CN116282692B - Recycling treatment method of bromine-containing wastewater of tail gas washing tower in production of refined terephthalic acid - Google Patents
Recycling treatment method of bromine-containing wastewater of tail gas washing tower in production of refined terephthalic acid Download PDFInfo
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 34
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005406 washing Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 131
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001223 reverse osmosis Methods 0.000 claims description 56
- 238000001728 nano-filtration Methods 0.000 claims description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000001471 micro-filtration Methods 0.000 claims description 44
- 238000000909 electrodialysis Methods 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 32
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 20
- 230000001105 regulatory effect Effects 0.000 claims description 20
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 6
- 230000005684 electric field Effects 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- -1 bromine ions Chemical class 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a recycling treatment method of bromine-containing wastewater of a tail gas washing tower in the production of refined terephthalic acid. The invention adopts a membrane technology to carry out resource treatment on bromine-containing wastewater of a tail gas washing tower in the production of the refined terephthalic acid, and the sodium bromide in the bromine-containing wastewater of the tail gas washing tower is recovered, and meanwhile, the water is also recycled; waste is changed into a safe; the production cost of the refined terephthalic acid is greatly reduced while the emission of pollution sources is reduced; has great environmental protection benefit and economic benefit. And a solution idea is provided for the recycling treatment of other bromine-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of industrial wastewater treatment, and particularly relates to a recycling treatment method of bromine-containing wastewater of a tail gas washing tower in the production of refined terephthalic acid.
Background
Refined terephthalic acid is an important raw material for producing polyester, and is mainly produced by a paraxylene air oxidation method at present. The tail gas generated in the air oxidation process of the paraxylene is subjected to washing and catalytic combustion to convert methyl bromide into HBr and Br2, and then the bromine-containing wastewater with higher concentration is obtained through alkaline washing. Typical components of the bromine-containing wastewater are: 500-2000ppm of bromine ions, 4500-18000ppm of carbonate/bicarbonate, 1600-6600ppm of sodium ions, trace acetic acid, formate, cobalt, manganese, alcohol, aldehyde and other components, and the purity of sodium bromide is 8-15%, thus having higher recovery value.
At present, bromine extraction methods comprise a steam distillation method, an air blowing method, an extraction method, an ion exchange adsorption method and the like after acidification and oxidation, and the principle is that bromine ions are oxidized into bromine simple substances by using chlorine or hydrogen peroxide and then extracted by a steam distillation method and an air blowing method. However, these extraction methods have a relatively large process limitation, and when wastewater contains a large amount of organic matters, organic solvents, ammonia nitrogen and inorganic mixed salts, the implementation of the above extraction process will be severely interfered. Therefore, based on the advantages and disadvantages of the technology and the water quality characteristics of the bromine-containing wastewater, no suitable bromine-containing wastewater recovery technology exists in the prior art, and the recycling treatment method is used in the refined terephthalic acid industry, namely, the bromine-containing wastewater directly enters a sewage treatment link, so that huge pressure is brought to environmental protection of enterprises, and certain resource waste is caused.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a recycling treatment method for bromine-containing wastewater of a tail gas washing tower in the production of refined terephthalic acid.
The technical scheme of the invention is as follows:
a recycling treatment method of bromine-containing wastewater of a tail gas washing tower in the production of refined terephthalic acid comprises the following steps:
(1) The pH value of the bromine-containing wastewater of the tail gas washing tower is adjusted to 8-13 to obtain an adjusting solution (the interception of the subsequent nanofiltration membrane to carbonate ions is higher than that of bicarbonate ions, the distribution conditions of carbonate ions and bicarbonate ions are different under different pH values, the higher the pH value is, the larger the ratio of carbonate ions is, the more favorable the nanofiltration membrane to the interception of carbonate ions is, and the bromide ions can effectively permeate the nanofiltration membrane to separate the bromide ions from the carbonate ions);
(2) Clarifying and filtering the regulating solution by using a microfiltration membrane with the filtering precision of 0.01-0.2um to remove insoluble matters in the regulating solution to obtain a microfiltration clear solution, wherein the microfiltration membrane has the operating pressure of 0.1-0.4MPa and the operating temperature of 25-60 ℃, and the microfiltration clear solution contains 500-2000ppm of bromide ions, 4500-18000ppm of carbonate/bicarbonate, 1600-6600ppm of sodium ions and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane by using a nanofiltration membrane system with the molecular weight cut-off of 100-800 daltons at 2-5 levels to obtain nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with the purity of more than or equal to 95%, wherein the operation pressure of the nanofiltration membrane system is 1.0-4.0MPa, the operation temperature is 25-45 ℃, and the purity of sodium bromide in the nanofiltration purified solution is more than or equal to 95%;
(4) Concentrating the nanofiltration purified solution by using a reverse osmosis membrane system at 1-2 levels to obtain reverse osmosis concentrated solution and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 3.0-6.3MPa, the operating temperature is 25-45 ℃, and the concentration of bromide ions in the reverse osmosis concentrated solution is not lower than 20000ppm and the purity of sodium bromide is not less than 98%;
(5) Concentrating the reverse osmosis concentrated solution by using an electrodialysis system to obtain an electrodialysis concentrated solution and an electrodialysis desalted solution, wherein the operation voltage of the electrodialysis system is 1.0-1.5V/pair of membranes, the concentration of bromide ions in the electrodialysis concentrated solution is not less than 80000ppm (and the purity of sodium bromide is not less than 98%).
(5) And (3) sending the electrodialysis concentrated solution into a bipolar membrane system, converting sodium bromide in the electrodialysis concentrated solution into hydrogen bromide and sodium hydroxide under the action of an electric field, wherein the operation voltage of the bipolar membrane system is 0.5-1.5V/pair of membranes, the concentration of sodium bromide in water inlet of the bipolar membrane system is controlled to be 1-1.5mol/L, and the concentration of Na 2SO4 in electrolyte is controlled to be 0.2-0.3mol/L.
In a preferred embodiment of the present invention, the microfiltration membrane in the microfiltration membrane system comprises at least one of a ceramic microfiltration membrane, a hollow microfiltration membrane and an organic tubular microfiltration membrane.
Further preferably, the microfiltration membrane in the microfiltration membrane system is a ceramic microfiltration membrane with a filtration precision of 0.1um or a hollow microfiltration membrane with a filtration precision of 0.2 um.
In a preferred embodiment of the invention, the nanofiltration membrane of the nanofiltration membrane system has a molecular weight cut-off of 200-400 daltons.
Further preferably, the nanofiltration membrane system has a number of stages of 3.
In a preferred embodiment of the invention, each stage of reverse osmosis membrane in the reverse osmosis membrane system is a 6-cartridge 4040 normal reverse osmosis membrane concentrate or a 6-cartridge 4040 anti-fouling high pressure resistant specialty reverse osmosis membrane concentrate. The common reverse osmosis has common pollution resistance and low tolerance pressure (the maximum tolerance pressure is 4.0 MPa), and is commonly used for concentrating low-concentration feed liquid; the special reverse osmosis has good pollution resistance and high tolerance pressure (the maximum tolerance pressure is 8.3 MPa), and is commonly used for concentrating high-concentration feed liquid.
Further preferably, the reverse osmosis membrane system has a stage number of 2.
In a preferred embodiment of the invention, the concentration of bromide ions in the electrodialysis concentrate is not less than 100000ppm.
In a preferred embodiment of the invention, the electrodialysis system employs a homogeneous or heterogeneous membrane and the bipolar membrane system employs a homogeneous or heterogeneous membrane.
Further preferably, the electrodialysis system employs homogeneous membranes with an operating voltage of 1.0V/pair of membranes.
Further preferably, the bipolar membrane system employs a homogeneous membrane with an operating voltage of 1.0V/pair of membranes.
In a preferred embodiment of the present invention, the step (1) is: and (3) regulating the pH value of the bromine-containing wastewater of the tail gas washing tower to 9-12 to obtain a regulating solution.
The beneficial effects of the invention are as follows:
1. The invention adopts a membrane technology to carry out resource treatment on bromine-containing wastewater of a tail gas washing tower in the production of the refined terephthalic acid, and the sodium bromide in the bromine-containing wastewater of the tail gas washing tower is recovered, and meanwhile, the water is also recycled; waste is changed into a safe; the production cost of the refined terephthalic acid is greatly reduced while the emission of pollution sources is reduced; has great environmental protection benefit and economic benefit. And a solution idea is provided for the recycling treatment of other bromine-containing wastewater.
2. The specific parameter limitation of the bipolar membrane system in the invention cooperates with other technical characteristics to obtain low energy consumption and higher current efficiency, the concentration of the recovered hydrogen bromide and sodium hydroxide can reach 1mol/L, and the purity is more than or equal to 98%.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
FIG. 2 is a schematic diagram of process equipment used in an embodiment of the present invention.
Detailed Description
The technical scheme of the invention is further illustrated and described below by the specific embodiments in combination with the accompanying drawings.
Example 1
As shown in fig. 1 and 2, the recycling treatment method of bromine-containing wastewater of the tail gas washing tower in the production of the purified terephthalic acid comprises the following steps:
(1) Regulating pH of bromine-containing wastewater (780 ppm of bromide ions, 6677ppm of carbonate/bicarbonate, 2425ppm of sodium ions, trace acetic acid, formate, cobalt, manganese, alcohol, aldehyde and other components, and sodium bromide purity of 14.2%) of a 5m 3 tail gas washing tower to 8.3 in a storage tank by using 30-32% liquid alkali to obtain a regulating solution;
(2) Clarifying and filtering the regulating solution with an organic tubular microfiltration membrane with a filtering precision of 0.01um to remove insoluble substances (including solid suspended substances and colloid) to obtain a microfiltration clear solution, wherein the microfiltration clear solution has an operating pressure of 0.13MPa and an operating temperature of 28 ℃, and contains 765ppm of bromide ions, 6670ppm of carbonate/bicarbonate, 2420ppm of sodium ions and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane with a nanofiltration membrane system with a molecular weight cut-off of 120 daltons at 2 levels (each level is provided with a nanofiltration membrane of 4040 on 6 cores), obtaining nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with a purity of 95.3%, wherein the operation pressure of the nanofiltration membrane system is 1.5MPa, the operation temperature is 33 ℃, and the purity of sodium bromide in the nanofiltration purified solution is 95.6%;
(4) Concentrating the nanofiltration purified liquid by a reverse osmosis membrane system at 1 level (each level is a common reverse osmosis membrane with 6 cores of 4040-BW 30X), obtaining reverse osmosis concentrated liquid and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 3.8MPa, the operating temperature is 35 ℃, the concentration of bromide ions in the reverse osmosis concentrated liquid is 18860ppm, the purity of sodium bromide is 95.6%, and the conductivity of the reverse osmosis dialyzate is 45us/cm, so that the reverse osmosis dialyzate can be used as equipment flushing water in daily production;
(5) Concentrating the reverse osmosis concentrated solution by an electrodialysis system (adopting a heterogeneous membrane) to obtain electrodialysis concentrated solution and desalted solution, wherein the electrodialysis concentrated solution has an operation voltage of 1.5V/pair of membrane, the concentration of bromide ions in the electrodialysis concentrated solution is 82860ppm, and the purity of sodium bromide is 96.1%;
(6) The electrodialysis concentrated solution is sent into a bipolar membrane system (heterogeneous membrane is adopted), sodium bromide in the electrodialysis concentrated solution is converted into hydrogen bromide and sodium hydroxide under the action of an electric field, the operation voltage of the bipolar membrane system is 0.5V/pair of membranes, the concentration of sodium bromide in water is 1.0mol/L, the concentration of Na 2SO4 in electrolyte is 0.2mol/L, and hydrogen bromide solution with the molar concentration of 1.02mol/L and the purity of 98.2% and sodium hydroxide solution with the molar concentration of 1.03mol/L and the purity of 98.1% are prepared, and the hydrogen bromide solution and the sodium hydroxide solution can be returned to production for use.
Example 2
As shown in fig. 1 and 2, the recycling treatment method of bromine-containing wastewater of the tail gas washing tower in the production of the purified terephthalic acid comprises the following steps:
(1) The pH value of bromine-containing wastewater (540 ppm of bromide ions, 5088ppm of carbonate/bicarbonate, 1820ppm of sodium ions, trace acetic acid, formate, cobalt, manganese, alcohol, aldehyde and other components of a 5m 3 tail gas washing tower, and the purity of sodium bromide is 8.5%) is adjusted to 10.5 by 30-32% liquid alkali in a storage tank, so as to obtain an adjusting solution;
(2) Clarifying and filtering the regulating solution by using a ceramic microfiltration membrane with the filtering precision of 0.1um to remove insoluble substances (including solid suspended substances and colloid) to obtain a microfiltration clear solution, wherein the microfiltration clear solution has the operating pressure of 0.28MPa and the operating temperature of 56 ℃, and contains 536ppm of bromide ions, 5055ppm of carbonate/bicarbonate, 1810ppm of sodium ions and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane with a nanofiltration membrane system with a molecular weight cut-off of 250 daltons at 3 levels (each level is provided with a nanofiltration membrane of 4040 on 6 cores), obtaining nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with a purity of 95.8%, wherein the operation pressure of the nanofiltration membrane system is 3.5MPa, the operation temperature is 28 ℃, and the purity of sodium bromide in the nanofiltration purified solution is 95.8%;
(4) Concentrating the nanofiltration purified solution by a reverse osmosis membrane system at 2 levels (each level is formed by concentrating a special reverse osmosis membrane with 6 cores of 4040-SW30XFR, pollution resistance and high pressure resistance), so as to obtain reverse osmosis concentrated solution and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 4.0MPa, the operating temperature is 41 ℃, the concentration of bromide ions in the reverse osmosis concentrated solution is 22620ppm, the purity of sodium bromide is 95.8%, and the conductivity of the reverse osmosis dialyzate is 39us/cm, so that the reverse osmosis dialyzate can be used as equipment flushing water in daily production;
(5) Concentrating the reverse osmosis concentrated solution by an electrodialysis system (adopting a heterogeneous membrane) to obtain electrodialysis concentrated solution and desalted solution, wherein the electrodialysis concentrated solution has an operation voltage of 1.0V/pair of membrane, the concentration of bromide ions in the electrodialysis concentrated solution is 96820ppm, and the purity of sodium bromide is 95.2%;
(6) The electrodialysis concentrated solution is sent into a bipolar membrane system (heterogeneous membrane is adopted), sodium bromide in the electrodialysis concentrated solution is converted into hydrogen bromide and sodium hydroxide under the action of an electric field, the operation voltage of the bipolar membrane system is 1.5V/pair of membranes, the concentration of sodium bromide in water is 1.2mol/L, the concentration of Na 2SO4 in electrolyte is 0.3mol/L, and hydrogen bromide solution with the molar concentration of 1.05mol/L and the purity of 98.5% and sodium hydroxide solution with the molar concentration of 1.03mol/L and the purity of 98.1% are prepared, and the hydrogen bromide solution and the sodium hydroxide solution can be returned to production for use.
Example 3
As shown in fig. 1 and 2, the recycling treatment method of bromine-containing wastewater of the tail gas washing tower in the production of the purified terephthalic acid comprises the following steps:
(1) Regulating pH of bromine-containing wastewater (1340 ppm of bromide ions, 12380ppm of carbonate/bicarbonate, 4520ppm of sodium ions, trace acetic acid, formate, cobalt, manganese, alcohol, aldehyde and other components, sodium bromide purity 11.3%) of a 5m 3 tail gas washing tower to 9.5 in a storage tank by using 30-32% liquid alkali to obtain a regulating solution;
(2) Clarifying and filtering the regulating solution by using a hollow microfiltration membrane with the filtering precision of 0.2um to remove insoluble substances (including solid suspended substances and colloid) to obtain a microfiltration clear solution, wherein the microfiltration clear solution has the operating pressure of 0.35MPa and the operating temperature of 55 ℃, and contains 1335ppm of bromide ions, 12300ppm of carbonate/bicarbonate, 4503ppm of sodium ions and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane with a nanofiltration membrane system with a molecular weight cut-off of 500 daltons at 4 levels (each level is provided with a nanofiltration membrane of 4040 on 6 cores), obtaining nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with a purity of 95.5%, wherein the operation pressure of the nanofiltration membrane system is 3.2MPa, the operation temperature is 37 ℃, and the purity of sodium bromide in the nanofiltration purified solution is 95.2%;
(4) Concentrating the nanofiltration purified liquid by a reverse osmosis membrane system at 2 levels (each level is formed by concentrating a special reverse osmosis membrane with 6 cores of 4040-SW30XFR, pollution resistance and high pressure resistance), so as to obtain reverse osmosis concentrated liquid and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 4.8MPa, the operating temperature is 28 ℃, the concentration of bromide ions in the reverse osmosis concentrated liquid is 25032ppm, the purity of sodium bromide is 95.2%, and the conductivity of the reverse osmosis dialyzate is 42us/cm, so that the reverse osmosis dialyzate can be used as equipment flushing water in daily production;
(5) Concentrating the reverse osmosis concentrated solution by an electrodialysis system (adopting a homogeneous membrane) to obtain electrodialysis concentrated solution and desalted solution, wherein the electrodialysis concentrated solution has an operation voltage of 1.0V/pair of membrane, the concentration of bromide ions in the electrodialysis concentrated solution is 100140ppm, and the purity of sodium bromide is 98.7%;
(6) The electrodialysis concentrated solution is sent into a bipolar membrane system (adopting a homogeneous membrane), sodium bromide in the electrodialysis concentrated solution is converted into hydrogen bromide and sodium hydroxide under the action of an electric field, the operation voltage of the bipolar membrane system is 1.5V/pair of membranes, the concentration of sodium bromide in water is 1.2mol/L, the concentration of Na 2SO4 in electrolyte is 0.3mol/L, and hydrogen bromide solution with the molar concentration of 1.33mol/L and the purity of 98.7% and sodium hydroxide solution with the molar concentration of 1.38mol/L and the purity of 98.6% are prepared, and the hydrogen bromide solution and the sodium hydroxide solution can be returned to production for use.
Example 4
As shown in fig. 1 and 2, the recycling treatment method of bromine-containing wastewater of the tail gas washing tower in the production of the purified terephthalic acid comprises the following steps:
(1) Regulating pH of bromine-containing wastewater (970 ppm of bromide ions, 9119ppm of carbonate/bicarbonate radicals, 3201ppm of sodium ions, trace acetic acid, formate, cobalt, manganese, alcohol, aldehyde and other components of a 5m 3 tail gas washing tower with sodium bromide purity of 10.3%) to 12 in a storage tank by using 30-32% liquid alkali to obtain a regulating solution;
(2) Clarifying and filtering the regulating solution with ceramic microfiltration membrane with 0.1um filtration precision to remove insoluble substances (including solid suspended substances and colloid) to obtain microfiltration clear solution, wherein the microfiltration clear solution has an operation pressure of 0.23MPa and an operation temperature of 37 ℃, and contains 962ppm of bromide ion, 9110ppm of carbonate/bicarbonate, 3186ppm of sodium ion and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane with a nanofiltration membrane system with a molecular weight cut-off of 300 daltons at 4 levels (each level is provided with a nanofiltration membrane of 4040 on 6 cores), obtaining nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with a purity of more than or equal to 95.8%, wherein the operation pressure of the nanofiltration membrane system is 1.9MPa, the operation temperature is 38 ℃, and the purity of sodium bromide in the nanofiltration purified solution is 96.8%;
(4) Concentrating the nanofiltration purified solution by a reverse osmosis membrane system at 2 levels (each level is formed by concentrating a special reverse osmosis membrane with 6 cores of 4040-SW30XFR, pollution resistance and high pressure resistance), so as to obtain reverse osmosis concentrated solution and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 4.8MPa, the operating temperature is 35 ℃, the concentration of bromide ions in the reverse osmosis concentrated solution is 26514ppm, the purity of sodium bromide is 96.8%, and the conductivity of the reverse osmosis dialyzate is 37us/cm, so that the reverse osmosis dialyzate can be used as equipment flushing water in daily production;
(5) Concentrating the reverse osmosis concentrated solution by an electrodialysis system (adopting a homogeneous membrane) to obtain electrodialysis concentrated solution and desalted solution, wherein the electrodialysis concentrated solution has an operation voltage of 1.0V/pair of membrane, the concentration of bromide ions in the electrodialysis concentrated solution is 121140ppm, and the purity of sodium bromide is 98.2%;
(6) The electrodialysis concentrated solution is sent into a bipolar membrane system (adopting a homogeneous membrane), sodium bromide in the electrodialysis concentrated solution is converted into hydrogen bromide and sodium hydroxide under the action of an electric field, the operation voltage of the bipolar membrane system is 1.0V/pair of membranes, the concentration of sodium bromide in water is 1.5mol/L, the concentration of Na 2SO4 in electrolyte is 0.3mol/L, and hydrogen bromide solution with the molar concentration of 1.30mol/L and the purity of 99.1% and sodium hydroxide solution with the molar concentration of 1.28mol/L and the purity of 98.9% are prepared, and the hydrogen bromide solution and the sodium hydroxide solution can be returned to production for use.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Claims (8)
1. A recycling treatment method of bromine-containing wastewater of a tail gas washing tower in the production of refined terephthalic acid is characterized by comprising the following steps: the method comprises the following steps:
(1) Regulating the pH value of the bromine-containing wastewater of the tail gas washing tower to 8-13 to obtain a regulating solution;
(2) Clarifying and filtering the regulating solution by using a microfiltration membrane with the filtering precision of 0.01-0.2um to remove insoluble matters in the regulating solution to obtain a microfiltration clear solution, wherein the microfiltration membrane has the operating pressure of 0.1-0.4MPa and the operating temperature of 25-60 ℃, and the microfiltration clear solution contains 500-2000ppm of bromide ions, 4500-18000ppm of carbonate/bicarbonate, 1600-6600ppm of sodium ions and trace amounts of acetic acid, formate, cobalt, manganese, alcohol and aldehyde;
(3) Purifying the clear solution of the microfiltration membrane by using a nanofiltration membrane system with the molecular weight cut-off of 200-400 daltons at 2-5 levels to obtain nanofiltration purified solution and nanofiltration concentrated solution, evaporating and concentrating the nanofiltration concentrated solution to obtain sodium carbonate solid with the purity of more than or equal to 95%, wherein the operation pressure of the nanofiltration membrane system is 1.0-4.0MPa, the operation temperature is 25-45 ℃, and the purity of sodium bromide in the nanofiltration purified solution is more than or equal to 95%;
(4) Concentrating the nanofiltration purified liquid by using a reverse osmosis membrane system at 1-2 levels to obtain reverse osmosis concentrated liquid and reverse osmosis dialyzate, wherein the operating pressure of the reverse osmosis membrane system is 3.0-6.3MPa, the operating temperature is 25-45 ℃, the concentration of bromide ions in the reverse osmosis concentrated liquid is not lower than 20000ppm, the purity of sodium bromide is not lower than 98%, and the conductivity of the reverse osmosis dialyzate is less than 50us/cm;
(5) Concentrating the reverse osmosis concentrated solution by using an electrodialysis system to obtain an electrodialysis concentrated solution and an electrodialysis desalted solution, wherein the operation voltage of the electrodialysis system is 1.0-1.5V/pair of membranes, the concentration of bromide ions in the electrodialysis concentrated solution is not less than 80000ppm, and the purity of sodium bromide is not less than 98%;
(6) And (3) sending the electrodialysis concentrated solution into a bipolar membrane system, converting sodium bromide in the electrodialysis concentrated solution into hydrogen bromide and sodium hydroxide under the action of an electric field, wherein the operation voltage of the bipolar membrane system is 0.5-1.5V/pair of membranes, the concentration of sodium bromide in water inlet of the bipolar membrane system is controlled to be 1-1.5mol/L, and the concentration of Na 2SO4 in electrolyte is controlled to be 0.2-0.3mol/L.
2. The recycling method according to claim 1, wherein: the microfiltration membrane in the microfiltration membrane system comprises at least one of a ceramic microfiltration membrane, a hollow microfiltration membrane and an organic tube type microfiltration membrane.
3. The recycling method according to claim 2, wherein: the microfiltration membrane in the microfiltration membrane system is a ceramic microfiltration membrane with the filtration precision of 0.1um or a hollow microfiltration membrane with the filtration precision of 0.2 um.
4. The recycling method according to claim 1, wherein: the number of stages of the nanofiltration membrane system is 3.
5. The recycling method according to claim 1, wherein: the electrodialysis system adopts a homogeneous membrane or a heterogeneous membrane, and the bipolar membrane system adopts a homogeneous membrane or a heterogeneous membrane.
6. The recycling method according to claim 5, wherein: the electrodialysis system adopts a homogeneous membrane, and the operation voltage is 1.0V/pair of membrane.
7. The recycling method according to claim 5, wherein: the bipolar membrane system adopts a homogeneous membrane, and the operating voltage is 1.0V/pair of membrane.
8. The recycling process according to any one of claims 1 to 7, characterized in that: the step (1) is as follows: and (3) regulating the pH value of the bromine-containing wastewater of the tail gas washing tower to 9-12 to obtain a regulating solution.
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