CN112266119A - Bromine extraction process and device for waste water generated in production of brominated butyl rubber - Google Patents
Bromine extraction process and device for waste water generated in production of brominated butyl rubber Download PDFInfo
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 173
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 239000002351 wastewater Substances 0.000 title claims abstract description 106
- 229920005557 bromobutyl Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000605 extraction Methods 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 72
- 230000003647 oxidation Effects 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910000435 bromine oxide Inorganic materials 0.000 claims abstract description 25
- FMSOWMGJJIHFTQ-UHFFFAOYSA-N oxidobromine(.) Chemical compound Br[O] FMSOWMGJJIHFTQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 11
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 56
- 239000007791 liquid phase Substances 0.000 claims description 55
- 239000012071 phase Substances 0.000 claims description 51
- 239000000945 filler Substances 0.000 claims description 41
- 238000005260 corrosion Methods 0.000 claims description 15
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 14
- 230000007797 corrosion Effects 0.000 claims description 14
- 238000010092 rubber production Methods 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BSKZDJXVMPWPRA-UHFFFAOYSA-N O.[Br] Chemical compound O.[Br] BSKZDJXVMPWPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 abstract 1
- 238000007664 blowing Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000001256 steam distillation Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
- C02F1/12—Spray evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/763—Devices for the addition of such compounds in gaseous form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physical Water Treatments (AREA)
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Abstract
The invention discloses a bromine extraction process and a device for waste water in production of brominated butyl rubber. The method comprises the following steps: (1) acidifying and filtering pretreatment of butyl bromide production wastewater; (2) oxidizing the pretreated bromine-containing wastewater by a supergravity oxidation device and a supergravity stripping device respectively, and extracting bromine; (3) contacting bromine-containing wastewater with chlorine in a supergravity oxidation device, and oxidizing bromide ions into free bromine by the chlorine to obtain bromine oxide liquid; (4) the bromine oxide solution is contacted with high-temperature steam in a hypergravity stripping device, and the steam blows out free bromine in the wastewater to form bromine-rich steam; (5) and cooling the bromine-rich steam, then feeding the cooled bromine-rich steam into a bromine water separation tank, and carrying out settling separation to obtain bromine for recycling. The method can obviously reduce the process energy consumption, reduce the consumption of chlorine and water vapor, improve the utilization rate and the blow-out rate of bromine, has the advantages of low operation cost, easy parking and starting, small amplification effect and the like, and can be widely applied to the extraction of bromine in the waste water produced by the brominated butyl rubber.
Description
Technical Field
The invention relates to a bromine extraction process and a bromine extraction device for waste water generated in production of brominated butyl rubber, and belongs to the field of treatment of waste water generated in rubber production.
Background
The brominated butyl rubber has the advantages of heat resistance, corrosion resistance, high vulcanization speed, good self-adhesion and the like, and is commonly used for manufacturing a radial tire inner tube and a tubeless tire. With the rapid development of the automobile industry, the demand of brominated butyl rubber is increasing year by year. The brominated butyl rubber is mainly prepared by a solution bromination method in China, but the problems of incomplete bromination reaction, low bromine utilization rate and the like exist in the prior art, and a large amount of bromine-containing wastewater can be generated. If the bromine is not recycled, serious environmental pollution and resource waste can be caused. In addition, bromine resources play a very important role in national economy, but the current bromine yield in China cannot meet the market demand. From the perspective of environmental protection and resource utilization, the finding of the bromine extraction process for the brominated butyl rubber production wastewater with low energy consumption and high bromine yield has important practical significance.
The method for extracting bromine from wastewater comprises various methods such as extraction, gaseous membrane separation, steam distillation, air blowing and the like. For example, chinese patent CN103613071A discloses a method for recovering bromine from brominated butyl rubber bromine-containing wastewater, which comprises acidifying and oxidizing pretreated brominated butyl rubber wastewater, extracting and separating liquid, recycling oil phase, and discharging water phase. Chinese patent CN103407965B discloses a method for extracting/enriching bromine from bromine-containing feed liquid or waste water, which comprises acidifying or acidifying and oxidizing the feed liquid or waste water, introducing the above mixed liquid into a gaseous membrane module for bromine extraction, and finally distilling the enriched liquid to obtain elemental bromine. At present, most of the bromine extraction processes adopted in domestic factories mainly adopt a steam distillation method and an air blowing method. The steam distillation method is to heat and blow out acidified and oxidized bromine by using steam, and when the bromine content of the wastewater is low, the steam consumption is high, and the treatment cost is high, so that the steam distillation method is suitable for treating wastewater with high bromine content (> 3 g/L). The principle of the air blowing method is that air is used as a carrier of free bromine, the free bromine after acidification and oxidation is blown out, and absorbents such as a sulfurous acid solution or an alkali solution are used for absorbing the free bromine, so that the enrichment of bromine is realized. For waste water with low bromine content (< 3 g/L), the air blowing method is more economical, but the method has the problems of high energy consumption, low bromine blowing rate, high liquid chlorine consumption and the like.
Aiming at the problems of the air blowing method, the predecessor discloses a process method for oxidizing and blowing in the process of extracting bromine from brine (such as Chinese patent CN101486445B and paper Liu Zhi, etc., modern chemical industry, 2009, 29(8): 78-81, etc.), and the air blowing method is mainly adopted for extracting bromine. The process is based on the supergravity process strengthening concept, acidified brine and chlorine are introduced into a rotary packed bed I, formed oxidizing liquid and air enter a rotary packed bed II, and finally free bromine is blown out. Due to the high-speed centrifugal action of the filler, the transfer resistance of the bromine-containing waste liquid is reduced, the liquid is divided into micron-sized liquid films, liquid threads, liquid drops and other forms, the mass transfer coefficient is obviously improved, and the single-stage bromine blowing rate can reach 94.5%. Therefore, the high gravity field can improve the oxidation rate and the blow-off rate of bromine, is beneficial to deep removal of low-content bromine, and simultaneously reduces the energy consumption of wastewater treatment. However, the bromine content of domestic waste water produced in the production of brominated butyl rubber is usually higher than 3 g/L, and if an air blowing method is directly adopted, the problems of overlarge material consumption and energy consumption and the like can be caused, and the concept of energy conservation and emission reduction is not met. In addition, the existing steam distillation equipment has the problems of low mass transfer efficiency, high energy consumption and the like, so that the oxidation degree of bromine is limited, and the bromine extraction efficiency is low. Therefore, the existing bromine extraction process for the waste water of the brominated butyl rubber production needs to be improved to realize the efficient and deep removal of bromine.
Disclosure of Invention
The invention provides a bromine extraction process for waste water in production of brominated butyl rubber, aiming at solving the problems of low oxidation rate and blowing rate of bromine, high energy consumption and the like in the bromine extraction process.
The invention provides a bromine extraction process for waste water produced in production of brominated butyl rubber.A bromine-containing waste water subjected to acidification and filtration pretreatment is firstly input into a super-gravity oxidation device through a corrosion-resistant pump, is uniformly sprayed on the inner edge of a filler through a first liquid phase inlet and a liquid distributor, and then flows from inside to outside along the filler layer; chlorine gas is conveyed to the supergravity oxidation device through the first gas phase inlet by the fan and axially passes through the packing layer; the gas phase and the liquid phase are in cross flow contact, bromide ions are oxidized into free bromine by chlorine, and the obtained bromine oxide liquid enters a liquid storage tank; the bromine oxide solution and the steam are respectively input into the hypergravity steam stripping device from a second liquid phase inlet and a second gas phase inlet, the bromine oxide solution is uniformly sprayed on the inner edge of the filler through a liquid distributor and contacts with the high-temperature steam in a cross flow manner, and the steam blows out free bromine in the wastewater to form bromine-rich steam; and cooling the bromine-rich steam, then feeding the bromine-rich steam into a bromine water separation tank, and performing settling separation to obtain liquid bromine.
The bromine extraction process of the brominated butyl rubber production wastewater specifically comprises the following steps:
(1) pretreating waste water generated in the production of brominated butyl rubber: acidifying pretreatment, namely adjusting the pH value to be within a range of 3-5 by adding acid; then, carrying out filtration treatment, and ensuring that the turbidity of inlet water is less than a safety value by adopting a filter;
(2) the pretreated bromine-containing wastewater is subjected to oxidation and bromine extraction treatment by a hypergravity oxidation device and a hypergravity stripping device which are connected in series; the motor is controlled by adjusting the frequency converter, so that the supergravity rotating speed is adjusted; controlling the gas-liquid ratio by adjusting a flow meter, and stably operating for 10-30 min;
(3) conveying bromine-containing wastewater to a supergravity oxidation device by a corrosion-resistant pump, uniformly spraying the bromine-containing wastewater on the inner edge of the filler by a distributor after the bromine-containing wastewater passes through a first liquid phase inlet, and flowing from inside to outside along the filler layer; chlorine is conveyed into the supergravity oxidation device through the first gas phase inlet by the fan and axially passes through the packing layer; bromine-containing wastewater flows horizontally from the inner edge of the filler to the outer edge of the filler, chlorine gas flows vertically from the bottom, gas-liquid phases are in cross flow contact, bromide ions are oxidized into free bromine by the chlorine gas, and bromine oxide solution is obtained, wherein the reaction mainly comprises the following steps:
2Br-+Cl2→Br2+2Cl- ①
(4) the bromine oxide solution and the steam are respectively input into the hypergravity steam stripping device from a second liquid phase inlet and a second gas phase inlet, the bromine oxide solution is uniformly sprayed on the inner edge of the filler through a liquid distributor and contacts with the high-temperature steam in a cross flow manner, and the steam blows out free bromine in the wastewater to form bromine-rich steam;
(5) and cooling the bromine-rich steam, then feeding the bromine-rich steam into a bromine water separation tank, performing sedimentation separation, and recycling the obtained bromine, wherein the debrominated wastewater is discharged after being treated according to the national wastewater discharge standard, or is recycled after being treated according to the water standard of the actual production process.
Preferably, in the bromine extraction process of the brominated butyl rubber production wastewater, hydrochloric acid or hydrobromic acid is adopted for acidification pretreatment, an anti-corrosion filter is adopted for filtration treatment, and the filtration precision is 10 μm;
preferably, in the bromine extraction process of the brominated butyl rubber production wastewater, the rotating speed of the supergravity oxidation device is controlled to be 800-1200 r/min, and the rotating speed of the supergravity stripping device is controlled to be 1000-1500 r/min;
preferably, in the bromine extraction process of the brominated butyl rubber production wastewater, the content of bromide ions in the wastewater is higher than 3 g/L, the chlorine blending rate is 100-120%, and the temperature is controlled at 20-30 ℃ in the oxidation process;
preferably, in the bromine extraction process of the brominated butyl rubber production wastewater, the gas-liquid ratio of chlorine to bromine-containing wastewater is 50-100 m3/m3The gas-liquid ratio of the water vapor to the bromine oxide solution is 50-100 m3/m3The temperature in the stripping process is controlled to be 80-100 ℃, and the temperature of the high-temperature steam is 110-120 ℃.
Preferably, in the bromine extraction process of the brominated butyl rubber production wastewater, the gas-liquid contact mode is cross-flow contact, and the filling mode of the filler in the supergravity device is silk screen winding or random stacking.
The invention provides a bromine extraction device for waste water in production of brominated butyl rubber, which comprises two series-connected hypergravity devices, in particular to a hypergravity oxidation device and a hypergravity stripping device, wherein the main structures of the hypergravity oxidation device and the hypergravity stripping device comprise a gas phase inlet, a gas phase outlet, a liquid phase inlet, a liquid phase outlet, a filler, a shell, a bracket, a rotating shaft, a frequency converter and a motor; the main difference between the two is that chlorine is introduced into a gas phase inlet of the supergravity oxidation device, and bromine-containing production wastewater is introduced into a liquid phase inlet of the supergravity oxidation device, and the supergravity oxidation device is mainly used for oxidation treatment of the bromine-containing production wastewater; steam is introduced into a gas phase inlet of the hypergravity stripping device, and oxidized bromine liquid after oxidation treatment is introduced into a liquid phase inlet and is mainly used for extracting bromine in the oxidized wastewater;
the bottom of the supergravity oxidation device is respectively provided with a first gas phase inlet and a first liquid phase outlet, and the top of the supergravity oxidation device is respectively provided with a first liquid phase inlet and a first gas phase outlet; a first liquid phase inlet of the supergravity oxidation device is connected with a bromine-containing production wastewater feeding pipeline, and the feeding pipeline is respectively provided with a corrosion-resistant pump, a control valve, a liquid flowmeter and a heat exchanger; a first gas phase inlet of the supergravity oxidation device is connected with a chlorine gas feeding pipeline, and a fan, a control valve and a gas flowmeter are respectively arranged on the feeding pipeline; the inside of the supergravity oxidation device is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft; a first liquid phase outlet of the supergravity oxidation device is connected with the liquid storage tank;
the bottom of the hypergravity stripping device is respectively provided with a second gas phase inlet and a second liquid phase outlet, and the top of the hypergravity stripping device is respectively provided with a second liquid phase inlet and a second gas phase outlet; the outlet end of the liquid storage tank is connected with a second liquid phase inlet of the hypergravity stripping device through a wastewater feeding pipeline, and the feeding pipeline is respectively provided with a corrosion-resistant pump, a control valve, a liquid flowmeter and a heat exchanger; a second gas phase inlet of the hypergravity stripping device is connected with a steam feeding pipeline, and a fan, a control valve and a gas flowmeter are respectively arranged on the feeding pipeline; the inside of the hypergravity stripping device is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft;
a second liquid phase outlet at the bottom of the hypergravity steam stripping device discharges debrominated wastewater; and condensing the bromine-containing steam discharged from the second gas phase outlet at the top by a heat exchanger, then feeding the condensed bromine-containing steam into a bromine-water separation tank, and performing sedimentation separation by means of density difference between bromine and water to obtain waste gas and bromine liquid.
Preferably, in the above device, the adopted supergravity device shell and the parts such as the filler support are sprayed with an anticorrosive coating, the rotating shaft and the bearing are anticorrosive by an isolation method, and the filler is made of polytetrafluoroethylene material so as to prevent components such as bromine and hydrobromic acid from corroding equipment.
The invention has the beneficial effects that:
(1) compared with the traditional tower equipment, the supergravity device has small amplification effect, small occupied area, low operation cost, low energy consumption and easy start and stop, and is suitable for the operation of extracting bromine from waste water in the production of brominated butyl rubber;
(2) compared with the oxidation reaction in the traditional static mixer, the supergravity device weakens the surface tension effect of the brominated butyl rubber production waste, and the liquid forms micron-sized liquid films, liquid threads and liquid drops under the shearing action, so that the interphase contact area is greatly increased, the interphase mass transfer coefficient is improved, and the consumption of chlorine is reduced;
(3) under the hypergravity environment, the turbulence degree of the bromine oxide liquid is enhanced, the gas-liquid interface is updated quickly, the lower liquid layer reaches the liquid surface quickly, so that free bromine can be in full contact with water vapor in a short time to complete mass transfer, the extremely short retention time is short, the bromine is discharged in time, the bromine blowing rate is further improved, and the water vapor consumption is reduced.
Drawings
FIG. 1 is a schematic diagram of a bromine extraction device for waste water from production of brominated butyl rubber.
In the figure: 1a corrosion-resistant pump; 2, a fan; 3-a control valve; 4-liquid flow meter; 5-gas flow meter; 6, a heat exchanger; 7 — an inlet for a first liquid phase; 8-a first gas phase outlet; 9-a supergravity oxidation unit; 10 — a first gas phase inlet; 11 — an outlet for the first liquid phase; 12-a frequency converter; 13-a motor; 14-a liquid storage tank; 15-a second liquid phase inlet; 16-a second gas phase outlet; 17-a hypergravity stripping device; 18-a second gas phase inlet; 19-a second liquid phase outlet; 20-bromine water separating tank. A is bromine-containing production wastewater, B is chlorine, C is bromine oxide solution, D is water vapor, E is bromine-rich steam, F is debrominated wastewater, G is waste gas, and H is bromine solution.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited to the following examples, and includes any other known variations within the scope of the supergravity treatment of brominated butyl rubber wastewater as claimed herein.
As shown in fig. 1, a bromine extraction device for waste water from production of brominated butyl rubber comprises two supergravity devices connected in series, specifically a supergravity oxidation device 9 and a supergravity stripping device 17, the main structures of which include a gas phase inlet, a gas phase outlet, a liquid phase inlet, a liquid phase outlet, a filler, a shell, a support, a rotating shaft, a frequency converter 12 and a motor 13; the main difference between the two is that chlorine B is introduced into a gas phase inlet of the supergravity oxidation device, and bromine-containing production wastewater A is introduced into a liquid phase inlet of the supergravity oxidation device, and the chlorine B and the liquid phase inlet are mainly used for oxidation treatment of the bromine-containing production wastewater; introducing steam D into a gas phase inlet of the hypergravity stripping device, and introducing oxidized bromine liquid C subjected to oxidation treatment into a liquid phase inlet, wherein the oxidized bromine liquid C is mainly used for extracting bromine in oxidized wastewater;
the bottom of the supergravity oxidation device 9 is respectively provided with a first gas phase inlet 10 and a first liquid phase outlet 11, and the top is respectively provided with a first liquid phase inlet 7 and a first gas phase outlet 8; a first liquid phase inlet 7 of the supergravity oxidation device is connected with a feed pipeline of bromine-containing production wastewater A, and the feed pipeline is respectively provided with a corrosion-resistant pump 1, a control valve 3, a liquid flowmeter 4 and a heat exchanger 6; a first gas phase inlet 10 of the supergravity oxidation device is connected with a chlorine gas B feeding pipeline, and a fan 2, a control valve 3 and a gas flowmeter 5 are respectively arranged on the feeding pipeline; the inside of the supergravity oxidation device is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft; a first liquid phase outlet 11 of the hypergravity oxidation device 9 is connected with a liquid storage tank 14;
the bottom of the hypergravity stripping device 17 is respectively provided with a second gas phase inlet 18 and a second liquid phase outlet 19, and the top is respectively provided with a second liquid phase inlet 15 and a second gas phase outlet 16; the outlet end of the liquid storage tank 14 is connected with a second liquid phase inlet 15 of a hypergravity stripping device 17 through a wastewater feeding pipeline, and the feeding pipeline is respectively provided with a corrosion-resistant pump 1, a control valve 3, a liquid flow meter 4 and a heat exchanger 6; a second gas phase inlet 18 of the hypergravity stripping device 17 is connected with a steam C feeding pipeline, and the feeding pipeline is respectively provided with a fan 2, a control valve 3 and a gas flowmeter 5; the inside of the hypergravity stripping device 17 is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft;
a second liquid phase outlet 19 at the bottom of the hypergravity stripping device 17 discharges debrominated wastewater F; and condensing the bromine-rich steam E discharged from the second gas phase outlet 16 at the top by a heat exchanger 6, and then feeding the condensed bromine-rich steam E into a bromine-water separation tank 20 for settling separation by virtue of the density difference between bromine and water, thereby obtaining waste gas G and bromine liquid H.
Preferably, in the above device, the adopted supergravity device shell and the parts such as the filler support are sprayed with an anticorrosive coating, the rotating shaft and the bearing are anticorrosive by an isolation method, and the filler is made of polytetrafluoroethylene material so as to prevent components such as bromine and hydrobromic acid from corroding equipment.
The process flow of the invention is as follows:
the pretreated bromine-containing production wastewater A after acidification and filtration is firstly input into a supergravity oxidation device 9 through a corrosion-resistant pump 1, is uniformly sprayed on the inner edge of a filler through a first liquid phase inlet 7 and a liquid distributor, and then flows from inside to outside along the filler layer; chlorine B is conveyed to the supergravity oxidation device 9 through the first gas phase inlet 10 by the fan 2 and passes through the packing layer along the axial direction; the gas phase and the liquid phase are in cross flow contact, bromide ions are oxidized into free bromine by chlorine, and the obtained bromine oxide liquid C enters the liquid storage tank 14; the bromine oxide solution C and the steam D are respectively input into a supergravity stripping device 17 from a second liquid phase inlet 15 and a second gas phase inlet 18, the bromine oxide solution C is uniformly sprayed on the inner edge of the filler through a liquid distributor and is in cross flow contact with the high-temperature steam D, and the steam D blows out free bromine in the wastewater to form bromine-rich steam E; and cooling the bromine-rich steam E, then feeding the cooled bromine-rich steam E into a bromine water separation tank 20, and performing settling separation to obtain liquid bromine H. The method specifically comprises the following steps:
(1) pretreating waste water generated in the production of brominated butyl rubber: acidifying pretreatment, namely adjusting the pH value to be within a range of 3-5 by adding acid; then, carrying out filtration treatment, and ensuring that the turbidity of inlet water is less than a safety value by adopting a filter;
(2) the pretreated bromine-containing wastewater is subjected to oxidation and bromine extraction treatment by a hypergravity oxidation device and a hypergravity stripping device which are connected in series; the motor is controlled by adjusting the frequency converter, so that the supergravity rotating speed is adjusted; controlling the gas-liquid ratio by adjusting a flow meter, and stably operating for 10-30 min;
(3) conveying bromine-containing wastewater to a supergravity oxidation device by a corrosion-resistant pump, uniformly spraying the bromine-containing wastewater on the inner edge of the filler by a distributor after the bromine-containing wastewater passes through a first liquid phase inlet, and flowing from inside to outside along the filler layer; chlorine is conveyed into the supergravity oxidation device through the first gas phase inlet by the fan and axially passes through the packing layer; bromine-containing wastewater flows horizontally from the inner edge of the filler to the outer edge of the filler, chlorine gas flows vertically from the bottom, gas-liquid phases are in cross flow contact, bromide ions are oxidized into free bromine by the chlorine gas, and bromine oxide solution is obtained, wherein the reaction mainly comprises the following steps:
2Br-+Cl2→Br2+2Cl- ①
(4) the bromine oxide solution and the steam are respectively input into the hypergravity steam stripping device from a second liquid phase inlet and a second gas phase inlet, the bromine oxide solution is uniformly sprayed on the inner edge of the filler through a liquid distributor and contacts with the high-temperature steam in a cross flow manner, and the steam blows out free bromine in the wastewater to form bromine-rich steam;
(5) and cooling the bromine-rich steam, then feeding the bromine-rich steam into a bromine water separation tank, performing sedimentation separation, and recycling the obtained bromine, wherein the debrominated wastewater is discharged after being treated according to the national wastewater discharge standard, or is recycled after being treated according to the water standard of the actual production process.
The following examples illustrate the practice of the invention:
example 1
The bromine content of the brominated butyl rubber wastewater is 3 g/L, the pH value is adjusted to 3.5, the rotating speed of the supergravity oxidation device 9 is 1000 r/min, the chlorine blending rate is 120 percent, and bromine ions are oxidized into free bromine by chlorine; the bromine oxide solution enters a supergravity bromine extraction device 17, the rotating speed is controlled to be 1200 r/min, and the gas-liquid ratio is adjusted to be 50 m3/m3The bromine oxidizing liquid is contacted with water vapor, and the water vapor blows off bromine in the bromine oxidizing liquid. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 91 percent, and the blowing rate is 95 percent.
Example 2
The pH was changed to 5 and the other conditions were identical to those of example 1. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 83 percent, and the blowing rate is 90 percent.
Example 3
The chlorine blending rate was changed to 100%, and the other conditions were the same as those in example 1. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 86 percent, and the blowing rate is 89 percent.
Example 4
The gas-liquid ratio of the hypergravity stripping device 17 is adjusted to be 100 m3/m3The other conditions were the same as in example 1. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 90 percent, and the blowing rate is 95 percent.
Example 5
The rotation speed of the supergravity oxidation device 9 was changed to 800 r/min, and the other conditions were the same as those in example 1. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 85 percent, and the blowing rate is 91 percent.
Example 6
The rotational speed of the hypergravity stripping device 17 was changed to 1000 r/min, and the other conditions were the same as in example 1. The result shows that the oxidation rate of bromine in the waste water of the production of the brominated butyl rubber is 92 percent, and the blowing rate is 90 percent.
The above-mentioned embodiments are only some embodiments of the present invention, and are not intended to limit the present invention, and all the obvious variations and modifications of the present invention are within the scope of the present invention.
Claims (9)
1. A bromine extraction process for waste water generated in production of brominated butyl rubber is characterized in that: conveying the pretreated bromine-containing production wastewater subjected to acidification and filtration into a supergravity oxidation device by a corrosion-resistant pump, uniformly spraying the wastewater on the inner edge of a filler by a liquid distributor through a first liquid phase inlet, and then flowing from inside to outside along the filler layer; chlorine gas is conveyed to the supergravity oxidation device through the first gas phase inlet by the fan and axially passes through the packing layer; the gas phase and the liquid phase are in cross flow contact, bromide ions are oxidized into free bromine by chlorine, and the obtained bromine oxide liquid enters a liquid storage tank; the bromine oxide solution and the steam are respectively input into the hypergravity steam stripping device from a second liquid phase inlet and a second gas phase inlet, the bromine oxide solution is uniformly sprayed on the inner edge of the filler through a liquid distributor and contacts with the high-temperature steam in a cross flow manner, and the steam blows out free bromine in the wastewater to form bromine-rich steam; and cooling the bromine-rich steam, then feeding the bromine-rich steam into a bromine water separation tank, and performing settling separation to obtain liquid bromine.
2. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 1, which is characterized in that: the method comprises the following steps:
(1) pretreating waste water generated in the production of brominated butyl rubber: acidifying pretreatment, namely adjusting the pH value to be within a range of 3-5 by adding acid; then, carrying out filtration treatment, and ensuring that the turbidity of inlet water is less than a safety value by adopting a filter;
(2) the pretreated bromine-containing wastewater is subjected to oxidation and bromine extraction treatment by a hypergravity oxidation device and a hypergravity stripping device which are connected in series; the motor is controlled by adjusting the frequency converter, so that the supergravity rotating speed is adjusted; controlling the gas-liquid ratio by adjusting a flow meter, and stably operating for 10-30 min;
(3) conveying bromine-containing wastewater to a supergravity oxidation device by a corrosion-resistant pump, uniformly spraying the bromine-containing wastewater on the inner edge of the filler by a distributor after the bromine-containing wastewater passes through a first liquid phase inlet, and flowing from inside to outside along the filler layer; chlorine is conveyed into the supergravity oxidation device through the first gas phase inlet by the fan and axially passes through the packing layer; the bromine-containing wastewater flows horizontally from the inner edge of the filler to the outer edge of the filler, the chlorine gas flows vertically from the bottom, the gas phase and the liquid phase are in cross flow contact, and bromide ions are oxidized into free bromine by the chlorine gas to obtain bromine oxide liquid;
(4) the bromine oxide solution and the steam are respectively input into the hypergravity steam stripping device from a second liquid phase inlet and a second gas phase inlet, the bromine oxide solution is uniformly sprayed on the inner edge of the filler through a liquid distributor and contacts with the high-temperature steam in a cross flow manner, and the steam blows out free bromine in the wastewater to form bromine-rich steam;
(5) and cooling the bromine-rich steam, then feeding the bromine-rich steam into a bromine-water separation tank, and performing settling separation to obtain liquid bromine for recycling.
3. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 2, which is characterized in that: hydrochloric acid or hydrobromic acid is adopted for acidification pretreatment, an anticorrosion filter is adopted for filtration treatment, and the filtration precision is 10 mu m.
4. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 2, which is characterized in that: the rotating speed of the hypergravity oxidation device is controlled to be 800-1200 r/min, and the rotating speed of the hypergravity stripping device is controlled to be 1000-1500 r/min.
5. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 2, which is characterized in that: the content of bromide ions in the bromine-containing production wastewater is higher than 3 g/L, the chlorine blending rate is 100-120%, and the temperature is controlled at 20-30 ℃ in the oxidation process.
6. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 2, which is characterized in that: the gas-liquid ratio of chlorine to bromine-containing wastewater is 50-100 m3/m3The gas-liquid ratio of the water vapor to the bromine oxide solution is 50-100 m3/m3Controlling the temperature to be 80-100 ℃ in the steam stripping process; the temperature of the high-temperature steam is 110-120 ℃.
7. The bromine extraction process for waste water from production of brominated butyl rubber according to claim 2, which is characterized in that: the gas-liquid contact mode is cross-flow contact, and the filling mode of the filler in the hypergravity oxidation device and the hypergravity stripping device is silk screen winding or bulk stacking.
8. A bromine extraction device for brominated butyl rubber production wastewater is used for implementing the bromine extraction process for brominated butyl rubber production wastewater according to any one of claims 1 to 7, and is characterized in that: the system comprises two series-connected hypergravity oxidation devices and a hypergravity stripping device, wherein the hypergravity oxidation devices are used for oxidizing bromine-containing production wastewater; the hypergravity steam stripping device is used for extracting bromine in the oxidation wastewater;
the bottom of the supergravity oxidation device is respectively provided with a first gas phase inlet and a first liquid phase outlet, and the top of the supergravity oxidation device is respectively provided with a first liquid phase inlet and a first gas phase outlet; a first liquid phase inlet of the supergravity oxidation device is connected with a bromine-containing production wastewater feeding pipeline, and the feeding pipeline is respectively provided with a corrosion-resistant pump, a control valve, a liquid flowmeter and a heat exchanger; a first gas phase inlet of the supergravity oxidation device is connected with a chlorine gas feeding pipeline, and a fan, a control valve and a gas flowmeter are respectively arranged on the feeding pipeline; the inside of the supergravity oxidation device is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft; a first liquid phase outlet of the supergravity oxidation device is connected with the liquid storage tank;
the bottom of the hypergravity stripping device is respectively provided with a second gas phase inlet and a second liquid phase outlet, and the top of the hypergravity stripping device is respectively provided with a second liquid phase inlet and a second gas phase outlet; the outlet end of the liquid storage tank is connected with a second liquid phase inlet of the hypergravity stripping device through a wastewater feeding pipeline, and the feeding pipeline is respectively provided with a corrosion-resistant pump, a control valve, a liquid flowmeter and a heat exchanger; a second gas phase inlet of the hypergravity stripping device is connected with a steam feeding pipeline, and a fan, a control valve and a gas flowmeter are respectively arranged on the feeding pipeline; the inside of the hypergravity stripping device is provided with a liquid distributor, a filler, a shell, a bracket and a rotating shaft;
a second liquid phase outlet at the bottom of the hypergravity steam stripping device discharges debrominated wastewater; and condensing the bromine-containing steam discharged from the second gas phase outlet at the top by a heat exchanger, then feeding the condensed bromine-containing steam into a bromine-water separation tank, and performing sedimentation separation by means of density difference between bromine and water to obtain waste gas and bromine liquid.
9. The bromine extraction device for waste water from production of brominated butyl rubber according to claim 8, characterized in that: the casing of the supergravity oxidation device and the supergravity stripping device and the filler support are sprayed with anticorrosive coatings, the rotating shaft and the bearing are anticorrosive by adopting an isolation method, and the filling filler is made of polytetrafluoroethylene material so as to prevent bromine and hydrobromic acid from corroding equipment.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114804155A (en) * | 2022-04-27 | 2022-07-29 | 宁波环洋新材料股份有限公司 | Bromine removal method for bromine-containing waste brine |
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| CN201351118Y (en) * | 2009-01-14 | 2009-11-25 | 中北大学 | Device for oxidation and blowout in process of bromine extraction from brine |
| CN103613071A (en) * | 2013-11-07 | 2014-03-05 | 浙江双益环保科技发展有限公司 | Method for recycling bromine from bromine-containing wastewater of brominated butyl rubber |
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| CN101486445A (en) * | 2009-01-14 | 2009-07-22 | 中北大学 | Oxidation and blowout technological process and apparatus for bittern bromine process |
| CN201351118Y (en) * | 2009-01-14 | 2009-11-25 | 中北大学 | Device for oxidation and blowout in process of bromine extraction from brine |
| CN103613071A (en) * | 2013-11-07 | 2014-03-05 | 浙江双益环保科技发展有限公司 | Method for recycling bromine from bromine-containing wastewater of brominated butyl rubber |
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Application publication date: 20210126 |