TWI421125B - Reactor reaction speed control method, reaction device and dimethyl ether manufacturing method - Google Patents
Reactor reaction speed control method, reaction device and dimethyl ether manufacturing method Download PDFInfo
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- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00327—Controlling the temperature by direct heat exchange
- B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
- B01J2208/00353—Non-cryogenic fluids
- B01J2208/00362—Liquid
Description
本發明關於對隔熱型反應器供給原料，藉伴隨發熱之平衡反應而製造目的物時進行反應器內部之溫度控制方法與反應裝置及二甲醚之製造方法。The present invention relates to a method for controlling a temperature inside a reactor, a reaction apparatus, and a method for producing a dimethyl ether, in which a raw material is supplied to a heat-insulating reactor and an object is produced by an equilibrium reaction with heat generation.
於製造工廠中，有在反應器內設置觸媒層，使原料流通其中並使其反應而獲得其反應生成物之製品的情形。用以使反應器內適切地進行反應之重要的運轉條件之一，可舉出有反應器內的溫度管理。一般係將原料調整至預先設定之溫度後，供給至反應器。In a manufacturing plant, there is a case where a catalyst layer is provided in a reactor, and a raw material is passed through and reacted to obtain a product of the reaction product. One of the important operating conditions for allowing the reaction to proceed appropriately in the reactor is temperature management in the reactor. Generally, the raw materials are adjusted to a predetermined temperature and then supplied to the reactor.
上述反應為發熱反應時，隨著原料朝向反應器內之下游側流通，即隨著進行反應，原料的溫度會上昇起來。一旦原料的溫度較適合於主反應之溫度範圍高時，會產生不好的副生成物(不純物)而造成原料的損失，或是因會促進填縫(caulking)而使觸媒變差，另一方面，一旦原料之溫度低於前述溫度範圍則收率會降低，因此已提出了將觸媒層內之溫度維持在目的之溫度範圍內之各種方法。已知用以維持如此反應器內之溫度之代表的例子有以下的手法。When the above reaction is an exothermic reaction, as the raw material flows toward the downstream side in the reactor, the temperature of the raw material rises as the reaction proceeds. Once the temperature of the raw material is higher than the temperature range suitable for the main reaction, a bad by-product (impurity) may be generated to cause loss of the raw material, or the catalyst may be deteriorated due to caulking. On the one hand, once the temperature of the raw material is lower than the above temperature range, the yield is lowered, and thus various methods for maintaining the temperature in the catalyst layer within the intended temperature range have been proposed. An example of a representative for maintaining the temperature in such a reactor is known as follows.
第14圖為多管式反應器100，建構成於多管式反應器100內將原料供給至多數垂設的管101內，而於此管101內進行反應，藉冷媒而從外部冷卻該管101。雖然此多管式反應器100可確實且快速地冷卻原料，但是必須有多量的冷媒，又，反應器100的構造複雜，因此裝置之成本變高而不適於更大型化。Fig. 14 is a multi-tubular reactor 100 constructed in a multi-tubular reactor 100 to supply raw materials into a plurality of vertically disposed tubes 101, and react in the tubes 101 to cool the tubes from the outside by means of a refrigerant. 101. Although the multi-tubular reactor 100 can reliably and rapidly cool the raw materials, it is necessary to have a large amount of refrigerant, and the structure of the reactor 100 is complicated, so that the cost of the apparatus becomes high and it is not suitable for a larger size.
第15圖表示連接多數座反應器102，並於此反應器102、012之間中介設置有熱交換器(中間熱交換器)103的裝置。此裝置中，已供給至第1段之反應器102內的原料在此第1段的反應器102內因反應而發熱，接著藉熱交換器103冷卻後被供給至第2段的反應器102，而在此第2段之反應器102反應進行起來。之後，雖然省略圖式，然而原料進而以熱交換器為中介而被供給至第3段以後的反應器。如此的構造中，為了提昇在反應器102內之溫度的控制性，必須增加反應器102及熱交換器103的座數，且必須有連接配管，因此裝置的成本變高，又，裝置構造變複雜。又，如此的熱交換器103，係建構成大多使用供給第1段之反應器102前之反應前的原料作為熱交換用的冷媒，而將與反應生成物之間熱交換之後的原料供給至第1段的反應器102。如此情形下，反應器102之出口的的溫度會影響反應器102之入口的溫度，而存在有難以控制反應器102內之溫度的問題。Fig. 15 shows a device in which a plurality of reactors 102 are connected, and a heat exchanger (intermediate heat exchanger) 103 is interposed between the reactors 102 and 012. In this apparatus, the raw material supplied to the first stage reactor 102 is heated by the reaction in the reactor 102 of the first stage, and is cooled by the heat exchanger 103 and supplied to the reactor 102 of the second stage. The reactor 102 in this second stage reacts. Thereafter, although the drawings are omitted, the raw materials are further supplied to the reactors after the third stage by the heat exchanger. In such a configuration, in order to improve the controllability of the temperature in the reactor 102, it is necessary to increase the number of seats of the reactor 102 and the heat exchanger 103, and it is necessary to have a connection pipe, so that the cost of the device becomes high, and the device configuration becomes complex. Further, in the heat exchanger 103, the raw material before the reaction before the supply of the reactor 102 in the first stage is used as a refrigerant for heat exchange, and the raw material after heat exchange with the reaction product is supplied to the heat exchanger 103. Reactor 102 of the first stage. In such a case, the temperature at the outlet of the reactor 102 affects the temperature of the inlet of the reactor 102, and there is a problem that it is difficult to control the temperature in the reactor 102.
因此，專利文獻1提出了將固定地板流通式之隔熱型反應器內之觸媒層分割成複數層，並於各層間設置用以冷卻原料的淬熄區，於此淬熄將淬熄流體的原料以液體狀來供給而冷卻反應器內的手法。此裝置中，一旦被加熱之原料被供給至上側，則於上游側之觸媒層進行發熱反應，原料的溫度會上昇。原料於淬熄區藉淬熄而冷卻，之後流向下游側的觸媒層，同樣進行反應。淬熄流體的流量係被調整成在供給淬熄流體後之淬熄區的下游側測定原料的溫度，而該部位的溫度在適合主反應的溫度範圍。Therefore, Patent Document 1 proposes dividing a catalyst layer in a fixed floor flow type insulated reactor into a plurality of layers, and providing a quenching zone for cooling the raw materials between the layers, where quenching will quench the fluid The raw material is supplied in a liquid form to cool the inside of the reactor. In this apparatus, when the heated raw material is supplied to the upper side, the catalyst layer on the upstream side undergoes an exothermic reaction, and the temperature of the raw material rises. The raw material is cooled by quenching in the quenching zone, and then flows to the catalyst layer on the downstream side, and the reaction is carried out in the same manner. The flow rate of the quenching fluid is adjusted such that the temperature of the raw material is measured on the downstream side of the quenching zone after the quenching fluid is supplied, and the temperature of the portion is in a temperature range suitable for the main reaction.
此裝置以一座反應器構成，又，由於不需要熱交換器，因此可抑制成本。又，使用非活性成分作為淬熄流體時，必須非活性成分之精製與分離，但是由於是利用原料，因此具有不需要如此操作的優點。This device is constructed as one reactor, and since the heat exchanger is not required, the cost can be suppressed. Further, when an inactive component is used as the quenching fluid, purification and separation of the inactive component are required. However, since the raw material is used, there is an advantage that such an operation is not required.
然而，伴隨著上述發熱之平衡反應的一例，係例如從甲醇製造二甲醚之反應器的話，反應器之出口溫度較通常運轉時之溫度稍微上昇的情形下，因不良的副反應而會產生副生成物。因此有必要使反應器內的溫度穩定化。However, an example of the equilibrium reaction with the above-mentioned heat generation is, for example, a reactor in which dimethyl ether is produced from methanol, and when the outlet temperature of the reactor rises slightly from the temperature during normal operation, it may be generated by a defective side reaction. By-product. It is therefore necessary to stabilize the temperature inside the reactor.
上述專利文獻1記載之反應器，係依據下游側之觸媒層之入口側的溫度調整淬熄流體的供給量，而控制反應器之內部溫度，但是，在控制系統的特性上難以將前述入口側之溫度一定化，且加上原料之溫度變化等要因而無法避免該入口側之溫度變化。In the reactor described in Patent Document 1, the supply amount of the quenching fluid is adjusted according to the temperature of the inlet side of the catalyst layer on the downstream side, and the internal temperature of the reactor is controlled. However, it is difficult to control the inlet of the control system. The temperature on the side is fixed, and the temperature change of the raw material is added, so that the temperature change on the inlet side cannot be avoided.
在如此的狀況下，一旦如專利文獻1將原料作為淬熄流體來供給時，由於原料多，因此平衡偏向反應生成物側。如此一來，相對於觸媒層之入口側的溫度變化，反應速度會敏感地改變，故觸媒層之入口側之溫度對反應器之出口側之溫度的影響大，結果則反應器之出口溫度的上下幅度大，轉化率的變化也大。因此，反應器之出口溫度變得過高會因不好的副反應而產生副生成物，會降低製品的純度，又，反應器之出口溫度變得過低會導致無法達到作為目的之收率。In such a case, when the raw material is supplied as a quenching fluid as in Patent Document 1, since the amount of the raw material is large, the equilibrium is biased toward the reaction product side. As a result, the reaction rate is sensitively changed with respect to the temperature change on the inlet side of the catalyst layer, so the temperature on the inlet side of the catalyst layer has a large influence on the temperature of the outlet side of the reactor, and as a result, the outlet of the reactor The temperature is up and down, and the conversion rate is also large. Therefore, if the outlet temperature of the reactor becomes too high, by-products may be generated due to poor side reactions, the purity of the product may be lowered, and the outlet temperature of the reactor may become too low, resulting in failure to achieve the desired yield. .
因此，企盼著在可大型化之單純構造的反應器，能以簡便的方法控制反應器內之溫度的技術。Therefore, there is a demand for a technique capable of controlling the temperature in the reactor in a simple manner in a reactor of a simple structure which can be enlarged.
專利文獻1：特開2004-298768(段落0014、0020、0021)Patent Document 1: JP-A-2004-298768 (paragraphs 0014, 0020, 0021)
本發明係鑑於上述情形而完成者，其目的在於提供將原料供給至隔熱型之反應器，當藉伴隨此反應器內之發熱的平衡反應而製造目的物時，可提昇反應器內之溫度之控制性，且可抑制因溫度上昇所導致之產生副生成物與因溫度降低所導致之收率降低的技術。The present invention has been made in view of the above circumstances, and an object thereof is to provide a reactor for supplying a raw material to a heat insulating type, which can raise the temperature in the reactor when an object is produced by an equilibrium reaction accompanying heat generation in the reactor. It is controlled, and it is possible to suppress a technique in which by-products and a decrease in yield due to a decrease in temperature due to an increase in temperature.
本發明之反應器內部的溫度控制方法，係將反應區域分割成複數，經分割之複數反應區域分配於一個或二個以上的隔熱型反應器，將原料供給至隔熱型反應器內，且藉伴隨發熱之平衡反應而製造目的物時進行的溫度控制方法，特點在於包含有以下步驟：將原料供給至第1段的反應區域，獲得包含目的物之反應生成物；接著，將從前段側之反應區域取出之反應生成物與從未反應之原料所構成之混合物，供給至順序為後段側的反應區域，獲得包含目的物之反應生成物；及於前述各反應區域之間之至少一處，將淬熄流體供給至前述混合物，且藉混合而冷卻該混合物，又，前述淬熄流體包含在較前述淬熄流體之供給區域後段側之反應區域所獲得之前述反應生成物的一部分、及在前述隔熱型反應器以外所獲得之與前述目的物相同化合物之至少一者。The temperature control method inside the reactor of the present invention divides the reaction zone into a plurality of plural, and the divided plural reaction zones are distributed to one or more heat insulation type reactors, and the raw materials are supplied to the heat insulation type reactor. Further, the temperature control method performed when the target product is produced by the equilibrium reaction with heat is characterized in that the raw material is supplied to the reaction zone of the first stage to obtain a reaction product containing the target product; a mixture of the reaction product taken out from the reaction zone on the side and the unreacted raw material is supplied to the reaction zone in the subsequent stage to obtain a reaction product containing the target product; and at least one between the respective reaction zones a quenching fluid is supplied to the mixture, and the mixture is cooled by mixing, and the quenching fluid includes a part of the reaction product obtained in a reaction region on a later stage side of the supply region of the quenching fluid, And at least one of the same compounds as the above-mentioned objects obtained in addition to the above-mentioned heat insulating reactor.
前述淬熄流體也可包含將最後段之反應區域所獲得之反應生成物冷卻後之反應生成物的一部分。The quenching fluid may also include a part of the reaction product obtained by cooling the reaction product obtained in the reaction zone of the last stage.
前述複數反應區域分別由觸媒層所構成為佳。Preferably, the plurality of reaction regions are each composed of a catalyst layer.
經分割之前述反應區域為三個為佳。The aforementioned reaction zone divided by three is preferred.
前述冷卻步驟係調整前述淬熄流體之供給量、組成及溫度之至少一者而進行為佳。Preferably, the cooling step is performed by adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid.
前述伴隨發熱之平衡反應，也可以甲醇作為原料而獲得水與目的物之二甲醚所構成之反應生成物的反應。此情形下，前述淬熄流體以包含二甲醚與二甲醚及水之混合流體之其中任一者為佳。In the above-described equilibrium reaction with heat generation, methanol may be used as a raw material to obtain a reaction of water and a reaction product composed of a dimethyl ether of a target. In this case, the quenching fluid is preferably one containing a mixed fluid of dimethyl ether and dimethyl ether and water.
本發明之反應裝置，係將原料供給至隔熱型反應器內且藉伴隨發熱之平衡反應而製造目的物之反應裝置，特點在於包含有：一個或二個以上的隔熱型反應器，將反應區域分割成複數，且分配經分割之複數反應區域者；原料供給機構，係將原料供給至第1段的反應區域者；淬熄區，係介於前述各反應區域之間之至少一處，用以將淬熄流體供給至從前段側之反應區域取出之前述反應生成物與未反應之原料所構成之混合物，且藉混合而冷卻該混合物者；及，淬熄流體供給機構，係將包含較前述淬熄區後段側之反應區域所獲得之前述反應生成物的一部分、及在前述隔熱型反應器以外所獲得之與前述目的物相同化合物之至少一者之流體作為淬熄流體供給至淬熄區者。The reaction apparatus of the present invention is a reaction apparatus that supplies a raw material into a heat-insulating reactor and produces an object by an equilibrium reaction with heat generation, and is characterized in that one or two or more heat-insulating reactors are included. The reaction zone is divided into a plurality and the divided plural reaction zones are allocated; the raw material supply mechanism supplies the raw materials to the reaction zone of the first stage; and the quenching zone is at least one place between the respective reaction zones. a quenching fluid is supplied to a mixture of the reaction product and the unreacted raw material taken out from the reaction zone on the front side, and the mixture is cooled by mixing; and the quenching fluid supply mechanism is a fluid containing at least one of the reaction product obtained in a reaction region on the rear side of the quenching zone and at least one of the same compounds as the above-mentioned object obtained outside the heat insulating reactor as a quenching fluid supply To the quenching zone.
前述反應裝置以包含有用以將最後段之反應區域所獲得之反應生成物冷卻的冷卻機構，且前述淬熄流體係包含以前述冷卻機構冷卻後之前述反應生成物之一部分的流體為佳。The reaction apparatus includes a cooling mechanism for cooling the reaction product obtained in the reaction zone of the last stage, and the quenching flow system preferably includes a portion of the reaction product cooled by the cooling means.
前述複數反應區域分別由觸媒層所構成為佳。Preferably, the plurality of reaction regions are each composed of a catalyst layer.
經分割之前述反應區域為三個為佳。The aforementioned reaction zone divided by three is preferred.
又，本發明之反應裝置以包含有調整前述淬熄流體之供給量、組成及溫度之至少一者，並將前述淬熄流體供給至前述淬熄區之控制部為佳。Moreover, it is preferable that the reaction apparatus of the present invention includes at least one of adjusting the supply amount, composition, and temperature of the quenching fluid, and supplying the quenching fluid to the quenching zone.
前述伴隨發熱之平衡反應，也可以甲醇作為原料而獲得水與目的物之二甲醚所構成之反應生成物的反應。此情形下，前述淬熄流體以包含二甲醚與二甲醚及水之混合流體之其中任一者為佳。In the above-described equilibrium reaction with heat generation, methanol may be used as a raw material to obtain a reaction of water and a reaction product composed of a dimethyl ether of a target. In this case, the quenching fluid is preferably one containing a mixed fluid of dimethyl ether and dimethyl ether and water.
本發明之二甲醚之製造方法，係將反應區域分割成複數，經分割之複數反應區域分配於一個或二個以上的隔熱型反應器，將甲醇供給至隔熱型反應器內，且藉脫水縮合反應而製造二甲醚之方法，特點在於包含有以下步驟：將甲醇供給至第1段的反應區域，獲得包含二甲醚與水所構成之反應生成物；接著，將從前段側之反應區域取出之反應生成物與從未反應之甲醇所構成之混合物，供給至順序為後段側的反應區域，獲得二甲醚與水所構成之反應生成物；及於前述各反應區域之間之至少一處，將淬熄流體供給至前述混合物，且藉混合而冷卻該混合物，又，前述淬熄流體包含在較前述淬熄流體之供給區域後段側之反應區域所獲得之二甲醚及水之至少一者、及在前述隔熱型反應器以外所獲得之二甲醚之其中任一者。The method for producing a dimethyl ether according to the present invention is that the reaction region is divided into a plurality of plural, and the divided plural reaction regions are distributed to one or two or more heat insulating reactors, and methanol is supplied to the heat insulating reactor, and A method for producing dimethyl ether by a dehydration condensation reaction, comprising the steps of: supplying methanol to a reaction zone of the first stage to obtain a reaction product comprising dimethyl ether and water; and then, from the front side a mixture of the reaction product taken out from the reaction zone and the unreacted methanol is supplied to the reaction zone in the subsequent stage to obtain a reaction product composed of dimethyl ether and water; and between the respective reaction zones In at least one portion, a quenching fluid is supplied to the mixture, and the mixture is cooled by mixing, and the quenching fluid includes dimethyl ether obtained in a reaction region on a later stage side of the supply region of the quenching fluid and At least one of water and any one of dimethyl ethers obtained outside the heat insulating reactor.
前述冷卻步驟係調整前述淬熄流體之供給量、組成及溫度之至少一者而進行為佳。Preferably, the cooling step is performed by adjusting at least one of a supply amount, a composition, and a temperature of the quenching fluid.
前述淬熄流體以在最後段之反應區域獲得，且包含冷卻後之二甲醚及水之其中任一者為佳。The quenching fluid is obtained in the reaction zone of the last stage and preferably comprises any of the cooled dimethyl ether and water.
前述複數反應區域分別由觸媒層所構成為佳。Preferably, the plurality of reaction regions are each composed of a catalyst layer.
經分割之前述反應區域為三個為佳。The aforementioned reaction zone divided by three is preferred.
前述淬熄流體以除去混合存在於二甲醚之副生成物之水與未反應之甲醇後之二甲醚的一部分為佳。The quenching fluid is preferably a part of removing dimethyl ether obtained by mixing water present in the by-product of dimethyl ether with unreacted methanol.
依據本發明，建構成將反應區域分割成複數，經分割之複數反應區域分配於一個或二個以上的隔熱型反應器，將原料供給至隔熱型反應器內，且藉伴隨發熱之平衡反應而製造目的物時，將包含原料供給至第1段的反應區域所獲得包含目的物之反應生成物與未反應之原料所構成之混合物，從此第1段之反應區域供給至順序為後段側的反應區域而獲得包含目的物之反應生成物，且於各反應區域之間之至少一處，將在較該反應區域後段側所獲得之反應生成物之一部分及在前述隔熱型反應器以外所獲得之與前述目的物相同化合物之至少一者作為淬熄流體來供給，而冷卻該混合物。因此，混合物中之反應生成物的量增加，平衝偏向於示料側，反應穩定地進行，故反應區域之入口側的溫度變化所造成之反應速度的變化少。其結果，可提昇反應器內之溫度的控制性，能抑制因溫度上昇而造成非預定之副生成物的產生，可簡便地抑制因溫度降低所造成收率的降低。According to the invention, the reaction zone is divided into a plurality of plural, and the divided plurality of reaction zones are distributed to one or more heat-insulating reactors, and the raw materials are supplied to the heat-insulating reactor, and the balance is accompanied by heat generation. When the target product is produced by the reaction, the raw material is supplied to the reaction zone of the first stage to obtain a mixture of the reaction product containing the target product and the unreacted raw material, and the reaction zone of the first stage is supplied to the subsequent stage. a reaction product containing the target product, and at least one portion between the respective reaction regions, a portion of the reaction product obtained on the side of the latter portion of the reaction region and outside the heat insulating reactor At least one of the same compounds obtained as the above-mentioned object is supplied as a quenching fluid, and the mixture is cooled. Therefore, the amount of the reaction product in the mixture increases, the flattening is biased toward the side of the sample, and the reaction proceeds stably, so that the change in the reaction rate due to the temperature change on the inlet side of the reaction zone is small. As a result, the controllability of the temperature in the reactor can be improved, and the occurrence of unintended by-products due to temperature rise can be suppressed, and the decrease in yield due to temperature drop can be easily suppressed.
第1圖表示用以實施本發明之製造方法之反應裝置之一例的概略構造圖。Fig. 1 is a schematic structural view showing an example of a reaction apparatus for carrying out the production method of the present invention.
第2圖表示上述反應裝置之反應器內原料之溫度變化之一例的概略圖。Fig. 2 is a schematic view showing an example of temperature change of a raw material in a reactor of the above reaction apparatus.
第3圖表示上述反應裝置之其他例的縱剖面圖。Fig. 3 is a longitudinal sectional view showing another example of the above reaction apparatus.
第4圖表示上述反應裝置之其他例的縱剖面圖。Fig. 4 is a longitudinal sectional view showing another example of the above reaction apparatus.
第5圖表示上述反應裝置之其他例的縱剖面圖。Fig. 5 is a longitudinal sectional view showing another example of the above reaction apparatus.
第6圖表示上述反應裝置之其他例的縱剖面圖。Fig. 6 is a longitudinal sectional view showing another example of the above reaction apparatus.
第7圖表示上述反應裝置之其他例的縱剖面圖。Fig. 7 is a longitudinal sectional view showing another example of the above reaction apparatus.
第8圖表示上述反應裝置之其他例的縱剖面圖。Fig. 8 is a longitudinal sectional view showing another example of the above reaction apparatus.
第9圖表示上述反應裝置之其他例的縱剖面圖。Fig. 9 is a longitudinal sectional view showing another example of the above reaction apparatus.
第10圖表示上述反應裝置之其他例的縱剖面圖。Fig. 10 is a longitudinal sectional view showing another example of the above reaction apparatus.
第11圖表示上述反應裝置之其他例的縱剖面圖。Fig. 11 is a longitudinal sectional view showing another example of the above reaction apparatus.
第12圖表示使用於本發明之實施例之比較例之裝置的概略圖。Fig. 12 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention.
第13圖表示使用於本發明之實施例之比較例之裝置的概略圖。Fig. 13 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention.
第14圖表示使用於合成反應之習知裝置的概略圖。Fig. 14 is a schematic view showing a conventional apparatus used for the synthesis reaction.
第15圖表示使用於合成反應之習知裝置的概略圖。Fig. 15 is a schematic view showing a conventional apparatus used for the synthesis reaction.
參照第1圖及第2圖來說明本發明之反應裝置及使用此裝置之溫度控制方法的實施樣態。第1圖表示包含用以製造目的物之反應裝置2之製造工廠全體的概要。反應裝置2具有例如固定地板流通式之隔熱型反應器之縱型的反應器20。此反應器20之塔頂部連接著供給原料之機構之原料氣體供給管20a之一端側，此原料氣體供給管20a之另一端側藉由熱交換器2a及蒸發器2b而連接著貯存有液體原料的原料貯存源4。蒸發器2b係用以使液體原料氣化而獲得原料氣體者。The embodiment of the reaction apparatus and the temperature control method using the same according to the present invention will be described with reference to Figs. 1 and 2 . Fig. 1 shows an outline of the entire manufacturing plant including the reaction device 2 for producing a target. The reaction device 2 has, for example, a vertical reactor 20 in which a floor-floor type heat insulating reactor is fixed. The top of the reactor 20 is connected to one end side of the raw material gas supply pipe 20a of the mechanism for supplying the raw material, and the other end side of the raw material gas supply pipe 20a is connected to the liquid raw material by the heat exchanger 2a and the evaporator 2b. Raw material storage source 4. The evaporator 2b is used to vaporize a liquid raw material to obtain a raw material gas.
反應器20之底部連接著生成氣體流出管20b之一端側，此生成氣體流出管20b連接著上述熱交換器2a。於此熱交換器2a建構成原料氣體供給管20a內的原料，與生成氣體流出管20b內之反應生成物及原料所構成之混合物之間，原料被加熱，混合物被冷卻並進行熱交換。此生成氣體流出管20b之另一端側連接於將於後述之第1蒸餾塔30之側壁。The bottom of the reactor 20 is connected to one end side of the generated gas outflow pipe 20b, and the generated gas outflow pipe 20b is connected to the heat exchanger 2a. The heat exchanger 2a is configured to form a raw material in the raw material gas supply pipe 20a, and a mixture of the reaction product and the raw material in the generated gas outflow pipe 20b, the raw material is heated, and the mixture is cooled and exchanged. The other end side of the generated gas outflow pipe 20b is connected to a side wall of a first distillation column 30 which will be described later.
反應器20的內部，用以獲得作為目的之反應收率所必須之反應區域，例如分割設成上游側與下游側，上游側之反應區域藉第1觸媒層22a而形成作為第1反應區域，下游側之反應區域藉第2觸媒層22b而形成作為第2反應區域。此等觸媒層22(22a、22b)係藉多數未以圖式顯示之形成有氣體供給孔的支撐構件23所支撐著。The inside of the reactor 20 is used to obtain a reaction zone necessary for the desired reaction yield. For example, the reaction zone is divided into an upstream side and a downstream side, and the upstream reaction zone is formed as a first reaction zone by the first catalyst layer 22a. The reaction zone on the downstream side is formed as a second reaction zone by the second catalyst layer 22b. These catalyst layers 22 (22a, 22b) are supported by a plurality of support members 23 which are not shown in the drawings and are formed with gas supply holes.
反應器20內之第1觸媒層22a與第2觸媒層22b之間的區域設有用以藉淬熄流體冷卻反應器20內之混合物的淬熄區Q。將反應生成物之一部分作為淬熄流體而供給至淬熄區之機構的淬熄流體供給管24連接於此淬熄區Q之反應器20側面，此淬熄流體供給管24於反應器20內之淬熄區Q之上方側之接近第1觸媒層22a的部位，連接著用以將淬熄流體均一地分散供給之形成有多數吐出孔24b的噴灑部24a。A quenching zone Q for cooling the mixture in the reactor 20 by quenching fluid is provided in a region between the first catalyst layer 22a and the second catalyst layer 22b in the reactor 20. A quenching fluid supply pipe 24 for supplying a portion of the reaction product as a quenching fluid to the quenching zone is connected to the side of the reactor 20 of the quenching zone Q, and the quenching fluid supply pipe 24 is inside the reactor 20. A portion of the upper portion of the quenching region Q that is close to the first catalyst layer 22a is connected to a shower portion 24a in which a plurality of discharge holes 24b are formed to uniformly disperse and supply the quenching fluid.
又，於反應器20的側面設有溫度檢測部29，建構成其一端側突出於反應器20內，例如於第2媒體層22b之上部側附近檢測已在淬熄區Q冷卻之混合物的溫度。建構成控制部3連接於此溫度檢測部29，此控制部3依據溫度檢測部29之檢測溫度而控制淬熄流體的流量，藉將於後述之流量調整閥27以使原料氣體之溫度在適於反應的溫度範圍。Further, a temperature detecting portion 29 is provided on the side surface of the reactor 20, and one end thereof is protruded from the inside of the reactor 20. For example, the temperature of the mixture cooled in the quenching zone Q is detected in the vicinity of the upper side of the second dielectric layer 22b. . The configuration control unit 3 is connected to the temperature detecting unit 29, and the control unit 3 controls the flow rate of the quenching fluid based on the detected temperature of the temperature detecting unit 29, and the flow rate adjusting valve 27 to be described later is used to adjust the temperature of the material gas. In the temperature range of the reaction.
於反應器20之後段設有用以將從反應器20獲得之混合物取出作為目的之反應生成物，並將其一部分作為淬熄流體而供給至反應器20的設備，於第1圖中設有包含用以獲得例如將二甲醚作為目的物之二條蒸餾塔30、40的設備。In the subsequent stage of the reactor 20, a reaction product for taking out the mixture obtained from the reactor 20 is provided, and a part of the reaction product is supplied as a quenching fluid to the reactor 20, and is provided in FIG. An apparatus for obtaining, for example, two distillation columns 30, 40 using dimethyl ether as a target.
第1蒸餾塔30係用以從未反應之原料與反應生成物所構成之混合物，分離精製目的物者，冷卻機構之目的物取出管31連接著塔頂部，排出管32之一端側連接著下端部。建構成從目的物取出管31排出之目的物被作為製品而被取出至系統外，但是，其一部分藉從此目的物取出管31分歧之前已說明之淬熄流體供給管24，使淬熄流體回到已說明之淬熄區Q。於淬熄流體供給管24中介設有流量調整閥27。The first distillation column 30 is a mixture of an unreacted raw material and a reaction product, and the object to be purified is separated and purified. The object take-out pipe 31 of the cooling mechanism is connected to the top of the column, and one end side of the discharge pipe 32 is connected to the lower end. unit. The object to be discharged from the object take-out pipe 31 is taken out as a product and taken out of the system, but a part thereof is taken out from the object take-out pipe 31 by the quenching fluid supply pipe 24 which has been described before, so that the quenching fluid is returned. Go to the quenching zone Q already described. A flow rate adjustment valve 27 is interposed in the quenching fluid supply pipe 24.
已說明之排出管32之另一端側連接著第2蒸餾塔40的側壁。此第2蒸餾塔40係用以從上述第1蒸餾塔30中已除去目的物之混合物，分離精製未反應的原料者，原料排出管41之一端側連接於塔頂部，排出管42連接於下端部。建構成原料排出管41之另一端部連接於已說明之蒸餾器2b之上游側的原料氣體供給管20a，將未反應之原料回復再使用。排出管42係用以廢棄已從混合物去除目的物及未反應之原料後所殘留之副生成物與不純物等者，此等物被排出至系統外。The other end side of the discharge pipe 32, which has been described, is connected to the side wall of the second distillation column 40. The second distillation column 40 is for separating and purifying unreacted raw materials from the mixture in which the target product has been removed from the first distillation column 30. One end side of the raw material discharge pipe 41 is connected to the top of the column, and the discharge pipe 42 is connected to the lower end. unit. The other end portion of the raw material discharge pipe 41 is connected to the raw material gas supply pipe 20a on the upstream side of the distiller 2b, and the unreacted raw material is returned for reuse. The discharge pipe 42 is used to discard the by-products and impurities remaining after the target product and the unreacted raw materials have been removed from the mixture, and the objects are discharged to the outside of the system.
接著參照第1圖及第2圖來說明運轉上述反應裝置2的方法。Next, a method of operating the above reaction apparatus 2 will be described with reference to Figs. 1 and 2 .
以一種物質或多種物質構成之液體原料，在設置於前段之蒸發器2b被氣化，又，於熱交換器2a中，從反應器20取出之未反應的原料與反應生成物所構成之混合物之間進行熱交換而被加熱至溫度T1。a liquid raw material composed of one substance or a plurality of substances, which is vaporized in the evaporator 2b provided in the preceding stage, and further, in the heat exchanger 2a, a mixture of unreacted raw materials and reaction products taken out from the reactor 20 Heat exchange is performed between them to be heated to a temperature T1.
之後，原料氣體藉由原料氣體供給管20a而被供給至反應器20，而在此反應器20內從上朝下方向流動。在第1觸媒層22a內依據以下式子(1)的平衡反應而產生包含目的物的反應生成物，構成包含此反應生成物與未反應之原料氣體的混合物的氣體。Thereafter, the material gas is supplied to the reactor 20 through the material gas supply pipe 20a, and flows in the reactor 20 from the top to the bottom. In the first catalyst layer 22a, a reaction product containing a target product is produced according to the equilibrium reaction of the following formula (1), and a gas containing a mixture of the reaction product and the unreacted source gas is formed.
原料氣體反應生成物(目的物+副生成物)＋反應熱……(1)Raw material gas Reaction product (target + by-product) + reaction heat... (1)
藉此時產生之反應熱，混合物之氣體溫度上昇而達溫度T2。At this time, the heat of reaction generated, the temperature of the gas of the mixture rises to reach the temperature T2.
製造二甲醚時，液體原料之甲醇氣化，在第1觸媒層22a內藉以下記載之式子(2)的平衡反應而產生二甲醚與水。When dimethyl ether is produced, methanol of the liquid raw material is vaporized, and dimethyl ether and water are produced in the first catalyst layer 22a by an equilibrium reaction of the formula (2) described below.
2CH3 OHCH3 OCH3 ＋H2 O＋ΔH…(2)2CH 3 OH CH 3 OCH 3 +H 2 O+ΔH...(2)
ΔH=-23.4kj/molΔH=-23.4kj/mol
接著於淬熄區Q，一旦從噴灑部24a供給淬熄流體，則此淬熄流體與藉前段的觸媒層22a的發熱反應而達高溫(T2)的混合物的氣體混合，混合物的溫度會達T3。此淬熄流體係在該反應裝置2獲得之反應生成物的一部分所構成的流體，而以液體狀或氣體狀供給。製造二甲醚時，淬熄流體係使用例如氣體的二甲醚。Next, in the quenching zone Q, once the quenching fluid is supplied from the spraying section 24a, the quenching fluid is mixed with the gas of the mixture of the high temperature (T2) by the exothermic reaction of the catalyst layer 22a of the preceding stage, and the temperature of the mixture reaches T3. The quenching flow system is supplied in a liquid or gas form by a fluid composed of a part of the reaction product obtained in the reaction apparatus 2. In the production of dimethyl ether, the quenching flow system uses, for example, a dimethyl ether of a gas.
如上所述，以將反應生成物之一部分作為淬熄流體來供給而於第2觸媒層22b內，上述式子(1)、(2)之右側之反應生成物的量變多，因此，式子(1)、(2)之平衡反應偏向原料側而抑制目的物產生之反應，故上述反心應可穩定地進行。As described above, a part of the reaction product is supplied as a quenching fluid, and the amount of the reaction product on the right side of the above formulas (1) and (2) is increased in the second catalyst layer 22b. Since the equilibrium reaction of the sub-groups (1) and (2) is biased toward the raw material side and the reaction of the target substance is suppressed, the above-mentioned anti-centering can be stably performed.
如此一來，已冷卻之混合物氣體，更詳細者為包含淬熄流體之混合物被供給至第2觸媒層22b，於第2觸媒層22b藉同樣的反應而穩定地產生反應生成物。此反應生成物與未反應的原料所構成之混合物藉在此第2觸媒層22b之反應所產生之反應熱而上昇至溫度T4。In this way, the mixture gas which has been cooled is supplied to the second catalyst layer 22b in more detail, and the mixture containing the quenching fluid is stably generated by the same reaction in the second catalyst layer 22b. The mixture of the reaction product and the unreacted raw material rises to a temperature T4 by the heat of reaction generated by the reaction of the second catalyst layer 22b.
之後，混合物藉由生成氣體流出管20b而從反應器20被取出，於熱交換器2a與原料之間進行熱交換。Thereafter, the mixture is taken out from the reactor 20 by the generation of the gas outflow pipe 20b, and heat exchange is performed between the heat exchanger 2a and the raw material.
以製造二甲醚的情形為例說明之後的流程，從反應器20排出之反應生成物之二甲醚及水與未反應原料之甲醇所構成之混合物被供給至第1蒸餾塔30，可分離目的物之二甲醚。從混合物分離精製之二甲醚從目的物取出管31被取出，在目的物取出管31之管壁等散熱而達已說明之溫度T2以下的溫度，一部分藉由淬熄流體供給管24作為淬熄流體而回到反應器20。剩餘的二甲醚當作製品而被取出至系統外。In the subsequent process, the dimethyl ether is produced as an example, and a mixture of the dimethyl ether of the reaction product discharged from the reactor 20 and methanol and the methanol of the unreacted raw material is supplied to the first distillation column 30 to be separated. The dimethyl ether of the target substance. The dimethyl ether separated and purified from the mixture is taken out from the target take-out tube 31, and is radiated to the temperature of the tube wall or the like of the target take-out tube 31 to a temperature equal to or lower than the temperature T2 described above, and a part is quenched by the quenching fluid supply tube 24 The fluid is returned to the reactor 20. The remaining dimethyl ether is taken out of the system as a product.
已被除去二甲醚的混合物從第1蒸餾塔30的下側排出而供給至第2蒸餾塔40，於此第2蒸餾塔40分離精製未反應之原料的甲醇。如已說明的情形，未反應的原料回到原料氣體供給管20a與從原料貯存源4供給之原料一同再次供給至反應器20。又，已去除目的物及未反應之原料之副生成物的廢棄物於此例子中被排出至系統外。The mixture in which the dimethyl ether has been removed is discharged from the lower side of the first distillation column 30 and supplied to the second distillation column 40, and the methanol in the unreacted raw material is separated and purified in the second distillation column 40. As has been explained, the unreacted raw material is returned to the raw material gas supply pipe 20a and supplied to the reactor 20 together with the raw material supplied from the raw material storage source 4. Further, the waste from which the target product and the by-product of the unreacted raw material have been removed is discharged to the outside of the system in this example.
藉溫度檢測部29檢測出觸媒層22b之入口的溫度T3，因應該溫度檢測值並藉由控制部3及流量調整閥27而控制淬熄流體的供給流量，因此可達到觸媒層22b之入口溫度T3的穩定化，但是，無法避免此入口溫度T3因某變動幅而變動。但是，由於本發明使用反應生成物作為淬熄流體，因此如已說明的情形，平衡反應偏向示料側而抑制目的物之產生的反應，對於觸媒層22b之出口溫度T4之觸媒層22a的入口溫度T1的影響變小。即，相對於觸媒層22a之入口溫度T1的變化，對目的生成物之反應速度的變化小，因此觸媒層22b之出口溫度T4的變化變得遲鈍，轉化率之變動幅變小。The temperature detecting unit 29 detects the temperature T3 of the inlet of the catalyst layer 22b, and controls the supply flow rate of the quenching fluid by the control unit 3 and the flow rate adjusting valve 27 in response to the temperature detection value, so that the catalyst layer 22b can be reached. The inlet temperature T3 is stabilized, but it is unavoidable that the inlet temperature T3 fluctuates due to a certain variation. However, since the present invention uses the reaction product as the quenching fluid, as described above, the equilibrium reaction is biased toward the sample side to suppress the reaction of the target, and the catalyst layer 22a for the outlet temperature T4 of the catalyst layer 22b. The influence of the inlet temperature T1 becomes small. In other words, the change in the reaction rate with respect to the target product is small with respect to the change in the inlet temperature T1 of the catalyst layer 22a. Therefore, the change in the outlet temperature T4 of the catalyst layer 22b becomes sluggish, and the fluctuation range of the conversion rate becomes small.
依據上述實施樣態，建構成將原料供給至隔熱型之反應器20內，要藉伴隨發熱之平衡反應而製造目的物時，於用以進行原料之反應的第1反應區域與第2反應區域之間設有淬熄區Q，將從第2反應區域取出之反應生成物的一部分冷卻而作為淬熄流體供給至此淬熄區Q，而冷卻原料與反應生成物所構成之混合物。因此，如已詳細說明的情形，混合物中的反應生成物的量增加，平衡偏向原料側而反應穩定地進行，因此容易進行反應器20內的溫度控制，其結果可抑制因溫度上昇而產生非預定的副生成物，且能抑制因溫度降低所造成收率的降低。而且，可抑制觸媒之填縫，可使觸媒之壽命長。而且，可抑制反應裝置2之急劇的溫度上昇(暴走反應)，可安全地運轉反應裝置2。爰此，與已知之方法比較，本發明可簡略化反應器20的構造，容易大型化，又，構成反應器20之構件數量少。According to the above-described embodiment, the raw material is supplied to the heat-insulating reactor 20, and the first reaction zone and the second reaction for reacting the raw material are produced when the target product is produced by an equilibrium reaction with heat generation. A quenching zone Q is provided between the zones, and a part of the reaction product taken out from the second reaction zone is cooled and supplied as a quenching fluid to the quenching zone Q, and a mixture of the raw material and the reaction product is cooled. Therefore, as described in detail, the amount of the reaction product in the mixture increases, the equilibrium shifts toward the raw material side, and the reaction proceeds stably, so that temperature control in the reactor 20 is easily performed, and as a result, generation of non-temperature due to temperature rise can be suppressed. A predetermined by-product is formed, and a decrease in yield due to a decrease in temperature can be suppressed. Moreover, the caulking of the catalyst can be suppressed, and the life of the catalyst can be long. Further, the rapid temperature rise (runaway reaction) of the reaction device 2 can be suppressed, and the reaction device 2 can be safely operated. Accordingly, the present invention can simplify the structure of the reactor 20 as compared with the known method, and is easy to increase in size, and the number of components constituting the reactor 20 is small.
上述淬熄流體可為氣體也可為液體。使用氣體之淬熄流體時，由於無法利用蒸發潛熱，因此較使用液體時必須更多的供給量，但是，由於反應器20內之反應生成物的量變多，因此抑制反應速度的效果大。相對於此，使用液體之淬熄流體時，比使用氣體時少的供給量即能混合物的溫度。又，例如原料之供給量少，因反應所造成之混合物之溫度上昇小的情形下，也可不使反應生成物冷卻而作為淬熄流體來供給。此情形下，反應器20內之反應生成物的量變多，因此可抑制反應速度。The quenching fluid may be a gas or a liquid. When the quenching fluid of the gas is used, since the latent heat of vaporization cannot be utilized, a larger amount of supply is required than when the liquid is used. However, since the amount of the reaction product in the reactor 20 is increased, the effect of suppressing the reaction rate is large. On the other hand, when a quenching fluid of a liquid is used, the supply amount which is less than the time of using a gas is the temperature of the mixture. Further, for example, when the supply amount of the raw material is small and the temperature of the mixture due to the reaction is small, the reaction product may be cooled and supplied as a quenching fluid. In this case, since the amount of the reaction product in the reactor 20 is increased, the reaction rate can be suppressed.
又，上述例子中，將觸媒層22設為兩層，惟，例如第3圖及第4圖所示，也可為此等以上的觸媒層。第3圖表示包含有三層觸媒層(2a、2b、2c)之反應器20，第4圖表示包含有五層觸媒層(22a、22b、22c、22d、22e)之反應器20。於第3圖、第4圖中，在各觸媒層22之間的淬熄區Q，藉溫度檢測部29檢測出混合物的溫度，而調整從噴灑部24a供給之淬熄流體的流量。如此的反應器20亦與上述的例子同樣係藉淬熄流體抑制反應速度的狀態進行反應。如此地將觸媒層22設為多數層的狀態，可獲得與上述例子同樣的效果。Further, in the above example, the catalyst layer 22 is formed in two layers. However, for example, as shown in FIGS. 3 and 4, the catalyst layer may be used. Fig. 3 shows a reactor 20 comprising three layers of catalyst layers (2a, 2b, 2c), and Fig. 4 shows a reactor 20 comprising five layers of catalyst layers (22a, 22b, 22c, 22d, 22e). In the quenching zone Q between the respective catalyst layers 22, the temperature detecting unit 29 detects the temperature of the mixture and adjusts the flow rate of the quenching fluid supplied from the spraying unit 24a in the third and fourth figures. Similarly to the above-described example, the reactor 20 is reacted in a state where the quenching fluid suppresses the reaction rate. By setting the catalyst layer 22 to a plurality of layers in this manner, the same effects as those of the above-described example can be obtained.
又，於一座反應器20內設置多數層觸媒層22的情形以外，例如也可如第5圖、第6圖所示，將設置一層觸媒層22之反應器20連接多數座。第5圖、第6圖分別表示連接三座、五座反應器20的例子，淬熄流體供給管24連接著用以連接各個反應器20之間的生成氣體流出管20b。而且，於如此的反應器20以外，也可如第7圖、第8圖所示組合並連接多數座設有至少一層觸媒層22之反應器20。第7圖表示串聯連接設有一層觸媒層22之反應器20與設有二層觸媒層(22a、22b)之反應器20的例子。第8圖表示串聯連接設有三二層觸媒層(22a、22b)之反應器20與設有三層觸媒層(22a、22b、22c)之反應器20的例子。此等觸媒層22之間也同樣建構成在淬熄區Q供給淬熄流體。於如此的構造中，也可獲得與上述例子同樣的效果。Further, in the case where a plurality of layer catalyst layers 22 are provided in one reactor 20, for example, as shown in Figs. 5 and 6, a reactor 20 provided with one catalyst layer 22 may be connected to a plurality of seats. Figs. 5 and 6 show an example in which three reactors and five reactors 20 are connected, and a quenching fluid supply pipe 24 is connected to a generated gas outflow pipe 20b for connecting between the respective reactors 20. Further, in addition to the reactor 20, the reactor 20 having at least one catalyst layer 22 may be combined and connected as shown in Figs. 7 and 8. Fig. 7 shows an example in which a reactor 20 provided with a catalyst layer 22 and a reactor 20 provided with two catalyst layers (22a, 22b) are connected in series. Fig. 8 shows an example in which a reactor 20 provided with three or two catalyst layers (22a, 22b) and a reactor 20 provided with three catalyst layers (22a, 22b, 22c) are connected in series. Similarly, between these catalyst layers 22, a quenching fluid is supplied to the quenching zone Q. In such a configuration, the same effects as the above examples can be obtained.
上述各例子中，各觸媒層22、22之間全部的觸媒層最好是設置淬熄區Q，但是，例如在溫度變化幅度小的情形下等，也可減少淬熄區Q的數量，亦即只要有至少一個以上的淬熄區Q即可。第9圖表示於已說明之第4圖所示之反應器20中，省略了從上游側起第2個觸媒層22b與第3個觸媒層22c之間的淬熄區Q的例子。於如此的反應器20中，也可獲得同樣的效果。In each of the above examples, it is preferable that all of the catalyst layers between the respective catalyst layers 22 and 22 have the quenching region Q. However, for example, in the case where the temperature variation range is small, the number of quenching regions Q can be reduced. That is, as long as there is at least one quenching zone Q. Fig. 9 shows an example in which the quenching zone Q between the second catalyst layer 22b and the third catalyst layer 22c from the upstream side is omitted in the reactor 20 shown in Fig. 4 which has been described. The same effect can be obtained in such a reactor 20.
又，上述的例子中，利用系統內的目的物作為淬熄流體，但是，也可利用與系統外之目的物相同的化合物作為淬熄流體。如此的例子中，也可例如第10圖所示，設置多數反應裝置2，而從一反應裝置2對另一反應裝置2供給淬熄流體。如此的情形下，係另一反應裝置2之淬熄流體供給管24連接一反應裝置2的目的物取出管31。又，以上第3圖至第10圖中，對於與第1圖相同的構造賦與相同符號。也可於此等淬熄流體之目的物混入未反應的原料。Further, in the above example, the target material in the system is used as the quenching fluid, but the same compound as the object outside the system may be used as the quenching fluid. In such an example, for example, as shown in FIG. 10, a plurality of reaction apparatuses 2 may be provided, and a quenching fluid may be supplied from one reaction apparatus 2 to the other reaction apparatus 2. In such a case, the quenching fluid supply pipe 24 of the other reaction device 2 is connected to the object take-out pipe 31 of the reaction device 2. In the above-described third to tenth drawings, the same configurations as those in the first embodiment are denoted by the same reference numerals. It is also possible to mix the unreacted raw materials with the object of the quenching fluid.
又，利用目的物作為淬熄流體以外，也可例如從原料產生目的物以外之反應生成物(副生成物)的情形下(於目的物以外也有於式子(1)之右邊側生成的物質的情形下)，可利用該反應生成物作為淬熄流體，例如於獲得二甲醚之反應中，可使用水作為淬熄流體。此情形下如第1圖所示，從目的物取出管31取出目的物之全量，廢棄物之一部分作為淬熄流體回到淬熄區Q。於此情形下，與上述例子同樣由於式子(1)、(2)之右邊側之反應生成物增加而可抑制反應，因此反應穩定地進行，反應器20出口之混合物的溫度的變化幅度變小。又，第11圖中，對於與第1圖相同的構造賦與相同符號。In addition, when the target product is used as a quenching fluid, for example, a reaction product (by-product) other than the target product may be produced from the raw material (the substance produced on the right side of the formula (1) in addition to the target product) In the case of the reaction, the reaction product can be used as a quenching fluid. For example, in the reaction for obtaining dimethyl ether, water can be used as the quenching fluid. In this case, as shown in Fig. 1, the entire amount of the object is taken out from the object take-out pipe 31, and a part of the waste is returned to the quenching zone Q as a quenching fluid. In this case, as in the above-described example, the reaction product on the right side of the formulas (1) and (2) is increased to suppress the reaction, so that the reaction proceeds stably, and the temperature of the mixture at the outlet of the reactor 20 changes. small. In the eleventh embodiment, the same configurations as those in the first embodiment are denoted by the same reference numerals.
又，也可將目的物與此副生成物一同作為淬熄流體使用，例如，在從甲醇獲得二甲醚的反應中，可將二甲醚與水作為淬熄流體使用。而且，也可將來自系統外之二甲醚作為淬熄流體使用。Further, the target product may be used together with the by-product as a quenching fluid. For example, in the reaction for obtaining dimethyl ether from methanol, dimethyl ether and water may be used as the quenching fluid. Further, dimethyl ether from outside the system can also be used as a quenching fluid.
又，上述各例子中，使用與反應生成物或目的物相同之系統外化合物作為淬熄流體，但是，只要是在可抑制反應速度之程度包含與反應生成物或目的物相同系統外之化合物的話，也可於此淬熄流體包含有未反應的原料。此情形下，也可例如於第1圖中，將中介設置有閥之分歧管(均未以圖式顯示)之一端側連接原料排出管41，而將此分歧管之另一端側連接淬熄流體供給管24，藉調整此閥之開度而積極地將未反應的原料作為淬熄流體之一部分使用。In addition, in the above-mentioned examples, the same system compound as the reaction product or the target product is used as the quenching fluid, but the compound other than the system of the reaction product or the target product can be suppressed to the extent that the reaction rate can be suppressed. It is also possible that the quenching fluid contains unreacted starting materials. In this case, for example, in the first drawing, one end side of the branch pipe (not shown in the figure) in which the valve is disposed is connected to the raw material discharge pipe 41, and the other end side of the branch pipe is connected and quenched. The fluid supply pipe 24 actively uses the unreacted raw material as a part of the quenching fluid by adjusting the opening degree of the valve.
而且，上述各例子中，藉控制部3而控制淬熄流體的流量而使反應器20之入口溫度T3穩定化，但是，也可建構成將淬熄流體之流量設為一定，藉由控制部3例如調整前述分歧管之閥及流量調整閥27之開度，並以調整淬熄流體所包含之反應生成物或與目的物相同系統外之化合物比率，亦即，以調整淬熄流體之組成而使入口溫度T3穩定化。又，也可建構成於淬熄流體供給管24設置未以圖式顯示之冷卻機構，而將淬熄流體之流量設為一定，藉由控制器3調整淬熄流體之溫度而使反應器20之入口溫度T3穩定化。而且，也可建構成藉由控制部3調整淬熄流體之流量、淬熄流體之組成及淬熄流體之溫度之複數組合而使反應器20之入口溫度T3穩定化。Further, in each of the above examples, the flow rate of the quenching fluid is controlled by the control unit 3 to stabilize the inlet temperature T3 of the reactor 20. However, the flow rate of the quenching fluid may be set to be constant by the control unit. 3, for example, adjusting the opening degree of the valve of the branch pipe and the flow regulating valve 27, and adjusting the ratio of the reaction product contained in the quenching fluid or the compound outside the same system as the target, that is, adjusting the composition of the quenching fluid The inlet temperature T3 is stabilized. Further, a quenching fluid supply pipe 24 may be provided with a cooling mechanism not shown in the drawing, and the flow rate of the quenching fluid may be constant, and the temperature of the quenching fluid may be adjusted by the controller 3 to cause the reactor 20 to be fixed. The inlet temperature T3 is stabilized. Further, the control unit 3 may be configured to adjust the flow rate of the quenching fluid, the composition of the quenching fluid, and the temperature of the quenching fluid to stabilize the inlet temperature T3 of the reactor 20.
本發明之目的物之溫度控制方法及反應裝置如上所述，也可適用於藉伴隨發熱之平衡反應而產生目的物時，例如從後述之實施例之甲醇脫水所構成之二甲醚的合成反應，或氫與氮所構成之氨的合成反應。又，前述合成反應之其他，也可適用於伴隨發熱之平衡反應例如氧化反應、氫化反應以外的反應，也可適用於液相中的此等反應。As described above, the temperature control method and the reaction apparatus of the object of the present invention can also be applied to a synthesis reaction of dimethyl ether composed of methanol dehydration in an example described later, when the target substance is produced by an equilibrium reaction with heat generation. , or the synthesis reaction of ammonia and hydrogen. Further, the other synthesis reaction may be applied to a reaction other than an equilibrium reaction such as an oxidation reaction or a hydrogenation reaction, or may be applied to such a reaction in a liquid phase.
以下說明用以確認本發明之方法的效果而進行的實驗。此實施例係使用甲醇作為上述原料，進行以已說明之式子(2)之伴隨發熱之平衡反應獲得作為目的物之二甲醚的實驗。The experiment conducted to confirm the effect of the method of the present invention will be described below. In this example, methanol was used as the above-mentioned raw material, and an experiment for obtaining a dimethyl ether as a target product by an equilibrium reaction with heat generation of the above formula (2) was carried out.
又，雖然以下各實驗設定了標準條件，但是此標準條件係將最終觸媒層出口之甲醇的轉化率及各觸媒層之出口的溫度設定為在分別的標準條件下為相等的條件。Further, although the standard conditions were set in the following experiments, the standard conditions were such that the conversion ratio of methanol at the outlet of the final catalyst layer and the temperature of the outlet of each catalyst layer were set to be equal under the respective standard conditions.
用以進行上述反應之裝置係使用已說明之第1圖所示之反應裝置2，而於反應器20之入口及觸媒層22a、22b之各個入口與出口設置溫度計。The apparatus for carrying out the above reaction uses the reaction apparatus 2 shown in Fig. 1 described above, and a thermometer is provided at each inlet and outlet of the reactor 20 and the catalyst layers 22a and 22b.
於此反應裝置2，供給流量F1的甲醇，將二甲醚作為淬熄流體並以流量F2供給至淬熄區Q，又，將未反應之甲醇以流量F3返回。副生成物之水從已說明之排出管42排出。又，各流量F1～F3表示分別流體的質量流量。In the reaction apparatus 2, methanol of a flow rate F1 is supplied, dimethyl ether is supplied as a quenching fluid, and is supplied to the quenching zone Q at a flow rate F2, and unreacted methanol is returned at a flow rate F3. The water of the by-product is discharged from the discharge pipe 42 which has been described. Further, each of the flow rates F1 to F3 indicates the mass flow rate of each fluid.
實驗條件係決定如以下的各條件使反應器20之出口之甲醇的轉化率及溫度分別為75%、340℃，並將此條件作為標準條件。又，將反應器20之入口的原料溫度從上述標準條件上下分別改變1℃，並對此等以外的條件，以與標準條件相同的條件進行了實驗。於各個條件下，比較反應器20之出口的溫度(第2觸媒層22b之出口側的溫度)及、又反應器20之出口之甲醇的轉化率。又，對於淬熄流體之二甲醚的流量F2及從原料排出管41回來之未反應的原料之甲醇的流量F3，設成與標準條件相同的流量。The experimental conditions were such that the conversion rates and temperatures of methanol at the outlet of the reactor 20 were 75% and 340 ° C, respectively, under the following conditions, and this condition was taken as a standard condition. Further, the temperature of the raw material at the inlet of the reactor 20 was changed from the above-mentioned standard conditions by 1 ° C, and the conditions were the same as those under the standard conditions. The temperature of the outlet of the reactor 20 (the temperature on the outlet side of the second catalyst layer 22b) and the conversion rate of methanol at the outlet of the reactor 20 were compared under various conditions. Further, the flow rate F2 of the dimethyl ether of the quenching fluid and the flow rate F3 of the methanol of the unreacted raw material returned from the raw material discharge pipe 41 are set to the same flow rate as the standard conditions.
(標準條件)(standard conditions)
反應器20之入口溫度：279℃Inlet temperature of reactor 20: 279 ° C
反應器20之入口的壓力：1.55Mpa(量規壓)Pressure at the inlet of the reactor 20: 1.55 MPa (gauge pressure)
對原料之流量之淬熄量的比(F2/(F1+F3))：0.18Ratio of quenching amount of raw material flow rate (F2/(F1+F3)): 0.18
淬熄二甲醚條件：1.5Mpa(量規壓)Quenching dimethyl ether conditions: 1.5Mpa (gauge pressure)
二甲醚飽和蒸氣(100%)Dimethyl ether saturated vapor (100%)
(實驗結果)(experimental results)
表1表示實驗結果。Table 1 shows the experimental results.
其結果，對應反應器20之入口溫度(第1觸媒層22a之入口側溫度)的變化，反應器20內的溫度也變化了。又，可得知反應器20之出口之溫度的變化較反應器20之入口之溫度的變化大。一旦反應器20內之溫度變高，則轉化率增加，又，一旦反應器20內之溫度變低，則轉化率減少。As a result, the temperature in the reactor 20 also changes in accordance with the change in the inlet temperature of the reactor 20 (the inlet side temperature of the first catalyst layer 22a). Further, it can be seen that the change in the temperature of the outlet of the reactor 20 is larger than the change in the temperature of the inlet of the reactor 20. Once the temperature in the reactor 20 becomes higher, the conversion rate increases, and once the temperature in the reactor 20 becomes lower, the conversion rate decreases.
(比較例1-1)(Comparative Example 1-1)
接著將蒸餾塔30、40連接於在已說明之第15圖之多數反應器102、102之間中介設置熱交換器103之裝置，並進行實驗以作為比較例1-1。第12圖表示此裝置。又，對於與已說明之第1圖相同構造的部位則賦與相同符號。於此裝置也測定了上游側之反應器(第1反應器)102及下游側之反應器(第2反應器)102之個別的入口及出口之原料的溫度。Next, the distillation columns 30, 40 were connected to a device in which the heat exchanger 103 was interposed between the plurality of reactors 102, 102 of the above-described Fig. 15, and an experiment was conducted as Comparative Example 1-1. Figure 12 shows this device. Further, the same components as those of the first embodiment described above are assigned the same reference numerals. The temperature of the raw materials of the inlet and outlet of the reactor (first reactor) 102 on the upstream side and the reactor (second reactor) 102 on the downstream side was also measured in this apparatus.
此裝置係建構成從供給路200將在蒸發器2b氣化後之原料氣體供給至熱交換器103，於此熱交換器103，此原料氣體，與因上游側之反應器102的反應而呈高溫的原料及反應生成物所構成之混合物之間進行熱交換(冷卻混合物)。又，建構成將在此熱交換器103已熱交換(被加熱)之後的原料氣體，於上游側之反應器102之前側回到原料氣體供給管20a。又，關於供給至此熱交換器103之流體以外的原料與反應生成物等的流動，設為與已說明之第1圖的反應裝置2同樣。This apparatus is configured to supply the raw material gas vaporized by the evaporator 2b from the supply path 200 to the heat exchanger 103, where the raw material gas is reacted with the reactor 102 on the upstream side. Heat exchange (cooling of the mixture) is carried out between the high-temperature raw material and the mixture of the reaction product. Further, the raw material gas after the heat exchanger 103 has been heat-exchanged (heated) is constructed to return to the raw material gas supply pipe 20a on the upstream side of the reactor 102 on the upstream side. In addition, the flow of the raw material other than the fluid supplied to the heat exchanger 103, the reaction product, and the like is the same as that of the reaction device 2 of the first embodiment described above.
與上述實施例1同樣，決定以下的條件使下游側之反應器102之出口之甲醇的轉化率及原料的溫度分別為75%、340℃，並以此條件作為標準條件。又，同樣將上游側之反應器102之入口的原料溫度從標準條件上下分別改變1℃，並對此等以外的條件，以與標準條件相同的條件進行了實驗。In the same manner as in the above-described first embodiment, the following conditions were determined such that the conversion ratio of methanol at the outlet of the reactor 102 on the downstream side and the temperature of the raw material were 75% and 340 ° C, respectively, and the conditions were used as standard conditions. Further, the raw material temperature at the inlet of the reactor 102 on the upstream side was also changed from the upper and lower conditions of the standard conditions by 1 ° C, and the conditions were the same as those under the standard conditions.
同樣測定下游側之反應器102之出口的溫度，又，比較了轉化率。而且，從原料排出管41回來之甲醇的量設成與標準條件相同流量。又，熱交換器103之淬熄流體與混合物之間之熱交換量(傳熱量)係設成即使改變上游側之反應器102之入口的溫度也不會變化者。The temperature of the outlet of the reactor 102 on the downstream side was also measured, and the conversion rate was compared. Further, the amount of methanol returned from the raw material discharge pipe 41 is set to the same flow rate as the standard conditions. Further, the amount of heat exchange (heat transfer amount) between the quenching fluid of the heat exchanger 103 and the mixture is set so as not to change even if the temperature of the inlet of the reactor 102 on the upstream side is changed.
(標準條件)(standard conditions)
反應器102之入口溫度：279℃Inlet temperature of reactor 102: 279 ° C
反應器102之入口的壓力：1.55Mpa(量規壓)Pressure at the inlet of the reactor 102: 1.55 MPa (gauge pressure)
(實驗結果)(experimental results)
表2表示實驗結果。Table 2 shows the experimental results.
其結果與實施例1同樣，對應上游側之溫度變化，各部的溫度及轉化率變化了，然而，其變化量較實施例1之變化量多。由此得知實施例1的話，使用反應生成物之二甲醚作為淬熄流體，藉此可抑制反應，而反應器20之內部的溫度與轉化率的控制性提昇了。As a result, in the same manner as in the first embodiment, the temperature and the conversion ratio of the respective portions were changed in accordance with the temperature change on the upstream side. However, the amount of change was larger than that in the first embodiment. Thus, in the case of Example 1, the dimethyl ether of the reaction product was used as the quenching fluid, whereby the reaction was suppressed, and the controllability of the internal temperature and the conversion rate of the reactor 20 was improved.
(比較例1-2)(Comparative Example 1-2)
其次，使用第1圖記載之裝置作為與已說明之專利文獻1記載之裝置同樣構造的裝置並進行了實驗。此裝置概略上具有與第1圖之反應器20約同樣構造之反應器20，惟，建構成從原料淬熄供給器200供給液體狀原料作為淬熄流體。又，於此第13圖中，對於第1圖相同構造的部位也賦與相同符號。Next, an experiment was carried out using the device described in Fig. 1 as a device having the same structure as the device described in Patent Document 1. This apparatus roughly has a reactor 20 having the same structure as that of the reactor 20 of Fig. 1, but is constructed to supply a liquid raw material from the raw material quenching feeder 200 as a quenching fluid. In addition, in the thirteenth figure, the same reference numerals are given to the same components in the first embodiment.
又，與上述實驗同樣，決定以下的條件使反應器300之出口側之甲醇的轉化率及原料的溫度分別為75%、340℃，並以此條件作為標準條件，同樣將反應器300之入口側的溫度上下分別改變1℃並進行了實驗。又，此情形下，從原料排出管41回來之未反應的甲醇的流量及淬熄流體的流量為一定。於此例子也表示F1為甲醇供給量，F2為淬熄甲醇之供給量，F3為再循環之甲醇流量。Further, in the same manner as the above experiment, the following conditions were determined such that the conversion ratio of methanol on the outlet side of the reactor 300 and the temperature of the raw material were 75% and 340 ° C, respectively, and the conditions were used as standard conditions, and the inlet of the reactor 300 was also obtained. The temperature of the side was changed by 1 ° C and the experiment was performed. Further, in this case, the flow rate of the unreacted methanol returned from the raw material discharge pipe 41 and the flow rate of the quenching fluid are constant. This example also shows that F1 is the methanol supply, F2 is the supply of quenched methanol, and F3 is the recycled methanol flow.
(標準條件)(standard conditions)
反應器300之入口溫度：279℃Inlet temperature of reactor 300: 279 ° C
反應器300之入口的壓力：1.55Mpa(量規壓)Pressure at the inlet of the reactor 300: 1.55 MPa (gauge pressure)
對原料之流量之淬熄量的比(F2/(F1＋F3))：0.09Ratio of quenching amount of raw material flow rate (F2/(F1+F3)): 0.09
淬熄甲醇條件：1.6Mpa(量規壓)、沸點中的液體Quenching methanol condition: 1.6Mpa (gauge pressure), liquid in boiling point
(實驗結果)(experimental results)
表3表示實驗結果。Table 3 shows the experimental results.
其結果，依據反應器300之入口溫度，反應器300內部之各部的溫度及轉化率改變了，與比較例1-1同樣，其變化量較實施例1大。As a result, the temperature and the conversion ratio of the respective portions inside the reactor 300 were changed depending on the inlet temperature of the reactor 300, and the amount of change was larger than that of the first embodiment as in the case of the comparative example 1-1.
從以上的結果得知在使用原料作為淬熄流體時，平衡反應偏向反應生成物，朝向目的生成物之反應速度變高了，因此發熱量變多，其結果雖然反應器102之出口的混合物溫度不鈞勻情形變大，但是，由於將反應生成物之一部分作為淬熄流體使用，因此可抑制向目的生成物的反應，能將反應器102之出口的混合物溫度的上下幅度設得小。From the above results, when the raw material is used as the quenching fluid, the equilibrium reaction is biased toward the reaction product, and the reaction rate toward the intended product is increased. Therefore, the amount of heat generation is increased, and as a result, the temperature of the mixture at the outlet of the reactor 102 is not high. In the case where a part of the reaction product is used as the quenching fluid, the reaction to the target product can be suppressed, and the temperature of the mixture at the outlet of the reactor 102 can be set to be small.
(實施例2)(Example 2)
其次，如已說明之第3圖所示，將觸媒層22設為三層時，進行確認反應器20之出口的溫度與轉化率如何變化的實驗。Next, as shown in FIG. 3, when the catalyst layer 22 is set to three layers, an experiment for confirming how the temperature and the conversion rate of the outlet of the reactor 20 are changed is performed.
實驗上使用第3圖之反應器20，決定以下的各條件使反應器20之出口之甲醇的轉化率及的溫度分別為75%、340℃，並以此條件作為標準條件，又，將反應器20之入口之原料的溫度上下分別改變1℃，並就此等以外的條件，以與標準條件相同的條件進行了實驗。在分別的條件下測定反應器20之各觸媒層22之入口的溫度與出口的溫度，又，比較在反應器20之出口之甲醇的轉化率。又，對於從淬熄流體之二甲醚的流量F2及原料排出管41回到未反應之原料之甲醇之流量F3的流量，設為與標準條件相同的流量。In the experiment, the reactor 20 of FIG. 3 was used to determine the following conditions, and the conversion rate and the temperature of the methanol at the outlet of the reactor 20 were respectively 75% and 340 ° C, and the conditions were taken as standard conditions, and the reaction was further carried out. The temperature of the raw material at the inlet of the device 20 was changed by 1 °C, and the conditions were the same as those under the standard conditions. The temperature of the inlet of each catalyst layer 22 of the reactor 20 and the temperature of the outlet were measured under separate conditions, and the conversion of methanol at the outlet of the reactor 20 was compared. Moreover, the flow rate of the flow rate F3 of methanol from the quenching fluid dimethyl ether flow rate F2 and the raw material discharge pipe 41 back to the unreacted raw material is set to the same flow rate as the standard condition.
(標準條件)(standard conditions)
反應器20之入口溫度：279℃Inlet temperature of reactor 20: 279 ° C
反應器20之入口的壓力：1.55Mpa(量規壓)Pressure at the inlet of the reactor 20: 1.55 MPa (gauge pressure)
對原料之流量之淬熄量的比(F2/(F1+F3))：0.18Ratio of quenching amount of raw material flow rate (F2/(F1+F3)): 0.18
淬熄二甲醚條件：1.5Mpa(量規壓)Quenching dimethyl ether conditions: 1.5Mpa (gauge pressure)
二甲醚飽和蒸氣(100%)Dimethyl ether saturated vapor (100%)
(實驗結果)(experimental results)
表4表示實驗結果。Table 4 shows the experimental results.
其結果，可得知以使用生成物作為淬熄流體，而與實驗例1的結果同樣，即使反應器20之入口側的溫度變化，也可抑制反應器20之出口側的溫度與轉化率的變化。As a result, it was found that the use of the product as the quenching fluid was similar to the result of Experimental Example 1, and the temperature and the conversion rate of the outlet side of the reactor 20 were suppressed even if the temperature on the inlet side of the reactor 20 was changed. Variety.
2．．．反應裝置2. . . Reaction device
3．．．控制部3. . . Control department
4．．．原料貯存源4. . . Raw material storage source
2a．．．熱交換器2a. . . Heat exchanger
2b．．．蒸發器2b. . . Evaporator
20．．．反應器20. . . reactor
20a．．．原料氣體供給管20a. . . Raw material gas supply pipe
20b．．．生成氣體流出管20b. . . Gas outflow tube
22．．．觸媒層twenty two. . . Catalyst layer
22a．．．第1觸媒層22a. . . First catalyst layer
22b．．．第2觸媒層22b. . . 2nd catalyst layer
23．．．支撐構件twenty three. . . Support member
24．．．淬熄流體供給管twenty four. . . Quenching fluid supply pipe
24a．．．噴灑部24a. . . Spraying department
24b．．．吐出孔24b. . . Spit hole
Q．．．淬熄區Q. . . Quenching zone
27．．．流量調整閥27. . . Flow regulating valve
29．．．溫度檢測部29. . . Temperature detection department
30．．．第1蒸餾塔30. . . First distillation tower
31．．．目的物取出管31. . . Target removal tube
32．．．排出管32. . . Drain pipe
40．．．第2蒸餾塔40. . . Second distillation tower
41．．．原料排出管41. . . Raw material discharge pipe
42．．．排出管42. . . Drain pipe
100．．．多管式反應器100. . . Multitubular reactor
101．．．管101. . . tube
102．．．反應器102. . . reactor
103．．．熱交換器103. . . Heat exchanger
200．．．原料淬熄供給路200. . . Raw material quenching supply road
300．．．反應器300. . . reactor
第1圖表示用以實施本發明之製造方法之反應裝置之一例的概略構造圖。Fig. 1 is a schematic structural view showing an example of a reaction apparatus for carrying out the production method of the present invention.
第2圖表示上述反應裝置之反應器內原料之溫度變化之一例的概略圖。Fig. 2 is a schematic view showing an example of temperature change of a raw material in a reactor of the above reaction apparatus.
第3圖表示上述反應裝置之其他例的縱剖面圖。Fig. 3 is a longitudinal sectional view showing another example of the above reaction apparatus.
第4圖表示上述反應裝置之其他例的縱剖面圖。Fig. 4 is a longitudinal sectional view showing another example of the above reaction apparatus.
第5圖表示上述反應裝置之其他例的縱剖面圖。Fig. 5 is a longitudinal sectional view showing another example of the above reaction apparatus.
第6圖表示上述反應裝置之其他例的縱剖面圖。Fig. 6 is a longitudinal sectional view showing another example of the above reaction apparatus.
第7圖表示上述反應裝置之其他例的縱剖面圖。Fig. 7 is a longitudinal sectional view showing another example of the above reaction apparatus.
第8圖表示上述反應裝置之其他例的縱剖面圖。Fig. 8 is a longitudinal sectional view showing another example of the above reaction apparatus.
第9圖表示上述反應裝置之其他例的縱剖面圖。Fig. 9 is a longitudinal sectional view showing another example of the above reaction apparatus.
第10圖表示上述反應裝置之其他例的縱剖面圖。Fig. 10 is a longitudinal sectional view showing another example of the above reaction apparatus.
第11圖表示上述反應裝置之其他例的縱剖面圖。Fig. 11 is a longitudinal sectional view showing another example of the above reaction apparatus.
第12圖表示使用於本發明之實施例之比較例之裝置的概略圖。Fig. 12 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention.
第13圖表示使用於本發明之實施例之比較例之裝置的概略圖。Fig. 13 is a schematic view showing an apparatus used in a comparative example of an embodiment of the present invention.
第14圖表示使用於合成反應之習知裝置的概略圖。Fig. 14 is a schematic view showing a conventional apparatus used for the synthesis reaction.
第15圖表示使用於合成反應之習知裝置的概略圖。Fig. 15 is a schematic view showing a conventional apparatus used for the synthesis reaction.
2．．．反應裝置2. . . Reaction device
3．．．控制部3. . . Control department
4．．．原料貯存源4. . . Raw material storage source
2a．．．熱交換器2a. . . Heat exchanger
2b．．．蒸發器2b. . . Evaporator
20．．．反應器20. . . reactor
20a．．．原料氣體供給管20a. . . Raw material gas supply pipe
20b．．．生成氣體流出管20b. . . Gas outflow tube
22．．．觸媒層twenty two. . . Catalyst layer
22a．．．第1觸媒層22a. . . First catalyst layer
22b．．．第2觸媒層22b. . . 2nd catalyst layer
23．．．支撐構件twenty three. . . Support member
24．．．淬熄流體供給管twenty four. . . Quenching fluid supply pipe
24a．．．噴灑部24a. . . Spraying department
24b．．．吐出孔24b. . . Spit hole
Q．．．淬熄區Q. . . Quenching zone
27．．．流量調整閥27. . . Flow regulating valve
29．．．溫度檢測部29. . . Temperature detection department
30．．．第1蒸餾塔30. . . First distillation tower
31．．．目的物取出管31. . . Target removal tube
32．．．排出管32. . . Drain pipe
40．．．第2蒸餾塔40. . . Second distillation tower
41．．．原料排出管41. . . Raw material discharge pipe
42．．．排出管42. . . Drain pipe
Claims (20)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007326460A JP5512083B2 (en) | 2007-12-18 | 2007-12-18 | A method for controlling a reaction rate inside a reactor, a reaction apparatus, and a method for producing dimethyl ether. |
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| TWI421125B true TWI421125B (en) | 2014-01-01 |
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| EP2311554A1 (en) * | 2009-10-07 | 2011-04-20 | Linde Aktiengesellschaft | Method for reaction control of exothermic reaction and apparatus therefore |
| EP2531482B1 (en) * | 2010-02-04 | 2017-10-11 | Haldor Topsøe A/S | Process for the preparation of dimethyl ether |
| US8617385B2 (en) | 2011-06-06 | 2013-12-31 | Jeffrey N. Daily | Controlling temperature within a catalyst bed in a reactor vessel |
| DE102011114228A1 (en) * | 2011-09-23 | 2013-03-28 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Cooled reactor for the production of dimethyl ether from methanol |
| DE102012018341A1 (en) * | 2012-09-15 | 2014-05-15 | Thyssenkrupp Uhde Gmbh | Process for the preparation of dimethyl ether and apparatus suitable therefor |
| CN106478383B (en) * | 2015-08-28 | 2019-07-09 | 中国石油化工股份有限公司 | The method and consersion unit of preparing dimethyl ether from methanol and the method and system of methanol-to-olefins |
| CN111093818B (en) | 2017-11-21 | 2022-04-29 | 卡萨乐有限公司 | Chemical reactor with adiabatic catalytic bed and axial flow |
| CN108786664A (en) * | 2018-05-21 | 2018-11-13 | 合肥嘉科工贸有限公司 | A kind of multistage thermostatic type cold shocking type methanol synthesis reactor |
| CN114939390A (en) * | 2022-06-15 | 2022-08-26 | 詹海敏 | Multi-functional reation kettle for chemical production |
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| JP2004298768A (en) * | 2003-03-31 | 2004-10-28 | Jgc Corp | Method for operating gas-phase reaction apparatus |
| JP2004298769A (en) * | 2003-03-31 | 2004-10-28 | Jgc Corp | Gas phase reaction apparatus |
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| US3843737A (en) * | 1973-10-31 | 1974-10-22 | Sun Ventures Inc | Adiabatic recycle design for exothermic heterogeneously catalyzed reactions |
| JPS5929565B2 (en) * | 1975-03-06 | 1984-07-21 | 帝人株式会社 | Production method of alkyltetralin |
| KR100599251B1 (en) * | 2003-09-20 | 2006-07-13 | 에스케이 주식회사 | Catalysts for the dimethyl ether synthesis and its preparation process |
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| AU2008339360B2 (en) | 2013-01-31 |
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| JP2009149531A (en) | 2009-07-09 |
| KR20100087388A (en) | 2010-08-04 |
| JP5512083B2 (en) | 2014-06-04 |
| WO2009078490A1 (en) | 2009-06-25 |
| CN101903323A (en) | 2010-12-01 |
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