Title of Invention	MICROREACTOR AND LIQUID PHASE CHEMICAL REACTION METHOD USING MICROREACTOR
Abstract	This invention provides a microreactor comprising a microchamber provided with a raw material introduction port and a product discharge port; wherein solid catalysts are aligned in a line m the longitudinal direction of the microchamber to fill the microchamber.

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DESCRIPTION MICROREACTORAND LIQUID PHASE CHEMICAL REACTION METHOD USING MICROREACTOR TECHNICAL FIELD [0001] The present invention relates to a microreactor and a liquid phase chemical reaction method using the micro reactor. More specifically, the present invention relates to a microreactor capable of conducting a chemical reaction at a high rate, and a method of high-yield liquid phase chemical reaction using the microreactor. Priority is claimed on Japanese Patent Application No. 2007-267148, fil«i October 12,2007, the content of which is incorporated here by referee. BACKGROUND ART [0002] Microreactor is a flow type reaction apparatus in which classical reactions take place in a space (microchannel) With size of 1mm or less {1 one side. Compared to the typical large scale reaction sppmum, in the microreaotCHr, the heat caused by the exothermic reaction can be removed rapidly and the ten1peratote distribution bias can be prevented, because the heat-1ansfisr efficiency is high. Further, expansion to ductrial production is easy since the microreactor can be scaled-i1 by increasing the number of micro channels in the industrial process. [0003] A microreactor can be manufactured by, for example, forming a groove as a flow channel on a flat substrate by a photolithographic method and covering die fiat substrate formed with the groove using a flat plate, the flat plat being provided with a raw material introduction port and a product discharge port (for example, Patent Document 1). Flow channels can be classified into T-shaped, J-shaped, Y-shaped, cyolone-shaped and pillar»shaped flow channels. The microreactor is placed so as to ke1 the flow channel in a horizontal position, and the chemical reaction takes place in to horizontal flow channel (microchamber). [0004] Meanwhile, the utilization of the microreactor in the gas-phase chemical reaction has a long history and plenty of studies have been nuute. However, the utilization of microreactor m the liquid phase chemical reaction has a slK)rttt history and many problems remain. For example, b the liquid phase diemical reaction in the microreactor, pressure loss is large and clogging may occur. Furthermore, in a reaction system in which gas is generated by the reaction, since the ps extrudes the contend, an expected reaction time cannot be retained, or since liw gas adhere to the nit&ce of the catalyst, contact between the raw material and the catalyst is inhibited, thereby making it impossible to increase the reaction rate. [0005] In order to enlarge the contact area between the catalysts and the reaction raw material in a chemical reaction reactor, a catalj1t having a la1 specific surface area is usually used. For example, a catalyst in which a granular support having a smaller size than the inner diameter of the chemical reaction reactor carries a metal catalyst can be cited as an example. However, when a liquid phase reaction is conducted in a microehamber filled with the granular solid catalysts, channeling (a phenomenon in which an unexpected thick flow channel is formed in a catalyst-filled layer and the raw material fluid only flows into the unexpectedly v flow channel, and does not flow into other flow channels.) occurs. Therefore, the contact area beset the reaction raw material and the catalysts may becomes smaller than the designed value and the reaction rate may become lower. [Patent Document 1] Japanese Unexamined Patent Ai1Ucidon, First Publication No. 2007-136345 DISCLOSURE OF INVENTION Problems to be Solved by the Invention [0006] The objective of the present invention is to provide a microreactor capable of conducting chemical reaction at a high rate, and a method of hii1-yield liquid phase chemical reaction using said microreactor. Means for Solving the Problems [0007] In order to thieves tie above ol1ect, the inventors of fte present invention conducted intensive investigations and discovered that the reaction rate can be improved by conducting a chemical reaction using a microreactor in wUch solid catalysts are aligned in a lit in the longitudinal direction of the microchamba* to fill the microchamber. The present invention was completed by conducting feather studies on the basis of this finding. [0008] The preset invention includes the following aspects: (1) a microreactor including a microchamber provided with a raw material introduction port and a product discharge port; wherein solid catalysts are aligned in a line in Use longitudinal direction of the microchamber to fill the micro chamber; (2) the microreactor according to (1), wherein the solid catalysts are pellet-shaped, tablet-shaped or disc-shaped; (3) the microreactor according to (1), wherein the solid catalysts are «}figured in such a manner that a pellet'Shi1, tablet-shi1d or disc-sbi1 suppcsrt carries a catalyst including a transition metal element and/or an acid, or, a tnmsition metal element and/or abase; (4) a liquid chemical reaction method using the microreactor according to any one of (1) to (3), including introducing a liquid raw material from the raw material Introduction port to the microchamber, conducting a ch«mice reaction in the n1crochamber to obtain a product, and dischaigii1 the product from the product disdas1 port of tabs microreactor, and (5) the liquid chemical reaction method according to (4), weird the product includes a product in Has farm of gas. Edicts of 1 Invention [0009] By using die microreactor of the present invention, a domical reaction can be conducted at a high rate. Furthermore, a high-yield product can be obtained by conducting a liquid chemical reaction using the microreactor of the present invention. Furthennore, in the microreactor of the present invention, unexpected channeling can be prevented and the contact area between a raw material and solid catalysts can be adjusted as designed value, thereby making it easy to design the microrwctor, BRIEF DESCRIPTION OF THE DRAWINGS [0010] FIQ 1 is a conceptual diagram showing an example of the microreactor of the present invention. FIQ 2 is a conceptual diagram showing another example of the microreactor of the present invention. FIQ 3 is conceptual diagram showing a miaorea1cnr in v1eh solid catalysts are randomly filled, FIQ 4 is a conceptual diagram showing an example of the microreactor provided with a raw material feetUng apparatus. The reference symbols shown in the figures are defined as follows: [0011] Rl, R2, R3: microchamber CI, C2: solid catalyst In: raw material introduction port Out: product discharge port BEST MODE FOR CARRYING OUT THE INVENTION [0012] In the embodiment of the present invention, a straight glass tube is used as a microchamber. The straight glass chamber is filled with solid cttalyrts (CI or C2), the solid catalysts being aligned in a line in the straight glass diamtm as shown in FIQ 1 or FIQ 2. A microchannel is formed between the glass tube and ttw solid catalysts, and a raw material compound is supplied from one end of the straight glass tube to conduct a reaction, and a desired product discharges from the other end of the straii1t glass tube. The product obtained from tiie microreactor of the present invention may include a gas by-product The temperature suitable for the mlcroreactor of the present invention is not particulariy limited. Although it can be selected according to the chemical reaction, it may be 25 to 250 *C, preferably 100 to 200 "C. The reaction wte can be easily controlled if the temperature is in the ranges described above. [0013] The mlcroreactor of the present invention hicludes a microehambo' provided with a raw meterial introduction port and a product discharge port, and the microchamber is filled with solid catalysts that are aligned therein in a line in the longitudinal direction of the microchamber. [0014] In the present invention, a microchamber which is the same as the conventional mi1oreactor can be used. Examples of the microchambff indude glass tube, chambers configured in such a manner that a plat pkite covers a substrate fixmed with a groove as a flow channel. A raw material introduction port is provided in at least one end of the microchamber; and a product discharge port is provided in the ottm end of the microchamber. The raw material is siipplied to the raw material introduction port and discharged from HM raw material discharge port. The layout of the flow channel of the microchamber can be selected according to the number and species of the raw materials. For example, it Is allowed that a Y-shaped or T-shaped flow channel is prepared to introduce two kinds of raw matnials from the two introduction ports, and the two kinds of mw materials are mixed in the junction of the flow channels to conduct a reaction. Further, it is also allowed that the raw material is introduced from one of the introduction ports and homogeneous catalysts are introduced fh)m the other introduction ports, and the raw material and the catalysts are mixed in the junction of the flow channels to conduct a reaction. The raw material to be introduced may be a material in the form of liquid or gas, aittough a material in the form of liquid is preferred since it derives advantages from the features of the microreactor. [0015] The inner volume of the microchamber is not particulaily limited, although it is preferably about 10 1m to 5000 \xa. per side. Furthor, ibe mietoohannel formed after filling the solid catalysts therein is preferably about 1 1m to 1000 \m per side. If one side of the microchannel is too small, it becomes difficult to simply the raw ourterial due to the increasing of the pressure loss. OntheoAerhaniifooesideofthe microchannel is too large, the advantages obtaining from the features of the microreactor decreases shine the heat-exchange efficiency decreases and a temperature distribution bias occurs. The length of the flow channel of1 microchamber is not particularly limited, although it is preferably 10 to 300 cm. [0016] The microreactor of the present invention is configure m such a maimed that solid catalysts are filled in the microchamber. As for the solid catalyst, a catalyst formed by solidifying a powder of a catalyst may be used, or a siqjported catalyst in which a catalyst is suj1ported by a support may be used. [0017] The catalysts can be selected according the species of taw chemical reaction. The representative examples of the catalysts include a catalyst bluing a transition metal element and/or an acid, or, a transition metal and/or a base. Examples of the transition metal element halide tantalum, molybdenum, tungsten, ruthenium, osmium, palladium, nickel, iron, cobalt, chromium, rhodium, iridium, platinum, gold, silver, copper, titanium and niobium. Examples of Fire catalysts including acid or base include acid catalyst such as silica-alumina composite oxide, zeolite, aNbjOj-MoOs composite oxide. Nb205'nH20, a proton type strong acidic beads-shaped fluoiine-oontaining resin or titania-silica composite oxide; a base catalyst such as mapesium alkoxide, magnesium oxide, calcium oxide or sodium alkoxide. [0018] Examples of the si1ort include carbon, silica, silica1ilumina, alumina, celite, calcium carbonate, zinc carbonate, barium carbonate, strontium carbonate and the like. Further, the shape of the support is not limited and examples of &e shape of the support include a pellet-shape, a tablet-shape, a disc-shape, a globular shape, a ring*i1pe, a mesh-shape, a honeycomb-shape, an indefinite shape, like. Among pellet-sh1e, tablet-shi1 and disc-she1 are preferable. Tb» size of solid catalyst can be selected according to die inner diameter of the mia1ochamber so that the solid catalysts are aligned in the microchamber in a line in a longitudinal direction. If the size of the solid catalyst is too small compared to the inner diameter of the microchamber, the solid catalysts may be aligned in two lines. Therefore, the size of the solid catalyst is preferably 70% or more of the inner diameter of the microchamber. In addition, the word "be aligned in a line" does not only mean that the solid catalysts are aligned only in a straight line, but also means that the solid catalysts are aligned hi a curved Ibe, such as aadgzagorthelike. [0019] The solid catalysts are aligned in the microchamber in a line in a longitudinal direction of the microchamber to fill the microchamber. Exainples of the solid catalyst include, as shown in Fiai, a solid catalyst made by aligning pellet'Shi1ed (colunm-shaped) solid catalysts (CI) in a line in a longitudinal direction of the microchamber (Rl) to fill the microchamber, the direction bdng 1}» same as the direction of the height of the column; ns shown in FIG. 2, a solid catalyst made by aligning globular shaped catalysts (C2) in a line in a longitudinal direction of the microchamber (C2) to fill the microchamber. By aligning the catalysts in suoh a manner as described above, the raw material is able to mainly pass tteoi1 the sqpMe (microdiannel) between the solid catalysts and the inner wall of the microchamber. As a result, unexpected channelhg can be prevented and it becomes easy to design the microreaetor since &e contact area between the raw material and the solid catalysts can be acUusted as the designed value. If the microchannel is straight along the gia» tt1, even in the case where a gas is generated by the liquid phase chemical reactioo. the gas is Msily extruded &om the product dischai1e port. Furthermore, by svqpportu1t and fixing the solid catalysts on the inner wall of the microchambor, the reaction [0020] The used amount ofthe catalyst is not particularly limited. Althou1 it can be selected according to the supplied amount ofthe raw material (reaction substance), it is generally 0.01 to 100 mol % with respwt to the reaction substance, preferably 0.1 to 50 mol %, and more preferably 0.1 to 10 mol %. [0021] The microreaetor is preferably provided with an apparatus supplying a raw material to the microchamber, for example, a pump or the like. ITie raw material-supplying apparatus is preferably an apparatus that does not cause a pulse when supplying the raw material. In order to deliver the solution steadily, an Electro Osmotic Flow can be used. [0022] In the present invention, the raw material may be supplied to the microreactor directly, or may be supplied to the microreactor aAer dissolving it in a solvent such as water, methanol, isopropylether, benzene, hexane. The supplied-amount pa hour {&oyf rate) of the raw material can be selected according to the amount of catalysts, although it is generally 0.1 to 500 ml/h, preferably 0.5 to 50 ml/h, and more preferably 1.0 to 5 ml/h. Further, the supplied-amount per hour of the raw material is preferably 1 to 1000 mmol/h, and more preferably 10 to 160 mmol/h vvb.ea. measured by the contact amount per Immol of catalyst [EXAMPLES] [0023] Next, the present invention will be described in more detail using the examples, al1ugh the scope of the present invention is m no way limited by these examples. [0024] The reaction was conducted using the apparatus shown in FIG 4. A microreactor (described in FIG 4 as MICROREACTOR) configured in such a numner that a stainless steel tube of 4 mm in diameter was filled wi& catalyst-si1jported pellets that are aligned therein in a line in a longitudinal dii1on, the catalyst being 3 mm in diameter and 3.5 mm in length, was used. As for the pellet, a pellet in which 0.5% by weight of palladium is supported on the sur&ce of an alumina (manu&ctured by N£. CHEMCAT CORPORATION) was used. [0025] Example 1 A150 mm-longtube $lled with 2150 mg of pellets (43 pellets, each weighing so mg were used, the supported palladium being 0.8S mol % with reafpect to tiie reactive substrate) was used as a tnicroreactor. A solutioQ obtained by dissolving 4.1 g (20 mmol) of iodobenzen and 2.0 g (20 mmol) of phenylacetylene in 3 ml of N,N«dimethylacetamide was filled in a gas tight syringe, end tiie reaction was conducted at a temperature of 100 T. The flow rate was set to 1.0 ml/h and the retraction time was set to 30 min. The resulting reaction solution was analyzed by high refinance liquid chromatography, and it was confined that the product was obtained quantitatively, [0026] Example 2 A150 sun-long tube filled with 2150 mg of pellets (43 pellets, eat1 weighing 50 mg were used, the si1pported palladium being 0.85 mol % with respect to the reactive substrate) was used as a microreactor. A solution obtain1 by dissolving 4.1 g (20 mmol) of iodobenzen, 2.1 g (24 mmol) of acrylic acid methyl esAier and 3.4 g (34 mmol) of triethylamine in 3 ml of N-methylpyroUdone was filled in a 1 tight syringe, and the reaction was conducted at a temperature of 120 **€. The flow rate and retention time was set as shown in Table 1. The resulting reaction solution was analyzed by high peifoimance liquid chromatography, and the results are shown as Table 1. 12 [0027] Table 1 Flow rate (ml/h) Retention time (min) Yield (»/o) 2-1 0.1 300 • 100 2-2 0.5 60 100 2-3 1.0 30 100 2-4 1.25 24 100 2-S 1.5 20 100 2-6 2.0 15 100 2-7 3.0 10 100 [0028] Example 3 A 250 mm-long tube filled with 3600 mg of pellets (72 pellets, each weighing SO mig were used, the siqiported palladimn being 0.85 mol % wi& respect to the reactive substrate) was used as a microreactor. A mixture obtahed by mixi&g 2.1 g (20 mmol) of benzaldehyde and 1.2 g QO mmol) of nitrome1iane was filled in a gas tight syringe, and the reaction was conducted at a temperature of 60 'C. The flow rate was set to 2.2 ml/h and the retention time was set to 1 hour, After analyzing the resulting product by 1H-NMR, it was confirmed that the inversion rate was 18%, and ibs objective substance of 2-nitro-l-ph1yl-ethanol was approximately obtidned quantitatively. [0029] Example 4. A 250 mm-long tube filled with 3600 mg of pellets (72 pellets, each weighing SO mg were used, the supported palMum being 3.38 mol % with respect to the reactive substrate) was used as a microreactor. A mixture obtained by mixing 528 mg (5 mmol) of phenylacetylene and 5 ml (12 mol equivalent with respect to phenyUcetylene) of arylbromide was filled in a gas tight syringe, and the reaction was conducted at room temperature. The flow rate was set to 1.1 ml/h and the retention time was set to 2 hours. After analyzing the resulting reaction solution by a gas cbromalogra1, it was confiimed that the inversion rate was 43Vo, and the desired products of l-bromo-l-phenyl-l,3-buthadien and l-bromo-2-ph«iyl-l-butaje were obtained at a yield of approximately 90%. [0030] Comparative Example! A100 mm-long tube filled with 0.5% by weight of i»allodium-supported alumina powder (the supported Pd being equivalent to 0.85 mol % with respect to the reactive substrate) was used as a microreactor. As in Example 1, a toms obtained by dissolving 4.1 g (20 mmol) of iodobenzen and 2.0 g (20 mmol) of phenylacetylene in 3 ml of N,N-dimethylacetamide was flll«i in a gas tight syringe to sounded a reaction at a temperature of 100 "X:. The flow rate was set to 1.0 ml/h and fl» retention time was set to40min. After analyzing the resulting reaction solution!1 ahigji performance liquid chromatography, it was confirmed that the product was obtained quantilitively, However, it was impossible to raise the flow rate flirtier since the pressure loss increases auto. the flow rate is raised to more than 0.1 ml/h. [0031] According to the Examples 1 to 4 and Congiarative Example 1, it is apparent that when using a microreactor in which solid catalysts are aligned in a Une (Examples 1 to 4), the pressure loss can be reduced and the flow rate can be raised compared to v1en a microreactor in which solid catalysts are randomly filled was used (Comparative Example 1), thereby enabling it to conduct a chemical reaction at a high efficiency. By using the mictoresctor of the present infraction, 1 poseur loss can be reduced and the flow rest can be raised, thereby making it pos1te to conduct a chemical reaction at a high efficiency. Furthermore, a high-yield pointiest cm be obtained by conductix1 a chemical inaction using the microreactor. Rushmore, in HM microreactor of the present invention, unexp1ted chinning can be prevented and the contact area between a material and solid catalyst can be ac1u1ed as designed value, thereby making it easy to design the microreactor. There&«e, the present invention is industrially useful. CLAIMS 1. A microreactor, comprising: a microchamber provided with a raw material introduction port and a product discharge port; wherein solid catalysts are aligned in a line in the longitudinal direction of the microchamber to fill the microchamber. 2. The microrector according to claim 1, wherein the solid catalysts are pellet-shaped, tablet-shaped or di8c-shq)ed. 3. The microreactor according to claim1, wherein the solid catalysts are configured in such a manner that a pellet-shaped, tablet-shaped or disc-shaped support carries a catalyst including a transition metal element and/or an add, or a transition metal element and/or a base. 4. A liquid chemical reaction method using the microreactor according to any one of claims 1 to 3, comprising: introducing a liquid raw material from the raw material introduction port to the microchamber, conducting a chemical reaction in the microchamber to obtain a product, and discharging the product from the product discharge port of the microreactor. 5. The liquid chemical reaction method according to claim 4, wherein the product includes a product in the form of gas.

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1934-chenp-2010 form-3 29-09-2010.pdf

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