CN108610447B - Material mixing method and device suitable for olefin copolymerization and olefin copolymerization method - Google Patents
Material mixing method and device suitable for olefin copolymerization and olefin copolymerization method Download PDFInfo
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- CN108610447B CN108610447B CN201611128818.7A CN201611128818A CN108610447B CN 108610447 B CN108610447 B CN 108610447B CN 201611128818 A CN201611128818 A CN 201611128818A CN 108610447 B CN108610447 B CN 108610447B
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
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- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/68—Vanadium, niobium, tantalum or compounds thereof
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Abstract
The invention relates to the field of olefin polymerization, in particular to a material mixing method and a material mixing device suitable for olefin copolymerization and an olefin copolymerization method. The material mixing method suitable for olefin copolymerization comprises the following steps: 1) mixing the first material and the second material to obtain a first mixture; 2) mixing the third material and the fourth material to obtain a second mixture; 3) mixing the first mixture with the second mixture; optionally, introducing a fifth material in step 2) or step 3); the first material and the second material are different and are selected from alpha-olefin, the third material is hydrogen, the fourth material is an organic solvent, and the fifth material is dialkene. The mixing method and the mixing device can obviously improve the mixing effect of immiscible gas and liquid, and can keep the content of hydrogen in the mixed material stable when the method is used for ethylene propylene rubber copolymerization, thereby obviously reducing gel generated in the polymerization process.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a material mixing method and a material mixing device suitable for olefin copolymerization and an olefin copolymerization method.
Background
Gelation is a phenomenon commonly found in polymerization reactions in synthetic rubbers. The gel has a serious detrimental effect on the polymerization itself and on the quality of the product, for example, in the polymerization of ethylene-propylene rubber under Ziegler Natta catalysis, the formation and accumulation of gel, which severely reduces the deterioration of the polymer properties and makes the polymerization itself impossible and thus forcibly halted. The gel damage is especially serious for the ethylene-propylene copolymerization reaction under the catalyst composed of transition metal vanadium and organic metal aluminide compared with other homopolymerization reactions.
There is still a need to continue to reduce gels during polymerization, such as co-polymerization of ethylene-propylene-diene or ethylene-propylene-diene under catalyst systems consisting of transition metal vanadium and organometallic aluminides. The homogeneous mixing of several reaction materials is one of the key factors for achieving the above-mentioned goal.
As shown in fig. 1, the mixing manner of the materials for olefin copolymerization, especially for full liquid-phase ethylene-propylene rubber copolymerization, which is currently used as the prior art, is as follows: the first material (molecular weight regulator, for example hydrogen) is mixed into the pump outlet line of the fourth material (organic solvent, for example hexane) through the first flow meter 7 and the first back pressure valve 17, the gauge pressure of the first pressure gauge 12 should be higher than that of the fourth pressure gauge 15; the second material (the first comonomer, for example, ethylene) passes through the second flowmeter 8 and the second backpressure valve 18 and is mixed into the pump outlet pipeline of the fourth material, and the gauge pressure of the second pressure gauge 13 is higher than that of the fourth pressure gauge 15; a third material (a second comonomer, such as propylene) passes through a third flow meter 9 and a third backpressure valve 19 and is mixed into a pump outlet pipeline of a fourth material, and the gauge pressure of a third pressure gauge 14 is higher than that of a fourth pressure gauge 15; a fifth material (a third comonomer, such as diolefin) is mixed into the pump outlet pipeline of the fourth material through a fifth flow meter 11 and a fifth back pressure valve 21, and the gauge pressure of a fifth pressure gauge 16 is higher than that of a fourth pressure gauge 15; the fourth material passes through a fourth flowmeter 10 and a fourth backpressure valve 20, is mixed with the materials respectively, and then goes to a mixer 23.
The above-mentioned material mixing has a problem that the solubility of the first material (for example, hydrogen) and the fourth material (for example, hexane) is extremely low, and the two materials cannot be uniformly mixed after contacting each other. The chromatographic analysis of the material after the mixer shows that the dissolution of the material cannot be improved even after the material passes through the mixer, and the content of hydrogen in the material is high or low, so that the gel content of part of the sample in the gel sample obtained by polymerization is high.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a material mixing method and a mixing apparatus suitable for olefin copolymerization, and an olefin copolymerization method. The mixing method can obviously improve the mixing effect of the immiscible gas and liquid, so that the content of the immiscible gas in the mixed material is kept stable, and the generation of gel in the polymerization process can be effectively reduced.
In order to achieve the above object, the present invention provides a method for mixing materials suitable for olefin copolymerization, the method comprising:
1) mixing the first material and the second material to obtain a first mixture;
2) mixing the third material and the fourth material to obtain a second mixture;
3) mixing the first mixture with the second mixture;
optionally, introducing a fifth material in step 2) or step 3);
the first material and the second material are different and are selected from alpha-olefin, the third material is hydrogen, the fourth material is an organic solvent, and the fifth material is dialkene.
The present invention also provides a mixing device for mixing a first material, a second material, a third material, a fourth material and optionally a fifth material, the device comprising: a first line, a second line, a third line, a fourth line, a sixth line, a first mixer, a second mixer, and optionally a fifth line;
wherein the first pipeline is communicated with the second pipeline, so that the first material is mixed into the second material passing through the second pipeline through the first pipeline to obtain the first mixture;
the third pipeline and the fourth pipeline are respectively communicated with the first mixer, so that the third material is added into the first mixer through the third pipeline and the fourth material is added into the first mixer through the fourth pipeline, and the second mixture is obtained;
the first mixer, the sixth pipeline and the second mixer are communicated in sequence, and the second pipeline is communicated with the sixth pipeline, so that the first mixture from the second pipeline is mixed into the second mixture passing through the sixth pipeline and enters the second mixer for mixing;
an optional fifth line is in communication with the first mixer such that the fifth material is added to the first mixer via the fifth line to mix with the third material and the fourth material; and/or the presence of a gas in the gas,
an optional fifth line communicates with the sixth line, and the fifth material is mixed into the second mixture passing through the sixth line via the fifth line to be mixed with the second mixture and the first mixture.
The invention also provides an olefin copolymerization method, which comprises the steps of mixing the materials by adopting the mixing method, and contacting the obtained mixture with a catalyst under the condition of olefin copolymerization.
The material mixing method and the material mixing device for olefin copolymerization can obviously improve the mixing effect of immiscible gas and liquid, and particularly can keep the content of hydrogen in the mixed material stable when the method is used for ethylene propylene rubber copolymerization, thereby obviously reducing gel generated in the polymerization process.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic diagram of a feed mixing apparatus for olefin copolymerization in the prior art.
Fig. 2 is a schematic view of a mixing device of the present invention.
Description of the reference numerals
1: first line, 2: second line, 3: third line, 4: fourth line, 5: fifth pipeline, 6: sixth line, 7: first flow meter, 8: second flow meter, 9: third flow meter, 10: fourth flow meter, 11: fifth flow meter, 12: first pressure measuring unit (may also be referred to as first pressure gauge), 13: second pressure measuring unit (may also be referred to as second pressure gauge), 14: third pressure measuring unit (may also be referred to as third pressure gauge), 15: fourth pressure measuring unit (may also be referred to as fourth pressure gauge), 16: fifth pressure measuring unit (may also be referred to as fifth pressure gauge), 17: first backpressure valve, 18: second backpressure valve, 19: third backpressure valve, 20: fourth back pressure valve, 21: fifth backpressure valve, 22: first mixer, 23: a second mixer.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a material mixing method suitable for olefin copolymerization, which is characterized by comprising the following steps:
1) mixing the first material and the second material to obtain a first mixture;
2) mixing the third material and the fourth material to obtain a second mixture;
3) mixing the first mixture with the second mixture;
optionally, introducing a fifth material in step 2) or step 3);
the first material and the second material are different and are selected from alpha-olefin, the third material is hydrogen, the fourth material is an organic solvent, and the fifth material is dialkene.
The present invention relates to a method and an apparatus for mixing olefin copolymerization materials, and more particularly to a method and an apparatus for mixing materials in the presence of immiscible gas and liquid materials. The temperature and time for mixing the above materials are not particularly limited, and may be carried out under the conditions conventional in the art.
According to the present invention, by mixing the first material and the second material, which are different α -olefins, respectively, and mixing the third material, which is hydrogen, and the fourth material, which is an organic solvent, and mixing the respective resulting mixtures, it is possible to more easily achieve sufficient mixing and dissolution of the respective materials, and finally obtain a polymer product having a low gel content. For terpolymerization reactions also requiring the use of dienes, the fifth feed can be introduced as a diene in step 2) or step 3), so that the gel content of the resulting terpolymerized product is also lower.
According to the invention, the first and second feeds are different kinds of alpha-olefins, which may be various alpha-olefins conventionally employed in the art for the copolymerization of olefins, such as C2-C10, as specific examples of such alpha-olefins, for example: one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, and the like.
Preferably, the first material is an alpha-olefin that is gaseous at normal temperature and pressure, more preferably ethylene, propylene or butene, and more preferably ethylene.
Preferably, the second material is propylene, butene or octene, more preferably propylene.
According to the present invention, the fourth material may be various organic solvents for olefin copolymerization known in the art. The organic solvent may be appropriately selected according to the desired product to be synthesized. Such a solvent may be, for example, a hydrocarbon compound having 5 to 11 carbon atoms, preferably a hydrocarbon compound having 5 to 9 carbon atoms. Preferably, the fourth material is one or more of n-pentane, n-hexane, n-heptane, cyclohexane and benzene, more preferably one or more of n-hexane, cyclohexane and benzene, more preferably n-hexane and/or cyclohexane, and most preferably n-hexane.
The fifth feed may be any of a variety of diolefin monomers used in the copolymerization of olefins as is well known in the art. Examples of such monomers include: one or more of ethylidene norbornene, dicyclopentadiene and 1, 4-hexadiene, preferably ethylidene norbornene.
In a preferred embodiment of the present invention, when the mixing method of the present invention is used for the synthesis of ethylene-propylene rubber, the gel content in the polymerization product can be significantly reduced. That is, when the third material is hydrogen used as a molecular weight regulator during the synthesis of ethylene propylene rubber, the first material is ethylene used as a first monomer during the synthesis of ethylene propylene rubber, the second material is propylene used as a second monomer during the synthesis of ethylene propylene rubber, the fourth material is one or more of n-hexane, cyclohexane and benzene used as a solvent during the synthesis of ethylene propylene rubber, and the fifth material is one or more of ethylidene norbornene, dicyclopentadiene and 1, 4-hexadiene used as a third monomer during the synthesis of ethylene propylene rubber, the mixing effect of hydrogen and an organic solvent can be remarkably improved when the materials are mixed by the method disclosed by the invention, so that the content of hydrogen in the mixed material is kept stable, the gel during the polymerization process is further reduced, and the content of the gel in the polymerization product is reduced.
The manner of mixing the first material and the second material according to the present invention is not particularly limited as long as the first material and the second material can be sufficiently mixed, and various mixing manners commonly used in the art may be used. Preferably, however, the first material and the second material are mixed in the following manner: the first material from the first line 1 is mixed into a second material via a second line 2, resulting in the first mixture. That is, the first mixture is obtained by introducing the first material into the first line 1 and introducing the first material passing through the first line 1 into the second line 2, and mixing the first material with the second material introduced into the second line 2.
According to the present invention, in order to more sufficiently mix the third material and the fourth material, it is preferable that the third material and the fourth material are mixed in such a manner that: the third material is fed to the first mixer via a third line 3 and the fourth material via a fourth line 4, resulting in the second mixture. That is, the third material introduced through the third line 3 is introduced into the first mixer 22, and the fourth material introduced through the fourth line 4 is also introduced into the first mixer 22, so that the third material and the fourth material can be more sufficiently mixed in the first mixer 22.
According to the invention, the first mixture is preferably mixed with the second mixture in such a way that: the first mixture from the second line 2 is mixed into the second mixture via a sixth line 6. That is, after the first material is introduced into the second line 2 and mixed with the second material, the resulting first mixed material is further fed into the sixth line 6 via the second line 2 to be mixed with the second mixture exiting the first mixer 22 and conveyed through the sixth line 6. By such a mixing method, raw materials with better mixing effect can be obtained, and a product with lower gel content can be obtained after the polymerization reaction.
According to the invention, with the use of a fifth material, this fifth material can be introduced either in step 2) or in step 3) as described hereinbefore. The mode for introducing the fifth material in the step 2) is preferably as follows: the fifth material is fed to the first mixer via a fifth line 5 to be mixed with the third and fourth materials. That is, the fifth material introduced through the fifth line 5 is also added to the first mixer 22, and the third material and the fourth material added to the first mixer 22 are mixed to form the second mixture. The mode for introducing the fifth material in the step 3) is preferably as follows: said fifth material is mixed via a fifth line 5 into the second mixture via a sixth line 6 to be mixed with the second mixture and the first mixture. That is, the fifth material introduced through the fifth line 5 is mixed in the sixth line 6 such that the third material and the fourth material are mixed in the first mixer 22 and then mixed with the fifth material in the sixth line 6 while being discharged through the sixth line 6; in particular, the fifth material is mixed with the second mixture prior to the first mixture and the second mixture, corresponding to the second line 2 being arranged at the connection point of the sixth line 6 after the connection point of the fifth line 5 and the sixth line 6 (downstream in the direction of flow), so that the fifth material can be mixed with the second mixture before the mixture obtained is mixed with the first mixture.
According to the present invention, preferably, the mixing of the first mixture and the second mixture may further include: the mixed materials are sent to a second mixer 23 to be mixed. So as to obtain the material with more sufficient mixing effect.
According to the present invention, in mixing the above materials through the respective lines, in order to ensure sufficient mixing between the materials and thereby reduce the generation of gel during polymerization, it is preferable that the pressure of the first material is higher than the pressure of the second material by at least 0.1 MPa; the pressure of the second material is at least 0.1MPa higher than that of the fourth material; the pressure of the third material is at least 0.1MPa higher than that of the fourth material; the pressure of the fifth material is at least 0.1MPa higher than that of the fourth material. In order to further fully mix the materials and reduce the gel in the polymerization process, the pressure of the third material is more preferably 0.1-0.5MPa higher than that of the fourth material; the pressure of the first material is 0.1-0.5MPa higher than that of the second material; the pressure of the second material is 0.1-0.5MPa higher than that of the fourth material; the pressure of the fifth material is 0.1-0.5MPa higher than that of the fourth material.
According to the present invention, the pressure of the third material is not particularly limited, and can be appropriately selected by those skilled in the art according to the target product to be synthesized. Preferably, the pressure of the third material is 0.17 to 11MPa, more preferably 0.2 to 5MPa, still more preferably 0.3 to 3MPa, more preferably 0.5 to 2 MPa.
In the present invention, the pressure is a gauge pressure.
In the present invention, the amount of each material and the introduction rate of each material are not particularly limited, and those skilled in the art can synthesize a target product as needed under conditions conventional in the art.
As shown in fig. 2, the present invention also provides a mixing device for mixing a first material, a second material, a third material, a fourth material and an optional fifth material, wherein the device comprises: a first line 1, a second line 2, a third line 3, a fourth line 4, a sixth line 6, a first mixer 22, a second mixer 23 and optionally a fifth line 5;
wherein the first pipeline 1 and the second pipeline 2 are communicated, so that the first material is mixed into the second material passing through the second pipeline 2 through the first pipeline 1 to obtain the first mixture;
the third line 3 and the fourth line 4 are in communication with the first mixer 22, respectively, so that the third material is added to the first mixer 22 via the third line 3 and the fourth material via the fourth line 4, obtaining said second mixture;
the first mixer 22, the sixth line 6 and the second mixer 23 are in communication in sequence, and the second line 2 is in communication with the sixth line 6, so that the first mixture from the second line 2 is mixed into the second mixture passing through the sixth line 6 and enters the second mixer 23 for mixing;
an optional fifth line 5 is in communication with the first mixer 22 such that a fifth material is added to the first mixer 22 via the fifth line 5 to mix with the third and fourth materials; and/or the presence of a gas in the gas,
an optional fifth line 5 communicates with a sixth line 6, and the fifth material is mixed into the second mixture passing through the sixth line 6 via the fifth line 5 to be mixed with the second mixture and the first mixture.
Wherein the above description of some parts of the device also applies to the description of the device here.
According to the present invention, preferably, the first pipeline 1, the second pipeline 2, the third pipeline 3, the fourth pipeline 4 and the fifth pipeline 5 are respectively provided with a first flow meter 7, a second flow meter 8, a third flow meter 9, a fourth flow meter 10 and a fifth flow meter 11 in sequence in the material flow direction; the first pipeline 1, the second pipeline 2, the third pipeline 3 and the fourth pipeline 6 are respectively provided with a first backpressure valve 17, a second backpressure valve 18, a third backpressure valve 19 and a fourth backpressure valve 20 in sequence in the material flowing direction; the fifth line 5 is provided with a fifth back-pressure valve (21) in the material flow direction. It will be appreciated that the arrangement of the fifth pipeline 5 may be configured accordingly in the case of a fifth material.
In order to measure the pressure of each material, first pressure measuring means 12, second pressure measuring means 13, third pressure measuring means 14, fourth pressure measuring means 15, and fifth pressure measuring means 16 are preferably provided between the first flowmeter 7, the second flowmeter 8, the third flowmeter 9, the fourth flowmeter 10, and the fifth flowmeter 11, and the first back pressure valve 17, the second back pressure valve 18), the third back pressure valve 19, the fourth back pressure valve 20, and the fifth back pressure valve 21, respectively.
More preferably, the connection point of the first line 1 to the second line 2 is arranged on the second line 2 between the second flowmeter 8 and the second backpressure valve 18; the connection point of the second line 2 and the sixth line 6 is arranged on the sixth line 6 between a fourth backpressure valve 20 and a second mixer 23. When the fifth line 5 is in communication with the sixth line 6, the connection point of the fifth line 5 and the sixth line 6 is provided between the fourth backpressure valve 20 of the sixth line 6 and the second mixer 23, and the connection point of the second line 2 and the sixth line 6 is located after the connection point of the fifth line 5 and the sixth line 6.
According to the invention, the mixing effect of mutually insoluble gas and liquid can be obviously improved by mixing the materials by using the device, and particularly, when the method is used for mixing the materials for preparing the ethylene propylene rubber, the content of hydrogen in the mixed materials can be kept stable, thereby obviously reducing gel generated in the polymerization process.
The invention also provides an olefin copolymerization method, which comprises the steps of mixing the materials by adopting the mixing method, and contacting the obtained mixture with a catalyst under the condition of olefin copolymerization. In particular as described above.
Wherein the olefin copolymerization conditions may be those conventional in the art, and may include, for example: the temperature is 15-30 deg.C, and the pressure is 2-3 MPa. The catalyst may be a catalyst conventional in the art, for example a vanadium oxytrichloride-alkylaluminium catalytic system (molar ratio Al/V from 5 to 15: 1).
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the gel content in the copolymerization product was determined by a suspended screen method, i.e., a gel sample to be measured was placed in a 200-mesh closed filter screen, suspended in decalin as a solvent, oscillated at room temperature for 6 hours, and then the closed filter screen was taken out and dried, and the weight gain of the suspended screen was the gel weight gain.
The mixing device shown in fig. 2 comprises: a first pipeline 1, a second pipeline 2, a third pipeline 3, a fourth pipeline 4, a fifth pipeline 5 and a sixth pipeline 6, wherein the first pipeline 1 is provided with a first flowmeter 7, a first pressure measuring unit 12 and a first backpressure valve 17 in sequence; a second flowmeter 8, a second pressure measuring unit 13, and a second back pressure valve 18 are disposed in this order on the second line 2; a third flow meter 9, a third pressure measuring means 14, and a third back pressure valve 19 are disposed in this order on the third line 3; a fourth flowmeter 10 and a fourth pressure measuring unit 15 are disposed in this order on the fourth line 4; a fourth back pressure valve 20 is sequentially arranged on the sixth pipeline 6; a fifth flow meter 11, a fifth pressure measuring unit 16, and a fifth back pressure valve 21 are disposed in this order on the fifth line 5; wherein the terminal end of the third line 3 and the terminal end of the fourth line 4 are in communication with the first mixer 22, the starting end of the sixth line 6 is in communication with the first mixer 22 and the terminal end of the sixth line 6 is in communication with the second mixer 23;
wherein the connection point of the first line 1 and the second line 2 is located between the second pressure measuring unit 13 and the second backpressure valve 18; the connection point of the fifth line 5 and the sixth line 6 is located between the fourth backpressure valve 20 and the second mixer 23, and the connection point of the second line 2 and the sixth line 6 is located between the connection point of the fifth line 5 and the sixth line 6 and the second mixer 23.
With the mixing device shown in fig. 2, the first material enters the second pipeline 2 through the first pipeline 1 and is mixed with the second material introduced from the second pipeline 2 to obtain a first mixture; the third material is introduced into the first mixer 22 through the third line 3 to be mixed with the fourth material introduced into the first mixer 22 through the fourth line 4, resulting in a second mixture; the fifth material enters the sixth pipeline through the fifth pipeline 5, is mixed with the second mixture output by the sixth pipeline, is mixed with the first mixture entering the sixth pipeline 6 through the second pipeline 2, and enters the second mixer 23.
Example 1
This example illustrates the synthesis of ethylene propylene rubber
The mixing apparatus shown in fig. 2 is used, except that the apparatus is not provided with a fifth pipeline and related parts on the pipeline, so that the fifth material is not used in the reaction process, and the specific process is as follows:
1) in the first line 1, the first material is metered by a first flow meter (gas flow meter) 7, the flow rate thereof is controlled to be 7g/min, and a first back pressure valve 17 is adjusted so that the gauge pressure of a first pressure gauge 12 is 1.4MPa, and then mixed into the second line 2 to be mixed with the second material from the second line 2; wherein the first material is ethylene and the second material is propylene;
2) in the second line 2, the second material is metered by a second flow meter (diaphragm metering pump) 8, the flow rate thereof is controlled to be 30g/min, and a second back pressure valve 18 is adjusted so that the gauge pressure of a second pressure gauge 13 becomes 1.3MPa, after which it is mixed into a sixth line 6;
3) in the third line 3, the third material is metered by a third flow meter (gas flow meter) 9, the flow rate thereof is controlled to 0.1g/h, and a third back pressure valve 19 is adjusted so that the gauge pressure of the first pressure gauge 14 becomes 1.5MPa, before being fed into a first mixer 23; the third material is hydrogen;
4) in the fourth line 4, the fourth material is metered by a fourth flow meter (diaphragm metering pump) 10, the flow rate thereof is controlled to be 180g/min, and a fourth back pressure valve 20 is adjusted so that the gauge pressure of a fourth pressure gauge 15 is 1.2MPa, and then, after being fed into a first mixer 22 to be mixed with the third material from the third line 3, it enters a sixth line to be mixed with the mixture of the first material and the second material, and enters a second mixer 23 to be further mixed; the fourth material was hexane.
After the materials are mixed, the materials are polymerized under a vanadium oxychloride-alkyl aluminum catalytic system, wherein the molar ratio of Al to V is 10:1, the temperature is 20 ℃, the pressure is 2.0MPa, the glue solution obtained after the polymerization reaction is ended by ethanol, and then the glue solution is dried in a drying oven at the temperature of 50 ℃ and the pressure of-0.1 MPa (gauge pressure) to obtain the ethylene propylene rubber, wherein the gel content of the ethylene propylene rubber is 22.6 percent by weight.
Example 2
This example illustrates the synthesis of ethylene propylene diene monomer.
The device shown in fig. 2 is adopted, and the specific process is as follows:
1) in the first line 1, the first material is metered by a first flow meter (gas flow meter) 7, the flow rate thereof is controlled to be 7g/min, and a first back pressure valve 17 is adjusted so that the gauge pressure of a first pressure gauge 12 is 1.4MPa, and then mixed into the second line 2 to be mixed with the second material from the second line 2; wherein the first material is ethylene and the second material is propylene;
2) in the second line 2, the second material is metered by a second flow meter (diaphragm metering pump) 8, the flow rate thereof is controlled to be 30g/min, and a second back pressure valve 18 is adjusted so that the gauge pressure of a second pressure gauge 13 becomes 1.3MPa, after which it is mixed into a sixth line 6;
3) in the third line 3, the third material is metered by a third flow meter (gas flow meter) 9, the flow rate thereof is controlled to 0.1g/h, and a third back pressure valve 19 is adjusted so that the gauge pressure of the first pressure gauge 14 becomes 1.5MPa, before being fed into a first mixer 23; the third material is hydrogen;
4) in the fourth line 4, the fourth material is metered by a fourth flow meter (diaphragm metering pump) 10, the flow rate thereof is controlled to be 180g/min, and a fourth back pressure valve 20 is adjusted so that the gauge pressure of a fourth pressure gauge 15 is 1.2MPa, and then the fourth material is fed into a first mixer 22 to be mixed with the third material from the third line 3, and then the mixture is fed into a sixth line; the fourth material is hexane;
5) in the fifth line 5, the fifth stream is metered by a fifth flow meter (diaphragm metering pump) 11, the flow rate thereof is controlled to 0.9g/min, and a fifth back pressure valve 21 is adjusted so that the gauge pressure of a fifth pressure gauge 16 becomes 1.3MPa, before entering the sixth line; the fifth material flow is ethylidene norbornene;
wherein the material from the first mixer 22 is mixed via a sixth line 6 with the fifth stream and the above described mixture of the first and second material, and further mixed in a second mixer 23.
After being mixed, the materials are polymerized under a vanadium oxychloride-alkyl aluminum catalytic system, wherein the molar ratio of Al/V is 10:1, the temperature is 20 ℃, the pressure is 2.0MPa, the glue solution obtained after the polymerization reaction is finished is terminated by ethanol, and then the glue solution is dried in a drying oven with the temperature of 50 ℃ and the pressure of-0.1 MPa (gauge pressure), so that the ethylene propylene diene monomer is obtained, and the gel content of the ethylene propylene diene monomer is 24.3 weight percent.
Comparative example 1
The procedure is as in example 1, except that the materials are mixed by the following method: as shown in fig. 1 (fifth line and its associated configuration not included), the first stream (hydrogen) is mixed into the fourth line 4 through the first flow meter (gas flow meter) 7 and the first back-pressure valve 17, the conditions in this line 1 being the conditions of step 3) of example 1); a second material (ethylene) is mixed into the fourth line 4 via a second gas flow meter (gas flow meter) 8 and a second back-pressure valve 18 (the conditions in this line 2 are those of step 1 of example 1); the third material (propylene) was mixed into the fourth line 4 via the third flow meter (diaphragm metering pump) 9 and the third back-pressure valve 19 (the conditions in this line 3 were those of step 2 of example 1); in a fourth line 4, in which the conditions are those of step 4 of example 1, a fourth material (hexane) is mixed with the respective materials coming from the first line 1, the second line 2 and the third line 3, respectively, through a fourth flow meter (diaphragm metering pump) 10 and a fourth back-pressure valve 20, going to a mixer 23.
After the materials are mixed, the materials are polymerized under a vanadium oxychloride-alkyl aluminum catalytic system, wherein the molar ratio of Al/V is 10:1, the temperature is 20 ℃, the pressure is 2.0MPa, the glue solution obtained after the polymerization reaction is finished is stopped by ethanol, and then the glue solution is dried in a drying oven with the temperature of 50 ℃ and the pressure of-0.1 MPa (gauge pressure), so that the ethylene propylene rubber is obtained, and the gel content of the ethylene propylene rubber is 30.2 weight percent.
Comparative example 2
The procedure is as in example 2, except that the materials are mixed by the following method: as shown in fig. 1 (including the fifth line and its associated configuration), the first stream (hydrogen) is mixed into the fourth line 4 via the first flow meter (gas flow meter) 7 and the first backpressure valve 17 (the conditions in this line 1 are those of step 3 of example 2); a second material (ethylene) is mixed into the fourth line 4 via a second gas flow meter (gas flow meter) 8 and a second back-pressure valve 18 (the conditions in this line 2 are those of step 1) of example 2); the third material (propylene) was mixed into the fourth line 4 via the third flow meter (diaphragm metering pump) 9 and the third back-pressure valve 19 (the conditions in this line 3 were those of step 2 of example 2); in the fourth line 5, a fifth material (ethylidene norbornene) was mixed into the fourth line 4 through a fifth flow meter (diaphragm metering pump) 11 and a fifth back pressure valve 21 (the conditions in this line 5 are those of step 5 of example 2); in a fourth line 4, in which the conditions are those of step 4 of example 2, a fourth material (hexane) is mixed with the respective materials coming from the first line 1, the second line 2 and the third line 3, respectively, through a fourth flow meter (diaphragm metering pump) 10 and a fourth back pressure valve 20, and then sent to a mixer 23.
After the materials are mixed, the materials are polymerized under a vanadium oxychloride-alkyl aluminum catalytic system, wherein the molar ratio of Al/V is 10:1, the temperature is 20 ℃, the pressure is 2.0MPa, the glue solution obtained after the polymerization reaction is finished is terminated by ethanol, and then the glue solution is dried in a drying oven with the temperature of 50 ℃ and the pressure of-0.1 MPa (gauge pressure), so that the ethylene propylene diene monomer is obtained, and the gel content of the ethylene propylene diene monomer is 34.6 weight percent.
Comparative example 3
The procedure is as in example 2, except that the materials are mixed by the following method: introducing a hydrogen stream into the line for the ethylene stream to mix the hydrogen with the ethylene, introducing the resulting mixture into the line for the propylene stream to mix with the propylene, and introducing the resulting mixture into the line for the hexane stream; the ethylidene norbornene is introduced into the hexane stream line to mix the ethylidene norbornene and hexane, and then mixed with the mixture introduced through the propylene stream line and further mixed in the mixer 23.
After the materials are mixed, the materials are polymerized under a vanadium oxychloride-alkyl aluminum catalytic system, wherein the molar ratio of Al/V is 10:1, the temperature is 20 ℃, the pressure is 2.0MPa, the glue solution obtained after the polymerization reaction is finished is terminated by ethanol, and then the glue solution is dried in a drying oven with the temperature of 50 ℃ and the pressure of-0.1 MPa (gauge pressure), so that the ethylene propylene diene monomer is obtained, and the gel content of the ethylene propylene diene monomer is 28.6 weight percent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A process for mixing materials suitable for the copolymerization of olefins, the process comprising:
1) mixing the first material and the second material to obtain a first mixture;
2) mixing the third material and the fourth material to obtain a second mixture;
3) mixing the first mixture with the second mixture;
optionally, introducing a fifth material in step 2) or step 3);
the first material and the second material are different and are selected from alpha-olefin, the third material is hydrogen, the fourth material is an organic solvent, and the fifth material is dialkene.
2. The process of claim 1, wherein the first material is ethylene, propylene, or butylene; the second material is propylene, butylene or octene; the fourth material is one or more of n-pentane, n-hexane, n-heptane, cyclohexane and benzene; the fifth material is one or more of ethylidene norbornene, dicyclopentadiene and 1, 4-hexadiene.
3. The method of claim 2, wherein the first material is ethylene, the second material is propylene, and the fourth material is one or more of n-hexane, cyclohexane, and benzene.
4. The method according to any one of claims 1 to 3,
the mixing mode of the first material and the second material is as follows: mixing the first material from the first pipeline into a second material passing through a second pipeline to obtain a first mixture;
the mode that third material and fourth material mix does: feeding the third material via a third line and the fourth material via a fourth line into a first mixer to obtain the second mixture;
the first mixture and the second mixture are mixed in the following way: mixing the first mixture from the second line into the second mixture passing through the sixth line;
optionally, step 2) introduces the fifth material in the following way: feeding the fifth material to the first mixer via a fifth line to mix with the third material and the fourth material;
optionally, step 3) introduces the fifth material in the following way: the fifth material is mixed into the second mixture passing through the sixth line via a fifth line to be mixed with the second mixture and the first mixture.
5. The method of claim 1, wherein the pressure of the first material is at least 0.1MPa higher than the pressure of the second material; the pressure of the third material is at least 0.1MPa higher than that of the fourth material; the pressure of the fifth material is at least 0.1MPa higher than that of the fourth material.
6. The method of claim 5, wherein the pressure of the first material is 0.1-0.5MPa higher than the pressure of the second material; the pressure of the third material is 0.1-0.5MPa higher than that of the fourth material; the pressure of the fifth material is 0.1-0.5MPa higher than that of the fourth material.
7. The process of any of claims 1-3 and 5-6, wherein the pressure of the third material is 0.17-11 MPa.
8. A mixing device for mixing a first material, a second material, a third material, a fourth material and optionally a fifth material, the first and second materials being different and selected from alpha-olefins, the third material being hydrogen, the fourth material being an organic solvent, the fifth material being a diene, the device comprising: a first line (1), a second line (2), a third line (3), a fourth line (4), a sixth line (6), a first mixer (22), a second mixer (23) and optionally a fifth line (5);
wherein the first pipeline (1) and the second pipeline (2) are communicated, so that the first material is mixed into the second material passing through the second pipeline (2) through the first pipeline (1) to obtain a first mixture;
the third line (3) and the fourth line (4) are respectively communicated with the first mixer (22), so that the third material is added into the first mixer (22) through the third line (3) and the fourth material is added into the first mixer (22) through the fourth line (4), and a second mixture is obtained;
the first mixer (22), the sixth pipeline (6) and the second mixer (23) are communicated in sequence, and the second pipeline (2) is communicated with the sixth pipeline (6), so that the first mixture from the second pipeline (2) is mixed into the second mixture passing through the sixth pipeline (6) and enters the second mixer (23) for mixing;
an optional fifth line (5) is in communication with the first mixer (22) such that a fifth material is added to the first mixer (22) via the fifth line (5) to mix with the third material and the fourth material; and/or the presence of a gas in the gas,
an optional fifth line (5) communicates with the sixth line (6) and the fifth material is mixed via the fifth line (5) into the second mixture passing through the sixth line (6) to mix with the second mixture and the first mixture.
9. The device according to claim 8, wherein the first line (1), the second line (2), the third line (3), the fourth line (4) and the fifth line (5) are provided with a first flow meter (7), a second flow meter (8), a third flow meter (9), a fourth flow meter (10), a fifth flow meter (11), respectively, in that order in the material flow direction; the first pipeline (1), the second pipeline (2), the third pipeline (3) and the fourth pipeline (4) are respectively provided with a first backpressure valve (17), a second backpressure valve (18), a third backpressure valve (19) and a fourth backpressure valve (20) in sequence in the material flowing direction; the fifth line (5) is provided with a fifth back-pressure valve (21) in the material flow direction.
10. The device according to claim 9, wherein a first pressure measuring unit (12), a second pressure measuring unit (13), a third pressure measuring unit (14), a fourth pressure measuring unit (15), and a fifth pressure measuring unit (16) are provided between the first flowmeter (7), the second flowmeter (8), the third flowmeter (9), the fourth flowmeter (10), and the fifth flowmeter (11) and the first back pressure valve (17), the second back pressure valve (18), the third back pressure valve (19), the fourth back pressure valve (20), and the fifth back pressure valve (21), respectively.
11. The device according to claim 10, wherein the connection point of the first line (1) to the second line (2) is provided on the second line (2) between a second flowmeter (8) and a second backpressure valve (18); the connection point of the second line (2) to the sixth line (6) is arranged on the sixth line (6) between a fourth backpressure valve (20) and a second mixer (23);
when a fifth line (5) is in communication with a sixth line (6), the connection point of the fifth line (5) with the sixth line (6) is arranged between a fourth backpressure valve (20) of the sixth line (6) and a second mixer (23), and the connection point of the second line (2) with the sixth line (6) is located after the connection point of the fifth line (5) with the sixth line (6).
12. A process for the copolymerisation of olefins, which process comprises mixing the materials according to any one of claims 1 to 7 and contacting the mixture with a catalyst under olefin copolymerisation conditions.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879361A (en) * | 1971-11-22 | 1975-04-22 | Ici Ltd | Polymerisation process |
| US5508366A (en) * | 1994-10-18 | 1996-04-16 | S. C. Johnson & Son, Inc. | Continuous production of reduced gel content hydroxylated addition polymers |
| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
| CN101410423A (en) * | 2006-04-03 | 2009-04-15 | 道达尔石油化学产品研究弗吕公司 | Process for improving the polymerization of ethylene and one or more optional co-monomer(s) in a polymerization loop reactor |
| CN102171251A (en) * | 2008-10-03 | 2011-08-31 | 英尼奥斯欧洲有限公司 | Method for controlling a process for polymerisation of an olefin |
| CN102532383A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Gel inhibiting method for ethylene-alphaolefin-non-conjugated diene terpolymer |
| CN103374088A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Ethylene-alpha olefin copolymer and preparation method thereof |
| CN104974294A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Material mixing method and material mixing device used for olefin copolymerization |
| CN104974277A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst feeding method used in olefin polymerization, ethylene propylene monomer or ethylene propylene diene monomer and preparation method thereof |
| CN105085757A (en) * | 2014-04-22 | 2015-11-25 | 中国石油化工股份有限公司 | Ethylene-alpha olefin-non-conjugated dialkene copolymer and preparation method thereof |
-
2016
- 2016-12-09 CN CN201611128818.7A patent/CN108610447B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879361A (en) * | 1971-11-22 | 1975-04-22 | Ici Ltd | Polymerisation process |
| US5508366A (en) * | 1994-10-18 | 1996-04-16 | S. C. Johnson & Son, Inc. | Continuous production of reduced gel content hydroxylated addition polymers |
| CN101410423A (en) * | 2006-04-03 | 2009-04-15 | 道达尔石油化学产品研究弗吕公司 | Process for improving the polymerization of ethylene and one or more optional co-monomer(s) in a polymerization loop reactor |
| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
| CN102171251A (en) * | 2008-10-03 | 2011-08-31 | 英尼奥斯欧洲有限公司 | Method for controlling a process for polymerisation of an olefin |
| CN102532383A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Gel inhibiting method for ethylene-alphaolefin-non-conjugated diene terpolymer |
| CN103374088A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Ethylene-alpha olefin copolymer and preparation method thereof |
| CN104974294A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Material mixing method and material mixing device used for olefin copolymerization |
| CN104974277A (en) * | 2014-04-10 | 2015-10-14 | 中国石油化工股份有限公司 | Catalyst feeding method used in olefin polymerization, ethylene propylene monomer or ethylene propylene diene monomer and preparation method thereof |
| CN105085757A (en) * | 2014-04-22 | 2015-11-25 | 中国石油化工股份有限公司 | Ethylene-alpha olefin-non-conjugated dialkene copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 乙丙橡胶的凝胶;娄诚玉;《石油化工》;19790731;第8卷(第7期);第496-503页 * |
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