Apparatus and method for producing terpolymer polypropylene

Abstract

This application discloses a production apparatus and method for ternary copolymer polypropylene belonging to the chemical industry, the production apparatus including a catalyst pre-coating unit, polymerization unit, degassing and deactivation unit, powder material drying unit, recovery unit, propylene supply piping, ethylene supply piping, butene supply piping, catalyst supply piping, and polypropylene discharge piping. The apparatus designed in this application is not only flexible and convenient to operate, safe and highly reliable, and highly automated, but also has fewer moving parts, a short construction period, a compact layout, and can adopt modular construction, thereby significantly reducing investment costs, enabling the production of many grades, and having superior product performance, making it more suitable for the production of high-end polyolefin products, pursuing high-end production, and enabling an apparatus layout with a high production capacity of 50,000 to 480,000 tons / year.

Description

TECHNICAL FIELD

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to the Chinese patent application filed with the China National Intellectual Property Administration, with application number 202311463163.9, filing date November 6, 2023, and titled "Apparatus and Method for Producing Terpolymerized Polypropylene", the entire content of which is incorporated into this application by reference.

[0002] The present application belongs to the field of chemical industry, and more specifically, relates to an apparatus and method for producing terpolymerized polypropylene. BACKGROUND ART

[0003] Research on polypropylene synthesis processes began as early as the 1950s. From the most traditional solvent polymerization method (also called slurry method), improvements were made to advanced solution polymerization methods, and further development to the current liquid phase bulk polymerization method and gas phase bulk polymerization method. With the continuous development of production processes, the most primitive solvent polymerization method is no longer used industrially at present.

[0004] An overview of the world's advanced polypropylene production processes shows that currently, the polypropylene produced by Basell every year accounts for more than 50% of the world's total output, mainly using the Spheripol double-loop gas phase polymerization process. In addition, the Spherizone polypropylene synthesis process first developed and commercialized by Basell, and the Borstar polypropylene synthesis process developed and commercialized by Borealis, are all widely popularized and applied.

[0005] The Spheripol double-loop gas-phase polypropylene technology, developed and operated by Basel, is currently the most experienced novel polypropylene synthesis process, producing higher quality and higher yields of polypropylene products compared to conventional production processes. The double-loop structure allows for the acquisition of superior performance polypropylene products by varying the pressure during the synthesis process, enabling control over the polypropylene polymer mass and morphology. The Spherizone process is the latest generation of PP production technology developed by LyondellBasel Industries based on the Spheripol process. Its main feature is the use of a single multi-domain circulating reactor instead of a loop reactor, and it belongs to the gas-phase polymerization reaction. The Borstar polypropylene synthesis process, developed by Borealis and based on Basel's polypropylene synthesis process, produces superior performance polypropylene products by connecting a gas-phase fluidized bed reactor in series with a double-loop structure reactor.

[0006] However, existing liquid-phase methods all have drawbacks such as long process flows, high investment costs, many moving pieces of equipment, and high energy consumption. On the other hand, mainstream gas-phase processes have drawbacks such as a tendency to solidify, poor stability, strong odor, and insufficient degassing effect. All of the above drawbacks are limiting the development of high-end polyolefins. [Overview of the project] [Problems that the invention aims to solve]

[0007] To address the shortcomings of existing technologies, the object of this invention is to provide a manufacturing apparatus and method for ternary copolymer polypropylene, which not only enables an apparatus layout with fewer moving parts, low energy consumption, and high production capacity, but is also easy to operate and more environmentally friendly. [Means for solving the problem]

[0008] To achieve the objectives of this application, this application employs the following technical solutions.

[0009] To achieve the above objective, a first aspect of the present application provides a manufacturing apparatus for ternary copolymer polypropylene, the manufacturing apparatus being: This includes a catalyst pre-coating unit, polymerization unit, degassing / deactivation unit (degassing / deactivation unit), powder material drying unit, recovery unit, propylene supply piping (supply line), ethylene supply piping, butene supply piping, catalyst supply piping, and polypropylene discharge piping, however, The catalyst pre-coating unit includes a catalyst stirring tank, the upper part of which is connected to the propylene supply piping and the catalyst supply piping, and the bottom part of which is connected to the top of the catalyst stirring tank and the first vertical gas-phase reactor, respectively. The polymerization unit includes a first vertical gas-phase reactor, a first reaction cyclone bag filter, a propylene vaporization tower, a second horizontal gas-phase reactor, a second reaction cyclone bag filter, and a propylene separation tower. The first vertical gas-phase reactor, the first reaction cyclone bag filter, and the propylene vaporization tower are connected in sequence, with the top of the first vertical gas-phase reactor connected to the top of the second horizontal gas-phase reactor and the bottom of the first reaction cyclone bag filter, respectively, and the top of the propylene vaporization tower connected to the top and bottom of the first vertical gas-phase reactor, respectively, and the bottom connected to the lower part of the first vertical gas-phase reactor. The second horizontal gas-phase reactor, the second reaction cyclone bag filter, and the propylene separation column are connected in sequence, the top of the second horizontal gas-phase reactor is connected to the bottom of the second reaction cyclone bag filter, and the top of the propylene separation column is connected to the top and bottom of the second horizontal gas-phase reactor, respectively, and the bottom is connected to the top of the second horizontal gas-phase reactor. The degassing and deactivation unit includes a low-pressure bag filter, a steamer, and a monomer compression and recovery unit, wherein the top of the low-pressure bag filter is connected to the monomer compression and recovery unit, the upper part is connected to the second horizontal gas-phase reactor, and the bottom is connected to the top of the steamer, and the monomer compression and recovery unit is connected to the propylene vaporization tower and / or propylene separation tower. The powder material drying unit includes a sequentially connected dryer, a drying cyclone separator, and a fine powder bag filter, the top of which is connected to the bottom of the steamer, and the bottom of which is connected to the polypropylene discharge piping. The recovery unit is used to recover hydrocarbons from gaseous and / or liquid emissions from each unit. The propylene supply piping is connected to the first vertical gas-phase reactor, the propylene vaporization tower, and the propylene separation tower. The ethylene supply piping is connected to the propylene vaporization tower and the propylene separation tower, The butene supply piping is connected to the propylene separation tower.

[0010] According to the present application, preferably, the manufacturing apparatus further includes a powder material mixing and transport (conveying) unit, The aforementioned powder material mixing and transport unit includes an additive transport unit, sequentially connected additive surge hopper (buffer hopper), mixer, powder material surge hopper, and metal detector. The powder material mixing and transport unit includes at least two sets of the additive transport units arranged in parallel, The additive transport unit includes sequentially connected unpacking stations (unpacking stations, sack unpacking stations) and additive differential weight (weightlessness) weighing scales, the additive differential weight weighing scales are connected to the additive surge hopper, The dryer is connected to the mixer, The metal detector is connected to the polypropylene discharge pipe.

[0011] In a powder material mixing and conveying unit, the material (material) dried in a dryer is mixed with additives, cooled to lower the temperature, then sequentially passed through a powder material surge hopper and a metal detector, and finally sent to a powder material extrusion bin (bunker) via a polypropylene discharge pipe. In this invention, the general additive addition order is changed, and the additives are added, mixed, and cooled before air blowing (pneumatic conveying), thereby reducing the hierarchical design of the extrusion process, improving the flexibility of powder material mixing and the operational stability of the extruder, and optimizing the standard configuration.

[0012] In this application, in order to achieve continuous polymerization, the manufacturing apparatus preferably includes at least two catalyst pre-coating units arranged in parallel, each catalyst pre-coating unit further including a catalyst suspension bucket device, the bottom of which is connected to the top of the catalyst stirring tank. The catalyst suspension bucket device is used to contain the catalyst mixture slurry that has passed (completed) the pre-mixing.

[0013] The hexane in the catalyst stirring tank plays a role in preparing and diluting the solvent. The aim is to solve the problem of selecting the type of pump for transporting large particle catalyst slurry after pre-coating (pre-filming). After catalyst pre-coating, under hexane dilution, it is possible to change from a normal metering pump to a high-flow centrifugal pump such as a canned motor pump, resulting in more stable operation and lower failure and leakage rates.

[0014] In the polymerization unit, the first vertical gas-phase reactor may be a vertical gas-phase crawler-stirred kettle. The polymerization reaction product is a large-particle product with a particle size of 1100-1700 μm, and is produced in large quantities as a homopolymer or random copolymer product, accounting for 50-70% of the production capacity of the apparatus. The tail gas after the reaction is discharged from the top of the first vertical gas-phase reactor, enters the first reaction cyclone bag filter, and after the active powder material is removed, enters the propylene vaporization column. The removed active powder material is then sent back into the first vertical gas-phase reactor and continues to participate in the reaction.

[0015] In the propylene vaporization column, propylene or ethylene can be continuously and quantitatively replenished based on the production load, and it is preferable that a hydrogen gas replenishment pipe is provided in the discharge pipe at the top of the propylene vaporization column to adjust the mass of the product in real time. Most of the material discharged from the top of the propylene vaporization column enters the first vertical gas-phase reactor and continues to participate in the reaction, adjusting the components and ensuring the mass of the product. A portion of the discharged material is used as a power source to transport the activated fine powder at the bottom of the first reaction cyclone bag filter into the first vertical gas-phase reactor and continues to participate in the reaction. Furthermore, a portion of the discharged material can be introduced into the filtered gas from the first reaction cyclone bag filter and used as a purge gas. Preferably, the top of the propylene vaporization column is connected to the top of the first reaction cyclone bag filter.

[0016] According to the present invention, preferably, a reflux pipe I is provided at the bottom of the propylene vaporization column, which is connected to the upper part of the propylene vaporization column and to the recovery unit, respectively. By installing a reflux pipe at the bottom of the propylene vaporization column, liquid phase circulation and liquid waste recovery are realized, thereby enabling timely adjustment of the amount of monomer propylene stored and inert components (for example, timely discharge of propane and heavy hydrocarbons), and preventing a decrease in reaction activity and an increase in system temperature.

[0017] The second horizontal gas-phase reactor can be a horizontal stirred reaction vessel. After the material from the first vertical gas-phase reactor enters the second horizontal gas-phase reactor, the polymerization reaction continues to obtain a copolymer with a rubber content of 40-55%. The tail gas after the reaction in the second horizontal gas-phase reactor is discharged from the top of the second horizontal gas-phase reactor and enters the second reaction cyclone bag filter. After the active powder material is removed, it enters the propylene separation column, and the removed active powder material is sent back into the second horizontal gas-phase reactor to continue participating in the reaction.

[0018] In the propylene separation column, monomer propylene or ethylene or butene can be continuously and quantitatively replenished based on the production load, and it is preferable that a hydrogen gas replenishment pipe is provided at the top discharge pipe of the propylene separation column in order to adjust the mass of the product in real time. Most of the material discharged from the top of the propylene separation column enters the second horizontal gas-phase reactor and continues to participate in the reaction, and a portion of the discharged material is used as a power source by introducing the activated powder material at the bottom of the second reaction cyclone bag filter into the second horizontal gas-phase reactor to continue participating in the reaction, and furthermore, a portion of the discharged material can be introduced into the filtered gas from the second reaction cyclone bag filter and used as a purge gas, and preferably the top of the propylene separation column is connected to the top of the second reaction cyclone bag filter.

[0019] According to the present invention, preferably, reflux piping II is provided at the bottom of the propylene separation column, which is connected to the upper part of the propylene separation column and the recovery unit, respectively. By installing reflux piping at the bottom of the propylene separation column, not only is the reaction monomer supplied to the second horizontal gas-phase reactor, but liquid-phase circulation and recovery of liquid waste are also realized, as well as timely adjustment of the amount of monomer propylene stored and inert components (timely discharge of propane and heavy hydrocarbons), thereby preventing a decrease in reaction activity.

[0020] In order to prevent mutual mixing of gas components between the two reactors and achieve effective isolation of gas components, preferably, an airlock device is further provided between the first vertical gas-phase reactor and the second horizontal gas-phase reactor. When a failure occurs in the second gas-phase reactor or during maintenance, the second gas-phase reactor is isolated by the switching valve, so that on-line maintenance can be realized without stopping the apparatus. The airlock device includes common equipment such as a high-frequency valve, a receiving tank, a material discharge tank, a switching valve and an ejector, which can realize material discharge of the first vertical gas-phase reactor and also effectively achieve airlocking, providing strong guarantee for the production of high impact resistance products by the second horizontal gas-phase reactor. Preferably, the first vertical gas-phase reactor is connected to the low-pressure bag filter. In order to adjust the reaction components and the mass of the product, both the first vertical gas-phase reactor and the second horizontal gas-phase reactor are provided with gas discharge outlets.

[0021] According to the present application, preferably, the degassing and deactivation unit further comprises a steaming cyclone separator and a steaming water washing tower, the top of the steamer is sequentially connected to the steaming cyclone separator and the steaming water washing tower, the bottom of the steaming cyclone separator is connected to the upper part of the steamer, and the steaming water washing tower is connected to the recovery unit.

[0022] The material from the second horizontal gas-phase reactor or the first vertical gas-phase reactor enters the steamer via a low-pressure bag filter. The material at the bottom of the steamer is sent to a powder material drying unit, the tail gas at the top enters a steaming water washing tower, and the separated gas is sent to a recovery unit where hydrocarbons are further recovered to reduce unit consumption. The separated liquid is filtered and detected before being discharged into a wastewater system. To improve monomer utilization, the mixed hydrocarbons in the low-pressure bag filter are recirculated to the polymerization unit via a monomer compression and recovery unit. Preferably, the monomer compression and recovery unit includes sequentially connected filters I, a cooler, a buffer tank, and a tail gas recovery compressor. To prevent crosslinking at the bottom of the low-pressure bag filter and subsequent material flow delays, it is preferable to install an air hammer device and an interlock system in the low-pressure bag filter. Furthermore, to prevent a decrease in reaction activity or deactivation due to backflow of steam in the steamer, it is preferable to install a highly efficient airlock rotary valve and a gate valve with an air seal device between the low-pressure bag filter and the steamer.

[0023] In the powder material drying unit of the present application, the model selection of the dryer is not particularly limited, and any one of the common vertical fluidized bed dryers, horizontal fluidized bed dryers, drum dryers or drying towers can be selected according to different production capacities of the main apparatus. In the present application, preferably, the powder material drying unit further includes a drying water washing tower, a filter II and a membrane recovery system connected in sequence, the top of the drying cyclone separator is connected to the upper part of the drying water washing tower, and the membrane recovery system is connected to the recovery unit and the dryer respectively. After the material from the bottom of the steamer is completely dried through the dryer, the powder material is sent to the powder material mixing and conveying unit, the tail gas is dedusted with high precision by the drying cyclone separator, the dedusted gas is sent into the drying water washing tower for gas-liquid separation, and the powder material in the dedusted tail gas is collected through the polypropylene discharge pipeline. The separated gas in the drying water washing tower passes through the filter II and the membrane recovery system to separate hydrocarbons and nitrogen gas, the separated hydrocarbons are sent to the recovery unit for further recovery of the hydrocarbons therein, so as to reduce the unit consumption of the reaction, and the separated nitrogen gas is sent back into the dryer as a drying material medium for recycling and reuse.

[0024] The installation of the recovery unit of the present application is to recover hydrocarbons in gas discharges, liquid discharges, cooling discharges and the like from each unit to reduce the unit consumption. Preferably, the recovery unit includes a water washing tower, the top of the water washing tower is provided with a propylene recovery pipeline, the middle part is connected to at least one of the polymerization unit, the degassing and deactivation unit, and the powder material drying unit respectively, and the bottom is connected to downstream equipment. After the gas discharges, liquid discharges and cooling discharges from each unit are washed with water in the water washing tower, the waste water and waste residue are filtered and chemically tested, then discharged to the waste water treatment system, and the vaporized hydrocarbons can be recovered and utilized via the boundary area (plant premises) pipeline.

[0025] In a second aspect of the present application, a method for producing a terpolymer polypropylene is provided, and the production method is carried out in the above production apparatus, specifically, Step 1) involves uniformly mixing the catalyst and propylene in a catalyst stirring tank to complete the pre-coating, and then sending the mixture to the first vertical gas-phase reactor to carry out the polymerization reaction. Step 2) involves sending the product of the polymerization reaction in the first vertical gas-phase reactor to the second horizontal gas-phase reactor, removing the fine powder from the tail gas generated in the reaction, sending it to a propylene vaporization column, discharging the vaporized gas from the top of the column, optionally adding hydrogen gas, and then returning it to the first vertical gas-phase reactor, and returning the bottom material to the first vertical gas-phase reactor. Step 3) involves the reaction product from the first vertical gas-phase reactor continuing to polymerize in the second horizontal gas-phase reactor, sending the reaction product to a low-pressure bag filter, sending the tail gas generated by the reaction to a propylene separation column after removing the fine powder, discharging the separated gas components from the top of the column, optionally adding hydrogen gas, and returning it to the second horizontal gas-phase reactor, and returning the bottom material to the second horizontal gas-phase reactor. Step 4) involves filtering the reaction product from the second horizontal gas-phase reactor using a low-pressure bag filter and then inactivating it with a steamer before sending it to a dryer. Step 5) involves removing dust and filtering the gaseous material dried in a dryer, then optionally adding additives, and finally collecting the final product. Step 6) involves recovering hydrocarbons from the gaseous and / or liquid emissions generated in steps 2) to 5).

[0026] Preferably, according to the present application, the catalyst comprises a main catalyst, a co-catalyst, an electron donor, hexane and / or white oil, the main catalyst comprises a titanium magnesium catalyst and / or a metallocene catalyst, the co-catalyst is a trialkylaluminum compound, the trialkylaluminum compound is triethylaluminum and / or tri-n-butylaluminum, and the electron donor is at least one of dicyclopentyldimethoxysilane, cyclohexyl(dimethoxy)methylsilane, and triethoxysilane.

[0027] In one specific embodiment of the present invention, a main catalyst, a co-catalyst, triethylaluminum, hexane, or white oil are mixed in a fixed proportion in a catalyst stirring tank, and then pre-coating is performed with monomer propylene under heat removal by jacket cooling water. After pre-polymerization and pre-coating for a certain period of time, the large particle catalyst is injected into a first vertical gas-phase reactor while being washed with cooled propylene after the passivation treatment is completed.

[0028] In the first vertical gas-phase reactor, under constant operating pressure and temperature, monomer propylene undergoes homopolymerization or random copolymerization to produce homopolymers or random copolymers with low fine powder content and large particle size, providing effective "positioning (space allocation, securing space)" for the impact-resistant copolymer produced in the second gas-phase reaction. The heat generated by the reaction in the first vertical gas-phase reactor is removed by endothermic heat from the vaporization of some of the liquid-phase propylene that enters the reactor, and some of it is removed by heat exchange with the refrigerant medium of the propylene vaporization tower and the refrigerant medium of the first circulating gas heat exchanger, thereby achieving heat removal and balance.

[0029] After the reaction, the tail gas generated enters the propylene vaporization tower after the fine powder has been removed by the first reaction cyclone bag filter. The propylene vaporization tower can continuously and quantitatively replenish monomer propylene or ethylene based on the production load, and a gas exhaust is provided at the top of the propylene vaporization tower. The vaporized gas components in the propylene vaporization tower are discharged from the top of the tower, and after hydrogen gas is added to adjust the mass of the product and control the product melting index, they enter the first circulating gas compressor together, and after heat is removed by the refrigerant in the first circulating gas heat exchanger, most of it enters the first vertical gas-phase reactor to continue the reaction, adjusting the components and ensuring product quality. A portion is used as the power source for the first fine powder injector, and the activated fine powder discharged from the bottom of the first reaction cyclone bag filter is continuously supplied to the first vertical gas-phase reactor to continue the reaction, while a portion is used as the purge gas for the first reaction cyclone bag filter. At the bottom of the propylene vaporization tower, a liquid phase circulation and liquid discharge system are provided, used to timely adjust the non-condensable components that continue to accumulate due to the reactions within the tower (for example, timely discharge of propane and heavy hydrocarbons).

[0030] The reaction products from the first vertical gas-phase reactor enter the second horizontal gas-phase reactor via an airlock device. However, the use of the airlock device effectively blocks the gas components, preventing cross-combination of components and providing strong assurance for the production of impact-resistant copolymers in the second horizontal gas-phase reactor. In the second horizontal gas-phase reactor, when copolymerization occurs using large particle size raw materials from the first vertical gas-phase reaction, production capacity increases, the rubber phase content becomes higher, and the product performance is superior. During the reaction in the second horizontal gas-phase reactor, heat is removed by endothermic heat from the vaporization of some of the liquid-phase propylene entering the reactor, and some of it is removed and balanced by heat exchange with the refrigerant medium of the propylene separation column and the refrigerant medium of the second circulating gas heat exchanger.

[0031] In the second horizontal gas-phase reactor, the tail gas generated by the reaction, after the fine powder is removed by the second reaction cyclone bag filter, enters the propylene separation column. Based on the production load of the propylene separation column, monomer propylene, ethylene, or butene can be continuously and quantitatively replenished, and a gas exhaust port is provided at the top of the propylene separation column. The separated gas components in the propylene separation column are discharged from the top of the column, and after hydrogen gas is added to adjust the mass of the product and control the product melting index, they enter the second circulating gas compressor together. After heat removal by the refrigerant in the second circulating gas heat exchanger, most of it enters the second horizontal gas-phase reactor to continue the reaction and adjust the components to ensure product quality. Some is used as the power source for the second fine powder injector, and activated fine powder discharged from the bottom of the second reaction cyclone bag filter is continuously introduced into the second horizontal gas-phase reactor to continue the reaction. Some is used as the purge gas for the second reaction cyclone bag filter. At the bottom of the propylene separation column, a liquid phase circulation and liquid discharge flow system is provided to supply reaction monomers to the second horizontal reactor for circulating use, and to allow for the timely adjustment of non-condensable components that continue to accumulate due to the reactions in the column (for example, timely discharge of propane and heavy hydrocarbons).

[0032] The gas emissions from the top of the propylene vaporization tower and propylene separation tower allow for timely adjustment of components such as ethylene and hydrogen gas. To control the reaction rate of the reaction system or the emergency deactivation (deactivation) system, the circulating gas system is equipped with an inhibitor or deactivator, and the medium is an O2 / N2 mixture, with the molar concentration of O2 not exceeding 4.5% for safety reasons.

[0033] Contaminating hydrocarbons in the product material from the first vertical gas-phase reactor and the second horizontal gas-phase reactor are recovered by a low-pressure bag filter and a tail gas compression recovery unit, and then sent to the second horizontal gas-phase reactor for recycling. This maintains a constant composition and provides stable component conditions for the production of ternary copolymers.

[0034] After the tail gas has been inactivated by the steamer, fine powder and hydrocarbon gases are further separated by a steaming cyclone separator. The fine powder is returned to the steamer, and the hydrocarbon gases separated in the steaming water scrubbing tower are sent to a recovery unit. The wastewater and waste are filtered and detected before being discharged to the wastewater treatment system.

[0035] After the wet material from the steamer is completely dried in the dryer, the tail gas is precisely dust-removed in a drying cyclone separator. The removed fine dust falls into a fine powder bag filter. The gas, now free of fine dust, enters a drying water scrubbing tower where wastewater and sludge are separated. Hydrocarbons and nitrogen gas are then separated via filter II and a membrane recovery system. The hydrocarbons are sent to a recovery unit, and the nitrogen gas, after being dried and heated, is returned to the dryer and recycled as a drying medium.

[0036] The additive passes through an unpacking station, an additive differential weight weighing system, and an additive surge hopper. After mixing with the powder material from the bottom of the dryer in a mixer, it undergoes cooling in a powder material surge hopper and detection by a metal detector. Finally, it is transported by nitrogen gas to a powder material extrusion bin along with the powder material from a fine powder bag filter, where a copolymerized polypropylene product is obtained.

[0037] Finally, hydrocarbon-containing gases, liquid waste, cooling waste, etc., discharged from each unit are subjected to water washing and vaporization treatment in a water washing tower. The treated wastewater and residue are then discharged to the wastewater treatment system after undergoing filtration and chemical testing. The vaporized hydrocarbons can be recovered and utilized via boundary area piping, thereby reducing unit consumption. [Effects of the Invention]

[0038] Compared to existing technologies, the advantages of this invention are as follows:

[0039] 1. This invention not only enables the production of high-performance ternary copolymer products, but also offers great operational flexibility, allowing for the realization of equipment layouts with a high production capacity of 50,000 to 480,000 tons / year.

[0040] 2. The apparatus designed in this invention is not only flexible and convenient to operate, safe and highly reliable, and highly automated, but also capable of producing a wide range of grades, has superior product performance, is more suitable for the production of high-end polyolefin products, and pursues high-end production.

[0041] 3. This invention has fewer movable parts, a shorter construction period for the device, a compact layout, and can adopt modular construction, significantly reducing investment costs.

[0042] 4. In this invention, by performing a pre-coating treatment on the catalyst in a catalyst pre-coating unit, catalytic activity can be suppressed, the particle size of the product can be increased, and the generation of fine powder can be reduced.

[0043] 5. This invention allows for the mixing and cooling of additives in the powder material mixing and transport unit before air blowing, thereby reducing the hierarchical design height of the extrusion process and optimizing the standard configuration. It also enables the cooling treatment of powder materials, resulting in lower investment costs and greater energy savings.

[0044] 6. This invention achieves nitrogen gas purification and hydrocarbon separation in a powder material drying unit, thereby reducing unit consumption, shortening drying time, and lowering energy consumption.

[0045] 7. In this invention, after collecting and processing cooling emissions, gas emissions, and liquid emissions in the recovery unit, the emissions are returned to the boundary area, resulting in the lowest possible unit consumption.

[0046] 8. In this application, wastewater and waste slag, which are among the three types of waste (wastewater, waste gas, and waste slag), are treated in an integrated manner, making it more environmentally friendly.

[0047] Other features and advantages of this application will be described in detail in the following section on specific embodiments.

[0048] The exemplary embodiments of this application will be described in more detail with reference to the accompanying drawings, making the above and other purposes, features and advantages of this application clearer, however, in the exemplary embodiments of this application, the same reference numerals usually indicate the same components. [Brief explanation of the drawing]

[0049] [Figure 1] A schematic diagram of a manufacturing apparatus in one embodiment of the present invention is shown. [Figure 2] A schematic diagram of a catalyst pre-coating unit in one embodiment of the present invention is shown. [Figure 3] A schematic diagram of a polymerization unit in one embodiment of the present invention is shown. [Figure 4] A schematic diagram of a degassing and deactivation unit in one embodiment of the present invention is shown. [Figure 5] A schematic diagram of a powder material drying unit in one embodiment of the present invention is shown. [Figure 6] A schematic diagram of a powder material mixing and transport unit in one embodiment of the present invention is shown. [Figure 7] A schematic diagram of a recovery unit in one embodiment of the present invention. [Modes for carrying out the invention]

[0050] To clarify the purpose, technical solutions, and advantages of the embodiments of this application, the technical solutions in the embodiments of this application are described below in a clear and complete manner, although obviously the embodiments described are only a selection of the embodiments of this application, not all of them. All other embodiments that a person skilled in the art could obtain without creative work based on the embodiments of this application are all within the scope of protection of this application. Unless otherwise explicitly stated, throughout the specification and claims, the term “includes” or variations thereof (e.g., “contains,” “includes,” etc.) means to include the described parts or components, and does not exclude other parts or components.

[0051] Furthermore, to better illustrate this application, many specific details are provided in the following specific embodiments. Those skilled in the art should understand that the application can be implemented even without some of the specific details. In some embodiments, detailed descriptions of raw materials, parts, methods, means, etc., which are well known to those skilled in the art, have been omitted in order to clarify the purpose of this application.

[0052] The following describes preferred embodiments of the present application in more detail. While preferred embodiments are described below, it should be understood that the application can be realized in various forms and is not limited to the embodiments described herein.

[0053] (Example 1) A manufacturing apparatus for ternary copolymer polypropylene, as shown in Figure 1, includes a catalyst pre-coating unit, a polymerization unit, a degassing and deactivation unit, a powder material drying unit, a powder material mixing and transport unit, a recovery unit, a propylene supply pipe, an ethylene supply pipe, a butene supply pipe, a catalyst supply pipe, and a polypropylene discharge pipe.

[0054] As shown in Figure 2, the catalyst pre-coating unit includes a catalyst stirring tank 3 and a catalyst suspension bucket device 2. The catalyst suspension bucket device 2 is connected to the catalyst stirring tank 3 via a hose. The catalyst stirring tank 3 has its upper part connected to a propylene supply pipe and a catalyst supply pipe, and its bottom is connected to the top of the catalyst stirring tank 3 and the first vertical gas-phase reactor 6, respectively.

[0055] As shown in Figure 3, the polymerization unit includes a first vertical gas-phase reactor 6, a first reaction cyclone bag filter 7, a first fine powder injector 8, a propylene vaporization tower 9, a first circulating gas compressor 11, a first circulating gas heat exchanger 12, a second horizontal gas-phase reactor 15, a second reaction cyclone bag filter 16, a second fine powder injector 17, a propylene separation tower 18, a second circulating gas compressor 19, and a second circulating gas heat exchanger 20. An airlock device 13 and a switching valve 14 are provided between the first vertical gas-phase reactor 6 and the second horizontal gas-phase reactor 15, and the switching valve 14 is connected to a low-pressure bag filter 22.

[0056] The first vertical gas-phase reactor 6, the first reaction cyclone bag filter 7, and the propylene vaporization tower 9 are connected in sequence, the top of the first vertical gas-phase reactor 6 is connected to the top of the second horizontal gas-phase reactor 15, the first fine powder injector 8 is connected to the top of the first vertical gas-phase reactor 6, the bottom of the first reaction cyclone bag filter 7, and the first circulating gas heat exchanger 12, respectively, and the top of the propylene vaporization tower 9 is connected to the first circulating gas compressor 11 and the first circulating gas heat exchanger 1 The devices are connected sequentially to the first circulating gas heat exchanger 12, which is connected to the bottom of the first vertical gas-phase reactor 6 and to the top of the first reaction cyclone bag filter 7, respectively. The bottom of the propylene vaporization tower 9 is connected to the bottom of the first vertical gas-phase reactor 6. The propylene vaporization tower 9 has a hydrogen gas replenishment pipe at the top of its discharge pipe and a reflux pipe I at its bottom that is connected to the top of the propylene vaporization tower 9 and to the water washing tower 49, respectively.

[0057] The second horizontal gas-phase reactor 15, the second reaction cyclone bag filter 16, and the propylene separation tower 18 are connected in sequence. The second fine powder injector 17 is connected to the bottom of the second reaction cyclone bag filter 16, the top of the second horizontal gas-phase reactor 15, and the second circulating gas heat exchanger 20, respectively. The top of the propylene separation tower 18 is connected in sequence to the second circulating gas compressor 19 and the second circulating gas heat exchanger 20. The second circulating gas heat exchanger 20 is connected to the bottom of the second horizontal gas-phase reactor 15 and the top of the second reaction cyclone bag filter 16, respectively. The bottom of the propylene separation tower 18 is connected to the top of the second horizontal gas-phase reactor 15. The propylene separation tower 18 has a hydrogen gas replenishment pipe in the discharge pipe at the top, and a reflux pipe II at the bottom that is connected to the top of the propylene separation tower 18 and the water washing tower 49, respectively.

[0058] The degassing and deactivation unit, as shown in Figure 4, includes a low-pressure bag filter 22, a steamer 28, a monomer compression and recovery unit, a steaming cyclone separator 29, and a steaming water scrubbing tower 31, wherein the monomer compression and recovery unit includes sequentially connected filters 23, a cooler 24, a buffer tank 25, and a tail gas recovery compressor 26, and the cooler 24 is connected to the propylene supply piping. The low-pressure bag filter 22 has its top connected to filter I23, its upper part connected to the second horizontal gas-phase reactor 15, and its bottom connected to the top of the steamer 28. The tail gas recovery compressor 26 is connected to the propylene vaporization tower 9 and the propylene separation tower 18. The top of the steamer 28 is sequentially connected to the steaming cyclone separator 29 and the steaming water scrubbing tower 31. The bottom of the steaming cyclone separator 29 is connected to the top of the steamer 28 via the fine powder rotary valve 30. The steaming water scrubbing tower 31 is connected to the water scrubbing tower 49.

[0059] As shown in Figure 5, the powder material drying unit includes a dryer 34, a drying cyclone separator 35, a fine powder bag filter 36, a drying water washing tower 37, a filter II 38, and a membrane recovery system 39, wherein the dryer 34, the drying cyclone separator 35, and the fine powder bag filter 36 are connected sequentially, the drying water washing tower 37, the filter II 38, and the membrane recovery system 39 are connected sequentially, the top of the dryer 34 is connected to the bottom of the steamer 28, the bottom of the fine powder bag filter 36 is connected to the polypropylene discharge piping, the top of the drying cyclone separator 35 is connected to the top of the drying water washing tower 37, and the membrane recovery system 39 is connected to the water washing tower 49 and the dryer 34, respectively.

[0060] As shown in Figure 6, the powder material mixing and transport unit includes an additive transport unit and sequentially connected additive surge hopper 44, mixer 45, powder material surge hopper 46, and metal detector 47. The powder material mixing and transport unit includes two sets of additive transport units arranged in parallel, and each additive transport unit includes sequentially connected unpacking station 42 and additive differential weight weighing scale 43. The additive differential weight weighing scale 43 is connected to the additive surge hopper 44, the dryer 34 is connected to the mixer 45, and the metal detector 47 is connected to the polypropylene discharge piping.

[0061] The recovery unit includes a water washing tower 49, which has a propylene recovery pipe at its top, is connected to a polymerization unit, a degassing / inactivation unit, and a powder material drying unit in the middle section, and is connected to a downstream device at its bottom.

[0062] The propylene supply piping is connected to the first vertical gas-phase reactor 6, the propylene vaporization tower 9, and the propylene separation tower 18; the ethylene supply piping is connected to the propylene vaporization tower 9 and the propylene separation tower 18; and the butene supply piping is connected to the propylene separation tower 18.

[0063] The specific procedure for producing ternary copolymer polypropylene using the above apparatus is as follows:

[0064] After mixing the main catalyst, co-catalyst, triethylaluminum, hexane, or white oil in a fixed ratio in the catalyst stirring tank 3, a pre-coating treatment is performed with monomer propylene under heat removal by jacket cooling water. After pre-polymerization and pre-coating for a certain period of time, the large particle catalyst is injected into the first vertical gas-phase reactor 6 after the passivation treatment is completed and it is washed with cooled propylene.

[0065] In the first vertical gas-phase reactor 6, monomer propylene undergoes homopolymerization or random copolymerization to produce a homopolymer or random copolymer with a low fine powder content and large particle size. The tail gas generated after the reaction passes through the first reaction cyclone bag filter 7 to remove the fine powder and then enters the propylene vaporization tower 9. The gas components after vaporization in the propylene vaporization tower 9 are discharged from the top of the tower, hydrogen gas is added, and then both enter the first circulating gas compressor 11. After being heated by the refrigerant in the first circulating gas heat exchanger 12, most of it enters the first vertical gas-phase reactor 6, while a portion is used as a power source for the first fine powder injector 8, continuously supplying the activated fine powder discharged from the bottom of the first reaction cyclone bag filter 7 to the first vertical gas-phase reactor 6. The heat generated by the reaction in the first vertical gas-phase reactor 6 is removed by endothermic heat absorption due to the vaporization of some of the liquid-phase propylene that enters the reactor, and some of it is removed by heat exchange with the refrigerant medium of the propylene vaporization tower 9 and the refrigerant medium of the first circulating gas heat exchanger 12, thereby achieving heat removal and balance.

[0066] The material produced in the first vertical gas-phase reactor 6 enters the second horizontal gas-phase reactor 15 via the airlock device 13 and switching valve 14 and undergoes a copolymerization reaction. After the reaction, the tail gas produced passes through the second reaction cyclone bag filter 16 to remove fine powder and then enters the propylene separation column 18. The gas components separated in the propylene separation column 18 are discharged from the top of the column, hydrogen gas is added, and then both enter the second circulating gas compressor 19. After that, the heat is removed by the refrigerant in the second circulating gas heat exchanger 20, and then most of it enters the second horizontal gas-phase reactor 15, while some of it is used as a power source for the second fine powder injector 17, continuously supplying the activated fine powder to the second horizontal gas-phase reactor 15. The heat generated during the reaction in the second horizontal gas-phase reactor 15 is removed by endothermic heat absorption due to the vaporization of some of the liquid-phase propylene that enters the reactor, and some of it is removed by heat exchange with the refrigerant medium of the propylene separation column 18 and the refrigerant medium of the second circulating gas heat exchanger 20, thereby achieving heat removal and balance.

[0067] Hydrocarbons mixed into the product material from the first vertical gas-phase reactor 6 and the second horizontal gas-phase reactor 15 are recovered after passing through the low-pressure bag filter 22, filter I 23, cooler 24, buffer tank 25, and tail gas recovery compressor 26, and then sent back into the second horizontal gas-phase reactor 15. The powder material filtered through the low-pressure bag filter 22 enters the steamer 28 via the material unloading valve 27.

[0068] The tail gas, inactivated in steamer 28, passes through steaming cyclone separator 29 to further separate fine powder and hydrocarbon gases. The fine powder is then returned to steamer 28, and the hydrocarbons separated from the hydrocarbon gas in steaming water scrubbing tower 31 are sent to water scrubbing tower 49. After filtering and detecting the wastewater and waste, the wastewater is discharged to the wastewater treatment system.

[0069] After the wet material from the steamer 28 is completely dried in the dryer 34, the tail gas passes again through the drying cyclone separator 35 for high-precision dust removal. The removed fine dust falls into the fine powder bag filter 36, and the gas from which the fine dust has been removed enters the drying water scrub tower 37. After further separation of wastewater and waste sludge, it passes through filter II 38 and the membrane recovery system 39 to separate hydrocarbons and nitrogen gas. The hydrocarbons are sent to the water scrub tower 49, and the nitrogen gas is sent back into the dryer 34 via the circulation fan 40 and the circulating nitrogen gas heater 41, where it is recycled and reused as a drying medium.

[0070] After passing through the unpacking station 42, the additive differential weight weighing scale 43, and the additive surge hopper 44, the additive is mixed with the powder material from the bottom of the dryer 34 in the mixer 45. After cooling of the powder material surge hopper 46 and detection by the metal detector 47, it is transported by nitrogen gas to the powder material extrusion bin together with the powder material from the fine powder bag filter 36, and copolymer polypropylene product is obtained in the powder material extrusion bin.

[0071] Finally, within the water washing tower 49, hydrocarbon-containing gases, liquid waste, and cooling waste discharged from each unit are subjected to water washing and vaporization treatment. The treated wastewater and waste residue are then filtered and chemically tested before being discharged to the wastewater treatment system, and the vaporized hydrocarbons can be recovered and utilized via boundary area piping.

[0072] The copolymerized polypropylene product manufactured according to this invention is a high-end elastomer-based impact copolymer that can be used in the manufacture of automotive interior materials, medical materials, and the like. Compared to copolymerized polypropylene manufactured by existing processes, it has characteristics such as high elasticity, odorlessness, high modulus of elasticity, and high toughness. It solves the low-temperature brittleness of conventional materials, reduces the difficulty of processing the product, improves product quality, solves the problem of strong odor in the final product, and enhances the competitiveness of the product.

[0073] Finally, it should be noted that the above embodiments are merely for illustrating and not limiting the technical solutions of the present application. Although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments or make equivalent substitutions for some of their technical features, and that such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of each embodiment of the present application. [Industrial applicability]

[0074] This application discloses a production apparatus and method for ternary copolymer polypropylene belonging to the chemical industry, the production apparatus including a catalyst pre-coating unit, polymerization unit, degassing and deactivation unit, powder material drying unit, recovery unit, propylene supply piping, ethylene supply piping, butene supply piping, catalyst supply piping, and polypropylene discharge piping. The apparatus designed in this application is not only flexible and convenient to operate, safe and highly reliable, and highly automated, but also has fewer moving parts, a short construction period, a compact layout, and can adopt modular construction, thereby significantly reducing investment costs, enabling the production of many grades, and having superior product performance, making it more suitable for the production of high-end polyolefin products, pursuing high-end production, and enabling an apparatus layout with a high production capacity of 50,000 to 480,000 tons / year. [Explanation of symbols]

[0075] 1…Propylene supply pump, 2…Catalyst suspension bucket device, 3…Catalyst stirring tank, 4…Catalyst mixing pump, 5…Propylene refrigeration economizer, 6…First vertical gas-phase reactor, 7…First reaction cyclone bag filter, 8…First fine powder injector, 9…Propylene vaporization tower, 10…First circulation pump, 11…First circulation gas compressor, 12…First circulation gas heat exchanger, 13…Airlock device, 14…Switching valve, 15…Second horizontal gas-phase reactor, 16…Second reaction cyclone bag filter, 17…Second fine powder injector, 18…Propylene separation tower, 19…Second circulation gas compressor, 20…Second circulation gas heat exchanger, 21…Second circulation pump, 22…Low-pressure bag filter, 23…Filter I 24...Cooler, 25...Buffer tank, 26...Tail gas recovery compressor, 27...Material unloading valve, 28...Steamer, 29...Steaming cyclone separator, 30...Fine powder rotary valve, 31...Steaming water washing tower, 32...Circulation pump, 33...Gas-liquid separation tank, 34...Dryer, 35...Drying cyclone separator, 36...Fine powder bag filter, 37...Drying water washing tower, 38...Filter II, 39...Membrane recovery system, 40...Circulation fan, 41...Circulating nitrogen gas heater, 42...Unpacking station, 43...Additive differential weight weighing scale, 44...Additive surge hopper, 45...Mixer, 46...Powder material surge hopper, 47...Metal detector, 48...Injector, 49...Water washing tower.

Claims

1. This includes a catalyst pre-coating unit, polymerization unit, degassing / inactivation unit, powder material drying unit, recovery unit, propylene supply piping, ethylene supply piping, butene supply piping, catalyst supply piping, and polypropylene discharge piping, however, The catalyst pre-coating unit includes a catalyst stirring tank, the upper part of which is connected to the propylene supply piping and the catalyst supply piping, and the bottom part of which is connected to the top of the catalyst stirring tank and the first vertical gas-phase reactor, respectively. The polymerization unit includes a first vertical gas-phase reactor, a first reaction cyclone bag filter, a propylene vaporization tower, a second horizontal gas-phase reactor, a second reaction cyclone bag filter, and a propylene separation tower. The first vertical gas-phase reactor, the first reaction cyclone bag filter, and the propylene vaporization tower are connected in sequence, with the top of the first vertical gas-phase reactor connected to the top of the second horizontal gas-phase reactor and the bottom of the first reaction cyclone bag filter, respectively, and the top of the propylene vaporization tower connected to the top and bottom of the first vertical gas-phase reactor, respectively, and the bottom connected to the lower part of the first vertical gas-phase reactor. The second horizontal gas-phase reactor, the second reaction cyclone bag filter, and the propylene separation column are connected in sequence, the top of the second horizontal gas-phase reactor is connected to the bottom of the second reaction cyclone bag filter, and the top of the propylene separation column is connected to the top and bottom of the second horizontal gas-phase reactor, respectively, and the bottom is connected to the top of the second horizontal gas-phase reactor. The degassing and deactivation unit includes a low-pressure bag filter, a steamer, and a monomer compression and recovery unit, wherein the top of the low-pressure bag filter is connected to the monomer compression and recovery unit, the upper part is connected to the second horizontal gas-phase reactor, and the bottom is connected to the top of the steamer, and the monomer compression and recovery unit is connected to the propylene vaporization tower and / or propylene separation tower. The powder material drying unit includes a sequentially connected dryer, a drying cyclone separator, and a fine powder bag filter, the top of which is connected to the bottom of the steamer, and the bottom of which is connected to the polypropylene discharge piping. The recovery unit is used to recover hydrocarbons from gaseous and / or liquid emissions from each unit, and the recovery unit includes a water scrubbing tower, the water scrubbing tower has a propylene recovery pipe at its top, its middle section is connected to at least one of the polymerization unit, the degassing / inactivation unit, and the powder material drying unit, and its bottom is connected to a downstream device. The propylene supply piping is connected to the first vertical gas-phase reactor, the propylene vaporization tower, and the propylene separation tower. The ethylene supply piping is connected to the propylene vaporization tower and the propylene separation tower, The butene supply piping is connected to the propylene separation tower, Further including a powder material mixing and transport unit, The aforementioned powder material mixing and transport unit includes an additive transport unit and sequentially connected additive surge hopper, mixer, powder material surge hopper, and metal detector. The powder material mixing and transport unit includes at least two sets of the additive transport units arranged in parallel. The additive transport unit includes sequentially connected unpacking stations and an additive differential weighing scale, the additive differential weighing scale being connected to the additive surge hopper, The dryer is connected to the mixer, The metal detector is connected to the polypropylene discharge pipe. A manufacturing apparatus for ternary copolymer polypropylene, characterized by the following features.

2. The catalyst pre-coating unit comprises at least two catalyst pre-coating units arranged in parallel, each catalyst pre-coating unit further comprising a catalyst suspension bucket device, the bottom of which is connected to the top of the catalyst stirring tank. The manufacturing apparatus according to feature 1.

3. The propylene vaporization tower is provided with a hydrogen gas replenishment pipe in the discharge pipe at the top, and a recirculation pipe I is provided at the bottom, which is connected to the upper part of the propylene vaporization tower and the recovery unit, respectively. The propylene separation tower is provided with a hydrogen gas replenishment pipe in the discharge pipe at the top, and a reflux pipe II is provided at the bottom, which is connected to the upper part of the propylene separation tower and the recovery unit, respectively. The manufacturing apparatus according to feature 1.

4. The top of the propylene vaporization tower is connected to the top of the first reaction cyclone bag filter, and the top of the propylene separation tower is connected to the top of the second reaction cyclone bag filter. An airlock device is further provided between the first vertical gas-phase reactor and the second horizontal gas-phase reactor, and the first vertical gas-phase reactor is connected to the low-pressure bag filter. The manufacturing apparatus according to feature 1.

5. The degassing and deactivation unit further includes a steaming cyclone separator and a steaming water scrubbing tower, the top of the steamer being connected sequentially to the steaming cyclone separator and the steaming water scrubbing tower, the bottom of the steaming cyclone separator being connected to the top of the steamer, and the steaming water scrubbing tower being connected to the recovery unit. The monomer compression and recovery unit includes sequentially connected filters I, a cooler, a buffer tank, and a tail gas recovery compressor. The manufacturing apparatus according to feature 1.

6. The powder material drying unit further includes sequentially connected drying water washing towers, filter II, and membrane recovery system, the top of the drying cyclone separator being connected to the top of the drying water washing tower, and the membrane recovery system being connected to the recovery unit and the dryer, respectively. The manufacturing apparatus according to feature 1.

7. The process is carried out in the manufacturing apparatus described in any one of claims 1 to 6 above, specifically, Step 1) involves uniformly mixing the catalyst and propylene in a catalyst stirring tank to complete the pre-coating, and then sending the mixture to the first vertical gas-phase reactor to carry out the polymerization reaction. Step 2) involves sending the product of the polymerization reaction in the first vertical gas-phase reactor to the second horizontal gas-phase reactor, removing the fine powder from the tail gas generated in the reaction, sending it to a propylene vaporization column, discharging the vaporized gas from the top of the column, optionally adding hydrogen gas, and then returning it to the first vertical gas-phase reactor, and returning the bottom material to the first vertical gas-phase reactor. Step 3) involves the reaction product from the first vertical gas-phase reactor continuing to polymerize in the second horizontal gas-phase reactor, sending the reaction product to a low-pressure bag filter, removing the fine powder from the tail gas generated by the reaction, sending it to a propylene separation column, discharging the separated gas components from the top of the column, optionally adding hydrogen gas, and returning it to the second horizontal gas-phase reactor, and returning the bottom material to the second horizontal gas-phase reactor. Step 4) involves filtering the reaction product from the second horizontal gas-phase reactor using a low-pressure bag filter and then inactivating it with a steamer before sending it to a dryer. Step 5) involves removing dust and filtering the gaseous material dried in a dryer, then optionally adding additives, and finally collecting the final product. Step 6) includes recovering hydrocarbons in the gaseous and / or liquid emissions generated in steps 2) to 5), A method for producing ternary copolymer polypropylene, characterized by the following features.

8. The catalyst comprises a main catalyst, a co-catalyst, an electron donor, hexane and / or white oil, the main catalyst comprises a titanium-magnesium catalyst and / or a metallocene catalyst, the co-catalyst is a trialkylaluminum compound, the trialkylaluminum compound is triethylaluminum and / or tri-n-butylaluminum, and the electron donor is at least one of dicyclopentyldimethoxysilane, cyclohexyl(dimethoxy)methylsilane, and triethoxysilane. The manufacturing method according to claim 7, characterized in that it

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