• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A continuous low pressure gas phase process for the production of solid particulate polymers during an exothermic polymerization reaction in a uniform diameter vertical fluidized bed reactor system which comprises feeding a polymerization catalyst and a gaseous stream containing at least one polymerizable monomer to a fluidized bed of polymer particles and removing the exothermic heat of reaction by indirect cooling means in the reactor and removing dry particulate polymer. Also, apparatus for the polymerization process is described.
    公开号:SU957770A3
    申请号:SU792754704
    申请日:1979-04-17
    公开日:1982-09-07
    发明作者:Лейф Браун Гейри；Франклин Уорнер Дэвид
    申请人:Юнион Карбид Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the technology of producing powdered coli olefins and can be used in the chemical industry.
    A known method for producing powdered olefins by polymerizing or copolymerizing olefins in a fluidized bed that is formed by passing gaseous monomers through a layer of polymer particles in the presence of a powdered oxide-chromium catalyst. The process is carried out in a vertical reactor consisting of a polymerization and upper expansion zones l,
    The disadvantage of this method is the adhesion of the polymer to the internal surfaces of the reactor.
    The closest to the proposed technical essence is a method for producing powdered polyolefins by continuous gas-phase copolymerization of ethylene with propylene or butene-1 at 85-103 ° C and a pressure of 21 kgf / cm in the presence of oxide-chromium or titanium catalysts, on a carrier during the process in a fluidized bed copolymer particles in vertical
    the cylindrical zone and the gas flow through the fluidized bed, 4-6 times the minimum mass velocity required for fluidization, while the heat of reaction is removed through the walls of the reaction zone using external cooling devices.
    The process according to this method is carried out in an installation made in the form of a vertical cylindrical apparatus with a cooling device for removing reaction heat and an unreacted gas recycle line, while the apparatus is equipped with fittings for the recycle gases in the apparatus cover to introduce recycle gases and fresh gas in the bottom apparatus and for the withdrawal of the target product, as well as a distribution grid to create a fluidized bed of copolymer particles in the lower part of the apparatus, located in the same plane with the pieces tserom for the desired product output choke above for introducing a recycle gas, wherein the cylindrical device has a diameter in the upper part than in the lower and ohlazkdayushee device is arranged outside the apparatus (cooling with rmbashka tsirkuliruk hlad CIM agent) 2.
    The disadvantage of the described method and installation — its implementation is the cortex formation on the inner surfaces of the reaction zone, which forces the process to be interrupted periodically and the adhered polymer is removed from the reaction zone.
    The purpose of the invention is to prevent crust formation on the inner surfaces of the remains of the reaction zone.
    The goal is achieved by the fact that according to the method of producing powdered polyolefins by continuous gas-phase copolymerization of ethylene with propylene or butene-1 at 85-103 ° C and a pressure of 21 kgf / cm in the presence of oxide-chromium or titanium catalysts on the carrier during the process in a fluidized bed of particles the copolymer in the vertical cylindrical zone and the gas flow through the fluidized bed, 4-6 times the minimum mass velocity required for fluidization, the heat of reaction is removed by internal cooling devices in the lower part of the reaction zone.
    In an apparatus for carrying out a method for producing powdered POLYolefins, made in the form of a vertical cylindrical apparatus with a cooling device for removing reaction heat and a recycle line of unreacted gases, the apparatus of which is equipped with fittings for outputting recycle gases in the apparatus cover, for introducing recycling gases and fresh gas in the bottom of the apparatus and for the withdrawal of the Target Product, as well as distribution, by a grating to create a fluidized bed of the copolymer particles in the lower part, located in one plane Spindles with a nozzle for outputting the target product above the nozzle for recycle gas inlet, the cylindrical apparatus has the same diameter throughout the height, and the cooling unit is designed as a coil with refrigerant circulating in it and is located inside the apparatus in its lower part above the distribution grid.
    The drawing shows a diagram of a pre-installation for carrying out the method.
    Reactor 1 consists of reaction zone 2, containing a layer of polymer-forming particles, polymer particles produced and a small amount of catalyst particles that are in the state of fluidization under the action of a continuous flow of polymerizable and modifying gaseous components in the form of recoverable raw material and circulating gas through the zone reaction. In order to maintain a viable fluidized bed, the mass flow rate of the gas flow through the bed must be higher than the minimum flow required for pseudo-cooling and, preferably,
    0 is 4-6 G min.
    To prevent the formation of local hot spots and catch and distribute the catalyst particles in the reaction zone. When starting the zone
    5 reactions are usually loaded with a layer of polymer particles before the gas is supplied. Such particles may be identical in nature to the polymer produced or differ from it. In the case of
    When they are different from them, they are withdrawn together with the polymer particles obtained as the primary product. Finally, the fluidized bed of the required particles
    5 polymer replaces the original layer.
    Partially or fully activated compound - starting material (catalyst, used
    Q in the fluidized bed is stored in the vessel 3 under a cushion of gas that is inert with respect to stored material, such as nitrogen or argon. Fluidization is achieved thanks to a high degree
     gas recirculation through the bed, usually 50 times the gas feed rate. The fluidized bed is a dense layer of viable particles formed
    0 due to the percolation of gas through this layer. The pressure drop in the bed is equal to or slightly above the bed weight divided by the cross sectional area. It thus depends
    5 from the geometry of the reactor.
    The process gas is supplied to the bed at a rate at least equal to the rate at which the polymer product is withdrawn as a powder. The composition of the process gas is determined using a gas analyzer 4 located above the bed. The gas analyzer determines the composition of the gas to be circulated, and
    5, the composition of the process gas, respectively, is adjusted so as to substantially maintain the gas composition of a constant state within the reaction zone.
    0 To ensure complete fluidization of the circulating gas and, where necessary, part of the process gas is returned to the reactor at point 5 below the bed. To facilitate pseudo-5 fluidization of the fluid over the cusp.
    There is a gas distribution grid 6.
    A portion of the gas stream, which does not react in the bed, forms a recycle gas, which is diverted from the polymerization zone through the transport and separation section 7 above. by layer. The recycle gas is then compressed in compressor 8 and returned to the reactor. In the reactor 1 there is an internal cooler which consists of a pipe system 9 placed inside the fluidized bed, which the heat of reaction is removed to the refrigerant. As an internal cooler, in addition to the Bare tubes shown in the drawing, finned tubes or flat, muddy coils can be used.
    The temperature of the polymer in the bed is controlled by adjusting the temperature and / or flow rate of the refrigerant entering the internal cooler, which is necessary to maintain the bed at a practically constant temperature. Due to the constant removal of the heat of reaction inside the layer, there is no perceptible temperature gradient. Since the gas of the cyclone is not cooled, the temperature of the gas entering the fluidized bed layer 2 through the distribution grid b has almost the same temperature as the recycle gas leaving the bed through the transport separation zone 7.
    The distribution grid b plays an important role in the operation of the reactor. The fluidized bed contains the formed and obtained particles of a powdered polymer, as well as catalyst particles. Since the polymer particles are hot and active, they must be prevented from settling, because if the mass is left at rest, any active catalyst contained in it can continue the reaction and cause fusion. The recycle gas flow through the bed at a rate sufficient to maintain fluidization within the bed is therefore important. The distribution grid B serves this purpose and can be made in the form of a sieve. with rectangular slots, perforated plate, cap column plates, and the like. The lattice elements can all be fixed and the lattice can be of a rolling type. Whatever the design, it must disperse the recycle gas over the bed in order to maintain it in a fluidized state, and also serve as a support resting layer of polymer particles when the reactor is not operating.
    Hydrogen can be used to control the molecular weight during the polymerization reaction. The ratio between hydrogen and ethylene is 0-2. Any gas may also be present in the gas flow 5.
    inert to the catalyst and reagents. The activator compound is preferably added to the reaction system in the recycle line. Thus, the activator can be fed into the gas recycle system kz of the dispenser 10 via line 11.
    For a fluidized reactor.
    It is important for the layer to work at a temperature below the melting point of the polymer particles. For tcro, in order for the fusion not to have htecxa, it is necessary that the working temperatures be below the melting point. For the preparation of ethylene copolymers, the operating temperatures are 75-103 0. Fluidized bed PeaKToiS
    5 at pressures of .21 kgf / cm.
    Partially or fully activated precursor (catalyst is injected into the bed at a rate equal to its flow rate at the point
    jj is viana distribution
     lattice b. Preferably catalysis-,. The torus is inserted at a point located approximately 1 / 4-3 / 4 to the edge of the layer. The introduction of the catalyst at a point above the distribution
     lattice, due to the fact that it is highly active. Introduction a fully activated catalyst in the zone below the distribution grid can cause the onset of polyme0
    implementation and possibly clogging of the distribution outlet. Introduction to a viable layer contributes to the distribution of catalyst a in the layer and prevents the formation of localized places with a high concentration of catalyst, which could lead to the formation of hot spots.
    Gas that is inert relative to the catalyst, such
    0 as nitrogen or argon, is used to transfer a partially or fully reduced starting material and any additional activator compound or non-gaseous modifier that must be introduced into the bed.
    The rate of formation of the layer is controlled by the rate of catalyst input. Productivity can be increased by simply increasing the catalyst introduction rate and decreasing by decreasing it.
    BECAUSE any change in the rate of introduction of the catalyst changes the rate of heat generation for the reactor, the temperature and / or the flow rate of the refrigerant in the internal refrigerator is adjusted from above or below in order to adapt this change to the heat generation rate. This ensures the maintenance of almost constant temperature in the layer. In order to cure any temperature change in the bed, perfect gearing of both the fluidized bed and the internal cooling system is necessary in order to enable the operator to adjust the temperature and / or coolant flow accordingly.
    For a given combination of working conditions, the fluidized bed maintains almost constant height by removing part of the bed as a product at a rate equal to the rate of formation of polymer powder. Since the rate of heat generation is directly related to the formation of the product, measuring the rise in temperature of the refrigerant in the reactor (the difference between the inlet and outlet temperatures of the refrigerant) limits the rate of formation of polymer powder at a constant rate of refrigerant. The polymer powder is in progress during the next operation through a couple automatic valves 12 and 13 defining the separation zone 13. When the valve 13 is closed, the gas passes through line 15. Thereafter, the valve 13 opens to release the product into the outdoor return zone. The valve 13 is then closed until the next product return operation.
    In addition, the fluidized bed reactor is equipped with an adequate purge system to ensure that the bed is purged at the beginning and at the end of the process. The reactor does not require the use of mixing devices and / or scraper devices.
    A highly active catalyst system with a carrier provides a fluidized product with an average particle size of 100-1500 microns /
    preferably about 500-1000 microns.
    I
    In order to have a good process flow, the coolants must be loaded into the fluidized part of the reactor bed 1. If the coolants are 5 tbs above or below the fluidized bed, the particles will settle on inclined surfaces, and since the particles contain an active catalyst, they will grow and the formation of lumps of solid, limer, which will hinder or stop the operation of the reactor.
    Cooling agent using-. In the reactor, it can be a cooler or a heat exchanger. Constructions
    coolant is such that the cross-sectional area of the coolant does not reduce the free cross-section of the layer so that it is 10 times
    1fe. An increase in the local surface velocity compared to the minimum fluidization rate. The cross-sectional area suitable for flow at the point where the area of the living section
    the internal refrigerator is the most, most consistent with the minimum free. cross-sectional area. Re.aktor can work at a ratio of diameter and height within
    1: 1-1: 10. The minimum depth of the fluidized bed depends on the design of the distribution grid and the size of the bubbles, and not on the diameter of the reactor, while the height of transfer cessation is a complex function of the distribution of particle sizes, gas velocity, particle density, gas density and other factors. Properties of the obtained polymers
    determined using the following research methods.
    When measuring the density for materials whose density / O, 940 g / cm, use the method of ASTM-1505, and
    the plate is held for 1 hour to achieve equilibrium transparency. For materials whose density is 0.940 g / cm, the modified method is used, with
    wherein the test plate was incubated for 1 hour at 120 ° C in order to achieve equilibrium transparency and then rapidly cooled to room temperature.
    Melt Index (Ml) is determined
    by the method of ASTM D-1238, condition E, at 190.C.
    The spreading rate (.H1M1) is determined by Le method ASTM D-1238, condition F, with a weight exceeding 10 times
    the weight used in the above definition of the index melted.
    The yield of the product in one pass per unit of time per unit volume of contact space is determined in kilograms of polymer obtained in one hour per 1 m of bed volume.
    Getting a catalyst. Catalyst A. To a solution of the required amount of CrO in 3 liters of distilled water, 500 g of a porous silica carrier with an average particle size of about 70 µm and a specific surface area of about 300 is added. The mixture of carrier and the dodes are mixed and allowed to stand for a minute, then
    Filtered to remove 2200-2300 ml of solution. Saturated
    SgO silicon dioxide is dried
    in a stream of nitrogen for 4 h at.
    About 400 g of precipitated on a carrier With a gO Turn into a slurry in about 2000 MP of dry isopentane and the required amount of tetra- (i-propyl) titanate is added to the slurry. The system is thoroughly mixed, after which the isopentane is dried by heating the reaction vessel.
    The dried material is transferred to an activator that heats the vessel, add the required amount (NN4) 251 F, and mix. The composition is heated under Ng for 1 hour and then for hours to ensure complete removal of isopentane and for the gradual removal of organic residues from the tetra- (isopropyl) titanate in order to avoid any fire hazard. The Ng stream is then replaced with a stream of dry air and the catalytic composition is subjected to activation at 300 for / V 8 hours and then at 825 ° C for the same time. The activated catalyst is cooled with dry air (at ambient temperature) to about and further from 150 ° C to room temperature with MI (at ambient temperature).
    The following are the amounts of chromium, titanium and fluorine compounds that are added to provide the required levels of these elements in the activated catalyst.
    Amount of compound added to carrier, wt.%:
    0.6
    SgO
    Ti (O-isopropyl 26 1.2
    (NN4) 5.5 FJ
    The content of the element in the activated catalyst, wt.%: Cg0,3
    Ti4,2
    F0,6
    Catalyst B. About 2000 g of carrier — porous silicon dioxide with an average particle size of about 300 m / g — is dehydrated in an activator (heating vessel). The silicon dioxide is heated to for 2 hours and then to within / v8. The dehydrated silica is cooled to room temperature by passing dry N through and filling it with nitrogen. A portion of the dehydrated silica, equal to 462 g, is converted to sludge in 400 ml. dry isopentane while 350 m (approximately 15 wt.%) of bis-cyclopentadienyl chromium (1g) (chromocene) in toluene is added and stirred for one hour in a closed vessel without evaporation of isopentane. The catalyst was dried for 30 hours by purging with Nfi and stored in NJI. The finished catalyst contains about 6 chromocene.
    Catalyst C. The catalyst was prepared by adding 1000. g of dewatered silica as described for Catalyst B to 5500 ml of dry isopentane at. The resulting slurry is stirred for 30 minutes, then 30 g of bis-triphenylsilyl chromate is added to the slurry and stirring is continued for 10 hours over a 30-minute period. 200 ml of a 20% solution of diethyl 5 aluminum ethoxide in hexane are added. Stirring is continued for an additional 4 hours, after which it is stopped and the liquid is filtered off from the catalyst. Stirring then begin
    0 again, the catalyst is dried for 24 hours with a slight purge and left in Nj. The finished catalyst contains about 3% by weight of bis-triphenylphenylyl chromate.
    5 and its molar ratio Af / Cr is about 6: 1.
    Catalyst oh
    Getting soaked starting material.
    0
    In a 12-liter flask equipped with a mechanical stirrer, ps 41.8 g (0.439 mol) anhydrous and 2.5 l of tetrahydrofuran (THF) are added. To this mixture, 27.7 g are added to the mixture for 1/2 h (0.184 mol) TiC. May be necessary | heat the mixture for about 1/2 hour to completely dissolve the material. Next, 500 g of porous silicon dioxide is added and the mixture is stirred for 1/4 h. The mixture is dried by flushing with N2 for v3-5 h to obtain a dry free flowing powder with a particle size of silicon dioxide. The absorbed composition of the original substance has the formula
    , o (THF) Activation operations.
    The required weight quantities of the feed composition of the starting material and the activator are added to the mixer along with sufficient amounts of an aliphatic hydrocarbon-free diluent, such as isopentane,
    5 to create a slurry system. The compounds of the activator and the starting material are used in such amounts as to obtain a partially activated composition of the starting material, the ratio in which A f / T is 0-10, preferably 4-8.
    The contents of the slurry system are then thoroughly mixed at room temperature and atmospheric pressure for 1 / 4-1 / 2 hours. The resulting slurry is dried by purging with a dry inert gas, such as nitrogen or argon, at atmospheric pressure and to remove the hydrocarbon diluent. This process typically requires about an hour. The catalyst formed is in the form of a partially activated starting material that is impregnated inside the pores of the silica. The material is a free flowing flash that has the size and shape of silica particles. It is not pyrophoric if the content of alkyl aluminum does not exceed a content of 10% by weight, is stored under a dry inert gas, such as nitrogen or argon, until further use.
    In order to complete the activation of the starting material composition, an additional activator compound is introduced into the reactor as a diluted solution in a hydrocarbon diluent such as isopentane. In these diluted solutions, 5-30 vol.% Of activator is contained. The activator compound is added to the polymerization reactor in order to maintain the A C / T ratio in the reactor at about 10-400, before: 15-60: 1.
    For the implementation of the method, a reactor similar to the reactor shown in the drawing is used, with an internal diameter of about 35 cm and a height of about 8 m. The gas velocity is 4-6 G ,, pressure 21.0 kgf / cm. The internal refrigerator consists of four vertical loops about 1.2 m long, made of stainless steel steel pipe with a diameter of 2.54 cm, through which softened water is passed as a refrigerant. A portion of the line between the compressor and the reactor is placed in a jacket to remove the heat generated by the circulation compressor.
    Example 1. An internal chilled nickname was replaced with an external one-way vertical shell-and-tube cooler, in which the recycle gas passes through the tubes and the softened water enters the body. A reactor with an external heat exchanger was used for the copolymerization of ethylene with butene-1 or propylene for two years. During the first year 1 | It was necessary to shut down the reactor 15 times to clean the external heat exchanger from the polymer deposited from the remaining particles. polymer, while in the second year it took 17 stops. During this two-year period of operation, cat 1Lyzzers A, B and C were used in the reactor.
    Example 2. The reactor used in Example 1 was the same.
    van to the reactor shown in the drawing, by eliminating the external heat exchanger and installing the internal refrigerator, as described in the outlets. This reactor was used for the copolymerization of ethylene with butene-1 or propylene and operated for 11 months, during which due to the internal refrigerator there was not a single stop. During . during this period, catalysts and D were used in the reactor.
    Catalyst A was loaded into the reactor at a gas velocity exceeding 5 times and a pressure of 21.0 kgf / cm. The catalyst contained 0.3 wt.% Cr, 4.2 wt.% Tt, and 0.6 wt.% F.
    Reaction conditions:
    Temperature, with 87.5
    The molar ratio of C4H9 / C H9 0.10
    Layer level, m 2.4
    Product yield
    kg / h / m 800
    Properties of polkmera: Melt index, 0.20
    g / 10 min
    Spread speed21, 8
    neither
    Density, g / cm 0.919 Average size
    965
    particles, micron
    Volume weight,
    , 39
    Catalyst B was loaded into the reactor at a gas velocity 4 times as high as 4 ° C and a pressure of 21.0 kgf / cm for the copolymerization of ethylene and propylene. The catalyst contained about 1.7 wt.% Cg.
    Reaction Conditions: Temperature, 95 ° C
    Molar ratio
    С5Нб / СгН40,15
    Molar ratio
    ,, 0.04
    Layer level, m 1,5
    Product yield, kg / h / m 563
    Polymer properties:
    Melt index, g / 10 min 1.7 Flow rate 33.4
    Density, g / cm 0.953
    The average size
    particles, micron, 810
    Volume weight, g / cm
    0.39
    The reactor operated uninterruptedly on catalyst B under these conditions for 26 hours.
    Catalyst C was loaded into the reactor at a gas velocity that was b times higher than Gj, J, c, at a pressure of 21.0 kgf / cm for the copolymerization of ethylene and butene-1, The catalyst contained 0.3 wt.% Cr and 0.9 wt. .% BUT.
    Reaction Conditions: Temperature, s 103
    Molar ratio
    Molar ratio
    ,
    Layer level, m
    Product yield
    kg / h / m
    Polymer properties:
    Melt Index
    g / 10 min
    Spreading speed
    Density, g / cm
    The average size
    660
    particles, micron
    Volume weight,
    g / cm
    0.40
    The reactor operated uninterruptedly on catalyst C under these conditions for 24 hours.
    Catalyst D was loaded into the reactor at a gas velocity of 4–6 times the higher bdsch, and at a pressure of 21.0 kgf / cm for the copolymerization of eleane and butene-1. The catalyst contained 1.0 wt.% Ti, 3.4 wt.% Md and about 9 wt.% THF.
    Reaction conditions:
    Temperature, C
    85
    Molar ratio
    0.42, С4НЗ / С2Н4
    Nano ratio
    0.26
    Ng / CgN, 1.5
    Layer level, m
    Product yield
    kg / h / m
    500
    Polymer properties:
    Melt Index
    1.87
    g / 10 gd 47.4
    Spreading speed
    Density, g / cm 0.927
    The average size
    965 0.25
    particles, um,
    Volume weight, g / cm
    The reactor operated uninterruptedly on catalyst D under these conditions for 16 hours.
    权利要求:
    Claims (2)
    [1]
    1. A method of producing powdered polyolefins by continuous gas-phase copolymerization of ethylene with propylene or butene-1 at 85-103 C and a pressure of 21 kgf / cg in the presence of supported chromium or titanium catalysts when
    the process in the fluidized bed of copolymer particles in the vertical cylindrical zone and the gas flow through the fluidized bed, 4-6 times the minimum mass velocity,
    0 necessary for fluidization, characterized in that, in order to prevent crust formation on the inner surfaces of the reaction zone, the heat of reaction is removed by means of.
    5 internal cooling devices in the lower part of the reaction zone.
    one.
    [2]
    2. Installation for the implementation of the method of obtaining pseudoobraznyh
    0 polyolefins, made in the form of a vertical cylindrical apparatus with a cooling unit, to remove the reaction heat and the recycle line of unreacted gases,
    5 wherein the apparatus is provided with fittings for withdrawing recycle gases in the apparatus lid, for introducing recycle gases and fresh gas in the bottom of the apparatus and for outputting the target product, as well as a distribution grid for creating a fluidized bed of copolymer particles in the lower part of the apparatus located in the same plane with fitting for outputting target
    5 of the product above the nozzle for the introduction of recycle gases, which means that, in order to prevent crust formation on the inner surfaces of the reaction zone, the cylindrical apparatus has the same diameter throughout its height, and the cooling device is designed as a coil with a refrigerant circulating in it and located inside the apparatus in the lower part above the distribution grid.
    Sources of information taken into account in the examination
    1. Australian patent 445455, cl. 9.4-22, published 1974.
    2. US patent 4003712, CL. 23-288, publish. 1977 (prototype).
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US05/964,989|US4255542A|1978-11-30|1978-11-30|Exothermic polymerization in a vertical fluid bed reactor system containing cooling means therein and apparatus therefor|
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