Bromine-containing liquid treatment system

Abstract

The utility model discloses a bromine-containing liquid treatment system, which comprises a bromine-containing liquid discharge port, a nanofiltration membrane group, monovalent ion separation type electrodialysis equipment, an evaporator or an adsorption tank, and an acid adding tank or an oxidation tank, the bromine-containing liquid is treated by the system, the bromine element in the bromine-containing liquid is extracted to become a product, and the product is recycled. The value of the bromine element is obtained.

Description

Technical Field

[0001] The utility model belongs to the technical field of liquid processing, and in particular relates to a processing system for bromine-containing liquid. Background Art

[0002] For some bromine-containing liquids (including bromine-containing slurries), the bromine element is not a pure substance and cannot be used as a product because it contains other components. If there is a system or equipment that can be used to process the bromine-containing liquid and extract the bromine element from it to turn it into a product, the value of the bromine element can be obtained. Utility Model Content

[0003] The utility model aims to provide a bromine-containing liquid processing system. The bromine-containing liquid (including bromine-containing slurry) is processed by the processing system to generate benefits of recycling and reusing bromine elements.

[0004] A treatment system for bromine-containing liquid, characterized in that the treatment system comprises: a discharge port for bromine-containing liquid, a nanofiltration membrane group, an electrodialysis device for separating monovalent ions, an evaporator or an adsorption tank, and an acid addition tank or an oxidation tank;

[0005] The discharge port of the bromine-containing liquid is connected to the feed port of the nanofiltration membrane group;

[0006] The nanofiltration membrane group mainly includes a nanofiltration membrane. The nanofiltration membrane is a device that separates monovalent ions and polyvalent ions in a solution under pressure (using a high-pressure pump, so a high-pressure pump must be provided before the nanofiltration membrane to provide power). For inorganic substances, the nanofiltration membrane allows monovalent ions to pass through the nanofiltration membrane and intercepts divalent and higher valent ions. Therefore, after passing through the nanofiltration membrane group, nanofiltration membrane fresh water rich in monovalent ions and nanofiltration membrane concentrated water rich in divalent and higher valent ions will be obtained; for example, if we want to separate sodium bromide and sodium carbonate, after treatment with the nanofiltration membrane, the nanofiltration membrane fresh water is rich in sodium bromide, and the nanofiltration membrane concentrated water is rich in sodium carbonate (sodium carbonate aqueous solution Users of sodium carbonate can use it as sodium carbonate. For example, the PTA industry uses sodium carbonate as a precipitant for the recovery of cobalt ions and manganese ions and as a dissolving agent for oxidation residues. This achieves the separation of monovalent bromide ions and divalent carbonate ions. However, the fresh water and concentrated water of the nanofiltration membrane are electrically neutral, so the sodium ion concentration is paired with the charge concentration of the anions in the fresh water and concentrated water of the nanofiltration membrane; or for example, the monovalent cations and divalent cations are separated by the nanofiltration membrane. The fresh water of the nanofiltration membrane is rich in monovalent cations, and the concentrated water of the nanofiltration membrane is rich in divalent cations. The anion concentration is paired with the charge concentration of the respective cations in the fresh water and concentrated water of the nanofiltration membrane;

[0007] or the discharge port of the bromine-containing liquid is connected to the feed port of the electrodialysis device for separating monovalent ions;

[0008] The electrodialysis equipment for separating monovalent ions refers to a new type of electrodialysis equipment with special functions derived from conventional electrodialysis equipment, which can obtain a salt solution mainly composed of monovalent cations and monovalent anions from the water outlet I from an aqueous solution containing monovalent ions, divalent or more ions in the inlet water, and can also have a concentration effect; its main working principle is to introduce a monovalent cation selective permeable membrane, a monovalent anion selective permeable membrane or a nanofiltration membrane into the anion selective permeable membrane and the cation selective permeable membrane of conventional electrodialysis according to needs and the ion characteristics of the inlet water. The monovalent cation selective permeable membrane theoretically only allows monovalent cations to pass through, the monovalent anion selective permeable membrane theoretically only allows monovalent anions to pass through, and the nanofiltration membrane theoretically only allows monovalent cations and monovalent anions to pass through; for example, if there is sodium carbonate and sodium bromide in the water, then the cation selective permeable membrane is used. + monovalent anion selective permeable membrane, or cation selective permeable membrane + nanofiltration membrane composed of a membrane stack corresponding to the monovalent ion separation type electrodialysis equipment (Note, the principle of ion permeation of each membrane is the same as conventional electrodialysis, the difference is that carbonate among anions is a divalent anion and cannot pass through the monovalent anion selective permeable membrane and nanofiltration membrane, only bromide ion is a monovalent anion that can pass through, so the anions that pass through the monovalent anion selective permeable membrane and nanofiltration membrane are only bromide ions, so combined with sodium ions that pass through the cation selective permeable membrane, only sodium bromide aqueous solution is obtained at the water outlet I), then the water outlet I is mainly sodium bromide aqueous solution, and the other outlet (i.e., water outlet II) is mainly sodium carbonate aqueous solution, which also contains a small amount of sodium bromide (it can be used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for the recovery of cobalt ions and manganese ions and as a dissolving agent for oxidation residues);

[0009] Or the discharge port of the bromine-containing liquid is connected to the feed port of the evaporator, and the outlet of the evaporator (referring to the material outlet, not the water vapor outlet) is connected to the feed port of the solid-liquid separation device;

[0010] When the bromine-containing liquid contains sodium carbonate and / or sodium bicarbonate, as well as sodium bromide, after the concentration of the concentrated salt is increased by the evaporator, the sodium carbonate (including sodium carbonate + carbon dioxide generated in the heating process of sodium bicarbonate, carbon dioxide escapes into the air and is discharged, and the remaining sodium carbonate is in the solution) has a relatively low solubility and will first precipitate into a solid, and be filtered and removed by the solid-liquid separation equipment (it can be used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for the recovery of cobalt ions and manganese ions and as a dissolving agent for oxidation residues), and the filtrate of the solid-liquid separation equipment is mainly sodium bromide;

[0011] Or the discharge port of the bromine-containing liquid is connected to the feed port of the evaporator, the outlet of the evaporator (referring to the material outlet, not the water vapor outlet) is connected to the feed port of the cooling unit, and the outlet of the cooling unit is connected to the feed port of the solid-liquid separation device;

[0012] When the bromine-containing liquid contains sodium carbonate and / or sodium bicarbonate, as well as sodium bromide, after the concentration of the concentrated salt is increased by the evaporator, the solubility of sodium carbonate (including sodium carbonate + carbon dioxide generated in the heating process of sodium bicarbonate, carbon dioxide escapes into the air and is discharged, and the remaining sodium carbonate is in the solution) is relatively low. When the temperature is lowered, the solubility of sodium bromide does not change significantly, but the solubility of sodium carbonate will drop sharply and accelerate precipitation, and then filtered and removed by the solid-liquid separation equipment (it can be used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for the recovery of cobalt ions and manganese ions and as a dissolving agent for oxidation residues), and the filtrate of the solid-liquid separation equipment is mainly sodium bromide;

[0013] Or the discharge port of the bromine-containing liquid is connected to the feed port of the adsorption tank, and the adsorption tank is also provided with a discharge port, a regeneration liquid inlet, and a regeneration liquid outlet;

[0014] The adsorption tank is filled with a filler having an adsorption capacity for bromine, preferably a resin, to adsorb bromine, so that the bromine concentration after passing through the adsorption tank is greatly reduced, and the bromine adsorbed on the resin is regenerated through a regeneration process (preferably using a sodium hydroxide aqueous solution) to obtain an aqueous solution containing sodium bromide (i.e., the aqueous solution at the regeneration liquid outlet is mainly sodium bromide);

[0015] When the bromine-containing liquid contains sodium carbonate and / or sodium bicarbonate, as well as sodium bromide, the bromine element is absorbed by the adsorption tank, and the remaining liquid discharged from the discharge port of the adsorption tank can be used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for recovering cobalt ions and manganese ions and as a dissolving agent for oxidized residues; or the liquid discharged from the discharge port of the adsorption tank is added with sodium hydroxide (to convert sodium bicarbonate into sodium carbonate) and then used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for recovering cobalt ions and manganese ions and as a dissolving agent for oxidized residues;

[0016] The fresh water outlet of the nanofiltration membrane group, the water outlet I of the electrodialysis device for separating monovalent ions, the liquid outlet of the solid-liquid separation device or the regeneration liquid outlet of the adsorption tank (all of which are aqueous solutions containing sodium bromide) are connected to the feed port of the acid addition tank or the feed port of the oxidation tank, and the oxidation tank is also provided with an oxidant feed port;

[0017] The acid adding tank is also provided with an acid inlet, and a non-volatile acid such as sulfuric acid or phosphoric acid is preferably added to the acid inlet to react the bromide ions into volatile HBr;

[0018] An oxidant is preferably added to the oxidant feed port, such as sodium hypochlorite, chlorine, nitric acid, hydrogen peroxide, ozone and the like, to oxidize bromide ions into bromine (bromine element).

[0019] Based on the above treatment system, preferably, the acid addition tank is also provided with an acid addition pipeline.

[0020] Based on the above treatment system, preferably, the acid adding tank is further provided with an air inlet and / or a heater, and the acid adding tank is further provided with an exhaust port; the purpose of the acid adding tank being further provided with an air inlet is to blow out HBr with gas (compressed air, compressed nitrogen, steam and other gases), and the purpose of the acid adding tank being further provided with a heater is to evaporate (volatize) HBr after heating;

[0021] Or the oxidation tank is further provided with an air inlet and / or a heater, and the oxidation tank is further provided with an exhaust port; the purpose of the oxidation tank being provided with an air inlet is to blow out bromine (bromine element) with gas (compressed air, compressed nitrogen, steam and other gases), and the purpose of the oxidation tank being provided with a heater is to evaporate (volatize) bromine (bromine element) by heating;

[0022] Or the oxidation tank is further provided with a stratification outlet I and a stratification outlet II; the reason why the oxidation tank is further provided with a stratification outlet I and a stratification outlet II is that bromine (bromine element) has a low solubility in water and will stratify with water (aqueous solution) after being still, and bromine (bromine element) is obtained at the stratification outlet I, and an aqueous solution is obtained at the stratification outlet II;

[0023] Or the outlet of the oxidation tank is connected to the stratification tank I, and the stratification tank I is also provided with a stratification outlet I and a stratification outlet II; the stratification tank I after the oxidation tank is passed through the stratification tank I, which is helpful for the continuity of the reaction, and the solubility of bromine (bromine elemental substance) in water is low, and it will be stratified with water (aqueous solution) after being still, and the bromine (bromine elemental substance) is obtained at the stratification outlet I, and the aqueous solution is obtained at the stratification outlet II;

[0024] Or the oxidation tank is further provided with an extractant inlet, and the oxidation tank is further provided with a layered outlet I and a layered outlet II; the extractant can more thoroughly extract bromine (bromine element) from the solution, and then the layered outlet I obtains bromine (bromine element) + extractant, and the layered outlet II is an aqueous solution, and the extractant is preferably a conventional extractant that can dissolve bromine (bromine element) such as benzene, xylene, and carbon tetrachloride;

[0025] Or the oxidation tank is further provided with an extractant inlet, the outlet of the oxidation tank is connected to the stratification tank III, and the stratification tank III is further provided with a stratification outlet I and a stratification outlet II; the extractant can more thoroughly extract bromine (bromine element) from the solution, and then the stratification outlet I obtains bromine (bromine element) + extractant, and the stratification outlet II is an aqueous solution, and the extractant is preferably a conventional extractant that can dissolve bromine (bromine element) such as benzene, xylene, and carbon tetrachloride;

[0026] Or the outlet of the oxidation tank is connected to the extraction tank, and the extraction tank is also provided with an extractant addition port, a stratification outlet I, and a stratification outlet II. The oxidation tank passing through the extraction tank is conducive to the continuity of the reaction, and the extractant can more thoroughly extract bromine (bromine element) from the solution. After that, bromine (bromine element) + extractant is obtained at the stratification outlet I, and the stratification outlet II is an aqueous solution. The extractant is preferably a conventional extractant that can dissolve bromine (bromine element) such as benzene, xylene, and carbon tetrachloride.

[0027] Or the outlet of the oxidation tank is connected to the extraction tank, the extraction tank is also provided with an extractant addition port, the outlet of the extraction tank is connected to the stratification tank II, the stratification tank II is also provided with stratification outlet I and stratification outlet II, the extractant can more thoroughly extract bromine (bromine element) from the solution, and then the stratification outlet I of the stratification tank II obtains bromine (bromine element) + extractant, and the stratification outlet II is an aqueous solution. The extractant is preferably a conventional extractant that can dissolve bromine (bromine element) such as benzene, xylene, and carbon tetrachloride.

[0028] Based on the above treatment system, preferably, the exhaust port of the acid addition tank is connected to the feed port of the condenser I, the feed port of the water absorption tank or the oxidation reaction system of the PTA plant; the gaseous HBr is condensed into liquid HBr acid through the condenser I; or the HBr vapor is absorbed by the water absorption tank to obtain liquid HBr acid;

[0029] Or the exhaust port of the oxidation tank is connected to the feed port of the condenser II or the inlet of the reduction tank; the gaseous bromine (bromine element) is condensed into liquid bromine (bromine element) through the condenser II; the bromine (bromine element) is collected into a product in the reduction tank or reacted with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) into HBr;

[0030] Or the layered outlet I of the oxidation tank is connected to the inlet of the collection tank or the reduction tank; the bromine (bromine element) is collected into a product in the reduction tank or reacts with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) into HBr;

[0031] Or the stratification outlet I of the stratification tank I is connected to the inlet of the collection tank or the reduction tank; the bromine (bromine element) is collected into a product in the reduction tank or reacts with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) into HBr;

[0032] Or the layered outlet I of the oxidation tank is connected to the feed port of the extractant evaporation tower I, the extractant evaporation tower I is provided with a gas phase outlet and a liquid phase outlet, the gas phase outlet of the extractant evaporation tower I is connected to the inlet of the condenser III or the inlet of the reduction tank; the extractant evaporation tower I is used to separate the extractant and bromine (bromine element), the gas phase outlet of the extractant evaporation tower I obtains bromine (bromine element), which is condensed into liquid bromine (bromine element) through the condenser III, and the liquid phase outlet of the extractant evaporation tower I obtains liquid extractant, which is reused; the bromine (bromine element) is collected in the reduction tank as a product or reacted with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr;

[0033] Or the stratification outlet I of the stratification tank III is connected to the feed port of the extractant evaporation tower IV, the extractant evaporation tower IV is provided with a gas phase outlet and a liquid phase outlet, the gas phase outlet of the extractant evaporation tower IV is connected to the inlet of the condenser VII or the inlet of the reduction tank; the extractant evaporation tower IV is used to separate the extractant and bromine (bromine element), the gas phase outlet of the extractant evaporation tower IV obtains bromine (bromine element), which is condensed into liquid bromine (bromine element) through the condenser VII, and the liquid phase outlet of the extractant evaporation tower IV obtains liquid extractant, which is reused; the bromine (bromine element) is collected in the reduction tank as a product or reacts with the reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr;

[0034] Or the stratification outlet I of the stratification tank II is connected to the feed port of the extractant evaporation tower II, the extractant evaporation tower II is provided with a gas phase outlet and a liquid phase outlet, the gas phase outlet of the extractant evaporation tower II is connected to the inlet of the condenser IV or the inlet of the reduction tank; the extractant evaporation tower II is used to separate the extractant and bromine (bromine element), the gas phase outlet of the extractant evaporation tower II obtains bromine (bromine element), which is condensed into liquid bromine (bromine element) through the condenser IV, and the liquid phase outlet of the extractant evaporation tower II obtains liquid extractant, which is reused; the bromine (bromine element) is collected in the reduction tank as a product or reacted with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr;

[0035] Or the stratified outlet I of the extraction tank is connected to the feed port of the extractant evaporation tower III, the extractant evaporation tower III is provided with a gas phase outlet and a liquid phase outlet, the gas phase outlet of the extractant evaporation tower III is connected to the inlet of the condenser V or the inlet of the reduction tank; the extractant evaporation tower III is used to separate the extractant and bromine (bromine element), the gas phase outlet of the extractant evaporation tower III obtains bromine (bromine element), which is condensed into liquid bromine (bromine element) through the condenser V, and the liquid phase outlet of the extractant evaporation tower III obtains liquid extractant, which is reused; the bromine (bromine element) is collected in the reduction tank as a product or reacts with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr.

[0036] Based on the above processing system, preferably, the extractant evaporation tower I, the extractant evaporation tower II or the extractant evaporation tower III is provided with a heater (eg, a reboiler).

[0037] Based on the above processing system, preferably, the acid adding tank is also provided with a liquid discharge port.

[0038] Based on the above processing system, preferably, the oxidation tank is also provided with a liquid discharge port.

[0039] Based on the above processing system, preferably, the stratification tank I is also provided with a liquid discharge port.

[0040] Based on the above processing system, preferably, the extraction tank is also provided with a liquid discharge port.

[0041] Based on the above processing system, preferably, the stratification tank II is also provided with a liquid discharge port.

[0042] Based on the above processing system, preferably,

[0043] The stratified outlet I of the oxidation tank is connected to the inlet of the collection tank or the reduction tank; that is, the bromine (bromine element) at the stratified outlet I is collected as a product or reacted with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr;

[0044] Or the stratification outlet I of the stratification tank I is connected to the inlet of a collection tank or a reduction tank; that is, the bromine (bromine element) at the stratification outlet I is collected as a product or reacts with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr.

[0045] Based on the above processing system, preferably,

[0046] The exhaust port of the acid addition tank is connected to the feed port of the condenser I or the feed port of the water absorption tank I, and the outlet of the condenser I or the outlet of the water absorption tank I is connected to a collection tank or an oxidation reaction system of the PTA process; that is, the HBr liquid product condensed by the condenser I or the HBr liquid product absorbed by the absorption tank I is collected into a product or used for HBr users (such as the oxidation reaction system of the PTA process);

[0047] Or the exhaust port of the oxidation tank is connected to the feed port of the condenser II, and the outlet of the condenser II is connected to the inlet of the collection tank or the reduction tank; that is, the bromine (bromine element) condensed by the condenser II is collected as a product or reacted with a reducing agent (in the reduction tank) to reduce the bromine (bromine element) to HBr;

[0048] Or the outlet of the condenser III is connected to the inlet of a collecting tank or a reducing tank; that is, the bromine (bromine element) at the liquid phase outlet is collected as a product or reacted with a reducing agent (in the reducing tank) to reduce the bromine (bromine element) to HBr;

[0049] Or the outlet of the condenser IV is connected to the inlet of a collecting tank or a reducing tank; that is, the bromine (bromine element) at the liquid phase outlet is collected as a product or reacted with a reducing agent (in the reducing tank) to reduce the bromine (bromine element) to HBr;

[0050] Or the outlet of the condenser V is connected to the inlet of a collecting tank or a reducing tank; that is, the bromine (bromine element) at the liquid phase outlet is collected as a product or reacted with a reducing agent (in the reducing tank) to reduce the bromine (bromine element) to HBr;

[0051] Or the outlet of the condenser VII is connected to the inlet of a collecting tank or a reducing tank; that is, the bromine (bromine element) at the liquid phase outlet is collected as a product or reacted with a reducing agent (in the reducing tank) to reduce the bromine (bromine element) to HBr.

[0052] Based on the above treatment system, preferably, the reduction tank is also provided with a reducing agent inlet, and the reducing agent is preferably an inorganic reducing agent (such as sulfur dioxide, sodium bisulfite, sodium sulfite, sodium thiosulfate, etc.), an organic acid reducing agent (such as formic acid, etc.), an alcohol reducing agent (such as methanol, ethanol, etc.), an aldehyde reducing agent (such as formaldehyde, acetaldehyde, etc.) and all substances that can reduce bromine (bromine element), and the outlet of the reduction tank is connected to the product tank (i.e., the HBr product); or the outlet of the reduction tank is connected to the oxidation reaction system of the PTA process (i.e., the HBr is used by a certain HBr user--the oxidation reaction system of the PTA process); or the reduction tank is also provided with an air inlet and / or a heater, and the reduction tank is also provided with an exhaust port, and the exhaust port of the reduction tank is connected to the PTA process. The oxidation reaction system of the TA process, the feed inlet of the condenser VI or the feed inlet of the water absorption tank II, the outlet of the condenser VI and or the outlet of the water absorption tank II are connected to the product tank or the oxidation reaction system of the PTA process; the outlet of the condenser VI or the outlet of the water absorption tank II is connected to the product tank or the oxidation reaction system of the PTA process, that is, if sulfur dioxide is used as a reducing agent to convert bromine (bromine element) into HBr+sulfuric acid (sulfurous acid), a mixed acid of HBr+sulfuric acid (sulfurous acid) will be obtained in the reduction tank, and the HBr needs to be volatilized to the gas phase by blowing or evaporated to the gas phase by heating, and then condensed into an HBr product through the condenser VI or the HBr in the gas phase is absorbed by the water absorption tank II to form a liquid HBr product.

[0053] Based on the above processing system, preferably, the oxidation tank is also provided with an acid addition port.

[0054] Based on the above treatment system, preferably, acetic acid, formic acid, oxalic acid, propionic acid, phosphoric acid, sulfuric acid and other acids are added to the acid adding port of the oxidation tank to provide hydrogen ions.

[0055] Based on the above treatment system, preferably, for example, the tail gas of a terephthalic acid plant is treated with organic matter therein (generally RTO incineration method, catalytic oxidation method, etc.) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the RTO incineration method or catalytic oxidation method. The alkaline absorption liquid (such as sodium hydroxide) is used to obtain a mixed aqueous solution (alkaline washing liquid) of sodium carbonate, sodium bicarbonate and sodium bromide. The mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0056] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), an alkali adding tank is provided between the discharge port of the bromine-containing liquid and the feed port of the nanofiltration membrane group, the feed port of the electrodialysis device for separating monovalent ions, or the feed port of the evaporator. The alkali adding tank is also provided with an alkali adding pipeline. The purpose of adding alkali is to convert bicarbonate in the water body into carbonate. Carbonate is negative divalent and bromide is negative monovalent. Therefore, the separation of carbonate and bromide ions (i.e., separation of sodium carbonate and sodium bromide) can be achieved by using the nanofiltration membrane group, and the separation of carbonate and bromide ions (i.e., separation of sodium carbonate and sodium bromide) can be achieved by using the electrodialysis device for separating monovalent ions. If alkali is added in advance in the evaporator, sodium bicarbonate will not be contained, and carbon dioxide will not be generated during the heating process, which not only improves the yield of sodium carbonate but also avoids the generation of a large amount of non-condensable gas (carbon dioxide) that affects multiple-effect evaporation or MVR.

[0057] Based on the above treatment system, preferably, for example, to treat the alkaline washing liquid (bromine-containing liquid), at least one reduction reactor is further provided, and the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the nanofiltration membrane group; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the electrodialysis equipment for separating monovalent ions; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the evaporator; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the adsorption tank. When the bromine-containing liquid has a certain oxidizing property, it needs to be reduced first to remove the oxidizing property of the bromine-containing liquid.

[0058] Based on the above treatment system, preferably, for example, to treat the alkaline washing liquid (bromine-containing liquid), at least one reduction reactor is further provided, and the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the alkali-adding tank; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the nanofiltration membrane group; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the electrodialysis equipment for separating monovalent ions; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the evaporator; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the adsorption tank. When the bromine-containing liquid has a certain oxidizing property, it needs to be reduced first to remove the oxidizing property of the bromine-containing liquid.

[0059] Based on the above treatment system, preferably, for example, to treat the alkaline washing liquid (bromine-containing liquid), the reduction reactor comprises a fixed bed reduction reactor, a reduction reaction tank, and the like.

[0060] Based on the above treatment system, preferably, for example, to treat the alkaline washing liquid (bromine-containing liquid), the fixed bed reduction reactor is equipped with a fixed reducing agent or adsorbent (adsorbing oxidizing agent).

[0061] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), the reduction reactor (such as the reduction reaction tank) is further provided with a reducing agent adding pipeline.

[0062] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), the reduction reactor (eg, the reduction reaction tank) is further provided with a stirrer.

[0063] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), the reducing agent comprises an inorganic reducing agent and / or an organic reducing agent.

[0064] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), the inorganic reducing agent comprises sodium bisulfite, sodium sulfite, sodium thiosulfate, and the like.

[0065] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), the organic reducing agent includes alcohol reducing agents (such as methanol, ethanol, etc.), aldehyde reducing agents (such as formaldehyde, acetaldehyde, etc.), carboxylic acid reducing agents (inflowing formic acid, acetic acid, etc.), and other organic reducing agents.

[0066] Based on the above treatment system, preferably, for example, when treating the alkaline washing liquid (bromine-containing liquid), a nanofiltration membrane group 'or the electrodialysis device for separating monovalent ions' is provided between the liquid outlet of the solid-liquid separation device and the feed port of the acid addition tank or the feed port of the oxidation tank, the liquid outlet of the solid-liquid separation device is connected to the feed port of the nanofiltration membrane group 'or the feed port of the electrodialysis device for separating monovalent ions', the fresh water outlet of the nanofiltration membrane group 'or the water outlet I of the electrodialysis device for separating monovalent ions' is connected to the feed port of the acid addition tank or the feed port of the oxidation tank, that is, the sodium carbonate still contained in the liquid outlet of the solid-liquid separation device is removed again by the nanofiltration membrane group 'or the electrodialysis device for separating monovalent ions'.

[0067] Based on the above treatment system, preferably, for example, to treat the alkaline washing liquid (bromine-containing liquid), the concentrate outlet of the nanofiltration membrane group' or the water outlet II of the electrodialysis device for separating monovalent ions' is connected to the discharge port of the bromine-containing liquid, or the concentrate outlet of the nanofiltration membrane group' or the water outlet II of the electrodialysis device for separating monovalent ions' (mainly containing sodium carbonate) can be used as an alkaline substance and can be used as sodium carbonate by users of sodium carbonate, for example, the PTA industry uses sodium carbonate as a precipitant for the recovery of cobalt ions and manganese ions and as a dissolving agent for oxidized residues.

[0068] Based on the above treatment system, preferably, the mother liquor extract of the PTA plant mainly contains acetic acid, and also contains benzoic acid and its acid radical (hereinafter referred to as BA, about 10000 ppm), phthalic acid and its acid radical (including ortho, meta and para positions, unless otherwise specified herein, all are collectively referred to as phthalic acid, hereinafter referred to as TA, mainly para position), cobalt ions, manganese ions, bromide ions, oxidation intermediate product p-carboxybenzaldehyde (hereinafter referred to as 4-CBA), oxidation intermediate product p-toluic acid (hereinafter referred to as PT acid), anthraquinone fluorenone with lower by-product concentration, and other impurities. A mixed solution of cyclic compounds (also called polycyclic compounds), trimellitic acid with lower by-product concentration, metal corrosion products (such as iron, chromium, and nickel ions, with iron ions being the main metal corrosion products at about 3 to 15 ppm), sodium ions (about 30 to 100 ppm), and water (water generated by the reaction of paraxylene with oxygen and water contained in the air), etc., with acetic acid being the main concentration (generally >70%, 75% to 95% in common processes, mass fraction). The mother liquor extract of the PTA plant is the liquid corresponding to the discharge port of the bromine-containing liquid described in the utility model.

[0069] Based on the above treatment system, preferably, the discharge port of the oxidized mother liquor extraction of the PTA plant is connected to the feed port of the solid-liquid separation device', and the liquid outlet of the solid-liquid separation device' (i.e., the bromine-containing liquid) is the discharge port of the bromine-containing liquid (i.e., providing bromine-containing liquid), which is connected to the feed port of the nanofiltration membrane group; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the electrodialysis device for separating monovalent ions; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the solid-liquid separation device; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the cooling unit, and the outlet of the cooling unit is connected to the feed port of the solid-liquid separation device; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the adsorption tank, and the adsorption tank is also provided with a discharge port, a regeneration liquid inlet, and a regeneration liquid outlet;

[0070] The fresh water outlet of the nanofiltration membrane group, the water outlet I of the electrodialysis device for separating monovalent ions, the liquid outlet of the solid-liquid separation device or the regeneration liquid outlet of the adsorption tank are connected to the feed inlet of the acid addition tank or the feed inlet of the oxidation tank;

[0071] Or the discharge port of the oxidation mother liquor extraction of the PTA plant is connected to the feed port of the cooler, the outlet of the cooler is connected to the feed port of the solid-liquid separation device', the liquid outlet of the solid-liquid separation device' (i.e., the bromine-containing liquid) is the discharge port of the bromine-containing liquid (i.e., providing the bromine-containing liquid), connected to the feed port of the nanofiltration membrane group; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the electrodialysis device for separating monovalent ions; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the solid-liquid separation device; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the solid-liquid separation device; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the cooling unit, and the outlet of the cooling unit is connected to the feed port of the solid-liquid separation device; or the liquid outlet of the solid-liquid separation device' is connected to the feed port of the adsorption tank, and the adsorption tank is also provided with a discharge port, a regeneration liquid inlet, and a regeneration liquid outlet;

[0072] The fresh water outlet of the nanofiltration membrane group, the water outlet I of the electrodialysis device for separating monovalent ions, the liquid outlet of the solid-liquid separation device or the regeneration liquid outlet of the adsorption tank are connected to the feed port of the acid addition tank or the feed port of the oxidation tank.

[0073] Based on the above processing system, preferably, an evaporation concentration tower is provided between the oxidation mother liquor extraction discharge port of the PTA plant and the feed port of the solid-liquid separation device' or the feed port of the cooler; or a filter' and an evaporation concentration tower are provided in sequence, and the filtrate outlet of the filter' is connected to the feed port of the evaporation concentration tower. The evaporation concentration tower evaporates part of the solvent (acetic acid) through heating to increase the solute concentration (mainly to increase the concentration of bromine), and is also called an acetic acid recovery tower or an acetic acid stripping tower.

[0074] Based on the above processing system, preferably, the solid outlet of the solid-liquid separation equipment' is connected to the crystallizer I (preferably a thin film evaporator) or is connected to the crystallizer I (preferably a thin film evaporator) after passing through a pulping tank, or the solid outlet of the solid-liquid separation equipment' is connected to the feed inlet of the washing tank, and the washing tank is also provided with an acid addition line (preferably acetic acid or an aqueous solution of acetic acid), the outlet of the washing tank is connected to the solid-liquid separation equipment', the solid outlet of the solid-liquid separation equipment' is connected to the oxidation reaction system of PTA; and / or the liquid outlet of the solid-liquid separation equipment' is connected to the crystallizer II (preferably a thin film evaporator), or the liquid outlet of the solid-liquid separation equipment' is connected to the crystallizer II (preferably a thin film evaporator) after passing through a concentration tower.

[0075] Based on the above processing system, preferably, the outlet of the adsorption tank is connected to the crystallizer III (preferably a thin film evaporator) or the outlet of the adsorption tank is connected to the crystallizer III (preferably a thin film evaporator) after passing through a concentration tower.

[0076] Based on the above treatment system, preferably, the adsorption tank is provided with an acid inlet and an acid outlet, and / or the adsorption tank is also provided with a cleaning water inlet and a cleaning water outlet, the acid is used to pickle the resin in the adsorption tank with an acid (preferably acetic acid or an acetic acid aqueous solution); the cleaning water is used to wash the resin in the adsorption tank with cleaning water.

[0077] Based on the above treatment system, preferably, the acid outlet of the adsorption tank is connected to the crystallizer IV or the acid outlet of the adsorption tank is connected to the crystallizer IV after passing through a concentration tower.

[0078] Based on the above treatment system, preferably, the solid outlet of the crystallizer I, crystallizer II, crystallizer III or crystallizer IV is connected to an alkali adding tank ', the purpose of which is to neutralize the benzene organic acid (TA, BA, 4-CBA, PT acid, etc.) with alkali and convert the cobalt ions and manganese ions into precipitates, and the alkali is preferably sodium carbonate.

[0079] Based on the above treatment system, preferably, the outlet of the alkali adding tank 'is connected to a filter ', and the filter 'is used to intercept insolubles of cobalt carbonate and manganese carbonate.

[0080] Based on the above treatment system, preferably, the filter' (containing insoluble cobalt carbonate and manganese carbonate) is periodically dissolved with acid and then enters the PTA oxidation reaction system, and the acid is preferably acetic acid and / or HBr acid.

[0081] Based on the above processing system, preferably, the cooler comprises a heat exchanger and / or a crystallizer.

[0082] Based on the above processing system, preferably, in order to ensure stable process operation, a concentration device is also provided at any position of the process.

[0083] Based on the above processing system, preferably, the concentration device includes an evaporation concentration device, a reverse osmosis concentration device, an electrodialysis concentration device and other concentration devices.

[0084] Based on the above processing system, preferably, in order to ensure stable process operation, a hardness removal device is also provided at any position of the process.

[0085] Based on the above processing system, preferably, the hardness removal device mainly comprises a resin column, and the resin column is filled with a resin that has an adsorption effect on hardness.

[0086] Based on the above treatment system, preferably, the resin column is also provided with a regeneration liquid inlet and a regeneration liquid outlet.

[0087] Based on the above processing system, preferably, in order to ensure stable process operation, a filtering device is also provided at any position of the process.

[0088] Based on the above processing system, preferably, the filtration device includes filters in the form of positive pressure filtration, negative pressure filtration, centrifugal filtration, etc.

[0089] Based on the above processing system, preferably, in order to ensure stable process operation, a cooling device is also provided at any position of the process.

[0090] Based on the above processing system, preferably, in order to ensure stable process operation, a pump is designed at any position of the process for transporting liquid.

[0091] The purposes of different steps, units, etc. designed in the utility model are different and independent of each other. Each step, unit, etc. can be used alone or selected and combined in different orders according to actual needs. It is also possible to select and apply only part of the steps, units, etc., all of which are within the scope of patent protection of the utility model.

[0092] Beneficial Effects

[0093] The utility model aims to provide a bromine-containing liquid processing system. After the bromine-containing liquid is processed by the system, bromine elements can be extracted and converted into products for reuse, thereby recovering the economic value of the bromine elements.

[0094] In addition, the system is simple to operate, the equipment is simple, the operation is easy and the operation is stable, which is very helpful in reducing the operating costs of the enterprise. BRIEF DESCRIPTION OF THE DRAWINGS

[0095] Figure 1 Schematic diagram of a processing system according to Embodiment 1.

[0096] Figure 2 Schematic diagram of the processing system of Example 2.

[0097] Figure 3 Schematic diagram of the processing system of Example 3.

[0098] Figure 4 Schematic diagram of the processing system of Example 4.

[0099] Figure 5 Schematic diagram of the processing system of Example 5.

[0100] Figure 6 Schematic diagram of the processing system of Example 6.

[0101] Figure 7 Schematic diagram of the processing system of Example 7.

[0102] legend:

[0103]

[0104]

[0105] DETAILED DESCRIPTION

[0106] The following non-limiting embodiments may enable a person skilled in the art to more fully understand the present invention, but do not limit the present invention in any way.

[0107] In the following examples, the nanofiltration membrane used in the nanofiltration membrane group is DuPont brand FilmTec TM NF270-400 / 34i, the reverse osmosis membrane used in the reverse osmosis concentration equipment is DuPont's SW30HRLE-440i, and the electrodialysis concentration equipment is a conventional commercially available electrodialysis equipment.

[0108] Embodiment 1

[0109] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, a nanofiltration membrane group 7, an electrodialysis concentration device 12, an acid adding tank 15, and a water absorption tank I 18.

[0110] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0111] The alkali adding tank 4 is connected to the feed port of the high-pressure pump I6, the outlet of the high-pressure pump I6 is connected to the feed port of the nanofiltration membrane group 7, and the concentrated water outlet 8 of the nanofiltration membrane group 7 is discharged; the fresh water outlet 9 of the nanofiltration membrane group 7 is connected to the water inlet of the intermediate tank 10, the water outlet of the intermediate tank 10 is connected to the water inlet of the electrodialysis concentration device 12, the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged, and the concentrated water outlet 13 of the electrodialysis concentration device 12 is connected to the acid adding tank 15, and the acid adding tank 15 is also provided with a heater 20, an air inlet 19, an exhaust port 17, and an acid adding pipeline 16, and the exhaust port 17 of the acid adding tank 15 is connected to the water absorption tank I18.

[0112] The above processing system operates as follows:

[0113] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0114] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0115] The aqueous solution in the alkali addition tank 4 is pumped into the nanofiltration membrane group 7 through the high-pressure pump Ⅰ6, and the concentrated water outlet 8 of the nanofiltration membrane group is discharged, and the fresh water outlet 9 of the nanofiltration membrane group is collected in the intermediate tank 10. The aqueous solution in the intermediate tank 10 passes through the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged, and the concentrated water outlet 13 of the electrodialysis concentration device 12 enters the acid addition tank 15.

[0116] The acid adding tank 15 adds acid through the acid adding pipeline 16, the heater 20 heats and blows the HBr produced by the reaction through the air inlet 19 to the water absorption tank I 18 for absorption with water to obtain the HBr product.

[0117] Run the experiment using the above system:

[0118] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reduction reactor 2, and controls the liquid ORP in the reduction reactor 2 to be less than 0mv to reflect the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate.

[0119] Adjust the control valve on the concentrated water outlet 8 of the nanofiltration membrane group to adjust the outlet pressure of the high-pressure pump I6 to 4 MPaG.

[0120] Phosphoric acid is added to the acid adding tank 15 from the acid adding pipe 16, and the pH is controlled to be 0.5-1. The acid adding tank 15 is heated by the heater 20 and air is blown into the acid adding tank 15 through the air inlet 19. The gas comes out from the exhaust port 17 and is absorbed by the water absorption tank I 18 (the water absorption tank I 18 is pre-filled with desalted water).

[0121] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0122] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0123] The water quality analysis of the fresh water outlet 9 of the nanofiltration membrane group is as follows: PH = 11.6, sodium carbonate 1731ppm, sodium bicarbonate 15ppm, sodium bromide 2412ppm;

[0124] The water quality analysis of the concentrated water outlet 8 of the nanofiltration membrane group is as follows: PH = 11.8, sodium carbonate 45121ppm;

[0125] The water quality analysis of the concentrated water outlet 13 of the electrodialysis is as follows: PH = 11.7, sodium carbonate 50125ppm, sodium bicarbonate 401ppm, sodium bromide 74312ppm;

[0126] The product analysis of the water absorption tank I18 is as follows: bromide ion = 11.3%, hydrogen ion = 1.41 mol / L, proving to be hydrobromic acid product.

[0127] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered through this treatment system and converted into hydrobromic acid product for reuse, thereby recovering the economic value.

[0128] Embodiment 2

[0129] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, a nanofiltration membrane group 7, an electrodialysis concentration device 12, an oxidation tank 11, and a reduction tank 25.

[0130] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0131] The alkali adding tank 4 is connected to the feed port of the high pressure pump I6, the outlet of the high pressure pump I6 is connected to the feed port of the nanofiltration membrane group 7, and the concentrated water outlet 8 of the nanofiltration membrane group 7 is discharged; the fresh water outlet 9 of the nanofiltration membrane group 7 is connected to the water inlet of the intermediate tank 10, the water outlet of the intermediate tank 10 is connected to the water inlet of the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged;

[0132] The concentrated water outlet 13 of the electrodialysis concentration device 12 is connected to the oxidation tank 11, which is also provided with a heater 23, an air inlet 22, an exhaust port 24, an acid addition port 27, and an oxidant feed port 21. The exhaust port 24 of the oxidation tank 11 is connected to the reduction tank 25, which is also provided with a reducing agent inlet 26.

[0133] The above processing system operates as follows:

[0134] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0135] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0136] The aqueous solution in the alkali addition tank 4 is pumped into the nanofiltration membrane group 7 through the high-pressure pump Ⅰ6, and the concentrated water outlet 8 of the nanofiltration membrane group is discharged, and the fresh water outlet 9 of the nanofiltration membrane group is collected in the intermediate tank 10. The aqueous solution in the intermediate tank 10 passes through the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged, and the concentrated water outlet 13 of the electrodialysis concentration device 12 enters the oxidation tank 11.

[0137] The oxidation tank 11 is added with acid through the acid adding port 27, heated by the heater 23, provided with oxidant through the oxidant feed port 21, and the bromine (elemental bromine) produced by the reaction is blown into the reduction tank 25 through the air inlet 22, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26.

[0138] Run the experiment using the above system:

[0139] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reduction reactor 2, and controls the liquid ORP in the reduction reactor 2 to be less than 0mv to reflect the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate.

[0140] Adjust the control valve on the concentrated water outlet 8 of the nanofiltration membrane group to adjust the outlet pressure of the high-pressure pump I6 to 4 MPaG.

[0141] Acid (acetic acid) is added through the acid adding port 27 and the pH is controlled to be 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feeding port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0142] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0143] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0144] The water quality analysis of the fresh water outlet 9 of the nanofiltration membrane group is as follows: PH = 11.6, sodium carbonate 1731ppm, sodium bicarbonate 15ppm, sodium bromide 2412ppm;

[0145] The water quality analysis of the concentrated water outlet 8 of the nanofiltration membrane group is as follows: PH = 11.8, sodium carbonate 45121ppm;

[0146] The water quality analysis of the concentrated water outlet 13 of the electrodialysis is as follows: PH = 11.7, sodium carbonate 50125ppm, sodium bicarbonate 401ppm, sodium bromide 74312ppm;

[0147] Red appears in the oxidation tank 11, which is elemental bromine.

[0148] The product analysis of reduction tank 25 is as follows: colorless, bromide ion = 7.5%, hydrogen ion = 0.94 mol / L, proving to be hydrobromic acid product.

[0149] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered through this treatment system and converted into hydrobromic acid product for reuse, thereby recovering the economic value.

[0150] Embodiment 3

[0151] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, a nanofiltration membrane group 7, an electrodialysis concentration device 12, an oxidation tank 11, a stratification tank I 28, and a reduction tank 25.

[0152] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0153] The alkali adding tank 4 is connected to the feed port of the high pressure pump I6, the outlet of the high pressure pump I6 is connected to the feed port of the nanofiltration membrane group 7, and the concentrated water outlet 8 of the nanofiltration membrane group 7 is discharged; the fresh water outlet 9 of the nanofiltration membrane group 7 is connected to the water inlet of the intermediate tank 10, the water outlet of the intermediate tank 10 is connected to the water inlet of the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged;

[0154] The concentrated water outlet 13 of the electrodialysis concentration device 12 is connected to the oxidation tank 11, and the oxidation tank 11 is also provided with an acid addition port 27 and an oxidant feed port 21. The oxidation tank 11 is connected to the stratification tank I 28, and the stratification outlet II 30 of the stratification tank I 28 is discharged. The stratification outlet I 29 of the stratification tank I 28 is connected to the reduction tank 25, and the reduction tank 25 is also provided with a reducing agent inlet 26.

[0155] The above processing system operates as follows:

[0156] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0157] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0158] The aqueous solution in the alkali addition tank 4 is pumped into the nanofiltration membrane group 7 through the high-pressure pump Ⅰ6, and the concentrated water outlet 8 of the nanofiltration membrane group is discharged, and the fresh water outlet 9 of the nanofiltration membrane group is collected in the intermediate tank 10. The aqueous solution in the intermediate tank 10 passes through the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged, and the concentrated water outlet 13 of the electrodialysis concentration device 12 enters the oxidation tank 11.

[0159] The oxidation tank 11 adds acid through the acid adding port 27, and the oxidant feed port 21 provides bromine (elemental bromine) produced by the oxidant, which is then stratified through the stratification tank I 28, and the bromine is discharged into the reduction tank 25 from the stratification outlet I 29 of the stratification tank I 28, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26.

[0160] Run the experiment using the above system:

[0161] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reduction reactor 2, and controls the liquid ORP in the reduction reactor 2 to be less than 0mv to reflect the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate.

[0162] Adjust the control valve on the concentrated water outlet 8 of the nanofiltration membrane group to adjust the outlet pressure of the high-pressure pump I6 to 4 MPaG.

[0163] Acid (acetic acid) is added through the acid adding port 27 and the pH is controlled to be 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feeding port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0164] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0165] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0166] The water quality analysis of the fresh water outlet 9 of the nanofiltration membrane group is as follows: PH = 11.6, sodium carbonate 1731ppm, sodium bicarbonate 15ppm, sodium bromide 2412ppm;

[0167] The water quality analysis of the concentrated water outlet 8 of the nanofiltration membrane group is as follows: PH = 11.8, sodium carbonate 45121ppm;

[0168] The water quality analysis of the concentrated water outlet 13 of the electrodialysis is as follows: PH = 11.7, sodium carbonate 50125ppm, sodium bicarbonate 401ppm, sodium bromide 74312ppm;

[0169] Red appears in the oxidation tank 11, which is elemental bromine.

[0170] The product analysis of reduction tank 25 is as follows: colorless, bromide ion=8.2%, hydrogen ion=1.02 mol / L, proving to be hydrobromic acid product.

[0171] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered through this treatment system and converted into hydrobromic acid product for reuse, thereby recovering the economic value.

[0172] Embodiment 4

[0173] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, a nanofiltration membrane group 7, an electrodialysis concentration device 12, an oxidation tank 11, an extraction tank 31, a layering tank II 32, an extractant evaporation tower II 36, and a reduction tank 25.

[0174] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0175] The alkali adding tank 4 is connected to the feed port of the high pressure pump I6, the outlet of the high pressure pump I6 is connected to the feed port of the nanofiltration membrane group 7, and the concentrated water outlet 8 of the nanofiltration membrane group 7 is discharged; the fresh water outlet 9 of the nanofiltration membrane group 7 is connected to the water inlet of the intermediate tank 10, the water outlet of the intermediate tank 10 is connected to the water inlet of the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged;

[0176] The concentrated water outlet 13 of the electrodialysis concentration device 12 is connected to the oxidation tank 11, and the oxidation tank 11 is also provided with an acid addition port 27 and an oxidant feed port 21. The oxidation tank 11 is connected to the extraction tank 31, and the extraction tank 31 is also provided with an extractant addition port 35. The extraction tank 31 is connected to the stratification tank II 32, and the stratification outlet II 34 of the stratification tank II 32 is discharged. The stratification outlet I 33 of the stratification tank II 32 is connected to the extractant evaporation tower II 36, and the gas phase outlet of the extractant evaporation tower II 36 is connected to the reduction tank 25. The reduction tank 25 is also provided with a reducing agent inlet 26. The liquid phase outlet of the extractant evaporation tower II 36 is connected to the extractant addition port 35 of the extraction tank 31.

[0177] The above processing system operates as follows:

[0178] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0179] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0180] The aqueous solution in the alkali addition tank 4 is pumped into the nanofiltration membrane group 7 through the high-pressure pump Ⅰ6, and the concentrated water outlet 8 of the nanofiltration membrane group is discharged, and the fresh water outlet 9 of the nanofiltration membrane group is collected in the intermediate tank 10. The aqueous solution in the intermediate tank 10 passes through the electrodialysis concentration device 12, and the fresh water outlet 14 of the electrodialysis concentration device 12 is discharged, and the concentrated water outlet 13 of the electrodialysis concentration device 12 enters the oxidation tank 11.

[0181] The oxidation tank 11 adds acid through the acid adding port 27, and the oxidant feed port 21 provides bromine (elemental bromine) produced by the oxidant, which is mixed with the extractant fed through the extractant adding port 35 in the extraction tank 31, and is stratified in the stratification tank II 32. The mixture of bromine and the extractant discharged from the stratification outlet I 33 of the stratification tank II 32 is then heated and separated in the extractant evaporation tower II 36. The gas phase (bromine, i.e., elemental bromine) of the extractant evaporation tower II 36 enters the reduction tank 25, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26. The liquid phase (extractant) of the extractant evaporation tower II 36 is circulated back to the extractant adding port 35 for recycling.

[0182] Run the experiment using the above system:

[0183] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reduction reactor 2, and controls the liquid ORP in the reduction reactor 2 to be less than 0mv to reflect the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate.

[0184] Adjust the control valve on the concentrated water outlet 8 of the nanofiltration membrane group to adjust the outlet pressure of the high-pressure pump I6 to 4 MPaG.

[0185] Acid (acetic acid) is added through the acid addition port 27 and the pH is controlled at 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feed port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Carbon tetrachloride is used as an extractant through the extractant addition port 35. Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0186] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0187] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0188] The water quality analysis of the fresh water outlet 9 of the nanofiltration membrane group is as follows: PH = 11.6, sodium carbonate 1731ppm, sodium bicarbonate 15ppm, sodium bromide 2412ppm;

[0189] The water quality analysis of the concentrated water outlet 8 of the nanofiltration membrane group is as follows: PH = 11.8, sodium carbonate 45121ppm;

[0190] The water quality analysis of the concentrated water outlet 13 of the electrodialysis is as follows: PH = 11.7, sodium carbonate 50125ppm, sodium bicarbonate 401ppm, sodium bromide 74312ppm;

[0191] Red appears in the oxidation tank 11, which is elemental bromine.

[0192] The product analysis of reduction tank 25 is as follows: colorless, bromide ion = 6.98%, hydrogen ion = 0.87 mol / L, proving to be hydrobromic acid product.

[0193] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered through this treatment system and converted into hydrobromic acid product for reuse, thereby recovering the economic value.

[0194] Embodiment 5

[0195] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, an electrodialysis device 37 for separating monovalent ions, an oxidation tank 11, and a reduction tank 25.

[0196] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0197] The alkali adding tank 4 is connected to the feed port of the electrodialysis equipment 37 for separating monovalent ions, and the water outlet II 39 of the electrodialysis equipment 37 for separating monovalent ions is discharged; the water outlet I 38 of the electrodialysis equipment 37 for separating monovalent ions is connected to the oxidation tank 11, and the oxidation tank 11 is also provided with a heater 23, an air inlet 22, an exhaust port 24, an acid adding port 27, and an oxidant feed port 21. The exhaust port 24 of the oxidation tank 11 is connected to the reduction tank 25, and the reduction tank 25 is also provided with a reducing agent inlet 26.

[0198] The above processing system operates as follows:

[0199] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0200] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0201] The aqueous solution in the alkali adding tank 4 is treated by the electrodialysis device 37 for separating monovalent ions. The water outlet II 39 of the electrodialysis device 37 for separating monovalent ions is used to discharge the sodium carbonate aqueous solution. The water outlet I 38 of the electrodialysis device 37 for separating monovalent ions enters the oxidation tank 11.

[0202] The oxidation tank 11 is added with acid through the acid adding port 27, heated by the heater 23, provided with oxidant through the oxidant feed port 21, and the bromine (elemental bromine) produced by the reaction is blown into the reduction tank 25 through the air inlet 22, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26.

[0203] Run the experiment using the above system:

[0204] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reduction reactor 2, and controls the liquid ORP in the reduction reactor 2 to be less than 0mv to reflect the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate.

[0205] Acid (acetic acid) is added through the acid adding port 27 and the pH is controlled to be 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feeding port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0206] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0207] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0208] The water quality analysis of the water outlet I 38 of the electrodialysis device 37 for separating monovalent ions is as follows: PH = 11.3, sodium carbonate 67644 ppm, sodium bicarbonate 743 ppm, sodium bromide 91843 ppm;

[0209] The water quality analysis of the outlet II 39 of the electrodialysis device 37 for separating monovalent ions is as follows: PH = 11.5, sodium carbonate 56987 ppm;

[0210] Red appears in the oxidation tank 11, which is elemental bromine.

[0211] The product analysis of reduction tank 25 is as follows: colorless, bromide ion = 10.1%, hydrogen ion = 1.26 mol / L, proving to be hydrobromic acid product.

[0212] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered and converted into hydrobromic acid product for reuse through this treatment system, and the economic value can be recovered. At the same time, it is also proved that the separation effect of sodium bromide (monovalent) and sodium carbonate (divalent carbonate) played by the electrodialysis device 37 for separating monovalent ions is the same as that of the nanofiltration membrane group 7, and the "electrodialysis device 37 for separating monovalent ions" and the "nanofiltration membrane group 7" can be interchangeable, that is, the "electrodialysis device 37 for separating monovalent ions" can be used to replace the "nanofiltration membrane group 7" in Example 1, Example 2, Example 3, and Example 4 to achieve the same effect.

[0213] Note: The electrodialysis equipment 37 for separating monovalent ions is a product provided by Bestbond Water Treatment and Environmental Protection Technology (Dalian) Co., Ltd. (corresponding to its patent ZL 202210205770.4).

[0214] Embodiment 6

[0215] A bromine-containing liquid treatment system mainly comprises a bromine-containing liquid discharge port 1, a reduction reactor 2, an alkali adding tank 4, a reverse osmosis concentration device 41, an evaporator 44, a cooling unit 46, a solid-liquid separation device 47, an oxidation tank 11, and a reduction tank 25.

[0216] The discharge port 1 of the bromine-containing liquid is connected to the reduction reactor 2 , which is also provided with a reducing agent adding pipeline 3 . The reduction reactor 2 is connected to the alkali adding tank 4 , which is also provided with an alkali adding pipeline 5 .

[0217] The alkali adding tank 4 is connected to the feed port of the high-pressure pump II 40, the outlet of the high-pressure pump II 40 is connected to the feed port of the reverse osmosis concentration device 41, the fresh water outlet 42 of the reverse osmosis concentration device 41 is discharged, the concentrated water outlet 43 of the reverse osmosis concentration device 41 is connected to the feed port of the evaporator 44, the evaporator 44 is also provided with a reboiler 45, the outlet of the evaporator 44 is connected to the feed port of the cooling unit 46, the outlet of the cooling unit 46 is connected to the feed port of the solid-liquid separation device 47, the solid outlet 48 of the solid-liquid separation device 47 is discharged, the liquid outlet 49 of the solid-liquid separation device 47 is connected to the oxidation tank 11, the oxidation tank 11 is also provided with a heater 23, an air inlet 22, an exhaust port 24, an acid adding port 27, an oxidant feed port 21, the exhaust port 24 of the oxidation tank 11 is connected to the reduction tank 25, and the reduction tank 25 is also provided with a reducing agent inlet 26.

[0218] The above processing system operates as follows:

[0219] The target substance treated in this embodiment is a bromine-containing liquid, which is the tail gas of a terephthalic acid plant after the organic matter therein is treated (catalytic oxidation method) to reduce the amount of organic matter therein, and the remaining tail gas mainly contains hydrogen bromide and carbon dioxide produced during the catalytic oxidation method. The alkaline absorption liquid (sodium hydroxide) is used to obtain a mixed aqueous solution of sodium carbonate, sodium bicarbonate, and sodium bromide (alkaline washing liquid), and the mixed aqueous solution (alkaline washing liquid) is the bromine-containing liquid treated by the utility model.

[0220] The bromine-containing liquid discharge port 1 passes the bromine-containing liquid into the reduction reactor 2, and the reducing agent is added to the reduction reactor 2 through the reducing agent adding pipeline 3. After that, the liquid in the reduction reactor 2 passes into the alkali adding tank 4, and alkali is added to the alkali adding tank 4 through the alkali adding pipeline 5 to adjust the pH, thereby converting sodium bicarbonate into sodium carbonate.

[0221] The aqueous solution in the alkali adding tank 4 is concentrated by the reverse osmosis concentration device 41, and the concentrated water obtained at the concentrated water outlet 43 of the reverse osmosis concentration device 41 is heated and concentrated by the evaporator 44, and then cooled by the cooling unit 46, the solubility of sodium carbonate is reduced and precipitated, and then the solid-liquid separation device 47 is used for solid-liquid separation, solid sodium carbonate is discharged, and the liquid (mainly containing sodium bromide aqueous solution) enters the oxidation tank 11.

[0222] The oxidation tank 11 is added with acid through the acid adding port 27, heated by the heater 23, provided with oxidant through the oxidant feed port 21, and the bromine (elemental bromine) produced by the reaction is blown into the reduction tank 25 through the air inlet 22, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26.

[0223] Run the experiment using the above system:

[0224] The reducing agent adding pipeline 3 feeds formic acid as a reducing agent into the reducing reactor 2, and controls the liquid ORP in the reducing reactor 2 to be less than 0mv, reflecting the reducing property; the alkali adding pipeline 5 feeds sodium hydroxide into the alkali adding tank 4 to adjust the pH to 11.5, at which time most of the sodium bicarbonate is converted into sodium carbonate. The cooling unit 47 controls 2°C.

[0225] Acid (acetic acid) is added through the acid adding port 27 and the pH is controlled to be 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feeding port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0226] The water quality analysis of the bromine-containing liquid discharge port 1 is as follows: PH = 9.1, sodium carbonate 2105ppm, sodium bicarbonate 11022ppm, sodium bromide 2332ppm;

[0227] The water quality analysis of the alkali adding tank 4 is as follows: PH = 11.5, sodium carbonate 12989ppm, sodium bicarbonate 35ppm, sodium bromide 2257ppm;

[0228] The concentrated water outlet 43 of the reverse osmosis concentration device 41 was analyzed as follows: PH = 11.8, sodium carbonate 51287ppm, sodium bicarbonate 151ppm, sodium bromide 9002ppm;

[0229] The water quality analysis of the liquid outlet 49 of the solid-liquid separation device 47 is as follows: PH = 11.5, sodium carbonate 33123ppm, sodium bromide 103125ppm;

[0230] Red appears in the oxidation tank 11, which is elemental bromine.

[0231] The product analysis of reduction tank 25 is as follows: colorless, bromide ion = 9.9%, hydrogen ion = 1.24 mol / L, proving to be hydrobromic acid product.

[0232] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered and converted into hydrobromic acid product for reuse through this treatment system, thereby recovering the economic value. It is also proved that the separation effect of sodium bromide and sodium carbonate played by the evaporator 44 + solid-liquid separation device 47 (based on the principle that the solubility of sodium carbonate is lower than that of sodium bromide) is the same as that of the nanofiltration membrane group 7, and the separation effect of sodium bromide and sodium carbonate played by the electrodialysis device 37 for separating monovalent ions is also the same.

[0233] Therefore, the "evaporator 44+solid-liquid separation device 47", "electrodialysis device for separating monovalent ions 37" and "nanofiltration membrane group 7" can be interchangeable as units, that is, the "evaporator 44+solid-liquid separation device 47" and "electrodialysis device for separating monovalent ions 37" can be used to replace the "nanofiltration membrane group 7" in Example 1, Example 2, Example 3 and Example 4 to achieve the same effect.

[0234] Embodiment 7

[0235] A bromine-containing liquid treatment system mainly includes an oxidation mother liquor extraction liquid discharge port 50 of a PTA plant, an evaporation concentration tower 51, a cooler 52, a solid-liquid separation device 53, a bromine-containing liquid discharge port 1, an adsorption tank 55, a washing tank 65, a solid-liquid separation device 67, a crystallizer II 70, a concentration tower 72, a crystallizer IV 73, a buffer tank 64, a reverse osmosis concentration device 41, an oxidation tank 11, and a reduction tank 25.

[0236] The oxidation mother liquor extraction liquid discharge port 50 of the PTA plant is connected to the evaporation concentration tower 51, and the evaporation concentration tower 51 is also provided with a reboiler 54. The bottom discharge port of the evaporation concentration tower 51 is connected to the feed port of the cooler 52, and the outlet of the cooler 52 is connected to the feed port of the solid-liquid separation device 53;

[0237] The solid outlet of the solid-liquid separation device '53 is connected to the washing tank 65, and the washing tank 65 is also provided with an acid addition pipeline 66. The discharge port of the washing tank 65 is connected to the feed port of the solid-liquid separation device '67. The solid outlet 68 of the solid-liquid separation device '67 is connected to the oxidation reaction system of the PTA plant; the liquid outlet 69 of the solid-liquid separation device '67 is connected to the crystallizer II 70.

[0238] The liquid outlet of the solid-liquid separation device '53 is connected to the discharge port 1 of the bromine-containing liquid, and the discharge port 1 of the bromine-containing liquid is connected to the feed port 56 of the adsorption tank 55. The adsorption tank 55 is also provided with an outlet 57, a regeneration liquid inlet 58, a regeneration liquid outlet 59, an acid inlet 60, an acid outlet 61, a washing water inlet 62, and a washing water outlet 63;

[0239] The outlet 57 of the adsorption tank 55 is connected to the crystallizer III 71 ; the acid outlet 61 of the adsorption tank 55 is connected to the concentration tower 72 , and the discharge port of the concentration tower 72 is connected to the crystallizer IV 73 .

[0240] The regeneration liquid outlet 59 of the adsorption tank 55 is connected to the buffer tank 64, the outlet of the buffer tank 64 is connected to the feed port of the high-pressure pump II 40, the outlet of the high-pressure pump II is connected to the feed port of the reverse osmosis concentration equipment 41, the fresh water outlet 42 of the reverse osmosis concentration equipment 41 is discharged, and the concentrated water outlet 43 of the reverse osmosis concentration equipment 41 is connected to the oxidation tank 11. The oxidation tank 11 is also provided with a heater 23, an air inlet 22, an exhaust port 24, an acid addition port 27, and an oxidant feed port 21. The exhaust port 24 of the oxidation tank 11 is connected to the reduction tank 25, and the reduction tank 25 is also provided with a reducing agent inlet 26.

[0241] The above processing system operates as follows:

[0242] The target product treated in this embodiment is a bromine-containing liquid, which is the mother liquor extract of the PTA plant, mainly containing acetic acid, benzoic acid and its acid radical (hereinafter referred to as BA, about 10000 ppm), phthalic acid and its acid radical (including ortho, meta and para positions, unless otherwise specified herein, all are collectively referred to as phthalic acid, hereinafter referred to as TA, mainly para position), cobalt ions, manganese ions, bromide ions, oxidation intermediate product p-carboxybenzaldehyde (hereinafter referred to as 4-CBA), oxidation intermediate product p-toluic acid (hereinafter referred to as PT acid), and anthracene with a lower by-product concentration. A mixed solution of heterocyclic compounds (also called polycyclic compounds) such as quinonefluorenone, trimellitic acid with a lower by-product concentration, metal corrosion products (such as iron, chromium, and nickel ions, with iron ions being the main metal corrosion products at about 3 to 15 ppm), sodium ions (about 30 to 100 ppm), and water (water generated by the reaction of p-xylene with oxygen and water contained in the air), with acetic acid being the main concentration (generally >70%, 75% to 95% in common processes, mass fraction). The mother liquor extract of the PTA plant is the liquid corresponding to the discharge port of the bromine-containing liquid described in the utility model.

[0243] The material from the oxidation mother liquor extraction outlet 50 of the PTA plant is concentrated by the evaporation concentration tower 51, cooled by the cooler 52, and then separated into solid and liquid by the solid-liquid separation equipment 53;

[0244] The solid separated by the solid-liquid separation device '53 is added with acid added by the acid adding pipeline 66 to the washing tank 65, and then is passed through the solid-liquid separation device "67" for solid-liquid separation. The solid separated by the solid-liquid separation device "67" is added to the oxidation reaction system of the PTA plant; the liquid separated by the solid-liquid separation device "67" is crystallized by the crystallizer II to obtain a solid;

[0245] The liquid separated by the solid-liquid separation device '53 passes through the bromine-containing liquid discharge port 1 and then passes through the adsorption tank 55 to adsorb bromine elements, and then is discharged from the outlet 57 of the adsorption tank 55 and then passes through the crystallizer III 71 to crystallize to obtain a solid;

[0246] The adsorption tank 55 is pickled with the acid from the acid inlet 66 of the adsorption tank 55, and the pickled liquid of the adsorption tank 55 is discharged from the acid outlet 61, concentrated by the concentration tower 72, and then crystallized by the crystallizer IV 73 to obtain a solid;

[0247] The adsorption tank 55 is washed with water from the washing water inlet 62 of the adsorption tank 55, and then discharged from the washing water outlet 63;

[0248] The adsorption tank 55 is regenerated by using the regeneration liquid provided by the regeneration liquid inlet 58 of the adsorption tank 55. The regeneration liquid is discharged from the regeneration liquid outlet 59 of the adsorption tank 55 and then buffered by the buffer tank 64. Thereafter, the regeneration liquid is concentrated by the reverse osmosis concentration device 41. The fresh water of the reverse osmosis concentration device 41 is discharged and the concentrated water of the reverse osmosis concentration device 41 enters the oxidation tank 11.

[0249] The oxidation tank 11 is added with acid through the acid adding port 27, heated by the heater 23, provided with oxidant through the oxidant feed port 21, and the bromine (elemental bromine) produced by the reaction is blown into the reduction tank 25 through the air inlet 22, and the reducing agent is added to the reduction tank 25 from the reducing agent inlet 26.

[0250] Run the experiment using the above system:

[0251] The concentration ratio of the evaporation concentration tower is 7-10 times, and the temperature is 132°C;

[0252] The temperature of cooler 52 is controlled at 10-20°C;

[0253] The acid addition line 66 of the washing tank 65 feeds acetic acid;

[0254] Acetic acid is fed into the acid inlet 60 of the adsorption tank 55;

[0255] An 8% sodium hydroxide aqueous solution is fed into the regeneration liquid inlet of the adsorption tank 55;

[0256] A control valve for controlling the concentrated water outlet 43 of the reverse osmosis concentration device 41 controls the outlet pressure of the high-pressure pump II 40 to 4 MPaG;

[0257] Acid (acetic acid) is added through the acid adding port 27 and the pH is controlled to be 4-5. Hydrogen peroxide (hydrogen peroxide) is fed into the oxidant feeding port 21 as an oxidant to oxidize bromide ions into bromine (elemental bromine). Formaldehyde is added as a reducing agent through the reducing agent inlet 26.

[0258] The liquid analysis of the bromine-containing liquid discharge port 1 is as follows: BA = 160312 ppm, 4-CBA = 1010 ppm, PT acid = 4501 ppm, bromide ion 6512 ppm, cobalt ion 2812 ppm, manganese ion 1398 ppm (solution with acetic acid as solvent).

[0259] The liquid at the outlet 57 of the adsorption tank 55 was analyzed as follows: BA = 163123 ppm, 4-CBA = 988 ppm, PT acid = 4213 ppm, bromide ion 277 ppm, cobalt ion 2982 ppm, manganese ion 1401 ppm (solution with acetic acid as solvent).

[0260] The regeneration liquid outlet 59 of the adsorption tank 55 was analyzed as follows: PH = 12.7, bromide ion = 41343 ppm

[0261] The concentrated water outlet 43 of the reverse osmosis concentration device 41 was analyzed as follows: PH = 13.1, bromide ion = 88167 ppm

[0262] Red appears in the oxidation tank 11, which is elemental bromine.

[0263] The product analysis of reduction tank 25 is as follows: colorless, bromide ion = 10.6%, hydrogen ion = 1.33 mol / L, proving to be hydrobromic acid product.

[0264] Conclusion: It is proved that the bromine element in the bromine-containing liquid can be recovered through this treatment system and converted into hydrobromic acid product for reuse, thereby recovering the economic value.

[0265] At the same time, since Examples 1, 2, 3 and 4 prove that an aqueous solution containing bromine, "e.g., pH = 13.1, bromide ion = 88167 ppm", can be treated by "acidification tank 15, water absorption tank 18" to obtain HBr (Example 1), "oxidation tank 11, reduction tank 25" to obtain HBr (Example 2, the same as the latter stage treatment of Example 7), "oxidation tank 11, separation tank I 28, reduction tank 25" to obtain HBr (Example 3), "extraction tank 31, stratification tank II 32, extractant evaporation tank II 36" to obtain HBr (Example 4);

[0266] Therefore, it can be inferred that the aqueous solution obtained from the concentrated water outlet 43 of the reverse osmosis concentration device 41 of the seventh embodiment can be treated by the same combination connection of "acid addition tank 15, water absorption tank 18" to obtain HBr; or the aqueous solution obtained from the concentrated water outlet 43 of the reverse osmosis concentration device 41 can be treated by the same combination connection of "oxidation tank 11, separation tank I 28, reduction tank 25" to obtain HBr; or the aqueous solution obtained from the concentrated water outlet 43 of the reverse osmosis concentration device 41 can be treated by the same combination connection of "extraction tank 31, stratification tank II 32, extractant evaporation tank II 36" to obtain HBr.

Claims

1. A system for treating bromine-containing liquid, characterized in that: The treatment system comprises: a discharge port for bromine-containing liquid, a nanofiltration membrane group, an electrodialysis device for separating monovalent ions, an evaporator or an adsorption tank, and an acid addition tank or an oxidation tank; The discharge port of the bromine-containing liquid is connected to the feed port of the nanofiltration membrane group; or the discharge port of the bromine-containing liquid is connected to the feed port of the electrodialysis device for separating monovalent ions; or the discharge port of the bromine-containing liquid is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the solid-liquid separation device; or the discharge port of the bromine-containing liquid is connected to the feed port of the evaporator, and the outlet of the evaporator is connected to the feed port of the cooling unit, and the outlet of the cooling unit is connected to the feed port of the solid-liquid separation device; or the discharge port of the bromine-containing liquid is connected to the feed port of the adsorption tank, and the adsorption tank is also provided with a discharge port, a regeneration liquid inlet, and a regeneration liquid outlet; The fresh water outlet of the nanofiltration membrane group, the water outlet I of the electrodialysis device for separating monovalent ions, the liquid outlet of the solid-liquid separation device or the regeneration liquid outlet of the adsorption tank are connected to the feed port of the acid addition tank or the feed port of the oxidation tank.

2. The processing system according to claim 1, characterized in that The acid adding tank is also provided with an air inlet and / or a heater, and the acid adding tank is also provided with an exhaust port; Or the oxidation tank is further provided with an air inlet and / or a heater, and the oxidation tank is further provided with an exhaust port; Or the oxidation tank is further provided with a stratified outlet I and a stratified outlet II; Or the outlet of the oxidation tank is connected to the stratification tank I, and the stratification tank I is further provided with stratification outlet I and stratification outlet II; Or the oxidation tank is further provided with an extractant inlet, and the oxidation tank is further provided with a stratified outlet I and a stratified outlet II; Or the oxidation tank is further provided with an extractant inlet, the outlet of the oxidation tank is connected to the stratification tank III, and the stratification tank III is further provided with stratification outlet I and stratification outlet II; Or the outlet of the oxidation tank is connected to the extraction tank, and the extraction tank is further provided with an extractant addition port, a stratification outlet I, and a stratification outlet II; Or the outlet of the oxidation tank is connected to the extraction tank, the extraction tank is also provided with an extractant addition port, the outlet of the extraction tank is connected to the stratification tank II, the stratification tank II is also provided with stratification outlet I and stratification outlet II.

3. The processing system according to claim 2, characterized in that The exhaust port of the acid addition tank is connected to the feed port of the condenser I, the feed port of the water absorption tank I or the oxidation reaction system of the PTA plant; or the exhaust port of the oxidation tank is connected to the feed port of the condenser II or the inlet of the reduction tank; or the stratification outlet I of the oxidation tank is connected to the inlet of the collecting tank or the reduction tank; or the stratification outlet I of the stratification tank I is connected to the inlet of the collecting tank or the reduction tank; or the stratification outlet I of the oxidation tank is connected to the feed port of the extractant evaporation tower I, the extractant evaporation tower I is provided with a gas phase outlet and a liquid phase outlet, and the gas phase outlet of the extractant evaporation tower I is connected to the inlet of the condenser III or the inlet of the reduction tank; or the stratification outlet I of the stratification tank III is connected to the extractant evaporation tower I. The feed inlet of evaporation tower IV, the extractant evaporation tower IV is provided with a gas phase outlet and a liquid phase outlet, and the gas phase outlet of the extractant evaporation tower IV is connected to the inlet of condenser VII or the inlet of reduction tank; or the stratification outlet I of the stratification tank II is connected to the feed inlet of extractant evaporation tower II, the extractant evaporation tower II is provided with a gas phase outlet and a liquid phase outlet, and the gas phase outlet of the extractant evaporation tower II is connected to the inlet of condenser IV or the inlet of reduction tank; or the stratification outlet I of the extraction tank is connected to the feed inlet of extractant evaporation tower III, the extractant evaporation tower III is provided with a gas phase outlet and a liquid phase outlet, and the gas phase outlet of the extractant evaporation tower III is connected to the inlet of condenser V or the inlet of reduction tank.

4. The processing system according to claim 3, characterized in that The exhaust port of the acid addition tank is connected to the feed port of the condenser I or the feed port of the water absorption tank I, and the outlet of the condenser I or the outlet of the water absorption tank I is connected to the collection tank or the oxidation reaction system of the PTA plant; Or the exhaust port of the oxidation tank is connected to the feed port of the condenser II, and the outlet of the condenser II is connected to the inlet of the collection tank or the reduction tank; Or the outlet of the condenser III is connected to the inlet of the collecting tank or the reduction tank; or the outlet of the condenser IV is connected to the inlet of the collecting tank or the reduction tank; or the outlet of the condenser V is connected to the inlet of the collecting tank or the reduction tank; Or the outlet of the condenser VII is connected to the inlet of the collecting tank or the reduction tank.

5. The processing system according to claim 3 or 4, characterized in that: The reduction tank is also provided with a reducing agent inlet, and the outlet of the reduction tank is connected to the product tank; or the outlet of the reduction tank is connected to the oxidation reaction system of the PTA process; or the reduction tank is also provided with an air inlet and / or a heater, and the reduction tank is also provided with an exhaust port, and the exhaust port of the reduction tank is connected to the oxidation reaction system of the PTA process, the feed port of the condenser VI or the feed port of the water absorption tank II, and the outlet of the condenser VI or the outlet of the water absorption tank II is connected to the product tank or the oxidation reaction system of the PTA process.

6. A processing system according to claim 1, 2, 3 or 4, characterized in that The oxidation tank is also provided with an acid adding port.

7. The processing system according to claim 1, characterized in that An alkali adding tank is provided between the discharge port of the bromine-containing liquid and the feed port of the nanofiltration membrane group, the feed port of the electrodialysis device for separating monovalent ions or the feed port of the evaporator, and the alkali adding tank is connected to the alkali adding pipeline.

8. The processing system according to claim 7, characterized in that At least one reduction reactor is also provided, and the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the alkali-adding tank; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the nanofiltration membrane group; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the electrodialysis equipment for separating monovalent ions; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the evaporator; or the reduction reactor is arranged between the outlet of the alkali-adding tank and the feed port of the adsorption tank.

9. The processing system according to claim 1, characterized in that At least one reduction reactor is also provided, and the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the nanofiltration membrane group; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the electrodialysis device for separating monovalent ions; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the evaporator; or the reduction reactor is arranged between the discharge port of the bromine-containing liquid and the feed port of the adsorption tank.

10. The processing system according to claim 8 or 9, characterized in that The reduction reactor is connected to a reducing agent adding pipeline.

11. The processing system according to claim 1, characterized in that A nanofiltration membrane group 'or an electrodialysis device for separating monovalent ions' is provided between the liquid outlet of the solid-liquid separation device and the feed port of the acid addition tank or the feed port of the oxidation tank. The liquid outlet of the solid-liquid separation device is connected to the feed port of the nanofiltration membrane group 'or the feed port of the electrodialysis device for separating monovalent ions', and the fresh water outlet of the nanofiltration membrane group 'or the water outlet I of the electrodialysis device for separating monovalent ions' is connected to the feed port of the acid addition tank or the feed port of the oxidation tank.

12. The processing system according to claim 1, characterized in that A solid-liquid separation device ' is also provided, the feed port of the solid-liquid separation device ' is connected to the discharge port of the oxidation mother liquor extraction of the PTA plant, and the liquid outlet of the solid-liquid separation device ' is the discharge port of the bromine-containing liquid; Or the oxidation mother liquor extraction liquid discharge port of the PTA plant is connected to the feed port of the cooler, the outlet of the cooler is connected to the feed port of the solid-liquid separation device', the liquid outlet of the solid-liquid separation device' is the discharge port of the bromine-containing liquid, and the treatment is carried out according to the route of claim 1.

13. The processing system according to claim 12, characterized in that An evaporation concentration tower is also provided between the oxidation mother liquor extraction discharge port of the PTA plant and the feed port of the solid-liquid separation device' or the feed port of the cooler; or a filter' and an evaporation concentration tower are also provided in sequence, and the filtrate outlet of the filter' is connected to the feed port of the evaporation concentration tower.

14. The processing system according to claim 1, 8 or 9, characterized in that The adsorption tank is provided with an acid inlet and an acid outlet, and / or the adsorption tank is further provided with a cleaning water inlet and a cleaning water outlet.

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