JPS59179158A - Device for producing catalyst - Google Patents

Abstract

PURPOSE:To produce easily a catalyst for test by packing successively catalysts, which are obtd. by absorbing successively the liquid contg. >=1 kind of effective components in granular carriers supplied at a constant rate on an endless belt and drying the carriers, into a reaction tube. CONSTITUTION:The carriers which are supplied from a constant volume feeder 21 through a conduit 22 fall into the U-groove of a U-shaped belt 23 having a shallow section and absorb the liquid contg. effective components supplied near the falling position. If two kinds of the effective components are used in this case, the one kind is stored and is kept stirred in a reservoir 30 and the other is stored in a reservoir 32 and is successively pumped 29 into the reservoir 30. The compsn. of the effective components in the reservoir 30 changes accordingly with time and is absorbed on the carriers on the belt. The carriers are thereafter dried in a drying chamber 26. The carriers after the drying are dropped and packed as a catalyst via a discharging chute 27 into a reaction tube 11 installed with a net near the bottom. The belt 23 is subjected to washing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an apparatus for producing a granular catalyst (hereinafter simply referred to as a catalyst).

Currently, in the chemical industry, a wide variety of catalysts are used for various chemical reactions, but these catalysts are
All of these have been put into practical use as a result of extensive research and development efforts. As is well known, catalysts are made by selecting the most suitable active ingredient (in many cases, multiple active ingredients are used) from among many types of metals, inorganic compounds, organic compounds, etc., and then supporting these active ingredients. The carrier for this purpose is selected from among many materials, and the optimal manufacturing conditions for the combination of both materials are studied before it is put into practical use. It is necessary.

As mentioned above, the purpose of this invention is to reduce the labor involved in the research and development of catalysts. While flowing the raw material fluid through a reaction tube filled with a plurality of catalysts with different values, and while analyzing the composition of the product fluid flowing out and covering the reaction tube, a part of the lengthwise portion of the catalyst-filled portion of the reaction tube is analyzed. Heat is applied from the outside to bring the catalyst inside only a portion of the heated reaction tube into an operating state, and by moving the heated portion of the reaction tube, catalysts of different compositions are successively brought into the operating state and at the outlet of the reaction tube. When implementing a method of knowing the performance of each part of the catalyst layer whose composition is known from the continuous analysis results of the fluid, it is necessary to use catalysts with different compositions to be filled into the reaction tube.
The purpose is to provide equipment for labor-saving manufacturing.

First, the principle of the catalyst testing method will be explained with reference to FIG.

In FIG. 1, reference numeral 11 denotes a reaction tube filled with catalysts of different compositions sequentially. A raw material fluid is allowed to flow through this reaction tube from a raw material fluid population 41 to a product fluid outlet 42 . On the other hand, a portion of the catalyst-filled portion of the reaction tube in the length direction is heated to a desired humidity by the heater 12.

The heater 12 is fixed to the ribs 1-44, and as a result of the nuts 1-44 fitting into the screws 43,
By rotating the screw 43 with the motor 10, the heater can be moved in the length direction of the reaction tube at a desired speed. Therefore, only a portion of the catalyst in the reaction tube, ie, a catalyst of a specific composition located in the heated portion, is in operation and causes a reaction in the feed fluid.

The result of the reaction is that the fluid exiting the product fluid outlet 42 is
It can be determined by well-known analytical means such as gas chroma mill graph or liquid chromatograph. By using the method based on this principle, if you know in advance where in the length direction of the reaction tube and what composition of catalyst is packed and 1C,
The performance of multiple catalysts filled in each part of the reaction tube can be known at once from the temporal changes in the analysis results of the produced fluid and the heater movement program.

In a catalyst testing method based on such a principle, it is necessary to know in advance the force V at which part of the reaction % and which composition of catalyst is packed. In conventional methods, the catalysts with the desired composition were usually manufactured in the desired size by hand, and each type was filled into a reaction tube to test the performance of the catalyst. Although this method can be used to simultaneously test the performance of a plurality of catalysts having different compositions as described above, it is not preferred because it requires a large amount of labor.

The present invention provides an apparatus aimed at reducing labor for catalyst production in catalyst research and development. In other words, 15, the tactile ts manufacturing device according to the present invention is characterized in that the active ingredient is contained in a granular carrier (
An apparatus for producing a granular catalyst supported on a granular catalyst (hereinafter simply referred to as a carrier), comprising: (a) a supplying apparatus for supplying a fixed amount of the carrier onto the endless bells 1 to 1 described in 1r1;
b) While loading the supplied carrier, carry out the following (c) and (d).
and (e) sequentially transferred to each device or process, and then (to) J3. and endless bells 1 to 1 which repeatedly circulate through the devices described in items 1 to 1 to finally reach the carrier supply position according to item (a), and a driving device for the belts; A device for supplying one type of carrier to the downstream side of the carrier supply position on the belt while controlling the supply amount separately, items (d), (b) and (
(c) A drying device for the carrier that has come to contain the liquid according to item (e) A step for discharging the catalyst formed by drying from above the belt; This is a catalyst manufacturing apparatus characterized in that it is equipped with: (1 to 1) a drying device for bells 1 to 1 washed in step (f); By using this apparatus, catalysts with different compositions can be continuously produced according to a desired program, and the produced catalysts are sequentially filled into the reaction tube,
If you conduct the catalyst performance test as described above, you can significantly save J3's labor in catalyst research and development! I can do it.

The apparatus according to the invention will be explained in detail with reference to FIG. Although FIG. 2 shows an example in which two types of active ingredients are supported on selected carriers, the qb range of the present invention is not limited to this example. In Figure 2,
Reference numeral 21 denotes a carrier feeder, and 22 a conduit for the supplied carrier. The carrier passing through this conduit has a shallow cross section of U
It falls into the (1) groove of the character-shaped belt 23 and absorbs the active ingredient-containing liquid supplied near this falling position. It is stored and stirred by a magnetic stirrer 31.Other active ingredient-containing liquids are stored in a32.The active ingredient-containing liquid in the reservoir 32 is sequentially supplied to the reservoir 30 from the pump 29t. .

Therefore, the composition of the active ingredient in the reservoir 30 changes over time, and the liquid in the reservoir 30 whose composition changes is supplied to the two pumps (U near the downstream side of the carrier falling part of the bell 1). The liquids are supplied into the grooves and absorbed by the carrier.The two liquids may be separately fed onto the belt by pumps whose supply amounts can be controlled independently.

As the belt moves, the carrier that has absorbed the active ingredient enters a drying chamber 26 equipped with a heater and is dried.

The dry carrier that has left the drying chamber is discharged as a catalyst and is discharged as a catalyst.
7, it is dropped and filled into a reaction tube 11 with a mesh installed near the bottom. On the other hand, bells 1~ are then placed in the belt washing water tank 2.
After being washed in step 5 and further dried in the belt drying chamber 24 d5, it returns to the carrier supplying position again. Since the supply of the carrier is a fixed quantity supply, the supply amount of the two types of active ingredient-containing liquids by the pump 29 is determined according to the time table marked 81.
If they are adjusted separately, desired amounts of catalysts having different contents for each of the two active ingredients can be filled into the reaction tube in a desired order. The same applies even if three or more types of active ingredients are used. The catalyst filled in the reaction tube is incorporated together with the reaction tube into a catalyst performance testing apparatus as shown in FIG. 1, and subjected to the performance test described above. Prior to carrying out the catalyst performance test, the catalyst in the reaction tube may be subjected to a heat treatment and/or a preliminary treatment (-1) at a desired temperature and in the presence of a gas of a desired composition. What is done is the same as in the conventional method.

The raw material 1 carrier used in this invention is preferably dried spherical or irregularly shaped granules. for example,
Alumina balls are similar to pumice stones, and their active ingredients include:
All compounds, metals,
The elements etc. can be used as a solution or suspension using water or an organic solvent.

A commonly used example of 1C is a metal nitrate aqueous solution. The drying conditions for the catalyst in this inventive device are determined by the properties of the active ingredients; It's good to choose. The time required for drying is usually one hour or less. After the required amount of catalyst has been filled, a net is placed above the catalyst layer of the reaction tube to prevent the catalyst from flowing out of the reaction tube, and the catalyst test apparatus is installed as shown in Figure 1. As mentioned above, the performance of the catalyst can be tested.

In the device of this invention, a carrier is made to absorb two or more types of active ingredient-containing liquids, and a washing device is added to remove soluble substances that are produced as a by-product of the chemical reaction of these active ingredient-containing liquids within the carrier. I can do it. In many cases, the location where this washing device should be added is midway between the supply location of the active ingredient-containing liquid and the entrance end of the drying chamber. It is also convenient to use a belt in the present invention that has projections in the U-shaped groove (for preventing the particulate carriers in the 1-shaped groove from rolling in the longitudinal direction of the belt.

As mentioned above, the advantage of this invention is that it reduces the labor involved in research and development of catalysts, and by using the apparatus according to this invention, test catalysts can be manufactured in less than half the man-hours of conventional methods. I can do it.

EXAMPLE Using the apparatus shown in Figure 2, a catalyst in which iron and nickel as active ingredients were continuously supported in different ratios on spherical alumina as a carrier was manufactured and filled into a reaction tube. A reaction tube was assembled as shown in Fig. 1, and a hydrocarbon synthesis reaction experiment using carbon oxide and hydrogen as raw materials was carried out.

Iron and nickel were prepared using reagent-grade commercially available nitric acid 2
Iron and nickel nitrate were dissolved in pure water using an ion exchange method, and 2 weighs of a solution containing 1 mol/j of active ingredient was prepared for 25 yi.
Prepare nickel nitrate solution in reservoir 30,
The ferric nitrate solution was charged into the reservoirs 32, respectively. As the carrier, dried alumina balls with a diameter of 3 mTn were used. An electromagnetic feeder used as a carrier feeding device fed alumina poles onto the belt via conduit 22 at a rate of 55 pieces/min. Bell 1~ is made by Gol＼ and has a depth of 5 IT.
The belt had a U-shaped cross-section of IITl and was rotated at a speed of 17 CTIl/min. pump 29
While the ferric nitrate solution in the reservoir 32 was transferred to the reservoir 30, the liquid in the reservoir 30 was supplied in a fixed amount onto the belt by two pumps. Therefore, the liquid supplied onto the belt is initially a liquid containing an active ingredient with a large amount of nickel, and gradually a liquid containing an active ingredient with a large amount of iron is supplied. At this time, both liquids are completely mixed in the reservoir 30 by a magnetic stirrer, so that nickel in the liquid supplied onto the belt decreases exponentially, and iron increases exponentially. Become. Each of the carrier particles that had absorbed the liquid supplied in this manner passed through a drying chamber maintained at 150° C. for 2 minutes while being placed on the bell 1, and was dried during this period. The dried catalyst was sequentially transferred to the central part 9 of a Pyrex glass reaction tube with an inner diameter of 10 mm and a length of 1300 mm.
It was filled over 00 myn.

The reaction tube filled with the catalyst as described above has a length of 10010 mm.
The thermal decomposition of nitrates at a temperature of 3/IO°C can be carried out at 240 °C by incorporating it into a 0O electric furnace and by first flowing air inside the furnace.
The reduction was carried out for 300 minutes at 370° C. while flowing hydrogen. As a result of the previous operations, the catalyst in the reaction tube will contain about 5% by weight of nickel and/or iron.

The reaction tube in which the catalyst had been reduced as described above was installed in the catalyst testing apparatus shown in FIG. The heater of this apparatus is an electric heater that can uniformly heat a portion of the reaction tube over a length of 80 myn. Heating was carried out while flowing a mixture of 2311 am/min of carbon monoxide, 70 m/min of hydrogen, and 20 xi/min of helium into the reaction tube under approximately atmospheric pressure, and controlling the temperature of the heated portion of the reaction tube to 245°C. 4. It moved from downstream to upstream of the reaction tube at a constant speed of 3 mm/min, and the residue flowing out from the reaction tube during that time was analyzed using a gas chromatograph with thermal conductivity detection and a paper towel analysis method.

The results of the analysis are shown in Figure 3. In Figure 3, the horizontal axis shows the mol% of nickel relative to the total number of moles of nickel and iron contained in the catalyst, and the vertical axis shows ethylene, ethane, and 1].
Supply of carbon monoxide converted to pyrene and propane -
It is a figure which does not show mole % with respect to carbon oxide. In this figure, curve A shows the mole percent of feed carbon oxide converted to ethylene, B to propylene, C to propane, and D to L-tan. This figure shows that the amount of each hydrocarbon produced differs as the composition of the catalyst changes;
In other words, the performance of the catalyst can be clearly known.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the principle of catalyst performance testing, and Figure 2 is a diagram showing the principle of catalyst performance testing.
These are examples of the catalyst manufacturing apparatus according to the present invention, and all are schematic external views. FIG. 3 shows the analysis results of the gas flow at the outlet of the reaction tube in the catalyst performance test described in the Examples. Symbol 1...S I ~ Stub valve 2...Flow control valve 3...Flow M meter 4...Gas chromatograph device 5...Mass spectrometer 6...Record cutter 12...Heater 13・・Temperature detector 14・・Cooler 15・・Rewinder 16・・String 21・・Carrier feeder 22・・Carrier conduit 23・・Belt 2/I・・Belt drying chamber 25・・Washing to bell 1 Water tank 26... Drying chamber 27... JJI output chute 29... Pump 30... Active ingredient containing liquid reservoir 31... Magnetic stirrer 32... Active ingredient containing liquid reservoir 41... Raw material fluid inlet 42... Produced fluid Outlet 43...Screw 44...Nut 45...Gas reservoir 46...Gas reservoir 47...Gas reservoir

Claims (1)

[Scope of Claims] An apparatus for producing a granular catalyst in which an active ingredient is supported on a granular carrier, comprising: (a) a feeding device for quantitatively feeding the carrier onto the endless belt according to (b); b) The supplied carriers are all placed on racks and sequentially transferred to each of the devices or processes described in (c), (d), and (e) below, and then passed through the equipment described in (f) and (g). , the endless bell I repeatedly revolves until finally reaching the carrier supply position according to item (a).
- and a drive device for the belt; (c) a device for supplying at least one of the active ingredient-containing liquids to the downstream side of the carrier supply position on the belt while controlling the supply amount separately; ) A drying device for the carrier that has come to contain the liquid according to items (a) and (c); (e) a step of discharging the catalyst formed by the drying from above the belt; (f) a step of discharging the catalyst. An FI characterized by comprising: a washing device for washing the belt after being washed; l! Media manufacturing equipment.