JP2018167195A - Photoreaction reactor and photoreaction apparatus - Google Patents
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Abstract
Description
本発明は光源から光反応管に試料を流通させ、光源から光反応管内の試料に光を照射して光反応を実施する光反応装置に関するものである。 The present invention relates to a photoreaction apparatus in which a sample is circulated from a light source to a photoreaction tube and light is irradiated from the light source to a sample in the photoreaction tube.
従来の光反応リアクターは円筒状の二層構造になっており、内層に密閉された円筒状の光反応管、外層に密閉された円筒状の冷却管を有し、光反応管の内側に光源を挿入して使用する。内層の光反応管に試料を導入する導入口と試料を排出する排出口を有し、導入口には光反応管の底部付近に達する導入管が設置されており、光反応管の底部付近から試料が導入される。導入管から導入された試料は光反応管内を上昇し排出口から排出される。光反応管内に導入された試料が排出口から排出される時間は平均滞留時間で表される。従って、試料が短時間で排出される場合や排出されずに長時間留まる場合もある。試料が短時間で排出された場合は光の照射時間が短くなるため目的物に変換されない。また、試料が光反応管内に長時間留まる場合は光の照射時間が長くなるため目的物がさらに反応を起こし副生成物に変換される。その結果、試料の変換率が低く、副生成物の生成率が高くなるなどの問題がある。 A conventional photoreactor has a cylindrical two-layer structure, and has a cylindrical photoreaction tube sealed in an inner layer and a cylindrical cooling tube sealed in an outer layer, and a light source inside the photoreaction tube. Insert and use. It has an inlet for introducing the sample into the inner layer photoreaction tube and an outlet for discharging the sample. The inlet has an introduction tube that reaches the bottom of the photoreaction tube. A sample is introduced. The sample introduced from the introduction tube rises in the photoreaction tube and is discharged from the discharge port. The time for which the sample introduced into the photoreaction tube is discharged from the discharge port is represented by an average residence time. Therefore, the sample may be discharged in a short time or may remain for a long time without being discharged. When the sample is discharged in a short time, the irradiation time of light is shortened, so that it is not converted into the target product. Further, when the sample stays in the photoreaction tube for a long time, the irradiation time of light becomes long, so that the target product further reacts and is converted into a by-product. As a result, there are problems such as a low sample conversion rate and a high by-product generation rate.
光源の周囲にらせん状の光反応管を設置した場合、らせん状の光反応管の導入口から導入された試料は光反応管に沿って流れ排出口から排出されるためショートパスを起こすことや長時間留まることがない。従って、光反応管内の滞留時間を調整できるので、試料の変換率を高くすることができ、さらに副生成物の生成も抑制することができる。 When a spiral photoreaction tube is installed around the light source, the sample introduced from the inlet of the spiral photoreaction tube flows along the photoreaction tube and is discharged from the discharge port. Does not stay for a long time. Therefore, since the residence time in the photoreaction tube can be adjusted, the conversion rate of the sample can be increased, and the production of by-products can be suppressed.
光源の周囲に密閉された円筒状の光反応管を設置した場合とらせん状の光反応管を設置した場合を比較すると、光反応管の内容量が同じであれば、らせん状の光反応管の流路の方が長くなるので、その結果、試料の光反応管内の滞留時間が長くなり、光の利用効率は高くなる。しかし、らせん状の光反応管が外部にむき出しになっているので破損しやすい、さらに加熱や冷却をして光反応管内の温度を制御することができないなどの問題がある。 Comparing the case where a sealed cylindrical photoreaction tube is installed around the light source and the case where a spiral photoreaction tube is installed, if the internal volume of the photoreaction tube is the same, the helical photoreaction tube As a result, the residence time of the sample in the photoreaction tube is increased, and the light utilization efficiency is increased. However, since the spiral photoreaction tube is exposed to the outside, it is easily damaged, and further, the temperature in the photoreaction tube cannot be controlled by heating or cooling.
このような問題から、光の利用効率を高くするためにランプとランプ内を貫通するように光反応管が設置した光反応管内蔵光反応リアクターが考案されている（特許文献１）。また、フタプレートと流路プレートをハウジングで固定し上部に設けた窓枠部より光を照射して光反応を行う光反応マイクロリアクターが考案されている（特許文献２）。さらに、光源の回りに冷却管が設置され、冷却管の回りに光反応に要求される波長の光を透過可能な材料からなるチューブがらせん状に巻かれているフロー反応装置も考案されている（特許文献３）。 From such a problem, a photoreaction reactor with a built-in photoreaction tube in which a photoreaction tube is installed so as to penetrate the inside of the lamp has been devised (Patent Document 1). In addition, a photoreaction microreactor has been devised in which a lid plate and a flow path plate are fixed by a housing and light is irradiated from a window frame provided at the upper portion to perform a photoreaction (Patent Document 2). In addition, a flow reaction device has been devised in which a cooling tube is installed around a light source, and a tube made of a material capable of transmitting light having a wavelength required for a photoreaction is spirally wound around the cooling tube. (Patent Document 3).
円筒状の二層構造になっている光反応リアクターは、試料への光照射時間が一定でないため、試料の変換率が低くなる、また副生成物の生成率が高くなるなどの問題がある。また、フタプレートと流路プレートをハウジングで固定し上部に設けた窓枠部より光を照射して光反応を行う光反応マイクロリアクターは、反応温度を制御するための装置を設置すると装置全体の構造が複雑となる問題がある。円筒状の光源の周囲にらせん状のチューブを設置したフロー反応装置は、チューブとして合成樹脂管やガラス管が使用可能であるが、合成樹脂からなるらせん状チューブは光の透過率が低いため、光の利用効率が悪く試料の転化率が低くなる、また、らせん状ガラス製チューブがむき出しになっている場合は破損しやすく危険であるなどの問題がある。 The photoreactor having a cylindrical two-layer structure has problems such as a low conversion rate of the sample and a high generation rate of by-products because the light irradiation time to the sample is not constant. In addition, a photoreaction microreactor that performs a photoreaction by irradiating light from a window frame provided at the top and fixing a lid plate and a flow path plate with a housing, installs a device for controlling the reaction temperature. There is a problem that the structure becomes complicated. A flow reactor equipped with a spiral tube around a cylindrical light source can use a synthetic resin tube or glass tube as the tube, but a spiral tube made of synthetic resin has low light transmittance. There are problems in that the light utilization efficiency is poor and the conversion rate of the sample is low, and when the spiral glass tube is exposed, it is easily broken and dangerous.
本願発明者らは、上記目的を達成するために鋭意検討した結果、以下の手段を採用することによって上記の課題を解決できることを見出した。 As a result of intensive studies to achieve the above object, the present inventors have found that the above-mentioned problems can be solved by adopting the following means.
第一の手段は、光源を設置するための貫通した空洞部を有する光反応リアクターであって、上記光反応リアクターは、冷却あるいは加熱するための媒体を導入かつ排出できる媒体流通管と媒体流通管内に試料を導入かつ排出できる光反応管とを備え、上記光反応管が上記空洞部の回りをらせん状に設置されていることを特徴とする光反応リアクターを提供することにより、上記の目的を達成したものである。 The first means is a photoreactor having a through-hole for installing a light source, the photoreactor comprising a medium flow tube and a medium flow tube in which a medium for cooling or heating can be introduced and discharged. And a photoreaction tube capable of introducing and discharging a sample, and providing the photoreaction reactor characterized in that the photoreaction tube is installed in a spiral around the cavity. Achieved.
第二の手段は、上記光反応リアクターと、上記光反応リアクターの上記空洞部内に設置した第１光源及び／または上記媒体流通管の外側に設置した第２光源とを備え、上記第１光源及び／または上記第２光源から上記光反応管内に流通する試料に光を照射して光反応を実施する光反応装置であって、上記媒体流通管内に媒体を流通させて上記光反応管内に流通する上記試料と上記光反応装置の温度を制御して光反応を実施するように上記媒体の温度を制御する温度コントローラーを備えたことを特徴とする光反応装置を提供することにより、上記の目的を達成したものである。 A second means includes the photoreactor, and a first light source installed in the cavity of the photoreactor and / or a second light source installed outside the medium flow tube, the first light source and / Or a photoreaction apparatus for performing a photoreaction by irradiating a sample flowing from the second light source into the photoreaction tube to circulate the medium in the medium flowpipe and flowing in the photoreaction tube By providing a photoreaction apparatus comprising a temperature controller for controlling the temperature of the medium so as to carry out a photoreaction by controlling the temperature of the sample and the photoreaction apparatus. Achieved.
第三の手段は、上記光反応リアクターと、上記光反応リアクターの上記空洞部内に設置した第１光源及び／または上記媒体流通管の外側に設置した第２光源とを備え、上記第１光源及び／または上記第２光源から上記光反応管内に流通する試料に光を照射して光反応を実施する光反応装置であって、上記光反応装置の外側を覆う光反射体を備え、上記媒体流通管内に媒体を流通させて上記光反応管内に流通する上記試料と上記光反応装置の温度を制御して光反応を実施するように上記媒体の温度を制御する温度コントローラーを備えたことを特徴とする光反応装置を提供することにより、上記の目的を達成したものである。 A third means comprises the photoreactor, and a first light source installed in the cavity of the photoreactor and / or a second light source installed outside the medium flow tube, the first light source and / Or a photoreaction apparatus for performing a photoreaction by irradiating light from the second light source to the sample that circulates in the photoreaction tube, comprising a light reflector that covers the outside of the photoreaction apparatus, and the medium flow A temperature controller for controlling the temperature of the medium so as to carry out the photoreaction by controlling the temperature of the sample and the photoreaction apparatus that circulates the medium in the tube and the photoreaction tube; The above object is achieved by providing a photoreaction apparatus.
本発明の第一の手段によれば、光反応リアクターの空洞部に光源を挿入することにより光源と光反応管との距離が近くなるため、光反応管内に流通する試料へ光の到達度が高くなり光の利用効率を上げることが可能になる。さらに、光反応管を媒体流通管の空洞部の回りをらせん状に設置することにより、光反応管を長くすることができる。これにより、光反応管内を流通する試料の滞留時間を長くすることができるので、試料の変換率を高くすることができる。また、媒体流通管内に光反応管を設置することにより光反応管内を流通する試料の温度と光反応装置の温度を制御して光反応を実施することができ、さらに光反応管の破損を防ぐことができる。 According to the first means of the present invention, since the distance between the light source and the photoreaction tube is reduced by inserting the light source into the cavity of the photoreactor, the degree of light reaching the sample flowing in the photoreaction tube is reduced. It becomes high and it becomes possible to raise the utilization efficiency of light. Furthermore, the photoreaction tube can be lengthened by installing the photoreaction tube spirally around the cavity of the medium flow tube. Thereby, since the residence time of the sample which distribute | circulates the inside of a photoreaction tube can be lengthened, the conversion rate of a sample can be made high. In addition, by installing a photoreaction tube in the medium flow tube, it is possible to control the temperature of the sample flowing through the photoreaction tube and the temperature of the photoreaction apparatus, and to prevent damage to the photoreaction tube. be able to.
本発明の第二の手段によれば、光反応リアクターの空洞部内に設置した光源及び／または媒体流通管の外側に設置した光源から光反応管内に流通する試料に光を照射することができるので、光強度の調整が容易になり、最適な反応条件で光反応を実施することができる。また、媒体流通管内に光反応管を設置することにより光反応管内に流通する試料の温度と光反応装置の温度を制御して光反応を実施することができ、さらに光反応管の破損を防ぐことができる。 According to the second means of the present invention, it is possible to irradiate light to the sample flowing in the photoreaction tube from the light source installed in the cavity of the photoreactor and / or the light source installed outside the medium flow tube. The light intensity can be easily adjusted, and the photoreaction can be carried out under optimum reaction conditions. Also, by installing a photoreaction tube in the medium flow tube, the photoreaction can be carried out by controlling the temperature of the sample flowing in the photoreaction tube and the temperature of the photoreaction device, and further preventing damage to the photoreaction tube be able to.
本発明の第三の手段によれば、光反応リアクターの空洞部内に設置した光源及び／または媒体流通管の外側に設置した光源から光反応管内に流通する試料に光を照射することができるので、光強度の調整が容易になり、最適な反応条件で光反応を実施することができる。また、光反応装置を光反射体で覆うことにより、光反応に使用されなかった光が光反射体によって反射される外部への光の漏洩を防ぐとともに、反射された光が光反応に使用されるので、より効率良く光反応を実施することができる。さらに、媒体流通管内に光反応管を設置することにより光反応管内に流通する試料の温度と光反応装置の温度を制御して光反応を実施することができ、光反応管の破損も防ぐことができる。 According to the third means of the present invention, it is possible to irradiate the sample flowing in the photoreaction tube from the light source installed in the cavity of the photoreactor and / or the light source installed outside the medium flow tube. The light intensity can be easily adjusted, and the photoreaction can be carried out under optimum reaction conditions. In addition, by covering the photoreaction device with a light reflector, light that has not been used for the photoreaction is prevented from leaking to the outside, which is reflected by the light reflector, and the reflected light is used for the photoreaction. Therefore, the photoreaction can be carried out more efficiently. Furthermore, by installing a photoreaction tube in the medium flow tube, the temperature of the sample flowing in the photoreaction tube and the temperature of the photoreaction device can be controlled, and the photoreaction tube can be prevented from being damaged. Can do.
本発明の光反応リアクターは、光源を設置するための貫通した空洞部を有する光反応リアクターであって、上記光反応リアクターは、冷却あるいは加熱するための媒体を導入かつ排出できる媒体流通管と上記媒体流通管内に試料を導入かつ排出できる光反応管とを備え、上記光反応管が上記空洞部の回りをらせん状に設置されていることを特徴とする。 The photoreactor of the present invention is a photoreactor having a hollow space for installing a light source, wherein the photoreactor comprises a medium flow pipe capable of introducing and discharging a medium for cooling or heating, and the above And a photoreaction tube capable of introducing and discharging a sample in the medium flow tube, wherein the photoreaction tube is spirally installed around the cavity.
図１に、本発明の一実施形態に係る光反応リアクター１０１を示す。本光反応リアクター１０１は媒体流通管１０２を有し、媒体流通管の中央には光源を設置するための空洞部１０３を有する。媒体流通管１０２には媒体導入口１０４と媒体排出口１０５と試料導入口１０６と試料排出口１０７が設置されている。媒体流通管１０２は、円筒状であることが好ましい。試料導入口１０６と試料排出口１０７の間は光反応管１０８によって接続されている。光反応管１０８は空洞部１０３の回りをらせん状に設置されている。試料は試料導入口１０６から導入され光反応管１０８を流通した後、試料排出口１０７より排出される。媒体は媒体導入口１０４から導入され媒体流通管１０２を流通した後、媒体排出口１０５より排出される。 FIG. 1 shows a photoreactor 101 according to an embodiment of the present invention. This photoreactor 101 has a medium flow tube 102, and a cavity 103 for installing a light source at the center of the medium flow tube. A medium introduction port 104, a medium discharge port 105, a sample introduction port 106, and a sample discharge port 107 are installed in the medium distribution pipe 102. The medium flow tube 102 is preferably cylindrical. A sample reaction port 108 is connected between the sample inlet 106 and the sample outlet 107. The photoreaction tube 108 is spirally installed around the cavity 103. The sample is introduced from the sample introduction port 106, flows through the photoreaction tube 108, and then discharged from the sample discharge port 107. The medium is introduced from the medium introduction port 104, circulates through the medium distribution pipe 102, and then discharged from the medium discharge port 105.
本発明の光反応装置は、上記光反応リアクターと、上記光反応リアクターの上記空洞部内に設置した第１光源及び／または上記媒体流通管の外側に設置した第２光源とを備え、上記第１光源及び／または上記第２光源から上記光反応管内に流通する試料に光を照射して光反応を実施する光反応装置であって、上記媒体流通管内に媒体を流通させて上記光反応管内に流通する上記試料と上記光反応装置の温度を制御して光反応を実施するように上記媒体の温度を制御する温度コントローラーを備えている。 The photoreaction apparatus of the present invention includes the photoreaction reactor, and a first light source installed in the cavity of the photoreaction reactor and / or a second light source installed outside the medium flow tube, A photoreaction apparatus for carrying out a photoreaction by irradiating light from a light source and / or a second light source to a sample flowing in the photoreaction tube, wherein the medium is circulated in the medium flow tube to enter the photoreaction tube. There is provided a temperature controller for controlling the temperature of the medium so as to carry out the photoreaction by controlling the temperature of the circulating sample and the photoreaction apparatus.
また、本発明の光反応装置は、上記光反応リアクターと、上記光反応リアクターの上記空洞部内に設置した第１光源及び／または上記媒体流通管の外側に設置した第２光源とを備え、上記第１光源及び／または上記第２光源から上記光反応管内に流通する試料に光を照射して光反応を実施する光反応装置であって、上記光反応装置の外側を覆う光反射体を備え、上記媒体流通管内に媒体を流通させて上記光反応管内に流通する上記試料と上記光反応装置の温度を制御して光反応を実施するように上記媒体の温度を制御する温度コントローラーを備えている。 The photoreaction apparatus of the present invention includes the photoreactor, and a first light source installed in the cavity of the photoreactor and / or a second light source installed outside the medium flow tube, A photoreaction apparatus that performs a photoreaction by irradiating light from the first light source and / or the second light source to a sample flowing in the photoreaction tube, and includes a light reflector that covers the outside of the photoreaction apparatus. A temperature controller for controlling the temperature of the medium so as to carry out the photoreaction by controlling the temperature of the sample and the photoreaction apparatus that circulates the medium in the medium flow tube and flows in the photoreaction tube. Yes.
図２に、本発明の一実施形態に係る光反応装置２００を示す。図２に示すように、媒体流通管１０２の空洞部１０３に光源２０１を挿入する。光源２０１は光源接続端子２０２を接続し、接続線２０３によって光源電子安定器２０４に接続される。光源電子安定器２０４は電気コード２０５とスイッチ２０６を経由して電源２０７に接続される。
試料タンク２０８内の試料２０９はポンプＡ ２１０を作動することによって試料用配管２１１を経由して試料導入口１０６から導入され光反応管１０８を流通し試料排出口１０７から排出され生成物用配管２１２を経由して生成物タンク２１３に移送される。
媒体タンク２１４内の媒体２１５はポンプＢ ２１６を作動することによって媒体用配管２１７を経由して媒体導入口１０４から導入され、媒体流通管１０２を流通し媒体排出口１０５から排出され媒体用配管２１７を経由して媒体タンク２１４に循環される。
FIG. 2 shows a photoreaction apparatus 200 according to an embodiment of the present invention. As shown in FIG. 2, the light source 201 is inserted into the cavity 103 of the medium flow tube 102. The light source 201 is connected to the light source connection terminal 202 and is connected to the light source electronic ballast 204 through the connection line 203. The light source electronic ballast 204 is connected to a power source 207 via an electric cord 205 and a switch 206.
The sample 209 in the sample tank 208 is introduced from the sample inlet 106 via the sample pipe 211 by operating the pump A 210, flows through the photoreaction tube 108, and is discharged from the sample outlet 107 to the product pipe 212. To the product tank 213.
The medium 215 in the medium tank 214 is introduced from the medium introduction port 104 via the medium pipe 217 by operating the pump B 216, circulates through the medium circulation pipe 102, and is discharged from the medium discharge port 105 to the medium pipe 217. Is circulated to the medium tank 214 via
媒体タンク２１４内の媒体２１５の温度は温度コントローラー２１８によって制御される。一実施形態において、媒体流通管１０２は光反射体２１９を用いて覆われる。ポンプＡ ２１０とポンプＢ ２１６は電気コード２０５を経由して電源２０７に接続される。
媒体タンク２１４内の媒体２１５は温度コントローラー２１８によって反応温度に調整した後、ポンプＢ ２１６を作動させて媒体２１５を媒体流通管１０２内に流通させて、光反応管１０８の温度を反応温度に調整する。
The temperature of the medium 215 in the medium tank 214 is controlled by the temperature controller 218. In one embodiment, the media flow tube 102 is covered with a light reflector 219. Pump A 210 and pump B 216 are connected to a power source 207 via an electrical cord 205.
The medium 215 in the medium tank 214 is adjusted to the reaction temperature by the temperature controller 218, and then the pump B 216 is operated to cause the medium 215 to flow through the medium flow pipe 102, thereby adjusting the temperature of the photoreaction tube 108 to the reaction temperature. To do.
ポンプＡ ２１０を作動させて光反応管１０８内の試料を流通させるとともに、光源電子安定器２０４のスイッチ２０６をＯＮにして光源２０１を点灯し、光反応管１０８内を流通する試料に光を照射して光反応を実施する。 The sample in the photoreaction tube 108 is circulated by operating the pump A 210 and the light source 201 is turned on by turning on the switch 206 of the light source electronic ballast 204 to irradiate the sample flowing in the photoreaction tube 108 with light. And carry out a photoreaction.
図３に、本発明の一実施形態に係る光反応装置３００を示す。図２と同じ符号は、図２と同じものを表す。反応性ガスを使用して光反応を実施する場合、ガス貯蔵タンク３０１とガス流量計３０２をガス配管３０３で接続する。ポンプＡ ２１０と試料導入口１０６の間にミキサー３０４を設置し、さらにガス流量計３０２からミキサー３０４の間に逆止弁３０５を設置しガス配管３０３を経由してミキサー３０４に接続する。 FIG. 3 shows a photoreaction apparatus 300 according to an embodiment of the present invention. The same reference numerals as those in FIG. 2 represent the same elements as those in FIG. When performing a photoreaction using a reactive gas, the gas storage tank 301 and the gas flow meter 302 are connected by a gas pipe 303. A mixer 304 is installed between the pump A 210 and the sample inlet 106, and a check valve 305 is installed between the gas flow meter 302 and the mixer 304 and connected to the mixer 304 via the gas pipe 303.
図３に示すように、媒体流通管１０２の空洞部１０３に光源２０１を挿入する。光源２０１は光源接続端子２０２を接続し、接続線２０３によって光源電子安定器２０４に接続される。光源電子安定器２０４は電気コード２０５とスイッチ２０６を経由して電源２０７に接続される。 As shown in FIG. 3, the light source 201 is inserted into the cavity 103 of the medium flow tube 102. The light source 201 is connected to the light source connection terminal 202 and is connected to the light source electronic ballast 204 through the connection line 203. The light source electronic ballast 204 is connected to a power source 207 via an electric cord 205 and a switch 206.
試料タンク２０８内の試料２０９はポンプＡ ２１０を作動することによって試料用配管２１１を経由してミキサー３０４に導入される。ガス貯蔵タンク３０１内の反応性ガス３０６はガス流量計３０２を作動することによってガス配管３０３を経由してミキサー３０４に導入され、試料２０９と反応性ガス３０６はミキサー３０４で混合し、試料導入口１０６から導入され光反応管１０８を流通し試料排出口１０７から排出され生成物タンク２１３に移送される。 The sample 209 in the sample tank 208 is introduced into the mixer 304 via the sample pipe 211 by operating the pump A 210. The reactive gas 306 in the gas storage tank 301 is introduced into the mixer 304 via the gas pipe 303 by operating the gas flow meter 302, and the sample 209 and the reactive gas 306 are mixed by the mixer 304, and the sample introduction port 106 is introduced from 106, passes through the photoreaction tube 108, is discharged from the sample outlet 107, and is transferred to the product tank 213.
媒体タンク２１４内の媒体２１５はポンプＢ ２１６を作動することによって媒体用配管２１７を経由して媒体導入口１０４から導入され、媒体流通管１０２を流通し媒体排出口１０５から排出され媒体用配管２１７を経由して媒体タンク２１４に循環される。 The medium 215 in the medium tank 214 is introduced from the medium introduction port 104 via the medium pipe 217 by operating the pump B 216, circulates through the medium circulation pipe 102, and is discharged from the medium discharge port 105 to the medium pipe 217. Is circulated to the medium tank 214 via
媒体タンク２１４内の媒体２１５の温度は温度コントローラー２１８によって制御される。一実施形態において、媒体流通管１０２は光反射体２１９を用いて覆われる。ポンプＡ ２１０とポンプＢ ２１６は電気コード２０５を経由して電源２０７に接続される。
媒体タンク２１４内の媒体２１５は温度コントローラー２１８によって反応温度に調整した後、ポンプＢ ２１６を作動させて媒体２１５を媒体流通管１０２内に流通させて、光反応管１０８の温度を反応温度に調整する。
The temperature of the medium 215 in the medium tank 214 is controlled by the temperature controller 218. In one embodiment, the media flow tube 102 is covered with a light reflector 219. Pump A 210 and pump B 216 are connected to a power source 207 via an electrical cord 205.
The medium 215 in the medium tank 214 is adjusted to the reaction temperature by the temperature controller 218, and then the pump B 216 is operated to cause the medium 215 to flow through the medium flow pipe 102, thereby adjusting the temperature of the photoreaction tube 108 to the reaction temperature. To do.
ポンプＡ ２１０とガス流量計３０２を作動させて光反応管１０８内に試料２０９と反応性ガス３０６の混合物を流通させるとともに、光源電子安定器２０４のスイッチ２０６をＯＮにして光源２０１を点灯し、光反応管１０８内を流通する試料に光を照射して光反応を実施する。 The pump A 210 and the gas flow meter 302 are operated to circulate the mixture of the sample 209 and the reactive gas 306 in the photoreaction tube 108, and the switch 206 of the light source electronic ballast 204 is turned on to turn on the light source 201, Light reaction is performed by irradiating the sample flowing through the photoreaction tube 108 with light.
本光反応装置は、光合成反応、光分解反応、光環化反応、光還元反応、光酸化反応、光ハロゲン化反応、光高分子反応、光洗浄反応、光殺菌反応、光脱臭反応などの反応を実施することができる。 This photoreactor can perform reactions such as photosynthesis reaction, photolysis reaction, photocyclization reaction, photoreduction reaction, photooxidation reaction, photohalogenation reaction, photopolymer reaction, photowashing reaction, photodisinfection reaction, photodeodorization reaction, etc. Can be implemented.
本光反応装置は、試料として、無機化合物、有機化合物などの化合物、水素ガス、酸素ガス、一酸化炭素、フッ素ガス、塩素ガス、臭素ガス、ヨウ素ガスなどの反応性ガスなどを使用することができる。また、不活性ガスとして窒素、アルゴンなどを使用しても良い。 This photoreactor may use as a sample a compound such as an inorganic compound or an organic compound, a reactive gas such as hydrogen gas, oxygen gas, carbon monoxide, fluorine gas, chlorine gas, bromine gas, or iodine gas. it can. Further, nitrogen, argon or the like may be used as an inert gas.
本媒体流通管および本光反応管に使用する材料は、光源からの光を透過して光反応管内に流通する試料に光を照射することができる材料が使用される。耐薬品性、耐圧性、耐熱性などの性能を有していれば、様々な光反応を実施することができるので好ましい。例えば、テフロン（登録商標）樹脂、パーフルオロアルコキシアルカン樹脂、ポリテトラフルオロエチレン樹脂などのフッ素樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポロエチレンテレフタレート樹脂、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、アクリル樹脂、メタクリル樹脂などの熱可塑性樹脂、ポリアミド樹脂、ポリカーボネート樹脂、フェノール樹脂、メラミン樹脂、不飽和ポリエステル樹脂エポキシ樹脂などの熱硬化性樹脂、並質ガラス、硬質ガラス、パイレックス（登録商標）ガラス、石英ガラスなどのガラスを使用することができる。光反応で要求される耐薬品性、耐圧性、耐熱性のすべてを兼ね備えているガラスを使用することが好ましい。 The material used for the medium distribution tube and the photoreaction tube is a material that can transmit light from a light source and irradiate the sample flowing through the photoreaction tube with light. It is preferable to have performances such as chemical resistance, pressure resistance, and heat resistance because various photoreactions can be performed. For example, fluorine resin such as Teflon (registered trademark) resin, perfluoroalkoxyalkane resin, polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polyvinyl chloride resin, polystyrene resin, ABS resin, acrylic resin, Thermosetting resins such as methacrylic resins, polyamide resins, polycarbonate resins, phenolic resins, melamine resins, unsaturated polyester resins, epoxy resins, etc., ordinary glass, hard glass, pyrex (registered trademark) glass, quartz glass, etc. Of glass can be used. It is preferable to use a glass having all of chemical resistance, pressure resistance, and heat resistance required for the photoreaction.
光反応に使用する光源は、光反応リアクターの空洞部に挿入できる光源（第１光源）を用いれば良く、目的とする光反応に有効な波長を持つランプを適宜使用すれば良い。例えば、紫外線ランプ、可視光ランプ、赤外線ランプ、蛍光ランプ、ブラックライト、ＬＥＤライト、水銀ランプ、キセノンランプなどのランプが使用できる。また、光源の点灯方式は、特に制限されないが、スタータ型、ラピッドスタート型、インバータ型、光源電子安定器などが使用することができる。 The light source used for the photoreaction may be a light source (first light source) that can be inserted into the cavity of the photoreactor, and a lamp having a wavelength effective for the desired photoreaction may be used as appropriate. For example, lamps such as an ultraviolet lamp, a visible light lamp, an infrared lamp, a fluorescent lamp, a black light, an LED light, a mercury lamp, and a xenon lamp can be used. The lighting method of the light source is not particularly limited, but a starter type, a rapid start type, an inverter type, a light source electronic ballast, or the like can be used.
本光反応装置は、空洞部に光源を挿入して使用するが、光の強度が不足して試料の変換率が悪い場合は、目的とする光反応に有効な波長を持つランプ（第２光源）を、媒体流通管の外側に設置して使用すれば良い。例えば、紫外線ランプ、可視光ランプ、赤外線ランプ、光源、ブラックライト、ＬＥＤライト、水銀ランプ、キセノンランプなどのランプが使用できる。このようにすれば、光反応管内に流通する試料に対して、光反応リアクターの空洞部に挿入した第１光源と媒体流通管の外側に設置した第２光源から光反応管に光を照射することによって、光反応を促進することができる。 This photoreaction apparatus is used with a light source inserted into the cavity, but if the light intensity is insufficient and the sample conversion rate is poor, a lamp (second light source) having an effective wavelength for the intended photoreaction is used. ) May be used outside the medium distribution pipe. For example, lamps such as an ultraviolet lamp, a visible light lamp, an infrared lamp, a light source, a black light, an LED light, a mercury lamp, and a xenon lamp can be used. In this way, the sample flowing through the photoreaction tube is irradiated with light from the first light source inserted into the cavity of the photoreactor and the second light source installed outside the medium flow tube. Thus, the photoreaction can be promoted.
本光反応で使用する試料は、光反応によって目的物に変換される試料を用いれば良く、例えば、液体試料、気体試料、粒子試料を液体に懸濁させたスラリーなどの試料を使用することができる。試料を２種類以上使用する場合はミキサーを用いて試料を混合すれば良い。また、気体試料を使用する場合、試料排出口と生成物タンクの間に背圧弁などの加圧装置を設置して加圧状態で光反応を実施すれば、気体試料の液体試料への溶解度を上げることができるので、光反応の速度を向上させることができるので好ましい。 The sample used in this photoreaction may be a sample that is converted into a target product by photoreaction. For example, a sample such as a liquid sample, a gas sample, or a slurry in which a particle sample is suspended in a liquid may be used. it can. When two or more types of samples are used, the samples may be mixed using a mixer. In addition, when using a gas sample, if a pressure device such as a back pressure valve is installed between the sample outlet and the product tank and the photoreaction is performed under pressure, the solubility of the gas sample in the liquid sample can be increased. This is preferable because the speed of the photoreaction can be improved.
本光反応で使用する媒体は、媒体容器内に保持され、冷却装置あるいは加熱装置を用いて反応温度に設定され、循環ポンプを用いて、媒体導入口から媒体流通管に導入され、光反応間内の試料を反応温度に制御した後、媒体排出口から排出され媒体容器に戻る。媒体は、光源からの光を吸収して光反応管内に流通する試料への光の照射を妨げない媒体を自由に用いることができる。例えば、通常用いられる水、アルコール類、シリコーンオイル類などを使用することができる。 The medium used in this photoreaction is held in a medium container, set to a reaction temperature using a cooling device or a heating device, introduced into a medium flow pipe from a medium introduction port using a circulation pump, After the inner sample is controlled to the reaction temperature, the sample is discharged from the medium discharge port and returned to the medium container. As the medium, a medium that absorbs light from the light source and does not interfere with irradiation of light to the sample flowing in the photoreaction tube can be freely used. For example, commonly used water, alcohols, silicone oils and the like can be used.
本光反応装置は、空洞部に光源を挿入して使用するが、媒体流通管の外側を光反射体で覆うことによって、光反応に使用されなかった光を光反射体によって反射させて光反応管内に流通する試料に光を照射することができるので、光を利用効率良く利用し、光反応を促進するとともに、光の外部への漏洩も防ぐ役割を持つ。光反射体は、光を透過しないで反射できる材料を用いれば良く、例えば、ガラスの表面にアルミニウムや銀などの金属を蒸着したガラス鏡、アクリル樹脂やポリエステル樹脂の表面にアルミニウムや銀などを蒸着したプラスチック鏡、アルミニウム板、ステンレス以板、アルミホイルなどの金属も用いることができる。光源からの発熱が大きい場合は、耐熱性のある光反射体を使用すれば良い。 This photoreaction device is used by inserting a light source into the cavity, but by covering the outside of the medium flow tube with a light reflector, light that has not been used for the photoreaction is reflected by the light reflector and photoreaction is performed. Since it is possible to irradiate the sample circulating in the tube with light, it has a role of utilizing light efficiently and promoting the photoreaction and preventing leakage of light to the outside. The light reflector may be made of a material that can reflect without transmitting light. For example, a glass mirror in which a metal such as aluminum or silver is deposited on the surface of glass, or aluminum or silver is deposited on the surface of acrylic resin or polyester resin. Metals such as plastic mirrors, aluminum plates, stainless steel plates, and aluminum foil can also be used. When the heat generated from the light source is large, a heat-reflective light reflector may be used.
光反応リアクターの空洞部に挿入した第１光源と媒体流通管の外側に設置した第２光源から光反応管に光を照射して光反応を実施する場合は、媒体流通管の外側に設置した第２光源の外側を光反射体で覆うことによって、光反応に使用されなかった光を光反射体によって反射して光反応管内に流通する試料に光を照射することができるので、光を効率良く利用し、光反応を促進するとともに、光の外部への漏洩も防ぐ役割を持つ。 When the light reaction tube is irradiated with light from the first light source inserted into the cavity of the photoreactor and the second light source installed outside the medium flow tube, the photoreaction is performed outside the medium flow tube. By covering the outside of the second light source with a light reflector, light that has not been used for the photoreaction can be reflected by the light reflector to irradiate the sample flowing in the photoreaction tube, so that the light can be efficiently used. It is often used to promote photoreaction and prevent light from leaking outside.
本光反応装置では、本光反応リアクターは、第一の光反応リアクターと第二の光リアクターを直列に接続して使用することや、第一の光反応リアクターと第二の光反応リアクターを並列に接続して使用することもできる。本光反応リアクターでは、光反応管と光源収納部としての空洞部と媒体流通管とがコンパクトにまとまっているため、多様な組み合わせが可能となる。 In this photoreaction apparatus, the photoreactor can be used by connecting the first photoreactor and the second photoreactor in series, or the first photoreactor and the second photoreactor in parallel. It can also be used by connecting to. In the present photoreactor, the photoreaction tube, the cavity as the light source housing and the medium flow tube are gathered in a compact manner, so that various combinations are possible.
本発明の光反応リアクターは、らせん状に設置されている光反応管が媒体流通管内に設置されているため、クランプなどの固定装置で容易に固定することができる。実施する反応を考慮して、光反応リアクターを横置き、縦置き、斜め置きなど自由な角度に設置して反応を実施すれば良い。光反応リアクターを縦置きあるいは斜め置きに設置して試料を流通させる場合、試料の流通方向をアップフローあるいはダウンフローどちらでも自由に選択することができる。もし、光反応で固体が生成する場合は、縦置きあるいは斜め置きにしてダウンフローで光反応を実施すれば、固体による閉塞を防ぐことが可能である。 The photoreaction reactor of the present invention can be easily fixed by a fixing device such as a clamp because the photoreaction tube installed in a spiral shape is installed in the medium flow tube. In consideration of the reaction to be carried out, the reaction may be carried out by installing the photoreactor at a free angle such as horizontally, vertically or diagonally. When the sample is circulated by installing the photoreactor vertically or obliquely, the flow direction of the sample can be freely selected by either up-flow or down-flow. If a solid is generated by a photoreaction, blockage by the solid can be prevented if the photoreaction is carried out in a downflow by placing it vertically or obliquely.
熱媒あるいは冷媒の媒体を媒体流通管に流通させる場合、試料の導入口側から媒体を流通させても良いし、試料の排出口側から媒体を流通させても良い。 When the medium of the heat medium or the refrigerant is circulated through the medium flow pipe, the medium may be circulated from the sample inlet side or the medium may be circulated from the sample outlet side.
本光反応装置は、試料をらせん状の光反応管に流通させて反応を実施することを想定して反応を実施するが、試料の光反応性が高い場合は、媒体流通管に試料を流通させて、らせん状の光反応管に媒体を流通させれば、媒体流通管に流通する試料の温度を制御して反応することもできる。 This photoreaction apparatus carries out the reaction assuming that the sample is circulated through the spiral photoreaction tube, but the sample is circulated through the medium flow tube when the photoreactivity of the sample is high. If the medium is allowed to flow through the spiral photoreaction tube, the reaction can be performed by controlling the temperature of the sample flowing through the medium flow tube.
以下に実施例を挙げて、本発明を具体的説明するが、本発明は、これらに限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
［実施例１］
図３に示す光反応装置を用いた。光反応リアクターを縦置きにしてクランプで固定した。混合液と塩素ガスを、光反応リアクターの上部の試料導入口から導入し、下部の試料排出口から排出した。光反応管は内径２．０ｍｍ、長さ１００ｃｍ、内容量３．１ｍｌのものを用いた。以下の方法で反応混合液の光反応管内の滞留時間を測定した。内容量５０ｍｌのガスタイトシリンジに炭酸エチレン１０．０ｇ（０．１１４モル）と水１０．０ｇの混合液を充填してシリンジポンプに装着した。シリンジポンプを作動して混合液を０．２ｍｌ／分の速度でミキサーに導入した。ガス流量計を作動して塩素ガスボンベから塩素ガスを２５ｍｌ／分の速度でミキサーに導入した。ミキサー内で混合液と塩素ガスが混合された後、光反応管内を上部の試料導入口に導入されてから下部の試料排出口から排出されるまでの試料の滞留時間を計測すると４０秒であった。
炭酸エチレンの光モノ塩素化反応を実施した。光反射板で覆いをした光反応リアクターをクランプで縦置きに固定した。空洞部に光源としてのブラックライト（３５２ｎｍ ４Ｗ）を挿入し、光源電子安定器からの光源接続端子を接続した。内容量５０ｍｌのガスタイトシリンジに炭酸エチレン１０．０ｇ（０．１１４モル）と水１０．０ｇの混合液を充填しシリンジポンプに装着した。媒体流通管に７０℃の温水を流通させて、光反応管を７０℃に加熱した。シリンジポンプを作動させて混合液を０．２ｍｌ／分の速度でミキサーに導入し、ガス流量計を作動させて塩素ガスを２５ｍｌ／分の速度でミキサーに導入し、混合液と塩素ガスをミキサーで混合して光導入口から光反応管に導入するとともに、ブラックライトの電源を入れて光反応管内の炭酸エチレンに光を照射して、光塩素化反応を実施した。生成物タンクに貯蔵された反応生成物はガスクロマトグラフィーを用いて分析をした。その結果、炭酸エチレンの転化率は２０．４％、モノクロロ炭酸エチレンの選択率は８９．５％、ジクロロ炭酸エチレンの選択率は１０．５％、トリクロロ炭酸エチレンは生成していなかった。
[Example 1]
The photoreaction apparatus shown in FIG. 3 was used. The photoreactor was placed vertically and fixed with a clamp. The mixed solution and chlorine gas were introduced from the upper sample inlet of the photoreactor and discharged from the lower sample outlet. A photoreaction tube having an inner diameter of 2.0 mm, a length of 100 cm, and an inner volume of 3.1 ml was used. The residence time of the reaction mixture in the photoreaction tube was measured by the following method. A gas tight syringe having an internal volume of 50 ml was filled with a mixed solution of 10.0 g (0.114 mol) of ethylene carbonate and 10.0 g of water and attached to a syringe pump. The syringe pump was operated to introduce the mixed solution into the mixer at a rate of 0.2 ml / min. The gas flow meter was operated to introduce chlorine gas from a chlorine gas cylinder into the mixer at a rate of 25 ml / min. After mixing the mixed liquid and chlorine gas in the mixer, the residence time of the sample from when it was introduced into the upper sample inlet until it was discharged from the lower sample outlet was 40 seconds. It was.
A photomonochlorination reaction of ethylene carbonate was carried out. A photoreactor covered with a light reflector was fixed vertically with a clamp. A black light (352 nm 4 W) as a light source was inserted into the cavity, and a light source connection terminal from a light source electronic ballast was connected. A gas tight syringe having an internal volume of 50 ml was filled with a mixed solution of 10.0 g (0.114 mol) of ethylene carbonate and 10.0 g of water and attached to a syringe pump. Hot water at 70 ° C. was passed through the medium flow tube, and the photoreaction tube was heated to 70 ° C. Operate the syringe pump to introduce the mixed solution into the mixer at a rate of 0.2 ml / min, operate the gas flow meter to introduce chlorine gas into the mixer at a rate of 25 ml / min, and mix the mixed solution and chlorine gas into the mixer Then, the mixture was introduced into the photoreaction tube from the light inlet, and the black light was turned on to irradiate the ethylene carbonate in the photoreaction tube with light to carry out the photochlorination reaction. The reaction product stored in the product tank was analyzed using gas chromatography. As a result, the conversion of ethylene carbonate was 20.4%, the selectivity of monochloroethylene carbonate was 89.5%, the selectivity of dichloroethylene carbonate was 10.5%, and no trichloroethylene carbonate was produced.
［比較例１］
炭酸エチレンの光モノ塩素化反応を実施した。内容量５０ｍｌの三つ口フラスコに温度計、塩素ガス導入管、頭部に塩素ガス排出管を付けた冷却管、および磁気撹拌子を取り付けた。同フラスコ内に炭酸エチレン１０．０ｇ（０．１１４モル）と水を仕込んだ。フラスコの下部をオイルバス上で加熱し、フラスコ内の炭酸エチレンを７０℃に昇温した。フラスコの横部にブラックライト（３６５ｎｍ、１５Ｗ）を設置し、フラスコ及び装置全体をアルミホイルで覆った。ブラックライトの電源を入れてフラスコ内の炭酸エチレンに光を照射した。ここに、塩素ガス２５ｍｌ／分の速度で３時間、トータル４５００ｍｌ（０．２０モル）を流通させた。反応終了後、反応生成物を室温まで冷却し、ガスクロマトグラフィーを用いて分析をした。その結果、炭酸エチレンの転化率は７１．７％、モノクロロ炭酸エチレンの選択率は１０．５％、ジクロロ炭酸エチレンの選択率は３５．２％、トリクロロ炭酸エチレンの選択率は３９．５％であった。
[Comparative Example 1]
A photomonochlorination reaction of ethylene carbonate was carried out. A thermometer, a chlorine gas inlet pipe, a cooling pipe with a chlorine gas discharge pipe at the head, and a magnetic stirrer were attached to a three-necked flask having an internal volume of 50 ml. Into the flask, 10.0 g (0.114 mol) of ethylene carbonate and water were charged. The lower part of the flask was heated on an oil bath, and the ethylene carbonate in the flask was heated to 70 ° C. A black light (365 nm, 15 W) was placed on the side of the flask, and the flask and the entire apparatus were covered with aluminum foil. The black light was turned on and the ethylene carbonate in the flask was irradiated with light. Here, a total of 4500 ml (0.20 mol) was circulated at a rate of chlorine gas of 25 ml / min for 3 hours. After completion of the reaction, the reaction product was cooled to room temperature and analyzed using gas chromatography. As a result, the ethylene carbonate conversion was 71.7%, monochloroethylene carbonate selectivity was 10.5%, dichloroethylene carbonate selectivity was 35.2%, and trichloroethylene carbonate selectivity was 39.5%. there were.
１０１ 光反応リアクター
１０２ 媒体流通管
１０３ 空洞部
１０４ 媒体導入口
１０５ 媒体排出口
１０６ 試料導入口
１０７ 試料排出口
１０８ 光反応管
２００ 光反応装置
２０１ 光源
２０２ 光源接続端子
２０３ 接続線
２０４ 光源電子安定器
２０５ 電気コード
２０６ スイッチ
２０７ 電源
２０８ 試料タンク
２０９ 試料
２１０ ポンプＡ
２１１ 試料用配管
２１２ 生成物用配管
２１３ 生成物タンク
２１４ 媒体タンク
２１５ 媒体
２１６ ポンプＢ
２１７ 媒体用配管
２１８ 温度コントローラー
２１９ 光反射体
３００ 光反応装置
３０１ ガス貯蔵タンク
３０２ ガス流量計
３０３ ガス配管
３０４ ミキサー
３０５ 逆止弁
３０６ 反応性ガス
DESCRIPTION OF SYMBOLS 101 Photoreactor 102 Medium flow pipe 103 Cavity part 104 Medium inlet 105 Medium outlet 106 Sample inlet 107 Sample outlet 108 Photoreaction tube 200 Photoreactor 201 Light source 202 Light source connection terminal 203 Connection line 204 Light source electronic ballast 205 Electric cord 206 Switch 207 Power supply 208 Sample tank 209 Sample 210 Pump A
211 Sample piping 212 Product piping 213 Product tank 214 Medium tank 215 Medium 216 Pump B
217 Pipe for medium 218 Temperature controller 219 Light reflector 300 Photoreactor 301 Gas storage tank 302 Gas flow meter 303 Gas pipe 304 Mixer 305 Check valve 306 Reactive gas
Claims (3)
A photoreactor according to claim 1, and a first light source installed in the cavity of the photoreactor and / or a second light source installed outside the medium flow tube, the first light source and / or Alternatively, a photoreaction apparatus that performs light reaction by irradiating a sample flowing from the second light source into the photoreaction tube, and includes a light reflector that covers the outside of the photoreaction apparatus, And a temperature controller for controlling the temperature of the medium so as to carry out the photoreaction by controlling the temperature of the sample and the photoreaction apparatus that circulates the medium in the photoreaction tube. Photoreactor.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP2021175567A (en) * | 2020-05-02 | 2021-11-04 | 株式会社MiChS | Flow type photoreactor and flow type photoreactor |
| CN114192078A (en) * | 2021-11-26 | 2022-03-18 | 江苏理文化工有限公司 | Bubbling reaction device and method for continuously producing chlorinated ethylene carbonate |
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