KR20070088900A - Reactor system for catalyst screening - Google Patents

Abstract

A reactor for catalyst screen is provided to estimate accurately and promptly the performance of the catalysts by being reflective of a real reaction condition, and dispense with secondary screening. A reactor for catalyst screen comprises a reactant inducing unit(10), a reacting unit(20) for performing reaction of reactants supplied from the reactant inducing unit, and a product analyzing unit(30) for analyzing products generated in the reacting unit. The reacting unit includes a plurality of reactors(124), a plurality of heaters(121) for independently heating the reactors, and a flow distributor(122) for distributing the reactants into the plurality of reactors, and a multi-position valve(127). The multi-position valve selects one of the plurality of reactors and samples products discharged from the selected reactor to transfer the sampled products to the product analyzing unit.

Description

Reactor for catalyst search {REACTOR SYSTEM FOR CATALYST SCREENING}

1 is a schematic view showing a reaction apparatus for catalyst search according to an embodiment of the present invention.

Figure 2 is a schematic diagram showing a reaction portion of the reaction apparatus for catalyst search according to another embodiment of the present invention.

Figure 3a is a perspective view showing an example of the bottom of the reactor equipped with a bullet.

FIG. 3B is a cross-sectional view of an example of a reactor bottom with the bullet of FIG. 3A installed.

Figure 4 is a graph showing the results of measuring the conversion rate of p-xylene on one catalyst by using a catalyst search reactor according to an embodiment of the present invention.

Figure 5 is a graph showing the results of measuring the conversion rate of propylene on the catalyst by using the catalyst for detecting catalyst according to an embodiment of the present invention.

[Industrial use]

The present invention relates to a catalyst searching device, and more particularly, to a device for searching a heterogeneous catalyst for gas phase reaction that can accurately and quickly evaluate catalyst performance by reflecting actual reaction conditions well.

[Prior art]

Traditional methods of evaluating the performance of heterogeneous catalysts (solid catalysts) used in gas phase reactions and selecting high performance catalysts evaluate the performance of one catalyst through one experiment in one reactor and the same process for other catalysts. Was repeated to evaluate and compare catalyst performance. However, such a "sequential method" of evaluating the performance of one catalyst at a time has a problem in that it takes time and cost to evaluate the performance of catalysts and to select a catalyst of good performance.

In order to solve this problem, a "parallel method" that compares and evaluates several catalyst performances at one time has been introduced and applied to research and development of various catalysts. U.S. Patent No. 6,653,138 B1 discloses a catalyst screening apparatus using a combination method, which has the advantage of screening catalysts at high speed, but the reaction conditions and analytical methods are far from the actual conditions, resulting in poor screening reliability and additional There was a problem that a catalyst performance verification procedure is required.

The Journal of Catalysis (Vol 198, 348-354) proposed a different type of experimental device for the search of high-speed catalysts, although reaction conditions and analytical methods reflect actual conditions better than combinatorial methods, but still scale up. There was a problem that additional verification experiments were required in a scale-up reactor, and a method of heating several reactors with a single heater lowers the uniformity of the reaction temperature and thereby causes a variation in the experimental conditions. There was this.

On the other hand, Catalysis Today (vol 60 (2000) 93-109) presented a six-channel parallel reactor, which reflects the actual reaction conditions, but the device is complicated by using an independent MFC to control the flow rate of reactants in each reactor. And, there is a problem in that the reaction temperature variation occurs for each reactor because it is a method of heating a plurality of reactors with one heater, there was a limitation in the temperature change experiment because it is impossible to control the independent reaction temperature for each reactor.

The present invention solves the above-mentioned problems of the present invention by screening the catalyst at high speed while utilizing the conventional single reactor type, reactor heating method, and reaction product analysis method as it is. In other words, by providing the advantages of a single reactor that reflects the actual reaction conditions, and the device applying a combination method (combinatorial method) or a high-throughput experiment technique, the performance of the heterogeneous catalyst for gas phase reaction in a short time reliability High evaluation was made possible.

It is an object of the present invention to provide a catalyst search reaction apparatus capable of accurately and quickly analyzing the performance of heterogeneous catalysts for gas phase reactions.

In order to achieve the above object, the present invention is a reactant introduction; A reaction unit for reacting the reactants supplied from the reactant introduction unit; And a reaction product analysis unit analyzing the reaction product generated in the reaction unit, wherein the reaction unit includes a plurality of independent reactors, a plurality of heaters for independently heating each reactor, and reacting the reactants provided from the reactant introduction unit. A flow splitter for distributing and supplying to a plurality of reactors, and a multi-position valve for selecting one of the plurality of independent reactors, and sampling the reaction product discharged therefrom to the analyzer, .

Hereinafter, the present invention will be described in more detail.

The reaction apparatus of the present invention includes a reactant introduction portion, a reaction portion, and a reaction product analysis portion.

The reactant introduction part is a part for providing a reactant of a chemical reaction to evaluate the performance of the catalyst. The reactant inlet may be the same as the reactant inlet of a conventional reactor, and is not particularly limited, and may include a gas flow controller and a liquid metering pump to adjust the reaction gas flow rate and the flow rate of the reaction liquid. The reactant inlet may also include a filter and a mixer, the filter for removing impurities such as dust in the reaction gas, the mixer evenly mixing the reaction gas and the reaction liquid to uniform the composition of the reactants entering the several reactors This is to increase the reaction efficiency in the reactor.

 The reaction part is a part in which a reactant provided from the reactant introduction part causes a chemical reaction on the catalyst. The reaction part is provided with several reactors and several heaters capable of independently controlling the temperature of each reactor. The number of reactors may be appropriately adjusted in consideration of the amount of reactants, analytical capability, and the like. In addition, the reaction section is also provided with a flow distributor for injecting the reaction mixture into each reactor, and a multi-position valve for selecting and delivering the reaction product discharged from each reactor to the analyzer .

The reactor may be U-shaped in order to increase efficiency during heating, but is not necessarily limited thereto. The heating device is preferably provided separately for each reactor in order to be able to independently control the temperature of several reactors.

Reaction device for catalyst search of the present invention can be carried out by several reactors at the same time to quickly analyze the performance of the catalyst, and by independently controlling the temperature of the reactor by a few heating devices accurately reflect the actual reaction conditions in all reactors This enables reliable catalyst performance evaluation.

The temperature of each reactor must be precisely adjusted to the desired reaction temperature in order to accurately evaluate the catalyst performance. Therefore, it is desirable to install an independent heating device per reactor. Although the kind of heating apparatus of this invention is not specifically limited, It is preferable that it is a heating apparatus using electricity, Specifically, an electric furnace or a heating wire can be used.

The flow distributor divides the flow rate of the reaction mixture evenly into the reaction section to make the experimental conditions uniform for each reactor. For even distribution of the reaction mixture flow rate, it is preferred to use a capillary flow distributor consisting of capillaries.

The inner diameter and length of the capillary used in the capillary flow distributor should be chosen such that the pressure drop across the capillary is similar to the differential pressure across the entire reactor line from the reactant introduction to the reaction product analysis. Capillary flow distributors that meet these conditions has the advantage of equally controlling the flow rate of reactants introduced into each reactor without a separate flow regulator.

The rear end of the flow distributor may further comprise a preheater for preheating the reaction mixture. The preheater is to sufficiently heat the reactants to introduce into the reactor, it is possible to control the reaction temperature more accurately when the preheater is mounted.

The multi-position valve may be configured to select, sample and deliver one of the reaction products exiting each reactor to the analyzer, and sequentially sample and deliver the reaction product exiting each reactor to the analyzer.

The flow distributor and the multi-position valve can be installed together in an oven type heating device, thereby eliminating the difficulty of individual line heating before and after the reactor inlet and outlet.

In order to increase the efficiency of the reaction apparatus, the flow distributor and the multi-position valve are preferably installed to be heated together by a single heating device, and in order to facilitate each temperature control, the flow distributor and the multi-position valve are separately provided. It is also preferably installed to be heated by a heating device. The heating device is not particularly limited but is preferably a heating chamber in the form of an oven or the like.

Heating flow distributors and multi-position valves can cause condensable components in the reaction mixture or product to condense if not heated, resulting in improper reactions, blockages, or inaccurate analysis.

The reaction product analyzer is a part for analyzing the reaction product generated in the reaction unit. The reaction product analyzer may include a trap for collecting the analyzer and the reaction product and a discharge pipe for discharging the reaction gas.

The analyzer uses a chromatographic method for more accurate analysis, of which an analytical apparatus using gas chromatography (GC) may be most preferably used.

The gas chromatography analyzer is preferably composed of a multi-valve system and a multi-column, whereby the reaction product can be separated within 5 minutes.

The trap may be composed of two stages for trapping the reaction product, which may include one trap for collecting a reaction sample in a liquid or solid state at room temperature and a trap for dissolving the remaining non-capture sample with a solvent. Can be.

The flow rate control and measurement, the temperature control and measurement, the operation of the multi-position valve and the like in the reactant introduction portion, the reaction portion, and the reaction product analysis portion can all be computer controlled.

Hereinafter, with reference to the drawings will be described in more detail.

1 is a block diagram schematically showing a reaction apparatus for catalyst search according to an embodiment of the present invention. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples.

The reaction apparatus for catalyst search according to the present embodiment includes a reactant introduction part 10, a reaction part 20, and a reaction product analysis part 30.

The reactant introduction part 10 includes a first valve 111 for controlling the inflow of the reaction gas, a pressure regulator 112 for adjusting the transfer pressure of the reaction gas, a filter 113 for removing dust in the reaction gas, and a gas flow rate. Regulator 114, check valve 115 to prevent backflow of reactant gas, pressure gauge 116 to measure pressure before reactor introduction, second valve 117 to shut off reactant gas flow, liquid metering pump ( 118, a third valve 119 capable of blocking liquid flow, and a mixer 110 for uniformly mixing the reactant gas and the liquid.

The reaction unit 20 is a heating device 121 for heating and warming the flow splitter and the multi-position valve, the flow distributor 122, the preheater 123, the reactor 124, a heating device for heating the reactor ( 125, a frame 126 for fixing the heating device, and a multi position valve 127.

The reaction product analyzer 30 may include a gas chromatography analyzer (GC) 130, first, second, third, and fourth traps 131, 132, 133, and 134, a gas chromatography analyzer, and a trap. The first needle valve 135 to adjust the flow rate to be delivered to the mass flow meter (136, 137), and the second and third needle valves (138, 139) to adjust the flow rate is discharged do.

The operation of the catalyst search reaction apparatus according to an embodiment of the present invention having the above configuration will be described.

The reaction gas that is controlled through the first valve 111 is controlled by the pressure regulator 112, the transfer pressure is adjusted, dust and the like is removed by the filter 113, the flow rate is controlled by the gas flow regulator 114 It is adjusted to flow into the mixer (110). At this time, the pressure gauge 116 measures the pressure before the reactor introduction, the second valve 117 can block the flow of gas when excessive gas inlet, the check valve 115 to prevent the back flow of the reaction gas Do it.

The reaction liquid injected into the metering pump is introduced into the mixer by adjusting its flow rate by the liquid metering pump 118, and the third valve 119 functions to block the flow of the liquid. The reaction liquid is heated and vaporized with a line heater before entering the mixer 110. The reaction gas and the reaction liquid introduced into the mixer 110 are uniformly mixed by the mixer 110.

The mixed reactant is introduced into the flow distributor 122 in the heater 121 of the reaction unit. The flow distributor divides the reaction mixture introduced at the reactant introduction portion evenly into eight channels, consisting of eight capillaries with an outer diameter of 1/16 "and a length of 20 cm.

The reaction mixture via the flow distributor 122 is preheated by a preheater 123 consisting of a 1/8 "tube coil. The reaction mixture via the preheater is introduced into a U-shaped quartz reactor 124 and the catalyst inside the quartz reactor. Quartz frit is installed to fill the.

The U-shaped reactor is heated in each independent electric furnace 125, and each electric furnace is fixed to one frame 126. The electric furnace may be substituted with a hot wire.

The frame is preferably to change the reactor by the hydraulic control to move up and down.

The reaction product exiting the reactor is delivered to the multi position valve 127. Of the eight reaction products delivered to the multi-position valve 127, one is delivered to the gas chromatography analyzer 130 via line 128 for analysis, and the remaining seven are combined into another line 129 for trapping. It discharges after going through 131 and 132 sequentially.

The multi position valve 127 delivers the reaction product to the gas chromatographic analyzer 130 while sequentially switching the reaction product discharged from the selected reactor at regular time intervals. The front and rear portions of the reactor, that is, the flow regulator 122, the preheater 123, and the multi-position valve 127 were heated by one oven 121 to remove the trouble of individual line heating.

The sample selected by the multi-position valve 127 is separated and transported to a line connected to the sampling valve line of the gas chromatography analyzer 130 by a trap, and the line passing through the sampling valve of the gas chromatography analyzer 130 is trapped again. 133, 134). The flow rate ratio delivered to the gas chromatography analyzer 130 and the trap is controlled by the needle valve 135.

The trap is composed of two stages. In the first trap 133, the reaction sample which is liquefied or solidified at room temperature is collected, and the remaining sample which is not collected is dissolved and collected as a solvent in the secondary trap 134. In addition, the reaction product in the gaseous state at room temperature is discharged through the discharge line.

Meanwhile, the remaining seven reaction products not selected by the multiposition valve 127 among the reaction products discharged from the eight reactors 124 are combined into one line 129 and delivered to separate traps 131 and 132. Even in this case, two traps are connected in series, and the first trap 131 collects most of the samples that are liquefied or solidified, and the second trap 132 collects them by using a solvent.

Gas components in the reaction product that do not condense are discharged through the discharge line. Needle valves 138 and 139 and mass flow meters 136 and 137 are connected in series to the discharge line after the trap to adjust the pressure of the discharged gas and measure the flow rate.

The gas chromatography analyzing apparatus 130 used to analyze the reaction product may be constituted by a multi-valve system and a multi-column to separate a desired reaction product within about 5 minutes.

2 is a block diagram showing a reaction unit of another form. In the catalyst searching device including the reaction part of FIG. 2, the reactant introduction part and the reaction product analysis part may be provided in the same manner as the device of FIG. 1.

The reaction mixture supplied from the reactant introduction is introduced into flow distributor 222 via injection line 221. Here, the flow distributor divides the reaction mixture introduced at the reactant introduction portion into eight channels, and the process of substantially evenly distributing the flow rate of the reaction mixture is performed using an outer diameter of 1/16 "and a length of 20 cm. Through the two capillaries 223. The reaction mixture through the capillary tubes 223 is introduced into a single-shaped 3/8 "stainless steel reactor 224, and inside the stainless steel reactor there is a bullet to fill the catalyst. 225 is installed.

The single-shaped reactor is separated into an upper portion 224a and a lower portion 224b, and the upper portion 224a and the lower portion 224b of the reactor are fixed to the upper frame 226 and the lower frame 227, respectively. The lower frame 227 fixed to the lower portion of the reactor is hydraulically adjustable to move up and down. In addition, the multi-position valve 228 is fixed to the lower frame 227 is provided to move together when the lower frame moves.

The catalyst-filled bullet 225 may be installed in the lower portion of the reactor 224b and the lower frame 227 may be moved upward so that the reaction may be performed when the upper portion of the reactor and the lower portion of the reactor are completely in contact with each other.

3A is a perspective view showing an example of the reactor bottom 224b in which the bullet 225 is installed, and FIG. 3B is a cross-sectional view of an example of the reactor bottom in which the bullet of FIG. 3A is installed. The reactor bullet 225 supports a catalyst and has a support net 225a through which gas can pass, and an outer O-ring for completely sealing the upper and lower portions of the reactor outside the bullet. ) 225b and 225c may be mounted. The material of the O-ring is not particularly limited, but is preferably a graphite ring.

In the reaction unit of FIG. 2, the flow distributor 222, the capillary 223, the reactor 224, the multi-position valve 228, and the transfer lines 128 and 129 connected to the multi-position valve, respectively, form a heating wire. It is preferable to wind and wind each. In FIG. 2, only the heating wire wound around the reactor is illustrated, and the heating wire is omitted from the flow distributor, the capillary tube, the multi-position valve, and the transfer line.

In the apparatus of FIG. 2, since a heating wire may be used in place of an oven and an electric furnace, there is an advantage in that the volume of the reaction apparatus is greatly reduced as compared to the reaction apparatus illustrated in FIG. 1. Meanwhile, the reaction product discharged from one reactor selected by the multi-position valve is transferred to GC through line 128 for analysis, and the reaction product discharged from the remaining seven reactors is combined and sent to the trap via line 129.

Experimental Example

Experimental Example 1

Using a reaction apparatus for catalyst search according to an embodiment of the present invention shown in FIG. 1, each reactor was filled with 0.2 g of a 200 μm WO ₃ powder catalyst, which is a p-xylene partial oxidation catalyst, and p- A reaction mixture consisting of xylene, oxygen, and nitrogen (total flow rate per reactor: 100 cc / min) was injected into each reactor. The injection concentration of P-xylene was 0.5% by volume and the oxygen / p-xylene molar ratio was 25. The remaining balance gas was nitrogen. The oxidation reaction temperature of P-xylene was adjusted to 500 ° C., and the p-xylene conversion at this temperature was measured using the reaction product analysis result of GC, and the result is shown in FIG. 4.

As shown in Figure 4, it was confirmed that the conversion rate in each reactor appeared uniformly.

Experimental Example 2

Mo ₁₂ Bi _1.5 Fe ₁ Co ₄ K _0.06 O _x (x is a constant determined as an oxidized state) in each reactor by using a reaction apparatus for catalyst search according to an embodiment of the present invention shown in FIG. 2. 0.1 g of catalyst was charged and propylene oxidation was carried out by flowing a reaction mixture of propylene, oxygen, water, and nitrogen at 7.5%, 12.8%, 8.5%, and 71.2%, respectively, on a molar basis. The space velocity of the reactants was adjusted to 5,000 hr ⁻¹ , and the conversion was measured three times at each temperature while changing the reaction temperature to 300 ° C., 320 ° C., and 340 ° C., and the results are shown in the graph of FIG. 5.

As shown in FIG. 5, the conversion in each reactor appeared uniformly and showed excellent reproducibility in repeated experiments.

The heterogeneous catalyst search apparatus for gas phase reaction of the present invention can accurately and quickly evaluate the catalyst performance by reflecting the actual reaction conditions well, and has the advantage that secondary screening is unnecessary due to the accuracy of the catalyst search.

Claims (10)

Reactant introduction; A reaction unit for reacting the reactants supplied from the reactant introduction unit; And Reaction product analysis unit for analyzing the reaction product generated in the reaction unit Including; The reaction unit Multiple independent reactors; A plurality of heaters for heating each reactor independently; A flow rate distributor for distributing and supplying the reactants provided from the reactant introduction unit to the plurality of reactors; And A multi-position valve for selecting one of said plurality of independent reactors, sampling and delivering the reaction product discharged therefrom to said analyzer. The method of claim 1, The multi-position valve is a catalyst search reactor for sequentially sampling the reaction products discharged from the plurality of reactors and delivers to the analyzer. The method of claim 1, Wherein the flow distributor and the multi-position valve are installed together in one heater or separately installed in separate heaters. The method of claim 1, Wherein the reaction unit further comprises a preheater for preheating the reaction mixture in the rear end of the flow distributor. The method of claim 1, The heating device is a catalyst search reactor for the electric furnace or selected from the hot wire. The method of claim 1, The reactant introduction portion A gas flow regulator for controlling the reaction gas flow rate; A liquid metering pump for adjusting the flow rate of the reaction liquid; A filter for removing impurities in the reaction gas; And Reactor for catalyst search comprising a mixer for mixing the reactants. The method of claim 1, The reaction product analyzer comprises a trap for trapping the reaction product (trap), and the reaction apparatus for catalyst search that comprises a discharge pipe. The method of claim 1, The analyzer is a reaction apparatus for catalyst search that is an analytical device using gas chromatography. The method of claim 1, Wherein the trap trap is composed of a primary trap for collecting the reaction sample present in the liquid or solid phase at room temperature and a secondary trap for collecting by dissolving the remaining non-captured sample in a solvent. The method of claim 1, The reaction unit includes a frame for fixing the plurality of heating devices, The frame is a catalyst for the reaction device for the vertical search can be adjusted hydraulically.

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