CN113620250A - Bromine-containing waste gas recovery method - Google Patents
Bromine-containing waste gas recovery method Download PDFInfo
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Abstract
The invention discloses a bromine-containing waste gas recovery method, wherein bromine-containing waste gas comprises hydrogen bromide gas and other waste gas, the hydrogen bromide gas is converted into hydrogen bromide solution and is oxidized by an oxidation device to form bromine-containing steam and reaction solution, the bromine-containing steam and the reaction solution are introduced into a purification device for purification and separation to obtain the bromine-containing steam, and the bromine-containing steam is condensed, separated and recovered to obtain the bromine. The steam containing the bromine simple substance formed by oxidation and the reaction solution are led into a purification device for purification and separation, the bromine simple substance in the reaction solution is fully separated and recovered, the yield and the purity of the bromine simple substance recovered from bromine-containing waste gas are further high, the recovery rate is more than 98%, and the purity of the obtained liquid bromine is more 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 method.
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 as an important disperse dye has a 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, can generate a large amount of bromine-containing waste gas in the production process, and 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 method.
In order to solve the technical problems, the invention adopts the technical scheme that:
a bromine-containing waste gas recovery method comprises the steps that bromine-containing waste gas comprises hydrogen bromide gas and other waste gas, the hydrogen bromide gas is converted into hydrogen bromide solution and is oxidized by an oxidation device to form steam and reaction solution containing bromine, the steam and the reaction solution containing the bromine are led into a purification device to be purified and separated to obtain steam containing the bromine, and the steam containing the bromine is condensed, separated and recovered to obtain the bromine.
Further, the purification device comprises a stripping zone, the reaction solution is stripped and separated by the stripping zone to obtain steam containing the bromine, and the steam containing the bromine is condensed, separated and recycled to obtain the bromine.
Further, the purification device comprises a separation tower, 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, steam containing the bromine formed by oxidation is introduced into the reaction area, the reaction solution is introduced into the stripping area, the steam generated in the stripping area strips out the bromine in the reaction solution and the steam containing the bromine in the reaction area, and the steam is condensed, separated and recovered;
preferably, the temperature of the stripping zone is 100-110 ℃.
Further, the bromine-containing waste gas enters a stripping tower and is absorbed by absorption liquid in the stripping tower in a contact manner, the hydrogen bromide gas is converted into a hydrogen bromide solution and is separated from other waste gas, and the hydrogen bromide solution enters an oxidation device for oxidation;
preferably, the boiling temperature in the stripping column is 110-125 ℃.
Further, the absorption liquid comprises salt-free water, and the salt-free water absorbs the hydrogen bromide gas;
preferably, the saltless water is sprayed from the top of the stripping tower to the bottom of the stripping tower.
And further, 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.
Further, an oxidant is introduced into the oxidation device, bromide ions in the hydrogen bromide solution are oxidized into bromine simple substances by the oxidant and are introduced into a purification device for purification and separation,
preferably, the oxidizing agent is a hydrogen peroxide solution,
preferably, the molar ratio of hydrogen bromide to hydrogen peroxide is 1: 0.51.
Further, the concentration of the hydrogen peroxide solution is 30-50%, and the time for mixed oxidation of the hydrogen bromide solution in the oxidation device is in the range of 20-60S.
Further, condensing the steam containing the bromine obtained by purification and separation by the purification device into liquid bromine and water by a condenser, introducing the liquid bromine and the water into a phase separation device, separating the liquid bromine from the water, and further rectifying and recovering the liquid bromine;
preferably, the steam containing the bromine is condensed into liquid bromine and water by a multi-stage condenser and is introduced into a phase separation device for separation.
Further, the waste gas which is not condensed and recycled by the steam containing the bromine and is introduced into the condenser is discharged through an exhaust pipe on the condenser.
After the technical scheme is adopted, compared with the prior art, the invention has the following beneficial effects.
1. The steam containing the bromine simple substance formed by oxidation and the reaction solution are led into a purification device for purification and separation, and the bromine simple substance in the reaction solution is fully separated and recovered, so that the yield and the purity of the bromine simple substance recovered from bromine-containing waste gas are high, the recovery rate is more than 98%, and the purity of the obtained liquid bromine is more than 99.5% through test calculation.
2. Through with the hydrogen bromide gas in the bromine-containing waste gas with other waste gas separation and absorption oxidation, carry out recycle to the bromine in the bromine-containing waste gas, practiced thrift the resource, reduced exhaust emission, still greatly reduced the use amount of the alkali lye that is used for absorbing the bromine-containing waste gas simultaneously, reduced the waste of waste water discharge and alkali lye resource, and the rate of recovery of the bromine in the bromine-containing waste gas is high, and the liquid bromine purity that retrieves and obtain is high.
3. The method has the advantages that the salt-free water is adopted to absorb the hydrogen bromide gas, the absorption rate is high, the purpose of separating the hydrogen bromide gas from bromine-containing waste gas is realized, and the liquid bromine purity can be effectively improved.
4. The concentration of the hydrogen peroxide solution is within the range of 30-50%, and the mixed oxidation time of the hydrogen bromide solution in the oxidation tank is less than 60S, so that the high recovery rate of bromine in short mixed oxidation time is ensured, the purity of liquid bromine is high, the recovery efficiency is effectively improved, and resources are saved.
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 hydrogen bromide solution circulation 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; 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 invention provides a bromine-containing waste gas recovery method, which is used for separating and purifying bromine in bromine-containing waste gas. At present, bromine-containing waste gas is mainly generated by dye industry, particularly, disperse red as an important disperse dye can generate a large amount of bromine-containing tail gas in the production process, and the bromine-containing tail gas mainly contains hydrogen bromide and SO2、SO3And the components are equal, the recovery method can efficiently recover the hydrogen bromide containing waste gas 676kg/h generated by the intermittent process in the disperse red production process, the recovery rate is high, and the purity of the obtained liquid bromine is also high.
The first embodiment is as follows:
this embodiment provides a bromine-containing waste gas recovery method, 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 this embodiment, 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 sufficiently separated out, and then the bromine is rectified, purified and recovered by the rectification device, so that the yield and 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 two:
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, the molar ratio of hydrogen bromide to 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 three:
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 four:
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%.
Example five:
as shown in fig. 1 and fig. 2, the present embodiment provides a bromine-containing waste gas recovery apparatus applying the above bromine-containing waste gas recovery method, for recovering 676kg/h of hydrogen bromide in the waste gas containing 676kg/h generated by the batch process in the production process 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、SO3Etc. and removing hydrogen bromide from the bromine-containing waste gasThe gas is converted into a hydrogen bromide solution, bromide ions are oxidized into bromine through an oxidizing device to form steam containing the bromine and a reaction solution, the steam containing the bromine and the reaction solution are introduced into a purifying device to be purified and separated to obtain steam containing the bromine, the obtained steam containing the bromine is condensed and introduced into a phase separating device to separate liquid bromine from a water phase, and the obtained liquid bromine is introduced into a rectifying device to be rectified and purified to obtain a final product. By 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, 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 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.
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. The reboiler 2 is disposed at a lower portion of the stripping column 1 to heat the liquid in the stripping column. 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 bromine-containing waste gas enters a stripping tower 1, absorption liquid is contained in the stripping tower 1, the bromine-containing waste gas is contacted and absorbed by the absorption liquid in the stripping tower 1, and hydrogen bromide gas is converted into hydrogen bromide solution and is mixed with other waste gas such as SO2、SO3And (4) separating, wherein the hydrogen bromide solution enters an oxidation tank for treatment, and other waste gases are stripped and connected to an alkali absorption system.
The absorption liquid comprises water, salt-free water and the like, preferably, the absorption liquid is salt-free water, and hydrogen bromide gas in the bromine-containing waste gas is dissolved in the salt-free water and can form hydrogen bonds with the salt-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 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 liquid, preferably no brine, is fed into a liquid inlet pipe 3, and the no brine is sprayed into the stripping tower 1 through a spraying hole 311 on a spraying section 31. Wherein bromine-containing waste gas is absorbed by non-saline water to form high-boiling hydrobromic acid, and further, the hydrobromic acid is positioned at the bottom of the stripping tower 1, and most SO is2And SO3Due to the relatively small thermodynamic interaction with the brine-free water, it is stripped away by the stripping steam generated by the reboiler 2 and not absorbed by the brine-free water. The boiling temperature in reboiler 2 was about 110 deg.C, and the stripped SO was removed2、SO3And steam is withdrawn through stripper vent 12.
The separation device comprises a waste gas discharge pipeline 14 and a hydrogen bromide solution flow pipeline 15, wherein the waste gas discharge pipeline 14 is communicated with the upper part of the stripping tower 1 and communicated with a stripping tower exhaust port 12 for discharging other waste gas such as SO2And SO3And one end of the hydrogen bromide solution circulation pipeline 15 is communicated with the bottom of the stripping tower 1, the other end of the hydrogen bromide solution circulation pipeline is communicated with an oxidation device, and the hydrogen bromide solution is introduced into the oxidation device through the hydrogen bromide solution circulation pipeline 15 to be oxidized into elemental bromine.
As shown in fig. 2, 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 column 6, and the phase separation apparatus includes a phase separator 10. 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 6. The hydrogen bromide solution is oxidized in the oxidation tank 5 to form steam containing bromine and 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 bottom of the separation tower 6 is provided with a heating device, 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 a steam stripping zone 62 of the separation tower 6, so that the bromine gas is ensured to be fully stripped, and the purity and the recovery rate of the bromine gas 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 includes oxidation tank feed inlet 51, oxidation tank feed inlet 51 with the stripping tower leakage fluid dram 13 intercommunication of stripping tower 1, the top of oxidation tank 5 oxidation tank gas vent 52 has, the lower part of oxidation tank 5 oxidation tank leakage fluid dram 53 has, the separator feed inlet includes first feed inlet 63 and the second feed inlet 64 that is located first feed inlet 63 top, oxidation tank gas vent 52 and second feed inlet 64 intercommunication, oxidation tank leakage fluid dram 53 and first feed inlet 63 intercommunication. Hydrobromic acid containing a small amount of sulfurous acid and sulfuric acid is led to the feed port 51 of the oxidation tank through the flow pipe 15 for a hydrogen bromide solution via the liquid outlet 13 of the stripping tower.
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, and bromide ions in the hydrogen bromide solution are oxidized into elemental bromine by the oxidant and are guided into the separation tower for separation. The oxidizing agent is introduced into the oxidation tank 5 through the oxidizing agent feed pipe 54, and oxidizes bromide ions in the hydrobromic acid in the oxidation tank 5 to convert the bromide ions into elemental bromine. The oxidant is added in real time through oxidant feed pipe 54, and the bromine in oxidation tank 5 passes through the second feed port 64 and enters reaction zone 61 through oxidation tank exhaust port 52 via a pipeline.
The upper part of the stripping area 62 is 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 a 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. Preferably, heater 65 is a bayonet tube heater.
The oxidation device further comprises 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, waste liquid passes through the fourth condenser 67 from the bottom of the separation tower 6 and then is pumped out to be neutralized with liquid caustic soda, and the waste liquid which is not processed is prevented from being discharged to pollute the environment.
Condensing the steam containing the bromine obtained by purification and separation of the purification device into liquid bromine and water through a condenser, introducing the liquid bromine and the water into a phase separation device, separating the liquid bromine from the water, and further rectifying and recovering the liquid bromine. Preferably, the steam containing the bromine is condensed into liquid bromine and water by a condenser and is introduced into a phase separation device for separation. Preferably, a multi-stage condenser is arranged between the separation tower 6 and the phase separator 10, the bromine is condensed into liquid bromine by the multi-stage condenser and enters the phase separator 10, an upper-layer water phase in the phase separator reflows to the separation tower 6 and is stripped again by the separation tower 6, the recovery rate of bromine is further improved, and the purity of the recovered liquid bromine is improved. The liquid bromine at the lower layer of the phase separator 10 enters a rectifying tower for rectification. The multistage condenser comprises a second condenser 7, wherein a second condenser air inlet 71 is formed in the upper part of the second condenser, a second condenser liquid outlet 72 is formed in the lower part of the second condenser, the second condenser air inlet 71 is communicated with the top of the separation tower 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 separator also comprises a third condenser 8 arranged between the second condenser 7 and the phase separator 10, the upper part 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 bromine gas in the second condenser 7 enters the third condenser 8 through the second condenser exhaust port 73 to be continuously condensed into liquid bromine and is led 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. Preferably, an exhaust pipe 84 is connected to the exhaust port 82, and the uncondensed residual gas enters the exhaust pipe 84 through the exhaust port 82, is discharged through the exhaust pipe 84 and is absorbed in a concentrated manner.
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 a pipeline, so that the liquid flowing into the separation tower 6 is fully stripped, the liquid bromine in the liquid bromine 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 rectifying tower 104, a pure bromine product is obtained at the bottom of the tower, a sixth condenser 1044 is connected to the bottom of the rectifying tower 104, the sixth condenser 1044 uses chilled water as a working fluid, and the pure bromine product obtained at the bottom of the tower is cooled, cooled and recovered by the sixth condenser 1044. The azeotropic bromine/water compound exits from the top of the rectification column 104. 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 exhaust pipe 84 is externally connected to the third condenser exhaust port 82, the exhaust pipe 84 is connected to an alkali absorption tank, and the exhaust gas discharged from the third condenser exhaust port 82 may contain part of bromine, and needs to be introduced into the alkali absorption tank for absorption.
In the embodiment, the bromine-containing waste gas recovery device adopting any one of the schemes or any combination of the schemes has the operation flexibility of 50-105%, and has high controllability and strong equipment operability on the premise of ensuring the recovery rate of bromine and the purity of liquid bromine.
Comparative example one:
in the conventional process, taking disperse red FB as an example, the main synthesis process of disperse red FB is to use 1-aminoanthraquinone as a raw material, use concentrated sulfuric acid as a solvent, add excess bromine, and perform bromination reaction, wherein exhaust gas is generated in the reaction process, and the main components in the exhaust gas are HBr, SO2 and SO3, wherein HBr is about 27%; about 39% SO 2; SO3 is about 32%, the remainder is air, and the off-gas is 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 into liquid bromine for recovery, the recovery effects of the conventional process for recovering bromine-containing waste gas and the recovery effect of the present invention for recovering bromine-containing waste gas are shown in table 1 below:
table 1:
the bromine recovery rate obtained by the invention is 98%, the recovery effect is good, the purity of the liquid bromine obtained by the invention is more than 99.5% through test calculation, the bromine with the purity completely meets the condition of recycling, and simultaneously,the invention converts HBr in the waste gas into liquid bromine, thereby reducing the usage amount of liquid caustic soda, not only saving resources, but also reducing the discharge of waste water. 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 third 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 third 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 three, the results of the recovery of tri HBr from comparative example two and example three 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. A bromine-containing waste gas recovery method is characterized in that: the bromine-containing waste gas comprises hydrogen bromide gas and other waste gases, the hydrogen bromide gas is converted into a hydrogen bromide solution and is oxidized by an oxidizing device to form steam and a reaction solution containing the bromine, the steam and the reaction solution containing the bromine are introduced into a purifying device for purification and separation to obtain the steam containing the bromine, and the steam containing the bromine is condensed, separated and recovered to obtain the bromine.
2. The method as claimed in claim 1, wherein the purification device comprises a stripping zone, the reaction solution is stripped and separated in the stripping zone to obtain steam containing elemental bromine, and the steam containing elemental bromine is condensed and separated to obtain elemental bromine.
3. The bromine-containing waste gas recovery method according to claim 2, wherein the purification device comprises a separation tower, the inner region of the separation tower is divided into a stripping zone and a reaction zone from the lower part of the separation tower to the upper part of the separation tower, steam containing bromine formed by oxidation is introduced into the reaction zone, the reaction solution is introduced into the stripping zone, and the steam generated in the stripping zone strips out the bromine in the reaction solution and the steam containing bromine in the reaction zone and is condensed, separated and recovered;
preferably, the temperature of the stripping zone is 100-110 ℃.
4. The bromine-containing waste gas recovery method according to any one of claims 1 to 3, wherein the bromine-containing waste gas enters a stripping tower and is absorbed by an absorption liquid in the stripping tower in a contacting manner, the hydrogen bromide gas is converted into a hydrogen bromide solution and is separated from other waste gases, and the hydrogen bromide solution enters an oxidation device for oxidation;
preferably, the boiling temperature in the stripping column is 110-125 ℃.
5. The method according to claim 4, wherein the absorption liquid comprises a salt-free water, and the salt-free water absorbs the hydrogen bromide gas;
preferably, the saltless water is sprayed from the top of the stripping tower to the bottom of the stripping tower.
6. The method according to claim 4, wherein the other waste gas is condensed by a condenser and returned to the stripping tower, and the non-condensable waste gas is introduced into an alkali absorption system.
7. The method for recovering the bromine-containing waste gas according to claim 1, wherein an oxidant is introduced into the oxidation device, bromide ions in the hydrogen bromide solution are oxidized into elemental bromine by the oxidant and introduced into a purification device for purification and separation;
preferably, the oxidizing agent is hydrogen peroxide solution;
preferably, the molar ratio of hydrogen bromide to hydrogen peroxide is 1: 0.51.
8. The method as claimed in claim 7, wherein the concentration of the hydrogen peroxide solution is 30-50%, and the time for the mixed oxidation of the hydrogen bromide solution in the oxidation device is 20-60S.
9. The bromine-containing waste gas recovery method according to claim 1, wherein the vapor containing bromine obtained by purification and separation by the purification device is condensed by a condenser into liquid bromine and an aqueous phase, the liquid bromine and the aqueous phase are introduced into a phase separation device, the liquid bromine and the aqueous phase are separated, and the liquid bromine is further rectified and recovered;
preferably, the steam containing the bromine is condensed into liquid bromine and a water phase by a multi-stage condenser and is introduced into a phase separation device for separation.
10. The method as claimed in claim 9, wherein the waste gas containing bromine is discharged through a vent pipe on the condenser.
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