CN108017733B - Catalyst material distribution device for olefin polymerization, distribution method and application - Google Patents
Catalyst material distribution device for olefin polymerization, distribution method and application Download PDFInfo
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- CN108017733B CN108017733B CN201610930941.4A CN201610930941A CN108017733B CN 108017733 B CN108017733 B CN 108017733B CN 201610930941 A CN201610930941 A CN 201610930941A CN 108017733 B CN108017733 B CN 108017733B
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
Abstract
The invention relates to a catalyst material distribution device for olefin polymerization, which comprises a catalyst storage tank, a catalyst feeding pump and a catalyst material distribution system which are communicated in sequence; the catalyst material distribution system comprises a multi-channel switching valve bank for controlling the flow direction of catalyst materials and a controller electrically connected with the multi-channel switching valve bank; the multi-channel switching valve group comprises a feed inlet, at least one flushing port and at least two discharge ports, wherein the total number of the feed inlet and the flushing port is equal to that of the discharge ports. The device can divide the catalyst material into a plurality of material flows according to a preset proportion, the material flows respectively enter the main polymerization reactors of the downstream production lines, and the parallel production mode that a plurality of polyolefin production lines share one set of catalyst storage and feeding device is realized by periodically switching the material flow direction. The invention also provides a catalyst material distribution method and application thereof.
Description
Technical Field
The invention belongs to the technical field of olefin polymerization, and particularly relates to a catalyst material distribution device for olefin polymerization, a distribution method and application.
Background
As the world's demand for polyolefins, particularly polypropylene, continues to increase, the expansion of petrochemical plants producing polypropylene is increasing, creating a situation where a single plant has multiple production lines. As the scale of ethylene production increases in newly built plants, the scale of propylene by-production increases accordingly. For example, a new 80 million ton annually ethylene plant will typically require 40 to 50 million ton annually polypropylene plants to be constructed, and many plants will choose to build two polypropylene production lines.
For example, the Spheripol process of Basell corporation uses 2 loop reactors connected in series, also called loop polypropylene process, whose gas phase reactor is in the form of dense phase fluidized bed, the Hypol process of three well oiling company uses a combination of stirred tank liquid phase reactor and gas phase fluidized bed reactor, the Borstar PP process of Borealis corporation includes 1 loop reactor and 2-3 gas phase fluidized bed reactors, the Unipol process of DOW chemical corporation uses gas phase fluidized bed reactor, homopolymerization and copolymerization are carried out in 2 fluidized beds connected in series, the Innovene gas phase process of INEOS (original BP-Amoco) corporation uses 2 horizontal gas phase reactors, internal mechanical stirring, residence time distribution of material is close to plug flow form, the Novolen gas phase process of ABB-L ummus corporation uses 2 vertical gas phase stirred tanks, and impact copolymer can be produced by using double reactors connected in series.
The Ziegler-Natta catalyst used for propylene polymerization is critical for the overall polypropylene production line, which is stopped once the catalyst feed is stopped. In order to ensure the continuous and stable operation of the polypropylene device, main equipment such as a catalyst pump, a cocatalyst pump and the like are provided with standby equipment which is usually used one by one. For plants with multiple polypropylene production lines, the catalyst feed pump for each polypropylene production line is currently used one after the other. Thus, multiple catalyst feed pumps installed throughout the plant cannot be kept on standby for each other because they are distributed on different polypropylene production lines.
The Ziegler-Natta catalyst may also be used in batch prepolymerization. In the prepolymerization reaction in the prior art, the catalyst is suspended in hexane, alkyl aluminum and an electron donor are added for pre-complexing to form an active catalyst, and then trace propylene is added for prepolymerization, wherein the prepolymerization multiple is usually less than 3 times. After the prepolymerization, the prepolymer was transferred to the polymerization reactor with hexane. In these processes, the catalyst feed pump delivers an active catalyst slurry containing the prepolymer, and sufficient flow velocity must be ensured during the delivery to prevent it from settling or sticking to each other and plugging the lines. The catalyst slurry has a tendency to foul, particularly when low temperature (e.g. 5 ℃) liquid propylene is used to entrain it into the reactor, the internal surfaces of the transfer lines must be smooth to prevent sticking of prepolymer. Both the Hypol polypropylene process and the HORIZONE gas phase polypropylene process take this form of batch prepolymerization.
For a factory with a plurality of polypropylene production lines, if a storage tank, a pump and a pipeline of a catalyst in a certain production line need to be maintained or modified and the catalyst cannot be normally conveyed to the production line, the whole production line needs to be stopped, and huge loss is caused. Although other production lines still have spare equipment such as a catalyst pump and the like, the equipment cannot play a role in the production line.
Therefore, there is a need to develop a catalyst material distribution device for olefin polymerization, a distribution method and applications thereof.
Disclosure of Invention
The present invention provides a catalyst material distribution device for olefin polymerization, a distribution method and applications thereof, aiming at the defects of the prior art. The catalyst material distribution device provided by the invention is particularly suitable for distributing catalyst materials for olefin polymerization to a plurality of polymerization production lines, so that catalyst storage and feeding equipment of one production line can meet the catalyst feeding requirements of a plurality of polyolefin production lines, the investment of newly-built polyolefin production lines is reduced, and the purpose of increasing the standby number of catalyst equipment is achieved.
To this end, the invention provides in a first aspect a catalyst material distribution device for olefin polymerization, comprising a catalyst storage tank, a catalyst feed pump and a catalyst material distribution system which are communicated in sequence;
the catalyst material distribution system comprises a multi-channel switching valve bank for controlling the flow of catalyst materials and a controller electrically connected with the multi-channel switching valve bank; the multi-channel switching valve group comprises a feed inlet, at least one flushing port and at least two discharge ports, wherein the total number of the feed inlet and the flushing port is equal to that of the discharge ports.
According to the invention, the feed opening is in communication with the catalyst feed pump.
According to the invention, a liquid olefin conveying pipeline is arranged upstream of the flushing port, and the flushing port is communicated with the liquid olefin conveying pipeline.
According to the invention, the feed inlet is not communicated with the flushing port; the feeding hole and the flushing hole are respectively communicated with different discharging holes in a periodically switching manner under the control of a controller, and the periodic interval is 0.01-60 minutes.
According to the invention, a polyolefin production line is arranged at the downstream of the discharge ports, the discharge ports are respectively communicated with a main polymerization reactor on the polyolefin production line arranged at the downstream of the discharge ports, and the discharge ports are not communicated with each other.
According to the invention, the multi-way switching valve bank comprises at least one four-way valve.
According to the invention, when the multi-way conversion valve group comprises two or more than two four-way valves, any discharge hole of the upstream four-way valve is communicated with the feed hole of the downstream four-way valve.
According to the invention, the olefins include ethylene, propylene and C4-C10α -olefin(s).
According to the invention, the olefin is propylene.
According to the invention, the catalyst is an active catalyst which allows the polymerization of the olefins in contact.
The second aspect of the invention provides a method for distributing catalyst materials for olefin polymerization by using the distribution device according to the first aspect of the invention, which comprises the steps of inputting the catalyst materials output from a catalyst storage tank into a feed inlet in a multi-way switching valve bank through a catalyst feed pump, inputting the liquid olefins output from a liquid olefin conveying pipeline into each flushing port in the multi-way switching valve bank, and periodically switching and communicating the feed inlet and the flushing ports with different discharge ports through a controller, so that the catalyst materials and the liquid olefins are periodically output from the different discharge ports to a main polymerization reactor on a polyolefin production line arranged at the downstream of the main polymerization reactor.
In a third aspect the present invention provides the use of a dispensing apparatus according to the first aspect of the invention or a dispensing method according to the second aspect of the invention in the production of polyolefins.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of a catalyst feed distribution system including a multi-way change-over valve block having a four-way ball valve.
Fig. 2 is a schematic structural diagram of two communication states of a four-way ball valve in a multi-way switching valve group comprising the four-way ball valve.
FIG. 3 is a flow chart of polypropylene production in a downstream production line using two Hypol process lines in parallel in example 1 of the present invention.
FIG. 4 is a flow chart of polypropylene production in a downstream line using two parallel HORIZONE process lines in example 2 of the present invention.
FIG. 5 is a schematic diagram of a catalyst feed distribution system including a multi-way change-over valve set with two four-way ball valves.
In the above drawings, like components are denoted by like reference numerals. The figures are not drawn to scale.
Detailed Description
The invention will be further described with reference to the following figures and examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
The inventor of the invention has conducted extensive and intensive experimental research in the technical field of polyolefin production and found that by adopting the catalyst material distribution system for olefin polymerization provided by the invention, a set of catalyst storage and feeding equipment of a production line can meet the catalyst feeding requirements of a plurality of polyolefin production lines, so that the investment for constructing a plurality of polyolefin production lines can be effectively reduced, and meanwhile, the spare degree of catalyst equipment of a plurality of polyolefin production lines can be improved by additionally arranging the catalyst material distribution system under the condition of not making large structural changes on the existing catalyst feeding device. The present invention has been made based on the above findings.
Accordingly, in a first aspect, the present invention relates to a catalyst mass distribution device for olefin polymerization, comprising a catalyst storage tank, a catalyst feed pump and a catalyst mass distribution system, which are connected in series.
The olefins of the present invention include ethylene, propylene and C4-C10α -at least one of an olefin, preferably propylene when the olefin is propylene, the polyolefin is polypropylene and the polyolefin catalyst is a polypropylene catalyst, the polypropylene can be homopolypropylene, random copolymer polypropylene or impact copolymer polypropylene4-C10α -olefins, such as at least one of ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl isoamylene, 1-octene and 1-decene.
The polyolefin catalyst in the present invention is not particularly limited, and may be an olefin polymerization catalyst commonly used in the art, such as a metallocene catalyst or a Ziegler-Natta catalyst. When the polyolefin is polypropylene, the catalyst is preferably a Ziegler-Natta catalyst with high stereoselectivity, and the device and the method provided by the invention can be used for preparing homopolymer with an isotactic index of more than 95%.
The ziegler natta catalyst having high stereoselectivity according to the present invention may be any of various catalysts commonly used in the art capable of catalyzing propylene to undergo isotactic polymerization. Generally, the ziegler natta catalyst with high stereoselectivity comprises: (1) the titanium-containing solid catalyst active component comprises the main components of magnesium, titanium, halogen and an internal electron donor; (2) an organoaluminum compound co-catalyst component; and optionally (3) an external electron donor component.
Specific examples of such active solid catalyst-containing components that may be used are disclosed in CN85100997, CN98126383.6, CN98111780.5, CN98126385.2, CN93102795.0, CN00109216.2, CN99125566.6, CN99125567.4, CN 02100900.7. The catalyst can be directly used or added after pre-complexing and pre-polymerizing.
The organoaluminum compound as the co-catalyst component of the catalyst is preferably an alkylaluminum compound, more preferably at least one member selected from the group consisting of trialkylaluminums (e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, trioctylaluminum, etc.), diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride and ethylaluminum dichloride.
The ratio of the titanium-containing solid catalyst active component to the organoaluminum compound co-catalyst component may be 1:25 to 1:1000 in terms of Ti/Al molar ratio.
The external electron donor compound as optional catalyst component is preferably an organosilicon compound of the general formula RnSi (OR')4-nWherein 0 < n.ltoreq.3, wherein R and R' are the same or different and are each independently selected from alkyl, cycloalkyl, aryl and haloalkyl groups, and R may also be halogen or hydrogen atom. Specifically, the organosilicon compound may be, but is not limited to: tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilaneSilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, and the like.
The ratio of the alkyl aluminum compound to the organosilicon compound may be 3:1 to 100:1 in terms of Al/Si molar ratio.
Three components of the ziegler natta catalyst with high stereoselectivity: the catalyst, the alkyl aluminum and the electron donor are pre-contacted (pre-complexed) to form the active catalyst. The active catalyst allows the polymerization of propylene, whereas the catalyst, which is not pre-complexed, does not allow the polymerization of propylene. The three catalyst components may be added directly to the prepolymerization reactor or may be added to the prepolymerization reactor after being subjected to precomplexation as is known in the art. In both cases, the catalyst is not an active catalyst during transport, neither suspended in propylene nor mineral oil has polymerization conditions. The prepolymerization is carried out continuously under liquid-phase bulk conditions.
The Ziegler Natta catalyst may also be employed in a batch prepolymerization. In the prepolymerization process, the catalyst is suspended in hexane, alkyl aluminum and an electron donor are added for pre-complexing to form an active catalyst, then, a trace amount of propylene is added for pre-polymerization, and the prepolymerization multiple is usually less than 3 times. After the prepolymerization, the prepolymer was transferred to the reactor with hexane. In these processes, the catalyst pump delivers the active catalyst slurry with the prepolymer and must ensure a sufficient flow rate during the delivery to prevent it from settling or sticking to each other and blocking the lines. This catalyst slurry has a tendency to foul, especially when low temperature propylene is used to entrain it into the reactor, and the internal surfaces of the transfer lines must be smooth to prevent sticking of the prepolymer. Both the Hypol polypropylene process and the HORIZONE gas phase polypropylene process take this form of batch prepolymerization.
The term "pressure" as used herein refers to reactor gauge pressure.
The expression "multiple of prepolymerization" as used herein means the number of grams of polymer produced per gram of catalyst.
The invention adopts an innovative catalyst material distribution system, which comprises a multi-channel switching valve bank for controlling the flow direction of catalyst materials and a controller electrically connected with the multi-channel switching valve bank; the multi-channel switching valve group comprises a feed inlet, at least one flushing port and at least two discharge ports, wherein the total number of the feed inlet and the flushing port is equal to that of the discharge ports.
The catalyst material distribution system can divide the catalyst material flow into a plurality of flows according to a preset proportion, and the flows respectively enter the main polymerization reactors on a plurality of production lines at the downstream. The distribution system can ensure that the catalyst material flow has enough flowing speed, and no dead angle exists in the system, so that the catalyst material distribution system is not easy to block, and can ensure long-term stable operation.
The catalyst material distribution system is a time slot control system, namely the time length of the catalyst material flowing to a specific production line is controlled by a multi-channel switching valve group to control the flow of the catalyst material flowing to the production line.
The terms "upstream" and "downstream" in the present invention are referred to the direction of flow of the material.
In the catalyst material distribution device, the feed inlet is communicated with the catalyst feed pump.
In some embodiments of the invention, a liquid propylene delivery conduit is provided upstream of the flushing port, the flushing port being in communication with the liquid propylene delivery conduit. According to the invention, through arranging the flushing port communicated with the liquid propylene conveying pipeline, a proper amount of liquid propylene can be continuously introduced to flush the device and the pipeline, so that no dead angle exists in the device, the residues of the catalyst materials introduced previously are not easy to deposit, the pipeline of the equipment is not easy to block, and the long-term stable operation is ensured.
In the catalyst material distribution device, the feed inlet is not communicated with the flushing port; the feeding port and the flushing port are respectively communicated with different discharging ports in a periodically switching manner under the control of a controller, and the periodic interval is 0.01-60 minutes, preferably 1-20 minutes, and more preferably 2-10 minutes.
In the catalyst material distribution device, a polypropylene production line is arranged at the downstream of the discharge ports, the discharge ports are respectively communicated with a main polymerization reactor on the polypropylene production line arranged at the downstream of the discharge ports, and the discharge ports are not communicated with each other.
The term "main polymerization reactor" as used herein means the first polymerization reactor after the prepolymerization reactor in each production line. For example, in some embodiments of the present invention, the primary polymerization reactor is a first polymerization reactor.
In the catalyst material distribution device, the multi-way conversion valve group is formed by combining one or more selected from a three-way valve, a four-way valve or a six-way valve, preferably the multi-way conversion valve group comprises at least one four-way valve, and preferably the four-way valve is a four-way ball valve.
In the catalyst material distribution device, when the multi-way conversion valve group comprises two or more four-way valves, any discharge port of the upstream four-way valve is communicated with a feed port of the downstream four-way valve. Through using a plurality of multichannel conversion subassemblies in series, can effectively reduce many production lines and share one set of catalyst and store and the transformation cost of feed arrangement.
In some embodiments of the invention, the catalyst feed distribution system functions to distribute catalyst feed from a catalyst feed pump through a multi-way diverter valve block into two parallel process lines (i.e., where the multi-way diverter valve block contains only one four-way ball valve). Fig. 1 is a schematic diagram of the structure of the catalyst material distribution system. The distribution system comprises a four-way ball valve 103, wherein the four-way ball valve 103 comprises a catalyst material feeding hole 1, a propylene flushing hole 2, a discharging hole 3 communicated with a production line A and a discharging hole 4 communicated with a production line B respectively; and a line 1012 communicating with the catalyst feed port 1, a line 1022 communicating with the propylene purge port 2, a line 1032 communicating with the A line, and a line 1031 communicating with the B line. The four-way ball valve is remotely controlled by a DCS control system. The typical control scheme is that a DCS control system transmits an electric signal to a field electromagnetic valve, and the electromagnetic valve controls compressed air to drive a four-way ball valve to act.
Fig. 2(a) and 2(b) show two states of communication of the four-way ball valve in the catalyst mass distribution system of fig. 1. The four ports of the four-way ball valve in the figure 2(a) and the figure 2(B) are respectively a catalyst material feeding port 1, a propylene flushing port 2 and a discharging port 3 or 4 communicated with the production line A or the production line B. In the state of fig. 2(a), the catalyst material flow enters the four-way ball valve 103 from the inlet port 1, and is output to the main polymerization reactor of the a line from the outlet port 3 communicating with the a line, and the liquid propylene enters the four-way ball valve 103 from the propylene flushing port 2, and is output to the main polymerization reactor of the B line from the outlet port 4 communicating with the B line, and the propylene for the pipeline is flushed. In the state of fig. 2(B), the catalyst material flow enters the four-way ball valve 103 from the catalyst material inlet 1, and is output to the main polymerization reactor of the B production line from the outlet 4 communicated with the B production line, and the liquid propylene enters the four-way ball valve from the propylene flushing port 2, and is output to the main polymerization reactor of the a production line from the outlet 3 communicated with the a production line, so that the propylene for the pipeline is flushed. The catalyst material feeding port 1 is not communicated with the propylene flushing port 2 all the time, and the discharging port communicated with the A production line is not communicated with the discharging port communicated with the B production line all the time. The flushing propylene entering the flushing port 2 is preferably low temperature propylene at a temperature close to the temperature of the prepolymerization reactor. The pipeline through which the material flow of the catalyst does not flow is always in a propylene flushing state, so that the catalyst material distribution system is not easy to block.
In the normal operation state of the catalyst material distribution system, the four-way ball valve is periodically switched between the state shown in fig. 2(a) (hereinafter referred to as the state A, the catalyst material passes through the A production line) and the state shown in fig. 2(B) (hereinafter referred to as the state B, the catalyst material passes through the B production line) under the control of a DCS control system control program. The switching period of the four-way ball valve is called as time T, and the time T of the A state is included in a complete switching periodATime T of B stateB. The switching cycle time T is generally in the range of 0.01 to 60 minutes, preferably 1 to 20 minutes, more preferably 2 to 10 minutes.
In the catalyst material distribution method, the controller is used for setting the catalyst material output rates of different discharge ports. When the number of the actually used discharge ports is n, the interval of the periodic switching communication is T, the feeding speed of the total catalyst material is set as V, and the time of the catalyst material output from different discharge ports is respectively set as T1、T2···、TnIs obviously T1+T2+···+TnT, the catalyst material rate V output from the different outlets1、V2···VnRespectively as follows:
V1＝V×T1/T，V2＝V×T2/T，···，Vn＝V×Tn/T。
the method provided by the invention can realize the independent adjustment of the speed of the catalyst material output from different discharge ports, thereby achieving the purpose of independently adjusting the production speed of polymerization reaction in different production lines.
In other embodiments of the invention, a catalyst feed distribution system comprising two four-way ball valves can be constructed by introducing a second four-way ball valve and connecting the feed inlet of the second four-way ball valve to the discharge outlet of the first four-way ball valve. A catalyst feed distribution system comprising two four-way ball valves can be implemented to distribute one catalyst feed to three production lines. Similarly, one catalyst material can be distributed to a plurality of production lines by combining a plurality of four-way ball valves.
The second aspect of the invention provides a method for distributing catalyst materials for olefin polymerization by using the distribution device according to the first aspect of the invention, which comprises the steps of inputting the catalyst materials output from a catalyst storage tank into a feed inlet in a multi-way switching valve bank through a catalyst feed pump, inputting the liquid olefins output from a liquid olefin conveying pipeline into each flushing port in the multi-way switching valve bank, and periodically switching and communicating the feed inlet and the flushing ports with different discharge ports through a controller, so that the catalyst materials and the liquid olefins are periodically output from the different discharge ports to a main polymerization reactor on a polyolefin production line arranged at the downstream of the main polymerization reactor.
A third aspect of the invention provides the use of a dispensing device according to the first aspect of the invention or a dispensing method according to the second aspect of the invention in the production of polypropylene.
After passing through the catalyst material distribution system, the catalyst enters a subsequent reactor for polymerization. The reactor may be a liquid phase reactor or a gas phase reactor. The liquid phase reactor may be a loop reactor or a stirred tank reactor. The gas phase reactor can be a horizontal stirred bed reactor, a vertical stirred bed reactor, a fluidized bed reactor and the like. The propylene polymerization conditions may include: the temperature is 50-100 ℃, preferably 60-95 ℃; the reaction pressure is 1-8MPa, preferably 1.2-5.5 MPa; the reaction time is 30 to 180 minutes, preferably 45 to 120 minutes.
After completion of the above polymerization, the polymerization may also be continued in a subsequent reactor in the presence of the obtained product. The polymerization may be carried out in the liquid phase or in the gas phase. The liquid phase reactor can be a loop reactor or a stirred tank reactor, etc., the gas phase reactor can be a horizontal stirred bed reactor, a vertical stirred bed reactor, a fluidized bed reactor, etc., and the liquid phase reactor and the gas phase reactor can also be matched and combined arbitrarily.
According to the process of the present invention, the subsequent gas-phase polymerization conditions may comprise: the temperature is 50-150 ℃, preferably 60-95 ℃; the reaction pressure is 1-4MPa, preferably 1.2-3.5 MPa; the reaction time is 10 to 180 minutes, preferably 10 to 90 minutes.
The invention is particularly suitable for feeding the catalyst with prepolymer to a subsequent reactor after the polyolefin catalyst has been subjected to batch prepolymerization.
The catalyst material distribution device provided by the invention is particularly suitable for distribution of polypropylene catalysts, and the subsequent reactor can be a polypropylene reactor of a liquid phase bulk method or a polypropylene reactor of a gas phase method.
By adopting the catalyst material distribution device, the catalyst storage and feeding facilities of one production line are built, so that the requirements of a plurality of polypropylene production lines can be met. Therefore, the investment for building a plurality of polypropylene production lines can be effectively reduced. By adopting the scheme of the invention, for the existing multiple polypropylene production lines, the standby degree of catalyst equipment of the multiple polypropylene production lines can be improved by additionally arranging the catalyst material distribution system without making large structural change on the existing catalyst feeding device.
Examples
Example 1
In this embodiment, a set of catalyst material distribution device is used to perform polypropylene production on two parallel Hypol process production lines, and the flow chart is shown in FIG. 3.
The catalyst material distribution device comprises a catalyst storage tank, a catalyst feeding pump 101 arranged at the downstream of the catalyst storage tank, and a catalyst material distribution system arranged at the downstream of the catalyst feeding pump 101. The catalyst material distribution system comprises a multi-way switching valve set and a controller (not shown in the figure) electrically connected with the multi-way switching valve set. The multi-channel switching valve group consists of a four-way ball valve 103. The catalyst material distribution system is structurally shown in fig. 1 and comprises a four-way ball valve 103, wherein the four-way ball valve 103 comprises a catalyst feeding hole 1, a propylene flushing hole 2, a discharging hole 3 communicated with a production line A and a discharging hole 4 communicated with a production line B respectively; and a line 1012 communicating with the catalyst feed port 1, a line 1022 communicating with the propylene purge port 2, a line 1032 communicating with the A line, and a line 1031 communicating with the B line. The four-way ball valve is remotely controlled by a DCS control system. The typical control scheme is that a DCS control system transmits an electric signal to a field electromagnetic valve, and the electromagnetic valve controls compressed air to drive a four-way ball valve to act. FIG. 2 shows two states of communication of a four-way ball valve in a catalyst feed distribution system comprising a four-way ball valve. These two states deliver catalyst feed to line a and line B, respectively.
The catalyst is pre-polymerized intermittently before being fed. Suspending the catalyst in hexane in the prepolymerization process, adding alkyl aluminum and an electron donor for pre-complexing to form an active catalyst, then adding trace propylene for prepolymerization, and controlling the slurry temperature to be about 10 ℃ in the prepolymerization process and the prepolymerization multiple to be 3 times. After prepolymerization, a hexane suspension of the catalyst and prepolymer was obtained.
The catalyst slurry with prepolymer is pressurized by the catalyst pump and enters catalyst transfer line 1012. In order to increase the transport speed of the catalyst in the pipe, a stream of propylene 1021 at a temperature of 5 ℃ was used to flush the catalyst transport line. The catalyst slurry with the propylene then enters the catalyst mass distribution system. The four-way ball valve is remotely controlled by a DCS control system, so that a catalyst material enters the four-way ball valve 103 through a catalyst material inlet 1 and enters a main polymerization reactor A201 (shown in figure 2 (a)) of a production line A through a discharge port 3, and liquid propylene enters the four-way ball valve 103 through a flushing port 2 and flushes a pipeline 1031 of a discharge port 4 entering a production line B; or the catalyst material enters the four-way ball valve 103 through the catalyst material inlet 1 and enters the main polymerization reactor B201 of the B production line through the discharge port 4 (as shown in fig. 2 (B)), and the liquid propylene enters the four-way ball valve 103 through the flushing port 2 and flushes the pipeline 1032 of the discharge port 3 which enters the A production line. Setting the switching period time T of the multi-channel switching valve group to be 10 minutes through program software, wherein the state that a catalyst material feed port 1 is communicated with a main polymerization reactor A201 of the production line A is kept TAKeeping T state that the catalyst material feed inlet 1 is communicated with the main polymerization reactor B201 of the B production line for 5 minutesBFor 5 minutes.
The catalyst material is divided into two streams according to the ratio of 1:1 by a catalyst material distribution system, and the two streams respectively enter a downstream A production line main polymerization reactor A201 and a downstream B production line main polymerization reactor B201.
Both polypropylene lines were 10 ten thousand tons/year Hypol polymerization process. Both lines run homopolymer grades. The main polymerization unit has the following process parameters: the first polymerization reactors A201 and B201 both carry out liquid-phase homopolymerization, the polymerization temperature is 70 ℃, the polymerization pressure is 3.0MPa, and the polymerization time is 40 minutes; the second polymerization reactors A202 and B202 were similarly subjected to liquid-phase homopolymerization at a polymerization temperature of 67 ℃ under a polymerization pressure of 2.7MPa for 40 minutes. The obtained solid polymer and a large amount of unreacted propylene monomer mixed materials enter a powder washing tower to remove a short-circuit catalyst and subdivide, and then respectively enter a first gas phase reactor A203 and a first gas phase reactor B203 to perform homopolymerization and evaporation heat removal of liquid propylene, wherein the polymerization temperature is 80 ℃, the polymerization pressure is 1.7MPa, and the polymerization time is 70 minutes; the solid polymer powder continuously enters a second gas phase reactor A204 and a second gas phase reactor B204 for homopolymerization, the polymerization reaction temperature is 70 ℃, the polymerization reaction pressure is 1.5MPa, and the polymerization reaction time is 60 minutes. The obtained polymer powder is subjected to gas-solid separation by a circulating gas separator, unreacted propylene monomers are recovered, and the solid polymer is subjected to washing, drying, granulation and packaging to finally obtain a homo-polypropylene product.
Example 2
In this example, a set of catalyst material distribution device was used to perform polypropylene production on two parallel HORIZONE process lines, the flow chart of which is shown in FIG. 4.
The catalyst material distribution device was the same as in example 1.
The catalyst is pre-polymerized intermittently before being fed. Suspending the catalyst in hexane in the prepolymerization process, adding alkyl aluminum and an electron donor for pre-complexing to form an active catalyst, then adding trace propylene for prepolymerization, controlling the slurry temperature to be about 10 ℃ in the prepolymerization process, and controlling the prepolymerization multiple to be 2 times. After prepolymerization, a hexane suspension of the catalyst and prepolymer was obtained.
The catalyst slurry with prepolymer is pressurized by the catalyst pump and enters catalyst transfer line 1012. In order to increase the transport speed of the catalyst in the pipe, a stream of propylene 1021 at a temperature of 5 ℃ was used to flush the catalyst transport line. The catalyst slurry with the propylene then enters the catalyst mass distribution system.
The catalyst mass distribution system was the same as that used in example 1. The switching period time T of the multi-channel switching valve group is 9 minutes, wherein the state that the catalyst material feed port 1 is communicated with the main polymerization reactor A201 of the production line A is kept TAKeeping T state that the catalyst material feed inlet 1 is communicated with the main polymerization reactor B201 of the B production line for 5 minutesBDay 4 min.
The two polypropylene production lines respectively carry out the brand production of the homo-polypropylene and the impact-resistant co-polypropylene. The A line of the polypropylene production line is a HORIZONE process of 25 ten thousand tons per year, and the production load of the polypropylene homopolymer is 31 tons per hour. The technological parameters of the main polymerization unit are as follows: the polymerization temperature of the first gas phase polymerization reactor A201 is 70 ℃, the polymerization pressure is 2.45MPa, and the polymerization time is 60 minutes; the polymerization temperature of the second gas-phase polymerization reactor A202 was 70 ℃, the polymerization pressure was 2.45MPa, and the polymerization time was 40 minutes. And recovering the propylene monomer from the obtained solid polymer and unreacted propylene monomer mixed material through flash evaporation and degassing, degassing and drying the solid polymer, granulating and packaging to finally obtain a homopolymerized propylene product.
The B line of the polypropylene production line was a 25 million ton/year HORIZONE process with a 25 ton/hour production load for impact copolymer grade production. The technological parameters of the main polymerization unit are as follows: the polymerization temperature of the first gas phase polymerization reactor B201 is 70 ℃, the polymerization pressure is 2.45MPa, and the polymerization time is 60 minutes; the polymerization temperature of the second gas-phase polymerization reactor B202 was 65 ℃, the polymerization pressure was 2.45MPa, and the polymerization time was 40 minutes. And recovering the propylene monomer from the obtained solid polymer and unreacted propylene monomer mixed material through flash evaporation and degassing, degassing and drying the solid polymer, and then granulating and packaging to finally obtain the impact-resistant co-polypropylene product.
Example 3
In this example, a set of catalyst material distribution device is used to perform polypropylene production on two parallel innoven process lines, and the flow chart is the same as that in fig. 4 of example 2. The difference from example 2 is that the catalyst was not subjected to a batch prepolymerization. Therefore, the catalyst is not activated and does not have polymerization activity after contacting propylene.
The catalyst material distribution device was the same as in example 1.
The catalyst slurry is pressurized under the action of the catalyst pump and enters a catalyst conveying pipeline. In order to accelerate the conveying speed of the catalyst in the pipeline, a strand of normal-temperature propylene is adopted to flush the catalyst conveying pipeline. The catalyst slurry with the propylene then enters the catalyst mass distribution system.
The catalyst mass distribution system was the same as that used in example 1. The switching period time T of the multi-channel switching valve group is 4 minutes, wherein the state that the catalyst material feed port 1 is communicated with the main polymerization reactor A201 of the production line A is kept TAKeeping T state that a catalyst material feed inlet 1 is communicated with a B production line main polymerization reactor B201 for 2 minutes B2 minutes.
The two polypropylene production lines respectively produce homo-polypropylene brands, are both Innovene processes with the output of 20 ten thousand tons per year, and the production load is 25 tons per hour. The technological parameters of the main polymerization unit are as follows: the polymerization temperature of the first gas phase polymerization reactors A201 and B201 is 66 ℃, the polymerization pressure is 2.2MPa, and the polymerization time is 60 minutes; the polymerization temperature of the second gas-phase polymerization reactors B201 and B202 was 66 ℃, the polymerization pressure was 2.2MPa, and the polymerization time was 40 minutes. And recovering the propylene monomer from the obtained solid polymer and unreacted propylene monomer mixed material through flash evaporation and degassing, degassing and drying the solid polymer, granulating and packaging to finally obtain a homopolymerized propylene product.
Example 4
In the embodiment, a set of catalyst material distribution device is adopted to produce polypropylene on three Innovene process production lines connected in parallel. Figure 5 shows a schematic diagram of three catalyst feed distribution systems for an innoven process line in parallel. The three lines were operated under the same conditions as the line a in example 2.
The catalyst mass distribution system is shown in figure 5. The material distribution system comprises two four-way ball valves. The four-way ball valve A103 is arranged at the upstream of the four-way ball valve B103, an upstream discharge port A4 is communicated with a downstream feed port B1, an upstream flushing port A2 is communicated with a liquid propylene conveying pipeline A1022, a downstream flushing port B2 is communicated with a liquid propylene conveying pipeline B1022, and discharge ports A3, B3 and B4 are respectively communicated with downstream production line main polymerization reactors A201, B201 and C201. The switching period time T of the multi-channel switching valve set is set to be 9 minutes by the controller, wherein a feed port A1 is communicated with a main polymerization reactor A201 of the production line AState of (1) is maintained at TAThe feed port A1 was connected to the main polymerization reactor B201 in line B for 3 minutes, and the connection was maintained at TBThe feed port A1 was connected to the main polymerization reactor C201 in line C for 3 minutes while maintaining TCDay 3 min. By adjusting the action of the two four-way ball valves, the catalyst material can be shunted to A, B, C three production lines through the material distribution system.
The catalyst material distribution system realizes the distribution of the catalyst material flowing out of the catalyst feeding pump into three production lines. The three production lines share one catalyst storage and feeding facility.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (8)
1. A catalyst material distribution device for olefin polymerization comprises a catalyst storage tank, a catalyst feeding pump and a catalyst material distribution system which are sequentially communicated;
the catalyst material distribution system comprises a multi-channel switching valve bank for controlling the flow direction of catalyst materials and a controller electrically connected with the multi-channel switching valve bank; the multi-channel switching valve group comprises a feed port, at least one flushing port and at least two discharge ports, and the total number of the feed port and the flushing port is equal to that of the discharge ports;
the feed inlet is communicated with the catalyst feed pump;
a liquid olefin conveying pipeline is arranged at the upstream of the flushing port, and the flushing port is communicated with the liquid olefin conveying pipeline;
the feeding hole is not communicated with the flushing hole; the feeding hole and the flushing hole are respectively communicated with different discharging holes in a periodically switching manner under the control of a controller;
and a polyolefin production line is arranged at the downstream of the discharge port, the discharge ports are respectively communicated with a main polymerization reactor on the polyolefin production line arranged at the downstream of the discharge port, and the discharge ports are not communicated with each other.
2. A dispensing device according to claim 1, wherein said period is 0.01-60 minutes.
3. The dispensing apparatus of claim 1, wherein the multi-way switching valve block comprises at least one four-way valve.
4. The distribution device of claim 3, wherein the multi-way switching valve set comprises two or more four-way valves, and any discharge port of an upstream four-way valve is communicated with a feed port of a downstream four-way valve.
5. The dispensing apparatus of claim 1 wherein the olefins comprise ethylene, propylene and C4-C10α -olefin(s).
6. The dispensing apparatus of claim 1 wherein the catalyst is an active catalyst that is three components of a ziegler natta catalyst with high stereoselectivity: the catalyst, the alkyl aluminum and the electron donor are pre-contacted to form the catalyst.
7. A method for distributing catalyst materials for olefin polymerization by the distribution device according to any one of claims 1 to 6, which comprises inputting the catalyst materials output from a catalyst storage tank into a feed inlet in a multi-way switching valve bank through a catalyst feed pump, inputting the liquid olefin output from a liquid olefin conveying pipeline into each flushing port in the multi-way switching valve bank, and periodically switching and communicating the feed inlet and the flushing ports with different discharge ports through a controller, so that the catalyst materials and the liquid olefin are periodically output from the different discharge ports to a main polymerization reactor on a polyolefin production line arranged downstream of the main polymerization reactor.
8. Use of a dispensing device according to any one of claims 1-6 or a dispensing method according to claim 7 in the production of polyolefins.
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