CN113620250B - Bromine-containing waste gas recovery method - Google Patents
Bromine-containing waste gas recovery method Download PDFInfo
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- CN113620250B CN113620250B CN202010384391.7A CN202010384391A CN113620250B CN 113620250 B CN113620250 B CN 113620250B CN 202010384391 A CN202010384391 A CN 202010384391A CN 113620250 B CN113620250 B CN 113620250B
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Abstract
The invention discloses a bromine-containing waste gas recovery method, wherein bromine-containing waste gas contains hydrogen bromide gas and other waste gases, the hydrogen bromide gas is converted into hydrogen bromide solution and oxidized by an oxidation device to form bromine-containing simple substance steam and reaction solution, the bromine-containing simple substance steam and the reaction solution are led into a purification device to be purified and separated to obtain bromine-containing simple substance steam, and the bromine-containing simple substance steam is condensed, separated and recovered to obtain bromine simple substance. The bromine in the reaction solution is fully separated and recovered by introducing the bromine-containing simple substance vapor formed by oxidation and the reaction solution into a purification device for purification and separation, so that the yield and purity of the bromine obtained by recovery from the bromine-containing waste gas are higher, the recovery rate is higher than 98%, and the purity of the obtained liquid bromine is higher 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 rapidly develops, and an independent industry from raw materials, intermediates, auxiliary agents to finished products is formed. The dye is a fine chemical product and has the characteristics of high added value, high price and high profit, but the production process has the characteristics of high energy consumption, high emission and high pollution. Because the waste gas of the dye production process is mostly intermittently discharged and the waste gas is of more types, the treatment effect of enterprises on the dye waste gas is poor at present, and the pollution is serious. The disperse red is used as an important disperse dye, has large global demand, is applied to the fields of printing, printing ink, plastic, color master batch, inkjet 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 is treated by the following steps: condensing the tail gas containing bromine, and liquid bromine in the tail gas after condensationRecovered hydrogen bromide and SO which cannot be condensed 2 、SO 3 And other waste gases are absorbed by alkali liquor. However, HBr and SO in the tail gas 2 、SO 3 After being absorbed by alkali liquor, the waste water can only be discharged into a sewage plant, so that not only is a large amount of alkali liquor consumed, but also bromine in the waste water is wasted, the recovery efficiency is poor, and the resource waste is serious.
The Chinese patent with the application number of CN201610741519.4 discloses a process and equipment for synthesizing disperse red FB, in particular to a process for carrying out bromination reaction by taking aminoanthraquinone as a raw material and chlorobenzene as a solvent, and the solvent is recycled after filtering the product; 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, separating the product by methanol to obtain a finished product disperse red FB, circularly using filtrate by distillation, and recycling sodium bromide solution by distillation residue; the synthesis equipment comprises a feed inlet, a four-mouth bottle kettle for bromination, a suction filtration tank, a waste liquid treatment device for bromination, a four-mouth bottle kettle for hydrolysis, a suction filtration tank, a waste liquid treatment device for hydrolysis, a condensation kettle, a suction filtration tank and a waste liquid treatment device for condensation. 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.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a bromine-containing waste gas recovery method.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that:
the bromine-containing waste gas comprises hydrogen bromide gas and other waste gases, the hydrogen bromide gas is converted into hydrogen bromide solution and is oxidized by an oxidation device to form bromine-containing simple substance steam and reaction solution, the bromine-containing simple substance steam and the reaction solution are led into a purification device to be purified and separated to obtain bromine-containing simple substance steam, and the bromine-containing simple substance steam is condensed, separated and recovered to obtain bromine simple substance.
Further, the purification device comprises a stripping zone, steam containing bromine is obtained by stripping and separating the reaction solution through the stripping zone, and bromine is obtained by condensing, separating and recycling the steam containing 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 bromine simple substance formed by oxidation is introduced into the reaction area, reaction solution is introduced into the stripping area, steam generated by the stripping area strips out the bromine simple substance in the reaction solution and the steam containing bromine simple substance in the reaction area, and condensation separation recovery is carried out;
preferably, the temperature of the stripping zone is from 100 to 110 ℃.
Further, the bromine-containing waste gas enters a stripping tower, is contacted and absorbed by absorption liquid in the stripping tower, and hydrogen bromide gas is converted into hydrogen bromide solution which is separated from other waste gases, and enters an oxidation device for oxidation;
preferably, the boiling temperature in the stripping column is 110-125 ℃.
Further, the absorption liquid includes a brine-free water that absorbs the hydrogen bromide gas;
preferably, the brine-free water is sprayed from the top of the stripping tower to the bottom of the stripping tower.
Further, the other waste gas is condensed and flows back to the stripping tower through the condenser, and the waste gas which cannot be condensed is connected into the alkali absorption system.
Further, oxidant is introduced into the oxidation device, bromine ions in the hydrogen bromide solution are oxidized into bromine simple substance by the oxidant and are led into the 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.
Further, the concentration of the hydrogen peroxide solution comprises 30% -50%, and the time of mixed oxidation of the hydrogen bromide solution in the oxidation device is in the range of 20-60S.
Further, the steam containing bromine simple substance obtained by purification and separation of the purification device is condensed into liquid bromine and water by a condenser, the liquid bromine and the water are led into a phase separation device, the liquid bromine and the water are separated, and the liquid bromine is further rectified and recovered;
preferably, the steam containing bromine simple substance is condensed into liquid bromine and water through a multi-stage condenser and is led into a phase separation device for separation.
Further, the waste gas which is not condensed and recovered by the steam containing bromine simple substance and introduced into the condenser is discharged through an exhaust pipe on the condenser.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects.
1. The bromine in the reaction solution is fully separated and recovered by introducing the bromine-containing simple substance vapor formed by oxidation and the reaction solution into a purification device for purification and separation, so that the yield and purity of the bromine obtained by recovery from the 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. The bromine in the bromine-containing waste gas is recycled by separating and absorbing and oxidizing the hydrogen bromide gas in the bromine-containing waste gas and other waste gas, so that the resource is saved, the 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 emission and alkali liquor resources is reduced, the recovery rate of bromine in the bromine-containing waste gas is high, and the purity of the recovered liquid bromine is high.
3. The brine-free absorption of the hydrogen bromide gas is high in absorption rate, so that the purpose of separating the hydrogen bromide gas from the bromine-containing waste gas is achieved, and the purity of liquid bromine can be effectively improved.
4. The concentration of the hydrogen peroxide solution is in the range of 30-50%, 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 the shorter mixed oxidation time is ensured, the purity of liquid bromine is also high, the recovery efficiency is effectively improved, and the resources are saved.
The following describes the 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 and 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. It is evident that the drawings in the following description are only examples, from which other drawings can be obtained by a person skilled in the art without the inventive effort.
FIG. 1 is a schematic view of the structure of the device of the present invention;
fig. 2 is a schematic view of the partial enlarged structure of the present invention at a.
1. A stripping column; 11. a stripper feed inlet; 12. a stripper vent; 13. a liquid outlet of the stripping tower; 14. an exhaust gas pipe; 15. the hydrogen bromide solution flows through the 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 tube; 6. a separation tower; 61. a reaction zone; 62. a stripping zone; 621. a liquid distributor; 63. a first feed port; 64. a second feed inlet; 65. a heater; 66. an exhaust port of the separation tower; 67. a fourth condenser; 671. a fourth condenser feed inlet; 672. a fourth condenser discharge port; 7. a second condenser; 71. a second condenser inlet; 72. a second condenser drain port; 73. a second condenser exhaust port; 8. a third condenser; 81. a third condenser air inlet; 82. a third condenser exhaust port; 83. a third condenser drain port; 84. an exhaust pipe; 9. a fifth condenser; 91. a fifth condenser inlet port; 92. a fifth condenser drain port; 93. a fifth condenser exhaust port; 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 rectifying tower feed inlet; 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 these drawings and the written description are not intended to limit the scope of the inventive concept in any way, but to illustrate the inventive concept to those skilled in the art by referring to the specific embodiments.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific 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 explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill 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, the bromine-containing waste gas is mainly produced more by the dye industry, particularly, disperse red is used as an important disperse dye to produce a large amount of bromine-containing tail gas in the production process, and the bromine-containing tail gas mainly contains hydrogen bromide and SO 2 、SO 3 And the like, the recovery method can efficiently recover the hydrogen bromide containing 676kg/h of waste gas generated by a batch process in the disperse red production process, and has high recovery rate and high purity of the obtained liquid bromine.
Embodiment one:
the present embodiment provides a bromine-containing waste gas recovery method, in which bromine-containing waste gas contains hydrogen bromide gas and other waste gas, and the hydrogen bromide gas is converted into hydrogen bromide solution and separated from the other waste gas. Oxidizing the hydrogen bromide solution by an oxidation device to form bromine-containing simple substance steam and a reaction solution, introducing the bromine-containing simple substance steam and the reaction solution into a purification device for purification and separation to obtain bromine-containing simple substance steam, and condensing, separating and recycling the bromine-containing simple substance steam to obtain the bromine simple substance. In the embodiment, the bromine element in the reaction solution is fully separated out by introducing the bromine element-containing steam formed by oxidation and the reaction solution into a purification device for purification and separation, and then the bromine element is rectified, purified and recovered by a rectification device, so that the yield and purity of the bromine element recovered from the 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.
The purification device comprises a stripping zone, hydrogen bromide gas in bromine-containing waste gas is converted into hydrogen bromide solution and is separated from other waste gas, the hydrogen bromide solution is oxidized in an oxidation device, steam containing bromine simple substance formed by oxidation and reaction solution are stripped and separated through the stripping zone to obtain steam containing bromine simple substance, and the steam containing bromine simple substance is condensed, separated and recovered to obtain bromine simple substance. As an implementation mode of the embodiment, the steam containing bromine simple substance formed by oxidation and the reaction solution are directly communicated into a stripping zone of the purifying device for purification and separation, so that the sufficient separation and extraction of the steam containing bromine simple substance can be realized.
As another implementation manner of this example, the purifying device includes a separation tower 6, an internal area of the separation tower 6 is divided into a stripping area 62 and a reaction area 61 from a lower part of the separation tower to an upper part of the separation tower, steam containing bromine simple substance formed by oxidation is introduced into the reaction area 61, reaction solution is introduced into the stripping area 62, and steam generated by the stripping area 62 strips out bromine simple substance in the reaction solution and steam containing bromine simple substance in the reaction area, and condensation separation recovery is performed. In the embodiment, the steam containing bromine simple substance and the reaction solution are respectively introduced into the reaction zone 61 and the stripping zone 62 to separate liquid phase and gas phase, so that the steam containing bromine simple substance is prevented from being secondarily fused into the reaction solution, and the purification and separation effects are reduced.
The bromine-containing waste gas enters the stripping tower 1, is contacted and absorbed by absorption liquid in the stripping tower 1, and hydrogen bromide gas is converted into hydrogen bromide solution and is separated from other waste gases. The hydrogen bromide solution enters an oxidation device for oxidation to obtain bromine-containing simple substance steam and reaction solution, the bromine-containing simple substance steam and the reaction solution are then led into a separation tower 6 for separation and purification to obtain bromine-containing simple substance steam, and the bromine-containing simple substance steam is condensed, separated and recovered to obtain bromine simple substance. The absorption liquid in this embodiment includes water, brine-free 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 bromine in the bromine-containing waste gas is more soluble in the brine-free water than other waste gas, the purpose of separating the bromine from other waste gas is realized, and the absorption effect is good. The brine is injected into the stripping tower 1 in advance, and then bromine-containing waste gas is introduced into the stripping tower 1. Or the brine-free water is sprayed and injected from the top of the stripping tower 1 to the bottom of the stripping tower, and the bromine-containing waste gas is simultaneously introduced into the stripping tower. The adding mode of the non-salt water effectively increases the contact area of the non-salt 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 returned to the stripping tower through the condenser, and the waste gases which cannot be condensed are connected to the alkali absorption system, so that the high-efficiency separation of bromine-containing waste gases and other waste gases is realized, and the bromine yield is effectively improved.
The steam containing bromine simple substance is obtained by purification and separation of the purification device, condensed into liquid bromine and water phase by a condenser, the liquid bromine and the water phase are led into a phase separation device, the liquid bromine and the water phase are separated, and the liquid bromine is further rectified and recovered. The recovery effect is better after the steam containing bromine simple substance is condensed; preferably, the steam containing bromine simple substance is condensed into liquid bromine and water phase through a multistage condenser and is led into a phase separation device for separation, so that the waste of the steam containing bromine simple substance is avoided. And the waste gas which is introduced into the condenser and is not condensed and recovered by the bromine-containing simple substance steam is discharged through an exhaust pipe on the condenser, so that the whole separation and recovery process is completed.
Embodiment two:
in this embodiment, the bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 110 ℃, and the hydrogen bromide solution obtained through water absorption and separation in the stripping tower is guided 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 hydrogen peroxide to obtain steam and reaction solution of bromine-containing simple substance. And (3) introducing bromine-containing simple substance steam and 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 bromine-containing simple substance steam purified and exported by the purification device, separating the bromine-containing simple substance steam 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 rate was 98%.
Embodiment III:
in this embodiment, the bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 115 ℃, and the hydrogen bromide solution obtained by the absorption and separation of the brine-free water in the stripping tower is guided 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 hydrogen peroxide to obtain steam and reaction solution of bromine-containing simple substance. And (3) introducing bromine-containing simple substance steam and 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 bromine-containing simple substance steam purified and exported by the purification device, separating the bromine-containing simple substance steam 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%.
Embodiment four:
in this embodiment, the bromine-containing waste gas enters a stripping tower, the temperature of the stripping tower is 125 ℃, and the hydrogen bromide solution obtained by the absorption and separation of the brine-free water in the stripping tower is guided 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 hydrogen peroxide to obtain steam and reaction solution of bromine-containing simple substance. The steam containing bromine simple substance and the reaction solution are fed into a purifying device for purification, the temperature of a stripping zone in the purifying device is 110 ℃, the steam containing bromine simple substance which is purified and led out by the purifying device is condensed and liquefied, the liquid bromine is obtained by separation of a phase separating device, and the obtained liquid bromine is rectified and purified 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%.
Fifth embodiment:
as shown in fig. 1 and 2, the present embodiment provides a bromine-containing waste gas recovery apparatus applying the above-described bromine-containing waste gas recovery method for recovering 676kg/h of hydrogen bromide containing waste gas generated by a batch process in the disperse red production process. The operating flexibility of the device was between 50-105% taking into account feed fluctuations. In the invention, 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. Wherein, separator, oxidation device, purification device, phase separation device and rectifying device pass through device pipeline intercommunication in proper order, and bromine-containing waste gas is handled through separator, oxidation device, purification device, phase separation device, rectifying device in proper order. Removing impurities other than bromine, such as SO, from bromine-containing waste gas by separation means 2 、SO 3 And the like, converting hydrogen bromide gas in bromine-containing waste gas into hydrogen bromide solution, oxidizing bromine ions into bromine simple substance through an oxidation device by the hydrogen bromide solution to form bromine-containing simple substance steam and reaction solution, then introducing the bromine-containing simple substance steam and the reaction solution into a purification device for purification and separation to obtain bromine-containing simple substance steam, condensing the obtained bromine-containing simple substance steam and introducing the obtained bromine-containing simple substance steam into a phase separation device for separating liquid bromine from water phase, and introducing the obtained liquid bromine into a rectification device for rectification and purification to obtain a final product. The device and the method separate other impurities except bromine from the bromine-containing waste gas, and the bromine in the reaction solution is fully separated and recovered by introducing the steam and the reaction solution which are formed by oxidation and contain the bromine into a purification device for purification and separation, so that the yield and purity of the bromine obtained by recovering the bromine-containing waste gas are high, the recovery rate is higher than 98%, and the purity of the obtained liquid bromine is higher than 99.5% through test calculation, thereby protecting the environment and effectively saving resources.
The separation device is connected in series before the oxidation device and is used for separating the hydrogen bromide gas from other waste gases and converting the hydrogen bromide gas into hydrogen bromideThe solution is guided into an oxidation device for oxidation. Specifically, the separation device comprises a stripping tower 1, a reboiler 2 and a liquid inlet pipe 3. The reboiler 2 is arranged in the lower part of the stripping column 1 for heating the liquid in the stripping column. The stripper 1 comprises a stripper feed 11 and a stripper vent 12, the stripper feed 11 being arranged at the bottom of the stripper 1 and in the upper part of the reboiler 2, and the stripper vent 12 being arranged at the top of the stripper 1. The bromine-containing waste gas enters a stripping tower 1, an 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 the hydrogen bromide gas is converted into hydrogen bromide solution and is mixed with other waste gas such as SO 2 、SO 3 And (3) separating, namely, introducing the hydrogen bromide solution into an oxidation tank for treatment, and stripping other waste gases and introducing the waste gases into an alkali absorption system.
The absorption liquid comprises water, brine-free water and the like, preferably, the absorption liquid is brine-free water, and 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 bromine in the bromine-containing waste gas is more soluble in the brine-free water than other waste gas, the purpose of separating the bromine from other waste gas is realized, and the absorption effect is good.
The liquid inlet pipe 3 comprises a spraying section 31 with spraying holes 311, wherein the spraying section 31 is arranged at the upper part in the stripping tower 1 and is positioned above the feeding hole 11 of the stripping tower and below the exhaust hole 12 of the stripping tower, and the spraying holes 311 are arranged towards the bottom of the stripping tower 1. The bromine-containing waste gas enters the stripping tower 1 through the feeding hole 11 of the stripping tower, the liquid inlet pipe 3 is filled with absorption liquid, preferably non-saline water, and the non-saline water is sprayed into the stripping tower 1 through the spraying holes 311 on the spraying section 31. Wherein the bromine-containing waste gas is absorbed by the brine-free water to form hydrobromic acid with high boiling point, and further, the hydrobromic acid is positioned at the bottom of the stripping tower 1, and most of SO is formed 2 And SO 3 Because of the relatively small thermodynamic interactions with the brine-free water, the stripping steam generated by reboiler 2 is stripped out and not absorbed by the brine-free water. The boiling temperature in reboiler 2 was about 110 ℃, and the stripped SO 2 、SO 3 And water vapor is conducted out through stripper vent 12.
The separation device comprises an exhaust gas discharge pipeline 14 and a hydrogen bromide solution flow pipeline15, the exhaust gas pipeline 14 is connected with the upper part of the stripping tower 1 and is connected with the exhaust port 12 of the stripping tower for exhausting other exhaust gases such as SO 2 And SO 3 And the like, wherein one end of the hydrogen bromide solution flow pipeline 15 is communicated with the bottom of the stripping tower 1, the other end of the hydrogen bromide solution flow pipeline 15 is communicated with an oxidation device, and the hydrogen bromide solution is guided into the oxidation device through the hydrogen bromide solution flow pipeline 15 to be oxidized into bromine simple substance.
The exhaust gas pipeline 14 is connected with the first condenser 4 in series, the exhaust gas pipeline 14 is communicated with the first condenser 4, the lower part of the first condenser 14 is communicated with the stripping tower 1, the first condenser 4 is also provided with an exhaust port, gasified vapor and hydrogen bromide gas are condensed and flow back to the inside of the stripping tower 1 through the first condenser 4, and other exhaust gases are exhausted through the exhaust port. Specifically, stripped SO 2 、SO 3 And the water vapor is condensed by the first condenser 4, and the gaseous SO 2 、SO 3 And saturated water vapor are 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 is refluxed 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.
As shown in fig. 2, the oxidizing apparatus includes an oxidation tank 5, and the hydrogen bromide solution is oxidized in the oxidation tank 5 to form steam containing bromine element and a reaction solution. The purification device comprises a stripping zone, the reaction solution is stripped and separated by the stripping zone to obtain steam containing bromine simple substance, and the steam containing bromine simple substance is condensed, phase separated and rectified to obtain bromine simple substance. 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 internal area 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 and a reaction solution containing bromine. The vapor of bromine-containing simple substance formed by oxidation is introduced into the reaction zone 61, and the reaction solution is introduced into the stripping zone 62. The steam generated in the stripping zone 62 strips out the bromine element in the reaction solution and the steam containing bromine element in the reaction zone 61, and the bromine element is condensed, separated and recovered by a phase separation device. Preferably, the temperature of the stripping zone is from 100 to 110 ℃.
The bottom of the separation tower 6 is provided with a heating device, the steam and the reaction solution containing bromine and output by the oxidation tank 5 enter the separation tower 6, and the steam is stripped by the stripping zone 62 of the separation tower 6 to enter the phase separator for separation, so that the bromine gas is fully stripped, and the purity and the recovery rate of the bromine gas are improved. Preferably, the stripping zone 62 is at a temperature of 100℃and the recovery of bromine is better in this temperature range. A separating tower feed port is arranged between the reaction zone 61 and the stripping zone 62 of the separating tower 6, and the oxidation tank 5 is communicated with the separating tower feed port. The heating means comprises a reboiler or a heater, said heater 65 being arranged in the stripping zone 62 such that the boiling temperature in the stripping zone 62 is about 100-110 c. Preferably, the heater 65 is disposed at the bottom of the separation column 6, and the feed inlet of the separation column is disposed at the middle of the separation column 6.
The oxidation tank 5 comprises an oxidation tank feed port 51, the oxidation tank feed port 51 is communicated with a stripping tower liquid outlet 13 of the stripping tower 1, an oxidation tank exhaust port 52 is arranged at the top of the oxidation tank 5, an oxidation tank liquid outlet 53 is arranged at the lower part of the oxidation tank 5, the separation tank feed port comprises a first feed port 63 and a second feed port 64 arranged above the first feed port 63, the oxidation tank exhaust port 52 is communicated with the second feed port 64, and the oxidation tank liquid outlet 53 is communicated with the first feed port 63. Hydrobromic acid containing a small amount of sulfurous acid and sulfuric acid is conducted through the hydrogen bromide solution flow conduit 15 via the stripper drain 13 to the oxidation tank feed inlet 51.
The oxidizing device further comprises an oxidant feeding pipe 54, the oxidant feeding pipe 54 is communicated with the oxidizing tank 5, oxidant is introduced into the oxidant feeding pipe 54, and bromine ions in the hydrogen bromide solution are oxidized into bromine elements by the oxidant and are led into the separating tower for separation. The oxidizing agent is introduced into the oxidation tank 5 through the oxidizing agent feed pipe 54, and oxidizes the bromide ions in hydrobromic acid in the oxidation tank 5 to convert them into elemental bromine. The oxidant is added in real time through the oxidant feed pipe 54, and the bromine element in the oxidation tank 5 passes through the pipeline through the oxidation tank exhaust port 52 and enters the reaction zone 61 through the second feed port 64.
The upper part of the stripping zone 62 is provided with a liquid distributor 621, the liquid in the oxidation tank 5 enters the first feed port 63 through a device pipeline through the liquid discharge port 53 of the oxidation tank, 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 zone 62, the heater 65 generates heat to generate steam, and the steam strips bromine simple substances. Preferably, the 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, and the waste liquid is pumped out to be neutralized with caustic soda after passing through the fourth condenser 67 from the bottom of the separation tower 6, so that the untreated waste liquid is prevented from being discharged and polluting the environment.
The steam containing bromine simple substance is obtained by purification and separation of the purification device, condensed into liquid bromine and water by a condenser, the liquid bromine and the water are led into a phase separation device, the liquid bromine and the water are separated, and the liquid bromine is further rectified and recovered. Preferably, the steam containing bromine simple substance is condensed into liquid bromine and water through a condenser and is led into a phase separation device for separation. Preferably, a multi-stage condenser is arranged between the separation tower 6 and the phase separator 10, bromine simple substance is condensed into liquid bromine by the multi-stage condenser and enters the phase separator 10, and an upper layer water phase in the phase separator flows back to the separation tower 6 and is stripped again by the separation tower 6, so that the recovery rate of bromine is further improved, and the purity of the recovered liquid bromine is improved. 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 the upper part of the second condenser is provided with a second condenser air inlet 71, the lower part of the second condenser is provided with a second condenser liquid outlet 72, 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 exhaust port 66, and the bottom of the separation column 6 has a separation column drain port. The separator vent 66 communicates with a second condenser inlet 71 and the second condenser drain 72 communicates with the phase separator 10. Bromine simple substance enters the second condenser air inlet 71 through the separation tower air outlet 66, is condensed by the second condenser 7, and liquefied simple substance bromine and water phase enter the phase separator 10 for the next phase separation.
The multistage separator further 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 air vent 73, the second condenser air vent 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 of the second condenser 7 enters the third condenser 8 through the second condenser air vent 73 to be continuously condensed into liquid bromine and is led into the phase separator 10 for further phase separation.
Further preferably, the third condenser 8 has a third condenser air outlet 82 at an upper portion thereof, and the remaining gas not condensed in the third condenser 8 is discharged through the third condenser air outlet 82. Preferably, the exhaust port 82 is connected to an exhaust pipe 84, and the uncondensed residual gas enters the exhaust pipe 84 through the exhaust port 82 and 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 103, and the second condenser drain 72 and the third condenser drain 83 are both in communication with the phase separator feed 103. The bottom of the phase separator 10 is provided with a first discharge port 101 of the phase separator, the phase separator 10 further comprises a second discharge port 102 of the phase separator, the second discharge port 102 of the phase separator is positioned at the upper part of the first discharge port 101 of the phase separator and the lower part of a feed port 103 of the phase separator, the first discharge port 101 of the phase separator is communicated with a rectifying device, and the second discharge port 102 of the phase separator is communicated with a separating tower 6. The liquefied elemental bromine and water are separated into an upper layer and a lower layer in the phase separator 10, the liquid bromine is used as a heavy phase and is positioned at the lower layer of the phase separator 10, and the water phase is used as a light phase and is positioned at the upper layer of the phase separator 10. The liquid bromine at the lower layer is led into the rectifying device through a first discharge hole 101 of the phase separator, the water phase at the upper layer is led into the separating tower 6 through a second discharge hole 102 of the phase separator, and the cycle is repeated. The liquid bromine is separated from the water phase in the process, so that the purity of the liquid bromine is improved.
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, and the liquid bromine in the liquid is further stripped out, thereby effectively improving the recovery rate of the liquid bromine.
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 the first discharge outlet 101 of the phase separator. The liquid bromine led out from the phase separator 10 may still contain a small amount of water and a small amount of hydrogen peroxide solution, and after passing through the rectifying tower 104, the pure bromine product is obtained at the bottom of the rectifying tower 104, a sixth condenser 1044 is connected to the bottom of the rectifying tower 104, the sixth condenser 1044 uses chilled water as working solution, and the pure bromine product obtained at the bottom of the rectifying tower is cooled and recovered by the sixth condenser 1044. Azeotropic bromine/hydrate exits from the top of the rectification column 104. Preferably, a tantalum reboiler is arranged at the bottom of the rectifying tower, and 0.6MPa steam heating is adopted.
The rectification apparatus further comprises at least one fifth condenser 9, the top of the fifth condenser 9 comprising a fifth condenser inlet 91 and a fifth condenser outlet 93, the bottom of the fifth condenser 9 comprising a fifth condenser drain 92. The top of the rectifying tower 104 is provided with a rectifying tower exhaust port 1043, the rectifying tower exhaust port 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 air outlet 93 is communicated with the third condenser air inlet 81. The vapor discharged from the rectifying column exhaust port 1043 enters the fifth condenser 9, is condensed by the fifth condenser 9, the condensed water is discharged from the fifth condenser liquid discharge port 92 to be led to the phase separator 10, the non-condensable vapor is discharged to the third condenser 8 through the fifth condenser exhaust port 93, and in the third condenser 8, the non-condensable vapor is discharged through the third condenser exhaust port 82. Further, an exhaust pipe 84 is externally connected to the third condenser exhaust port 82, the exhaust pipe 84 is connected to the alkali absorption tank, and part of bromine may be contained in the exhaust gas exhausted from the third condenser exhaust port 82, and the exhaust gas needs to be connected to the alkali absorption tank for absorption.
The bromine-containing waste gas recovery device adopting any one of the schemes or the combination scheme of any one of the schemes is high in controllability and equipment operability on the premise of ensuring bromine recovery rate and liquid bromine purity, and the operation elasticity of the bromine-containing waste gas recovery device is 50-105%.
Comparative example one:
in the traditional process, taking disperse red FB as an example, the main synthesis process of the disperse red FB takes 1-aminoanthraquinone as a raw material, concentrated sulfuric acid as a solvent, and excessive bromine is added to carry out bromination reaction, waste gas is generated in the reaction process, and main components in the waste gas are HBr, SO2 and SO3, wherein the HBr is about 27%; SO2 about 39%; SO3 is about 32%, the remainder is air, and the off-gas is directly absorbed by the liquid caustic without HBr separation and oxidation to liquid bromine recovery. Comparing the invention with the traditional process, wherein HBr is separated and oxidized into liquid bromine for recovery, the recovery effect of the traditional process for recovering bromine-containing waste gas and the recovery effect of the invention for recovering bromine-containing waste gas are shown in the following table 1:
table 1:
as can be obtained from the table 1, the recovery rate of bromine obtained by the method is 98%, the recovery effect is good, the purity of bromine liquid obtained by the method is more than 99.5% through test calculation, the bromine of the purity completely meets the condition of recycling, and simultaneously, the method converts HBr in waste gas into bromine liquid, so that the consumption of liquid alkali is reduced, resources are saved, and the discharge of waste water is reduced. In addition, after HBr is removed by a bromine-containing waste gas recovery device, SO is contained 2 、SO 3 The gas of the catalyst can enter a sulfuric acid recovery system for recovery again, and is further reused, SO that the waste of resources is reduced, and meanwhile, the part of SO is recycled 2 、SO 3 The gas of the water heater does not need to be recycled by alkali liquor, and the waste of energy sources is reduced.
Comparative example two:
the bromine-containing waste gas recovery device in this comparative example comprises a separation device, an oxidation device, a phase separation device, a rectification device and a device pipeline. Wherein, separator, oxidation unit, phase separation device and rectifier unit pass through device pipeline intercommunication in proper order, and bromine-containing waste gas is handled through separator, oxidation unit, phase separation device, rectifier unit in proper order. The comparative example and the third example are used for recovering 676kg/h hydrogen bromide containing waste gas produced by batch process during the production of disperse red. The difference between the separation device, the oxidation device, the phase separation device and the rectifying device in the control and recovery process is that the third embodiment comprises a purifying device, the steam and the reaction solution containing bromine formed by oxidation are led into the purifying device for purification and separation, and the second comparative embodiment does not comprise the purifying device, namely lacks the step of purifying the steam and the reaction solution containing bromine, but directly leads out the upper water phase in the phase separation device, and the lower liquid bromine in the phase separation device is led into the rectifying device for rectification, purification and separation. Comparison of comparative example two with example three shows HBr recovery effect as shown in table 2 below:
table 2:
from the above table 2, it is possible to obtain a bromine-containing simple substance obtained by further purifying and separating the steam formed by oxidation and the reaction solution by introducing them into the purifying apparatus, and 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 large amount of bromine is mixed in the upper aqueous phase in the phase separation device due to the lack of the purification device, and the upper aqueous phase in the phase separation device is directly discharged to cause a large amount of bromine to be discharged together with the upper aqueous phase, so that 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 bromine simple substance is reduced. Further, since the second comparative example lacks a purification device, a large amount of liquid is introduced into the phase separation device, and thus the volume of the phase separation device needs to be increased. In addition, in the second comparative example, it is necessary to add a pipeline for guiding out the upper aqueous phase in the phase separation device to the phase separation device, which results in complicated pipeline of the bromine-containing waste gas recovery device in the second comparative example and poor recovery effect. In conclusion, adding the purification device in the bromine-containing waste gas recovery device can fully strip and separate bromine in the reaction liquid led out by the oxidation device, so that almost all bromine elements generated by the oxidation device are condensed and enter the phase separation device for separation, the yield is high, and the purity of the obtained bromine elements is as high as 99.5%.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (8)
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 hydrogen bromide solution and oxidized by an oxidation device to form bromine-containing simple substance steam and reaction solution, an oxidant is introduced into the oxidation device, and bromine ions in the hydrogen bromide solution are oxidized into bromine simple substance by the oxidant and are led into a purification device for purification and separation; the oxidant is hydrogen peroxide solution with the concentration of 30% -50%; the molar ratio of the hydrogen bromide to the hydrogen peroxide is 1:0.51; the time of mixing and oxidizing the hydrogen bromide solution in an oxidation device is within the range of 20-60 s;
the bromine-containing simple substance steam and the reaction solution are led into a purification device to be purified and separated to obtain bromine-containing simple substance steam, and the bromine-containing simple substance steam is condensed, separated and recovered to obtain bromine simple substance;
the purification device comprises a stripping zone, the reaction solution is stripped and separated by the stripping zone to obtain steam containing bromine simple substance, and the steam containing bromine simple substance is condensed and separated to recover bromine simple substance;
the bromine-containing waste gas enters a stripping tower, is contacted and absorbed by absorption liquid in the stripping tower, hydrogen bromide gas is converted into hydrogen bromide solution, the hydrogen bromide solution is separated from other waste gases, and the hydrogen bromide solution enters an oxidation device for oxidation;
the absorption liquid comprises a brine-free water, and the brine-free water absorbs the hydrogen bromide gas;
the purification device comprises a separation tower, wherein 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 bromine simple substance formed by oxidation is introduced into the reaction area, reaction solution is introduced into the stripping area, steam generated by the stripping area strips out the bromine simple substance in the reaction solution and the steam containing bromine simple substance in the reaction area, and condensation separation recovery is carried out.
2. A bromine-containing waste gas recovery method according to claim 1 wherein the temperature of the stripping zone is 100-110 ℃.
3. A bromine-containing waste gas recovery method according to claim 1 or 2 wherein the boiling temperature in the stripping column is 110-125 ℃.
4. A bromine-containing waste gas recovery method according to claim 3 wherein the brine-free water is sprayed from the top of the stripping column to the bottom of the stripping column.
5. A bromine-containing waste gas recovery method according to claim 3 wherein the other waste gas is condensed back to the stripping tower by a condenser and the waste gas which cannot be condensed is connected to the alkali absorption system.
6. The bromine-containing waste gas recovery method according to claim 1, wherein the steam purified and separated by the purifying device is condensed into liquid bromine and water phase by a condenser, the liquid bromine and the water phase are led into the phase separating device, the liquid bromine and the water phase are separated, and the liquid bromine is further recovered by rectification.
7. The method for recycling bromine-containing waste gas according to claim 6, wherein the steam of bromine-containing simple substance is condensed into liquid bromine and water phase by a multi-stage condenser and is led into a phase separation device for separation.
8. The method for recovering bromine-containing waste gas according to claim 7 wherein waste gas from which bromine-containing simple substance vapor introduced into the condenser is not condensed and recovered is discharged through an exhaust pipe on the condenser.
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