Preparation of mpo and its post-treatment system

Abstract

The utility model discloses a preparation and post -treatment system of MPO, including the first reation kettle and second reation kettle of being linked, be equipped with methyl dichlorophosphine feed pipe, butadiene feed pipe, n - butanol feed pipe and methyl dichlorophosphine steam pipe on the first reation kettle, be equipped with sulfonic acid feed pipe and chloro butane steam pipe on the second reation kettle. Four kinds of materials enter the first reation kettle, then flow into the second reation kettle, and sulfonic acid is added into the second reation kettle through the sulfonic acid feed pipe, 3 - methyl - 1 - phosphorus heterocyclic ring hex - 3 - en - 1 - chloride and n - butanol react to obtain 1 - methyl - 1 - oxo - 2, 3 - dihydro - phosphorus heterocyclic ring pentene (MPO), chloro butane and hydrogen chloride, chloro butane is produced and hangs distillation out of chloro butane through the chloro butane steam pipe, and 3 - methyl - 1 - phosphorus heterocyclic ring hex - 3 -en - 1 - chloride is isomerized into 2 position MPO under the action of sulfonic acid under high temperature.

Description

Technical Field

[0001] This invention belongs to the field of phosphoric cyclopentene preparation technology, specifically relating to an MPO preparation and post-processing system. Background Technology

[0002] 1-Methyl-1-oxo-2,3-dihydrophosphacyclopentene (MPO) is a highly efficient catalyst mainly used in the synthesis of carbodiimides, polycarbodiimides, and modified carbodiimide isocyanates, as well as in phosgenation synthesis. Currently, there are no domestic R&D and manufacturing companies specializing in this product, leaving the domestic market largely untapped. The goal is to produce this product domestically and establish a foothold in the market. Conventional production methods primarily yield 3-position MPO, while 2-position MPO exhibits superior performance. A preparation system with a high 2-position MPO content is currently lacking. Utility Model Content

[0003] The purpose of this invention is to solve the problems of the prior art and provide a system for the preparation and post-processing of MPO. Methylphosphine dichloride and butadiene flow into the first reaction vessel through the methylphosphine dichloride feed pipe and the butadiene feed pipe, respectively. The methylphosphine dichloride and butadiene react to obtain 3-methyl-1-phosphacyclohex-3-ene-1-chloride, resulting in a mixture of 3-methyl-1-phosphacyclohex-3-ene-1-chloride and methylphosphine dichloride. After recovering methylphosphine dichloride under reduced pressure through the methylphosphine dichloride distillation pipe, n-butanol is then passed through the n-butanol distillation pipe. The solid is fully dissolved in the second reactor through the feed pipe and then flows into the second reactor. Sulfonic acid is added to the second reactor through the sulfonic acid feed pipe. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride reacts with n-butanol to obtain 1-methyl-1-oxo-2,3-dihydrophosphacyclopentene (MPO), chlorobutane, and hydrogen chloride. Chlorobutane is distilled off through the chlorobutane distillation pipe. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride is isomerized to 2-position MPO under high temperature and with the help of a transposition agent (sulfonic acid).

[0004] This utility model is achieved through the following technical solution: An MPO preparation system includes a first reaction vessel and a second reaction vessel connected together. The first reaction vessel is provided with a methylphosphine dichloride feed pipe, a butadiene feed pipe, a n-butanol feed pipe and a methylphosphine dichloride evaporation pipe. The second reaction vessel is provided with a sulfonic acid feed pipe and a chlorobutane evaporation pipe.

[0005] Preferably, the first reactor is connected to the second reactor via a first feed pipe.

[0006] Preferably, the first reactor is provided with a first temperature control unit, which includes a first temperature sensor and a first heat exchange jacket on the first reactor. The first heat exchange jacket is provided with a first heat exchange inlet pipe and a first heat exchange outlet pipe, and a first heat exchange valve is provided on the first heat exchange inlet pipe. The second reactor is provided with a second temperature control unit, which includes a second temperature sensor and a second heat exchange jacket on the second reactor. The second heat exchange jacket is provided with a second heat exchange inlet pipe and a second heat exchange outlet pipe, and a second heat exchange valve is provided on the second heat exchange inlet pipe.

[0007] Preferably, the first reactor is provided with a first stirring device, and the second reactor is provided with a second stirring device.

[0008] Preferably, the first reactor is equipped with a first pressure gauge, and the second reactor is equipped with a second pressure gauge.

[0009] Preferably, the methyl dichloride evaporation pipe is equipped with a methyl dichloride cooler, a methyl dichloride storage tank, and a first exhaust pipe.

[0010] Preferably, the chlorobutane distillation pipe is equipped with a chlorobutane cooler, a chlorobutane storage tank, and a second exhaust pipe.

[0011] Preferably, the first exhaust pipe and the second exhaust pipe are connected to the exhaust manifold, and a vacuum pump is installed on the exhaust manifold.

[0012] Preferably, the first feed pipe, the methyl dichloride feed pipe, the butadiene feed pipe, the n-butanol feed pipe, the sulfonic acid feed pipe, the methyl dichloride distillation pipe, the chlorobutane distillation pipe, the first exhaust pipe, and the second exhaust pipe are all equipped with switch valves, and the methyl dichloride feed pipe, the butadiene feed pipe, the n-butanol feed pipe, and the sulfonic acid feed pipe are all equipped with flow meters.

[0013] A post-processing system for MPO includes the aforementioned MPO preparation system and a regulating vessel. The second reaction vessel is connected to the regulating vessel via a second feed pipe. The regulating vessel is equipped with a third feed pipe and a trioctylamine-toluene mixture feed pipe. The third feed pipe is connected to a separation device, which is connected to an aqueous phase distillation tank and an organic phase separation tank, respectively. The organic phase separation tank is equipped with a liquid alkali feed pipe.

[0014] Compared with the prior art, this utility model has the following advantages and beneficial effects: I. This utility model provides an MPO preparation system in which methylphosphine dichloride and butadiene flow into a first reaction vessel through methylphosphine dichloride feed pipe and butadiene feed pipe, respectively. The reaction of methylphosphine dichloride and butadiene yields 3-methyl-1-phosphacyclohexane-3-ene-1-chloride, resulting in a mixture of 3-methyl-1-phosphacyclohexane-3-ene-1-chloride and methylphosphine dichloride. After methylphosphine dichloride is recovered under reduced pressure through a methylphosphine dichloride distillation pipe, n-butanol is added to a second reaction vessel through a n-butanol feed pipe. The solid is fully dissolved in the reactor and then flows into the second reactor. Sulfonic acid is added to the second reactor through the sulfonic acid feed pipe. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride reacts with n-butanol to obtain 1-methyl-1-oxo-2,3-dihydrophosphacyclopentene (MPO), chlorobutane, and hydrogen chloride. Chlorobutane is distilled off through the chlorobutane distillation pipe. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride is isomerized to 2-position MPO under high temperature and with the help of a transposition agent (sulfonic acid).

[0015] II. The MPO preparation system provided by this utility model has a first temperature control unit that facilitates the adjustment of the temperature inside the first reaction vessel, so that the reaction between methylphosphine dichloride and butadiene to obtain 3-methyl-1-phosphacyclohex-3-ene-1-chloride is more complete. III. The MPO preparation system provided by this utility model has a second temperature control unit that facilitates the adjustment of the temperature inside the second reaction vessel, resulting in a more thorough reaction of 3-methyl-1-phosphacyclohex-3-ene-1-chloride with n-butanol to obtain 1-methyl-1-oxo-2,3-dihydro-phosphacyclopentene (MPO), chlorobutane, and hydrogen chloride; more thorough recovery of methylphosphine dichloride; more thorough distillation of chlorobutane; and better high-temperature isomerization of 1-methyl-1-oxo-2,3-dihydro-phosphacyclopentene.

[0016] IV. The MPO preparation system provided by this utility model, with the configuration of a methylphosphine dichloride cooler, a methylphosphine dichloride storage tank, a chlorobutane cooler, and a chlorobutane storage tank, makes the recovery of methylphosphine dichloride more thorough and the distillation of chlorobutane more thorough.

[0017] V. The MPO preparation system provided by this utility model, with its switch valve and flow meter settings, enables more precise feeding of methylphosphine dichloride, butadiene, and n-butanol, and more thorough distillation of methylphosphine dichloride and chlorobutane.

[0018] VI. The present invention provides a post-processing system for MPO. The MPO prepared by the MPO preparation system flows into the regulating vessel through the second feed pipe. The trioctylamine-toluene mixture enters the regulating vessel through the trioctylamine-toluene mixture feed pipe to adjust the pH value. Trioctylamine acts as an acid-binding agent to neutralize acid, and toluene facilitates the separation of the product phase. Trioctylamine can be recycled (liquid alkali is added to the organic phase separation tank through the liquid alkali feed pipe, and trioctylamine is obtained after phase separation when the pH is 7-8). The operation is simple and cost-effective. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the structure of this utility model; Figure 2 This is a schematic diagram of the structure of Embodiment 2 of this utility model.

[0020] The components are: 1. First reactor; 2. Second reactor; 3. Methylphosphine dichloride feed pipe; 4. Butadiene feed pipe; 5. n-Butanol feed pipe; 6. Methylphosphine dichloride distillation pipe; 7. Chlorobutane distillation pipe; 8. First discharge pipe; 9. First temperature sensor; 10. First heat exchange jacket; 11. First heat exchange inlet pipe; 12. First heat exchange outlet pipe; 13. First heat exchange valve; 14. Second temperature sensor; 15. Second heat exchange jacket; 16. Second heat exchange inlet pipe; 17. Second heat exchange outlet pipe; 18. Second heat exchange valve; 19. First stirring device; 20. Second stirring device. ; 21. First pressure gauge; 22. Second pressure gauge; 23. Methylphosphine dichloride cooler; 24. Methylphosphine dichloride storage tank; 25. First exhaust pipe; 26. Chlorobutane cooler; 27. Chlorobutane storage tank; 28. Second exhaust pipe; 29. ​​Main exhaust pipe; 30. Vacuum pump; 31. Switch valve; 32. Flow meter; 33. Sulfonic acid feed pipe; 34. Adjusting vessel; 35. Trioctylamine-toluene mixture feed pipe; 36. Separation device; 37. Aqueous phase distillation tank; 38. Organic phase separation tank; 39. Second discharge pipe; 40. Third discharge pipe; 41. Liquid alkali feed pipe. Detailed Implementation

[0021] The present invention will be further described in detail below with reference to the embodiments, but the implementation of the present invention is not limited thereto.

[0022] Example 1 like Figure 1 As shown, this embodiment provides an MPO preparation system, including a first reaction vessel 1 and a second reaction vessel 2 connected together. The first reaction vessel 1 is provided with a methyl dichloride feed pipe 3, a butadiene feed pipe 4, a n-butanol feed pipe 5 and a methyl dichloride distillation pipe 6. The second reaction vessel 2 is provided with a chlorobutane distillation pipe 7 and a sulfonic acid feed pipe 33.

[0023] Example 2 like Figure 2 As shown, this embodiment provides an MPO preparation system, including a first reaction vessel 1 and a second reaction vessel 2 connected together. The first reaction vessel 1 is provided with a methyl dichloride feed pipe 3, a butadiene feed pipe 4, a n-butanol feed pipe 5 and a methyl dichloride distillation pipe 6. The second reaction vessel 2 is provided with a chlorobutane distillation pipe 7 and a sulfonic acid feed pipe 33.

[0024] The first reactor 1 is connected to the second reactor 2 via a feed pipe 8.

[0025] The first reaction vessel 1 is provided with a first temperature control unit, which includes a first temperature sensor 9 and a first heat exchange jacket 10. The first heat exchange jacket 10 is provided with a first heat exchange inlet pipe 11 and a first heat exchange outlet pipe 12. The first heat exchange inlet pipe 11 is provided with a first heat exchange valve 13.

[0026] The second reaction vessel 2 is provided with a second temperature control unit, which includes a second temperature sensor 14 and a second heat exchange jacket 15. The second heat exchange jacket 15 is provided with a second heat exchange inlet pipe 16 and a second heat exchange outlet pipe 17. The second heat exchange inlet pipe 16 is provided with a second heat exchange valve 18.

[0027] The first reaction vessel 1 is equipped with a first stirring device 19, and the second reaction vessel 2 is equipped with a second stirring device 20.

[0028] The first reactor 1 is equipped with a first pressure gauge 21, and the second reactor 2 is equipped with a second pressure gauge 22.

[0029] The methyl dichloride evaporation pipe 6 is equipped with a methyl dichloride cooler 23, a methyl dichloride storage tank 24, and a first exhaust pipe 25.

[0030] The chlorobutane distillation pipe 7 is equipped with a chlorobutane cooler 26, a chlorobutane storage tank 27, and a second exhaust pipe 28.

[0031] The first exhaust pipe 25 and the second exhaust pipe 28 are connected to the exhaust manifold 29, and a vacuum pump 30 is installed on the exhaust manifold 29.

[0032] Among them, the feed pipe 8, the methyl dichloride feed pipe 3, the butadiene feed pipe 4, the n-butanol feed pipe 5, the methyl dichloride distillation pipe 6, the chlorobutane distillation pipe 7, the first exhaust pipe 25 and the second exhaust pipe 28 are all equipped with switch valves 31, and the methyl dichloride feed pipe 3, the butadiene feed pipe 4, the n-butanol feed pipe 5, the methyl dichloride distillation pipe 6 and the chlorobutane distillation pipe 7 are all equipped with flow meters 32.

[0033] Among them, the first temperature sensor 9, the first heat exchange jacket 10, the first heat exchange valve 13, the second temperature sensor 14, the second heat exchange jacket 15, the second heat exchange valve 18, the first stirring device 19, the second stirring device 20, the first pressure gauge 21, the second pressure gauge 22, the methylphosphine dichloride cooler 23, the methylphosphine dichloride storage tank 24, the chlorobutane cooler 26, the chlorobutane storage tank 27, the vacuum pump 30, the switching valve 31, and the flow meter 32 are all prior art and will not be described in detail here.

[0034] A post-processing system for MPO includes the aforementioned MPO preparation system and a regulating vessel 34. The second reaction vessel 2 is connected to the regulating vessel 34 via a second feed pipe 39. The regulating vessel 34 is equipped with a third feed pipe 40 and a trioctylamine-toluene mixture feed pipe 35. The third feed pipe 40 is connected to a separation device 36. The separation device 36 is connected to an aqueous phase distillation tank 37 and an organic phase separation tank 38, respectively. The organic phase separation tank 38 is equipped with a liquid alkali feed pipe 41.

[0035] Compared with the prior art, this utility model has the following advantages and beneficial effects: I. This utility model provides an MPO preparation system in which methylphosphine dichloride and butadiene flow into the first reaction vessel 1 through the methylphosphine dichloride feed pipe 3 and the butadiene feed pipe 4, respectively. The methylphosphine dichloride and butadiene react to obtain 3-methyl-1-phosphacyclohexane-3-ene-1-chloride, resulting in a mixture of 3-methyl-1-phosphacyclohexane-3-ene-1-chloride and methylphosphine dichloride. After the methylphosphine dichloride is recovered under reduced pressure through the methylphosphine dichloride distillation pipe 6, n-butanol is added to the second reaction vessel through the n-butanol feed pipe 5. The solid is fully dissolved in reactor 2 and then flows into the second reactor 2. Sulfonic acid is added to the second reactor 2 through sulfonic acid feed pipe 33. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride reacts with n-butanol to obtain 1-methyl-1-oxo-2,3-dihydrophosphacyclopentene (MPO), chlorobutane, and hydrogen chloride. Chlorobutane is distilled off through chlorobutane distillation pipe 7. 3-Methyl-1-phosphacyclohex-3-ene-1-chloride is isomerized to 2-position MPO under high temperature and with the help of a transposition agent (sulfonic acid).

[0036] II. The MPO preparation system provided by this utility model has a first temperature control unit that facilitates the adjustment of the temperature inside the first reaction vessel 1, so that the reaction of methylphosphine dichloride and butadiene to obtain 3-methyl-1-phosphacyclohex-3-ene-1-chloride is more thorough. III. The MPO preparation system provided by this utility model has a second temperature control unit that facilitates the adjustment of the temperature inside the second reaction vessel 2, resulting in a more thorough reaction of 3-methyl-1-phosphacyclohex-3-ene-1-chloride with n-butanol to obtain 1-methyl-1-oxo-2,3-dihydro-phosphacyclopentene (MPO), chlorobutane, and hydrogen chloride; more thorough recovery of methylphosphine dichloride; more thorough distillation of chlorobutane; and better high-temperature isomerization effect of 1-methyl-1-oxo-2,3-dihydro-phosphacyclopentene.

[0037] IV. The MPO preparation system provided by this utility model, with the setting of methyl dichloride cooler 23, methyl dichloride storage tank 24, chlorobutane cooler 26 and chlorobutane storage tank 27, makes the recovery of methyl dichloride more thorough and the distillation of chlorobutane more thorough.

[0038] V. The MPO preparation system provided by this utility model, with the setting of the switching valve 31 and the flow meter 32, makes the feeding of methylphosphine dichloride, butadiene and n-butanol more precise, and the distillation of methylphosphine dichloride and chlorobutane more thorough.

[0039] VI. The present invention provides a post-processing system for MPO. The MPO prepared by the MPO preparation system flows into the regulating tank 34 through the second feed pipe 39. The trioctylamine-toluene mixture enters the regulating tank 34 through the trioctylamine-toluene mixture feed pipe 35 to adjust the pH value. Trioctylamine acts as an acid-binding agent to neutralize acid, and toluene facilitates the separation of the product phase. Trioctylamine can be recycled (liquid alkali is added to the organic phase separation tank 38 through the liquid alkali feed pipe 41, and trioctylamine is obtained after phase separation when the pH is 7-8). The operation is simple and cost-effective.

[0040] The above description is merely a preferred embodiment of the present utility model and is not intended to limit the present utility model in any way. Any simple modifications or equivalent changes made to the above embodiments based on the technical essence of the present utility model shall fall within the protection scope of the present utility model.

Claims

1. A system for preparing MPO, characterized in that: The reactor includes a first reactor (1) and a second reactor (2) connected to each other. The first reactor (1) is provided with a methyl dichloride feed pipe (3), a butadiene feed pipe (4), a n-butanol feed pipe (5) and a methyl dichloride distillation pipe (6). The second reactor (2) is provided with a chlorobutane distillation pipe (7) and a sulfonic acid feed pipe (33).

2. The MPO preparation system according to claim 1, characterized in that: The first reactor (1) is connected to the second reactor (2) through the first feed pipe (8).

3. The MPO preparation system according to claim 2, characterized in that: The first reactor (1) is provided with a first temperature control unit, which includes a first temperature sensor (9) and a first heat exchange jacket (10) on the first reactor (1). The first heat exchange jacket (10) is provided with a first heat exchange inlet pipe (11) and a first heat exchange outlet pipe (12). The first heat exchange inlet pipe (11) is provided with a first heat exchange valve (13). The second reactor (2) is provided with a second temperature control unit, which includes a second temperature sensor (14) and a second heat exchange jacket (15) on the second reactor (2). The second heat exchange jacket (15) is provided with a second heat exchange inlet pipe (16) and a second heat exchange outlet pipe (17). The second heat exchange inlet pipe (16) is provided with a second heat exchange valve (18).

4. The MPO preparation system according to claim 3, characterized in that: The first reactor is equipped with a first stirring device (19), and the second reactor is equipped with a second stirring device (20).

5. The MPO preparation system according to claim 4, characterized in that: The first reactor is equipped with a first pressure gauge (21), and the second reactor is equipped with a second pressure gauge (22).

6. The MPO preparation system according to claim 5, characterized in that: The methyl dichloride evaporation pipe (6) is equipped with a methyl dichloride cooler (23), a methyl dichloride storage tank (24), and a first exhaust pipe (25).

7. The MPO preparation system according to claim 6, characterized in that: The chlorobutane distillation pipe (7) is equipped with a chlorobutane cooler (26), a chlorobutane storage tank (27), and a second exhaust pipe (28).

8. The MPO preparation system according to claim 7, characterized in that: The first exhaust pipe (25) and the second exhaust pipe (28) are connected to the exhaust manifold (29), and a vacuum pump (30) is installed on the exhaust manifold (29).

9. The MPO preparation system according to claim 8, characterized in that: A switch valve (31) is provided on the first feed pipe (8), the methyl dichloride feed pipe (3), the butadiene feed pipe (4), the n-butanol feed pipe (5), the methyl dichloride distillation pipe (6), the chlorobutane distillation pipe (7), the first exhaust pipe (25), and the second exhaust pipe (28). A flow meter (32) is provided on the methyl dichloride feed pipe (3), the butadiene feed pipe (4), the n-butanol feed pipe (5), the methyl dichloride distillation pipe (6), and the chlorobutane distillation pipe (7).

10. A post-processing system for MPO, characterized in that: The system includes the preparation system of MPO according to any one of claims 1-9 and the regulating vessel (34), wherein the second reaction vessel (2) is connected to the regulating vessel (34) through the second feed pipe (39), the regulating vessel (34) is provided with a third feed pipe (40) and a trioctylamine-toluene mixture feed pipe (35), the third feed pipe (40) is connected to a separation device (36), the separation device (36) is connected to an aqueous phase distillation tank (37) and an organic phase separation tank (38) respectively, and the organic phase separation tank (38) is provided with an alkaline solution feed pipe (41).

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