CN110606592A - Comprehensive utilization method of brominated butyl rubber bromine-containing wastewater - Google Patents
Comprehensive utilization method of brominated butyl rubber bromine-containing wastewater Download PDFInfo
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Abstract
The invention discloses a comprehensive utilization method of brominated butyl rubber bromine-containing wastewater, which comprises the following steps: s1, stabilizing the brominated butyl rubber bromine-containing wastewater in a stable water tank, then feeding the stabilized butyl rubber bromine-containing wastewater into a multi-media filter, adding a coagulant, and removing large-particle suspended matters and organic pollutants to obtain pretreated wastewater; s2, filtering the pretreated wastewater by a heat-resistant ultrafiltration membrane component to obtain ultrafiltration wastewater; s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the acidification to acidity, adding an oxidant to perform oxidation reaction, and oxidizing free bromine into bromine to obtain bromine-containing wastewater; s4, allowing the bromine-containing wastewater to flow through a hollow fiber hydrophobic membrane component, allowing bromine to volatilize at the interface between the membrane and water, penetrate through the hydrophobic membrane, and be absorbed by absorption liquid to obtain a bromine-containing solution for recycling, and allowing the bromine-extracted wastewater to enter a conventional industrial wastewater treatment process. The method of the invention reasonably utilizes the heat of the waste water, has high separation efficiency, simple process and no pollution.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a comprehensive utilization method of brominated butyl rubber bromine-containing wastewater.
Background
Brominated butyl rubber (BIIR) is an isobutylene-isoprene copolymer elastomer containing active bromine. Its research and development began in the 50's of the 20 th century, and because of its heat resistance, ozone resistance, corrosion resistance, low air permeability, flex resistance and easy sharing with other rubber products, it is widely used in various rubber products, especially in the manufacture of radial tire inner tube, tubeless tire and irreplaceable raw materials for special medical industry products. In recent years, due to the vigorous development of the automobile industry, the demand and industrial yield of domestic brominated butyl rubber are increasing. Inevitably produces a large amount of industrial waste water of brominated butyl rubber.
Bromine is an important raw material in the manufacturing process of brominated butyl rubber, and the generated industrial wastewater mainly has the following characteristics: (1) the waste water contains a certain amount of large sticky rubber particles, stearate and other suspended matters; (2) the waste water contains certain hexane, alkylphenol, other hydroxyl and other organic matters; (3) high salinity in waste water, containing NaBr and Na2SO4And Na2SO3And inorganic matters, wherein the Br concentration can reach 2000-9000 mg/L, and the inorganic matters are typical industrial wastewater with high salt and low COD. The adoption of a common wastewater treatment method can not only cause the discharge of bromine-containing wastewater to pollute the environment, but also cause the great waste of bromine resources.
Chinese patent CN 102464417A concentrates bromine-containing wastewater, mixes the concentrated bromine-containing wastewater with a chlorine-containing bactericide, and adds the mixture into industrial circulating cooling water for sterilization treatment, although reasonable utilization of wastewater resources can be realized, on one hand, suspended matters and hardness in the wastewater are easy to cause equipment pollution, and at the same time, bromine elements in the circulating water cannot be treated and recovered.
Chinese patent CN 103613071A and the application of extraction technology in the treatment of brominated butyl rubber bromine-containing wastewater (Xuzhou sea, resource saving and environmental protection, 3 rd period 2014) adopt an extraction method, free bromine in the brominated butyl rubber industrial wastewater is oxidized and then extracted, separated and purified by adopting an organic solvent, and bromine is recovered and treated. However, toxic extractant needs to be adopted in the treatment process, and meanwhile, the extractant can cause serious loss along with the extraction process, so that the bromine extraction cost is increased, and the environment is also polluted.
Moreover, the methods do not pay attention to the recovery of the heat of the wastewater, the heat loss of the wastewater in the operation process is large, and the energy consumption is increased invisibly.
Therefore, it is urgently needed to develop a novel and technically feasible comprehensive utilization method for brominated butyl rubber bromine-containing wastewater, which can recycle heat and has the advantages of high separation efficiency, simple process and low cost.
Disclosure of Invention
The invention aims to solve the technical problem of providing a comprehensive utilization method of brominated butyl rubber bromine-containing wastewater aiming at the defects of the prior art. The method adopts ultrafiltration, oxidation and membrane separation and absorption as main process steps, avoids using a large amount of steam, greatly reduces energy consumption, avoids using and wasting organic solvent caused by similar extraction method, greatly reduces the overall recovery cost, and has great economic benefit and environmental protection benefit; meanwhile, the waste water is directly treated at high temperature by using the temperature-resistant ultrafiltration membrane, so that the heat loss caused by the front-end temperature reduction of the conventional method is avoided, and the waste water temperature is always maintained at a higher temperature because the temperature reduction treatment is not needed during the extraction, thereby accelerating the speed of the subsequent oxidation process on one hand, and saving the heating energy consumption in the process of extracting bromine by membrane separation on the other hand.
Therefore, the invention provides a comprehensive utilization method of brominated butyl rubber bromine-containing wastewater, which comprises the following steps:
s1, mixing the brominated butyl rubber bromine-containing wastewater with backwashing water of a multi-media filter and backwashing water of an ultrafiltration membrane component in a stable water tank, then feeding the mixture into the multi-media filter, adding a coagulant, and removing large suspended solids and organic pollutants to obtain pretreated wastewater;
s2, filtering the pretreated wastewater by an ultrafiltration membrane component to remove micro particles to obtain ultrafiltration wastewater;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the acidification to acidity, adding an oxidant to perform oxidation reaction, and oxidizing free bromine into bromine to obtain bromine-containing wastewater;
s4, allowing the bromine-containing wastewater to flow through a hollow fiber hydrophobic membrane component, allowing the bromine to volatilize at the interface between the membrane and water, allowing the bromine to permeate through the hydrophobic membrane and be absorbed by an absorption liquid to obtain a bromine-containing solution for recycling, and allowing the bromine-extracted wastewater to enter a conventional industrial wastewater treatment process.
In some preferred embodiments of the invention, the coagulant is Polyacrylamide (PAM) and/or polyaluminium chloride (PAC).
In some preferred embodiments of the present invention, the coagulant is used in an amount of 6 to 15ppm based on the volume of the brominated butyl rubber industrial wastewater,
in some further preferred embodiments of the present invention, the coagulant is used in an amount of 7 to 12ppm, based on the volume of the brominated butyl rubber industrial wastewater.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the ultrafiltration membrane is at least one selected from a heat-resistant polyvinylidene fluoride ultrafiltration membrane, a heat-resistant polyether sulfone ultrafiltration membrane, a ceramic membrane or a metal membrane.
In some preferred embodiments of the present invention, the ultrafiltration membrane has a membrane pore size of 0.01 to 0.1 μm and a wall thickness of 0.5 to 1 nm.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the filling rate of the ultrafiltration membrane component is 50-70%, and the membrane flux of the ultrafiltration membrane component is 25-45 L.m-2·h-1The water yield is 90-95%.
In some preferred embodiments of the present invention, the operating mode of the ultrafiltration membrane module is: running for 35-50min, performing back washing and air scrubbing for 15-40s, and performing positive washing for 15-40s to form a cycle, and performing alkali liquor chemical cleaning after 18 cycles.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, in step S2, the turbidity of the ultrafiltration wastewater is less than 0.5 NTU; the pollution index (SDI) is less than 3.
In some preferred embodiments of the present invention, in step S2, the turbidity of the ultrafiltration wastewater is less than 0.3 NTU; the pollution index (SDI) is less than 2.5.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, in step S3, the ultrafiltration wastewater is adjusted to be acidic by hydrochloric acid or sulfuric acid.
In some preferred embodiments of the invention, the ultrafiltration waste water is adjusted to a pH of 2 to 5.
In some further preferred embodiments of the present invention, the ultrafiltration waste water is adjusted to a pH of 3 to 4.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, in step S3, the oxidant is at least one selected from chlorine, sodium hypochlorite, hydrogen peroxide or potassium permanganate.
In some preferred embodiments of the invention, the amount of the oxidizing agent is 100% to 125% by weight of the theoretical amount of oxidizing agent required for complete oxidation of bromine.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane is at least one selected from polyvinylidene fluoride (PVDF) hydrophobic membrane, Polytetrafluoroethylene (PTFE) hydrophobic membrane or polypropylene (PP) hydrophobic membrane.
In some preferred embodiments of the present invention, the hollow fiber hydrophobic membrane has an inner diameter of 0.5 to 3 nm.
In some further preferred embodiments of the present invention, the hollow fiber hydrophobic membrane has an inner diameter of 1 to 2.5 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a wall thickness of 0.05 to 1 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a wall thickness of 0.3 to 1 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a porosity of 65-75%.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane component is of an internal pressure immersion type structure.
According to the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane component comprises a wastewater inlet, a wastewater outlet, an absorption liquid inlet and an absorption liquid outlet.
In some preferred embodiments of the present invention, the shell material of the hollow fiber hydrophobic membrane module is perchloroethylene (c-PVC), hard polyethylene (u-PVC) or stainless steel.
In some preferred embodiments of the present invention, the hollow fiber hydrophobic membrane module is sealed with an antioxidant adhesive and an antioxidant sealing ring.
In some preferred embodiments of the present invention, in step S4, the bromine-containing wastewater and the absorption liquid cross-flow through the hollow fiber hydrophobic membrane.
According to the method for recovering bromine from brominated butyl rubber industrial wastewater, in step S4, the absorbent is at least one selected from sodium hydroxide, sodium methoxide and sodium formate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts ultrafiltration, oxidation and membrane separation and absorption as main process steps, and compared with the traditional steam method, the method avoids the use of a large amount of steam and greatly reduces the energy consumption;
(2) the use and waste of organic solvent caused by similar extraction method are avoided, the integral recovery cost is greatly reduced, and great economic benefit and environmental protection benefit are achieved;
(3) the waste water is directly treated at high temperature by using a temperature-resistant ultrafiltration membrane, so that the heat loss caused by the temperature reduction of the waste water at the front end in the conventional method is avoided, and the temperature of the waste water is always kept at a higher temperature because the temperature reduction treatment is not needed during the extraction, thereby accelerating the speed of the subsequent oxidation process on one hand, and saving the heating energy consumption in the process of extracting bromine by membrane separation on the other hand;
(4) under the condition of exerting respective functions, all the process steps are combined to realize the recovery of bromine from the brominated butyl rubber industrial wastewater, and the aim of recycling bromine in the wastewater is fulfilled;
(5) the device can be integrated, the occupied area is relatively small, the operation is convenient, and the manual management cost is low.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a schematic process flow diagram according to some embodiments of the invention. In the figures, the reference numerals have the following meanings:
1-a temperature stabilizing water tank; 2-a multi-media filter; 3-an ultrafiltration membrane module; 4-acidifying the oxidation water tank; 5-a hollow fiber hydrophobic membrane module; 6-evaporative crystallization unit; 7-a sludge tank;
brominating butyl rubber bromine-containing wastewater; secondly, wastewater is pretreated; ③ ultrafiltering the wastewater; fourthly, bromine-containing waste water; containing bromide solution; sixthly, bromine-containing solid salt; seventhly, absorbing liquid; eighthly, extracting bromine from the wastewater; ninthly, large particle suspended matters and organic matters; backwash water for the multimedia filter on r;backwashing water of the ultrafiltration membrane module.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
In view of the technical problems of high energy consumption, high cost, environmental pollution, high energy loss and the like of the conventional bromine-containing wastewater treatment process, the inventor of the invention finds that the bromine-containing wastewater of the brominated butyl rubber is comprehensively utilized by adopting ultrafiltration, oxidation and membrane separation and absorption as main process steps, thereby avoiding the mass use of steam, greatly reducing the energy consumption, avoiding the use and waste of organic solvents caused by similar extraction methods, greatly reducing the overall recovery cost and having great economic benefit and environmental protection benefit; meanwhile, the waste water is directly treated at high temperature by using the temperature-resistant ultrafiltration membrane, so that the heat loss caused by the front-end temperature reduction of the conventional method is avoided, and the waste water temperature is always maintained at a higher temperature because the temperature reduction treatment is not needed during the extraction, thereby accelerating the speed of the subsequent oxidation process on one hand, and saving the heating energy consumption in the process of extracting bromine by membrane separation on the other hand. The present invention has been made based on the above findings.
Therefore, the invention relates to a comprehensive utilization method of brominated butyl rubber bromine-containing wastewater, which comprises the following steps:
s1, mixing the brominated butyl rubber bromine-containing wastewater with backwashing water of a multi-media filter and backwashing water of an ultrafiltration membrane component in a stable water tank, then feeding the mixture into the multi-media filter, adding a coagulant, and removing large suspended solids and organic pollutants to obtain pretreated wastewater;
s2, filtering the pretreated wastewater by an ultrafiltration membrane component to remove micro particles to obtain ultrafiltration wastewater;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the acidification to acidity, adding an oxidant to perform oxidation reaction, and oxidizing free bromine into bromine to obtain bromine-containing wastewater;
s4, allowing the bromine-containing wastewater to flow through a hollow fiber hydrophobic membrane component, allowing bromine to volatilize at the interface between the membrane and water, allowing the bromine to permeate through the hydrophobic membrane and be absorbed by absorption liquid to obtain a bromine-containing solution for recycling, and allowing the bromine-extracted wastewater to enter a conventional industrial wastewater treatment process.
In some preferred embodiments of the invention, the coagulant is Polyacrylamide (PAM) and/or polyaluminium chloride (PAC).
In some preferred embodiments of the present invention, the coagulant is used in an amount of 6 to 15ppm based on the volume of the brominated butyl rubber industrial wastewater,
in some further preferred embodiments of the present invention, the coagulant is used in an amount of 7 to 12ppm, based on the volume of the brominated butyl rubber industrial wastewater.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the ultrafiltration membrane is at least one selected from a heat-resistant polyvinylidene fluoride ultrafiltration membrane, a heat-resistant polyethersulfone ultrafiltration membrane, a ceramic membrane or a metal membrane.
In some preferred embodiments of the present invention, the ultrafiltration membrane has a membrane pore size of 0.01 to 0.1 μm and a wall thickness of 0.5 to 1 nm.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the filling rate of the ultrafiltration membrane component is 50-70%, and the membrane flux of the ultrafiltration membrane component is 25-45 L.m-2·h-1The water yield is 90-95%.
In some preferred embodiments of the present invention, the operating mode of the ultrafiltration membrane module is: running for 35-50min, performing back washing and air scrubbing for 15-40s, and performing positive washing for 15-40s to form a cycle, and performing alkali liquor chemical cleaning after 18 cycles.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, in step S2, the turbidity of the ultrafiltration wastewater is less than 0.5 NTU; the pollution index (SDI) is less than 3.
In some preferred embodiments of the present invention, in step S2, the ultrafiltration wastewater has a turbidity of less than 0.3NTU and a contamination index (SDI) of less than 2.5.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, in step S3, hydrochloric acid or sulfuric acid is used to adjust the ultrafiltration wastewater to be acidic.
In some preferred embodiments of the invention, the ultrafiltration waste water is adjusted to a pH of 2 to 5.
In some further preferred embodiments of the present invention, the ultrafiltration waste water is adjusted to a pH of 3 to 4.
In the above comprehensive utilization method of brominated butyl rubber bromine-containing wastewater, in step S3, the oxidant is at least one selected from chlorine, sodium hypochlorite, hydrogen peroxide or potassium permanganate.
In some preferred embodiments of the invention, the amount of the oxidizing agent is 100% to 125% by weight of the theoretical amount of oxidizing agent required for complete oxidation of bromine.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane is at least one selected from polyvinylidene fluoride (PVDF) hydrophobic membrane, Polytetrafluoroethylene (PTFE) hydrophobic membrane or polypropylene (PP) hydrophobic membrane.
In some preferred embodiments of the present invention, the hollow fiber hydrophobic membrane has an inner diameter of 0.5 to 3 nm.
In some further preferred embodiments of the present invention, the hollow fiber hydrophobic membrane has an inner diameter of 1 to 2.5 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a wall thickness of 0.05 to 1 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a wall thickness of 0.3 to 1 nm.
In some preferred embodiments of the invention, the hollow fiber hydrophobic membrane has a porosity of 65-75%.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane component is of an internal pressure immersion type structure.
In the comprehensive utilization method of the brominated butyl rubber bromine-containing wastewater, the hollow fiber hydrophobic membrane component comprises a wastewater inlet, a wastewater outlet, an absorption liquid inlet and an absorption liquid outlet.
In some preferred embodiments of the present invention, the shell material of the hollow fiber hydrophobic membrane module is perchloroethylene (c-PVC), hard polyethylene (u-PVC) or stainless steel.
In some preferred embodiments of the present invention, the hollow fiber hydrophobic membrane module is sealed with an antioxidant adhesive and an antioxidant sealing ring.
In some preferred embodiments of the present invention, in step S4, the bromine-containing wastewater and the absorption liquid cross-flow through the hollow fiber hydrophobic membrane.
In the above comprehensive utilization method of brominated butyl rubber bromine-containing wastewater, in step S4, the absorbent is at least one selected from sodium hydroxide, sodium methoxide and sodium formate.
The relevant data in the embodiment of the invention are obtained according to the following test instruments and calculation methods:
(1) pH: adopting a WTW 3210pH meter;
(2) anion: adopting an ICS-2000 ion chromatograph of Thermo scientific;
(3) cation: adopting an ICS-5000 ion chromatograph of Thermo scientific;
(4) total Suspended Solids (TSS) test method: after the wastewater passes through the filter paper, weighing a solid filtered by the filter paper to obtain the wastewater;
(5) turbidity: a hash portable turbidimeter 2100P;
(6) contamination index (SDI): shanghai precision SDI-100 portable pollution index tester;
(7) water production rate is water production flow/water inflow.
Examples
Example 1
The analysis of the water quality data of the industrial wastewater generated by preparing brominated butyl rubber by a certain company as the raw water in the embodiment is shown in the following table 1:
TABLE 1
The comprehensive utilization method of brominated butyl rubber bromine-containing wastewater is adopted to treat the wastewater, and comprises the following specific steps:
s1, introducing the brominated butyl rubber bromine-containing wastewater into a temperature stabilizing water tank, mixing the brominated butyl rubber bromine-containing wastewater with backwash water of a multi-media filter and backwash water of an ultrafiltration membrane component, preserving the temperature, pumping the mixed water into the multi-media filter, adding 8ppm of PAC and 0.2ppm of PAM coagulant into each liter of brominated butyl rubber industrial wastewater, removing large-particle suspended matters and organic pollutants, and obtaining pretreated wastewater with the removal rate of COD reaching 65%;
s2, lifting the pretreated wastewater to an ultrafiltration membrane component by a pump for filtering; in this exampleThe heat-resistant PVDF hollow fiber ultrafiltration membrane external pressure type component with the average membrane pore diameter of 0.03 mu m and the wall thickness of 0.8nm is adopted, the component filling rate is 50 percent, the water production rate is 90 percent, and the working membrane flux is 35 L.m-2·h-1(ii) a Running for 40min, performing back flushing and air scrubbing for 30s, performing positive flushing for 30s to form a cycle, performing multi-cycle running to further remove micro particles to obtain ultrafiltration wastewater, wherein the turbidity is 0.16NTU, and the SDI is 2.4;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the pH of the ultrafiltration wastewater to 2.5 by hydrochloric acid, introducing chlorine gas as an oxidant for oxidation reaction, wherein the proportion of the chlorine gas is 110 wt%, and oxidizing free bromine into bromine to obtain bromine-containing wastewater; in the oxidation reaction process, the temperature of the wastewater in the acidification oxidation water tank is kept at 65 ℃;
s4, adopting saturated sodium hydroxide solution as absorption liquid, and preheating the absorption liquid to 40 ℃; a polytetrafluoroethylene hollow fiber membrane is adopted as an immersed membrane component, the inner diameter of the hollow fiber membrane is 2nm, the wall thickness is 0.5nm, and the porosity is 70%. The membrane component shell is made of c-PVC materials, the width is 15cm, the length is 100cm, and the filling density is 60%. Wastewater containing bromine flows through a hollow fiber hydrophobic membrane in a cross flow manner, bromine volatilizes at the interface of the membrane and water, permeates the hydrophobic membrane under the action of concentration gradient, and is absorbed and reacted by sodium hydroxide at the other side of the membrane to generate sodium bromide, so that an aqueous solution containing the sodium bromide is obtained and enters an evaporation crystallization unit for recovery; the wastewater after bromine extraction enters a conventional industrial wastewater treatment process.
Through the treatment process, the recovery rate of bromine is 87%, and the initial energy utilization rate of the wastewater is 64%.
Example 2
The water quality data of the brominated butyl rubber industrial wastewater used in this example are the same as those of example 1.
The comprehensive utilization method of brominated butyl rubber bromine-containing wastewater is adopted to treat the wastewater, and comprises the following specific steps:
s1, introducing the brominated butyl rubber bromine-containing wastewater into a temperature stabilizing water tank, mixing the brominated butyl rubber bromine-containing wastewater with backwash water of a multi-media filter and backwash water of an ultrafiltration membrane component, preserving the temperature, pumping the mixed water into the multi-media filter, adding 10ppm of PAC and 0.5ppm of PAM coagulant into each liter of brominated butyl rubber industrial wastewater, removing large suspended solids and organic pollutants, and obtaining pretreated wastewater with the removal rate of COD reaching 68%;
s2, lifting the pretreated wastewater to an ultrafiltration membrane component by a pump for filtering; in the example, a heat-resistant PES hollow fiber ultrafiltration membrane external pressure type component with the average membrane pore diameter of 0.05 mu m and the wall thickness of 0.6nm is adopted, the component filling rate is 65 percent, the water production rate is 93 percent, and the working membrane flux is 30 L.m-2·h-1(ii) a Running for 45min, performing back flushing and air wiping for 35s, performing positive flushing for 20s to form a cycle, and performing multi-cycle running to further remove micro particles to obtain ultrafiltration wastewater with turbidity of 0.22NTU and SDI of 1.8;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the pH of the ultrafiltration wastewater to 2 by hydrochloric acid, carrying out oxidation reaction by using sodium hypochlorite as an oxidant, wherein the amount of the oxidant is 120% of the theoretical amount of the oxidant required by complete oxidation of bromine, and oxidizing free bromine into bromine to obtain bromine-containing wastewater; in the oxidation reaction process, the temperature of the wastewater in the acidification oxidation water tank is kept at 60 ℃;
s4, adopting saturated sodium methoxide solution as absorption liquid, and preheating the absorption liquid to 40 ℃; the polyvinylidene fluoride hollow fiber membrane is used as an immersed membrane component, the inner diameter of the hollow fiber membrane is 1nm, the wall thickness is 0.3nm, and the porosity is 75%. The shell of the membrane component is made of u-PVC material, the width is 15cm, the length is 100cm, and the filling density is 60%. The wastewater containing bromine flows through a hollow fiber hydrophobic membrane in a cross flow manner, bromine volatilizes at the interface of the membrane and water, permeates the hydrophobic membrane under the action of concentration gradient, and is absorbed and reacted by sodium methoxide at the other side of the membrane to generate sodium bromide, so as to obtain an aqueous solution containing the sodium bromide, the aqueous solution is recycled, and the wastewater after bromine extraction enters a conventional industrial wastewater treatment process.
Through the treatment process, the recovery rate of bromine is 90%, and the initial energy utilization rate of the wastewater is 59%.
Example 3
The water quality data of the brominated butyl rubber industrial wastewater used in this example are the same as those of example 1.
The comprehensive utilization method of brominated butyl rubber bromine-containing wastewater is adopted to treat the wastewater, and comprises the following specific steps:
s1, introducing the brominated butyl rubber bromine-containing wastewater into a temperature stabilizing water tank, mixing the brominated butyl rubber bromine-containing wastewater with backwash water of a multi-media filter and backwash water of an ultrafiltration membrane component, preserving the temperature, pumping the mixed water into the multi-media filter, adding 7ppm of PAC and 1ppm of PAM coagulant into each liter of brominated butyl rubber industrial wastewater, removing large-particle suspended matters and organic pollutants, and obtaining pretreated wastewater with the removal rate of COD reaching 70%;
s2, lifting the pretreated wastewater to an ultrafiltration membrane component by a pump for filtering; in this example, a ceramic plate-type membrane module with an average membrane pore diameter of 0.05 μm was used, the water yield was 90%, and the flux of the working membrane was 40 L.m-2·h-1(ii) a Running for 35min, performing back flushing and air scrubbing for 20s, performing positive flushing for 30s to form a cycle, performing multi-cycle running to further remove micro particles to obtain ultrafiltration wastewater, wherein the turbidity is 0.18NTU, and the SDI is 1.9;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the pH of the ultrafiltration wastewater to 3 by hydrochloric acid, carrying out oxidation reaction by using hydrogen peroxide as an oxidant, wherein the amount of the oxidant is 100% of the theoretical amount of the oxidant required by complete oxidation of bromine, and oxidizing free bromine into bromine to obtain bromine-containing wastewater; in the oxidation reaction process, the temperature of the wastewater in the acidification oxidation water tank is kept at 55 ℃;
s4, adopting saturated sodium formate solution as absorption liquid, and preheating the absorption liquid to 40 ℃; the polypropylene hollow fiber membrane is used as an immersed membrane component, the inner diameter of the hollow fiber membrane is 1.5nm, the wall thickness is 0.5nm, and the porosity is 75%. The membrane component shell is made of stainless steel, the width of the membrane component shell is 15cm, the length of the membrane component shell is 100cm, and the filling density of the membrane component shell is 60%. Wastewater containing bromine flows through a hollow fiber hydrophobic membrane in a cross flow manner, bromine volatilizes at the interface of the membrane and water, permeates the hydrophobic membrane under the action of concentration gradient, and is absorbed and reacted by sodium formate at the other side of the membrane to generate sodium bromide, so that an aqueous solution containing the sodium bromide is obtained and recovered, and the wastewater after bromine extraction enters a conventional industrial wastewater treatment process.
Through the treatment process, the recovery rate of bromine is 84%, and the initial energy utilization rate of the wastewater is 62%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A comprehensive utilization method of brominated butyl rubber bromine-containing wastewater comprises the following steps:
s1, mixing the brominated butyl rubber bromine-containing wastewater with backwashing water of a multi-media filter and backwashing water of an ultrafiltration membrane component in a stable water tank, then feeding the mixture into the multi-media filter, adding a coagulant, and removing large suspended solids and organic pollutants to obtain pretreated wastewater;
s2, filtering the pretreated wastewater by a heat-resistant ultrafiltration membrane component to remove micro particles to obtain ultrafiltration wastewater;
s3, introducing the ultrafiltration wastewater into an acidification oxidation water tank, adjusting the acidification to acidity, adding an oxidant to perform oxidation reaction, and oxidizing free bromine into bromine to obtain bromine-containing wastewater;
s4, allowing the bromine-containing wastewater to flow through a hollow fiber hydrophobic membrane component, allowing the bromine to volatilize at the interface between the membrane and water, allowing the bromine to permeate through the hydrophobic membrane and be absorbed by an absorption liquid to obtain a bromine-containing salt solution for recycling, and allowing the bromine-extracted wastewater to enter a conventional industrial wastewater treatment process.
2. The method according to claim 1, characterized in that the coagulant is polyacrylamide and/or polyaluminium chloride; the dosage of the coagulant is 6-15ppm, preferably 7-12ppm based on the volume of the brominated butyl rubber industrial wastewater.
3. The method according to claim 1 or 2, wherein in step S2, the ultrafiltration membrane is selected from at least one of a heat-resistant polyvinylidene fluoride ultrafiltration membrane, a heat-resistant polyethersulfone ultrafiltration membrane, a ceramic membrane, or a metal membrane; preferably, the pore diameter of the ultrafiltration membrane is 0.01-0.1 μm, and the wall thickness of the ultrafiltration membrane is 0.5-1 nm.
4. The method according to any one of claims 1 to 3, wherein in step S2, the fill rate of the ultrafiltration membrane module is 50-70%; the membrane flux is 25-45 L.m-2·h-1(ii) a The water yield is 90-95%; and/or
The running mode of the ultrafiltration membrane component is as follows: running for 35-50min, performing back washing and air scrubbing for 15-40s, and performing positive washing for 15-40s to form a cycle, and performing alkali liquor chemical cleaning after 18 cycles.
5. The method according to any one of claims 1 to 4, wherein in step S2, the turbidity of the ultrafiltration wastewater is less than 0.5NTU, preferably less than 0.3 NTU; the fouling index is less than 3, preferably less than 2.5.
6. The method according to any one of claims 1 to 5, wherein in step S3, the ultrafiltration waste water is adjusted to acidity using hydrochloric acid or sulfuric acid; preferably, the ultrafiltration waste water is adjusted to pH 2 to 5, more preferably, the ultrafiltration waste water is adjusted to pH 3 to 4.
7. The method of any one of claims 1 to 6, wherein in step S3, the oxidant is selected from at least one of chlorine gas, sodium hypochlorite, hydrogen peroxide or potassium permanganate; the amount of the oxidant is 100 wt% -125 wt% of the theoretical amount of the oxidant required for complete oxidation of bromine.
8. The method according to any one of claims 1 to 7, wherein in step S4, the hollow fiber hydrophobic membrane is selected from at least one of polyvinylidene fluoride hydrophobic membrane, polytetrafluoroethylene hydrophobic membrane or polypropylene hydrophobic membrane; preferably, the hollow fiber hydrophobic membrane has an inner diameter of 0.2 to 3nm, preferably 1 to 2.5 nm; the wall thickness is 0.05-1nm, preferably 0.3-1 nm; the porosity is 65-75%.
9. The method according to any one of claims 1 to 8, wherein in step S4, the hollow fiber hydrophobic membrane module is an internal pressure submerged structure; the hollow fiber hydrophobic membrane component comprises a wastewater inlet, a wastewater outlet, an absorption liquid inlet and an absorption liquid outlet; preferably, the shell material of the hollow fiber hydrophobic membrane component is perchloroethylene, hard polyethylene or stainless steel; more preferably, the hollow fiber hydrophobic membrane component is sealed by antioxidant adhesive and antioxidant sealing ring.
10. The method according to any one of claims 1 to 9, wherein in step S4, the bromine-containing wastewater is cross-flowed with the absorption liquid through the hollow fiber hydrophobic membrane and/or the hollow fiber hydrophobic membrane
The absorbent of the absorption liquid is at least one selected from sodium hydroxide, sodium methoxide or sodium formate.
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| US4324665A (en) * | 1979-03-05 | 1982-04-13 | Ishihara Sangyo Kaisha, Ltd. | Process for recovering bromine from waste liquid |
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