JPH0249322B2 - OREFUINJUGOYOSHOKUBAISEIBUNNOKYOKYUHOHOOYOBIKYOKYUSOCHI - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for supplying a catalyst component for olefin polymerization to a reaction tank and an apparatus for carrying out the method.

Conventionally, Ziegler catalysts used for producing polyolefins, for example, have generally been supplied by pumping. In such a catalyst supply method using a pump, the catalyst slurry with a high concentration can clog the catalyst supply line, and if the concentration is high, it becomes difficult to supply the catalyst in a constant quantity, making it impossible to supply the catalyst smoothly. It was necessary to supply the catalyst diluted with an inert solvent. However, if the catalyst is diluted with an inert solvent, the catalytic activity will decrease due to impurities in the inert solvent, and it is necessary to separate and remove the inert solvent in the post-treatment process, which requires a lot of energy. However, it also had the disadvantage of being contrary to the demand for resource conservation.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method and apparatus for supplying a catalyst that can smoothly supply a catalyst to a reaction tank while keeping the catalyst at a high concentration.

In the supply method according to the present invention, a rotating body having two channels that do not intersect with each other is arranged in the flow of the carrier fluid flowing into the reaction tank, and the carrier fluid is caused to flow through one of the channels. When the other channel is filled with high concentration catalyst,
The purpose is achieved by rotating the rotating body so that the high-concentration catalyst is appropriately supplied into the carrier fluid, and the high-concentration catalyst is carried by the carrier fluid and supplied to the reaction tank. It is something to do.

Further, the supply device according to the present invention appropriately rotates a rotary body having first and second flow paths that do not intersect with each other, and when this rotary body is located at a predetermined rotation angle, the first flow path The carrier fluid inlet into which the carrier fluid flows is connected by the channel to the catalyst supply line which supplies the catalyst to the reaction tank to form a flow of the carrier fluid to the reaction tank, and the second channel has a catalyst storage tank. The catalyst inlet is communicated with the flow path so that the catalyst is filled in the flow path, and when the rotating body is rotated by a predetermined rotation angle from this state, the first flow path removes the carrier fluid. When the rotor is further rotated by a predetermined rotation angle, the second flow path is connected to the carrier fluid inlet and the catalyst flow outlet. The catalyst in the second flow path communicating with the outlet is supplied to be replaced by the carrier fluid in the flow of the carrier fluid flowing into the reaction tank, and the catalyst is carried by the carrier fluid and flows through the catalyst supply line. In order to achieve the above object, the catalyst is supplied to the reaction tank through the catalyst, and a catalyst inlet is communicated with the first flow path so that the catalyst is filled with the catalyst.

Embodiments of the present invention will be described below based on the drawings.

FIG. 1 shows process steps when an embodiment of the apparatus for supplying catalyst components for olefin polymerization according to the present invention is applied to a polymerization reaction process. In this figure, a catalyst component supply device 1 is connected to a polymerization reaction tank 3 as a reaction tank via a catalyst supply line 2, and a cocatalyst is appropriately supplied to a predetermined position of the catalyst supply line 2 from a cocatalyst supply line 4. supply is becoming available.

Further, a catalyst storage tank 6 is connected to the supply device 1 via a catalyst inflow line 5, and a catalyst 7 in the catalyst storage tank 6 is connected to the supply device 1 via a catalyst inflow line 5.
is supplied to the supply device 1, and is returned to the catalyst storage tank 6 via a catalyst return line 8 as required. Furthermore, a carrier fluid supply line 9 and a carrier fluid removal line 10 are connected to the supply device 1 .

FIG. 2 shows the external appearance of the feeding device 1, and FIGS. 3 and 4 show a partially cutaway front view and a partially cutaway right side view of the main parts, respectively. In these figures, a truncated conical valve body 12 serving as a rotating body is fitted into a substantially thick-walled cylindrical main body 11 so as to be rotatable in the axial direction, and the supply device 1 is configured in a so-called rotary valve type.

The main body 11 is provided with a carrier fluid inlet 13 and a catalyst outlet 14 facing in opposite directions from each other with the valve body 12 as the center on the same virtual straight line along the horizontal direction in the drawing. The catalyst return ports 16 are arranged in opposite directions around the valve body 12 and on the same imaginary horizontal plane as the carrier fluid inlet 13 and the catalyst outlet 14, and with respect to the carrier fluid inlet 13 and the catalyst outlet 14. It is provided facing perpendicularly. Here, the carrier fluid supply line 9 is connected to the carrier fluid inlet 13.
A catalyst supply line 2 is connected to the catalyst outlet 14, a catalyst inflow line 5 is connected to the catalyst inlet 15, and a catalyst return line 8 is connected to the catalyst return port 16.

The valve body 12 is housed in a cylindrical hollow part 21 provided at the center of the main body 11, and a conical recess 22 is formed at the center of the bottom surface of the valve body 12. The valve body 12 is rotatably supported by a carbide ball 23 inserted by a predetermined amount. The carbide ball 23 is connected to the valve body 12
A predetermined amount of the bearing material 24 is inserted into a conical recess 25 formed at the center of the upper end surface of a disc-shaped bearing material 24 located below the main body 11. It is biased upward in the figure by a compression coil spring 27 interposed between the valve body 12 and the bearing member 24, and thereby the valve body 12 is supported in a state in which it is biased upward in the figure.

A short cylindrical guide ring 28 is fitted and fixed on the outer circumference of the valve body 12, and this guide ring 28 guides the rotation of the valve body 12 in the hollow portion 21, and also guides the valve body 12 in the vertical direction. The amount of movement is regulated. Further, a communication hole 29 is bored at a predetermined position of the guide ring 28 .

A first flow path 31A and a second flow path 31B are formed in the valve body 12 so that they do not intersect with each other inside the valve body 12. These two channels 31A, 31B are arranged to face perpendicularly to each other when viewed from above in the figure, and the openings at both ends of the channels 31A, 31B are located at approximately the same height on the outer periphery of the valve body 12, and They are spaced 90 degrees from each other along the direction. These channels 31A, 31
When the valve body 12 is positioned at the rotation angle shown in FIG. 3 due to B, the carrier fluid inlet 13 and the catalyst outlet 14 are communicated through the first flow path 31A, and the second flow path 31B communicates with each other. Catalyst inlet 1
5 and the catalyst return port 16 are communicated with each other, and when the valve body 12 is rotated by 90 degrees from this rotation angle, the catalyst inlet 15 and the catalyst return port 16 are communicated with each other through the first flow path 31A, and the second flow path 31B
carrier fluid inlet 13 and catalyst outlet 14
are now being communicated. Note that the communication hole 29 of the guide ring 28 is connected to the flow paths 31A and 31B.
The guide ring 28 does not block the flow of the carrier fluid through the catalyst 7.

Carrier fluid inlet 13 and catalyst inlet 1 of main body 11
As shown in FIGS. 5 and 6, a carrier fluid discharge port 41 is provided at an intermediate position between the valve body 12 and the flow path 31 when the valve body 12 is positioned at a predetermined rotation angle.
A or 31B is adapted to be communicated with the carrier fluid removal line 10 via the joint 80.

A stem 51 is provided on the valve body 12, and this stem 51 is rotatably supported by the main body 11 via an O-ring 52. As shown in FIGS. 2 and 3, the stem 51 is connected to a drive shaft 54 via a ratchet 53, and when the drive shaft 54 is rotated by an actuator 55 serving as a drive source, the stem 51
1 is also rotated, but the stem 51 is always rotated in only one direction by the ratchet 53, and in this embodiment, the valve body 12 is rotated only in the counterclockwise direction when viewed from above in the figure. I'm starting to do that.

A control section 56 supported by the upper part of the main body 11 via a yoke 61 is provided above the ratchet 53. The control unit 56 includes a limit switch 57 that detects the rotation speed of the drive shaft 54, as well as a solenoid valve 58, an actuator 55, and a speed control 60, and the valve body 12 is rotated or stopped as appropriate by the action of these elements. ing.

Note that, as shown in FIG. 3, the valve body 12 includes a first
An adjustment hole 71 is formed in the main body 11, and a second adjustment hole 72 is formed in the main body 11 to communicate with the catalyst outlet 14 and the hollow part 21.
1 and 72, the pressure around the valve body 12 is adjusted.

Next, the operation of this embodiment will be explained with reference to FIGS. 7A to 7C.

A catalyst storage tank 6 is filled with a catalyst 7 in the form of a highly concentrated slurry and pressurized with an inert gas such as nitrogen to maintain the internal pressure in the tank slightly higher than that in the polymerization reaction tank 3.

When the rotating body 12 of the supply device 1 is stopped in the state shown in FIG. 7A, the first flow path 31
The carrier fluid supply line 9 and the catalyst supply line 2 are connected by A, and the carrier fluid is supplied to the polymerization reaction tank 3. Most preferably, the carrier fluid is the monomer itself for the polymerization reaction.

On the other hand, a catalyst inflow line 5 is communicated with the second flow path 31B, and a catalyst 7 is filled in the second flow path 31B. At this time, the excess catalyst 7 is returned to the catalyst storage tank 6 via a transport return line 8.

From this, when the rotating body 12 is rotated counterclockwise in FIG. 7 to the state shown in FIG. 7B, the carrier fluid supply line 9, the catalyst supply line 2, and
The catalyst inflow line 5 and the catalyst return line 8 are temporarily disconnected from each other, and the first flow path 3
1A is connected to the carrier fluid removal line 10, and the first
The carrier fluid in the flow path 31A is discharged to the carrier fluid removal line 10. On the other hand, a certain amount of the catalyst 7 remains filled in the second flow path 31B.

Further, when the rotating body 12 is rotated counterclockwise and stopped after rotating exactly 90 degrees from the state shown in FIG. 7C, that is, the state shown in FIG. The fluid supply line 9 and the catalyst supply line 2 are communicated with each other, and the catalyst 7 filling the second flow path 31B is transferred to the catalyst supply line 2 by the carrier fluid flowing into the supply device 1 from the carrier fluid supply line 9. It is pushed out and supplied to the polymerization reaction tank 3 along with the flow of the carrier fluid. On the other hand, the catalyst inflow line 5 is communicated with the empty first flow path 31A, and the catalyst 7 is filled in the first flow path 31A.

By repeatedly rotating and stopping the rotating body 12 as described above, appropriate
A predetermined amount of the catalyst 7 is supplied without being diluted in a highly concentrated slurry state to replace the carrier fluid, and the catalyst 7 is carried by the carrier fluid and supplied to the polymerization reaction tank 3.

While the rotating body 12 reaches the state shown in FIG. 7A to B, the carrier fluid supply line 9 and the catalyst supply line 2 are temporarily disconnected, but this time is usually within a very short period of time, within a few seconds. Therefore, there is no possibility that the flow in the catalyst supply line 2 will stagnate and cause clogging. Note that the rotating body 12 does not necessarily need to be temporarily stopped in the states shown in FIGS. is selected as necessary. That is, the flow paths 31A, 31
Since the amount of catalyst 7 filled in B is constant,
For example, when trying to supply more catalysts 7 to a carrier fluid with a constant flow rate, the controller 56
The rotation speed of the rotating body 12 may be increased by the operation of
The rotational speed of the rotating body 12 may be made to correspond to the changing flow rate of the carrier fluid so that the catalyst 7 is always supplied at a constant rate even if the flow rate of the carrier fluid fluctuates.

Further, when a monomer for a polymerization reaction is used as the carrier fluid, the co-catalyst may be supplied from the co-catalyst supply line 4 and prepolymerization may be carried out in the catalyst supply line 2.

This embodiment has the following effects.

The catalyst 7 can be extremely smoothly supplied to the polymerization reaction tank 3 as a highly concentrated slurry without being diluted.
For example, in the conventional method of supplying catalyst by pump transfer, the ratio of solid (g) to inert solvent () is usually 10 g/~, depending on the inert solvent such as heptane and the properties of the solid component. Previously, it was necessary to dilute the inert solvent to a range of 0.1 g/distance, but according to this example, the inert solvent can be diluted to at most 0.02 g/m
% to 2% is no longer necessary. That is,
It can be supplied at concentrations 50 to 5000 times higher than conventional methods.

Therefore, not only is it possible to prevent a decrease in the activity of the catalyst 7, but it also eliminates the use of inert solvents that complicate the post-treatment process as much as possible, meeting the demand for resource conservation and greatly improving unit manufacturing costs. can contribute. Furthermore, the volatile content in the product caused by the inert solvent during the drying process of the produced polymer can be significantly reduced.

Furthermore, the supply amount of the catalyst 7 can be easily adjusted by controlling the rotational state of the rotating body 12.

In addition, when using the monomer itself for the polymerization reaction as the carrier fluid, there is no need to separate the carrier fluid, and since the monomer itself is a polymerization reaction product, any amount can be supplied, resulting in a high concentration. Even if catalyst slurry is supplied, catalyst supply line 2
No blockage occurs at all.

In addition, in the case of the above-mentioned catalyst component supply device 1,
The flow paths 31A and 31B are both oriented perpendicularly to the rotation axis of the rotating body 12, but, for example, in a conventional rotary ammunition, the plurality of flow paths of the rotating body are oriented perpendicularly to the rotation axis of the rotating body. It may be provided along a direction parallel to the axis.

Further, in the above description, the case of a polymerization reaction has been described, but the present invention is not limited to the polymerization reaction of the present invention, but can be applied to any chemical reaction process that requires a catalyst.

As described above, according to the present invention, it is possible to provide a method and apparatus for supplying a catalyst component for olefin polymerization, which smoothly supplies a catalyst at a high concentration to a reaction tank.

Next, the present invention will be explained in more detail with reference to the following examples.

Example Bulk polymerization was carried out in the polymerization reaction tank 3 using propylene, which is a polymerization reaction monomer, as a carrier fluid. At this time, the catalyst 7 is a catalyst slurry (Ti catalyst supported on Mg) in which the proportion of the solvent (heptane) in the solid component is 50ωt%, and the concentration is
700g (solid)/(heptane),
A catalyst with a catalyst/magnesium oxide ratio of 1/2 (weight ratio) was used. Depending on the properties of the catalyst solid component, a fluidity improver may be used, and in this example, magnesium oxide was used as the fluidity improver.

The catalyst storage tank 6 used had an internal capacity of 1, and the internal pressure was maintained at 36 kg/cm ² with nitrogen gas. Further, liquid propylene was flowed into the carrier fluid supply line 9 at a flow rate of 0.3 m/sec.

The volumes of flow paths 31A and 31B are both 5 ml,
In the state shown in FIGS. 7A and 7C, the rotating body 12 was stopped for about 5 minutes, and the rotating operation itself was relatively quick, lasting about several seconds, so that it rotated 12 times in one hour. Therefore, although the rotating body 12 is not particularly stopped in the state shown in FIG. 7B, the liquid propylene is quickly purged under reduced pressure through the carrier fluid removal line 10. Furthermore, while the rotating body 12 is rotating, the carrier fluid supply line 9 and the catalyst supply line 2 are disconnected, but the time during this period is extremely short, within several seconds, and the flow rate of the catalyst supply line 2 is stagnant. The catalyst supply line 2 will not be blocked.

According to this example, the volatile components in the product polymer are
It was less than 0.5%. In contrast, conventional pumping resulted in a volatile content of 2% in the product polymer. In addition, in this example, it was possible to supply a catalyst with a slurry concentration 70 times higher than in the case of pump transfer, and the catalytic activity reached 4.9 times the amount of polypropylene produced per unit titanium. .

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram showing an embodiment of the catalyst component supply device according to the present invention applied to a polymerization reaction process, and FIG. 2 is a perspective view showing the external appearance of an embodiment of the catalyst component supply device according to the present invention. Figure 3 is a partially cutaway front view of the embodiment described above, Figure 4 is a right side view of the main part of Figure 3 with a portion cut away, and Figure 5 is a part of Figure 3. FIG. 6 is a cross-sectional view along the - line in FIG. 5, and FIG.
2A and 2B are schematic configuration diagrams showing the operating states of the embodiments, respectively. 1... Catalyst component supply device, 2... Catalyst supply line, 3... Polymerization reaction tank as a reaction tank, 5...
Catalyst inflow line, 6...catalyst storage tank, 7...catalyst,
9... Carrier fluid supply line, 10... Carrier fluid removal line, 11... Main body, 12... Valve body as a rotating body, 13... Carrier fluid inlet, 14... Catalyst outlet, 15... Catalyst. Inlet, 31A, 31B...
...first and second channels, 41...conveyed fluid discharge port,
56...Control unit.

Claims (1)

[Claims] 1. A rotating body having two channels that do not intersect with each other is arranged in the flow of the carrier fluid flowing into the reaction tank, and the carrier fluid is caused to flow through one of the channels. Sometimes, the other channel is filled with a high-concentration catalyst, and the rotating body is rotated to appropriately supply the high-concentration catalyst into the carrier fluid, and the high-concentration catalyst is transported into the carrier fluid. A method for supplying a contact component for olefin polymerization, comprising: supplying a contact component for olefin polymerization to the reaction tank. 2. A rotating body having first and second flow paths that do not intersect with each other, a catalyst inlet communicating with the catalyst storage tank, an outlet to the catalyst supply line that supplies the catalyst to the reaction tank, and a carrier fluid. a carrier fluid inlet into which the carrier fluid flows, and a carrier fluid discharge port for discharging the carrier fluid in the flow path, and when the rotating body is located at a predetermined rotation angle, the carrier fluid is removed by the first flow channel. The inlet and the catalyst outlet are in communication with each other, and the second flow path is in communication with the catalyst inlet,
When the rotating body is rotated by a predetermined angle, the first channel is communicated with the carrier fluid discharge port, and when the rotating body is further rotated by a predetermined angle, the first channel is communicated with the catalyst inlet and the second channel is communicated with the catalyst inlet. A supply device for a catalyst component for olefin polymerization, characterized in that the flow path is configured to communicate with a carrier fluid inlet and a catalyst outlet.