CN117085606A - Production device and production method of high-impact-resistance copolymerized polypropylene product - Google Patents

Production device and production method of high-impact-resistance copolymerized polypropylene product Download PDF

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CN117085606A
CN117085606A CN202310897655.2A CN202310897655A CN117085606A CN 117085606 A CN117085606 A CN 117085606A CN 202310897655 A CN202310897655 A CN 202310897655A CN 117085606 A CN117085606 A CN 117085606A
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reactor
polypropylene
outlet
inlet
propylene
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张毅
崔忠
刘立新
李建
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Beijing Xinmeige Engineering Design Co ltd
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Beijing Xinmeige Engineering Design Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a production device and a production method of a high impact copolymer polypropylene product, wherein the production device comprises a prepolymerization reactor, a loop liquid phase reactor, an intermediate flash separation system, a dehydrogenation and conveying system, a horizontal gas phase reactor, a powder post-treatment system, an additive and a granulating system which are connected in sequence. The production device, the process flow and the new additive formula solve the problem that the quality of the impact-resistant copolymerized polypropylene product produced by the existing loop process is poor, and also overcome the defect that the impact-resistant copolymerized polypropylene product cannot be produced by the existing liquid-phase loop reactor and horizontal stirring gas-phase reactor process, and can produce the high-quality high-impact-resistant copolymerized polypropylene product.

Description

Production device and production method of high-impact-resistance copolymerized polypropylene product
Technical Field
The invention relates to a production device and a production method of a high-impact-resistance copolymerized polypropylene product, in particular to a production device and a production method for producing high-impact-resistance copolymerized polypropylene resin by a propylene multistage polymerization process and an additive granulation process combined by loop liquid phase bulk polymerization and horizontal reactor gas phase polymerization, and belongs to the technical field of petrochemical industry.
Background
Polypropylene is a semi-crystalline thermoplastic plastic, and is a polymer obtained by copolymerizing propylene serving as a polymerization monomer and one or more alpha-olefins such as ethylene, butene-1 and the like. The polypropylene product has good processing and application properties, and is widely applied to various product fields such as automobiles, electric appliances, daily necessities, furniture, packaging, medical treatment and health. The high-flow high-impact copolymerized polypropylene is widely applied to automobile interior trim parts, daily necessities, small household appliance shells and the like, and the demand of the high-flow high-impact copolymerized polypropylene product is greatly increased along with the rapid development of industries such as automobiles, household appliances and the like, so that the high-impact copolymerized polypropylene product becomes a great hotspot in the field of polyolefin material research and development and application with respect to the preparation and application of the high-flow high-impact copolymerized polypropylene product.
The method for producing the impact copolymerization product by adopting a loop reactor, a slurry vaporization sleeve, a medium pressure degassing filter and a gas-phase fluidized bed reactor in the existing loop process has the following problems:
1. The fluidized bed reactor has small volume and short material residence time, and can not produce high-impact copolymerization products;
2. the materials of the high-impact copolymerization product are sticky, the fluidized bed reactor is easy to stick to a kettle, and the high-impact copolymerization product is not suitable for production;
3. the fluidized bed reactor is a full mixed flow reactor, and the conditions of partial uneven mixing of materials exist, so that the produced impact-resistant product has low quality;
4. the ethylene polymerization rate is 3.5 times of the ethylene-propylene polymerization rate, and the fluidized bed reactor lacks a polymerization inhibition system, so that more ethylene is polymerized to generate polyethylene instead of ethylene and propylene to generate a block ethylene propylene rubber component, and the impact strength of the impact-resistant product is low;
5. the dehydrogenation effect of the medium-pressure filter is poor, the hydrogen amount entering the fluidized bed reactor from the medium-pressure filter is large, and excessive hydrogen is used as a chain transfer agent to enter the gas phase reactor, so that the molecular weight and the intrinsic viscosity IV of the rubber phase EPR generated by the copolymerization reaction are low, the impact strength of the product is low, and the quality of the impact copolymerization product is poor.
The above causes that the existing loop process cannot produce high-performance high-impact copolymerized polypropylene products.
Currently, impact copolymer product 1 produced on the market using the loop process: melt index 8.0g/10min, rubber content 19.2% (EPR%/CryteQC method), TS yield strength 23.0MPa, FM flexural modulus 1230MPa, IZ (notched impact at ambient temperature) 15kJ/m 2 ；
Impact copolymer product 2: melt index 22.0g/10min, rubber content 27.0% (EPR%/CryteQC method), TS yield strength 21.5MPa, FM flexural modulus 1100MPa, IZ (Normal temperature notched impact) 40.0kJ/m 2 ；
Impact copolymer product 3: 33.0g/10min melt index, 19.5% rubber content (EPR%/CryteQC method), 25.0MPa TS yield strength, 1250MPa FM flexural modulus, 8.0kJ/m IZ (Normal temperature notched impact) 2 。
From the above data, it can be seen that the impact copolymer product produced by the loop process is low in terms of rubber phase content (rubber phase content is usually less than 30% (wt)), and also in terms of flexural modulus, impact strength, etc.
Chinese patent CN201911379654 reports a method for producing homo-or random co-polypropylene products using a liquid phase loop reactor + a horizontal stirred gas phase reactor. The patent adopts a liquid phase loop reactor to be directly connected with a horizontal gas phase reactor, slurry of the liquid phase loop reactor directly enters the horizontal gas phase reactor, a separation and conveying system between the two reactors is absent, and reaction components in the second reactor cannot be controlled, so that the method cannot produce an impact copolymer polypropylene product.
Chinese patent CN202222829671 reports a propylene polymerization apparatus employing a liquid phase polymerization unit (loop reactor) +an intermediate separation unit (two cyclones connected in parallel) +a gas phase polymerization unit (horizontal reactor), wherein two stages of cyclones are added to the liquid phase loop reactor and the horizontal gas phase reactor, slurry (liquid propylene+polypropylene powder solid) from the liquid phase loop reactor enters the cyclones, the liquid propylene is partially vaporized by flash evaporation, and the materials enter the horizontal reactor after gas, liquid and solid three-phase separation in the cyclones. The slurry (liquid-phase propylene and polypropylene powder solid) from the liquid-phase loop reactor enters a cyclone separator, and then part of liquid-phase propylene is gasified rapidly, so that the operation conditions in the cyclone separator are fluctuated severely, the three-phase separation effect of gas, liquid and solid in the cyclone separator is poor, a large amount of gas-phase and liquid-phase reactants enter a horizontal gas-phase reactor along with polypropylene powder, the reaction components in the horizontal gas-phase reactor cannot be controlled at all, and the effective impact copolymerization reaction cannot be carried out to generate a qualified rubber phase, so that the propylene polymerization device cannot produce impact copolymerization polypropylene products.
Therefore, the invention provides a novel production device and a novel production method for producing high-performance high-impact-resistance polypropylene copolymer products, which have important research significance and practical production value, and meanwhile, the quality of the impact-resistance polypropylene copolymer products produced by the existing loop pipe device is improved by the method, so that the novel activity and competitiveness are brought to a plurality of loop pipe devices, and the novel production device has extremely important economic value and social value.
Disclosure of Invention
First, the technical problem to be solved
The invention aims at solving the problems existing in the prior art and provides a production device and a production method of a high-impact-resistance copolymerized polypropylene product; the production device, the process flow and the new additive formula solve the problem that the quality of the impact-resistant copolymerized polypropylene product produced by the existing loop process is poor, and also overcome the defect that the impact-resistant copolymerized polypropylene product cannot be produced by the existing liquid-phase loop reactor and horizontal stirring gas-phase reactor process, and can produce the high-quality high-impact-resistant copolymerized polypropylene product.
(II) technical scheme
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention relates to a production device of a high impact copolymer polypropylene product, which comprises a prepolymerization reactor, a loop liquid phase reactor, an intermediate flash separation system, a dehydrogenation and conveying system, a horizontal gas phase reactor, a powder post-treatment system, an additive and a granulating system which are connected in sequence.
Wherein the prepolymerization reactor: a tubular or kettle type prepolymerization reactor is adopted.
Wherein, the loop liquid phase reactor adopts a single loop or double loop reactor.
The intermediate flash separation system is formed by connecting a flash evaporation line consisting of a plurality of sections of jacket pipes heated by steam and a medium-pressure filter in series.
Wherein, the dehydrogenation and conveying system consists of a plurality of groups of dehydrogenation and conveying units.
The horizontal gas phase reactor consists of a reactor cylinder, 1-2 domes for gas-solid separation, a stirrer, a reactor front end and rear end sealing system, a quenching liquid distributor, a circulating gas distributor, a driving motor and a speed reducer, wherein the domes are fixed at the top of the reactor cylinder, the stirrer is arranged inside the reactor, the reactor front end and rear end sealing system are respectively arranged at the front end and the rear end of the stirrer, the quenching liquid distributor is arranged at the upper part of the reactor, the circulating gas distributor is arranged at the lower part of the reactor, one end of the speed reducer is connected with the driving end of the stirrer, and the other end of the speed reducer is connected with the driving motor.
Wherein the horizontal gas phase reactor is a plug flow type plug flow reactor.
The length-diameter ratio of the horizontal gas phase reactor cylinder is 2-8:1, a step of; the rotation speed of the stirrer is 5-25rpm; the stirrer blade adopts a paddle type or a gate type, etc.
The quenching liquid distributor adopts a conical, spiral or rotary liquid distributor and is used for atomizing the quenching liquid into mist drops; the circulating gas distributor adopts an annular gas distributor and is used for uniformly distributing the circulating gas in the bed layer.
Wherein, the powder aftertreatment system: consists of a low-pressure filter, a steam stripper and a nitrogen dryer; the inlet of the low-pressure filter is connected with the discharge port of the horizontal gas phase reactor, the outlet of the low-pressure filter is connected with the inlet of the steam stripper, the outlet of the steam stripper is connected with the inlet of the nitrogen dryer, and the outlet of the nitrogen dryer is connected with the inlet of the polypropylene powder rotary feeder in the additive system.
Wherein the additive and granulating system consists of an additive system and an extrusion granulating system; the additive system consists of a polypropylene powder rotary feeder, a polypropylene powder metering scale, a solid additive feeding hopper, a solid additive tank, a stirrer, a solid additive metering scale and a spiral mixer; the polypropylene powder rotary feeder adopts a star-shaped and annular balance type for conveying the polypropylene powder; the polypropylene powder metering scale adopts an impact plate type or a Coriolis type and is used for metering the polypropylene powder; the solid additive metering scale adopts a weightless type and is used for metering the solid additive; the spiral mixer adopts a single-screw or double-screw mixer and is used for uniformly mixing the polypropylene powder and the solid additive.
The inlet of the polypropylene powder rotary feeder is connected with the outlet of a nitrogen dryer in the powder aftertreatment system, the outlet of the polypropylene powder rotary feeder is connected with the inlet of a polypropylene powder metering scale, the outlet of the polypropylene powder metering scale is connected with the inlet of a spiral mixer, various additives are manually added into a solid additive charging hopper, the outlet of the solid additive charging hopper is connected with the inlet of a solid additive tank, the outlet of the solid additive tank is connected with the inlet of the solid additive metering scale, a stirrer is stirred in the solid additive tank to prevent solid additives from accumulating and bridging to influence conveying, the outlet of the solid additive metering scale is connected with the inlet of the spiral mixer, polypropylene powder and various additives are uniformly mixed in the spiral mixer, and the outlet of the spiral mixer is connected with the inlet of an extruder;
the extrusion granulating system consists of an extruder, a dryer, a dehumidifying fan, a vibrating screen, a granulating water filter, a granulating water tank, a granulating water cooler and a granulating water pump; the extruder adopts a double screw type; the dryer adopts a centrifugal type; the dehumidifying fan adopts a centrifugal type; the vibrating screen is linear; the grain cutting water filter adopts a basket type; the grain cutting water tank is square or round; the grain cutting water cooler adopts a plate type; the granulating water pump adopts a centrifugal type.
The extruder inlet is connected with the outlet of the spiral mixer, polypropylene powder and additives are subjected to shearing mixing, extrusion and underwater granulating in the extruder to obtain polypropylene granules, the extruder outlet is connected with the inlet of the dryer, the material outlet of the dryer is connected with the inlet of the vibrating screen, the inlet of the dehumidifying fan is connected with the outlet of the dryer, the outlet of the granulating water outlet of the dryer is connected with the inlet of the granulating water filter, the outlet of the granulating water filter is connected with the inlet of the granulating water tank, the outlet of the granulating water tank is connected with the inlet of the granulating water cooler, the outlet of the granulating water cooler is connected with the inlet of the granulating water pump, and the outlet of the granulating water pump is connected with the extruder.
The inside of the central tube of the steam jacket tube is polypropylene slurry, and the inside of the jacket is steam; polishing in the central tube, wherein the polishing precision is Ra0.8-Ra6.4; the elbow is a 5D-15D large-radius elbow; the length of each jacket pipe clamp sleeve is 2-10 m.
The medium-pressure filter consists of an equipment cylinder, a filter element and a back-flushing system, wherein the filter element is fixed on the upper part of the equipment cylinder, and the back-flushing system is positioned between the filter element and an upper end socket of the equipment cylinder.
Each group of dehydrogenation and conveying units consists of a degassing tank, an ejector, a group of switching valves and a gas-phase fresh propylene pipeline.
The degassing tank is respectively connected with a medium-pressure filter, a horizontal gas phase reactor, a switching valve, an ejector and a gas phase fresh propylene pipeline in the intermediate flash separation system, and the ejector is respectively connected with the degassing tank, the medium-pressure filter, the switching valve and the gas phase fresh propylene pipeline in the intermediate flash separation system.
The low-pressure filter consists of an equipment cylinder, a filter element and a back-flushing system, wherein the filter element is fixed on the upper part of the equipment cylinder, and the back-flushing system is positioned between the filter element and an upper end socket of the equipment cylinder.
The steam stripper comprises an equipment cylinder, a steam jacket, a steam distribution plate, a stirrer sealing system, a driving motor and a speed reducer, wherein the steam jacket is arranged outside the equipment cylinder, the steam distribution plate is positioned at the lower part of the equipment cylinder, the stirrer is arranged inside the equipment cylinder, the stirrer sealing system is arranged at the driving end of the stirrer, one end of the speed reducer is connected with the driving end of the stirrer, and the other end of the speed reducer is connected with the driving motor. Steam stripper barrel aspect ratio is 2-8:1, a step of; the rotational speed of the stirrer is 2-10rpm; the steam distribution plate is a tongue-shaped distribution plate; the stirrer blade adopts a paddle type or a gate type, etc. The polypropylene powder enters from the top of the steam stripper, low-pressure steam at 100-120 ℃ enters from the bottom of the steam stripper, and contacts with the polypropylene powder in a countercurrent way through a steam distribution plate, so that the catalyst is deactivated by the steam, and hydrocarbons and oligomers in the polypropylene powder are thoroughly removed; low pressure steam is introduced into the steam jacket, and the operation temperature of the steam stripper is maintained at 80-120 ℃.
The nitrogen dryer consists of an equipment cylinder body, a dipleg and two layers of hot nitrogen distribution plates, wherein the dipleg is arranged below a lower end socket of the equipment cylinder body, one layer of hot nitrogen distribution plate is positioned at the lower part of the equipment cylinder body, and the other layer of hot nitrogen distribution plate is positioned at the lower part of the dipleg. The length-diameter ratio of the nitrogen dryer cylinder is 2-5:1, a step of; the hot nitrogen distribution plate is a tongue-shaped distribution plate. The water-containing polypropylene powder enters from the top of a nitrogen dryer, hot nitrogen at 90-130 ℃ enters from the bottom of the nitrogen dryer, and the hot nitrogen is in countercurrent contact with the water-containing polypropylene powder through a hot nitrogen distribution plate to remove the water in the polypropylene powder; the operating temperature of the nitrogen drier is 80-120 ℃.
The invention relates to a production method of a production device for producing a high-impact-resistance copolymerized polypropylene product, which comprises the following steps:
(1) A prepolymerization reactor: propylene is taken as a prepolymerized monomer, and liquid phase bulk prepolymerization reaction is carried out in a prepolymerization reactor under the combined action of a Z-N catalyst, alkyl aluminum and an external electron donor;
(2) Loop liquid phase reactor: feeding the prepolymerization slurry obtained in the step (1) into a loop liquid phase reactor, and carrying out liquid phase propylene homopolymerization in the loop reactor by taking liquid phase propylene as a monomer;
(3) Intermediate flash separation system: heating and gasifying liquid-phase propylene in a flash evaporation line to obtain slurry consisting of homopolymerized polypropylene powder, liquid-phase propylene and hydrogen in a loop liquid-phase reactor in the step (2), and then carrying out gas-solid separation on the homopolymerized polypropylene powder and reaction gas consisting of propylene and hydrogen in a medium-pressure filter;
(4) Dehydrogenation and delivery system: further removing hydrogen carried by the polypropylene powder in a dehydrogenation and conveying system by the homo-polymerization polypropylene powder and entrained reaction gas obtained by the separation of the intermediate flash separation system in the step (3), and conveying the powder to a horizontal gas phase reactor;
(5) Adding propylene, ethylene and hydrogen into a horizontal gas phase reactor to carry out a block copolymerization reaction of propylene and ethylene to generate an ethylene propylene rubber phase copolymer; because hydrogen carried in polypropylene powder is removed in the dehydrogenation and conveying system in the step (4), the ratio of hydrogen to ethylene to propylene in the reactor can be effectively controlled in the horizontal gas phase reactor, so that the intrinsic viscosity value of a rubber phase in an impact copolymerization product is improved, and the impact strength and the impact copolymerization product quality of the copolymerization product are improved; meanwhile, inhibitors such as low-purity oxygen and the like are added into the reaction system to prevent unwanted ethylene polymerization reaction from generating polyethylene products, so that the content of ethylene propylene copolymer generated by block copolymerization of propylene and ethylene is improved, and the shock resistance of the products is improved.
(6) And (3) carrying out gas-solid separation on the polypropylene powder from the horizontal gas phase reactor in the step (5) and byproducts of reaction gas, catalyst and oligomer, deactivating the catalyst, and removing the oligomer from the powder.
(7) Additive and granulating system: the additives and the granulating system are added with a plurality of additives such as a main antioxidant, an auxiliary antioxidant, a nucleating agent, an acid absorbent and an antistatic agent into the polypropylene powder, the additives and the polypropylene powder processed by the powder post-treatment system in the step (6) are fed into the granulating system after being precisely metered and proportioned, and finally the polypropylene granular product with high shock resistance is obtained through shearing mixing, extrusion and granulating actions of a double-screw extruder.
According to the method of the invention, the primary antioxidant and the secondary antioxidant are used for protecting the polypropylene high polymer material from degradation. The main antioxidant is one of Irganox 1330, ethanox 330, irganox 1010, irganox 1076, irganox 3114 and Irganox 1790, preferably Irganox 1330, irganox 1010 and Irganox 3114, and more preferably Irganox 1010; the weight ratio of the polypropylene powder amount to the main antioxidant addition amount is 1000: (0.3 to 2.0), preferably 1000: (0.5 to 1.5), and more preferably 1000: (0.5-1.0). The auxiliary antioxidant is one of Irgafos 168, lowinox DSTDP, HP136, triphosphite, 626 and PEPQ, preferably Irgafos 168, lowinox DSTDP, HP136 and 626, and more preferably Irgafos 168; the weight ratio of the polypropylene powder to the auxiliary antioxidant is 1000: (0.3 to 2.0), preferably 1000: (0.5 to 1.5), and more preferably 1000: (0.5-1.0).
According to the method of the invention, the nucleating agent is a substance which plays a role of crystal nucleus in polypropylene crystallization, the heterogeneous nucleation of polypropylene is promoted by adding crystal nucleus to improve the crystallization speed and crystallinity, the size of crystal grains is changed, the crystal grains are further formed into spherulites, the polypropylene added with the nucleating agent contains a large number of tiny spherulites to form a miniature texture structure, and finally, the physical and mechanical properties of the nucleated polypropylene are greatly improved, including hardness and rigidity, heat distortion temperature, optical properties, crystallization temperature, i.e. processing period and the like. The nucleating agents include two classes: transparent nucleating agent and stiffening nucleating agent. According to the method of the present invention, the nucleating agent is preferably a stiffening nucleating agent. The stiffening nucleating agent is one of HPN-68L, HPN-20E, HPN-600ei, HPN-900ei, sodium benzoate, hydrated magnesium silicate, talcum powder, hydrotalcite (DHT-4A, AC207), calcium carbonate, substituted aluminum benzoate ALPTBBA, NAA-325, NAP-50, NA-11, NA-21, NA71, carboxylate (NAA 613, NAA 615), organic phosphate, rosin nucleating agent and amide nucleating agent, preferably substituted benzoate, carboxylate and aryl phosphate, and more preferably substituted aluminum benzoate and aryl phosphate; the weight ratio of the polypropylene powder to the addition of the stiffening nucleating agent is 1000: (0.1 to 1.5), preferably 1000: (0.2 to 1.2), and more preferably 1000: (0.3-1.0).
According to the method of the invention, the acid absorbent is used for absorbing residual acid chloride ions of the Z-N catalyst, reducing the yellow index of the product and eliminating the possible corrosiveness to downstream processing equipment. The acid absorbent is one of zinc oxide, calcium stearate, zinc stearate, hydrotalcite, sodium benzoate and hydroalcite DHT-4A, preferably calcium stearate, hydrotalcite, sodium benzoate and DHT-4A, and more preferably calcium stearate, hydrotalcite and sodium benzoate; the weight ratio of the polypropylene powder amount to the acid absorbent addition amount is 1000: (0.1 to 1.0), preferably 1000: (0.2 to 0.8), and more preferably 1000: (0.3-0.6).
According to the method of the present invention, an antistatic agent (lubricant) is used to reduce the polypropylene surface resistance, eliminate charge accumulation and dust collection. The antistatic agent (lubricant) is one of glyceryl monostearate (GMS 40, GMS90, etc.), oleamide, erucamide, calcium stearate, zinc stearate, ethoxyamine, polyvinyl alcohol and polyethylene wax, preferably glyceryl monostearate (GMS 40, GMS90, etc.), oleamide, erucamide, calcium stearate, zinc stearate and ethoxyamine, more preferably glyceryl monostearate (GMS 40, GMS90, etc.), erucamide; the weight ratio of the polypropylene powder amount to the addition amount of the antistatic agent (lubricant) was 1000: (0.1 to 2.0), preferably 1000: (0.2 to 1.5), and more preferably 1000: (0.3-1.0).
According to the method, propylene is taken as a prepolymerization monomer in the prepolymerization reactor, the prepolymerization temperature is 5-50 ℃, the prepolymerization pressure is 2-5 MPa, and the prepolymerization residence time is 1-30 min; the loop liquid phase reactor takes liquid phase propylene as a polymerization monomer to carry out homopolymerization reaction, the polymerization temperature is 40-80 ℃, the polymerization pressure is 2-5 MPa, and the polymerization residence time is 30-120 min; the intermediate flash separation system adopts low-pressure steam to heat and gasify polypropylene slurry, the operation temperature is 50-100 ℃, the intermediate pressure filter can also be a separation tank, the operation temperature is 50-100 ℃, and the operation pressure is 2-5 MPa; the horizontal gas phase reactor uses gas phase propylene, ethylene, butene-1 and other alpha-olefins as polymerization monomers to carry out block copolymerization reaction to produce a rubber phase with impact resistance, the polymerization temperature is 40-120 ℃, the polymerization pressure is 1.0-5.0 MPa, and the polymerization residence time is 20-100 min.
According to the process of the invention, the procatalyst is a Ziegler-Natta catalyst, tiCl 4 、TiCl 3 、CCl 3 、ZrCl 3 One of them.
According to the method of the present invention, the alkylaluminum is one of triethylaluminum, triisobutylaluminum, trimethylaluminum, tri-n-propylaluminum, tri-n-hexylaluminum, dimethylaluminum monochloride, ethylaluminum dichloride, diethylaluminum monochloride, di-n-propylaluminum monochloride, isobutylaluminum dichloride, diisobutylaluminum monochloride, n-hexylaluminum dichloride, dimethylaluminum hydride, diethylaluminum hydride, di-n-propylaluminum hydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride, methylaluminum hydride, ethylaluminum hydride, n-propylaluminum hydride, n-hexylaluminum monochloride, and aluminum dichloride hydride.
According to the method of the invention, the external electron donor is a silane compound, and is selected from one of methylcyclohexyldimethoxy silane, tetramethoxy silane, tetraethoxy silane, tetra-n-propoxy silane, tert-butyltrimethoxy silane, isopropyl trimethoxy silane, diisopropyl dimethoxy silane, n-propyl cyclopentyl dimethoxy silane, diphenyl dimethoxy silane, methyl tert-butyl dimethoxy silane, ethyl cyclopentyl dimethoxy silane, isopropyl cyclopentyl dimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silane and dicyclohexyldimethoxy silane.
According to the method of the invention, the inhibitor is one of low-purity oxygen and hydroxyethyl alkylamine, and the concentration of the low-purity oxygen in the horizontal gas phase reactor is 1-50ppm.
According to the inventionIn the prepolymerization reactor, the mol ratio of the main metal element to propylene in the main catalyst is 1 multiplied by 10 -7 ～1×10 -4 :1, preferably 1X 10 -6 ～1×10 -4 :1, a step of; the molar ratio of aluminum element in the aluminum alkyl to main metal element in the main catalyst is 5-500: 1, preferably 50 to 200:1, a step of; the molar ratio of aluminum element in the aluminum alkyl to the external electron donor is 1-50: 1, preferably 2 to 30:1.
According to the method of the invention, the comonomer in the horizontal gas phase reactor can be switched into one or more of ethylene, butene-1 and other alpha-olefins.
According to the method of the invention, the content of alpha-olefin such as ethylene in the impact copolymerization product is 5-30%, and the content of rubber phase produced by block copolymerization of propylene and alpha-olefin such as ethylene in the impact copolymerization product is 10-60%.
According to the method of the invention, the loop liquid phase reactor can be replaced by a kettle type liquid phase reactor.
According to the method of the invention, the horizontal gas phase reactor is not added with alpha-olefin such as ethylene, and only propylene and hydrogen are added, so that a homopolymerized polypropylene product can be produced.
Or according to the method of the invention, one or more of ethylene, butene-1 and other alpha-olefins are simultaneously added into the loop liquid phase reactor and the horizontal gas phase reactor, so that polypropylene products such as random copolymerization, ternary polymerization and the like can be produced.
(III) the beneficial effects brought by the technical scheme of the invention are as follows:
1. the invention can effectively perform impact copolymerization reaction to generate qualified rubber phase, thus being capable of producing impact copolymerization polypropylene products;
2. the invention solves the problem of poor quality of the impact copolymer polypropylene product produced by the existing loop process, also overcomes the defect that the impact copolymer polypropylene product cannot be produced by the existing liquid phase loop reactor and horizontal stirring gas phase reactor process, and can produce high-quality high-impact copolymer polypropylene product.
Drawings
Fig. 1 is a schematic structural view of the present invention.
In the figure:
1. a prepolymerization reactor; 2. a loop liquid phase reactor; 3. an intermediate flash separation system; 4. a dehydrogenation and delivery system; 5. a horizontal gas phase reactor; 6. a powder post-treatment system; 7. additive and granulating system.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Propylene (Daqing Haiding Material science, inc.), ethylene (Daqing Haiding Material science, inc.), hydrogen (Daqing Haiding Material, inc.), CS-shaped spherical TiCl 4 /MgCl 2 Supported catalyst (Yingkou city, catalyst Limited), triethylaluminum (Yingkou city, catalyst Limited), and cyclohexylmethyldimethoxysilane (Shandong Lu crystallization engineering Co., ltd.).
Example 1
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 3.5kg/h, the feeding amount of triethylaluminum is 5.5kg/h, and the feeding amount of cyclohexylmethyl dimethoxy silane is 0.8kg/h.
2) Loop liquid phase reactor: the prepolymerization slurry obtained in step 1) was directly fed into a loop liquid phase reactor, the reaction temperature was 73 ℃, the pressure was maintained at 3.9MPa, propylene and hydrogen were added at a hydrogen concentration of 2000ppmv, and the residence time was 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.2MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 25.0% (mol), the hydrogen concentration is 1.14% (mol), the oxygen concentration is 10ppm, and the propylene and ethylene gas phase polymerization is carried out for 40min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.6:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.6:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.6:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.4:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.5:1000.
The properties of the resulting polypropylene impact product are shown in Table 1.
Example 2
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 2.9kg/h, the feeding amount of triethylaluminum is 6.13kg/h, and the feeding amount of the cyclohexylmethyl dimethoxy silane is 1.0kg/h.
2) Loop liquid phase reactor: the prepolymerization slurry obtained in step 1) was directly fed into a loop liquid phase reactor, the reaction temperature was 70℃and the pressure was maintained at 3.6MPa, propylene and hydrogen were added at a hydrogen concentration of 4800ppmv and the residence time was 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.3MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 21.2% (mol), the hydrogen concentration is 1.32% (mol), the oxygen concentration is 12ppm, and the propylene and ethylene gas phase polymerization is carried out, and the residence time is 40min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.6:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.6:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.54:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.4:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.5:1000.
the properties of the resulting polypropylene impact product are shown in Table 1.
Example 3
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 2.5kg/h, the feeding amount of triethylaluminum is 6.0kg/h, and the feeding amount of the cyclohexylmethyl dimethoxy silane is 0.9kg/h.
2) Loop liquid phase reactor: directly inputting the prepolymerization slurry obtained in the step 1) into a loop liquid phase reactor, wherein the reaction temperature is 70 ℃, the pressure is maintained at 4.3MPa, propylene and hydrogen are added, the hydrogen concentration is 3000ppmv, and the residence time is 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.4MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 25.5% (mol), the hydrogen concentration is 1.0% (mol), the oxygen concentration is 10ppm, and the propylene and ethylene gas phase polymerization is carried out for 40min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.6:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.6:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.8:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.5:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.6:1000.
The properties of the resulting polypropylene impact product are shown in Table 1.
Example 4
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 2.5kg/h, the feeding amount of triethylaluminum is 6.0kg/h, and the feeding amount of the cyclohexylmethyl dimethoxy silane is 0.9kg/h.
2) Loop liquid phase reactor: the prepolymerization slurry obtained in step 1) was directly fed into a loop liquid phase reactor, the reaction temperature was 70℃and the pressure was maintained at 4.3MPa, propylene and hydrogen were added at a hydrogen concentration of 3300ppmv, and the residence time was 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.4MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 25.0% (mol), the hydrogen concentration is 1.2% (mol), the oxygen concentration is 13ppm, and the propylene and ethylene gas phase polymerization is carried out, wherein the residence time is 40min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.6:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.6:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 1.0:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.5:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.6:1000.
the properties of the resulting polypropylene impact product are shown in Table 1.
Example 5
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 2.5kg/h, the feeding amount of triethylaluminum is 6.0kg/h, and the feeding amount of the cyclohexylmethyl dimethoxy silane is 0.9kg/h.
2) Loop liquid phase reactor: the prepolymerization slurry obtained in step 1) was directly fed into a loop liquid phase reactor, the reaction temperature was 70℃and the pressure was maintained at 4.3MPa, propylene and hydrogen were added at a hydrogen concentration of 4000ppmv and the residence time was 70min.
4) Horizontal gas phase reactor: and (3) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.3MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 18.5% (mol), the hydrogen concentration is 1.35% (mol), the oxygen concentration is 11ppm, and the propylene and ethylene gas phase polymerization is carried out for a residence time of 35min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.7:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.7:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.6:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.5:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.6:1000.
The properties of the resulting polypropylene impact product are shown in Table 1.
Example 6
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 2.0kg/h, the feeding amount of triethylaluminum is 5.0kg/h, and the feeding amount of cyclohexylmethyl dimethoxy silane is 0.8kg/h.
2) Loop liquid phase reactor: the prepolymerization slurry obtained in step 1) was directly fed into a loop liquid phase reactor, the reaction temperature was 70℃and the pressure was maintained at 4.5MPa, propylene and hydrogen were added at a hydrogen concentration of 5600ppmv and the residence time was 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 75 ℃, the pressure is maintained at 2.5MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 18.0% (mol), the hydrogen concentration is 2.0% (mol), the oxygen concentration is 10ppm, and the propylene and ethylene gas phase polymerization is carried out for a residence time of 35min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.7:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.7:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.5:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.4:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.6:1000.
example 7
1) A prepolymerization reactor: a certain amount of liquid-phase propylene, 30% (wt) of catalyst slurry (white oil as a solvent), triethylaluminum and cyclohexylmethyl dimethoxy silane are added into a prepolymerization reactor for catalyst prepolymerization reaction, the operation temperature is 10 ℃, the residence time is 10min, the feeding amount of the liquid-phase propylene is 2400kg/h, the feeding amount of the main catalyst is 3.5kg/h, the feeding amount of triethylaluminum is 5.5kg/h, and the feeding amount of cyclohexylmethyl dimethoxy silane is 0.8kg/h.
2) Loop liquid phase reactor: directly inputting the prepolymerization slurry obtained in the step 1) into a loop liquid phase reactor, wherein the reaction temperature is 70 ℃, the pressure is maintained at 4.0MPa, propylene and hydrogen are added, the hydrogen concentration is 2500ppmv, and the residence time is 70min.
4) Horizontal gas phase reactor: and (2) feeding the homopolymerized polypropylene slurry obtained in the step (2) into a horizontal gas phase reactor after heating and gasifying, gas-solid separation and dehydrogenation of an intermediate flash separation system and a dehydrogenation and conveying system, wherein the reaction temperature is 70 ℃, the pressure is maintained at 2.4MPa, propylene, ethylene, hydrogen and low-purity oxygen are added, the ethylene content is 25.0% (mol), the hydrogen concentration is 1.0% (mol), the oxygen concentration is 15ppm, and the propylene and ethylene gas phase polymerization is carried out for 50min.
5) Additive and granulating system: after the polypropylene powder obtained in the step 4) is subjected to gas-solid separation, catalyst deactivation, oligomer removal and other treatments by a powder post-treatment system, the treated and clean polypropylene powder enters an additive and granulating system, and the weight ratio of the main antioxidant Irganox 1010 to the polypropylene powder is 0.7:1000, the weight ratio of the auxiliary antioxidant Irgafos 168 to the polypropylene powder is 0.7:1000, the weight ratio of the aluminum benzoate replaced by the nucleating agent to the polypropylene powder is 0.2:1000, the weight ratio of the calcium stearate of the acid absorbent to the polypropylene powder is 0.4:1000, the weight ratio of the amount of antistatic agent (lubricant) GMS40 to the amount of polypropylene powder is 0.4:1000.
The properties of the resulting polypropylene impact product are shown in Table 1.
TABLE 1
As can be seen from the above examples, the impact resistant product obtained by the apparatus and method for producing high impact resistant polypropylene copolymer product of the present invention has high rubber phase content, high TS yield strength and high FM flexural modulus, and high IZ (notched at ambient temperature) impact resistance.
Representative embodiments of the present invention have been described in detail. These detailed descriptions are not intended to limit the scope of the invention. Various modifications and equivalent arrangements of this invention will occur to those skilled in the art, and are intended to be within the spirit and scope of the invention.

Claims (10)

1. A production device of high impact copolymer polypropylene products comprises a prepolymerization reactor, a loop liquid phase reactor, an intermediate flash separation system, a dehydrogenation and conveying system, a horizontal gas phase reactor, a powder post-treatment system, an additive and a granulating system which are connected in sequence.
2. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the prepolymerization reactor: a tubular or kettle type prepolymerization reactor is adopted.
3. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the loop liquid phase reactor adopts a single loop or double loop reactor.
4. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the intermediate flash separation system is formed by connecting a flash evaporation line consisting of a plurality of sections of sleeve pipes heated by steam and a medium-pressure filter in series.
5. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the dehydrogenation and conveying system consists of a plurality of groups of dehydrogenation and conveying units.
6. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the horizontal gas phase reactor consists of a reactor cylinder body, 1 to 2 domes for gas-solid separation, a stirrer, a sealing system at the front end and the rear end of the reactor, a quenching liquid distributor, a circulating gas distributor, a driving motor and a speed reducer, wherein the domes are fixed at the top of the reactor cylinder body, the stirrer is arranged inside the reactor, the sealing system at the front end and the rear end of the reactor is respectively arranged at the front end and the rear end of the stirrer, the quenching liquid distributor is arranged at the upper part of the reactor, the circulating gas distributor is arranged at the lower part of the reactor, one end of the speed reducer is connected with the driving end of the stirrer, and the other end of the speed reducer is connected with the driving motor.
7. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the horizontal gas phase reactor is a plug flow type plug flow reactor.
8. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the powder post-treatment system comprises: consists of a low-pressure filter, a steam stripper and a nitrogen dryer; the inlet of the low-pressure filter is connected with the discharge port of the horizontal gas phase reactor, the outlet of the low-pressure filter is connected with the inlet of the steam stripper, the outlet of the steam stripper is connected with the inlet of the nitrogen dryer, and the outlet of the nitrogen dryer is connected with the inlet of the polypropylene powder rotary feeder in the additive system.
9. The apparatus for producing high impact copolymer polypropylene product according to claim 1, wherein: the additive and granulating system consists of an additive system and an extrusion granulating system; the additive system consists of a polypropylene powder rotary feeder, a polypropylene powder metering scale, a solid additive feeding hopper, a solid additive tank, a stirrer, a solid additive metering scale and a spiral mixer;
the inlet of the polypropylene powder rotary feeder is connected with the outlet of a nitrogen dryer in the powder aftertreatment system, the outlet of the polypropylene powder rotary feeder is connected with the inlet of a polypropylene powder metering scale, the outlet of the polypropylene powder metering scale is connected with the inlet of a spiral mixer, various additives can be added into a solid additive charging hopper, the outlet of the solid additive charging hopper is connected with the inlet of a solid additive tank, the outlet of the solid additive tank is connected with the inlet of the solid additive metering scale, a stirrer is stirred in the solid additive tank to prevent solid additives from accumulating and bridging to influence conveying, the outlet of the solid additive metering scale is connected with the inlet of the spiral mixer, polypropylene powder and various additives are uniformly mixed in the spiral mixer, and the outlet of the spiral mixer is connected with the inlet of the extruder;
The extrusion granulating system consists of an extruder, a dryer, a dehumidifying fan, a vibrating screen, a granulating water filter, a granulating water tank, a granulating water cooler and a granulating water pump;
the extruder inlet is connected with the outlet of the spiral mixer, polypropylene powder and additives are subjected to shearing mixing, extrusion and underwater granulating in the extruder to obtain polypropylene granules, the extruder outlet is connected with the inlet of the dryer, the material outlet of the dryer is connected with the inlet of the vibrating screen, the inlet of the dehumidifying fan is connected with the outlet of the dryer, the outlet of the granulating water outlet of the dryer is connected with the inlet of the granulating water filter, the outlet of the granulating water filter is connected with the inlet of the granulating water tank, the outlet of the granulating water tank is connected with the inlet of the granulating water cooler, the outlet of the granulating water cooler is connected with the inlet of the granulating water pump, and the outlet of the granulating water pump is connected with the extruder.
10. The method for producing a production apparatus for producing a high impact copolymer polypropylene product according to claim 1, comprising the steps of:
(1) A prepolymerization reactor: propylene is taken as a prepolymerized monomer, and liquid phase bulk prepolymerization reaction is carried out in a prepolymerization reactor under the combined action of a Z-N catalyst, alkyl aluminum and an external electron donor;
(2) Loop liquid phase reactor: feeding the prepolymerization slurry obtained in the step (1) into a loop liquid phase reactor, and carrying out liquid phase propylene homopolymerization in the loop reactor by taking liquid phase propylene as a monomer;
(3) Intermediate flash separation system: heating and gasifying liquid-phase propylene in a flash evaporation line to obtain slurry consisting of homopolymerized polypropylene powder, liquid-phase propylene and hydrogen in a loop liquid-phase reactor in the step (2), and then carrying out gas-solid separation on the homopolymerized polypropylene powder and reaction gas consisting of propylene and hydrogen in a medium-pressure filter;
(4) Dehydrogenation and delivery system: further removing hydrogen carried by the polypropylene powder in a dehydrogenation and conveying system by the homo-polymerization polypropylene powder and entrained reaction gas obtained by the separation of the intermediate flash separation system in the step (3), and conveying the powder to a horizontal gas phase reactor;
(5) Adding propylene, ethylene and hydrogen into a horizontal gas phase reactor to carry out a block copolymerization reaction of propylene and ethylene to generate an ethylene propylene rubber phase copolymer; because hydrogen carried in polypropylene powder is removed in the dehydrogenation and conveying system in the step (4), the ratio of hydrogen to ethylene to propylene in the reactor can be effectively controlled in the horizontal gas phase reactor, so that the intrinsic viscosity value of a rubber phase in an impact copolymerization product is improved, and the impact strength and the impact copolymerization product quality of the copolymerization product are improved; meanwhile, inhibitors such as low-purity oxygen and the like are added into the reaction system to prevent unwanted ethylene polymerization reaction from generating polyethylene products, so that the content of ethylene propylene copolymer generated by block copolymerization of propylene and ethylene is improved, and the shock resistance of the products is improved.
(6) And (3) carrying out gas-solid separation on the polypropylene powder from the horizontal gas phase reactor in the step (5) and byproducts of reaction gas, catalyst and oligomer, deactivating the catalyst, and removing the oligomer from the powder.
(7) Additive and granulating system: the additives and the granulating system are added with a plurality of additives such as a main antioxidant, an auxiliary antioxidant, a nucleating agent, an acid absorbent and an antistatic agent into the polypropylene powder, the additives and the polypropylene powder processed by the powder post-treatment system in the step (6) are fed into the granulating system after being precisely metered and proportioned, and finally the polypropylene granular product with high shock resistance is obtained through shearing mixing, extrusion and granulating actions of a double-screw extruder.
CN202310897655.2A 2023-07-21 2023-07-21 Production device and production method of high-impact-resistance copolymerized polypropylene product Pending CN117085606A (en)

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