トの反応を実施例１と同じ条件で連続的に行った。この
反応後液からアニオン交換樹脂を分離した後、反応後液
を操作圧力が１０５３ｈＰａである塔径３２ｍｍ、高さ
３０ｃｍの放散塔に塔頂から供給し、塔底から酸素濃度
３モル％に調製した窒素ガス７２ｇ／ｈを供給して放散
を行った。放散後の塔頂ガスを操作圧力が１０１３ｈＰ
ａである塔径３２ｍｍ、高さ２０ｃｍの吸収塔に塔底か
ら供給し、塔頂から吸収液としてアクリル酸２８８ｇ／
ｈを供給した。吸収液は２０℃で供給した。塔底からの
吸収液を分析した結果、エチレンオキシドは１３．５重
量％であった。これは未反応エチレンオキシド回収効率
６５．０％に相当する。Comparative Example 1 The reaction of hydroxyethyl acrylate was carried out continuously under the same conditions as in Example 1. After separating the anion exchange resin from the liquid after the reaction, the liquid after the reaction is fed from the top of a stripping tower having an operating pressure of 1053 hPa and having a diameter of 32 mm and a height of 30 cm from the top, and adjusting the oxygen concentration to 3 mol% from the bottom of the tower. 72 g / h of the supplied nitrogen gas was supplied for emission. The operating pressure of the top gas after emission is 1013 hP
a) is supplied from the bottom of the column to an absorption tower having a tower diameter of 32 mm and a height of 20 cm, and 288 g of acrylic acid /
h. The absorbing solution was supplied at 20 ° C. As a result of analyzing the absorption liquid from the bottom of the tower, ethylene oxide was found to be 13.5% by weight. This corresponds to an unreacted ethylene oxide recovery efficiency of 65.0%.
【００２６】[0026]
【発明の効果】本発明によれば、（メタ）アクリル酸と
アルキレンオキシドを反応させ、反応液中の未反応アル
キレンオキシドを放散させて溶剤に吸収させる工程を含
む、ヒドロキシアルキル（メタ）アクリレートを製造す
る方法において、未反応アルキレンオキシドを経済的、
且つ、効率良く回収再利用できる。According to the present invention, a hydroxyalkyl (meth) acrylate comprising a step of reacting (meth) acrylic acid with an alkylene oxide, dispersing the unreacted alkylene oxide in the reaction solution and absorbing it in a solvent is provided. In the method for producing, the unreacted alkylene oxide is economically
And it can be efficiently collected and reused.
【図１】本発明の製造方法の一例（吸収塔１本、吸収後
液の一部を冷却・再供給）を表すフロー図。FIG. 1 is a flowchart showing an example of the production method of the present invention (one absorption tower, cooling and resupply of a part of the liquid after absorption).
【図２】本発明の製造方法の一例（吸収塔１本、吸収後
液の一部を冷却・塔頂に再供給）を表すフロー図。FIG. 2 is a flow chart showing an example of the production method of the present invention (one absorption tower, part of liquid after absorption is cooled and resupplied to the top of the tower).
【図３】本発明の製造方法の一例（吸収塔２本、最底部
の塔からの吸収後液の一部を冷却・最底部の塔に再供
給）を表すフロー図。FIG. 3 is a flowchart showing an example of the production method of the present invention (two absorption towers, part of the liquid after absorption from the bottom tower is cooled and resupplied to the bottom tower).
【図４】本発明の製造方法の一例（吸収塔１本、吸収工
程途中の吸収液の一部を冷却・再供給）を表すフロー
図。FIG. 4 is a flowchart showing an example of the production method of the present invention (one absorption tower, cooling and resupply of a part of the absorbing liquid during the absorbing step).
【図５】本発明の製造方法の一例（吸収塔２本、最上部
の塔からの吸収液の一部または全量を冷却・最底部の塔
に再供給）を表すフロー図。FIG. 5 is a flowchart showing an example of the production method of the present invention (two absorption towers, cooling or resupplying part or all of the absorption liquid from the top tower to the bottom tower).
【図６】本発明の製造方法の一例（吸収塔２本、最上部
の塔からの吸収液の一部または全量を冷却・最上部およ
び最底部の塔に再供給）を表すフロー図。FIG. 6 is a flow chart showing an example of the production method of the present invention (two absorption towers, cooling or resupplying part or all of the absorption liquid from the top tower to the top and bottom towers).
１ 反応器 ２ 放散塔 ３ 吸収塔 ４ 吸収塔 １１ 不活性ガス導入ライン １２ 放散後液抜き出しライン １３ 放散ガスライン １４ 吸収後液抜き出しライン １５ 再供給ライン １６ 吸収溶剤導入ライン １７ 廃ガスライン ２１ 冷却器 ２２ 液再分散器 ２３ チムニートレイ DESCRIPTION OF SYMBOLS 1 Reactor 2 Stripping tower 3 Absorption tower 4 Absorption tower 11 Inert gas introduction line 12 Liquid extraction line after emission 13 Release gas line 14 Liquid absorption line after absorption 15 Resupply line 16 Absorption solvent introduction line 17 Waste gas line 21 Cooler 22 Liquid redispersing device 23 Chimney tray
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新谷 恭宏 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 (72)発明者 上岡 正敏 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 (72)発明者 米田 幸弘 兵庫県姫路市網干区興浜字西沖992番地の １ 株式会社日本触媒内 Ｆターム(参考） 4H006 AA02 AC48 AD17 AD18 BA72 BA94 BC10 BC11 BC19 BC31 BC51 BC52 BD33 BD51 BN10 KA19 4H039 CA66 CF90 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuhiro Shintani 992, Nishioki, Okihama-shi, Aboshi-ku, Himeji-shi, Hyogo Japan Nippon Shokubai Co., Ltd. Inside Nippon Shokubai (72) Inventor Yukihiro Yoneda 992, Nishioki, Okihama-shi, Abashiri-ku, Himeji-shi, Hyogo 1 Nippon Shokubai Co., Ltd. CF90
Claims (3)
を反応させ、反応液中の未反応アルキレンオキシドを放
散させて溶剤に吸収させる工程を含む、ヒドロキシアル
キル（メタ）アクリレートを製造する方法において、前
記吸収溶剤としてヒドロキシアルキル（メタ）アクリレ
ート溶液を用いることを特徴とする、ヒドロキシアルキ
ル（メタ）アクリレートの製造方法。1. A method for producing a hydroxyalkyl (meth) acrylate, comprising the step of: reacting (meth) acrylic acid with an alkylene oxide, dispersing unreacted alkylene oxide in a reaction solution and absorbing the same in a solvent. A method for producing hydroxyalkyl (meth) acrylate, comprising using a hydroxyalkyl (meth) acrylate solution as an absorption solvent.
を反応させ、反応液中の未反応アルキレンオキシドを放
散させて溶剤に吸収させる工程を含む、ヒドロキシアル
キル（メタ）アクリレートを製造する方法において、前
記吸収工程の吸収後液の一部を冷却後、吸収工程に再供
給することを特徴とする、ヒドロキシアルキル（メタ）
アクリレートの製造方法。2. A method for producing a hydroxyalkyl (meth) acrylate, comprising the step of reacting (meth) acrylic acid with an alkylene oxide, dispersing unreacted alkylene oxide in the reaction solution and absorbing the same in a solvent. Hydroxyalkyl (meth), characterized in that part of the liquid after absorption in the absorption step is cooled and then re-supplied to the absorption step
Method for producing acrylate.
を反応させ、反応液中の未反応アルキレンオキシドを放
散させて溶剤に吸収させる工程を含む、ヒドロキシアル
キル（メタ）アクリレートを製造する方法において、前
記吸収工程途中の吸収液の一部または全量を抜き出し、
冷却後、吸収工程に再供給することを特徴とする、ヒド
ロキシアルキル（メタ）アクリレートの製造方法。3. A method for producing a hydroxyalkyl (meth) acrylate, comprising the step of reacting (meth) acrylic acid with an alkylene oxide, dispersing unreacted alkylene oxide in the reaction solution and absorbing the unreacted alkylene oxide into a solvent. Withdraw part or all of the absorbent during the absorption process,
A method for producing a hydroxyalkyl (meth) acrylate, comprising re-feeding after cooling to an absorption step.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000032340A JP3721290B2 (en) | 1999-10-06 | 2000-02-09 | Method for producing hydroxyalkyl (meth) acrylate |
| EP00119915A EP1090903A3 (en) | 1999-10-06 | 2000-09-13 | production process for hydroxyalkyl (meth)acrylate |
| TW089118851A TW550253B (en) | 1999-10-06 | 2000-09-14 | Production process for hydroxyalkyl (meth)acrylate |
| US09/664,953 US6458988B1 (en) | 1999-10-06 | 2000-09-16 | Production process for hydroxyalkyl(meth)acrylate |
| CNB001290851A CN1190409C (en) | 1999-10-06 | 2000-09-29 | Method for producing (methyl) hydroxyalkyl acrylate |
| KR10-2000-0057879A KR100495246B1 (en) | 1999-10-06 | 2000-10-02 | Production process for hydroxyalkyl (meth)acrylate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28588899 | 1999-10-06 | ||
| JP11-285888 | 1999-10-06 | ||
| JP2000032340A JP3721290B2 (en) | 1999-10-06 | 2000-02-09 | Method for producing hydroxyalkyl (meth) acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001172228A true JP2001172228A (en) | 2001-06-26 |
| JP3721290B2 JP3721290B2 (en) | 2005-11-30 |
Family
ID=26556065
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000032340A Expired - Fee Related JP3721290B2 (en) | 1999-10-06 | 2000-02-09 | Method for producing hydroxyalkyl (meth) acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3721290B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008143814A (en) * | 2006-12-07 | 2008-06-26 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| JP2011116721A (en) * | 2009-12-07 | 2011-06-16 | Mitsubishi Rayon Co Ltd | Method for treating alkylene oxide and method for producing hydroxyalkyl (meth)acrylate using same |
-
2000
- 2000-02-09 JP JP2000032340A patent/JP3721290B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008143814A (en) * | 2006-12-07 | 2008-06-26 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| JP2011116721A (en) * | 2009-12-07 | 2011-06-16 | Mitsubishi Rayon Co Ltd | Method for treating alkylene oxide and method for producing hydroxyalkyl (meth)acrylate using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3721290B2 (en) | 2005-11-30 |
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