A production system for brominated pyrazole compounds

Abstract

A production system for bromopyrazole compounds comprises a reaction unit, a distillation kettle, a quenching kettle, a neutralization kettle and a first solid-liquid separator which are connected in sequence. The solid phase outlet of the first solid-liquid separator is connected in sequence to a washing separation unit and a first dryer for producing the product bromopyrazole compounds; the liquid phase outlet of the first solid-liquid separator is connected in sequence to a mother liquor evaporation unit, a crystallization separation unit, a refining unit and a second dryer for producing a by-product phosphate. The utility model can produce two substances at the same time, is simple to operate, highly economical, energy-saving and efficiency-enhancing, and safe and environmentally friendly.

Description

Technical Field

[0001] The utility model belongs to the field of chemical synthesis, and specifically relates to a production system of brominated pyrazole compounds. Background Art

[0002] Ethyl 3-bromo-1-(3-chloro-2-pyridinyl)-4,5-dihydro-1H-pyrazole-5-carboxylate (bromopyrazoles) is an upstream raw material for 3-bromo-1-(3-chloro-2-pyridinyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid and an important intermediate in the synthesis of o-formylaminobenzamide insecticides. These insecticides offer high efficacy, broad spectrum, low toxicity, and environmental friendliness, lacking cross-resistance with traditional insecticides and possessing promising market prospects.

[0003] In patent CN115557931A, 2-(3-chloro-2-pyridyl)-5-hydroxypyrazole-3-carboxylic acid ethyl ester is subjected to bromination reaction with tribromophosphorus oxybromide in butyronitrile. After the reaction is completed, the pH is adjusted to neutral, the liquid is allowed to stand, and the layers are separated. The upper butyronitrile solvent phase is collected and distilled, and azeotropic dehydration is performed to obtain 3-bromo-1-(3-chloro-2-pyridyl)-4,5-dihydro-1H-pyrazole-5-carboxylic acid ethyl ester. After the reaction is completed, it is directly neutralized, and a mixed salt of phosphate and bromide salt is produced in the solution. The separated mixed salt can only be used as hazardous waste, with high disposal costs and great harm to the environment. If water is added directly after the reaction is completed, hydrogen bromide gas will escape during quenching, which is very harmful to the human body and the environment.

[0004] The existing production equipment for brominated pyrazole compounds still has deficiencies in process cleanliness, safety and environmental protection. Therefore, it is very necessary to develop an improved industrial production system for brominated pyrazole compounds. Utility Model Content

[0005] The utility model provides a production system of brominated pyrazole compounds with simple operation, high economy, energy saving and efficiency improvement, safety and environmental protection, comprising a reaction unit, a first distillation kettle, a quenching kettle, a neutralization kettle, a first solid-liquid separator, a washing separation unit, a first dryer, a mother liquor evaporation unit, a crystallization separation unit, a refining unit, and a second dryer; the first solid-liquid separator is provided with a liquid phase discharge port and a solid phase discharge port; the discharge port of the reaction unit is connected to the feed port of the first distillation kettle, the discharge port of the first distillation kettle is connected to the feed port of the quenching kettle, the discharge port of the quenching kettle is connected to the feed port of the neutralization kettle, and the discharge port of the neutralization kettle is connected to the first solid-liquid separator. The feed port of the separator, the solid phase discharge port of the first solid-liquid separator is connected to the feed port of the washing and separation unit, the solid phase discharge port of the washing and separation unit is connected to the feed port of the first dryer, and the discharge port of the first dryer outputs the product bromopyrazole compound; the liquid phase discharge port of the first solid-liquid separator is connected to the feed port of the mother liquor evaporation unit, the discharge port of the mother liquor evaporation unit is connected to the feed port of the crystallization separation unit, the solid phase discharge port of the crystallization separation unit is connected to the feed port of the refining unit, the discharge port of the refining unit is connected to the feed port of the second dryer, and the discharge port of the second dryer outputs the by-product phosphate;

[0006] The first dryer and the second dryer are selected from one of a disc dryer, a rake dryer, a vacuum dryer, a drum dryer, a belt dryer, and a film dryer.

[0007] In an optional embodiment, the crystallization separation unit further includes a crystallization kettle and a second solid-liquid separator, and the discharge port of the crystallization kettle is connected to the feed port of the second solid-liquid separator; the feed port of the crystallization kettle is the feed port of the crystallization separation unit, and the solid phase discharge port of the second solid-liquid separator is the solid phase discharge port of the crystallization separation unit.

[0008] In an optional embodiment, the crystallization separation unit further includes a liquid discharge port, and the liquid discharge port is provided on the second solid-liquid separator.

[0009] In an optional embodiment, the refining unit includes a dissolving kettle and a third solid-liquid separator, and the discharge port of the dissolving kettle is connected to the feed port of the third solid-liquid separator; the feed port of the dissolving kettle is the feed port of the refining unit, and the discharge port of the third solid-liquid separator is the discharge port of the refining unit.

[0010] In an optional embodiment, the refining unit is connected to the dissolving reagent recovery unit, the dissolving kettle is provided with a dissolving reagent inlet, and the third solid-liquid separator is provided with a drain port; the drain port of the third solid-liquid separator is connected to the inlet of the dissolving reagent recovery unit, and the dissolving reagent inlet of the dissolving kettle is connected to the outlet of the dissolving reagent recovery unit.

[0011] In an optional embodiment, the dissolving reagent recovery unit includes a second distillation kettle and a distillation tower, the discharge port of the third solid-liquid separator is connected to the inlet of the second distillation kettle, the outlet of the second distillation kettle is connected to the inlet of the distillation tower, and the outlet of the distillation tower is connected to the dissolving reagent inlet of the dissolving kettle.

[0012] In an optional embodiment, the washing and separation unit includes a beating kettle and a fourth solid-liquid separator, the beating kettle is provided with a washing reagent inlet, a beating liquid outlet and a feed port, the fourth solid-liquid separator is provided with a drain port and a solid phase discharge port, the beating liquid outlet of the beating kettle is connected to the feed port of the fourth solid-liquid separator, the feed port of the beating kettle is the feed port of the washing and separation unit, and the solid phase discharge port of the fourth solid-liquid separator is the solid phase discharge port of the washing and separation unit.

[0013] An optional embodiment further includes at least one falling film absorption tower, the falling film absorption tower is provided with a hydrogen bromide inlet, the quenching kettle is provided with a hydrogen bromide outlet, and the hydrogen bromide inlet of the falling film absorption tower is connected to the hydrogen bromide outlet of the quenching kettle.

[0014] An optional embodiment further includes a mixing unit, which includes a first mixing kettle and a second mixing kettle, the first mixing kettle being provided with an inlet for a substituted pyrazolidine compound and an inlet for a solvent, the second mixing kettle being provided with an inlet for a bromination reagent and an inlet for a solvent, and the solvent outlet of the first distillation kettle being connected to the solvent inlet of the first mixing kettle and / or the solvent inlet of the second mixing kettle.

[0015] In an optional embodiment, the mother liquor evaporation unit includes a preheater, a first heater, a first separator, a second heater, and a second separator; the discharge port of the preheater is connected to the feed port of the first heater, the discharge port of the first heater is connected to the feed port of the first separator, the discharge port of the first separator is respectively connected to the feed port of the first heater and the feed port of the second heater, the discharge port of the second heater is connected to the feed port of the second separator, and the concentrated liquid outlet of the second separator is respectively connected to the feed port of the second heater and the feed port of the crystallization separation unit; the steam outlet of the first separator is connected to the heat medium inlet of the second heater, and the steam outlet of the second separator is connected to the heat medium inlet of the preheater.

[0016] The technical solution provided by the utility model has the following advantages compared with the prior art:

[0017] 1. The production system provided by the utility model concentrates, crystallizes and refines saline wastewater by setting up an evaporation unit, a crystallization separation unit and a refining unit to obtain high-purity by-product phosphate, thereby reducing the amount of three wastes and improving the economic efficiency of the product.

[0018] 2. A double-effect evaporation separator is set up in the mother liquor evaporation unit. The steam from the first separator is used as the heat medium for the second heater, and the steam from the second separator is used as the heat medium for the preheater. Through heat integration energy-saving technology, comprehensive utilization of heat is achieved and energy consumption is reduced.

[0019] 3. A dissolving reagent recovery unit is set up in the refining unit to recover the dissolving reagent through distillation and reuse it, thereby improving the utilization rate of the dissolving reagent and saving production costs.

[0020] 4. At least one falling film absorption tower is connected to the hydrogen bromide outlet of the quenching kettle to absorb the hydrogen bromide generated during the quenching process. This not only avoids the safety hazards caused by the escape of hydrogen bromide and reduces the production of bromide salts, but also recovers the high-value-added hydrobromic acid by-product, which is both safe and environmentally friendly and improves the economic efficiency of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] In order to more clearly illustrate the specific implementation methods of the utility model or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the utility model. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0022] Figure 1 A schematic diagram of the structure of the device used in the embodiment of the present disclosure;

[0023] Figure 2 A schematic diagram of the structure of the device used in the embodiment of the present disclosure;

[0024] Figure 3 A schematic diagram of the structure of the device used in the embodiment of the present disclosure;

[0025] Figure 4 A schematic diagram of the structure of the device used in the embodiment of the present disclosure;

[0026] Figure 5 This is a schematic structural diagram of the mother liquor evaporation unit device used in an embodiment of the present disclosure.

[0027] Description of reference numerals:

[0028] Among them, 1-reaction unit, 2-first distillation kettle, 3-quenching kettle, 4-neutralization kettle, 5-first solid-liquid separator, 6-washing separation unit, 61-slurrying kettle, 62-fourth solid-liquid separator, 7-first dryer, 8-mother liquor evaporation unit, 81-preheater, 82-first heater, 83-first separator, 84-second heater, 85-second separator, 9-crystallization separation unit, 91-crystallization kettle, 92-second solid-liquid separator, 10-refining unit, 101-dissolution kettle, 102-third solid-liquid separator, 11-second dryer, 12-dissolved reagent recovery unit, 121-second distillation kettle, 122-distillation tower, 13-mixing unit, 131-first mixing kettle, 132-second mixing kettle, 14-falling film absorption tower. DETAILED DESCRIPTION

[0029] The following is a clear and complete description of the technical solution of the present invention in conjunction with the accompanying drawings. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0030] In the description of this utility model, it should be noted that the terms "upper," "lower," "left," "right," "inner," and "outer," etc., indicating directions or positional relationships, are based on the directions or positional relationships shown in the accompanying drawings and are intended solely to facilitate the description of this utility model and simplify the description. They are not intended to indicate or imply that the devices or components referred to must have a specific direction, be constructed, or operate in a specific direction. Therefore, they should not be construed as limitations on this utility model. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0031] In addition, the technical features involved in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0032] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0033] Please refer to Figure 1-Figure 5 The utility model provides a production system for brominated pyrazole compounds. Example

[0034] This embodiment provides a production system for brominated pyrazole compounds, and its structural diagram is shown in FIG. Figure 1As shown, it includes a reaction unit 1, a first distillation kettle 2, a quenching kettle 3, a neutralization kettle 4, a first solid-liquid separator 5, a washing separation unit 6, a first dryer 7, a mother liquor evaporation unit 8, a crystallization separation unit 9, a refining unit 10, and a second dryer 11; the first solid-liquid separator 5 is provided with a liquid phase discharge port and a solid phase discharge port; the discharge port of the reaction unit 1 is connected to the feed port of the first distillation kettle 2, the discharge port of the first distillation kettle 2 is connected to the feed port of the quenching kettle 3, the discharge port of the quenching kettle 3 is connected to the feed port of the neutralization kettle 4, the quenching kettle 3 is also provided with a quenching agent inlet, the discharge port of the neutralization kettle 4 is connected to the feed port of the first solid-liquid separator 5, and the neutralization kettle 4 is also provided with an alkali liquid inlet. In order to obtain a high-purity product, the solid phase discharge port of the first solid-liquid separator 5 is connected to the feed port of the beating kettle 61, and the beating kettle 61 is also provided with a washing reagent inlet for adding a washing reagent, and the beating liquid discharge port of the beating kettle 61 is connected to At the feed port of the fourth solid-liquid separator 62, the solid phase discharge port of the fourth solid-liquid separator 62 is connected to the feed port of the first dryer 7, and the discharge port of the first dryer 7 outputs the product bromopyrazole compound; the liquid phase discharge port of the first solid-liquid separator 5 is connected to the feed port of the mother liquor evaporation unit 8, the discharge port of the mother liquor evaporation unit 8 is connected to the feed port of the crystallization kettle 91, and the solid phase discharge port of the crystallization kettle 91 is connected to the feed port of the second solid-liquid separator 92. In order to obtain high-purity phosphate, the solid phase discharge port of the second solid-liquid separator 92 is connected to the feed port of the dissolution kettle 101. The second solid-liquid separator 92 is also provided with a drain port for discharging the separated liquid. The discharge port of the dissolution kettle 101 is connected to the feed port of the third solid-liquid separator 102, and the discharge port of the third solid-liquid separator 102 is connected to the feed port of the second dryer 11. The discharge port of the second dryer 11 outputs the by-product phosphate.

[0035] In order to obtain by-product phosphate and at the same time comprehensively utilize the thermal energy of steam, improve thermodynamic efficiency and reduce energy consumption, the mother liquor separation unit 8 includes a preheater 81, a first heater 82, a first separator 83, a second heater 84 and a second separator 85; the discharge port of the preheater 81 is connected to the feed port of the first heater 82, the discharge port of the first heater 82 is connected to the feed port of the first separator 83, the discharge port of the first separator 83 is respectively connected to the feed port of the first heater 82 and the feed port of the second heater 84, the discharge port of the second heater 84 is connected to the feed port of the second separator 85, and the concentrated liquid outlet of the second separator 85 is respectively connected to the feed port of the second heater 84 and the feed port of the crystallization separation unit 9; the steam outlet of the first separator 83 is connected to the heat medium inlet of the second heater 84, and the steam outlet of the second separator 85 is connected to the heat medium inlet of the preheater 81. Example

[0036] This embodiment provides a production system for brominated pyrazole compounds, and its structural diagram is shown in FIG. Figure 2As shown, the difference from Example 1 is that this embodiment is further provided with a dissolving reagent recovery unit 12, which can improve the utilization rate of the dissolving reagent and reduce the dissolving reagent loss.

[0037] Based on Example 1, the dissolving reagent recovery unit 12 includes a second distillation kettle 121 and a distillation tower 122, the discharge port of the third solid-liquid separator 102 is connected to the inlet of the second distillation kettle 121, the outlet of the second distillation kettle 121 is connected to the inlet of the distillation tower 122, and the outlet of the distillation tower 122 is connected to the dissolving reagent inlet of the dissolving kettle 101. Example

[0038] This embodiment provides a production system for brominated pyrazole compounds, and its structural diagram is shown in FIG. Figure 3 As shown, the difference from embodiment 2 is that this embodiment further includes a mixing unit 13.

[0039] On the basis of Example 2, the mixing unit 13 includes a first mixing kettle 131 and a second mixing kettle 132. The first mixing kettle 131 is provided with a substituted pyrazolidine compound inlet and a solvent inlet, and the second mixing kettle 132 is provided with a bromination reagent inlet and a solvent inlet. The solvent outlet of the first distillation kettle 2 is connected to the solvent inlet of the second mixing kettle 132. Example

[0040] This embodiment provides a production system for brominated pyrazole compounds, and its structural diagram is shown in FIG. Figure 4 As shown, the difference from Example 3 is that the solvent outlet of the first distillation kettle 2 in this embodiment is connected to the solvent inlet of the first mixing kettle 131 and the solvent inlet of the second mixing kettle 132 respectively. Example

[0041] This embodiment provides a production system for brominated pyrazole compounds, and its structural diagram is shown in FIG. Figure 4 As shown, the difference from Example 3 is that this embodiment is provided with a falling film absorption tower 14.

[0042] On the basis of Example 3, the quenching kettle 3 is provided with a hydrogen bromide outlet, the hydrogen bromide inlet of the falling film absorption tower 14 is connected to the hydrogen bromide outlet of the quenching kettle 3, and the falling film absorption tower 14 is at least one stage; the falling film absorption tower 14 can reduce the harm of hydrogen bromide to the human body and the environment and improve the economic efficiency of the product. The hydrogen bromide gas generated by the quenching kettle 3 and the absorption liquid are absorbed by the absorption liquid in the falling film absorption tower connected in one or two stages in series, and the by-product hydrobromic acid is recovered.

[0043] The first dryer and the second dryer in the above embodiment are both selected from one of a disc dryer, a rake dryer, a vacuum dryer, a drum dryer, a belt dryer, and a film dryer.

[0044] The foregoing description is intended only to provide specific embodiments of the present disclosure, intended to enable those skilled in the art to understand and implement the present disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present disclosure. Therefore, the present disclosure is not intended to be limited to the embodiments described herein, but rather to be construed in the broadest manner consistent with the principles and novel features disclosed herein.

Claims

1. A production system for brominated pyrazole compounds, characterized in that: It comprises a reaction unit (1), a first distillation kettle (2), a quenching kettle (3), a neutralization kettle (4), a first solid-liquid separator (5), a washing and separation unit (6), a first dryer (7), a mother liquor evaporation unit (8), a crystallization and separation unit (9), a refining unit (10), and a second dryer (11); The first solid-liquid separator (5) is provided with a liquid phase discharge port and a solid phase discharge port; the discharge port of the reaction unit (1) is connected to the feed port of the first distillation kettle (2), the discharge port of the first distillation kettle (2) is connected to the feed port of the quenching kettle (3), the discharge port of the quenching kettle (3) is connected to the feed port of the neutralization kettle (4), the discharge port of the neutralization kettle (4) is connected to the feed port of the first solid-liquid separator (5), the solid phase discharge port of the first solid-liquid separator (5) is connected to the feed port of the washing and separation unit (6), and the solid phase discharge port of the washing and separation unit (6) is connected to The feed inlet of the first dryer (7) and the discharge outlet of the first dryer (7) output the product bromopyrazole compound; the liquid phase discharge outlet of the first solid-liquid separator (5) is connected to the feed inlet of the mother liquid evaporation unit (8), the discharge outlet of the mother liquid evaporation unit (8) is connected to the feed inlet of the crystallization separation unit (9), the solid phase discharge outlet of the crystallization separation unit (9) is connected to the feed inlet of the refining unit (10), the discharge outlet of the refining unit (10) is connected to the feed inlet of the second dryer (11), and the discharge outlet of the second dryer (11) outputs the byproduct phosphate; The first dryer and the second dryer are selected from a disc dryer, a rake dryer, a vacuum dryer, a drum dryer, a belt dryer, and a film dryer.

2. A production system for brominated pyrazole compounds according to claim 1, characterized in that: The crystallization separation unit (9) further comprises a crystallization kettle (91) and a second solid-liquid separator (92), wherein the discharge port of the crystallization kettle (91) is connected to the feed port of the second solid-liquid separator (92); the feed port of the crystallization kettle (91) is the feed port of the crystallization separation unit (9), and the solid phase discharge port of the second solid-liquid separator (92) is the solid phase discharge port of the crystallization separation unit (9).

3. A production system for brominated pyrazole compounds according to claim 2, characterized in that: The crystallization separation unit (9) further comprises a liquid discharge port, wherein the liquid discharge port is arranged on the second solid-liquid separator (92).

4. A production system for brominated pyrazole compounds according to claim 1, characterized in that: The refining unit (10) comprises a dissolving kettle (101) and a third solid-liquid separator (102); the discharge port of the dissolving kettle (101) is connected to the feed port of the third solid-liquid separator (102); the feed port of the dissolving kettle (101) is the feed port of the refining unit (10), and the discharge port of the third solid-liquid separator (102) is the discharge port of the refining unit (10).

5. A production system for brominated pyrazole compounds according to claim 4, characterized in that: The refining unit (10) is connected to a dissolving reagent recovery unit (12); the dissolving kettle (101) is provided with a dissolving reagent inlet; the third solid-liquid separator (102) is provided with a liquid discharge port; the liquid discharge port of the third solid-liquid separator (102) is connected to the inlet of the dissolving reagent recovery unit (12); the dissolving reagent inlet of the dissolving kettle (101) is connected to the outlet of the dissolving reagent recovery unit (12).

6. A production system for brominated pyrazole compounds according to claim 5, characterized in that: The dissolving reagent recovery unit (12) comprises a second distillation kettle (121) and a distillation tower (122); the discharge port of the third solid-liquid separator (102) is connected to the inlet of the second distillation kettle (121); the outlet of the second distillation kettle (121) is connected to the inlet of the distillation tower (122); and the outlet of the distillation tower (122) is connected to the dissolving reagent inlet of the dissolving kettle (101).

7. The production system of a brominated pyrazole compound according to claim 1, characterized in that: The washing and separation unit (6) comprises a beating kettle (61) and a fourth solid-liquid separator (62), wherein the beating kettle (61) is provided with a washing agent inlet, a beating liquid outlet and a feed inlet, and the fourth solid-liquid separator (62) is provided with a liquid discharge port, a solid phase discharge port and a beating liquid inlet, wherein the beating liquid outlet of the beating kettle (61) is connected to the beating liquid inlet of the fourth solid-liquid separator (62), the feed inlet of the beating kettle (61) is the feed inlet of the washing and separation unit (6), and the solid phase discharge port of the fourth solid-liquid separator (62) is the solid phase discharge port of the washing and separation unit (6).

8. The production system of a brominated pyrazole compound according to claim 1, characterized in that: It also comprises at least one falling film absorption tower (14), the falling film absorption tower (14) being provided with a hydrogen bromide inlet, the quenching kettle (3) being provided with a hydrogen bromide outlet, and the hydrogen bromide inlet of the falling film absorption tower (14) being connected to the hydrogen bromide outlet of the quenching kettle (3).

9. The production system of a brominated pyrazole compound according to claim 1, characterized in that: The invention also comprises a mixing unit (13), wherein the mixing unit (13) comprises a first mixing kettle (131) and a second mixing kettle (132), wherein the first mixing kettle (131) is provided with a substituted pyrazolidine compound inlet and a solvent inlet, and the second mixing kettle (132) is provided with a bromination reagent inlet and a solvent inlet, and the solvent outlet of the first distillation kettle (2) is connected to the solvent inlet of the first mixing kettle (131) and / or the solvent inlet of the second mixing kettle (132).

10. A production system for brominated pyrazole compounds according to any one of claims 1 to 9, characterized in that: The mother liquor evaporation unit (8) comprises a preheater (81), a first heater (82), a first separator (83), a second heater (84), and a second separator (85); the discharge port of the preheater (81) is connected to the feed port of the first heater (82), the discharge port of the first heater (82) is connected to the feed port of the first separator (83), the discharge port of the first separator (83) is respectively connected to the feed port of the first heater (82) and the feed port of the second heater (84), the discharge port of the second heater (84) is connected to the feed port of the second separator (85), and the concentrated liquid outlet of the second separator (85) is respectively connected to the feed port of the second heater (84) and the feed port of the crystallization separation unit (9); the steam outlet of the first separator (83) is connected to the heat medium inlet of the second heater (84), and the steam outlet of the second separator (85) is connected to the heat medium inlet of the preheater (81).

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