CN113620251A - Bromine-containing waste gas recovery system - Google Patents
Bromine-containing waste gas recovery system Download PDFInfo
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- CN113620251A CN113620251A CN202010384392.1A CN202010384392A CN113620251A CN 113620251 A CN113620251 A CN 113620251A CN 202010384392 A CN202010384392 A CN 202010384392A CN 113620251 A CN113620251 A CN 113620251A
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Abstract
The invention discloses a bromine-containing waste gas recovery system, which comprises a separation device, an oxidation device, a purification device, a phase separation device and a rectification device, wherein bromine-containing waste gas is separated by the separation device to obtain a hydrogen bromide solution, the hydrogen bromide solution is introduced into the oxidation device through a pipeline to be oxidized to form steam containing a bromine simple substance and a reaction solution, the steam containing the bromine simple substance and the reaction solution are introduced into the purification device to be purified and separated to obtain steam containing the bromine simple substance, the steam containing the bromine simple substance is condensed and liquefied to enter the phase separation device to be separated to obtain liquid bromine, and the liquid bromine is rectified and recovered by the rectification device. The bromine-containing steam formed by oxidation of the oxidation device and the reaction solution are introduced into the purification device for purification and separation, and the bromine in the reaction solution is fully separated and recovered, so that the yield and the purity of the bromine recovered from bromine-containing waste gas are high, the recovery rate is greater than 98%, and the purity of the obtained liquid bromine is greater than 99.5% through test calculation.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a bromine-containing waste gas recovery system.
Background
In recent years, the dye industry in China is rapidly developed, and an independent industry from raw materials, intermediates and auxiliaries to finished products is formed. The dye is a fine chemical product, has the characteristics of high added value, high price and high profit, but has the characteristics of high energy consumption, high emission and high pollution in the production process. Because the waste gas of the dye production process is mostly discharged intermittently, the types of the waste gas are more, the treatment effect of the current enterprises on the dye waste gas is poor, and the pollution is very serious. The disperse red is an important disperse dye, has large global demand, is applied to the fields of printing, printing ink, plastics, color masterbatch, ink-jet ink and the like, is an irreplaceable important raw material, and can generate a large amount of bromine-containing waste gas in the production process. At present, the treatment mode of the part of bromine-containing tail gas is as follows: condensing the bromine-containing tail gas, recovering liquid bromine in the condensed bromine-containing tail gas, and recovering uncondensed hydrogen bromide and SO2、SO3And other waste gases are absorbed by the alkali liquor. However, HBr and SO in the exhaust gas2、SO3The bromine is absorbed by alkali liquor and then can only be discharged into a sewage plant, so that a large amount of alkali liquor is consumed, bromine in the alkali liquor is wasted, the recovery efficiency is poor, and the resource waste is serious.
Chinese patent application No. CN201610741519.4 discloses a process and apparatus for synthesizing disperse red FB, specifically, a bromination reaction is performed with aminoanthraquinone as raw material and chlorobenzene as solvent, and the solvent is recycled after the product is filtered; dissolving the dried product in a solvent and concentrated sulfuric acid for hydrolysis reaction, and recycling the solvent; carrying out condensation reaction on the product and phenol, carrying out methanol segregation on the product to obtain a finished product of disperse red FB, circularly using filtrate by distillation, and recovering a sodium bromide solution from a distillation residue kettle; the synthesis equipment comprises a feeding port, a brominated four-mouth bottle kettle, a suction filter tank, a brominated waste liquid treatment device, a hydrolyzed four-mouth bottle kettle, a suction filter tank, a hydrolyzed waste liquid treatment device, a condensation kettle, a suction filter tank and a condensation waste liquid treatment device. The process only carries out recovery treatment on the wastewater, and does not effectively recover the waste gas generated in the production process.
The present invention has been made in view of this situation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a bromine-containing waste gas recovery system.
In order to solve the technical problems, the invention adopts the technical scheme that:
the utility model provides a contain bromine waste gas recovery system, contains bromine waste gas and contains hydrogen bromide gas and other waste gases, contains bromine waste gas recovery system including the separator, oxidation device, purification device, phase separation device and the rectifier unit that connect gradually, contain bromine waste gas and form the steam and the reaction solution that contain the bromine simple substance after separator, oxidation device in proper order, the steam and the reaction solution that contain the bromine simple substance get into the purification device purification separation and obtain the steam that contains the bromine simple substance, and the steam that contains the bromine simple substance gets into phase separation device, rectifier unit and retrieves after the condensation liquefaction.
Further, the purification device comprises a separation tower, a heating device is arranged at the bottom of the separation tower, the separation tower is communicated with the oxidation device through a pipeline, the steam containing the bromine and the reaction solution are introduced into the separation tower through the pipeline, the reaction solution is heated through the heating device in the separation tower, and the steam containing the bromine in the separation tower is stripped and separated.
Furthermore, the inner area of the separation tower is divided into a stripping area and a reaction area from the lower part of the separation tower to the upper part of the separation tower, the oxidation device comprises an oxidation tank, the reaction area is communicated with the upper part of the oxidation tank through a first pipeline, the stripping area is communicated with the lower part of the oxidation tank through a second pipeline, the steam containing the bromine simple substance enters the reaction area through the first pipeline, the reaction solution enters the stripping area through the second pipeline, the bromine simple substance in the reaction solution and the steam containing the bromine simple substance in the reaction area are stripped by the steam generated in the stripping area, and the steam is condensed, separated, rectified and recovered;
preferably, the first pipeline and the second pipeline are communicated with the middle part of the separation tower.
Further, separator includes the strip tower, strip tower bottom sets up the reboiler, and bromine-containing waste gas gets into the strip tower, and hydrogen bromide gas mixes with the absorption liquid in the strip tower and forms hydrogen bromide solution, strip tower lower part and oxidation unit pass through the third pipeline intercommunication, hydrogen bromide solution lets in oxidation unit through the third pipeline and oxidizes, and other waste gases are stripped and are discharged by strip tower upper portion through the steam that the reboiler produced.
Furthermore, a liquid inlet pipe is arranged at the upper part of the separation device, and the liquid inlet pipe is used for introducing absorption liquid into the stripping tower;
preferably, the liquid inlet pipe is provided with a spray hole, and the spray hole is arranged in the stripping tower towards the bottom of the stripping tower.
Further, the phase separation device comprises a phase separator, the top of the separation tower is communicated with the phase separator through a pipeline, the bromine-containing steam is condensed and enters the phase separator for separation, the upper layer of liquid in the phase separator is a water phase, and the lower layer of liquid is liquid bromine.
Further, a condenser is arranged between the separation tower and the phase separator, and the steam containing the bromine in the separation tower is condensed by the condenser and enters the phase separator for separation;
preferably, a multi-stage condenser is arranged between the separation tower and the phase separator, and the steam containing the bromine enters the phase separator for separation through the multi-stage condenser.
Furthermore, an exhaust pipe is arranged at the top of the condenser, and waste gas which is not condensed and recycled by the steam containing the bromine introduced into the condenser is discharged through the exhaust pipe on the condenser.
Further, the upper part of the phase separator is communicated with the separation tower through a fourth pipeline, and the upper aqueous phase in the phase separator is refluxed to the separation tower through the fourth pipeline.
Further, the bottom of the separation tower is provided with a liquid drainage pipeline for draining waste liquid in the separation tower;
preferably, the liquid discharge pipeline is provided with a fourth condenser, and waste liquid in the separation tower is condensed and discharged through the fourth condenser.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
1. The bromine-containing steam formed by oxidation of the oxidation device and the reaction solution are introduced into the purification device for purification and separation, and the bromine in the reaction solution is fully separated and recovered, so that the yield and the purity of the bromine recovered from bromine-containing waste gas are high, the recovery rate is greater than 98%, and the purity of the obtained liquid bromine is greater than 99.5% through test calculation.
2. The bromine-containing waste gas is separated and absorbed by the separating device, and then is oxidized by the oxidizing device, so that bromine in the bromine-containing waste gas is recycled, resources are saved, waste gas emission is reduced, the use amount of alkali liquor for absorbing the bromine-containing waste gas is greatly reduced, the waste of waste water discharge and alkali liquor resources is reduced, the recovery rate of bromine in the bromine-containing waste gas is high, and the recovered liquid bromine is high in purity.
3. After HBr is removed by a bromine-containing waste gas recovery system, SO is contained2、SO3The gas can enter a sulfuric acid recovery system for recycling again, the gas is further recycled, the waste of resources is reduced, and meanwhile, part of SO2、SO3The gas is not required to be recycled by alkali liquor, so that the waste of energy is reduced.
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention, are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention to the right. It is obvious that the drawings in the following description are only some embodiments, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a schematic view of the present invention at a position A with a partially enlarged structure.
1. A stripping column; 11. a stripping tower feed inlet; 12. a stripper vent; 13. a liquid outlet of the stripping tower; 14. an exhaust gas duct; 15. a third pipeline; 2. a reboiler; 3. a liquid inlet pipe; 31. a spraying section; 311. spraying holes; 4. a first condenser; 41. the liquid outlet end of the first condenser; 5. an oxidation tank; 51. a feed inlet of the oxidation tank; 52. an oxidation tank exhaust port; 53. a liquid outlet of the oxidation tank; 54. an oxidant feed conduit; 55. a first pipeline; 56. a second pipeline; 57. a fourth pipeline; 6. a separation column; 61. a reaction zone; 62. a stripping zone; 621. a liquid distributor; 63. a first feed port; 64. a second feed port; 65. a heater; 66. a separation column vent; 67. a fourth condenser; 671. a fourth condenser feed inlet; 672. a discharge port of a fourth condenser; 7. a second condenser; 71. a second condenser air inlet; 72. a second condenser liquid outlet; 73. a second condenser exhaust; 8. a third condenser; 81. a third condenser air inlet; 82. a third condenser exhaust; 83. a third condenser liquid outlet; 84. an exhaust pipe; 9. a fifth condenser; 91. a fifth condenser air inlet; 92. a fifth condenser liquid outlet; 93. a fifth condenser exhaust; 10. a phase separator; 101. a first discharge port of the phase separator; 102. a second discharge port of the phase separator; 103. a phase separator feed inlet; 104. a rectifying tower; 1041. a feed inlet of the rectifying tower; 1042. a discharge hole of the rectifying tower; 1043. an exhaust port of the rectifying tower; 1044. and a sixth condenser.
It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
The first embodiment is as follows:
as shown in FIGS. 1 and 2, the present invention provides a bromine-containing waste gas recovery system for recovering 676kg/h of hydrogen bromide containing waste gas generated by a batch process during the production of disperse red. The operating flexibility of the device is between 50 and 105% taking into account feed fluctuations. The bromine-containing waste gas recovery device comprises a separation device, an oxidation device, a purification device, a phase separation device, a rectification device and a device pipeline. The device comprises a separation device, an oxidation device, a purification device, a phase separation device and a rectification device, wherein the separation device, the oxidation device, the purification device, the phase separation device and the rectification device are sequentially communicated through a device pipeline, and bromine-containing waste gas is sequentially treated through the separation device, the oxidation device, the purification device, the phase separation device and the rectification device. Removing impurities such as SO except bromine in bromine-containing waste gas by a separation device2、SO3And the like, and converting the hydrogen bromide gas in the bromine-containing waste gas into a hydrogen bromide solution. Oxidizing bromine ions into bromine simple substance by the hydrogen bromide solution through an oxidizing device to form steam containing the bromine simple substance and reaction solution. Then introducing the steam containing the bromine simple substance and the reaction solution into a purification device for purification and separation to obtain the bromine simple substanceAnd condensing the obtained bromine-containing steam and introducing the bromine-containing steam into a phase separation device to separate liquid bromine from a water phase. And further, introducing the obtained liquid bromine into a rectifying device for rectifying and purifying to obtain a final product. Through the device and the method, other impurities except bromine in the bromine-containing waste gas are separated, the steam containing the bromine formed by oxidation and the reaction solution are introduced into the purification device for purification and separation, so that the bromine in the reaction solution is fully separated, and the bromine is rectified, purified and recovered through the rectification device, so that the yield and the purity of the bromine recovered from the bromine-containing waste gas are high, the recovery rate is higher than 98%, the purity of the obtained liquid bromine is higher than 99.5% through test calculation, the environment is protected, and resources are effectively saved.
As shown in fig. 1, the oxidation apparatus includes an oxidation tank 5, and the hydrogen bromide solution is oxidized in the oxidation tank 5 to form a vapor containing elemental bromine and a reaction solution. The purification device comprises a stripping zone, the reaction solution is stripped and separated by the stripping zone to obtain the steam containing the bromine, and the steam containing the bromine is condensed, phase-separated, rectified and recycled to obtain the bromine. Specifically, as shown in fig. 2, the purification apparatus includes a separation tower 6, a heating apparatus is disposed at the bottom of the separation tower 6, the separation tower 6 is communicated with the oxidation apparatus through a pipeline, the bromine-containing steam and the reaction solution are introduced into the separation tower 6 through the pipeline, the reaction solution is heated by the heating apparatus in the separation tower, and the bromine-containing steam in the separation tower 6 is stripped and separated.
Further, the inner region of the separation column 6 is divided into a stripping region 62 and a reaction region 61 from the lower part of the separation column to the upper part of the separation column 6, and the hydrogen bromide solution is oxidized in the oxidation tank 5 to form steam containing bromine and a reaction solution. The steam containing bromine formed by oxidation is passed to reaction zone 61 and the reaction solution is passed to stripping zone 62. The steam generated in the stripping zone 62 strips out the bromine in the reaction solution and the steam containing the bromine in the reaction zone 61, and is separated and recovered by a condensation and phase separation device. Preferably, the temperature of the stripping zone is 100-110 ℃. The steam containing the bromine and the reaction solution output by the oxidation tank 5 enter the separation tower 6 and enter a phase separator for separation through the steam stripping of the steam stripping zone 62 of the separation tower 6, so that the steam containing the bromine can be fully stripped, and the purity and recovery rate of bromine recovery are improved. Preferably, the temperature in the stripping zone 62 is 100 ℃, and the bromine recovery is better in this temperature range.
A separation tower feed inlet is arranged between the reaction zone 61 and the stripping zone 62 of the separation tower 6, and the oxidation tank 5 is communicated with the separation tower feed inlet. The heating means comprises a reboiler or heater and the heater 65 is disposed within the stripping zone 62 such that the boiling temperature within the stripping zone 62 is about 100-. Preferably, the heater 65 is arranged at the bottom of the separation column 6, and the feed inlet of the separation column is arranged at the middle part of the separation column 6.
The oxidation tank 5 comprises an oxidation tank feeding hole 51, and the oxidation tank feeding hole 51 is communicated with a stripping tower liquid outlet 13 of the stripping tower 1. The top of the oxidation tank 5 is provided with an oxidation tank exhaust port 52, and the lower part of the oxidation tank 5 is provided with an oxidation tank liquid outlet 53. The separation column feed openings include a first feed opening 63 and a second feed opening 64 located above the first feed opening 63. The oxidation tank exhaust port 52 is communicated with the second feed port 64 through a first pipeline 55, the steam containing the bromine enters the reaction zone 61 through the first pipeline 55, the oxidation tank liquid outlet 53 is communicated with the first feed port 63 through a second pipeline 56, and the reaction solution enters the stripping zone 62 through the second pipeline 56. The steam generated in the stripping zone 62 strips the bromine in the reaction solution and the steam containing the bromine in the reaction zone 61, and the steam is condensed, separated, rectified and recovered. Hydrobromic acid containing a small amount of sulfurous acid and sulfuric acid is directed to the oxidizer feed port 51 via stripper drain 13 via third line 15.
The oxidation device further comprises an oxidant feeding pipe 54, the oxidant feeding pipe 54 is communicated with the oxidation tank 5, an oxidant is introduced into the oxidant feeding pipe 54, the oxidant is introduced into the oxidation tank 5 through the oxidant feeding pipe 54, and bromide ions in hydrobromic acid in the oxidation tank 5 are oxidized and converted into elemental bromine. The oxidizer is added in real time through oxidizer feed tube 54.
Further preferably, the oxidizing agent is a hydrogen peroxide solution. Bromine ions in the oxidation tank 5 are oxidized by the hydrogen peroxide solution to form elemental bromine, and the elemental bromine passes through the second inlet 64 and enters the reaction zone 61 through the exhaust port 52 of the oxidation tank through a pipeline. The upper part of the stripping area 62 is also provided with a liquid distributor 621, the liquid in the oxidation tank 5 enters the first feed inlet 63 through the liquid outlet 53 of the oxidation tank via the device pipeline and enters the liquid distributor 621 to be further heated by the heater 65, in the separation tower 6, the heater 65 is arranged in the stripping area 62, the heater 65 generates heat to generate steam, and the steam strips out the bromine simple substance. Preferably, heater 65 is a bayonet tube heater.
And the front of the oxidation device is connected with a separation device in series, and the separation device is used for separating the hydrogen bromide gas from other waste gases and converting the hydrogen bromide gas into a hydrogen bromide solution which is introduced into the oxidation device for oxidation. Specifically, the separation apparatus comprises a stripping column 1, a reboiler 2, and a liquid inlet pipe 3. Reboiler 2 sets up in 1 lower part of strip tower for the liquid in the heating strip tower, bromine-containing waste gas gets into the strip tower, and the hydrogen bromide gas mixes with the absorption liquid in the strip tower and forms the hydrogen bromide solution, 1 lower part and the oxidation unit of strip tower pass through third pipeline 15 intercommunication, the hydrogen bromide solution lets in the oxidation unit through third pipeline 15 and oxidizes, and other waste gases are stripped and are discharged by 1 upper portion of strip tower through the steam that reboiler 2 produced.
The stripping tower 1 comprises a stripping tower feed inlet 11 and a stripping tower exhaust outlet 12, the stripping tower feed inlet 11 is arranged at the bottom of the stripping tower 1 and is positioned at the upper part of the reboiler 2, and the stripping tower exhaust outlet 12 is positioned at the top of the stripping tower 1. The liquid inlet pipe 3 comprises a spraying section 31 with spraying holes 311, the spraying section 31 is arranged at the upper part in the stripping tower 1 and is positioned above a feeding hole 11 of the stripping tower and below an exhaust hole 12 of the stripping tower, and the spraying holes 311 are arranged towards the bottom of the stripping tower 1. Bromine-containing waste gas enters the stripping tower 1 through a feeding hole 11 of the stripping tower, absorption water, preferably no-salt water, is introduced into a liquid inlet pipe 3, and the no-salt water is sprayed into the stripping tower 1 through a spraying hole 311 on a spraying section 31, wherein the bromine-containing waste gas is absorbed by the no-salt water to form hydrobromic acid. Further, hydrobromic acid will be at the bottom of stripping column 1. Most of the SO2And SO3Because of the relatively small thermodynamic interaction with the brine-free water, the water is stripped by the stripping steam generated by the reboiler 2 and is not absorbed by the brine-free water. The boiling temperature in the reboiler 2 is about 110-125 ℃, and the stripped SO2、SO3And steam is withdrawn through stripper vent 12.
Stripper gas vent 12 is connected with exhaust gas pipeline 14, and first condenser 4 of establishing ties on exhaust gas pipeline 14, exhaust gas pipeline 14 and first condenser 4 intercommunication, first condenser 14 lower part and stripper 1 intercommunication, still have the gas vent on the first condenser 4, inside vapor and the hydrogen bromide gas that have vapourized flow back to stripper 1 through first condenser 4 condensation, other waste gases are discharged by the gas vent. In particular, stripped SO2、SO3And water vapor is condensed by the first condenser 4, gaseous SO2、SO3And saturated water vapor is separately led out and collected. Preferably, the first condenser 4 further comprises a first condenser liquid outlet end 41, the first condenser liquid outlet end 41 is communicated with the liquid inlet pipe 3, condensed water in the first condenser 4 flows back into the liquid inlet pipe 3, and is further sprayed into the stripping tower 1 through the spraying holes 311, so that recycling is realized.
The phase separation device comprises a phase separator 10, the top of the separation tower 6 is communicated with the phase separator 10 through a pipeline, the bromine-containing steam is condensed and enters the phase separator 10 for separation, the upper layer of liquid in the phase separator 10 is a water phase, and the lower layer of liquid is liquid bromine. Preferably, a condenser is arranged between the separation tower 6 and the phase separator 10, and the vapor containing the bromine in the separation tower 6 is condensed by the condenser and enters the phase separator 10 for separation.
More preferably, a multi-stage condenser is arranged between the separation tower 6 and the phase separator 10, and the steam containing the bromine enters the phase separator 10 for separation through the multi-stage condenser. Specifically, the multistage condenser comprises a second condenser 7 having a second condenser air inlet 71 at the upper part and a second condenser liquid outlet 72 at the lower part, wherein the second condenser air inlet 71 is communicated with the top of the separation column 6, and the second condenser liquid outlet 72 is communicated with the phase separator 10. Specifically, the top of the separation column 6 has a separation column vent 66, and the bottom of the separation column 6 has a separation column drain. The separation column vent 66 is in communication with a second condenser air inlet 71 and the second condenser liquid outlet 72 is in communication with the phase separator 10. The bromine enters a second condenser air inlet 71 through a separation tower air outlet 66, is condensed by a second condenser 7, and the liquefied bromine and the water phase enter a phase separator 10 for next phase separation.
The multistage condenser further comprises a third condenser 8 arranged between the second condenser 7 and the phase separator 10, the upper portion of the second condenser 7 comprises a second condenser exhaust port 73, the second condenser exhaust port 73 is communicated with the third condenser 8, the bottom of the third condenser 8 is communicated with the phase separator 10, and the residual uncondensed waste gas of the second condenser 7 enters the third condenser 8 through the second condenser exhaust port 73 to be continuously condensed into liquid bromine which is introduced into the phase separator 10 to be subjected to next phase separation.
Further preferably, the third condenser 8 has a third condenser exhaust 82 at the upper part, and the residual gas not condensed in the third condenser 8 is exhausted through the third condenser exhaust 82. In an embodiment of this embodiment, the exhaust port 82 is connected to an exhaust pipe 84, and the exhaust gas, which is introduced into the third condenser 8 and is recovered by condensing the steam containing the bromine, is discharged through the exhaust pipe 84 of the third condenser 8.
The top of the phase separator 10 includes a phase separator feed inlet 103 and the second condenser drain 72 and the third condenser drain 83 are both in communication with the phase separator feed inlet 103. The bottom of the phase separator 10 is provided with a first phase separator discharge hole 101, the phase separator 10 further comprises a second phase separator discharge hole 102 which is positioned at the upper part of the first phase separator discharge hole 101 and the lower part of the phase separator feed hole 103, the first phase separator discharge hole 101 is communicated with a rectifying device, and the second phase separator discharge hole 102 is communicated with the separation tower 6. The liquefied elemental bromine and water are separated into upper and lower layers in the phase separator 10, the liquid bromine is in the lower layer of the phase separator 10 as the heavy phase, and the water phase is in the upper layer of the phase separator 10 as the light phase. The lower layer of liquid bromine is introduced into the rectification apparatus through the first discharge port 101 of the phase separator, and the upper layer of aqueous phase is introduced into the separation column 6 through the second discharge port 102 of the phase separator, and the above cycle is repeated. The above process separates liquid bromine from water phase, and improves the purity of the liquid bromine.
Further preferably, the second discharge port 102 of the phase separator is communicated with the upper part of the separation tower 6 through the fourth pipeline 57, so that the liquid flowing into the separation tower 6 is fully stripped, the liquid bromine in the liquid is further stripped, and the recovery rate of the liquid bromine is effectively improved.
The rectifying device comprises a rectifying tower 104, a rectifying tower feed inlet 1041 is formed in the top of the rectifying tower 104, a rectifying tower discharge outlet 1042 is formed in the bottom of the rectifying tower 104, and the rectifying tower feed inlet 1041 is communicated with a first phase separator discharge outlet 101. The liquid bromine derived from the phase separator 10 may still contain a small amount of water and a trace amount of hydrogen peroxide solution, and after passing through the rectification tower, a pure bromine product is obtained at the tower bottom, the tower bottom of the rectification tower 104 is connected with a sixth condenser 1044, the sixth condenser 1044 uses chilled water as a working solution, and the pure bromine product obtained at the tower bottom is cooled, cooled and recovered by the sixth condenser 1044. The azeotropic bromine/water compound exits from the top of the column. Preferably, a tantalum reboiler is arranged at the bottom of the rectifying tower and is heated by adopting 0.6MPa steam.
The rectifying device also comprises at least one fifth condenser 9, the top of the fifth condenser 9 comprises a fifth condenser air inlet 91 and a fifth condenser air outlet 93, and the bottom of the fifth condenser 9 comprises a fifth condenser liquid outlet 92. The top of the rectifying tower 104 is provided with a rectifying tower exhaust outlet 1043, the rectifying tower exhaust outlet 1043 is communicated with the fifth condenser air inlet 91, the fifth condenser liquid outlet 92 is communicated with the phase separator 10, and in addition, the fifth condenser exhaust outlet 93 is communicated with the third condenser air inlet 81. The steam discharged from the exhaust port 1043 of the rectifying tower enters the fifth condenser 9 and is condensed by the fifth condenser 9, condensed water is discharged from the drain port 92 of the fifth condenser and guided to the phase separator 10, uncondensed steam is discharged to the third condenser 8 through the exhaust port 93 of the fifth condenser, and the uncondensed steam is discharged through the exhaust port 82 of the third condenser 8. Furthermore, an alkali absorption tank is externally connected to the exhaust port 82 of the third condenser, and the exhaust gas discharged from the exhaust port 82 of the third condenser may contain part of bromine, which needs to be introduced into the alkali absorption tank for absorption.
In the invention, the bottom of the separation tower 6 is provided with a liquid drainage pipeline for draining the waste liquid in the separation tower 6, preferably, the liquid drainage pipeline is provided with a fourth condenser 67, the fourth condenser 67 comprises a fourth condenser feed inlet 671 and a fourth condenser discharge outlet 672, the fourth condenser feed inlet 671 is communicated with the bottom of the separation tower 6, and the waste liquid is condensed by the fourth condenser 67 from the bottom of the separation tower 6 and then pumped out for neutralizing with liquid alkali, so that the waste liquid which is not treated is prevented from being discharged to pollute the environment.
The embodiment adopts the bromine-containing waste gas recovery system of any one of the schemes or any combination of the schemes. And introducing the bromine-containing waste gas into a separation device to remove other impurities except bromine in the bromine-containing waste gas, and introducing into a rectification device for further purification to obtain pure bromine. Specifically, the spraying section 31 of the liquid inlet pipe 3 in the separation device sprays salt-free water to the bottom of the stripping tower 1, the oxidant in the oxidation tank 5 in the oxidation device comprises hydrogen peroxide solution, the concentration of the hydrogen peroxide solution is 30%, the mixed liquid in the oxidation tank 5 is mixed and oxidized for 60S, the operation flexibility of the bromine-containing waste gas recovery device is 50%, and the molar ratio of the hydrogen peroxide used in the oxidation process to the hydrogen bromide to be oxidized is about 0.51: 1.
The embodiment adopts the bromine-containing waste gas recovery system of any one of the schemes or any combination of the schemes. Introducing the bromine-containing waste gas into a separation device to remove other impurities except bromine in the bromine-containing waste gas, introducing the bromine-containing waste gas into an oxidation device to oxidize bromine ions into bromine simple substances, and introducing the bromine-containing waste gas into a rectification device to further purify to obtain pure bromine. Specifically, the spraying section 31 of the liquid inlet pipe 3 in the separation device sprays salt-free water to the bottom of the stripping tower 1, the oxidant in the oxidation tank 5 in the oxidation device comprises hydrogen peroxide solution, the concentration of the hydrogen peroxide solution is 50%, the mixed liquid in the oxidation tank 5 is mixed and oxidized for 20S, the operation flexibility of the bromine-containing waste gas recovery device is 85%, and the molar ratio of the hydrogen peroxide used in the oxidation process to the hydrogen bromide to be oxidized is about 0.51: 1.
Example two:
this embodiment provides a bromine-containing waste gas recovery method that adopts above-mentioned bromine-containing waste gas recovery system, and bromine-containing waste gas contains hydrogen bromide gas and other waste gases, and hydrogen bromide gas converts hydrogen bromide solution and separates with other waste gases. Oxidizing the hydrogen bromide solution by an oxidation device to form steam containing the bromine and a reaction solution, introducing the steam containing the bromine and the reaction solution into a purification device for purification and separation to obtain the steam containing the bromine, and condensing, separating and recovering the steam containing the bromine to obtain the bromine. In the embodiment, the steam containing the bromine formed by oxidation and the reaction solution are introduced into the purification device for purification and separation, and the bromine in the reaction solution is fully separated and recovered, so that the yield and the purity of the bromine recovered from the bromine-containing waste gas are high, the recovery rate is greater than 98%, and the purity of the obtained liquid bromine is greater than 99.5% through test calculation.
The purification device comprises a stripping zone, the hydrogen bromide gas in the bromine-containing waste gas is converted into a hydrogen bromide solution and is separated from other waste gas, the hydrogen bromide solution enters an oxidation device for oxidation, the steam containing the bromine formed by oxidation and the reaction solution are stripped and separated in the stripping zone to obtain the steam containing the bromine, and the steam containing the bromine is condensed, separated and recycled to obtain the bromine. As an implementation manner of this embodiment, the steam containing the elemental bromine and the reaction solution formed by oxidation are directly introduced into the stripping zone of the purification apparatus for purification and separation, so that sufficient separation and extraction of the steam containing the elemental bromine can be achieved.
As another embodiment of this embodiment, the purification apparatus includes a separation column 6, the inner region of the separation column 6 is divided into a stripping zone 62 and a reaction zone 61 from the lower part of the separation column to the upper part of the separation column, the steam containing the elemental bromine formed by oxidation is introduced into the reaction zone 61, the reaction solution is introduced into the stripping zone 62, the steam generated in the stripping zone 62 strips the elemental bromine in the reaction solution and the steam containing the elemental bromine in the reaction zone, and the steam is condensed, separated and recovered. In the embodiment, the steam containing the bromine and the reaction solution are respectively introduced into the reaction zone 61 and the stripping zone 62, so that the liquid phase and the gas phase are separated, the steam containing the bromine is prevented from being secondarily fused into the reaction solution, and the purification and separation effects are reduced.
And the bromine-containing waste gas enters the stripping tower 1, the bromine-containing waste gas is contacted and absorbed by the absorption liquid in the stripping tower 1, and the hydrogen bromide gas is converted into a hydrogen bromide solution and is separated from other waste gas. The hydrogen bromide solution enters an oxidation device for oxidation to obtain steam containing the bromine and reaction solution, the steam containing the bromine and the reaction solution are introduced into a separation tower 6 for separation and purification to obtain steam containing the bromine, and the steam containing the bromine is condensed, separated and recycled to obtain the bromine. The absorption liquid in this embodiment includes water, non-saline water, and the like. Preferably, the absorption liquid is brine-free, and the hydrogen bromide gas in the bromine-containing waste gas is dissolved in the brine-free water and can form hydrogen bonds with the brine-free water. Therefore, the hydrogen bromide in the bromine-containing waste gas is easier to dissolve in the brine-free water than other waste gases, the aim of separating the hydrogen bromide from other waste gases is fulfilled, and the absorption effect is good. The salt-free water is injected into a stripping tower 1 before being extracted, and then bromine-containing waste gas is introduced into the stripping tower 1. Or no salt water is sprayed and injected from the top of the stripping tower 1 to the bottom of the stripping tower, and simultaneously bromine-containing waste gas is introduced into the stripping tower. The addition mode of the salt-free water effectively increases the contact area of the salt-free water and the bromine-containing waste gas, so that the hydrogen bromide gas in the bromine-containing waste gas is more fully separated from other waste gases. Other waste gases are condensed and refluxed to the stripping tower through the condenser, and the waste gases which cannot be condensed are connected into the alkali absorption system, so that the high-efficiency separation of the bromine-containing waste gases and other waste gases is realized, and the bromine yield is effectively improved.
Condensing the steam containing the bromine obtained by purification and separation of the purification device into liquid bromine and a water phase through a condenser, introducing the liquid bromine and the water phase into a phase separation device, separating the liquid bromine from the water phase, and further rectifying and recovering the liquid bromine. The recovery effect is better after the steam containing the bromine is condensed; preferably, the bromine-containing steam is condensed into liquid bromine and a water phase by a multi-stage condenser and is introduced into a phase separation device for separation, so that the waste of the bromine-containing steam is avoided. And the waste gas which is not condensed and recovered by the steam containing the bromine simple substance and is introduced into the condenser is discharged through an exhaust pipe on the condenser, so that the whole separation and recovery process is completed.
Example three:
in the embodiment, bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 110 ℃, and hydrogen bromide solution obtained by absorption and separation of water in the stripping tower is introduced into an oxidation device for oxidation. The oxidant in the oxidation device is hydrogen peroxide, and the molar ratio of the hydrogen bromide to the hydrogen peroxide is 1: 0.51, the concentration of hydrogen peroxide is 30% and the oxidation time is 20S. Oxidizing the hydrogen bromide solution by oxidizing hydrogen to obtain bromine-containing steam and a reaction solution. Introducing the steam containing the bromine and the reaction solution into a purification device for purification, wherein the temperature of a stripping zone in the purification device is 100 ℃, condensing and liquefying the steam containing the bromine led out by purification of the purification device, separating by a phase separation device to obtain liquid bromine, and rectifying and purifying the obtained liquid bromine to obtain a liquid bromine product. The purity of the liquid bromine product obtained in this example was 97% and the bromine recovery was 98%.
Example four:
in the embodiment, bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 115 ℃, and a hydrogen bromide solution obtained by absorption and separation of non-saline water in the stripping tower is introduced into an oxidation device for oxidation. The oxidant in the oxidation device is hydrogen peroxide, the molar ratio of hydrogen bromide to hydrogen peroxide is 1: 0.51, the concentration of hydrogen peroxide is 40%, and the oxidation time is 40S. Oxidizing the hydrogen bromide solution by oxidizing hydrogen to obtain bromine-containing steam and a reaction solution. Introducing the steam containing the bromine and the reaction solution into a purification device for purification, wherein the temperature of a stripping zone in the purification device is 105 ℃, condensing and liquefying the steam containing the bromine led out by purification of the purification device, separating by a phase separation device to obtain liquid bromine, and rectifying and purifying the obtained liquid bromine to obtain a liquid bromine product. The purity of the liquid bromine product obtained in this example was 99.5% and the bromine recovery was 98.5%.
Example five:
in the embodiment, bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 125 ℃, and a hydrogen bromide solution obtained through absorption and separation of non-saline water in the stripping tower is introduced into an oxidation device for oxidation. The oxidant in the oxidation device is hydrogen peroxide, the molar ratio of hydrogen bromide to hydrogen peroxide is 1: 0.51, the concentration of hydrogen peroxide is 50%, and the oxidation time is 60S. Oxidizing the hydrogen bromide solution by oxidizing hydrogen to obtain bromine-containing steam and a reaction solution. Introducing the steam containing the bromine and the reaction solution into a purification device for purification, wherein the temperature of a stripping zone in the purification device is 110 ℃, condensing and liquefying the steam containing the bromine led out by purification of the purification device, separating by a phase separation device to obtain liquid bromine, and rectifying and purifying the obtained liquid bromine to obtain a liquid bromine product. The purity of the liquid bromine product obtained in this example was 99.8% and the bromine recovery was 99%.
Comparative example one:
in the conventional process, taking disperse red FB as an example, the main synthesis process of disperse red FB is to perform bromination reaction by taking 1-aminoanthraquinone as a raw material and concentrated sulfuric acid as a solvent and adding excessive bromine, wherein waste gas is generated in the reaction process, and the main components in the waste gas are HBr and SO2And SO3Where HBr is about 27%; s02 about 39%; s03 about 32%, the remainder being air, and the off-gas being directly absorbed by the caustic without separation and oxidation of HBr to liquid bromine recovery.
Comparing the present invention with the conventional process, wherein the present invention separates and oxidizes HBr to liquid bromine recovery, the comparison of the recovery effects of the conventional process and the process of the present invention is shown in table 1 below:
table 1:
the recovery rate of the bromine obtained by the invention is more than 98%, the recovery effect is good, the purity of the liquid bromine obtained by the invention is more than 99.5% through test calculation, and the bromine with the purity completely meets the condition of recycling. Meanwhile, HBr in the waste gas is converted into liquid bromine, so that the use amount of liquid caustic soda is reduced, resources are saved, and the discharge of waste water is reduced. In addition, SO is contained after HBr is removed by a bromine-containing waste gas recovery device2、SO3The gas can enter a sulfuric acid recovery system for recycling again, the gas is further recycled, the waste of resources is reduced, and meanwhile, part of SO2、SO3The gas is not required to be recycled by alkali liquor, so that the waste of energy is reduced.
Comparative example two:
the bromine-containing waste gas recovery device in the comparative example comprises a separation device, an oxidation device, a phase separation device, a rectification device and a device pipeline. The separation device, the oxidation device, the phase separation device and the rectification device are communicated through device pipelines in sequence, and bromine-containing waste gas is treated through the separation device, the oxidation device, the phase separation device and the rectification device in sequence. The comparative example and the fourth example are both used for recovering 676kg/h of hydrogen bromide containing waste gas generated by a batch process in the production process of disperse red. The difference is that the fourth embodiment only comprises a purification device, steam containing bromine and reaction solution formed by oxidation are led into the purification device for purification and separation, while the second comparative embodiment does not comprise a purification device, namely the step of re-purifying the steam containing the bromine and the reaction solution is lacked, but upper aqueous phase in the phase separation device is directly led out, and lower liquid bromine in the phase separation device is led into the rectification device for rectification, purification and separation. Comparing comparative example two with example four, the results of the four HBr recovery of comparative example two with example four are shown in table 2 below:
table 2:
from table 2 above, it can be obtained that by introducing the steam containing the bromine simple substance formed by oxidation and the reaction solution into the purification device for further purification and separation, the bromine simple substance in the reaction solution is sufficiently separated and recovered, so that the yield and purity of the bromine simple substance recovered from the bromine-containing waste gas are high. In the second comparative example, a purification device is not provided, and a large amount of bromine is mixed in the upper aqueous phase in the phase separation device, and the upper aqueous phase in the phase separation device is directly discharged, so that a large amount of bromine is discharged together with the upper aqueous phase, and the yield of bromine is seriously reduced. And a certain amount of sulfuric acid is mixed in the liquid bromine at the lower layer of the phase separation device, so that the purity of the bromine is reduced. In addition, since comparative example two lacks a purification apparatus, a large amount of liquid is conducted to the phase separation apparatus, and therefore, it is necessary to increase the volume of the phase separation apparatus. In addition, in the second comparative example, it is necessary to add a pipe for leading out the upper aqueous phase in the phase separation apparatus to the phase separation apparatus, which makes the piping of the bromine-containing waste gas recovery apparatus in the second comparative example complicated and poor in recovery effect. In conclusion, the bromine in the reaction liquid led out by the oxidation device can be fully stripped and separated by adding the purification device into the bromine-containing waste gas recovery device, so that bromine generated by the oxidation device is almost completely condensed and enters the phase separation device for separation, the yield is high, and the purity of the obtained bromine is as high as 99.5%.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The utility model provides a bromine-containing waste gas recovery system, bromine-containing waste gas contain hydrogen bromide gas and other waste gases, its characterized in that: including separator, oxidation device, purification device, phase separation device and the rectifier unit that connects gradually, contain bromine waste gas and form the steam and the reaction solution that contain the bromine simple substance after separator, oxidation device in proper order, the steam and the reaction solution that contain the bromine simple substance get into the purification device and purify the separation and obtain the steam that contains the bromine simple substance, get into phase separation device, rectifier unit and retrieve after the steam condensation liquefaction that contains the bromine simple substance.
2. The bromine-containing waste gas recovery system according to claim 1, characterized in that: the purification device comprises a separation tower, a heating device is arranged at the bottom of the separation tower, the separation tower is communicated with an oxidation device through a pipeline, steam containing the bromine and a reaction solution are introduced into the separation tower from the oxidation device through the pipeline, the reaction solution is heated by the heating device in the separation tower, and the steam containing the bromine in the separation tower is stripped and separated.
3. The bromine-containing waste gas recovery system according to claim 2, characterized in that: the inner area of the separation tower is divided into a stripping area and a reaction area from the lower part of the separation tower to the upper part of the separation tower, the oxidation device comprises an oxidation tank, the reaction area is communicated with the upper part of the oxidation tank through a first pipeline, the stripping area is communicated with the lower part of the oxidation tank through a second pipeline, steam containing bromine enters the reaction area through the first pipeline, the reaction solution enters the stripping area through the second pipeline, the bromine in the reaction solution and the steam containing the bromine in the reaction area are stripped by the steam generated in the stripping area, and condensation separation, rectification and recovery are carried out;
preferably, the first pipeline and the second pipeline are communicated with the middle part of the separation tower.
4. A bromine-containing waste gas recovery system according to any one of claims 1 to 3, characterized in that: the separation device comprises a stripping tower, a reboiler is arranged at the bottom of the stripping tower, bromine-containing waste gas enters the stripping tower, hydrogen bromide gas and absorption liquid in the stripping tower are mixed to form hydrogen bromide solution, the lower part of the stripping tower is communicated with the oxidizing device through a third pipeline, the hydrogen bromide solution is introduced into the oxidizing device through the third pipeline to be oxidized, and other waste gas is stripped through steam generated by the reboiler and discharged from the upper part of the stripping tower.
5. The bromine-containing waste gas recovery system according to claim 4, characterized in that: a liquid inlet pipe is arranged at the upper part of the separation device and is used for introducing absorption liquid into the stripping tower;
preferably, the liquid inlet pipe is provided with a spray hole, and the spray hole is arranged in the stripping tower towards the bottom of the stripping tower.
6. The bromine-containing waste gas recovery system according to claim 2, characterized in that: the phase separation device comprises a phase separator, the top of the separation tower is communicated with the phase separator through a pipeline, the bromine-containing steam is condensed and enters the phase separator for separation, the upper layer of liquid in the phase separator is a water phase, and the lower layer of liquid is liquid bromine.
7. The bromine-containing waste gas recovery system according to claim 6, characterized in that: a condenser is arranged between the separation tower and the phase separator, and the steam containing the bromine in the separation tower is condensed by the condenser and enters the phase separator for separation;
preferably, a multi-stage condenser is arranged between the separation tower and the phase separator, and the steam containing the bromine enters the phase separator for separation through the multi-stage condenser.
8. The bromine-containing waste gas recovery system according to claim 7, characterized in that: the top of the condenser is provided with an exhaust pipe, and the waste gas which is not condensed and recovered by the steam containing the bromine introduced into the condenser is discharged through the exhaust pipe on the condenser.
9. The bromine-containing waste gas recovery system according to claim 1, characterized in that: the upper part of the phase separator is communicated with the separation tower through a fourth pipeline, and the internal upper water phase of the phase separator flows back to the separation tower through the fourth pipeline.
10. A bromine-containing waste gas recovery system according to any one of claims 5 to 9, characterized in that: the bottom of the separation tower is provided with a liquid discharge pipeline for discharging waste liquid in the separation tower;
preferably, the liquid discharge pipeline is provided with a fourth condenser, and waste liquid in the separation tower is condensed and discharged through the fourth condenser.
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| CN114229798A (en) * | 2021-12-29 | 2022-03-25 | 江苏吉华化工有限公司 | Method and equipment for recovering bromine in bromine-containing waste gas |
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