CN110305065B - Continuous production equipment and production method of bromochlorohydantoin - Google Patents
Continuous production equipment and production method of bromochlorohydantoin Download PDFInfo
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
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Abstract
The invention discloses a continuous production device and a continuous production method of bromochlorohydantoin, belonging to the technical field of bromochlorohydantoin production, wherein water, 5-dimethylhydantoin and alkali are added into a dissolution-bromination kettle in proportion, a brominating agent is added after stirring and dissolution, the obtained absorption kettle stock solution is continuously pumped into an absorption kettle, and then the absorption kettle stock solution is discharged from a bottom valve of the absorption kettle and pumped into the absorption kettle through a jet device to form circulation; the air suction port of the ejector is communicated with the air outlet of the synthesis kettle, so that the interior of the synthesis kettle is in a negative pressure state; filling chlorine gas into the synthesis kettle, and carrying out chlorination reaction with the materials; and (4) removing liquid of the material after the chlorination reaction, and drying to obtain a finished product of the bromochlorohydantoin. The invention can realize the continuous production of the bromochlorohydantoin, improves the production efficiency of the bromochlorohydantoin and is suitable for the large-scale production of the bromochlorohydantoin. Meanwhile, the continuous production method of the bromochlorohydantoin provided by the invention shortens the reaction time and reduces the side reaction, and the production yield of the bromochlorohydantoin reaches more than 95 percent and the purity reaches more than 98.5 percent.
Description
Technical Field
The invention belongs to the technical field of production of bromochlorohydantoin, and particularly relates to continuous production equipment and a production method of bromochlorohydantoin.
Background
The halogenated hydantoin is a high-efficiency disinfectant, bactericide and algicide. The most representative of these is bromochlorohydantoin (the chemical name of which is 1-bromo 3-chloro 5, 5-dimethylhydantoin). The bromochlorohydantoin serving as a disinfecting, sterilizing and algae-killing agent with excellent performance has the advantages of broad spectrum, high efficiency, high action speed, wide applicable pH value range, no foaming, good compatibility with scale inhibitors and corrosion inhibitors, insensitivity to organic matters and nitrogen-containing compounds in water, convenience in management and control and the like. Therefore, the method is widely applied to industrial water treatment and disinfection of mineral spring (hot spring) bathing pools, and is used for disinfection, deodorization, disinfection and bleaching of toilets, and is agriculturally used for disinfection and sterilization of flowers and seeds, cultivation industry, fruit preservation and the like in various water treatments. The 5, 5-dimethyl hydantoin residue after the disinfection and sterilization of the bromochlorohydantoin can be rapidly degraded into ammonia and carbon dioxide under natural conditions, has small influence on the environment, and is a water treatment chemical advocated and encouraged by the nation.
At present, the existing methods for producing bromochlorohydantoin mainly comprise two methods: one method is to synthesize the compound by taking 5, 5-dimethylhydantoin, hypohalite and hydrochloric acid as raw materials. The method is low in production efficiency, and the product bromine-chlorine hydantoin is gradually eliminated due to high impurity content; the other method is to synthesize the product by taking 5, 5-dimethylhydantoin, inorganic base, chlorine and bromine (or sodium bromide) as raw materials, and the production method has high yield and good product quality, and is mainly used by domestic bromochlorohydantoin production enterprises. The methods disclosed in Chinese patents CN1611492A, CN1388122A and CN103333115A belong to the latter production method, and are all carried out in batch production. The intermittent production method has low single kettle capacity, needs multi-kettle parallel operation when the capacity is required to be improved, has large floor area, more equipment facilities and easy fluctuation of product quality, and is inconvenient to manage; meanwhile, the emptying of the synthesis kettle is directly connected with a tail gas treatment device, tail gas is not fully utilized, raw material consumption is high, and large-scale production is not facilitated.
Disclosure of Invention
The invention aims to provide continuous production equipment and a production method of bromochlorohydantoin, and aims to solve the technical problems that an intermittent production method in the prior art is low in productivity, large in occupied area, multiple in equipment facilities, low in raw material utilization rate and not beneficial to large-scale production.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a continuous production device for bromochlorohydantoin comprises a dissolving-brominating kettle, an absorption kettle, a synthesis kettle, a liquid removal device and a dryer, wherein a feed inlet for adding raw materials is formed in the top of the dissolving-brominating kettle, the dissolving-brominating kettle is connected with the absorption kettle through a material transfer pump, a bottom outlet of the absorption kettle is connected with a top inlet of the absorption kettle through a circulating pump and an ejector, and an air suction port of the ejector is communicated with an emptying pipe of the synthesis kettle; an overflow port at the upper part of the absorption kettle is communicated with a synthesis kettle, a stirring device is arranged in the synthesis kettle, and the synthesis kettle is communicated with a chlorine pipe; the dissolving-brominating kettle, the absorption kettle and the synthesis kettle are all provided with cooling devices; the upper overflow port of the synthesis kettle is connected with the feed inlet of the liquid removal device, and the solid filter cake outlet of the liquid removal device is connected with the inlet of the dryer.
The invention also provides a continuous production method of the bromine-chlorine hydantoin, which comprises the following steps:
adding water, 5-dimethyl hydantoin and inorganic base into a dissolving-brominating kettle, and stirring for dissolving; controlling the temperature of the dissolution-bromination kettle to be 5-20 ℃, and adding a brominating agent to prepare an absorption kettle stock solution; wherein the content of each component in the absorption kettle stock solution is,
the mass ratio of water to 5, 5-dimethyl hydantoin is 9-12: 1;
when the brominating agent is added to be bromine, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the bromine is as follows: 1:2.0-2.1: 0.45-0.50;
when the brominating agent is added to be sodium bromide or potassium bromide, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the brominating agent is as follows: 1:2.0-2.1: 1.9-2.1;
(2) continuously conveying the absorption kettle stock solution to an absorption kettle through a transfer pump, and circulating the absorption kettle stock solution in the absorption kettle to a top inlet of the absorption kettle through an absorption kettle bottom valve, a circulating pump and an ejector to form external circulation; the side wall overflow port of the absorption kettle is connected with the synthesis kettle, and the air suction port of the ejector is communicated with the emptying pipe of the synthesis kettle, so that the inside of the synthesis kettle is in a negative pressure state of-10 to-100 Pa;
controlling the temperature of the materials in the absorption kettle to be 5-20 ℃, and controlling the pH value of the materials to be 10-14;
(3) chlorination reaction: the middle part of the synthesis kettle is provided with a stirring device, a guide cylinder is arranged in the synthesis kettle, the distance between the bottom of the guide cylinder and the bottom of the synthesis kettle is 400-600mm, and the inner diameter ratio of the guide cylinder to the synthesis kettle is 0.8-1.2: 2; the ratio of the inner diameter of the synthesis kettle to the height of the straight cylinder section of the kettle body of the synthesis kettle is 1: 1.2-1.4;
adding chlorine into the synthesis kettle, under the stirring action of a stirring device, moving the materials in the guide cylinder from top to bottom to the bottom of the synthesis kettle, and then moving the materials upwards to the upper part of the guide cylinder along the outer side of the guide cylinder and the annular space on the inner wall of the synthesis kettle, thereby forming circulation; the materials are continuously mixed and reacted with chlorine gas in the circulation process;
controlling the chlorination reaction temperature in the synthesis kettle to be 5-18 ℃; controlling the pH value of the discharged material of the synthesis kettle to be 4.0-6.5;
(4) liquid removal and drying: an overflow port is arranged on the side wall of the synthesis kettle, and the distance between the bottom of the overflow port and the upper end of the guide cylinder is 30-150 mm; the materials in the synthesis kettle flow to a liquid removal device from an overflow port on the side wall of the upper part of the synthesis kettle for liquid removal, the obtained solid filter cake materials are sent to a dryer, and the solid filter cake materials are dried to obtain a finished product of the bromochlorohydantoin;
when the next batch is produced, the feed liquid in the synthesis kettle and the absorption kettle is the feed liquid in the previous batch, so that the continuous production of the bromochlorohydantoin is realized.
Preferably, in step (1), the inorganic base is sodium hydroxide or potassium hydroxide.
Preferably, in the step (2), the temperature of the materials in the absorption kettle is 8-16 ℃; the pH value of the materials in the absorption kettle is controlled to be 12-14; the inside of the synthesis kettle is under the micro negative pressure of-10 to-20 Pa.
Preferably, a chlorine gas distributor communicated with a chlorine gas pipe is arranged at the top of the guide cylinder; the ratio of the inner diameter of the guide shell to the inner diameter of the synthesis kettle is 1:2.
Preferably, in the step (3), the chlorination reaction temperature in the synthesis kettle is controlled to be 10-15 ℃; the pH value of the discharged material of the synthesis kettle is 4.5-5.5.
Preferably, the distance between the bottom of an overflow port on the side wall of the synthesis kettle and the upper end of the guide shell is 80 mm.
Preferably, the stirring device in the synthesis kettle is a stirrer, the stirring speed of the stirrer is 200-600 rpm, three layers of stirring blades are arranged on the stirring shaft of the stirrer, each layer of stirring blades is radially and uniformly distributed, and the stirring shaft is vertically arranged in the synthesis kettle.
Preferably, the stirring speed of the stirrer in the synthesis kettle is 300-400 rpm.
Preferably, the outer wall of the synthesis kettle is provided with a jacket, the outer wall of the guide cylinder is provided with a spiral half pipe, and cold saline is introduced into the jacket and the spiral half pipe for cooling; the dissolving-brominating kettle and the absorption kettle are both internally provided with coil pipe heat exchangers and externally provided with jackets, and ice brine is introduced into the jackets and the coil pipe heat exchangers for cooling.
Preferably, the liquid removing device is a centrifuge or a vacuum liquid removing machine.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in: compared with the prior art, the method can realize continuous production of the bromochlorohydantoin, improves the production efficiency of the bromochlorohydantoin, and is suitable for large-scale production of the bromochlorohydantoin; the synthesis kettle tail gas is secondarily utilized, and the utilization rate of raw materials is improved. Meanwhile, the continuous production method of the bromochlorohydantoin provided by the invention reduces the equipment investment, shortens the reaction time, reduces the side reaction, and ensures that the production yield of the bromochlorohydantoin reaches more than 95 percent and the purity reaches more than 98.5 percent.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a process flow diagram of a continuous production facility of bromochlorohydantoin provided by the embodiment of the invention;
in the figure: 1-a dissolution-bromination kettle, 2-an absorption kettle, 3-a synthesis kettle, 4-a liquid removal device, 5-a dryer, 6-a material transfer pump, 7-a circulating pump, 8-an ejector, 9-a guide cylinder, 10-a chlorine gas distributor and 11-a stirrer.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The continuous production equipment for bromochlorohydantoin shown in fig. 1 comprises a dissolving-brominating kettle 1, an absorption kettle 2, a synthesis kettle 3, a liquid removal device 4 and a dryer 5, wherein the top of the dissolving-brominating kettle 1 is provided with feed inlets for adding water (or a mother solution of dibromohydantoin), 5-dimethylhydantoin, inorganic base and a brominating agent, the dissolving-brominating kettle 1 is connected with the absorption kettle 2 through a material transfer pump 6, the bottom outlet of the absorption kettle 2 is connected with the top inlet of the absorption kettle 2 through a circulating pump 7 and an ejector 8, and the air suction port of the ejector 8 is communicated with the air exhaust port of the synthesis kettle 3; an overflow port at the upper part of the absorption kettle 2 is communicated with a synthesis kettle 3, a three-layer three-blade propeller stirrer 11 is arranged in the synthesis kettle 3, and the synthesis kettle 3 is communicated with a chlorine pipe; an overflow port at the upper part of the synthesis kettle 3 is connected with a feed inlet of a liquid removal device 4, and a solid filter cake outlet of the liquid removal device 4 is connected with an inlet of a dryer 5.
Wherein, the dissolving-brominating kettle 1, the absorption kettle 2 and the synthesis kettle 3 are all provided with cooling devices, and cold saline water is introduced into the cooling devices for cooling. The cooling device of the synthesis kettle 3 comprises a spiral coil arranged on the outer wall of the jacket of the synthesis kettle 3 and the outer wall of the guide cylinder 9, a spiral half pipe is wound from bottom to top, and cold saline is introduced into the jacket and the spiral half pipe for cooling. The cooling devices of the dissolution-bromination kettle 1 and the absorption kettle 2 are both internally provided with coil heat exchangers and externally provided with jackets, and ice brine is introduced into the jackets and the coil heat exchangers for cooling.
The invention also provides a continuous production method of the bromine-chlorine hydantoin, which comprises the following steps:
(1) preparing an absorption kettle stock solution:
adding water, 5-dimethylhydantoin and inorganic base into a dissolving-brominating kettle 1, wherein the dissolving-brominating kettle 1 is provided with a stirrer and is convenient to stir and dissolve; the outer wall of the dissolution-bromination kettle is provided with a jacket, a half-pipe type spiral coil is arranged in the kettle body, ice salt water is filled in the jacket and the half-pipe type spiral coil, the dissolution-bromination kettle 1 is cooled, and the temperature in the dissolution-bromination kettle 1 is controlled to be 5-20 ℃, preferably 8-16 ℃; adding brominating agent to obtain absorption kettle stock solution.
Wherein, the content of each component in the absorption kettle stock solution is that the mass ratio of water to 5, 5-dimethyl hydantoin is 9-12: 1. the inorganic base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide. If liquid caustic soda is used, the water in the liquid caustic soda needs to be correspondingly subtracted when water is added.
When the brominating agent is bromine, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the brominating agent is as follows: 1:2.0-2.1: 0.45-0.50; when the brominating agent is sodium bromide or potassium bromide, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the brominating agent is as follows: 1:2.0-2.1: 1.9-2.1.
In the early stage dissolving process of preparing the absorption stock solution, because sodium hydroxide or potassium hydroxide is added, the temperature of the ice salt water is controlled to prevent the temperature of the material from rising, and 5, 5-dimethyl hydantoin is decomposed in an alkaline environment; in the later adding process of the brominating agent in the preparation of the absorption stock solution, if bromine is used as the brominating agent, the temperature of the brominating agent also needs to be controlled by using ice brine to prevent the decomposition of materials.
In addition, the brominating agent can also be selected from a dibromo hydantoin mother liquor containing sodium bromide or potassium bromide, but the addition amount of the dibromo hydantoin mother liquor is calculated according to the concentration of the sodium bromide or the potassium bromide in the dibromo hydantoin mother liquor, and meanwhile, the addition amount of water during preparation of the absorption kettle stock solution is correspondingly reduced. If the mother liquor of dibromohydantoin is used as brominating agent, when preparing absorption stock solution, the mother liquor of dibromohydantoin is directly used to dissolve 5, 5-dimethylhydantoin, alkali and brine ice for controlling temperature, and no brominating agent is needed to be added in later period.
In the early stage dissolving process of preparing the absorption stock solution, because sodium hydroxide or potassium hydroxide is added, the temperature of the ice salt water is controlled to prevent the temperature of the material from rising, and 5, 5-dimethyl hydantoin is decomposed in an alkaline environment; in the later stage of adding brominating agent in the course of preparing absorption stock solution, if using bromine as brominating agent, it also has need of using ice-salt water to control temperature so as to prevent material decomposition.
(2) And continuously conveying the absorption kettle stock solution to the absorption kettle through a material transfer pump, and circulating the absorption kettle stock solution in the absorption kettle to a top inlet of the absorption kettle through an absorption kettle bottom valve, a circulating pump and an ejector to form external circulation. And a flow meter is arranged on a pipeline between the jet device and the material transferring pump and is used for controlling the storage liquid of the absorption kettle to be uniformly input into the absorption kettle.
The side wall overflow port of the absorption kettle is connected with the synthesis kettle, the air suction port of the ejector is communicated with the emptying pipe of the synthesis kettle, so that the inside of the synthesis kettle is in a negative pressure state of-10 to-100 Pa, preferably-10 to-20 Pa. If the negative pressure in the synthesis kettle is increased, the tail gas (mainly chlorine) discharged to the absorption kettle in the synthesis kettle is excessive, so that the pH value of the tail gas absorption liquid is reduced, the absorption rate of the tail gas of the synthesis kettle is reduced, and the unabsorbed tail gas is discharged into an environment-friendly treatment device through an absorption kettle emptying pipe to be treated, so that the consumption of the chlorine is increased; if the synthesis kettle does not form negative pressure, part of tail gas of the synthesis kettle is directly discharged into an environment-friendly treatment device for treatment, and the consumption of chlorine is increased.
Controlling the temperature of the materials in the absorption kettle to be 5-20 ℃, preferably 8-16 ℃; controlling the pH value of the material at 10-14, preferably 12-14 ℃;
(3) chlorination reaction: the stirring device of the synthesis kettle is a stirrer and is designed into three-layer three-blade propelling type stirring, and the stirring speed of the stirrer is 200-600 revolutions per minute, preferably 300-400 revolutions per minute; three layers of stirring blades are arranged on a stirring shaft of the stirrer, each layer of stirring blades is uniformly distributed in three radial directions, and the stirring shaft is vertically arranged in the middle of the synthesis kettle.
A guide cylinder is arranged in the synthesis kettle, a stirring blade of the stirrer is arranged in an inner cavity of the guide cylinder, a chlorine distributor communicated with a chlorine pipe is arranged at the top of the guide cylinder, and chlorine is introduced into the synthesis kettle by controlling the flow rate through a flowmeter; the materials in the absorption kettle extend into the guide shell through the overflow port on the side wall of the absorption kettle through a pipeline. The distance between the bottom of the guide cylinder and the bottom of the synthesis kettle is 400-600mm, and the inner diameter ratio of the guide cylinder to the synthesis kettle is 0.8-1.2: 2, preferably 1: 2; the ratio of the inner diameter of the synthesis kettle to the height of the straight cylinder section of the kettle body of the synthesis kettle is 1: 1.2-1.4;
chlorine is added into the synthesis kettle, under the drive of a stirrer, the materials move from top to bottom in the guide cylinder to the bottom of the synthesis kettle and then move upwards to the upper part of the guide cylinder along the outer side of the guide cylinder and the annular space on the inner wall of the synthesis kettle, so as to form circulation; the materials are continuously mixed and reacted with chlorine gas in the circulation process;
the chlorination reaction temperature in the synthesis kettle is controlled at 5-18 ℃, preferably 10-15 ℃; controlling the pH value of the discharged material of the synthesis kettle to be 4.0-6.5, preferably 4.5-5.5;
(4) liquid removal and drying: an overflow port is arranged on the side wall of the synthesis kettle, and the distance between the bottom of the overflow port and the upper end of the guide shell is 30-150mm, preferably 80 mm; and (3) allowing the materials in the synthesis kettle to flow to a liquid removal device from an overflow port on the side wall of the upper part of the synthesis kettle for liquid removal, conveying the obtained solid filter cake materials to a dryer, and drying to obtain the finished product of the bromochlorohydantoin. The liquid removing device is a centrifuge or a vacuum liquid removing machine. However, the water content of the material treated by the vacuum liquid removing equipment is about 5-15% higher than that of the material subjected to centrifugal liquid removing, so that the drying load of a dryer is increased and the drying cost is increased in the later material drying process;
when the next batch is produced, the feed liquid in the synthesis kettle and the absorption kettle is the feed liquid in the previous batch, so that the continuous production of the bromochlorohydantoin is realized.
In order to quickly reduce the temperature of the dissolution-bromination kettle, the absorption kettle and the synthesis kettle and ensure the temperature required by production, a jacket is arranged on the outer wall of the synthesis kettle, a half-pipe type spiral coil is arranged on the outer wall of the guide cylinder, and cold saline is introduced into the jacket and the spiral coil for cooling; and the dissolution-bromination kettle and the absorption kettle are both externally provided with a jacket and a built-in coil heat exchanger, and ice brine is introduced into the jacket and the coil heat exchanger for cooling. The dissolving-brominating kettle and the absorption kettle can also use an external heat exchanger, and the feed liquid in the kettle is circularly cooled by the heat exchanger by a pump, but the capital investment and the power consumption of equipment are increased.
The following are examples of 8 specific production batches:
example 1:
2200L of water was added to a 3000L enamel dissolution-bromination kettle, and stirring was started. 145.8kg of 98.5 percent sodium hydroxide is added, stirred and dissolved, and simultaneously, ice brine is introduced into an internal coil heat exchanger for cooling. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 230kg of 5, 5-dimethylhydantoin is added and stirred until the materials are completely dissolved. Controlling the temperature of the brine ice water of the materials in the dissolution-bromination kettle to be 5-10 ℃, dropwise adding 143kg of bromine, and completing the dropwise adding of the bromine to prepare the stock solution of the absorption kettle for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
Adding water into the synthesis kettle to an overflow port, and starting the stirrer. And conveying the absorption kettle stock solution to an overflow port of the absorption kettle by using a material transfer pump, and starting the ejector and the circulating pump. And opening a chlorine valve, introducing chlorine until the pH value of the materials in the synthesis kettle reaches 6.0, starting a material transferring pump, adjusting the flow, and adding the storage liquid in the absorption kettle into the absorption kettle. After the absorption kettle material absorbs the tail gas of the synthesis kettle, the tail gas overflows into the guide cylinder of the synthesis kettle. Simultaneously, the flow rate of chlorine gas added into the synthesis kettle and the adding rate of absorption stock solution in the absorption kettle are adjusted, the pH value of overflowing materials in the synthesis kettle is maintained between 5.5 and 6.5, and the pH value of materials in the absorption kettle is above 13.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of materials in the synthesis kettle is 8-13 ℃, and the temperature of materials in the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is kept between-10 Pa and-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 5.432 tons of finished bromochlorohydantoin. In the liquid removing process, the water washing is used for further desalting, so that the content of the bromochlorohydantoin can be further increased. The content of bromochlorohydantoin is 98.9 percent and the yield is 95.3 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirrer of the synthesis kettle is three-layer three-blade propeller type stirring, and the stirring speed is 320 revolutions per minute.
Example 2:
1900L of water was added to a 3000L enamel dissolution-bromination kettle, and stirring was started. 448.7kg of 32% sodium hydroxide aqueous solution is added, stirred and dissolved, and simultaneously, ice brine is introduced into an internal coil heat exchanger for cooling. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 230kg of 5, 5-dimethylhydantoin is added and stirred until the materials are completely dissolved. Controlling the temperature of the brine ice water of the materials in the dissolution-bromination kettle to be 5-10 ℃, dropwise adding 143kg of bromine, and completing the dropwise adding of the bromine to prepare the stock solution of the absorption kettle for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The feed liquid obtained after 8 hours of continuous production in example 1 was fed into the synthesis reactor and the absorption reactor. Regulating the chlorine flow rate in the synthesis kettle and the material transferring pump to convey the liquid from the absorption kettle while maintaining the pH value of the overflowed material in the synthesis kettle at 4.5-5.0 and the pH value of the material in the absorption kettle at over 12.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of materials in the synthesis kettle is 8-13 ℃, and the temperature of materials in the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is kept between-10 Pa and-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 8.647 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 99.3 percent and the yield is 96.4 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the bottom of the kettle is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
Example 3:
2200L of water was added to a 3000L enamel dissolution-bromination kettle, and stirring was started. 183kg of 95% potassium hydroxide was added thereto, and the mixture was dissolved by stirring while cooling with ice brine. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 220kg of 5, 5-dimethylhydantoin is added and stirred until the materials are completely dissolved. Controlling the temperature of the brine ice water of the materials in the dissolution-bromination kettle to be 10-15 ℃, dropwise adding 137.2kg of bromine, and finishing the dropwise adding of the bromine to prepare the stock solution of the absorption kettle for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The feed liquid obtained after 8 hours of continuous production in example 2 was fed into the synthesis reactor and the absorption reactor. Regulating the chlorine gas feeding flow rate of the synthesis kettle and the speed of the material transferring pump for conveying the absorption kettle stock solution, and maintaining the pH value of the overflowing material in the synthesis kettle between 5.0 and 5.5 and the pH value of the material in the absorption kettle above 12.5. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of materials in the synthesis kettle is 10-15 ℃, and the temperature of materials in the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is kept between-10 Pa and-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 7.958 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 98.8 percent and the yield is 95.9 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
Example 4:
2300L of water was added to a 3000L enamel dissolution-bromination kettle, and stirring was started. 126.8kg of 98.5 percent sodium hydroxide is added, stirred and dissolved, and simultaneously, the temperature is reduced by ice brine. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 200kg of 5, 5-dimethyl hydantoin and 160.6kg of sodium bromide are added, the temperature of brine ice is controlled to be 15-20 ℃, and the materials are stirred until the materials are completely dissolved, so that the stock solution of the absorption kettle is prepared for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The feed liquid obtained after 8 hours of continuous production in example 3 was fed into the synthesis reactor and the absorption reactor. Regulating the chlorine flow rate in the synthesis kettle and the material transferring pump to convey the liquid from the absorption kettle while maintaining the pH value of the overflowed material in the synthesis kettle at 5.5-6.0 and the pH value of the material in the absorption kettle at over 12.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of the synthesis kettle is 10-15 ℃ and the temperature of the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is-10 to-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 7.212 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 98.6 percent and the yield is 95.3 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
Example 5:
2300L of water was added to a 3000L dissolution-bromination kettle, and stirring was started. 126.8kg of 98.5 percent sodium hydroxide is added, stirred and dissolved, and simultaneously, the temperature is reduced by ice brine. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 200kg of 5, 5-dimethyl hydantoin and 185.7kg of potassium bromide are added, the temperature of brine ice is controlled to be 15-20 ℃, and the mixture is stirred until the mixture is completely dissolved, so that the stock solution of the absorption kettle is prepared for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The feed liquid obtained after 8 hours of continuous production in example 4 was fed into the synthesis reactor and the absorption reactor. Regulating the chlorine gas feeding flow rate of the synthesis kettle and the speed of the material transferring pump for conveying the absorption kettle stock solution, and maintaining the pH value of the overflowing material in the synthesis kettle to be between 5.5 and 6.0 and the pH value of the material in the absorption kettle to be above 12.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of the synthesis kettle is 10-15 ℃ and the temperature of the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is-10 to-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 7.119 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 98.9 percent and the yield is 96.7 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
Example 6:
2200L of mother liquor of dibromohydantoin with the sodium bromide content of 7.0 percent is added into a 3000L dissolution-bromination kettle, and stirring is started. Adding 120kg of 98.5% sodium hydroxide, stirring to dissolve, and cooling with ice brine. When the temperature of the materials in the kettle is reduced to 16 ℃, 191.8kg of 5, 5-dimethyl hydantoin is added, the temperature of the brine ice is controlled to be 15-20 ℃, and the mixture is stirred until the mixture is completely dissolved, so that the absorption kettle stock solution is prepared for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The synthesis kettle and the absorption kettle are filled with feed liquid during normal continuous production. Regulating the chlorine gas feeding flow rate of the synthesis kettle and the speed of the material transferring pump for conveying the absorption kettle stock solution, and maintaining the pH value of the overflowing material in the synthesis kettle to be between 5.5 and 6.0 and the pH value of the material in the absorption kettle to be above 12.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of the synthesis kettle is 10-15 ℃ and the temperature of the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is kept between-10 Pa and-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 7.105 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 98.6 percent and the yield is 96.9 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
Example 7:
to a 3000L dissolution-bromination kettle, 1900L of water was added, and stirring was started. 448.7kg of 32% sodium hydroxide aqueous solution was added, and the mixture was dissolved by stirring while cooling with ice brine. When the temperature of the materials in the kettle is reduced to 16 ℃, 230kg of 5, 5-dimethylhydantoin is added and stirred until the materials are completely dissolved. Controlling the temperature of the brine ice water of the materials in the dissolution-bromination kettle to be 12-16 ℃, dropwise adding 143kg of bromine, and completing the dropwise adding of the bromine to prepare the stock solution of the absorption kettle for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
The synthesis kettle and the absorption kettle are filled with feed liquid during continuous production. Regulating the chlorine gas feeding flow rate of the synthesis kettle and the speed of the material transferring pump for conveying the absorption kettle stock solution, and maintaining the pH value of the overflowing material in the synthesis kettle between 5.0 and 5.5 and the pH value of the material in the absorption kettle above 13.0. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of the synthesis kettle is 10-13 ℃ and the temperature of the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is kept between-10 Pa and-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 8.821 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 99.5 percent and the yield is 96.6 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1.1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.3;
the distance between the bottom of the overflow port and the upper end of the guide shell is 100 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 450 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 400 r/min.
Example 8:
2200L of water was added to a 3000L dissolution-bromination kettle and stirring was started. 152.5kg of 98.5 percent sodium hydroxide is added, stirred and dissolved, and simultaneously, the temperature is reduced by ice brine. When the temperature of the materials in the dissolution-bromination kettle is reduced to 16 ℃, 240kg of 5, 5-dimethylhydantoin is added and stirred until the materials are completely dissolved. Controlling the temperature of the ice salt water in the kettle to be 12-16 ℃, dropwise adding 149kg of bromine, and finishing the dropwise adding of the bromine to prepare a stock solution of the absorption kettle for later use. The absorption kettle stock solution can be continuously prepared according to the operation.
Adding water into the synthesis kettle to an overflow port, and starting stirring. And (4) transferring the absorption kettle stock solution to an overflow port of the absorption kettle by using a pump, and starting a circulating pump of the ejector. And opening a chlorine valve, introducing chlorine until the pH value of the feed liquid in the synthesis kettle reaches 6.0, starting a material transferring pump from the dissolution-bromination kettle to the absorption kettle, adjusting the flow, and adding the absorption stock solution into the absorption kettle. After the materials in the absorption kettle absorb the tail gas of the synthesis kettle, the materials overflow into the guide cylinder of the synthesis kettle. And simultaneously, the chlorine gas inlet flow rate of the synthesis kettle and the speed of conveying the absorption kettle stock solution by a material transfer pump are adjusted, the pH value of the overflowing material of the synthesis kettle is maintained between 5.5 and 6.5, and the pH value of the material in the absorption kettle is above 12.5. Introducing ice salt water into a spiral coil and a coil heat exchanger of the synthesis kettle and the absorption kettle to control the temperature, so that the temperature of the synthesis kettle is 12-16 ℃ and the temperature of the absorption kettle is 10-15 ℃; the micro negative pressure in the synthesis kettle is-10 to-20 Pa. And (3) continuously producing for 8 hours, feeding the material liquid overflowing from the synthesis kettle into a centrifugal machine, removing liquid, washing with water, removing liquid, and drying a filter cake by using a dryer to obtain 9.015 tons of finished bromochlorohydantoin. The content of bromochlorohydantoin is 98.7 percent and the yield is 96.2 percent through iodometry detection.
In this example, the synthesis kettle related parameters are as follows:
the ratio of the inner diameter of the guide cylinder of the synthesis kettle to the inner diameter of the synthesis kettle is 1: 2;
the ratio of the inner diameter of the synthesis kettle to the height of the kettle body cylinder is 1: 1.25;
the distance between the bottom of the overflow port and the upper end of the guide shell is 80 mm. The distance between the lower end of the guide cylinder and the kettle bottom is 500 mm;
the stirring of the synthesis kettle is three-layer three-blade propelling type stirring, and the stirring speed is 320 revolutions per minute.
The batch-wise production of bromochlorohydantoin according to the feed ratios of examples 1-8 required 8 hours. The production yield and the chlorine consumption of the intermittent production method and the continuous production method are shown in the following table:
as can be seen from the above table, the yield of example 1 is lower because the starting material in the synthesis kettle of example 1 is water, and the yield of the continuous production method is 1.68 times that of the batch production method. In examples 2 to 8, the continuous production methods were all the batch production methods with a yield of 2 times or more. Therefore, the method is suitable for the large-scale production of the bromochlorohydantoin.
In addition, according to the data of the examples 1 to 8 in the table above, the continuous production method reduces the consumption of bromochlorohydantoin by 5 to 8 percent compared with the batch production method, improves the utilization rate of raw materials, reduces the discharge amount of synthetic tail gas in the production process, and reduces the production cost.
In conclusion, the continuous industrial production method of the bromochlorohydantoin provided by the invention effectively solves the technical problem of the intermittent production method in the prior art, greatly improves the production efficiency of equipment, and is suitable for large-scale production of the bromochlorohydantoin; the synthesis kettle tail gas is secondarily utilized, so that the utilization rate of raw materials is improved, and the tail gas treatment capacity is reduced. The continuous production method of the bromochlorohydantoin provided by the invention reduces the equipment investment, shortens the reaction time, reduces the side reaction, and has the production yield of the bromochlorohydantoin of more than 95 percent and the purity of more than 98.5 percent.
In the description above, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and thus the present invention is not limited to the specific embodiments disclosed above.
Claims (9)
1. A continuous production method of bromochlorohydantoin is characterized in that the used continuous production equipment of bromochlorohydantoin comprises a dissolving-brominating kettle, an absorption kettle, a synthesis kettle, a liquid removal device and a dryer, wherein the top of the dissolving-brominating kettle is provided with a feed inlet for adding raw materials, the dissolving-brominating kettle is connected with the absorption kettle through a material transfer pump, the bottom outlet of the absorption kettle is connected with the top inlet of the absorption kettle through a circulating pump and an ejector, and the air suction port of the ejector is communicated with the emptying pipe of the synthesis kettle; an overflow port at the upper part of the absorption kettle is communicated with a synthesis kettle, a stirring device is arranged in the synthesis kettle, and the synthesis kettle is communicated with a chlorine pipe; the dissolving-brominating kettle, the absorption kettle and the synthesis kettle are all provided with cooling devices; an overflow port at the upper part of the synthesis kettle is connected with a feed inlet of a liquid removal device, and a solid filter cake outlet of the liquid removal device is connected with an inlet of a dryer; the method is characterized in that the continuous production method of the bromochlorohydantoin comprises the following steps:
(1) preparing an absorption kettle stock solution:
adding water, 5-dimethyl hydantoin and inorganic base into a dissolving-brominating kettle, and stirring for dissolving; controlling the temperature of the dissolution-bromination kettle to be 5-20 ℃, and adding a brominating agent to prepare an absorption kettle stock solution; wherein the content of each component in the absorption kettle stock solution is,
the mass ratio of water to 5, 5-dimethyl hydantoin is 9-12: 1;
when the brominating agent is added to be bromine, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the bromine is as follows: 1:2.0-2.1: 0.45-0.50;
when the brominating agent is added to be sodium bromide or potassium bromide, the molar ratio of the 5, 5-dimethylhydantoin, the inorganic base and the brominating agent is as follows: 1:2.0-2.1: 1.9-2.1;
(2) continuously conveying the absorption kettle stock solution to an absorption kettle through a transfer pump, and circulating the absorption kettle stock solution in the absorption kettle to a top inlet of the absorption kettle through an absorption kettle bottom valve, a circulating pump and an ejector to form external circulation; the side wall overflow port of the absorption kettle is connected with the synthesis kettle, and the air suction port of the ejector is communicated with the emptying pipe of the synthesis kettle, so that the inside of the synthesis kettle is in a negative pressure state of-10 to-100 Pa;
controlling the temperature of the materials in the absorption kettle to be 5-20 ℃, and controlling the pH value of the materials to be 10-14;
(3) chlorination reaction: the middle part of the synthesis kettle is provided with a stirring device, a guide cylinder is arranged in the synthesis kettle, the distance between the bottom of the guide cylinder and the bottom of the synthesis kettle is 400-600mm, and the inner diameter ratio of the guide cylinder to the synthesis kettle is 0.8-1.2: 2; the ratio of the inner diameter of the synthesis kettle to the height of the straight cylinder section of the kettle body of the synthesis kettle is 1: 1.2-1.4;
adding chlorine into the synthesis kettle, under the stirring action of a stirring device, moving the materials in the guide cylinder from top to bottom to the bottom of the synthesis kettle, and then moving the materials upwards to the upper part of the guide cylinder along the outer side of the guide cylinder and the annular space on the inner wall of the synthesis kettle, thereby forming circulation; the materials are continuously mixed and reacted with chlorine in the circulating process;
controlling the chlorination reaction temperature in the synthesis kettle to be 5-18 ℃; controlling the pH value of the discharged material of the synthesis kettle to be 4.0-6.5;
(4) liquid removal and drying: an overflow port is arranged on the side wall of the synthesis kettle, and the distance between the bottom of the overflow port and the upper end of the guide cylinder is 30-150 mm; the materials in the synthesis kettle flow to a liquid removal device from an overflow port on the side wall of the upper part of the synthesis kettle for liquid removal, the obtained solid filter cake materials are sent to a dryer, and the solid filter cake materials are dried to obtain a finished product of the bromochlorohydantoin;
when the next batch is produced, the feed liquid in the synthesis kettle and the absorption kettle is the feed liquid in the previous batch, so that the continuous production of the bromochlorohydantoin is realized.
2. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: in the step (1), the inorganic base is sodium hydroxide or potassium hydroxide.
3. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: in the step (2), the temperature of the materials in the absorption kettle is 8-16 ℃; the pH value of the materials in the absorption kettle is controlled to be 12-14; the inside of the synthesis kettle is under the micro negative pressure of-10 to-20 Pa.
4. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: the top of the guide cylinder is provided with a chlorine distributor communicated with a chlorine pipe; the ratio of the inner diameter of the guide shell to the inner diameter of the synthesis kettle is 1:2.
5. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: in the step (3), the chlorination reaction temperature in the synthesis kettle is controlled at 10-15 ℃; the pH value of the discharged material of the synthesis kettle is 4.5-5.5.
6. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: the distance between the bottom of an overflow port on the side wall of the synthesis kettle and the upper end of the guide cylinder is 80 mm.
7. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: the stirring device in the synthesis kettle is a stirrer, the stirring speed of the stirrer is 200-600 revolutions per minute, three layers of stirring blades are arranged on a stirring shaft of the stirrer, each layer of stirring blades is radially and uniformly distributed, and the stirring shaft is vertically arranged in the synthesis kettle.
8. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: the outer wall of the synthesis kettle is provided with a jacket, the outer wall of the guide cylinder is provided with a spiral half pipe, and cold saline is introduced into the jacket and the spiral half pipe for cooling; the dissolving-brominating kettle and the absorption kettle are both internally provided with coil pipe heat exchangers and externally provided with jackets, and ice brine is introduced into the jackets and the coil pipe heat exchangers for cooling.
9. The continuous production method of bromochlorohydantoin according to claim 1, characterized in that: the liquid removing device is a centrifuge or a vacuum liquid removing machine.
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