A polymerization reaction device and process

Abstract

The present invention discloses a polymerization reaction device, comprising a tower body (1), comprising a top section (11), a middle section (12) and a bottom section (13) arranged in sequence from top to bottom; in the middle section (12) and the bottom section (13) of the tower body, at least a vertically arranged partition (120) is provided inside the middle section (12), and the partition (120) divides the inner cavity at the corresponding position of the tower body into a first partition distillation zone (120a) and a second partition distillation zone (120b); the middle section (12) of the tower body has a first feed inlet (121) and a second feed inlet (122) which are connected to the first partition distillation zone (120a); the middle section (12) of the tower body has a third feed inlet (123) which is connected to the second partition distillation zone (120b). The present invention also discloses a polymerization reaction process using the above-mentioned polymerization reaction device. Compared with the prior art, the present invention can shorten the polymerization process and improve the reaction conversion rate.

Description

Technical Field

[0001] The invention relates to the technical field of polymerization reaction, in particular to a polymerization reaction device and process. Background Art

[0002] Copolymerization is an addition polymerization reaction in which two or more monomers participate together. The polymer molecular chain formed contains two or more monomer units. This polymer is called a copolymer. In terms of operational complexity, it is often more convenient to purchase comonomers directly. However, for some special comonomers, such as reaction intermediates and substances that are easier to decompose, a comonomer reaction section and a matching separation section are usually added. The comonomers generated by the reaction are separated and purified before entering the copolymerization unit for copolymerization reaction. The copolymerization products are then sent to the product separation section. It can be seen that the polymerization process in the above case is long and the process is complicated.

[0003] The baffle distillation tower (also called the next-door distillation tower) is essentially to add a vertical baffle inside the tower, dividing the interior of the conventional distillation tower into two, and completing the mass transfer and heat transfer process in one distillation tower at the same time. Compared with the fully thermally coupled distillation tower, the baffle distillation tower combines the pre-fractionation tower and the main tower of the fully thermally coupled distillation tower in the same distillation tower, saving equipment investment. At the same time, since the heat is repeatedly recycled in the same tower, it also saves energy consumption. Generally, the baffle tower technology is applied to the distillation separation process of 3 components or more. For example, the Chinese invention patent "A process for continuous distillation separation of trimethyl orthoformate" with patent application number 201210199674.X (publication number CN102690176A) introduces the technology of baffle distillation tower to separate the distillate of the light tower into methanol, trimethyl orthoformate and solvent oil.

[0004] Specifically, Figure 1 As shown, the partition plate distillation tower includes a tower body, a condenser and a reboiler.

[0005] The tower body includes a top section, a middle section and a bottom section arranged in sequence from top to bottom. A first common distillation zone is formed inside the top section of the tower body; a vertically arranged partition is provided inside the middle section of the tower body, and the partition divides the inner cavity of the middle section of the tower body into a first partition distillation zone and a second partition distillation zone; a second common distillation zone is formed inside the bottom section of the tower body;

[0006] The condenser is arranged at the top of the tower body and is used to condense the material distilled from the top section of the tower body.

[0007] The reboiler is arranged at the bottom of the tower body and is used to vaporize the material distilled from the bottom section of the tower body.

[0008] The feed port is usually fed with three components (the three components are recorded as X, Y and Z, and the saturation temperatures of X, Y and Z are recorded as TX 、T Y and T Z ), assuming T Z >T Y >T X , that is, Z is the heavy component, X is the light component, Y is the middle component, the light component X is discharged from the top of the tower body, the heavy component Z is discharged from the bottom of the tower body, and the middle component is discharged from the left and right middle of the right side of the partition. Summary of the invention

[0009] The first technical problem to be solved by the present invention is to provide a polymerization reaction device which can shorten the polymerization process in view of the current status of the prior art.

[0010] The second technical problem to be solved by the present invention is to provide a polymerization reaction process using the above-mentioned polymerization reaction device, which can shorten the polymerization process and improve the reaction conversion rate.

[0011] The technical solution adopted by the present invention to solve the above-mentioned first technical problem is: a polymerization reaction device, comprising a tower body, including a top section, a middle section and a bottom section arranged in sequence from top to bottom;

[0012] A condensing unit is provided at the top of the tower body and is used to condense the material distilled from the top section of the tower body; and

[0013] The reboiling unit is arranged at the bottom of the tower body and is used to vaporize the material distilled from the bottom section of the tower body;

[0014] It is characterized in that: a mixing zone is formed inside the top section of the tower body;

[0015] A vertically arranged partition is provided at least inside the middle section of the middle section and the bottom section of the tower body, and the partition divides the inner cavity at the corresponding position of the tower body into a first partition distillation zone and a second partition distillation zone;

[0016] The middle section of the tower body has a first feed inlet and a second feed inlet which are connected to the first baffle distillation zone, and are used to feed substance A and substance B respectively, so that substance A and substance B generate comonomer C and high boiling product E in the first baffle distillation zone;

[0017] The middle section of the tower body has a third feed port which is connected to the second partition distillation zone and is used to feed the comonomer D so that the comonomer C and the comonomer D generate the copolymer P in the second partition distillation zone;

[0018] The top section of the tower body is provided with a solvent inlet which is communicated with the mixing zone.

[0019] In order to improve the conversion rate of substance A, substance B and comonomer C, the top section of the tower body has a first discharge port that is connected to the mixing zone;

[0020] The middle section of the tower body has a first return port and a second return port which are connected to the first partition distillation zone, and are used to respectively return the material A and the material B condensed by the condensation unit;

[0021] The middle section of the tower body has a third return port which is in communication with the second partition distillation zone and is used for returning the comonomer C condensed by the condensation unit.

[0022] In order to improve the conversion rate of comonomer D, the middle section of the tower body has a fourth return port connected to the second partition distillation zone for returning the comonomer D condensed by the condensation unit. When the comonomer D and the substance B are the same substance, the fourth return port is not required.

[0023] In order to realize the step-by-step condensation of A, B, C, D, solvent, the condensation unit comprises

[0024] A first condenser, whose gas phase inlet is connected to the first discharge port, and whose liquid phase outlet is connected to the solvent inlet;

[0025] A second condenser, whose gas phase inlet is connected to the gas phase outlet of the first condenser, and whose liquid phase outlet is connected to the third return port;

[0026] A third condenser, whose gas phase inlet is connected to the gas phase outlet of the second condenser, and whose liquid phase outlet is connected to the fourth return port;

[0027] A fourth condenser, whose gas phase inlet is connected to the gas phase outlet of the third condenser, and whose liquid phase outlet is connected to the second return port; and

[0028] The fifth condenser has a gas phase inlet connected to the gas phase outlet of the fourth condenser, and a liquid phase outlet connected to the first return port.

[0029] In order to conveniently control the concentration of substance A and substance B in the first partition distillation zone, a first flow regulating valve is provided on the pipeline between the condensing unit and the first return port;

[0030] A second flow regulating valve is provided on the pipeline between the condensing unit and the second feed return port.

[0031] There are two ways to set the above partition:

[0032] In the first solution, the partition is provided inside the middle section of the tower body;

[0033] A common distillation zone is formed inside the bottom section of the tower body;

[0034] The bottom section of the tower body has a third discharge port which is connected with the common distillation zone;

[0035] The bottom section of the tower body has a sixth return port which is connected with the common distillation zone and is used for returning the material vaporized by the reboiler unit.

[0036] In order to provide a certain amount of ascending steam flow, the reboiler unit includes a second reboiler, the liquid phase inlet of the second reboiler is connected to the third discharge port, and the gas phase outlet of the second reboiler is connected to the sixth return port.

[0037] In order to recover the solvent, a post-processing unit is also included to post-process the materials distilled from the bottom section of the tower body and separate them from each other;

[0038] The liquid phase inlet of the post-processing unit is connected to the third discharge port, and the solvent outlet of the post-processing unit is connected to the solvent inlet.

[0039] In the second solution, the partitions are provided inside the middle section and the bottom section of the tower body;

[0040] The bottom section of the tower body has a second discharge port interpenetrating with the first partition plate distillation zone and a third discharge port interpenetrating with the second partition plate distillation zone;

[0041] The bottom section of the tower body has a fifth return port communicating with the first partition distillation zone and a sixth return port communicating with the second partition distillation zone, which are used to supply the material vaporized by the reboiler unit for return.

[0042] In order to provide a certain amount of rising steam flow, the reboiler unit includes

[0043] A first reboiler, whose liquid phase inlet is connected to the second discharge port, and whose gas phase outlet is connected to the fifth return port; and

[0044] The second reboiler has a liquid phase inlet connected to the third discharge port, and a gas phase outlet connected to the sixth return port.

[0045] In order to recover the solvent, a post-processing unit is also included to post-process the materials distilled from the bottom section of the tower body and separate them from each other;

[0046] The liquid phase inlet of the post-processing unit is connected to the second discharge port and the third discharge port, and the solvent outlet of the post-processing unit is connected to the solvent inlet.

[0047] Compared with the second option, in the above first option, the copolymer monomer C generated in the first partition distillation zone can mainly enter the common distillation zone in liquid form and then enter the second partition distillation zone for copolymerization reaction. Compared with the operation of vaporizing all C and condensing it in the condenser at the top of the tower body and then returning it to the second partition distillation zone, some energy consumption can be saved.

[0048] In order to conveniently provide catalysts for participating in the copolymerization reaction, the middle section of the tower body has a catalyst inlet which is connected with the second partition distillation zone.

[0049] The technical solution adopted by the present invention to solve the above-mentioned second technical problem is: a polymerization reaction process using the above-mentioned polymerization reaction device, characterized in that it includes the following steps: substance A and substance B enter the first baffle distillation zone through the first feed port and the second feed port, comonomer D enters the second baffle distillation zone through the third feed port, and the solvent enters the mixing zone through the solvent inlet. Substance A and substance B generate comonomer C and high boiling point E through a reversible reaction in the first baffle distillation zone, and comonomer C subsequently enters the second baffle distillation zone and reacts with comonomer D in the second baffle distillation zone to generate copolymer P, unreacted substance A, substance B, comonomer C and comonomer D and part of the solvent are distilled off at the top section of the tower body, and high boiling point E, copolymer P and part of the solvent are distilled off at the bottom section of the tower body.

[0050] Compared with the prior art, the advantages of the present invention are:

[0051] (1) The present invention ingeniously utilizes two regions of the baffle tower (i.e., the first baffle distillation region and the second baffle distillation region) as two different reaction regions, respectively, and completes the process of "comonomer reaction section + comonomer separation section + copolymerization section" with a simple structure, thus significantly saving investment;

[0052] (2) In the process of the present invention, a reversible reaction is carried out in the first partition distillation zone, and substances A and B react and concentrate, which can improve the reversible reaction conversion rate. In the end, except for a small amount of raw material loss caused by non-condensable gas, the rest of the feed A, B, C and D are effectively reacted and converted. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 It is a structural schematic diagram of a partition plate distillation tower in the background technology;

[0054] Figure 2 It is a structural schematic diagram of the first polymerization reaction device of the present invention;

[0055] Figure 3 It is a structural schematic diagram of a second polymerization reaction device of the present invention;

[0056] Figure 4 for Figure 2 A schematic diagram of the structure of the first polymerization reaction device after the copolymerization reaction is eliminated;

[0057] Figure 5 for Figure 2 A schematic diagram of the structure of the first polymerization reaction device after the number of condensers is reduced to three;

[0058] Figure 6 for Figure 5 A schematic diagram of the structure when the bottom distillate in the first polymerization reaction device contains C and / or D;

[0059] Figure 7 This is a schematic diagram of the structure of the polymerization reaction device in Example 1 of the present invention;

[0060] Figure 8 This is a schematic diagram of the structure of a polymerization reaction device in Example 2 of the present invention;

[0061] A, B: monomer substances of comonomer reaction;

[0062] C, D: comonomer substances of copolymerization reaction;

[0063] E: product of monomer reaction, high boiling point;

[0064] P: copolymer produced by copolymerization;

[0065] T1: baffle distillation tower;

[0066] E1~E5: top condenser;

[0067] E6, E7: bottom reboiler;

[0068] C1: compressor or fan;

[0069] V A , V A , V AB : Flow control valve. DETAILED DESCRIPTION

[0070] The present invention is further described in detail below with reference to the accompanying drawings.

[0071] For the following reaction:

[0072]

[0073] The comonomer C is produced by the following reaction:

[0074]

[0075] The above-mentioned reversible reaction refers to a reaction that can proceed in the forward reaction direction and in the reverse reaction direction under the same conditions, and finally reach equilibrium, which also means that the conversion rate of the reversible reaction will not be too high. When in equilibrium, even if the effective reaction volume is increased, the equilibrium will not change. To change the original equilibrium conditions, there are usually the following methods: 1) increase the amount of reactants; 2) remove the reactants in time; 3) change the reaction temperature. Therefore, for some reversible reactions, reactive distillation operations have appeared, increasing the reflux ratio and removing the target reaction products in time, thereby improving the conversion rate of the reactants. Of course, reactive distillation also has some requirements, such as the reaction must be carried out in the liquid phase, it cannot be a strongly endothermic reaction, and there are also requirements for the life and morphology of the catalyst.

[0076] The present invention ingeniously utilizes the baffle distillation tower technology to develop a polymerization reaction device, which replaces the comonomer synthesis section + comonomer separation section + polymerization section of the original ordinary process, greatly simplifying the process.

[0077] To illustrate the principle of the present invention, the generation of C in reaction 2 is taken as an example for specific description, and the saturation temperatures of A, B, C, D, and the solvent are respectively denoted as T A 、T B 、T C 、T D 、T 溶剂 .

[0078] For T A <T C And T B <T C For example, Figure 2 The first polymerization reaction device shown includes a tower body 1 , a condensing unit 2 , a reboiling unit 3 and a post-treatment unit 4 .

[0079] The tower body 1 includes a top section 11, a middle section 12 and a bottom section 13 which are arranged in sequence from top to bottom.

[0080] Specifically, a mixing zone 111 is formed inside the tower top section 11 , a first discharge port 112 communicating with the mixing zone 111 is provided at the top of the tower top section 11 , and a solvent inlet 113 communicating with the mixing zone 111 is provided in the middle of the tower top section 11 .

[0081] A vertically arranged partition 120 is provided inside the middle section 12 of the tower body, and the partition 120 divides the inner cavity of the middle section 12 of the tower body into a first partition distillation zone 120a located on the left and a second partition distillation zone 120b located on the right; the middle part of the middle section 12 of the tower body has a first feed port 121 and a second feed port 122 which are connected to the first partition distillation zone 120a, and are used to feed substance A and substance B respectively, so that substance A and substance B can generate comonomer C and high boiling product E through a reversible reaction in the first partition distillation zone 120a; the middle part of the middle section 12 of the tower body has a first feed port 121 and a second feed port 122 which are connected to the first partition distillation zone 120b. The third feed port 123 and the catalyst inlet 124 are connected, and are used to feed the comonomer D and the catalyst, respectively, so that the comonomer C and the comonomer D can generate the copolymer P through polymerization reaction in the second partition distillation zone 120b; the upper part of the middle section 12 of the tower body has a first return port 125 and a second return port 126 connected with the first partition distillation zone 120a, and are used to feed the material A and the material B respectively; the upper part of the middle section 12 of the tower body has a third return port 127 and a fourth return port 128 connected with the second partition distillation zone 120b, and are used to feed the comonomer C and the comonomer D respectively. Figure 1 In the embodiment, the first feed port 121 and the second feed port 122 share the same port.

[0082] A common distillation zone 131 is formed inside the tower bottom section 13 . The bottom of the tower bottom section 13 has a third discharge port 133 communicating with the common distillation zone 131 . The upper part of the tower bottom section 13 has a sixth return port 135 communicating with the common distillation zone 131 .

[0083] The condensation unit 2 is disposed at the top of the tower body 1 and is used to condense the material distilled from the top section 11 of the tower body. Figure 1 In the embodiment, the condensing unit 2 includes a first condenser 21 , a second condenser 22 , a third condenser 23 , a fourth condenser 24 and a fifth condenser 25 .

[0084] Specifically, the gas phase inlet of the first condenser 21 is connected to the first discharge port 112, and the liquid phase outlet is connected to the solvent inlet 113; the gas phase inlet of the second condenser 22 is connected to the gas phase outlet of the first condenser 21, and the liquid phase outlet is connected to the third return port 127; the gas phase inlet of the third condenser 23 is connected to the gas phase outlet of the second condenser 22, and the liquid phase outlet is connected to the fourth return port 128; the gas phase inlet of the fourth condenser 24 is connected to the gas phase outlet of the third condenser 23, and the liquid phase outlet is connected to the second return port 126; the gas phase inlet of the fifth condenser 25 is connected to the gas phase outlet of the fourth condenser 24, and the liquid phase outlet is connected to the first return port 125. In addition, a first flow regulating valve 251 is provided on the pipeline between the liquid phase inlet of the fifth condenser 25 and the first return port 125; a second flow regulating valve 241 is provided on the pipeline between the liquid phase outlet of the fourth condenser 24 and the second return port 126.

[0085] The reboiler unit 3 is disposed at the bottom of the tower body 1 and is used to vaporize the material distilled from the bottom section 13 of the tower body. Figure 2 In the embodiment, the reboiler unit 3 includes a second reboiler 32 , a liquid phase inlet of the second reboiler 32 is connected to the third discharge port 133 , and a gas phase outlet of the second reboiler 32 is connected to the sixth return port 135 .

[0086] The post-processing unit 4 is used to post-process and separate the materials distilled from the tower bottom section 13. Specifically, the liquid phase inlet of the post-processing unit 4 is connected to the third discharge port 133, and the solvent outlet of the post-processing unit 4 is connected to the solvent inlet 113.

[0087] The working principle of the first polymerization reaction device is as follows: the reactants A and B of reaction 2 enter the first baffle distillation zone 120a through the first feed port 121 and the second feed port 122, and reaction 2 occurs in the first baffle distillation zone 120a. A <T C And T B <T C In the case of, A and B are light substances relative to C, and therefore will be gradually concentrated in the mixing zone 111 at the top of the tower body 1. Here, in order to ensure that there is no A and B in the common distillation zone 131, a small amount of C needs to be entrained at the top of the first partition distillation zone 120a, and the partition 120 is not directly connected to the bottom wall of the tower bottom section 13. Figure 2 As shown, the unconnected portion leaves enough distillation area (i.e., the above-mentioned common distillation zone 131), and after C+E (high boiling substances)+solvent undergoes reaction distillation in the first baffle distillation zone 120a, it enters the common distillation zone 131 from the middle and lower part of the first baffle distillation zone 120a, and part of the comonomer C reacts 1 with D in the common distillation zone 131, and part of it is purified upwards to continue to react with D, and the high boiling substances E of reaction 2 and the copolymer P of reaction 1 are concentrated at the bottom of the tower body 1.

[0088] For T C <T B And T C <T B For example, Figure 3 The second polymerization reaction device shown in FIG. Figure 2 Compared with the first polymerization reaction device shown, the difference is:

[0089] Figure 3In the polymerization reaction device shown, a vertically arranged partition 120 is provided inside the middle section 12 and the bottom section 13 of the tower body, and the partition 120 divides the inner cavity of the middle section 12 and the bottom section 13 of the tower body into a first partition distillation zone 120a and a second partition distillation zone 120b; the bottom of the tower body bottom section 13 has a second discharge port 132 communicating with the first partition distillation zone 120a and a third discharge port 133 communicating with the second partition distillation zone 120b; the upper part of the tower body bottom section 13 has a fifth return port 134 communicating with the first partition distillation zone 120a and a sixth return port 135 communicating with the second partition distillation zone 120b.

[0090] The reboiler unit 3 includes a first reboiler 31 and a second reboiler 32. Specifically, the liquid phase inlet of the first reboiler 31 is connected to the second discharge port 132, and the gas phase outlet is connected to the fifth return port 134; the liquid phase inlet of the second reboiler 32 is connected to the third discharge port 133, and the gas phase outlet is connected to the sixth return port 135.

[0091] The liquid phase inlet of the post-processing unit 4 is connected to the second discharge port 132 and the third discharge port 133 , and the solvent outlet of the post-processing unit 4 is connected to the solvent inlet 113 .

[0092] The working principle of the second polymerization reaction device is as follows: the partition 120 is directly connected to the bottom wall of the tower bottom section 13, and the comonomer C is completely vaporized and condensed through the condensation unit 2 at the top of the tower body 1 and then enters the second partition distillation zone 120b.

[0093] Compare the above two polymerization reaction devices: Figure 3 In the embodiment, the partition 120 is directly connected to the bottom wall of the tower body bottom section 13, two reboilers are arranged at the bottom of the tower body 1, and an E (high boiling product) outlet and a P (copolymer) outlet are respectively arranged on both sides of the bottom of the partition 120, and the two reboiler outlets enter the corresponding partition side respectively. In the first partition distillation zone 120a, all A, B and product C are evaporated to the top of the tower body 1 and refluxed after condensation. A and B enter the first partition distillation zone 120a, and C enters the second partition distillation zone 120b for copolymerization reaction 1; Figure 2In the embodiment, the partition 120 is not directly connected to the bottom wall of the tower bottom section 13, so that there is a common distillation zone 131 below the partition 120, and only one common reboiler can be set at the bottom of the tower body 1. The high boiling product E generated by reaction 2 in the first partition distillation zone 120a and the copolymer P generated by reaction 1 in the second partition distillation zone 120b are further enriched in the common distillation zone 131 after being enriched in their respective areas, and finally discharged from the bottom of the tower body 1. The purpose of such design is that the comonomer C generated in the first partition distillation zone 120a can mainly enter the common distillation zone 131 in the form of liquid phase and then enter the second partition distillation zone 120b for copolymerization reaction. Compared with the operation of completely vaporizing C and condensing it in the condenser at the top of the tower body 1 and then returning it to the second partition distillation zone, part of the energy consumption can be saved.

[0094] To ensure fluidity, the material discharged from the bottom of the tower body 1 needs to be mixed with a certain solvent. The solvent should be one that can easily dissolve the polymer. This not only makes the polymer solution easy to flow, but also reduces the temperature of the reboiler at the bottom of the tower; and T 溶剂 >T A 、T 溶剂 >T B , more preferably T 溶剂 >T A , T 溶剂 >T B , T 溶剂 >T C And T 溶剂 >T D The gas phase at the top of the tower body 1 contains A, B, C, D, solvent and non-condensable gas. According to the saturation temperature of the substance in the gas phase at the top of the tower body 1 under the operating state, the top of the tower body 1 adopts a step-by-step cooling method using multiple condensers. After the substances are initially separated, the logistics with higher A and B contents (relative to C and D) are returned to the inlet at the left side of the tower body 1 slightly below the top of the partition 120 (i.e., the first return port 125 and the second return port 126), the logistics with higher C and D contents (relative to A and B) are returned to the inlet at the right side of the tower body 1 slightly below the top of the partition 120 (i.e., the third return port 127 and the fourth return port 128), and the logistics with higher solvent content (relative to A, B, C, D) are returned to the solvent inlet 113 at the top of the tower body 1. In this embodiment, T 溶剂 >T C >T D >T B >T AThe higher the saturation temperature, the easier it is to condense (for the gas phase). The condensation unit 2 condenses step by step. For example, the condensation temperatures are 100°C, 80°C, 50°C, 35°C, etc. At 100°C, the solvent has been cooled down (after all, it is a mixture, and a small part of other substances will also be condensed), and the rest is still in the gas phase (there is still a small part of the solvent, and most of it should have been condensed). It goes to 80°C to continue condensing, and so on. The materials are recycled in the order of solvent, C, D, B, and A.

[0095] For reaction 2 in the first partition distillation zone 120a, the reaction is a reversible reaction to generate copolymer monomers. Therefore, by setting a flow regulating valve for the reflux liquid (reflux liquid with higher A and B) of the condensing unit 2 at the top of the tower body 1 (i.e., the first flow regulating valve 251 and the second flow regulating valve 241 mentioned above, increasing the opening of the first flow regulating valve 251 and the second flow regulating valve 241, the total conversion rate of substances A and B increases), the concentrations of A and B in the first partition distillation zone 120a can be controlled, so that A and B in the feed are completely converted into C and E.

[0096] The present invention ingeniously utilizes two regions of the baffle tower (i.e., the first baffle distillation region 120a and the second baffle distillation region 120b) as the reaction regions for reaction 2 and reaction 1, respectively. In addition, for a common baffle distillation tower, for example Figure 1 As shown, the left side is generally a three-component feed, assuming T Z >T Y >T X , that is, Z is the heavy component, X is the light component, Y is the intermediate component, the light component X is discharged from the top of the tower body, the heavy component Z is discharged from the bottom of the tower body, and the intermediate component is discharged from the middle of the right side of the partition. In the process of the present invention, on the one hand, the high boiling point E and copolymer P (and solvent) generated by the reaction are regarded as the heavy component Z discharged from the bottom of the tower body 1; the non-condensable gas is regarded as the light component X discharged from the top of the tower body 1; the remaining components are regarded as the intermediate components (in the present invention, it is assumed that the comonomer D is not added to the second partition distillation zone 120b, and it is still considered as ordinary partition distillation, then there should be a discharge of C material in the middle of the second partition distillation zone 120b, which is reacted from the first partition distillation zone 120a, the light component non-condensable gas is discharged from the top of the tower body 1, and the heavy component E (high boiling point) is discharged from the bottom of the tower body 1, such as Figure 4As shown; on the other hand, the outlet of the middle component of the traditional baffle tower is changed to the inlet of the comonomer D in reaction 1 (for the light component non-condensable gas and the heavy component E or P of the present invention, the A, B, C and D components are all considered as middle components, so C and D will be enriched in the middle area of ​​the second baffle distillation zone 120b), so that C and D are copolymerized in the enriched area of ​​the second baffle distillation zone 120b, and the generated copolymer P is a heavy component, which is discharged from the bottom of the tower body 1. This also means that through the process design of the present invention, all raw materials (middle components) are converted into light components and heavy components through reaction 1 and reaction 2 (non-condensable gas will take away a small amount of one or more of A, B, C and D, and there will be a small loss). The present invention only uses a combination of a baffle distillation tower and a plurality of condensers at the top of the tower body 1 to complete the process of "comonomer reaction section + comonomer separation section + copolymerization section", which saves investment significantly. In addition, it can be seen that the present process only has light component and heavy component outlets, and the other A, B, C and D are subjected to vapor-liquid contact in the first baffle distillation zone 120a or the second baffle distillation zone 120b in the form of internal reflux to carry out reaction 1 and reaction 2. In the end, except for a small amount of raw material loss caused by non-condensable gas, the rest of the feed A, B, C and D are effectively reacted and converted. Therefore, the raw material conversion rate of the process of the present invention reaches or exceeds the conversion rate of the current ordinary copolymer synthesis process.

[0097] As for the number of condensers at the top of tower body 1, the ideal setting should be to condense the gas at the top of tower body 1 step by step, and enrich substances A, B, C, D and solvent in different reflux liquids. Therefore, 5 condensers are required in the ideal situation, such as Figure 2 and Figure 3 As shown, these five condensers are all partial condensers, that is, they have both gas phase outlet and liquid phase outlet. The liquid phase returns to the tower body 1 as reflux liquid, and the gas phase enters the next stage condenser. The gas phase outlet of the last stage condenser is non-condensable gas for discharge. The solvent here is special and does not participate in the reaction. Therefore, a separate condenser can be set for enrichment, or it can be enriched in the reflux liquid together with one of the substances A, B, C, and D.

[0098] When T C <T A <T D And T C <T B <T D or T D <T A <T C And T D <T B <T C , A and B can be considered as a kind of intermediate boiling point substance, that is, A and B can be enriched in a reflux liquid; when T A <T C <T B And TA <T D <T B or T B <T C <T A And T B <T D <T A , C and D can be considered as a kind of intermediate boiling point substance, that is, C and D can be enriched in a reflux liquid; in the above case, the top condenser of the tower body 1 can be reduced to four.

[0099] When T A <T C 、T A <T D 、T B <T C And T B <T D or T C <T A 、T C <T B 、T D <T A And T D <T B , A and B can be considered as an intermediate boiling point substance, that is, A and B can be enriched in a reflux liquid, C and D can be considered as an intermediate boiling point substance, that is, C and D can be enriched in a reflux liquid; in the above case, the top condenser of the tower body 1 can be reduced to three, such as Figure 5 shown.

[0100] like Figure 5 As shown, when materials A and B are refluxed as the same reflux liquid, the first flow regulating valve 251 and the second flow regulating valve 241 are reduced by one. In addition, raw materials A, B, and D directly enter the tower body 1, and only raw materials A, B, and D (or in the form of C) are slightly lost in the non-condensable gas. Therefore, the feed streams of raw materials A, B, and D should be adjusted by flow ratio, and the ratio coefficient should match the stoichiometric coefficients of reaction 1 and reaction 2.

[0101] The bottom discharge of the tower body 1 contains high boiling products E, copolymer P and solvent. The target product P needs to be separated by the post-processing unit 4. At the same time, the solvent is separated and supplemented to the top of the tower body 1 as a circulating solvent. 溶剂 <T C And / or T 溶剂 <T D , then part of C and / or D can be discharged from the bottom of the tower body 1 together with the solvent and the copolymer P, and after C and / or D are recovered in the post-processing unit 4, they are returned to the second partition distillation zone 120b below the highest point of the partition, such as Figure 6As shown,

[0102] There are three main sources of solvent in the present invention, one is the reflux liquid of the rich solvent phase of the condenser at the top of the tower body 1, one is the circulating solvent separated by the post-processing unit 4, and the other is a fresh supplementary solvent (to make up for the loss), which can be combined into a stream of materials and enter the top of the tower body 1. The copolymerization reaction 1 usually has catalysts, co-catalysts, etc. added, which are uniformly represented by CAT here, and can be added together with the D raw material or added to the tower body 1 separately.

[0103] For some special copolymerization reactions, for example, one of the comonomers is formed by the reaction of another comonomer and other substances, as follows:

[0104]

[0105]

[0106] The comonomer C is obtained by the reaction of A and B, and B is another monomer in the copolymerization reaction. The present invention is also applicable to such reactions and can be appropriately simplified. One of the top condensers of the tower body 1 can be eliminated. Figure 7 and Figure 8 shown.

[0107] In the present invention, if substance B is a low-carbon hydrocarbon gas that is not easily liquefied at normal pressure, such as ethylene, propylene, etc., the condenser at the top of the tower body 1 needs to be deep-cooled to condense substance B, and when substance B is condensed, non-condensable gas will also be condensed, and the separation effect is not achieved. In this case, a condenser at the top of the tower body 1 can be eliminated, and part of substance B is recovered from the last stage of non-condensable gas, and returned to the first partition distillation zone 120a after being pressurized by a compressor or a fan, such as Figure 7 and Figure 8 shown.

[0108] Embodiment 1:

[0109] The copolymerization reaction of this embodiment is in the following form:

[0110]

[0111]

[0112] Specifically:

[0113]

[0114]

[0115] Among them, CPD is cyclopentadiene, NBE is norbornene, and HB is a high boiling product.

[0116] The polymerization reaction device used in this embodiment is as follows Figure 7 As shown, in this embodiment, the boiling points of NBE and the solvent are relatively close, and the solvent does not participate in the reaction. To simplify the process, NBE and the solvent in the top stream of tower body 1 are condensed as the same stream and returned to tower body 1. Because substance B is gas phase ethylene, in order to ensure the reaction effect of reaction 3 and reaction 4, the feed of ethylene is close to the lower area of ​​the partition. The normal pressure boiling points of the substances involved in the above reaction are shown in Table 1 below.

[0117] Table 1:

[0118] name Ethylene CPD NBE HB Solvents Code B A C E - Normal pressure boiling point -103.7 41.5 94.2 255 69

[0119] In the polymerization reaction of this embodiment, the molecular weight is generally controlled by adding hydrogen. Hydrogen and ethylene are mixed and enter the area on the right side of the partition. In addition, ethylene contains a trace amount of ethane. Therefore, for this process, hydrogen and ethane are non-condensable gases. In order to prevent accumulation, they need to be discharged in time. However, the boiling point of ethylene is very low and it is difficult to condense. Therefore, a compressor is provided to compress part of the exhaust gas and return it to the first partition distillation zone 120a. In addition, the atmospheric boiling point of the comonomer NBE is higher than that of the solvent. Therefore, part of the unreacted NBE leaves the bottom of the tower and needs to be recovered through the post-processing unit 4. The flow data of raw materials, products and key logistics are shown in Table 2 below.

[0120] Table 2:

[0121]

[0122]

[0123] As can be seen from the above table, the total ethylene feed is 40.3716+43.8635=84.2351kg / h, the total conversion rate is (1-2.506 / 84.2351)*100%=97%, and the conversion rate of CPD is 98.93% (HB can be sold as a by-product). It can be said that the conversion rates of these two raw materials are very high. The main function of E1 in the figure is to condense the solvent and NBE (after two-stage condensation at different temperatures, it is obvious that the CPD substance in the S9 logistics is concentrated), and the reflux liquid returns to the top of the tower body 1; the main function of E2 is to condense CPD, and the reflux liquid returns to the first partition distillation zone 120a; because the boiling point of ethylene is very low, the condenser for recovering ethylene is cancelled, and most of the non-condensable gas in E2 is recovered after being pressurized by a compressor; V A The function is to control the concentration of CPD on the left side of the partition (relative to the product NBE, increase the concentration of reactant CPD). In this embodiment, the returned stream is S9, and the absolute flow rate of CPD is 61.9 kg / h; V in the figure BThe function of is to control the concentration of ethylene in the first partition distillation zone 120a (relative to the product NBE, increase the concentration of reactant ethylene). In this embodiment, the returned logistics is S10, and the absolute flow rate of ethylene is 44kg / h. In this embodiment, NBE is a high-boiling substance (relative to the raw material CPD), so part of the unreacted NBE leaves from the bottom of the tower body 1 together with P and HB, and then the solvent is recovered together with the solvent through the post-processing unit 4 and returned to the tower body 1. There will be some loss of solvent in the post-processing unit 4, and the lost solvent can be supplemented at the supplementary solvent inlet. In this embodiment, the raw material ethylene and CPD are respectively provided with flow control valves and set to adjust the ratio.

[0124] Embodiment 2:

[0125] The copolymerization reaction of this embodiment is in the following form:

[0126]

[0127]

[0128] Specifically:

[0129]

[0130]

[0131] Wherein DMON is tetracyclododecene.

[0132] The polymerization reaction device used in this embodiment is as follows Figure 8 As shown, in this embodiment, the boiling points of DMON and the solvent are quite different, and the solvent does not participate in the reaction. To simplify the process, NBE and the solvent in the top stream of tower body 1 are condensed as the same stream and returned to tower body 1. Because substance B is gas phase ethylene, to ensure the reaction effect of reaction 3 and reaction 4, the feed of ethylene is close to the lower area of ​​the partition. The normal pressure boiling points of the substances involved in the above reaction are shown in Table 3 below.

[0133] Table 3:

[0134] name Ethylene NBE DMON HB Solvents Code B A C E - Normal pressure boiling point -103.7 94.2 224 332 69

[0135] In the polymerization reaction of this embodiment, the molecular weight is generally controlled by adding hydrogen. The hydrogen and ethylene are mixed and enter the area on the right side of the partition. In addition, ethylene contains a trace amount of ethane. Therefore, for this process, hydrogen and ethane are non-condensable gases. In order to prevent accumulation, they need to be discharged in time. The boiling point of ethylene is very low and it is difficult to condense. Therefore, a compressor is provided to compress part of the exhaust gas and return it to the first partition distillation zone 120a. In addition, the atmospheric boiling point of the comonomer DMON is higher than that of the solvent. Therefore, part of the unreacted DMON leaves the bottom of the tower and needs to be recovered by a recovery unit. The stream data of raw materials, products and key logistics are shown in Table 4 below.

[0136] Table 4:

[0137]

[0138]

[0139] As can be seen from the above table, the total ethylene feed is 53.3+47.5=100.8 kg / h, the total conversion rate is (1-2.9 / 100.8)*100%=97.1%, and the conversion rate of CPD is 99% (HB can be sold as a by-product), E1 mainly functions to condense high-boiling-point DMON substances, and E2 mainly condenses a mixture of solvent and NBE, and the rest of the settings are consistent with Example 1.

Claims

1. A polymerization reaction device, comprising The tower body (1) comprises a top section (11), a middle section (12) and a bottom section (13) which are arranged in sequence from top to bottom; A condensation unit (2) is disposed at the top of the tower body (1) and is used to condense the material distilled from the tower body top section (11); and A reboiling unit (3) is disposed at the bottom of the tower body (1) and is used to vaporize the material distilled from the bottom section (13) of the tower body; Features: A mixing zone (111) is formed inside the tower body top section (11); A vertically arranged partition (120) is provided inside the middle section (12) of the tower body, and the partition (120) divides the inner cavity of the middle section (12) of the tower body into a first partition distillation zone (120a) and a second partition distillation zone (120b); A common distillation zone (131) is formed inside the tower bottom section (13); The tower body middle section (12) has a first feed inlet (121) and a second feed inlet (122) which are connected to the first baffle distillation zone (120a), and are used to feed substance A and substance B respectively, so that substance A and substance B generate comonomer C and high boiling products E in the first baffle distillation zone (120a); The tower body middle section (12) has a third feed port (123) intersecting with the second partition distillation zone (120b) for feeding the comonomer D, so that the comonomer C and the comonomer D generate a copolymer P in the second partition distillation zone (120b); The tower body top section (11) is provided with a solvent inlet (113) which is in communication with the mixing zone (111).

2. The polymerization reaction device according to claim 1, characterized in that: The tower body top section (11) has a first discharge port (112) which is in communication with the mixing zone (111); The tower body middle section (12) has a first return port (125) and a second return port (126) which are connected to the first baffle distillation zone (120a), and are used to respectively return the substance A and the substance B condensed by the condensation unit (2); The middle section (12) of the tower body has a third return port (127) which is in communication with the second partition plate distillation zone (120b) and is used for returning the comonomer C condensed by the condensation unit (2).

3. The polymerization reaction device according to claim 2, characterized in that: The middle section (12) of the tower body has a fourth return port (128) which is in communication with the second partition distillation zone (120b) and is used for returning the comonomer D condensed by the condensation unit (2).

4. The polymerization reaction device according to claim 3, characterized in that: The condensing unit (2) comprises A first condenser (21), whose gas phase inlet is connected to the first discharge port (112), and whose liquid phase outlet is connected to the solvent inlet (113); A second condenser (22), whose gas phase inlet is connected to the gas phase outlet of the first condenser (21), and whose liquid phase outlet is connected to the third return port (127); A third condenser (23), whose gas phase inlet is connected to the gas phase outlet of the second condenser (22), and whose liquid phase outlet is connected to the fourth return port (128); a fourth condenser (24), wherein the gas phase inlet is connected to the gas phase outlet of the third condenser (23), and the liquid phase outlet is connected to the second return port (126); as well as The fifth condenser (25) has a gas phase inlet connected to the gas phase outlet of the fourth condenser (24), and a liquid phase outlet connected to the first return port (125).

5. The polymerization reaction device according to claim 2, characterized in that: A first flow regulating valve (251) is provided on the pipeline between the condensing unit (2) and the first return port (125); A second flow regulating valve (241) is provided on the pipeline between the condensing unit (2) and the second return port (126).

6. The polymerization reaction device according to any one of claims 1 to 5, characterized in that: The tower body bottom section (13) has a third discharge port (133) which is in communication with the common rectification zone (131); The tower bottom section (13) has a sixth return port (135) which is in communication with the common distillation zone (131) and is used for returning the vaporized material from the reboiling unit (3).

7. The polymerization reaction device according to claim 6, characterized in that: The reboiler unit (3) comprises a second reboiler (32), the liquid phase inlet of the second reboiler (32) is connected to the third discharge port (133), and the gas phase outlet of the second reboiler (32) is connected to the sixth return port (135).

8. A polymerization process using the polymerization reaction apparatus according to any one of claims 1 to 7, characterized in that The method comprises the following steps: a substance A and a substance B enter a first baffle distillation zone (120a) through a first feed port (121) and a second feed port (122), a comonomer D enters a second baffle distillation zone (120b) through a third feed port (123), a solvent enters a mixing zone (111) through a solvent inlet (113), a substance A and a substance B generate a comonomer C and a high boiling product E through a reversible reaction in the first baffle distillation zone (120a), the comonomer C subsequently enters a second baffle distillation zone (120b), and reacts with the comonomer D in the second baffle distillation zone through a polymerization reaction to generate a copolymer P, unreacted substance A, substance B, comonomer C and comonomer D and part of the solvent are distilled out at the top section (11) of the tower body, and the high boiling product E, the copolymer P and part of the solvent are distilled out at the bottom section (13) of the tower body.

Images