Composite Ziegler-Natta catalyst preparation device and preparation method
By adopting a composite preparation device during the preparation process of Ziegler-Natta catalyst, the solid-liquid separation efficiency is improved by using suction filtration and screening mechanisms, the problems of low solid-liquid separation efficiency and complicated screening process in the prior art are solved, and the more Efficient catalyst preparation and production efficiency.
Patent Information
- Application Number
- CN202411416563.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-11
- Publication Date
- 2024-12-31
AI Technical Summary
The solid-liquid separation efficiency and complex catalyst screening process during the preparation of existing Ziegler-Natta catalysts affect the preparation efficiency and product yield.
A composite Ziegler-Natta catalyst preparation device is designed, including a reactor body, a suction filter mechanism and a screening mechanism. Solid-liquid separation is achieved through the action of the suction filter driver and gravity, simplifying the screening process and improving the catalyst collection efficiency.
The solid-liquid separation efficiency during the catalyst preparation process is improved, the catalyst screening process is shortened, the production efficiency and product yield are improved, and the loss of catalyst activity is reduced.
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Figure CN119215828A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of olefin polymerization catalysts, and more specifically to a composite Ziegler-Natta catalyst preparation device and a preparation method. Background Art
[0002] Common polyolefin catalysts mainly include three categories: Ziegler-Natta catalysts, metallocene catalysts and non-metallocene catalysts. Among them, Ziegler-Natta catalysts are the most widely used catalysts for polypropylene.
[0003] Ziegler-Natta catalyst commonly refers to a spherical catalyst of titanium tetrachloride supported by magnesium chloride, which involves multiple reaction steps such as preparation of the carrier and titanium loading. In the reaction stage, it involves solid-liquid separation of multiple solvent systems and catalyst collection in the post-treatment stage, which has a great influence on production efficiency, catalyst activity and product yield. In the prior art, the solid-liquid separation efficiency in the catalyst preparation process is low and the catalyst screening and collection process is complicated, which in turn affects the catalyst preparation efficiency.
[0004] Therefore, how to improve the efficiency of solid-liquid separation during catalyst preparation, shorten the catalyst screening process, and ensure the continuity of subsequent preparation processes has become a technical problem that needs to be urgently solved by those skilled in the art. Summary of the invention
[0005] In view of this, the object of the present invention is to provide a composite Ziegler-Natta catalyst preparation device to improve the efficiency of solid-liquid separation in the catalyst preparation process, shorten the catalyst screening process, and ensure the continuity of subsequent preparation processes.
[0006] Another core of the present invention is to disclose a method for preparing a composite Ziegler-Natta catalyst using the composite Ziegler-Natta catalyst preparation device.
[0007] To achieve the above object, the present invention provides the following technical solutions:
[0008] A composite Ziegler-Natta catalyst preparation device, comprising:
[0009] A reactor body, the reactor body comprising an inert gas inlet, an inert gas outlet, a solid feeder, a liquid feeder and an agitator, and the agitator is arranged in the reactor body;
[0010] The suction filtration mechanism is arranged at the bottom of the reaction kettle body, and the suction filtration mechanism includes a suction filtration membrane, a first top and bottom valve and a suction filtration driver. The first top and bottom valve is arranged at the bottom of the reaction kettle body, the first top and bottom valve includes a liquid outlet, the suction filtration membrane is arranged at the liquid inlet of the first top and bottom valve, and the suction filtration driver provides suction filtration power;
[0011] A screening mechanism, the screening mechanism is connected to the reaction kettle body;
[0012] The jacket is arranged on the outside of the reaction kettle body to adjust the temperature of the reaction kettle body.
[0013] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation device, the suction filtration membrane is detachably connected to the first top and bottom valves.
[0014] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation device, the liquid outlet is connected to a nitrogen backflushing mechanism.
[0015] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation device, the screening mechanism is connected to the reaction kettle body through a second top and bottom valve, the second top and bottom valve includes a feed port, a first discharge port and a second discharge port, the feed port is connected to the reaction kettle body, the first discharge port is connected to the screening mechanism, and the second discharge port is connected to the screening mechanism and the catalyst collecting mechanism, so as to transfer the powdered catalyst screened by the screening mechanism to the catalyst collecting mechanism.
[0016] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation device, the first discharge port and the second discharge port are arranged along the first direction, the first discharge port is arranged between the reaction kettle body and the screening mechanism, and along the first direction, the second discharge port is arranged at the lower part of the screening mechanism, and the first discharge port and the second discharge port are arranged obliquely relative to the axial direction of the valve core of the second top and bottom valve.
[0017] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation device, the agitator includes a stirring propeller, and the stirring propeller includes at least one of a double-screw stirring propeller, an anchor stirring propeller, and a frame stirring propeller.
[0018] A method for preparing a composite Ziegler-Natta catalyst, wherein the composite Ziegler-Natta catalyst is prepared by using a composite Ziegler-Natta catalyst preparation device, wherein the composite Ziegler-Natta catalyst preparation device is the composite Ziegler-Natta catalyst preparation device described above, and the method for preparing the composite Ziegler-Natta catalyst comprises:
[0019] Purging the reactor with nitrogen;
[0020] preparing a magnesium alcoholate carrier, adding a magnesium halide and an organic alcohol solvent into a reaction kettle, turning on a stirrer, stirring at a first preset temperature for a first preset time to dissolve the magnesium halide, and then adding cyclohexane into the reaction kettle multiple times to obtain a magnesium alcoholate carrier;
[0021] preparing a mixture solution of magnesium and titanium, adding titanium halide to a reaction kettle, cooling the reaction kettle to a second preset temperature, and stirring at the second preset temperature for a first preset time to obtain a mixture solution of magnesium and titanium;
[0022] Preparing a precursor solution, heating a mixture solution of magnesium and titanium, slowly raising the temperature to a third preset temperature, adding an internal electron donor compound into a reaction kettle, and reacting at the third preset temperature for a second preset time to obtain a precursor solution;
[0023] Prepare a solid Ziegler-Natta catalyst, cool the precursor solution to a fourth preset temperature, conduct a constant temperature reaction at the fourth preset temperature for a second preset time, and after the reaction is completed, discharge the liquid in the reactor body in sequence through a suction filtration mechanism to obtain a slurry product, and then wash and dry in sequence to obtain a solid Ziegler-Natta catalyst;
[0024] Prepare a solid-phase composite Ziegler-Natta catalyst, add n-hexane and triethylaluminum into a reactor body, stir for a first preset time at a fifth preset temperature, so that the n-hexane, triethylaluminum and the solid Ziegler-Natta catalyst are fully mixed; add a vinyl compound into the reactor body, react for a third preset time at a sixth preset temperature, discharge the liquid through a suction filtration mechanism after the reaction is completed, and vacuum dry at a fourth preset temperature to obtain a solid-phase composite Ziegler-Natta catalyst;
[0025] The block catalyst and the powder catalyst are separated, and the solid phase powder composite Ziegler-Natta catalyst is transferred to a screening mechanism for screening, so that the block composite Ziegler-Natta catalyst and the powder composite Ziegler-Natta catalyst are separated.
[0026] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation method, the first preset temperature is 30° C., and the first preset time is 1 h to 2 h;
[0027] The second preset temperature is -30°C;
[0028] The third preset temperature is 100°C to 120°C, and the second preset time is 2h to 4h;
[0029] The fourth preset temperature is 60°C to 80°C;
[0030] The fifth preset temperature is 0°C to 50°C, the sixth preset temperature is 0°C to 60°C, and the third preset time is 1h to 48h.
[0031] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation method, in the step of preparing the magnesium alcoholate carrier, the step of adding cyclohexane to the reaction kettle body multiple times specifically includes:
[0032] The cyclohexane solution is added into the reactor body, and the temperature is raised to the seventh preset temperature. At this temperature, the solution is stirred for the fourth preset time to obtain a colorless and transparent alcoholate solution. Subsequently, the cyclohexane solution cooled to the eighth preset temperature is added into the reactor body, and the solution is stirred for the fifth preset time. The liquid in the reactor body is then discharged through the suction filtration mechanism, and then cyclohexane is added again for washing and suction filtration until the magnesium alcoholate carrier is obtained.
[0033] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation method, the seventh preset temperature is 100°C to 150°C; the fourth preset time is 2h to 5h; the eighth preset temperature is -50°C to 0°C; and the fifth preset time is 30min to 60min.
[0034] Optionally, in the above-mentioned composite Ziegler-Natta catalyst preparation method, in the step of preparing the solid Ziegler-Natta catalyst, the obtained slurry product is washed with cyclohexane, and after the washing, the reactor body is vacuum dried at a ninth preset temperature;
[0035] The ninth preset temperature is 70°C to 80°C.
[0036] It can be seen from the above scheme that the composite Ziegler-Natta catalyst preparation device disclosed in the present invention has a suction filtration mechanism arranged at the bottom of the reactor body, which can discharge the liquid generated in the reactor body by gravity, and the setting of the suction filtration driver can improve the solid-liquid separation efficiency, realize the rapid separation of solid and liquid in the catalyst preparation stage, so as to improve the work efficiency, and the setting of the suction filtration membrane can reduce the loss of the catalyst and improve the catalyst yield. The screening mechanism is directly connected to the reactor body, which can shorten the process, avoid the loss of the catalyst amount and the reduction of activity due to the long process, shorten the screening process of the catalyst, improve the production efficiency, and shorten the production cycle.
[0037] The composite Ziegler-Natta catalyst preparation method disclosed in the present invention adopts the composite Ziegler-Natta catalyst preparation device, and thus has all the technical effects of the composite Ziegler-Natta catalyst preparation device, which will not be described in detail here. BRIEF DESCRIPTION OF THE DRAWINGS
[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.
[0039] Figure 1 It is a schematic diagram of the structure of a preparation device for a composite Ziegler-Natta catalyst disclosed in an embodiment of the present invention;
[0040] Figure 2 This is a morphological diagram of the composite Ziegler-Natta catalyst obtained by screening by the screening mechanism 2 according to the embodiment of the present invention;
[0041] Figure 3 The morphology diagram of the composite Ziegler-Natta catalyst obtained without being screened by the screening mechanism 2 is disclosed in the embodiment of the present invention.
[0042] Among them, 1 is a reactor body, 2 is a screening mechanism 2, 3 is a stirring paddle, 4 is a stirrer, 5 is a solid feeder, 6 is a liquid feeder, 7 is an inert gas inlet, 8 is an inert gas outlet, 9 is a temperature detection element, 10 is a suction filtration membrane, 11 is a liquid outlet, 12 is a first top and bottom valve, 13 is a second top and bottom valve, 14 is a first discharge port, 15 is a second discharge port, 16 is a hot medium circulation pipe, 17 is a cold medium circulation pipe, and 18 is a nitrogen backflush mechanism. DETAILED DESCRIPTION
[0043] The core of the invention is to disclose a composite Ziegler-Natta catalyst preparation device to improve the efficiency of solid-liquid separation in the catalyst preparation process, shorten the catalyst screening process, and ensure the continuous progress of subsequent preparation processes.
[0044] Another core of the present invention is to disclose a method for preparing a composite Ziegler-Natta catalyst using the composite Ziegler-Natta catalyst preparation device.
[0045] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0046] like Figure 1As shown, an embodiment of the present invention discloses a composite Ziegler-Natta catalyst preparation device, including a reaction kettle body 1, a suction filtration mechanism, a screening mechanism 2 and a jacket.
[0047] The reactor body 1 is used for preparing a polyolefin catalyst, and comprises an inert gas inlet 7, an inert gas outlet 8, a solid feeder 5, a liquid feeder 6 and an agitator 4. The agitator 4 is arranged in the reactor body 1 to play a stirring role. As shown in the figure, the inert gas inlet 7 and the inert gas outlet 8 are both located at the top of the reactor body 1 and on both sides of the central axis of the reactor body 1. In other specific embodiments, the inert gas inlet 7 and the inert gas outlet 8 can also be located on the same side of the central axis of the reactor body 1, which is not specifically limited here.
[0048] The suction filtration mechanism is arranged at the bottom of the reactor body 1 to achieve solid-liquid separation of the reactor body 1, and the liquid generated in the reactor body 1 is discharged through the suction filtration mechanism. Specifically, the suction filtration mechanism includes a suction filtration membrane 10, a first top and bottom valve 12 and a suction filtration driver. The first top and bottom valve 12 is arranged at the bottom of the reactor body 1, including a liquid outlet 11, and the liquid outlet 11 is arranged obliquely relative to the valve core axis of the first top and bottom valve 12. The suction filtration membrane 10 is arranged at the liquid inlet of the first top and bottom valve 12. The suction filtration driver provides suction filtration power, and the suction filtration driver is preferably a vacuum suction filtration pump.
[0049] The screening mechanism 2 is connected to the reaction kettle body 1 to screen the prepared polyolefin catalyst, thereby screening the solid catalyst, reducing the content of the block catalyst, and shortening the process flow.
[0050] When in use, raw materials for preparing the composite Ziegler-Natta catalyst are added through the solid feeder 5 and the liquid feeder 6, and the temperature of the reactor body 1 is adjusted by the jacket to ensure the reaction temperature required for the reaction. When the liquid generated in the reactor body 1 needs to be discharged during the preparation process, the valve core of the first top and bottom valve 12 is moved downward by rotating the hand wheel of the first top and bottom valve 12, and the suction filter drive is started, and the liquid in the reactor body 1 is discharged through the liquid outlet 11. During the reaction stage, the second top and bottom valve 13 is in a closed state.
[0051] The composite Ziegler-Natta catalyst preparation device disclosed in the embodiment of the present invention has a suction filtration mechanism disposed at the bottom of the reactor body 1, which can discharge the liquid generated in the reactor body 1 by gravity, and the setting of the suction filtration driver can improve the solid-liquid separation efficiency, realize the rapid separation of solid and liquid in the catalyst preparation stage, and the setting of the suction filtration membrane 10 can reduce the loss of the catalyst and improve the catalyst yield. The screening mechanism 2 is directly connected to the reactor body 1, which can shorten the process, avoid the loss of the catalyst amount and the reduction of the activity due to the long process, shorten the screening process of the catalyst, improve the production efficiency, and shorten the production cycle.
[0052] It should be noted that the composite Ziegler-Natta catalyst preparation device disclosed in the embodiment of the present invention can be used not only to prepare composite Ziegler-Natta catalysts, but also to prepare other types of catalysts.
[0053] In some specific embodiments, the jacket includes a hot medium circulation pipe 16 and a cold medium circulation pipe 17, and the temperature of the reactor body 1 is adjusted by the cooperation of the two. Preferably, water is selected as the medium, and the jacket temperature is controlled by a hot water machine and a cold water machine connected to the jacket. In order to measure the temperature of the medium in the reactor body 1, a temperature detection element 9 is provided in the reactor body 1. The liquid outlet 11 is connected to the waste liquid recovery mechanism. In order to facilitate observation and sampling, the liquid outlet 11 is provided with an observation window and a sampling port. Furthermore, the observation window is made of a pressure-resistant transparent material, and the pressure-resistant transparent material includes pressure-resistant organic glass, pressure-resistant sapphire, and pressure-resistant quartz material, preferably pressure-resistant organic glass. The sampling port can be sampled at any time and the extracted liquid can be analyzed.
[0054] In order to improve the convenience of disassembly and assembly of the suction filtration membrane 10, the suction filtration membrane 10 is detachably connected to the first top and bottom valve 12. The material of the suction filtration membrane 10 includes metal material, glass material and polyvinylidene fluoride material, preferably metal material, and the pore size of the suction filtration membrane 10 is between 0.5um and 200um, preferably 20um to 100um, more preferably 20um to 80um, and first preferably 50um to 80um.
[0055] In order to reduce the occurrence of clogging of the suction filtration membrane 10 and improve the filtration efficiency, the liquid outlet 11 is connected to the nitrogen backflush mechanism 18 or to an external vacuum air source to clean the clogged suction filtration membrane 10 through nitrogen backflush or vacuum air source.
[0056] In some specific embodiments, the screening mechanism 2 is connected to the reaction kettle body 1 through a second top and bottom valve 13. The second top and bottom valve 13 includes a feed port, a first discharge port 14 and a second discharge port 15. The feed port is connected to the reaction kettle body 1, the first discharge port 14 is connected to the screening mechanism 2, and the second discharge port 15 is connected to the catalyst collecting mechanism to transfer the powdered catalyst screened by the screening mechanism 2 to the catalyst collecting mechanism.
[0057] After the reaction for preparing the catalyst is completed, the prepared solid catalyst is obtained in the reactor body 1. By rotating the handwheel of the second top and bottom valve 13, the valve core of the second top and bottom valve 13 moves downward. At this time, the reactor body 1 is connected with the screening mechanism 2, and the solid catalyst is transferred to the screening mechanism 2 through the feed port and the first discharge port 14 for screening. After the screening is completed, the handwheel of the second top and bottom valve 13 is further rotated to make the valve core of the second top and bottom valve 13 continue to move downward, so that the screened powder catalyst is transferred to the catalyst collection mechanism through the second discharge port 15.
[0058] In the composite Ziegler-Natta catalyst preparation device disclosed in the embodiment of the present invention, the screening mechanism 2 is connected to the reactor body 1 through the second top and bottom valves 13. The second top and bottom valves 13 can achieve the function of one valve with two controls. On the one hand, it controls the solid catalyst in the reactor body 1 to be transferred to the screening mechanism 2. On the other hand, it controls the powdered catalyst screened by the screening mechanism 2 to be transferred to the catalyst collecting mechanism. This can shorten the screening process of the catalyst and reduce the activity loss during the catalyst transfer process.
[0059] On the basis of the above embodiment, the first discharge port 14 and the second discharge port 15 are arranged along the first direction, the first discharge port 14 is arranged between the reactor body 1 and the screening mechanism 2, along the first direction, the second discharge port 15 is arranged at the lower part of the screening mechanism 2, and the first discharge port 14 and the second discharge port 15 are arranged obliquely relative to the first direction. It should be noted that the first direction here refers to the vertical direction, and the prepared solid catalyst can be transferred to the screening mechanism 2 by gravity.
[0060] In some specific embodiments, the screening mechanism 2 can be an ultrasonic vibrating screen, a multi-layer graded rocking screen or a linear vibrating screen, preferably an ultrasonic vibrating screen. In order to facilitate the cleaning and replacement of the screen of the ultrasonic vibrating screen, the screen is preferably connected in a detachable manner, and the screen is preferably a metal screen. The pore size of the screen is between 10um and 200um, preferably 100um to 150um, and the second preferred range is 50um to 150um.
[0061] In the composite Ziegler-Natta catalyst preparation device disclosed in the embodiment of the present invention, the agitator 4 includes a stirring paddle 3, and the stirring paddle 3 preferably includes one or a combination of two of a double-screw stirring paddle, an anchor stirring paddle, and a frame stirring paddle.
[0062] The embodiment of the present invention also discloses a method for preparing a composite Ziegler-Natta catalyst. The composite Ziegler-Natta catalyst is prepared by using the composite Ziegler-Natta catalyst preparation device disclosed in the above embodiment, comprising the following steps:
[0063] Step S1, purging the reactor body 1 with nitrogen;
[0064] Nitrogen is introduced into the reactor body 1 through the inert gas inlet 7 for purging, and the nitrogen is discharged from the reactor body 1 through the inert gas outlet 8 to ensure that the reaction process is carried out in a closed oxygen-free environment.
[0065] Step S2, preparing a magnesium alcoholate carrier;
[0066] Magnesium halide and organic alcohol solvent are added into the reactor body 1 through the solid feeder 5 and the liquid feeder 6 respectively, the agitator 4 is turned on, and the reactor body 1 is maintained at a first preset temperature through the jacket. The reactor body 1 is stirred at this temperature for a first preset time to dissolve the magnesium halide, and then cyclohexane is added to the reactor body 1 through the liquid feeder 6 for multiple times to obtain a magnesium alcoholate carrier.
[0067] Step S3, preparing a mixture solution of magnesium and titanium;
[0068] Titanium halide is added to the reactor body 1 through the liquid feeder 6, and the reactor body 1 is cooled through the jacket to a second preset temperature, and then the stirrer 4 is turned on to stir at the second preset temperature for a first preset time to obtain a mixture solution of magnesium and titanium.
[0069] Step S4, preparing a precursor solution;
[0070] The mixture solution of magnesium and titanium obtained in step 3 is heated by a jacket so that the mixture solution of magnesium and titanium is slowly heated to a third preset temperature, and the internal electron donor compound is added to the reactor body 1 through the solid feeder 5, and reacted at the third preset temperature for a second preset time to obtain a precursor solution.
[0071] Step S5, preparing a solid Ziegler-Natta catalyst;
[0072] The precursor solution obtained in step S4 is cooled to a fourth preset temperature, and is subjected to a constant temperature reaction at the fourth preset temperature for a third preset time. After the reaction is completed, the liquid in the reactor body 1 is discharged through a suction filtration mechanism to obtain a slurry product, which is then washed and dried in sequence to obtain a solid Ziegler-Natta catalyst.
[0073] Step S6, preparing a composite Ziegler-Natta catalyst;
[0074] n-hexane and triethylaluminum are added into the reactor body 1 through the liquid feeder 6, and stirred for a first preset time at a fifth preset temperature to fully mix the n-hexane, triethylaluminum and the solid Ziegler-Natta catalyst; then, the vinyl compound is added into the reactor body 1 through the liquid feeder 6, and reacted for a third preset time at a sixth preset temperature. After the reaction is completed, the liquid is discharged through a suction filtration mechanism, and vacuum drying is performed at the fourth preset temperature to obtain a composite Ziegler-Natta catalyst.
[0075] Step S7, separating the bulk catalyst and the powdered catalyst;
[0076] Specifically, by adjusting the second top and bottom valve 13 and rotating the handwheel of the second top and bottom valve 13, the valve core of the second top and bottom valve 13 is lowered until the screening mechanism 2 is connected to the reactor body 1, and the composite Ziegler-Natta catalyst is transferred to the screening mechanism 2 through the first discharge port 14 for screening, so that the block composite Ziegler-Natta catalyst and the powder composite Ziegler-Natta catalyst are separated. After the screening is completed, the handwheel of the second top and bottom valve 13 is continued to be rotated, so that the valve core of the second top and bottom valve 13 continues to descend, and descends to transfer the solid phase powder composite Ziegler-Natta catalyst to the catalyst collection mechanism through the second discharge port 15.
[0077] In some specific embodiments, the first preset temperature is 30°C, and the first preset time is 1h~2h; the second preset temperature is -30°C; the third preset temperature is 100°C~120°C, and the second preset time is 2h~4h; the fourth preset temperature is 60°C~80°C; the fifth preset temperature is 0°C~50°C, the sixth preset temperature is 0°C~60°C, and the third preset time is 1h~48h.
[0078] In some specific embodiments, in step S2, the step of adding cyclohexane to the reactor body 1 multiple times specifically includes: adding a cyclohexane solution into the reactor body 1, heating the reactor body 1 to a seventh preset temperature through a jacket, stirring at this temperature for a fourth preset time to obtain a colorless and transparent alcoholate solution; then adding the cyclohexane solution cooled to an eighth preset temperature into the reactor body 1, continuing to stir for a fifth preset time, and then discharging the liquid in the reactor body 1 through a suction filtration mechanism, and then adding cyclohexane again for washing and suction filtration until a magnesium alcoholate carrier is obtained.
[0079] Specifically, the seventh preset temperature is 100° C. to 150° C., the fourth preset time is 2 h to 5 h, the eighth preset temperature is -50° C. to 0° C., and the fifth preset time is 30 min to 60 min.
[0080] In some specific embodiments, in step S5, the obtained slurry product is washed with cyclohexane, preferably 3 to 5 times, and after washing, the reactor body 1 is vacuum dried at a ninth preset temperature, which is 70°C to 80°C.
[0081] In a specific embodiment, the reactor body 1 is firstly subjected to nitrogen-vacuum replacement to make the reactor body 1 anhydrous and oxygen-free environment. Subsequently, 50 g of anhydrous magnesium chloride and 200 ml of ethanol are added to the reactor body 1 through the solid feeder 5 and the liquid feeder 6, the stirrer 3 is turned on, and the mixture is stirred at a constant temperature of 30° C. for a first preset time of 1 h to 2 h, and then 500 ml of cyclohexane solution is added to the reactor body 1 through the liquid feeder 6, and the temperature of the reactor body 1 is controlled to be 100° C. through the jacket, and stirred for 2 h to obtain a colorless and transparent magnesium chloride alcoholate solution. A n-hexane solution cooled to -20°C is added to the reactor body 1 through the liquid feeder 6, stirred for 30 minutes, and filtered to obtain a magnesium alcoholate carrier; 2500 ml of cold titanium tetrachloride solution is added to the reactor body 1 through the liquid feeder 6, and reacted with the magnesium alcoholate carrier obtained above for 2 hours to obtain a mixture containing magnesium and titanium, the magnesium-titanium mixture solution system is gradually heated to 100°C at a heating rate of 10°C / min through a jacket, 50 ml of 2,2-dibutyl-1,3-propylene glycol dimethyl ether is added to react for 3 hours, the solution is cooled to 60°C and the reaction is continued for 3 hours, and then 2500 ml of titanium tetrachloride solution is added to wash twice, and filtered through a suction filtration mechanism, and finally the obtained solid phase product is washed with cyclohexane for 3 to 5 times, filtered, and vacuum dried to obtain a Ziegler-Natta catalyst. 5L of n-hexane, 30ml of triethylaluminum and 100ml of 3-methyl-1-butene are added into the reactor body 1 through the liquid feeder 6, and the reaction is carried out at 0℃~60℃ for 1h~48h. After the reaction is completed, the liquid is discharged through the suction filtration mechanism, and the solid phase catalyst is vacuum dried at 60℃~80℃ to obtain a composite Ziegler-Natta catalyst. The morphology of the composite Ziegler-Natta catalyst obtained at this time is shown in the figure Figure 2 shown.
[0082] Finally, the second top and bottom valve 13 between the screening mechanism 2 and the reactor body 1 was opened, and the obtained composite Ziegler-Natta catalyst was transferred to the screen of the screening mechanism 2. The screening mechanism 2 was opened to screen the block composite Ziegler-Natta catalyst and the powder composite Ziegler-Natta catalyst, and finally 135 g of solid-phase powder composite Ziegler-Natta catalyst was obtained. The morphology of the obtained solid-phase powder composite Ziegler-Natta catalyst is shown in the figure below. Figure 3 shown.
[0083] In addition, an embodiment of the present invention also discloses a method for preparing a composite Ziegler-Natta catalyst. Since the above-mentioned composite Ziegler-Natta catalyst preparation device is adopted, all the technical effects of the above-mentioned composite Ziegler-Natta catalyst preparation device are combined, which will not be repeated here.
[0084] It should be noted that the various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.
[0085] As shown in this application and claims, unless the context clearly indicates an exception, the words "a", "an", "a kind" and / or "the" do not refer to the singular, but also include the plural. Generally speaking, the terms "include" and "comprise" only indicate the inclusion of clearly identified steps and elements, and these steps and elements do not constitute an exclusive list. The method or device may also include other steps or elements. The elements defined by the sentence "includes a..." do not exclude the existence of other identical elements in the process, method, commodity or device that includes the elements.
[0086] In the following, the terms "first" and "second" are used for descriptive purposes only and are not to be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features.
[0087] The principles and implementation methods of the present invention are described in this article using specific examples. The description of the above embodiments is only used to help understand the core idea of the present invention. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims
1. A composite Ziegler-Natta catalyst preparation device, characterized in that: include: A reaction kettle body (1), the reaction kettle body (1) comprising an inert gas inlet (7), an inert gas outlet (8), a solid feeder (5), a liquid feeder (6) and a stirrer (4), the stirrer (4) being arranged in the reaction kettle body (1); A suction filtration mechanism is arranged at the bottom of the reaction kettle body (1), the suction filtration mechanism comprises a suction filtration membrane (10), a first top and bottom valve (12) and a suction filtration driver, the first top and bottom valve (12) is arranged at the bottom of the reaction kettle body (1), the first top and bottom valve (12) comprises a liquid outlet (11), the suction filtration membrane (10) is arranged at the liquid inlet of the first top and bottom valve (12), and the suction filtration driver provides suction filtration power; A screening mechanism (2), the screening mechanism (2) being in communication with the reaction kettle body (1); A jacket is arranged on the outside of the reaction kettle body (1) to adjust the temperature of the reaction kettle body (1).
2. The composite Ziegler-Natta catalyst preparation device according to claim 1, characterized in that: The suction filtration membrane (10) is detachably connected to the first top and bottom valves (12).
3. The composite Ziegler-Natta catalyst preparation device according to claim 2, characterized in that: The liquid outlet (11) is connected to a nitrogen backflush mechanism (18).
4. The composite Ziegler-Natta catalyst preparation device according to claim 1, characterized in that: The screening mechanism (2) is connected to the reaction kettle body (1) via a second top and bottom valve (13); the second top and bottom valve (13) comprises a feed port, a first discharge port (14) and a second discharge port (15); the feed port is connected to the reaction kettle body (1); the first discharge port (14) is connected to the screening mechanism (2); and the second discharge port (15) is connected to the screening mechanism (2) and a catalyst collecting mechanism, so as to transfer the powdered catalyst screened by the screening mechanism (2) to the catalyst collecting mechanism.
5. The composite Ziegler-Natta catalyst preparation device according to claim 4, characterized in that: The first discharge port (14) and the second discharge port (15) are arranged along a first direction, the first discharge port (14) is arranged between the reaction kettle body (1) and the screening mechanism (2), the second discharge port (15) is arranged at a lower part of the screening mechanism (2) along the first direction, and the first discharge port (14) and the second discharge port (15) are arranged obliquely relative to the axial direction of the valve core of the second top and bottom valve (13).
6. The composite Ziegler-Natta catalyst preparation device according to claim 4, characterized in that: The agitator (4) comprises a stirring paddle (3), wherein the stirring paddle (3) comprises at least one of a double-screw stirring paddle, an anchor stirring paddle, and a frame stirring paddle.
7. A method for preparing a composite Ziegler-Natta catalyst, wherein the composite Ziegler-Natta catalyst is prepared using a composite Ziegler-Natta catalyst preparation device, characterized in that: The composite Ziegler-Natta catalyst preparation device is a composite Ziegler-Natta catalyst preparation device as claimed in any one of claims 1 to 6, and the composite Ziegler-Natta catalyst preparation method comprises: Purging the reactor body (1) with nitrogen; preparing a magnesium alcoholate carrier, adding a magnesium halide and an organic alcohol solvent into the reaction kettle (1), turning on a stirrer (4), stirring at a first preset temperature for a first preset time to dissolve the magnesium halide, and then adding cyclohexane to the reaction kettle (1) multiple times to obtain a magnesium alcoholate carrier; preparing a mixture solution of magnesium and titanium, adding titanium halide to the reaction kettle body (1), cooling the reaction kettle body (1) to a second preset temperature, and stirring at the second preset temperature for the first preset time to obtain a mixture solution of magnesium and titanium; Preparing a precursor solution, heating the mixture solution of magnesium and titanium, slowly raising the temperature to a third preset temperature, adding an internal electron donor compound to the reaction kettle body (1), reacting at the third preset temperature for a second preset time, and obtaining a precursor solution; preparing a solid Ziegler-Natta catalyst, cooling the precursor solution to a fourth preset temperature, conducting a constant temperature reaction at the fourth preset temperature for the second preset time, discharging the liquid in the reaction kettle body (1) through the suction filtration mechanism after the reaction is completed to obtain a slurry product, and then washing and drying in sequence to obtain a solid Ziegler-Natta catalyst; Preparation of a composite Ziegler-Natta catalyst, adding n-hexane and triethylaluminum into the reaction kettle (1), stirring at a fifth preset temperature for a first preset time, so that the n-hexane, the triethylaluminum and the solid Ziegler-Natta catalyst are fully mixed; adding a vinyl compound into the reaction kettle (1), reacting at a sixth preset temperature for a third preset time, discharging the liquid through the suction filtration mechanism after the reaction is completed, and vacuum drying at the fourth preset temperature to obtain a composite Ziegler-Natta catalyst; The bulk catalyst and the powdered catalyst are separated, and the composite Ziegler-Natta catalyst is transferred to the screening mechanism (2) for screening, so that the bulk composite Ziegler-Natta catalyst and the powdered composite Ziegler-Natta catalyst are separated.
8. The method for preparing a composite Ziegler-Natta catalyst according to claim 7, characterized in that: The first preset temperature is 30° C., and the first preset time is 1 h to 2 h; The second preset temperature is -30°C; The third preset temperature is 100° C. to 120° C., and the second preset time is 2h to 4h; The fourth preset temperature is 60°C to 80°C; The fifth preset temperature is 0°C to 50°C, the sixth preset temperature is 0°C to 60°C, and the third preset time is 1h to 48h.
9. The method for preparing a composite Ziegler-Natta catalyst according to claim 7, characterized in that: In the step of preparing the magnesium alcoholate carrier, the step of adding cyclohexane to the reaction kettle body (1) multiple times specifically comprises: The cyclohexane solution is added into the reaction kettle (1), the temperature is raised to a seventh preset temperature, and the mixture is stirred at this temperature for a fourth preset time to obtain a colorless transparent alcoholate solution; the cyclohexane solution cooled to an eighth preset temperature is then added into the reaction kettle (1), the mixture is stirred for a fifth preset time, and the liquid in the reaction kettle (1) is then discharged through the suction filtration mechanism, and cyclohexane is then added again for washing and suction filtration until the magnesium alcoholate carrier is obtained.
10. The method for preparing a composite Ziegler-Natta catalyst according to claim 9, characterized in that: The seventh preset temperature is 100° C. to 150° C.; the fourth preset time is 2 hours to 5 hours; the eighth preset temperature is -50° C. to 0° C.; and the fifth preset time is 30 minutes to 60 minutes.
11. The method for preparing a composite Ziegler-Natta catalyst according to claim 7, characterized in that: In the step of preparing the solid Ziegler-Natta catalyst, the obtained slurry product is washed with cyclohexane, and after washing, the reactor body (1) is vacuum dried at a ninth preset temperature; The ninth preset temperature is 70°C to 80°C.