CN214528133U - Continuous flow method synthesis system of bromine chloride - Google Patents
Continuous flow method synthesis system of bromine chloride Download PDFInfo
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- CN214528133U CN214528133U CN202120616427.XU CN202120616427U CN214528133U CN 214528133 U CN214528133 U CN 214528133U CN 202120616427 U CN202120616427 U CN 202120616427U CN 214528133 U CN214528133 U CN 214528133U
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Abstract
The utility model discloses a bromine chloride continuous flow method synthesis system, which comprises a reaction unit, a cooling unit and a separation and refining unit; the product outlet of the reaction unit is connected with the inlet of the cooling unit; the inlet of the separation refining unit is connected with the outlet of the cooling unit; the reaction unit comprises one or more continuous flow reactors. The utility model discloses a continuous flow method synthesis system makes reaction time shorten greatly, reduced the energy consumption, practiced thrift the cost, improved the security and the stability of bromine chloride production greatly, and selectivity is high, the side reaction is few, subsequent processing is simple, easily separates, easily carries out the industry and enlarges.
Description
Technical Field
The utility model relates to a bromine chloride continuous flow method synthesis system.
Background
Bromine chloride (BrCl) is an interhalogen compound, first synthesized by Balard in 1826, but its presence was determined by comparison of the absorption spectra in 1929. The bromine chloride has wide application range, can be used in the aspects of bactericides, oxidants, bleaches, industrial disinfectants, industrial water treatment agents and the like, and can also be used for removing mercury from coal-fired flue gas. The most important application of bromine chloride is also as a brominating agent for bromination of flame retardants, dye intermediates and pharmaceutical intermediates. Compared with bromination reaction, the reaction speed of the chlorination and bromination reaction is two orders of magnitude faster, the metal corrosion rate is 1-2 times smaller, the solidifying point is lower (no heat preservation is needed in cold regions), the effective bromine content per unit mass is 40%, and the bromine atom utilization rate is high.
An industrial device adopting bromine chloride as a brominating agent is not available at home, and one important reason for limiting the use of the bromine chloride is the lack of a stable and mature bromine chloride production technology. Bromine chloride is obtained by directly combining bromine simple substance and chlorine simple substance, the process is exothermic reaction, particularly, the exothermic reaction of chlorine and liquid phase bromine has relatively large heat release, and the low temperature is favorable for the synthesis reaction of BrCl. In the prior art, a batch kettle type reaction process is mostly adopted for synthesizing bromine chloride, and from the thermodynamic perspective, the reaction is thorough under a low-temperature condition. The low-temperature normal-pressure kettle type reaction process has the problems of high refrigeration energy consumption, high equipment heat preservation condition, long reaction time, uncontrollable reaction condition and the like.
The synthesis of bromine chloride generally adopts the reaction of chlorine gas and liquid bromine, which is a reaction with reduced volume, so that the synthesis of bromine chloride is facilitated by increasing the pressure. Because of the problems caused by the above-mentioned reduction of the reaction temperature, the completion of the reaction should not be pursued too much from the thermodynamic point of view, but the reaction rate should be increased by increasing the temperature from the kinetic point of view, and the reaction pressure should be increased to promote the equilibrium of the reaction to move forward and increase the substrate concentration. CN101264864A proposes that a medium-pressure reactor is adopted to synthesize bromine chloride, chlorine gas is slowly introduced into liquid bromine, the temperature and pressure in the reaction process are increased to 70 ℃ and 10atm, compared with a low-temperature normal-pressure kettle type reaction process, refrigeration is not needed, the reaction time is shortened, and the feasibility of synthesizing the bromine chloride from the aspect of kinetic control is verified. However, the essence of the method is still a tank reaction process, the temperature and pressure are not controlled, the industrial implementation is difficult, and the method has dangerousness, and the patent does not mention the collection and treatment of products, such as temperature reduction, pressure reduction and other operations.
In view of the above-mentioned drawbacks of the batch-tank reaction process for synthesizing bromine chloride, the continuous flow process for synthesizing bromine chloride is under development.
SUMMERY OF THE UTILITY MODEL
The utility model provides a technical problem overcome and adopt cauldron formula intermittent type formula reaction synthesis bromine chloride to have reaction time long, the energy consumption is high among the prior art, temperature and pressure are uncontrolled, exist danger, be difficult to the industrialization to product bromine chloride is difficult to defects such as store, provides a high-efficient, safe, low-cost and easily enlarge continuous flow method bromine chloride synthesis system of production, and the bromine chloride of synthesis simultaneously can directly be used for the bromination reaction, has solved the problem that bromine chloride is difficult to store.
Although it is well known to those skilled in the art that continuous flow reactions allow the reaction process to be operated under controlled conditions, the residence time of the microchannel reactor commonly used in continuous flow reactions is generally short, and the reactions with small equilibrium constants of the bromine chloride synthesis reaction have the problems of incomplete reaction and impure products. In addition, bromine chloride is synthesized in a liquid phase at a relatively high pressure and temperature, but has a relatively low boiling point under normal pressure conditions (5 ℃ at 1 atm; 70 ℃ at 10 atm), and thus has a problem that collection of the bromine chloride product is difficult. The utility model discloses an inventor explores through long-term experiment, creatively discovers, through the molar ratio of ingenious control reaction pressure, reaction temperature, reaction dwell time and raw materials liquid bromine and chlorine when process design, can creatively solve above-mentioned difficult problem, reaches unexpected technological effect.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
the utility model provides a bromine chloride continuous flow method synthesis system, which comprises a reaction unit, a cooling unit and a separation refining unit;
the product outlet of the reaction unit is connected with the inlet of the cooling unit; the inlet of the separation refining unit is connected with the outlet of the cooling unit;
the reaction unit comprises one or more continuous flow reactors.
In the utility model, when the reaction unit comprises a plurality of continuous flow reactors, the continuous flow reactors are connected in series or in parallel; each continuous flow reactor is provided with one or more material inlets and one or more material outlets; each of the continuous flow reactors may effect feed, mixing, heat exchange and reaction of the raw materials.
Wherein, the reaction unit can be set as the same temperature zone, and different sub-temperature zones can be set for different continuous flow reactors.
Wherein the continuous flow reactor may be conventional in the art, such as one or more of a microchannel reactor, a tubular reactor, a cascade mixer, a static mixer, preferably a microchannel reactor.
The utility model discloses in, cooling unit can adopt the conventional heat exchanger in this field, for example one or more in shell and tube heat exchanger, plate heat exchanger, fountain heat exchanger and the formula of immersing coil heat exchanger.
The utility model discloses in, the refined unit of separation can be the rectifier unit for separate bromine chloride in the result and unreacted liquid bromine.
The utility model discloses in, preferably, still include compounding jar and backflow pipeline.
The reflux pipeline is used for connecting the tower bottom of the rectifying device and a feed inlet of the mixing tank and recycling liquid bromine discharged from the tower bottom of the rectifying device; and the mixing tank is used for mixing the raw material liquid bromine and the recovered liquid bromine.
And the outlet of the mixing tank is connected with the inlet of a feed pump, and the bromine in the mixed liquid in the mixing tank is pumped into the reaction unit by the feed pump.
The overhead distillate of the rectifying device is liquefied to obtain bromine chloride liquid, and the bromine chloride liquid can be directly used for subsequent bromination reaction, so that the problem that bromine chloride is difficult to store is solved.
The utility model also provides a bromine chloride's continuous flow synthesis technology, its continuous flow synthesis system that adopts foretell bromine chloride, it includes following step:
in a continuous flow reactor, liquid bromine and chlorine gas are subjected to the following reaction;
Br2+Cl2→2BrCl
the reaction temperature is 0-50 ℃, the reaction pressure is 5-20 bar, the reaction residence time is 10-200 s, and the molar ratio of the liquid bromine to the chlorine is 1 (0.9-1.0).
In the utility model, the raw materials of the reaction can also be used as the diluent of the diluent bromine.
Among them, the diluent may be a diluent conventional in the art, preferably a chlorine-containing solvent such as dichloroethane, carbon tetrachloride and chloroform, more preferably dichloroethane.
Wherein a mixed liquid obtained by mixing the diluent with the liquid bromine is pumped into the continuous flow reactor through a feed pump.
Wherein, the mass percentage of the liquid bromine in the mixed liquid can be 20-100%, preferably 40-100%, such as 40%, 60%, 80%, 100%.
The addition of the diluent can increase the contact area of the liquid bromine and the chlorine gas, thereby improving the reaction conversion rate.
In the present invention, preferably, the molar ratio of the liquid bromine to the chlorine gas is 1: (0.94 to 1.0), for example, 1:0.95, 1:0.96, 1:0.97, 1:0.98, 1:0.99, more preferably (0.97 to 1.0): 1.
the utility model discloses in, the mole flow of chlorine can not be too high, and this is because chlorine can not recycle, and too much chlorine not only can cause the chlorine loss, reduces chlorine atom utilization ratio, also increases subsequent processing's procedure and cost simultaneously. However, the molar flow rate of chlorine gas cannot be too low, and the higher the flow rate of chlorine gas, the higher the bromine chloride yield. The utility model discloses the atomic utilization ratio of considering comprehensively chlorine, subsequent processing and bromine chloride's yield, simultaneously through the cooperation with dwell time, reaction temperature and reaction pressure, guaranteed that bromine chloride's crude and product yield are at higher level.
In certain embodiments of the present invention, the feed flow rate of the mixed liquor can be (33-38) ml/min, such as 33.66ml/min, 34.32ml/min, 34.35ml/min, 35.79ml/min, 37.24 ml/min.
In certain embodiments of the present invention, the feed flow rate of chlorine gas may be (0.2-3.0) kg/h, such as 0.24kg/h, 0.25kg/h, 0.26kg/h, 0.62kg/h, 1.07kg/h, 1.62kg/h, 2.55kg/h, 2.60 kg/h.
The utility model discloses in, the joining mode of raw materials can be for this area conventionality, preferably, will liquid bromine carries through the constant flow pump reaction unit obtains through gasification of gasification pot liquid chlorine carries reaction unit.
In certain embodiments, the temperature of the reaction can be 0-50 deg.C, such as 0 deg.C, 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 50 deg.C, preferably 0-30 deg.C, more preferably 0-20 deg.C.
In certain embodiments of the present invention, the pressure of the reaction may be 5 to 20bar, such as 5bar, 8bar, 11bar, 13bar, 15bar, 20bar, preferably 8 to 18bar, more preferably 8 to 15 bar.
In the present invention, the pressure of the reaction can be regulated by conventional methods in the art, preferably by a pressure regulating valve.
In certain embodiments of the present invention, the residence time of the reaction can be 10-200 s, such as 10s, 50s, 55s, 70s, 80s, 200s, preferably 10-100 s, more preferably 10-80 s.
In the utility model, the temperature of the cooling unit is preferably-10 to 0 ℃, more preferably-10 to-5 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined at will to obtain the preferred embodiments of the present invention.
The utility model discloses an actively advance the effect and lie in:
(1) the utility model overcomes the poor defect of cauldron formula reactor mass transfer heat transfer performance, reaction time shortens greatly (some embodiments can reduce to 50 ~ 80s), and reaction temperature is more close the normal atmospheric temperature, has reduced the energy consumption, has practiced thrift the running cost.
(2) The utility model discloses operating procedure is few, easy operation, and stability is high.
(3) The utility model discloses it is small to hold liquid in the reactor, can effectively avoid the production of this exothermic reaction well focus, improves the security of technology from essence.
(4) The utility model discloses the conversion is high, and selectivity is high, and the side reaction is few, and coarse product impurity is few, and the aftertreatment is simple, easily separates.
(5) The process has no amplification effect, can still complete the reaction in a short time on an industrial scale, and has the product content and the yield which are basically the same as those of a laboratory scale. No problems of waste water treatment, environmental pollution and the like.
Drawings
FIG. 1 is a schematic flow chart of a process for synthesizing bromine chloride by a continuous flow method.
Description of the reference numerals
1-a feed pump; 2-a reaction unit; 3-a cooling unit; 4-back pressure valve; 5-a separation and purification unit; 6-raw material liquid bromine inlet; 7-a chlorine inlet; an 8-bromine chloride outlet; 9-inlet of recovered liquid bromine; and 10-mixing tank.
Detailed Description
The present invention is further illustrated by way of the following examples, which are not intended to limit the scope of the invention.
Example 1
In the continuous flow bromine chloride synthesis system shown in fig. 1, the outlet of the reaction unit 2 is connected with the inlet of the temperature reduction unit 3, and the outlet of the temperature reduction unit 3 is connected with the inlet of the separation and purification unit 5 through the backpressure valve 4.
The method comprises the steps that raw material liquid bromine enters a mixing tank 10 through a raw material liquid bromine inlet 6 and recovered liquid bromine from a separation and refining unit 5 through a recovered liquid bromine inlet 9 to be mixed, then the mixture is pumped into a reaction unit 2 through a feeding pump 1 to be mixed and reacted with chlorine from a chlorine inlet 7, after the reaction is finished, reaction liquid enters a cooling unit 3, after cooling, a back pressure valve 4 is adjusted, obtained feed liquid is conveyed to the separation and refining unit 5, rectification and refining are carried out by utilizing the boiling point difference of the liquid bromine and bromine chloride, the distillate at a bromine chloride outlet is bromine chloride 8, the distillate at the tower bottom is liquid bromine, and the bromine flowing out of the tower bottom can be recycled.
Example 2
The continuous flow synthesis process of bromine chloride of this example employs the continuous flow synthesis system of bromine chloride of example 1, which includes the following steps: liquid bromine and a diluent dichloroethane are mixed in advance to obtain a raw material mixed solution, wherein the liquid bromine accounts for 20% by mass. The mixture was pumped into the reaction unit at a flow rate of 35.79 mL/min. Liquid chlorine was gasified in a gasification tank and then introduced into the reaction unit at a flow rate of 0.25 kg/h. The reaction temperature of the reaction unit was controlled at 5 ℃, the reaction pressure at 8bar, and the residence time of the reaction at 50 s. Reacting liquid bromine and chlorine in a reaction unit, cooling and liquefying reaction liquid obtained at an outlet of the reactor by a cooling unit at the temperature of-5 ℃, then, introducing the reaction liquid into a separation and refining unit for rectification and separation, liquefying bromine chloride obtained at the top of the tower, then, storing the liquefied bromine chloride in a pressure vessel, and recycling the liquid bromine obtained at the bottom of the tower.
Examples 3 to 9
The process parameter settings of examples 3-9 are shown in Table 1, and the other operations are the same as in example 2.
Comparative examples 1 to 4
The process parameter settings of comparative examples 1 to 4 are shown in Table 1, and the other operations are the same as in example 2.
Effects of the embodiment
The product purity detection method comprises the following steps: the bromine content is determined by iodometry, so that the weight of bromine chloride is calculated, and the ratio of the weight of bromine chloride to the total weight of the product is the purity of the product.
The crude product yield calculation method comprises the following steps: actual collected material weight gain/theoretical material weight gain. The weight gain of the material refers to the difference between the discharged weight and the fed weight in a certain time.
The product yield calculation method comprises the following steps: the weight ratio of the pure material obtained after rectification to the theoretical product weight.
The effect data of examples 2 to 9 and comparative examples 1 to 5 are shown in table 2.
TABLE 1 Process parameter settings for the examples and comparative examples
TABLE 2 Effect data of examples and comparative examples
As shown in table 2, the yields of the crude products obtained in examples 2 to 9 are all above 95%, the yields of the obtained products are also above 80%, and the purities of the obtained products are above 99%, especially in example 9, the yields of the crude products and the purities of the products are both above 99%, and the yield of the products is also above 98%. In comparative examples 1 to 4, when the reaction temperature, pressure or residence time is out of the protection range, the yield of the obtained product is greatly reduced compared with the embodiment, and the crude product and the product yield are relatively greatly reduced when the molar ratio of the liquid bromine to the chlorine gas in comparative example 4 is beyond the range defined in claim 1.
Claims (6)
1. A bromine chloride continuous flow method synthesis system is characterized by comprising a reaction unit, a cooling unit and a separation and refining unit;
the product outlet of the reaction unit is connected with the inlet of the cooling unit; the inlet of the separation refining unit is connected with the outlet of the cooling unit;
the reaction unit comprises one or more continuous flow reactors.
2. The bromine chloride continuous-flow synthesis system of claim 1, wherein when the reaction unit comprises a plurality of continuous flow reactors, each of the continuous flow reactors are connected in series or in parallel; each continuous flow reactor is provided with one or more material inlets and one or more material outlets; each of the continuous flow reactors may effect feed, mixing, heat exchange and reaction of the raw materials.
3. The bromine chloride continuous-flow synthesis system of claim 1, wherein the continuous-flow reactor is one or more of a microchannel reactor, a tubular reactor, a cascade mixer, a static mixer.
4. The continuous-flow bromine chloride synthesis system of claim 3, wherein the continuous-flow reactor is a microchannel reactor.
5. The continuous flow bromine chloride synthesis system of claim 1, wherein the heat exchanger of the temperature reduction unit is one or more of a shell and tube heat exchanger, a plate heat exchanger, a trickle heat exchanger, and a submerged coil heat exchanger.
6. The continuous-flow bromine chloride synthesis system of claim 1, wherein the separation and refinement unit further comprises a mixing tank and a return line;
the separation and refining unit is a rectifying device, the reflux pipeline is used for connecting the tower bottom of the rectifying device and the feed inlet of the mixing tank, and liquid bromine discharged from the tower bottom of the rectifying device is recycled;
and the mixing tank is used for mixing the raw material liquid bromine and the recovered liquid bromine.
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Effective date of registration: 20230707 Address after: Fuzhouwan Town, Wafangdian City, Dalian City, Liaoning Province 116309 Patentee after: DALIAN YANHUA GROUP Co.,Ltd. Address before: 116308 No.5-2, Mujia Road, songmudao chemical industry park, puwan New District, Dalian City, Liaoning Province Patentee before: Dalian haihuibo Technology Co.,Ltd. |