CN119549071A - A homogeneous metallocene catalyst preparation system and method - Google Patents
A homogeneous metallocene catalyst preparation system and method Download PDFInfo
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- CN119549071A CN119549071A CN202311129850.7A CN202311129850A CN119549071A CN 119549071 A CN119549071 A CN 119549071A CN 202311129850 A CN202311129850 A CN 202311129850A CN 119549071 A CN119549071 A CN 119549071A
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Abstract
The invention provides a homogeneous metallocene catalyst preparation system and a method. The system comprises a homogeneous metallocene catalyst synthesis unit, a solvent condensing and collecting unit and a gas purifying unit, wherein the homogeneous metallocene catalyst synthesis unit comprises a fluidized bed reactor, the solvent condensing and collecting unit comprises a condenser, and the gas purifying unit comprises a fluidized bed gas purifier. The method comprises the steps of adding solid metallocene ligand and solvent into a fluidized bed reactor, introducing protective gas, spraying metal ion solution to generate a homogeneous metallocene catalyst, introducing the protective gas entraining the solvent into a condenser for condensation, and then introducing the protective gas into a fluidized bed gas purifier for purification. The invention adopts double fluidized beds to complete the synthesis of homogeneous metallocene catalyst and the purification of gas, reduces the content of water and oxygen in the atmosphere of the reaction process of metallocene ligand and metal ions, and improves the conversion rate of active centers in the reaction process.
Description
Technical Field
The invention relates to the technical field of homogeneous metallocene catalysts, in particular to a homogeneous metallocene catalyst preparation system and a homogeneous metallocene catalyst preparation method.
Background
The homogeneous metallocene catalyst system is a catalyst system which takes pentadentate coordination compound formed by cyclopentadiene and derivatives thereof (such as indene, fluorene and the like) and IVB group transition metals (such as titanium, zirconium and the like) as a main catalyst and takes Methylaluminoxane (MAO) or organic boride and the like as a cocatalyst. Compared with the traditional Ziegler-Natta catalyst, the metallocene complex as the main catalyst has more accurate regulation capability, which is mainly based on the structure of the metallocene ligand, namely, on one hand, the metallocene ligand is complexed with metal of a fourth group to form a single active site, and on the other hand, the metallocene ligand 'standardizes' the solid space geometry around the single active site, so that the coordination insertion chain growth reaction of olefin molecules in the active site is standardized, and further, the polymer with high stereoregularity can be produced.
The homogeneous metallocene catalyst has the advantages that (1) the homogeneous metallocene catalyst (metallocene complex used as a main catalyst in the scheme) is extremely sensitive to water and oxygen and has extremely harsh synthesis conditions, (2) the reaction conversion rate of metal ions and ligands is low in the preparation process of the homogeneous metallocene catalyst, so that the catalyst synthesis efficiency is low, and (3) the synthesis steps of the homogeneous metallocene catalyst with complex molecular structure are more, the reaction flow is long, the byproducts are complex, so that the separation of the catalyst and the recovery and regeneration of the solvent are very difficult.
In the prior art, the preparation of homogeneous metallocene catalysts is in a laboratory stage, and the conventional mode is to adopt the standard Schlenk anhydrous anaerobic technology in all the synthesis and treatment of metallocene complexes and sensitive substances. The anhydrous anaerobic technology uses high-purity nitrogen as shielding gas to perform standard operation through double discharge pipes, and the operation in a glove box is required to be performed when special operation requirements exist. All glass instruments used in the experiment process need to be baked in vacuum under an air lamp and cooled to room temperature for reuse. The anhydrous solvent adopted in the experimental process is used after special treatment. For example, aprotic solvents such as anhydrous tetrahydrofuran, anhydrous toluene, anhydrous diethyl ether and the like are required to be added with metallic sodium and benzophenone under the atmosphere of high-purity nitrogen, refluxed to mauve, and then steamed into an ampoule filled with the 4A molecular sieve for storage. For another example, anhydrous n-pentane, n-hexane and methylene dichloride are added with a proper amount of calcium hydride under the atmosphere of protective gas, stirred for 2-3 days, and then steamed into an ampoule filled with the 4A molecular sieve for storage.
CN210058286U discloses a preparation device for a catalyst system. The preparation device comprises a preparation kettle, a feeding tank, a gas injection pipeline, a liquid level control unit and a pressure control unit. The preparation device can improve the controllability of the complex reaction of the gaseous catalyst and the liquid accelerator and the quality of the catalyst system, and the feeding tank is positioned above the preparation kettle, so that the accelerator in the feeding tank automatically flows into the preparation kettle, external energy is not needed, and energy consumption is saved.
CN204224504U discloses a metallocene catalyst preparation apparatus for producing low-crystallization-point polyethylene. The preparation device comprises an alkyl aluminum configuration tank which is connected with a current limiting pore plate, an alkyl aluminum charging sprayer and a catalyst carrier configuration tank in sequence. According to the preparation device, the flow limiting pore plate is additionally arranged on the pipeline, so that the feeding rate of the alkyl aluminum can be controlled, and the alkyl aluminum feeding injector is additionally arranged on the pipeline, so that the uniform reaction of the alkyl aluminum and the silica gel is ensured, a uniform carrier is obtained, and the performance of the catalyst is improved.
CN112745404a discloses a metallocene catalyst composition and a method for preparing polyolefin elastomer using the same. The metallocene catalyst composition includes a metallocene compound having a single active site and a cocatalyst. When the metallocene catalyst composition is used for copolymerization of ethylene and 1-octene, the catalyst activity is greater than 1X 10 6 g (mPE)/mol (cat) h, the density of the prepared polyolefin elastomer is between 0.865 and 0.935g/cm 3, the number average molecular weight is 104-106 daltons, and the molecular weight distribution is 1.2-8.5.
EP 041685A 2 discloses a metallocene catalyst and a process for its preparation. The catalyst substitutes one Cp ring of the traditional organic metal compound containing double Cp rings with hetero atom N, and connects the other Cp ring with N atom with Si bridging group to form a space four-ring structure with geometric tension. The four-ring structure limits the free rotation of Cp around the metal center, so that the structure of the catalyst has rigidity, and the opening degree of the metal active center is increased due to lack of steric hindrance, thereby improving the insertion rate of the long-chain alpha-olefin comonomer.
However, the prior art does not provide a solution to the problems of low ion reaction conversion rate, high sensitivity to water and oxygen and the like in the preparation process of the homogeneous metallocene catalyst. Therefore, developing a new homogeneous metallocene catalyst preparation system and method is still one of the problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a homogeneous metallocene catalyst preparation system and a homogeneous metallocene catalyst preparation method. The invention adopts double fluidized beds to complete the synthesis of homogeneous metallocene catalyst and the purification of gas, can reduce the content of water and oxygen in the atmosphere in the process of the combination reaction of metallocene ligand and metal ions, and can improve the conversion rate of active centers in the process of the combination reaction.
In order to achieve the above object, the first aspect of the present invention provides a homogeneous metallocene catalyst preparation system, which at least comprises a homogeneous metallocene catalyst synthesis unit, a solvent condensing and collecting unit, and a gas purifying unit;
The homogeneous metallocene catalyst synthesis unit comprises a fluidized bed reactor, a temperature and pressure detection component, wherein the fluidized bed reactor comprises a reactor shell, an air inlet, an air outlet, a metallocene ligand feeding port, a metal ion solution feeding port, a solvent feeding port, a discharge port and a nozzle, the air inlet and the discharge port are arranged at the lower part of the reactor shell, the metallocene ligand feeding port, the metal ion solution feeding port and the solvent feeding port are arranged on the side wall of the reactor shell, the air outlet is arranged at the top of the reactor shell, the nozzle is arranged on the inner wall of the reactor shell, the nozzle is communicated with the metal ion solution feeding port, and the temperature and pressure detection component is arranged at the top of the reactor shell and is used for detecting the temperature and the pressure inside the reactor shell;
The solvent condensing and collecting unit comprises a condenser, wherein the condenser is at least provided with a condensing medium inlet, a condensing medium outlet, an air inlet, an air outlet and a solvent outlet, the condensing medium inlet is arranged at the lower part of the condenser, the condensing medium outlet is arranged at the upper part of the condenser, the air inlet is arranged at the upper part of the condenser, the air outlet is arranged at the top of the condenser, and the solvent outlet is arranged at the bottom of the condenser;
The gas purification unit comprises a fluidized bed gas purifier, wherein the fluidized bed gas purifier comprises a purifier shell, a gas inlet and a gas outlet, the gas inlet is arranged at the lower part of the purifier shell, the gas outlet is arranged at the top of the purifier shell, and adsorbent particles are arranged in the purifier shell;
the air outlet of the fluidized bed reactor is connected with the air inlet of the condenser through a pipeline;
The air outlet of the condenser is communicated with the air inlet of the fluidized bed gas purifier through a pipeline;
The gas outlet of the fluidized bed gas purifier is connected with the gas inlet of the fluidized bed reactor through a pipeline.
In the above homogeneous metallocene catalyst preparation system, preferably, the homogeneous metallocene catalyst synthesis unit and the gas purification unit further comprise a level detection assembly respectively disposed inside the reactor housing and inside the purifier housing.
In the above homogeneous metallocene catalyst production system, preferably, the gas purification unit further includes a gas impurity detection assembly disposed at a gas outlet of the fluidized bed gas purifier.
In the above homogeneous metallocene catalyst production system, preferably, in the fluidized bed reactor, the number of the nozzles is one or more, and all the nozzles are disposed on the inner wall of the reactor shell. It will be appreciated by those skilled in the art that when a plurality of nozzles are provided, the number of the metal ion solution feed ports is also plural, and the metal ion solution feed ports are respectively communicated with the plurality of nozzles.
In the above homogeneous metallocene catalyst production system, preferably, a gas distributor is further provided inside the fluidized bed reactor, the gas distributor being located above the gas inlet of the fluidized bed reactor. The gas distributor used is a device conventional in the art, and the specific structure of the gas distributor is not particularly limited in the invention.
In the above homogeneous metallocene catalyst production system, preferably, a compressor is provided on a line connecting an outlet of the fluidized bed gas purifier and an inlet of the fluidized bed reactor.
In the above homogeneous metallocene catalyst production system, preferably, the condenser comprises a shell-and-tube condenser. More preferably, the condenser comprises a condenser shell, a plurality of heat exchange tubes and a plurality of baffle plates, wherein the heat exchange tubes and the baffle plates are arranged in the condenser shell, the condensing medium inlet and the condensing medium outlet are communicated with the heat exchange tubes, and the baffle plates are arranged in a staggered manner along the vertical direction of the condenser shell.
In the homogeneous metallocene catalyst preparation system described above, preferably, a pressure release valve is provided at the top of the condenser.
In the above homogeneous metallocene catalyst preparation system, preferably, a gas-compensating port is provided on a side wall of the condenser.
According to the invention, the air supply port and the pressure relief valve of the condenser can control the pressure of the system, can supplement or relieve the pressure for the system, and avoid accidents of abnormal working conditions such as overhigh pressure of the system, incomplete condensation and the like.
In the above homogeneous metallocene catalyst production system, preferably, a solution concentration detector is provided at a solvent outlet of the condenser. The solution concentration detector is used for detecting the concentration and composition of the liquid discharged from the solvent outlet of the condenser. The solution concentration detector used may be a device conventional in the art, and the specific structure thereof is not particularly limited in the present invention.
In the above-mentioned homogeneous metallocene catalyst production system, it is preferable that the plurality of baffles in the condenser constitute a baffle group having a zigzag shape in a vertical direction.
In the homogeneous metallocene catalyst preparation system, the adsorbent particles in the purifier shell are particles capable of adsorbing water and oxygen. Preferably, the adsorbent comprises a molecular sieve. Specifically, the molecular sieve comprises one or a combination of a plurality of 5A molecular sieve, 3A molecular sieve, 4A molecular sieve, 13X molecular sieve and the like.
In the above homogeneous metallocene catalyst production system, preferably, the gas cleaning unit further comprises an initial shielding gas transfer line communicating with the gas inlet of the fluidized bed gas cleaner for providing an initial shielding gas into the system.
In the above homogeneous metallocene catalyst preparation system, preferably, the gas impurity detection component includes a gas chromatograph and an online sampling probe thereof.
In the above homogeneous metallocene catalyst preparation system, preferably, the gas purification unit further comprises a shielding gas return line, one end of the shielding gas return line is connected to the gas impurity detection assembly, and the other end of the shielding gas return line is communicated with the gas inlet of the fluidized bed gas purifier, so that the shielding gas with unsatisfactory water and oxygen content after being detected by the gas impurity detection assembly is re-introduced into the fluidized bed gas purifier for purification.
In the above homogeneous metallocene catalyst production system, preferably, a gas distributor is further provided inside the fluidized bed gas purifier, and the gas distributor is located above the gas inlet of the fluidized bed gas purifier. The gas distributor used is a device conventional in the art, and the specific structure of the gas distributor is not particularly limited in the invention.
In the above homogeneous metallocene catalyst production system, preferably, the solvent outlet of the condenser is connected to the solvent feed inlet of the fluidized bed reactor by a pipeline.
In the above-mentioned homogeneous metallocene catalyst preparation system, the temperature and pressure detecting component, the level detecting component and the level detecting component in the homogeneous metallocene catalyst synthesis unit and the gas purifying unit are all conventional devices in the art, and the specific structure of the system is not particularly limited in the present invention.
According to a specific embodiment of the present invention, preferably, the above system further comprises a ligand synthesis unit for synthesizing a metallocene ligand. The ligand synthesizing unit may employ a ligand synthesizing apparatus in the prior art, and the structure thereof is not particularly limited in the present invention.
According to a specific embodiment of the present invention, preferably, the above system further comprises a recrystallization unit for performing recrystallization purification of the metallocene ligand synthesized by the ligand synthesis unit. The recrystallization unit may be carried out by using a device in the prior art, and the present invention is not particularly limited. The recrystallisation unit may be connected by a line to the metallocene ligand feed inlet of the fluidised bed reactor.
According to a specific embodiment of the present invention, preferably, the above system further comprises a raw material storage unit including a storage device for raw materials for synthesizing the ligand, a storage device for metal ion solution, a storage device for solvent, and the like, wherein the storage device for raw materials for synthesizing the ligand is connected to the ligand synthesizing unit, the storage device for metal ion solution is connected to the metal ion solution feed inlet of the fluidized bed reactor, and the storage device for solvent is connected to the solvent feed inlet of the fluidized bed reactor. These storage devices may be any storage devices in the prior art, and the present invention is not limited thereto.
According to a specific embodiment of the present invention, it is preferable that the above system further comprises a raw material refining unit connected to the raw material storage unit for refining raw materials for synthesizing the ligand, raw materials for synthesizing the metal ion solution, a solvent, and the like. The raw material refining unit may be a raw material refining apparatus of the prior art, and the present invention is not limited in particular to the structure thereof.
According to a specific embodiment of the present invention, the above system preferably further comprises a solvent recovery unit connected to the solvent outlet of the condenser by a line for recovering the solvent. The recovered solvent can be returned to the raw material refining unit and the raw material storage unit, and then returned to the homogeneous metallocene catalyst synthesis unit again, so that the solvent can be reused. As will be appreciated by those skilled in the art, the solvent recovered by the solvent recovery unit includes the solvent in the metal ion solution and the solvent entering the system from the solvent feed inlet of the fluidized bed reactor. In addition, it will be appreciated by those skilled in the art that when the system of the present invention does not include a solvent recovery unit, the solvent outlet of the condenser may be directly connected to the solvent feed inlet of the fluidized bed reactor by a line, as described above.
According to a specific embodiment of the present invention, the above system preferably further comprises a catalyst storage unit connected to the discharge port of the fluidized bed reactor by a pipeline for storing the prepared homogeneous metallocene catalyst.
In the present invention, fluidized bed refers to a mass of solid particles suspended in a moving fluid such that the particles have certain apparent characteristics of the fluid. Specifically, as the velocity of the fluid through the bed increases gradually to a certain value, the particles loosen, the inter-particle voids increase, and the bed volume expands. If the fluid velocity is increased even further, the bed will not remain stationary. At this point, the particles are all suspended in the fluid, exhibiting rather irregular movement. As the flow rate increases, the movement of the particles becomes more severe and the expansion of the bed increases, but the particles remain in the bed and are not carried out by the fluid. At this point, the bed is similar in state to a liquid. This state of fluid contact is known as solids fluidization, i.e., fluidized bed.
The well fluidized bed exhibits liquid-like properties. The fluidized bed has the characteristics that fluid with density smaller than the average density of the bed layer can be suspended on the bed surface, the bed surface is kept horizontal, the bed layer is subjected to hydrostatic relation, namely, the pressure difference delta p=ρgl of two sections with the height difference L, particles have fluidity similar to that of liquid, and the fluidized bed has bulk fluidization, and the two communicated fluidized beds adopted by the invention can self-regulate the upper surface of the bed layer to be on the same horizontal plane.
The preparation system of the homogeneous metallocene catalyst provided by the invention adopts the double fluidized beds to complete the synthesis of the homogeneous metallocene catalyst and the purification of gas. In the catalyst synthesis process, the metal ion solution and the metallocene ligand can be fully contacted, and the reaction can be fully performed due to the uniform temperature and uniform concentration of the reaction system in the fluidized bed reactor, so that the conversion rate of the active center in the chemical combination reaction process is improved, namely the conversion rate of the ion reaction is improved. In the gas purification process, the protective gas can be fully contacted with the adsorbent particles, so that the content of impurities such as water and oxygen in the gas is greatly reduced, and the purified gas is suitable for being used as a reaction atmosphere in the synthesis process of the homogeneous metallocene catalyst. In addition, by adopting the homogeneous metallocene catalyst preparation system, the prepared catalyst is easy to separate, and the solvent is easy and efficient to recycle. Therefore, the invention solves the problems of low ion reaction conversion rate, high water and oxygen content in the atmosphere and the like in the synthesis process of the homogeneous metallocene catalyst in the prior art. The invention improves the synthesis efficiency and yield of the homogeneous metallocene catalyst, improves the purity of the homogeneous metallocene catalyst, and reduces the cost of the catalyst.
The second aspect of the present invention provides a method for preparing a homogeneous metallocene catalyst by using the above-mentioned system, comprising the steps of:
(1) Adding a solid metallocene ligand and a solvent into the fluidized bed reactor, then introducing a protective gas into the fluidized bed reactor, wherein the protective gas is the protective gas purified by the fluidized bed gas purifier, the protective gas strongly disturbs the solid metallocene ligand to form a fluidized bed, spraying a metal ion solution into the fluidized bed reactor in a mist form through the nozzle, reacting the metal ion with the metallocene ligand to generate a homogeneous metallocene catalyst, and discharging the protective gas entraining solvent from an air outlet of the fluidized bed reactor;
(2) The protective gas discharged from the gas outlet of the fluidized bed reactor entrains the solvent into the condenser, the protective gas obtained after condensation is discharged from the gas outlet of the condenser, and the obtained solvent is discharged from the solvent outlet of the condenser;
(3) And (3) introducing the protective gas discharged from the gas outlet of the condenser into the fluidized bed gas purifier, strongly disturbing the adsorbent particles in the fluidized bed gas purifier to form a fluidized bed, adsorbing the water oxygen in the protective gas by the adsorbent particles to obtain purified protective gas, discharging the protective gas from the gas outlet of the fluidized bed gas purifier, and introducing the discharged protective gas into the fluidized bed reactor.
In the above-mentioned production method, preferably, in the step (1), the reaction temperature in the fluidized-bed reactor is from-40 to 40 ℃.
In the above production method, preferably, in the step (1), the reaction pressure in the fluidized bed reactor is 0.1 to 2MPa.
In the above preparation method, the temperature and pressure in the fluidized bed reactor may be detected by a temperature and pressure detecting assembly at the top of the fluidized bed reactor.
In the above production method, preferably, in the step (1), the fluidization velocity in the fluidized bed reactor is 0.1 to 5m/s. It will be appreciated by those skilled in the art that the fluidization velocity refers to the apparent velocity of the fluid formed by the solid metallocene ligand.
In the above-mentioned production method, preferably, in the step (1), the crystal size of the solid metallocene ligand is 10 to 100. Mu.m.
In the above-mentioned production method, preferably, in the step (1), the solid metallocene ligand has a particle size of 500 to 5000. Mu.m.
In the above preparation process, preferably, in step (1), the solid metallocene ligand and the solvent are used in a ratio of 50 to 500g:1L.
In the above-mentioned production method, preferably, in the step (1), the metal ion concentration in the metal ion solution is 0.1 to 100g/L.
In some embodiments of the present invention, the solid metallocene ligand, the solvent, and the metal ion solution may all be conventional raw materials for preparing homogeneous metallocene catalysts in the art, and the present invention is not limited in particular to the specific compounds selected for them.
In the above-mentioned production method, preferably, in the step (2), the temperature in the condenser is-50 to 50 ℃.
In the above production method, preferably, in the step (2), the pressure in the condenser is 0.1 to 2MPa. The pressure in the condenser may be regulated by a pressure relief valve at the top of the condenser and/or by make-up shielding gas through a make-up port.
In the above-mentioned production method, preferably, in the step (2), the residence time of the shielding gas entrainment solvent discharged from the gas outlet of the fluidized bed reactor in the condenser is from 0.1 to 20min. The residence time in the condenser can ensure that the solvent entrained in the shielding gas is sufficiently settled, so that the design of a pipeline in the condenser is long enough to ensure that the solvent can be sufficiently settled.
In the above-mentioned production method, preferably, in the step (2), the flow rate of the shielding gas entrainment solvent in the condenser is 1m/min or less. If the flow rate is too high, there is an adverse effect on the settling of the entrained solvent in the shielding gas.
According to the specific embodiment of the invention, the solvent entrained in the protective gas is condensed and recovered in an over-condensing mode, so that all gaseous solvents are completely liquefied, the residence time of the protective gas is increased in a folded plate condensing mode, and the recovery efficiency of the solvent is improved.
In the above-mentioned production method, preferably, in the step (3), the temperature in the fluidized bed gas purifier is from-50 to 50 ℃.
In the above production method, preferably, in the step (3), the pressure in the fluidized bed gas purifier is 0.1 to 2MPa.
In the above production method, preferably, in the step (3), the fluidization velocity in the fluidized bed gas cleaner is 0.1 to 5m/s. As will be appreciated by those skilled in the art, the fluidization velocity refers to the apparent velocity of the fluid from which the sorbent particles are formed.
In the above preparation method, preferably, the step (3) further comprises the step of re-entering the protective gas into the fluidized bed gas purifier for purification if the water and oxygen contents are not satisfactory after the gas impurity detection component detects the water and oxygen contents in the protective gas at the gas outlet of the fluidized bed gas purifier. More preferably, the water content in the shielding gas is less than 5ppm and the oxygen content is less than 5ppm, as desired.
According to the specific embodiment of the invention, the protective gas is purified by the fluidized bed gas purifier, and in the purification process, the protective gas strongly disturbs adsorbent particles (such as molecular sieves and the like) to form a fluidized bed, so that water and oxygen in the protective gas are efficiently adsorbed, the protective gas which does not meet the requirements of water and oxygen content is purified again, and the protective gas meeting the requirements of water and oxygen content enters the fluidized bed reactor.
In the above production method, preferably, in step (3), the purified shielding gas discharged from the gas outlet of the fluidized bed gas purifier is compressed by a compressor and then introduced into the fluidized bed reactor. More preferably, the pressure of the purified shielding gas after being compressed by the compressor is 0.1-2MPa, and the temperature is-50 ℃. The invention adopts a compressor to provide the pressure of the whole reaction system.
In the above-described production method, preferably, the shielding gas includes one or a combination of several of nitrogen, helium, neon, and the like.
In the above-mentioned production method, it is preferable that the prepared homogeneous metallocene catalyst (i.e., metallocene complex) has a crystal size of 10 to 100. Mu.m, and a particle size of 500 to 5000. Mu.m.
The invention provides a homogeneous metallocene catalyst preparation system and a method. The invention adopts double fluidized beds to complete the synthesis of the homogeneous metallocene catalyst and the purification of gas, reduces the content of water and oxygen in the atmosphere in the process of the combination reaction of the metallocene ligand and the metal ions, improves the conversion rate of active centers in the process of the combination reaction, and can realize the efficient, green and stable synthesis of the homogeneous metallocene catalyst. The homogeneous metallocene catalyst preparation system and the method are particularly suitable for the production of the homogeneous metallocene catalyst for synthesizing polyolefin elastomer.
The technical scheme of the invention has at least the following beneficial effects:
The ionic reaction conversion rate of the homogeneous metallocene catalyst and the water-oxygen content of the reaction system determine the purity and the synthesis efficiency of the catalyst. The invention adopts double fluidized beds to complete the synthesis of homogeneous metallocene catalyst and the purification of gas, thus realizing the deep purification of atmosphere and the efficient combination of metal ions and metallocene ligands. Therefore, the technical scheme of the invention improves the synthesis efficiency and yield of the homogeneous metallocene catalyst, improves the purity of the homogeneous metallocene catalyst, and reduces the cost of the catalyst. The purity of the homogeneous metallocene catalyst provided by the invention is more than 97%, and the yield is more than 85%. In addition, the technical scheme of the invention ensures that the prepared catalyst is easy to separate, and the recovery of the solvent is simple and efficient.
Drawings
FIG. 1 is a schematic structural diagram of a homogeneous metallocene catalyst preparation system in one embodiment of the present invention.
Reference numerals illustrate:
1-a fluidized bed reactor, 2-a temperature and pressure detection assembly, 3-a first material level detection assembly, 11-a nozzle, 12-a first gas distributor;
4-condenser, 41-baffle plate, 42-relief valve and 43-air supplementing port;
5-fluidized bed gas purifier, 51-second gas distributor, 6-gas impurity detection component, 7-second material level detection component, 8-compressor, 9-initial shielding gas conveying pipeline and 10-shielding gas return pipeline.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Some embodiments of the invention provide a homogeneous metallocene catalyst preparation system, the structure of which is shown in figure 1, the system at least comprises a homogeneous metallocene catalyst synthesis unit, a solvent condensation and collection unit and a gas purification unit;
The homogeneous metallocene catalyst synthesis unit comprises a fluidized bed reactor 1 and a temperature and pressure detection component 2, wherein the fluidized bed reactor 1 comprises a reactor shell, an air inlet, an air outlet, a metallocene ligand feed inlet, a metal ion solution feed inlet, a solvent feed inlet, a discharge outlet and a nozzle 11, the air inlet and the discharge outlet are arranged at the lower part of the reactor shell, the metallocene ligand feed inlet, the metal ion solution feed inlet and the solvent feed inlet are arranged on the side wall of the reactor shell, the air outlet is arranged at the top of the reactor shell, the nozzle 11 is arranged on the inner wall of the reactor shell, the nozzle 11 is communicated with the metal ion solution feed inlet, and the temperature and pressure detection component 2 is arranged at the top of the reactor shell and is used for detecting the temperature and the pressure inside the reactor shell;
The solvent condensing and collecting unit comprises a condenser 4, wherein the condenser 4 is at least provided with a condensing medium inlet, a condensing medium outlet, an air inlet, an air outlet and a solvent outlet, the condensing medium inlet is arranged at the lower part of the condenser 4, the condensing medium outlet is arranged at the upper part of the condenser 4, the air inlet is arranged at the upper part of the condenser 4, the air outlet is arranged at the top of the condenser 4, and the solvent outlet is arranged at the bottom of the condenser 4;
The gas purifying unit comprises a fluidized bed gas purifier 5, wherein the fluidized bed gas purifier 5 comprises a purifier shell, a gas inlet and a gas outlet, the gas inlet is arranged at the lower part of the purifier shell, the gas outlet is arranged at the top of the purifier shell, and adsorbent particles are arranged in the purifier shell;
the air outlet of the fluidized bed reactor 1 is connected with the air inlet of the condenser 4 through a pipeline;
The air outlet of the condenser 4 is communicated with the air inlet of the fluidized bed gas purifier 5 through a pipeline;
The gas outlet of the fluidized bed gas purifier 5 is connected to the gas inlet of the fluidized bed reactor 1 through a pipeline.
In one embodiment, the homogeneous metallocene catalyst synthesis unit further comprises a first level detection assembly 3, which is arranged inside the reactor shell.
In one embodiment, the gas cleaning unit further comprises a second level detection assembly 7, which is arranged inside the cleaner housing.
In one embodiment, the gas cleaning unit further comprises a gas impurity detection assembly 6 disposed at the gas outlet of the fluidized bed gas cleaner 5.
In one embodiment, in the fluidized bed reactor 1, the number of nozzles 11 is one or more, all disposed on the inner wall of the reactor shell. It will be understood by those skilled in the art that when a plurality of nozzles 11 are provided, the number of the metal ion solution feed ports is also plural, and the metal ion solution feed ports are respectively communicated with the plurality of nozzles 11.
In one embodiment, the interior of the fluidized bed reactor 1 is further provided with a first gas distributor 12, the first gas distributor 12 being located above the gas inlet of the fluidized bed reactor 1. The gas distributor used is a device conventional in the art, and the specific structure of the gas distributor is not particularly limited in the invention.
In one embodiment, a compressor 8 is provided in the line connecting the gas outlet of the fluidized bed gas purifier 5 with the gas inlet of the fluidized bed reactor 1.
In one embodiment, condenser 4 is a shell-and-tube condenser. Specifically, the condenser 4 includes a condenser shell, a plurality of heat exchange tubes (not shown in fig. 1) and a plurality of baffles 41, the plurality of heat exchange tubes and the plurality of baffles 41 are disposed inside the condenser shell, a condensing medium inlet and a condensing medium outlet are communicated with the plurality of heat exchange tubes, the plurality of baffles 41 are staggered along the vertical direction of the condenser shell, the plurality of baffles 41 can be in sealing sleeve joint with the plurality of heat exchange tubes, and the plurality of baffles 41 form a baffle group in a zigzag shape in the vertical direction. Wherein the condensing medium may be conventional in the art, such as, but not limited to, water and the like.
In one embodiment, the top of the condenser 4 is provided with a pressure relief valve 42.
In one embodiment, the side wall of the condenser 4 is provided with a make-up port 43.
The air supplementing port 43 and the pressure relief valve 42 of the condenser 4 can control the pressure of the system, can supplement or relieve the pressure for the system, and avoid accidents of abnormal working conditions such as overhigh pressure of the system, incomplete condensation and the like.
In one embodiment, a solution concentration detector is provided at the solvent outlet of the condenser 4 for detecting the concentration and composition of the liquid discharged at the solvent outlet of the condenser. The solution concentration detector used is a device conventional in the art, and the specific structure thereof is not particularly limited in the present invention.
In one embodiment, the adsorbent particles inside the purifier housing are particles that can adsorb water, oxygen. Preferably, the adsorbent comprises a molecular sieve. Specifically, the molecular sieve comprises one or a combination of a plurality of 5A molecular sieve, 3A molecular sieve, 4A molecular sieve, 13X molecular sieve and the like.
In one embodiment, the gas cleaning unit further comprises an initial shielding gas transfer line 9, the initial shielding gas transfer line 9 being in communication with the gas inlet of the fluidized bed gas cleaner 5 for providing an initial shielding gas into the system.
In one embodiment, the gaseous impurity detection assembly 6 comprises a gas chromatograph and its on-line sampling probe.
In one embodiment, the gas purification unit further comprises a protective gas return line 10, wherein one end of the protective gas return line 10 is connected to the gas impurity detection assembly 6, and the other end of the protective gas return line is communicated with the gas inlet of the fluidized bed gas purifier 5, so that the protective gas with unsatisfactory water and oxygen content after being detected by the gas impurity detection assembly 6 is re-introduced into the fluidized bed gas purifier 5 for purification.
In one embodiment, the interior of the fluidized bed gas purifier 5 is further provided with a second gas distributor 51, the second gas distributor 51 being located above the gas inlet of the fluidized bed gas purifier 5. The gas distributor used is a device conventional in the art, and the specific structure of the gas distributor is not particularly limited in the invention.
In one embodiment, the solvent outlet of the condenser 4 is connected by a line to the solvent feed inlet (not shown in fig. 1) of the fluidized bed reactor 1.
In the above-described embodiment, the temperature and pressure detecting assembly 2 and the first level detecting assembly 3 in the homogeneous metallocene catalyst synthesis unit, and the second level detecting assembly 7 in the gas purification unit are all conventional apparatuses in the art, and the specific structure thereof is not particularly limited by the present invention.
In the above embodiments, the necessary valves, such as a shut-off valve, etc., may be provided on each line, and those skilled in the art may perform conventional settings according to the actual situation.
In one embodiment, the above system further comprises a ligand synthesis unit for synthesizing a metallocene ligand. The ligand synthesizing unit may employ a ligand synthesizing apparatus in the prior art, and the structure thereof is not particularly limited in the present invention.
In one embodiment, the above system further comprises a recrystallization unit for performing recrystallization purification of the metallocene ligand synthesized by the ligand synthesis unit. The recrystallization unit may be carried out by using a device in the prior art, and the present invention is not particularly limited. The recrystallisation unit may be connected by a line to the metallocene ligand feed inlet of the fluidised bed reactor.
In one embodiment, the system further comprises a raw material storage unit, wherein the raw material storage unit comprises a storage device of raw materials for synthesizing the ligand, a storage device of metal ion solution, a storage device of solvent and the like, the storage device of raw materials for synthesizing the ligand is connected to the ligand synthesizing unit, the storage device of the metal ion solution is connected to a metal ion solution feed inlet of the fluidized bed reactor, and the storage device of the solvent is connected to a solvent feed inlet of the fluidized bed reactor. These storage devices may be any storage devices in the prior art, and the present invention is not limited thereto.
In one embodiment, the system further comprises a raw material refining unit connected to the raw material storage unit for refining raw materials for synthesizing the ligand, raw materials for synthesizing the metal ion solution, solvent, and the like. The raw material refining unit may be a raw material refining apparatus of the prior art, and the present invention is not limited in particular to the structure thereof.
In one embodiment, the system further comprises a solvent recovery unit connected by a line to the solvent outlet of the condenser for recovering solvent. The recovered solvent can be returned to the raw material refining unit and the raw material storage unit, and then returned to the homogeneous metallocene catalyst synthesis unit again, so that the solvent can be reused. As will be appreciated by those skilled in the art, the solvent recovered by the solvent recovery unit includes the solvent in the metal ion solution and the solvent entering the system from the solvent feed inlet of the fluidized bed reactor. In addition, it will be appreciated by those skilled in the art that when the system of the present invention does not include a solvent recovery unit, the solvent outlet of the condenser may be directly connected to the solvent feed inlet of the fluidized bed reactor by a line, as described above.
In one embodiment, the system further comprises a catalyst storage unit connected to the discharge port of the fluidized bed reactor by a pipeline for storing the prepared homogeneous metallocene catalyst.
In other embodiments, the present invention provides a method for preparing a homogeneous metallocene catalyst by using the above-mentioned system, which comprises the following steps:
(1) Adding a solid metallocene ligand and a solvent into a fluidized bed reactor 1, and then introducing a protective gas into the fluidized bed reactor 1, wherein the protective gas is the protective gas purified by a fluidized bed gas purifier 5, the protective gas strongly disturbs the solid metallocene ligand to form a fluidized bed, a metal ion solution is sprayed onto the bed layer of the fluidized bed reactor 1 in a mist form through a nozzle 11, the bed temperature of the fluidized bed reactor 1 and the pressure in the fluidized bed reactor 1 are regulated, the bed temperature of the fluidized bed reactor 1 is regulated by the feeding temperature and the reaction heat release, the metal ions are attached to the solid metallocene ligand to react to generate a homogeneous metallocene catalyst, and the protective gas entrains the solvent to be discharged from an air outlet of the fluidized bed reactor 1;
(2) The protective gas discharged from the gas outlet of the fluidized bed reactor 1 entrains the solvent into the condenser 4, the protective gas obtained after condensation is discharged from the gas outlet of the condenser 4, and the obtained solvent is discharged from the solvent outlet of the condenser 4;
(3) In the initial stage of preparation, the protective gas is made to enter the fluidized bed gas purifier 5 through the initial protective gas conveying pipeline 9, after the amount of the protective gas meets the reaction requirement in the fluidized bed reactor 1, the protective gas is not provided through the initial protective gas conveying pipeline 9 any more, the protective gas discharged from the gas outlet of the condenser 4 enters the fluidized bed gas purifier 5, the protective gas severely perturbs the adsorbent particles in the fluidized bed gas purifier 5 to form a fluidized bed, the adsorbent particles adsorb the water and oxygen in the protective gas, the purified protective gas is obtained and discharged from the gas outlet of the fluidized bed gas purifier 5, the gas impurity detection component 6 detects the water and oxygen content of the protective gas at the gas outlet of the fluidized bed gas purifier 5, if the water and oxygen content does not meet the requirement, the protective gas is made to reenter the fluidized bed gas purifier 5 for purification, if the water content in the protective gas is less than 5ppm, the oxygen content is less than 5ppm, the protective gas meeting the requirement is compressed by the compressor 8, and then enters the fluidized bed reactor 1.
In this example, in step (1), the reaction temperature in the fluidized bed reactor 1 is from-40 to 40 ℃, specifically 0 ℃. The reaction pressure in the fluidized bed reactor 1 is 0.1-2MPa, specifically 0.5MPa. The temperature and pressure inside the fluidized bed reactor 1 can be detected by a temperature and pressure detecting assembly 2 at the top of the fluidized bed reactor 1. The fluidization velocity in the fluidized-bed reactor 1 is 0.1 to 5m/s, in particular 2m/s. It will be appreciated by those skilled in the art that the fluidization velocity refers to the apparent velocity of the fluid formed by the solid metallocene ligand.
In this example, in step (1), the solid metallocene ligand has a crystal size of 10 to 100. Mu.m, specifically about 50. Mu.m. The particle size of the solid metallocene ligand is 500 to 5000. Mu.m, in particular 2000 to 3000. Mu.m. The ratio of the solid metallocene ligand to the solvent is 50-500 g/1L, in particular 100 g/1L. The concentration of metal ions in the metal ion solution is 0.1-100g/L, specifically 50g/L.
In this example, the solid metallocene ligand, solvent, and metal ion solution may all be conventional materials for preparing homogeneous metallocene catalysts in the art, and the specific compounds selected for them are not particularly limited in the present invention.
In this embodiment, in step (2), the temperature within the condenser 4 is from-50 to 50 ℃, specifically 0 ℃. The pressure in the condenser 4 is 0.1-2MPa, specifically 1MPa. The pressure in the condenser may be regulated by a pressure relief valve 42 at the top of the condenser 4 and/or by make-up shielding gas via a make-up port 43. The residence time of the protective gas entrainment solvent in the condenser 4, which is discharged from the gas outlet of the fluidized-bed reactor 1, is from 0.1 to 20min, in particular 10min. The flow rate of the shielding gas entrainment solvent in the condenser 4 is 1m/min or less.
In this embodiment, the solvent entrained in the shielding gas is condensed and recovered by using an over-condensation manner, so as to ensure that all the gaseous solvents are completely liquefied, and the retention time of the shielding gas is increased by using a folded plate condensation manner, so that the recovery efficiency of the solvent is improved.
In this embodiment, in step (3), the temperature within the fluidized bed gas purifier 5 is from-50 to 50 ℃, specifically 0 ℃. The pressure in the fluidized bed gas purifier 5 is 0.1-2MPa, specifically 0.5MPa. The fluidization velocity in the fluidized-bed gas cleaner 5 is 0.1-5m/s, in particular 2m/s. As will be appreciated by those skilled in the art, the fluidization velocity refers to the apparent velocity of the fluid from which the sorbent particles are formed.
According to the specific embodiment of the invention, the protective gas is purified by the fluidized bed gas purifier, and in the purification process, the protective gas strongly disturbs adsorbent particles (such as molecular sieves and the like) to form a fluidized bed, so that water and oxygen in the protective gas are efficiently adsorbed, the protective gas which does not meet the requirements of water and oxygen content is purified again, and the protective gas meeting the requirements of water and oxygen content enters the fluidized bed reactor.
In this embodiment, in step (3), the pressure of the shielding gas after compression by the compressor 8 is 0.1-2MPa, specifically 0.5MPa, and the temperature is-50 to 50 ℃, specifically 0 ℃. The present embodiment employs a compressor 8 to provide the pressure of the entire reaction system.
In this embodiment, the shielding gas is nitrogen.
In this example, the homogeneous metallocene catalyst prepared had a crystal size of about 50. Mu.m, and a particle size of 2000 to 3000. Mu.m.
The detection shows that the purity of the homogeneous metallocene catalyst provided by the embodiment is more than 97%, and the yield is more than 85%.
Claims (15)
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| CN202311129850.7A CN119549071A (en) | 2023-09-04 | 2023-09-04 | A homogeneous metallocene catalyst preparation system and method |
| PCT/CN2023/137511 WO2025050546A1 (en) | 2023-09-04 | 2023-12-08 | System and method for preparing homogeneous metallocene catalyst |
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| CN112745404A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Metallocene catalyst composition and method for preparing polyolefin elastomer by using same |
| CN114195920B (en) * | 2021-11-29 | 2023-07-18 | 青岛科技大学 | Synthesis of an improved metallocene catalyst and its synthesis equipment and application |
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