Treatment method for resource recycling of PTA oxidation residues

Abstract

The invention discloses a treatment method for resource recovery of PTA (pure terephthalic acid) oxidation residues, which is used for treating the PTA oxidation residues, recovering the value of bromine in the PTA oxidation residues and turning waste into wealth, and meanwhile, a mixture containing organic acids such as benzoic acid and phthalic acid is separated and can be incinerated to generate steam and a heat value is recovered; or the separated mixed organic matter containing benzoic acid and phthalic acid is separated into two products including benzoic acid and phthalic acid, and value can also be generated; or the separated mixed organic matter containing benzoic acid and phthalic acid is subjected to esterification reaction to generate ester, and value can also be generated; or the separated mixed organic matters containing benzoic acid and phthalic acid are separated into two products including benzoic acid and phthalic acid, and the two products are respectively subjected to esterification reaction to generate esters, so that values can also be generated.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical production, and in particular relates to a treatment method for resource recovery of PTA oxidation residue. Background Art

[0002] The main process of the PTA plant is divided into two systems: oxidation system and refining system, with oxidation system first and refining system second.

[0003] The oxidation system refers to: in an oxidation reactor, in the presence of acetic acid as a solvent and a three-way catalyst containing cobalt, manganese and bromine (hereinafter referred to as the cobalt-manganese-bromine three-way catalyst), PX is oxidized with oxygen in the air to produce terephthalic acid;

[0004] The refining system refers to the process of hydrogenating the terephthalic acid obtained from the oxidation process to reduce the impurities in the terephthalic acid product from the oxidation process and improve the quality of the terephthalic acid product.

[0005] In the oxidation system, a portion of the oxidation circulating mother liquor (acetic acid as the solvent) is extracted. The main purpose is to extract some impurities in the oxidation circulating mother liquor to avoid the higher concentration of impurities in the oxidation circulating mother liquor. The extraction of the oxidation circulating mother liquor inevitably extracts the solvent acetic acid, cobalt manganese catalyst, and bromine catalyst (it also contains benzene series, mainly phthalic acid and benzoic acid). The extract is first evaporated to recover most of the solvent acetic acid. During the process, the amount of solvent acetic acid decreases and the solute concentration increases. After that, the solvent acetic acid is further evaporated again through a heated crystallizer (commonly used thin film evaporator) to obtain an oxidation residue (the oxidation residue actually still has a little water, and the temperature is relatively high (generally >100°C) and it generally appears slightly viscous and paste-like).

[0006] At present, an aqueous solution of sodium carbonate is added to the oxidation residue to dissolve the phthalic acid, benzoic acid, etc. in the oxidation residue, and at the same time, the cobalt and manganese ions are converted into carbonate insolubles to recover the cobalt and manganese, which are then discharged into the sewage. However, in this operation, the benzoic acid and phthalic acid are dissolved by sodium carbonate and eventually enter the sewage, which is a waste of benzoic acid and phthalic acid. The oxidation residue contains bromide ions, which eventually enter the sewage, also wasting the value of the bromide ions. At the same time, benzoic acid, phthalic acid, and bromine are not good for the sewage device, and the sewage device is difficult to treat.

[0007] If there is a method to further treat the oxidation residue before adding sodium carbonate to extract the organic acids (mainly benzoic acid and phthalic acid), the amount of sodium carbonate added can be reduced, and the extracted organic acids (mainly benzoic acid and phthalic acid) can be incinerated to generate steam to recover heat value and generate benefits; or the two products of benzoic acid and phthalic acid can be separated to recover value; or the separated mixed organic matter containing benzoic acid and phthalic acid can be subjected to esterification reaction to generate esters, which can also generate value; or the separated mixed organic matter containing benzoic acid and phthalic acid can be separated into two products, benzoic acid and phthalic acid, and the two products are subjected to esterification reaction to generate esters, which can also generate value. Summary of the Invention

[0008] The purpose of the present invention is to provide a method for resource recovery of PTA oxidation residue, which performs deep treatment on the oxidation residue and recovers the material value therein. The present invention processes the oxidation residue, namely, processes the solid discharge of a heated crystallizer (i.e., the heated crystallizer I described in the present invention, which is commonly a thin-film evaporator) (the solid discharge of the heated crystallizer I actually still contains a little moisture, is relatively high in temperature (generally >100°C), and is generally slightly viscous or paste-like). The material value therein is recovered, mainly referring to the separation and recovery of the value of bromine therein. At the same time, the separated mixed organic matter containing benzoic acid and phthalic acid can be incinerated to generate steam for heat recovery; or the separated mixed organic matter containing benzoic acid and phthalic acid can be separated into two products, benzoic acid and phthalic acid, which can also generate value; or the separated mixed organic matter containing benzoic acid and phthalic acid can be subjected to an esterification reaction to generate esters, which can also generate value; or the separated mixed organic matter containing benzoic acid and phthalic acid can be separated into two products, benzoic acid and phthalic acid, which can be subjected to esterification reactions to generate esters, which can also generate value.

[0009] A method for recycling PTA oxidation residues, comprising the following steps:

[0010] A liquid is added to the PTA oxidation residue for slurrying (e.g., water is added for slurrying), and then solid-liquid separation is performed in a solid-liquid separator I. The resulting filtrate is subjected to an organic matter elimination treatment to remove organic matter, and then subjected to a cobalt-manganese recovery treatment to remove cobalt and manganese ions therein. The aqueous solution after the cobalt-manganese recovery treatment to remove cobalt and manganese ions is collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0011] The cobalt-manganese recovery treatment is to add an alkaline substance to the aqueous solution after the organic matter is removed by the organic matter elimination treatment, solidify the cobalt-manganese ions, and then remove the solidified substance of the cobalt-manganese ions through a solid-liquid separator IV and recover them; or the cobalt-manganese recovery treatment is a cobalt-manganese ion adsorption device, which adsorbs the cobalt-manganese ions in the aqueous solution after the organic matter is removed by the organic matter elimination treatment.

[0012] Based on the above technical solution, preferably, the device for adding liquid to the PTA oxidation residue for slurrying is named mixing tank I;

[0013] The equipment corresponding to the organic matter elimination treatment is named organic matter elimination equipment;

[0014] The equipment corresponding to the cobalt-manganese recovery process is named cobalt-manganese recovery equipment.

[0015] Constructing a PTA oxidation residue resource recovery processing system, that is, the system includes: a mixing tank I, a solid-liquid separator I, an organic matter elimination device, a cobalt and manganese recovery device, and also a collection tank, a heating crystallizer II, a bipolar membrane electrodialysis device or an evaporation tank;

[0016] The material at the solid outlet of the heating crystallizer I is the PTA oxidation residue (the solid discharge of the heating crystallizer I actually still has a little moisture, the temperature is relatively high (generally > 100°C), and it generally appears slightly viscous or paste-like);

[0017] The inlet of the mixing tank I is connected to the solid outlet of the heating crystallizer I, and the mixing tank I is also provided with a liquid adding port. The outlet of the mixing tank I is connected to the inlet of the solid-liquid separator I, and the liquid outlet of the solid-liquid separator I is connected to the inlet of the organic matter elimination device, and the outlet of the organic matter elimination device is connected to the inlet of the cobalt and manganese recovery device;

[0018] The liquid outlet of the cobalt-manganese recovery device is connected to the inlet of the collecting tank, the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis device or the inlet of the evaporation tank;

[0019] The solid outlet of the heating crystallizer I is the oxidation residue of the PTA. After being slurried in the mixing tank I and subjected to solid-liquid separation in the solid-liquid separator I, the obtained solid product is the solid organic acid (mainly phthalic acid and benzoic acid) originally in the oxidation residue of the PTA. The obtained liquid product mainly contains the inorganic ions (mainly cobalt, manganese, bromine, sodium, etc.) originally in the oxidation residue of the PTA and a small amount of dissolved organic acid (mainly phthalic acid and benzoic acid) and salts of organic acids as anions.

[0020] The cobalt-manganese recovery equipment includes a mixing tank IV and a solid-liquid separator IV. The mixing tank IV is also provided with a dosing port. The outlet of the mixing tank IV is connected to the inlet of the solid-liquid separator IV. The inlet of the mixing tank IV is the inlet of the cobalt-manganese recovery equipment, and the liquid outlet of the solid-liquid separator IV is the liquid outlet of the cobalt-manganese recovery equipment; or the cobalt-manganese ion recovery equipment includes a cobalt-manganese ion adsorption equipment, and the cobalt-manganese ion adsorption equipment is filled with a filler that has an adsorption effect on cobalt-manganese ions.

[0021] The liquid is then passed through the organic matter elimination device to remove a small amount of dissolved organic acids (mainly phthalic acid and benzoic acid) and the organic acids as anions contained in the liquid, that is, the organic acids (mainly phthalic acid and benzoic acid) and their organic acid anions (mainly phthalic acid and benzoic acid anions) are removed. The liquid is then passed through the cobalt and manganese recovery device to remove cobalt and manganese (recover cobalt and manganese). The liquid then mainly contains bromide ions and sodium ions, which can be collected in the collection tank as an aqueous solution mainly containing sodium bromide; the heated crystallizer II can be used to crystallize a solid mainly containing sodium bromide; the bipolar membrane electrodialysis device can be used to convert sodium bromide into two products, HBr and NaOH; the evaporation tank and subsequent treatment can also be used to obtain the HBr product;

[0022] The bipolar membrane electrodialysis device is a device that converts salt into a base corresponding to its cation and an acid corresponding to its anion. For example, by treating sodium bromide, a base corresponding to its cation (sodium ion) (i.e., sodium hydroxide) and an acid corresponding to its anion (bromide ion) (i.e., hydrobromic acid) can be obtained.

[0023] Based on the above technical solution, preferably, water is added to the liquid adding port of the mixing tank I to slurry the PTA oxidation residue.

[0024] Based on the above technical solution, preferably, water is added to the liquid adding port of the mixing tank I to slurry the PTA oxidation residue. The added water is preferably low-temperature water. Lowering the water temperature is conducive to reducing the solubility of organic matter and precipitation.

[0025] Based on the above technical solution, preferably, the mixing tank I is also provided with a stirrer.

[0026] Based on the above technical solution, preferably, a water adding point is provided between the liquid outlet of the solid-liquid separator I and the organic matter elimination equipment. The purpose of adding water is to increase the amount of solvent water and avoid organic acids (mainly phthalic acid and benzoic acid) from precipitating into solid blockage.

[0027] Based on the above technical solution, preferably, a heater is provided between the liquid outlet of the solid-liquid separator I and the organic matter elimination equipment. The purpose of heating is to increase the solubility of organic acids (mainly phthalic acid and benzoic acid) to avoid precipitation into solid blockage.

[0028] Based on the above technical solution, preferably, the mixing tank IV is further provided with a dosing port for adding alkaline substances to convert the cobalt and manganese ions therein into insoluble substances, which are separated from the aqueous solution, and the pH is controlled at about 8-9.5. At this time, the aqueous solution after solid-liquid separation mainly removes the cobalt and manganese ions and mainly contains sodium bicarbonate and sodium bromide.

[0029] Based on the above technical solution, preferably, the mixing tank IV is further provided with a dosing port for adding alkaline substances, preferably sodium carbonate or sodium hydroxide.

[0030] Based on the above technical solution, preferably, the cobalt-manganese ion adsorption device is filled with a filler that has an adsorption effect on cobalt-manganese ions, and the filler is preferably a resin that has an adsorption effect on cobalt-manganese ions.

[0031] Based on the above technical solution, preferably, the cobalt-manganese ion adsorption equipment is further provided with an inlet and an outlet for the regeneration liquid.

[0032] Based on the above technical solution, preferably, the cobalt-manganese ion adsorption equipment is further provided with an inlet and an outlet for a regeneration liquid, and the regeneration liquid is preferably an aqueous hydrobromic acid solution.

[0033] Based on the above technical solution, preferably, the organic matter adsorption equipment is further provided with an inlet and an outlet for a water washing liquid.

[0034] Based on the above technical solution, preferably, the organic matter elimination treatment includes at least one of the following processes:

[0035] Adsorbing organic matter using an organic matter adsorption device, wherein the organic matter adsorption device is filled with a filler having an adsorption effect on the organic matter;

[0036] or using an electrodialysis device to extract an aqueous solution containing inorganic matter with a relatively small proportion of organic matter, i.e., concentrated water from the electrodialysis device, thereby eliminating organic matter from the aqueous solution;

[0037] Or concentration (the corresponding equipment is named concentration equipment I) to reduce the amount of water. Reducing the amount of solvent will cause the organic matter in it to form insoluble matter and precipitate, and then the solid-liquid separation is removed;

[0038] Or concentrate (the corresponding equipment is named Concentration Equipment I) to reduce the amount of water, and cool to reduce the solubility of organic matter, so that the organic matter therein forms insoluble matter and precipitates, and then removes it by solid-liquid separation;

[0039] Or remove the organic matter in the aqueous solution by extraction process (the corresponding equipment is named extraction equipment);

[0040] For example, when the organic matter elimination treatment adopts a combination of ≥2 processes among the above processes, the adopted processes can be implemented in any order to deeply remove the organic matter.

[0041] Based on the above technical solution, preferably, the equipment corresponding to the organic matter elimination treatment is named organic matter elimination equipment, that is:

[0042] The organic matter elimination device is an organic matter adsorption device, the interior of the organic matter adsorption device is filled with a filler that has an adsorption effect on organic matter, and the inlet and outlet of the organic matter adsorption device are the inlet and outlet of the organic matter elimination device;

[0043] Alternatively, the organic matter elimination device is an electrodialysis device, wherein the inlet of the electrodialysis device is the inlet of the organic matter elimination device, and the ion concentrate outlet of the electrodialysis device is the outlet of the organic matter elimination device; the electrodialysis is used to draw ions in the aqueous solution to the ion concentrate outlet and discharge them. The electrodialysis attraction process has a weak attraction for organic matter, so it can achieve the separation of organic and inorganic ions. Since it is originally desired to obtain inorganic salt ions containing less organic matter, the electrodialysis device can achieve this design goal;

[0044] Or the organic matter elimination equipment is a concentration equipment I and a solid-liquid separator III, the outlet of the concentration equipment I is connected to the inlet of the solid-liquid separator III, the inlet of the concentration equipment I is the inlet of the organic matter elimination equipment, and the liquid outlet of the solid-liquid separator III is the outlet of the organic matter elimination equipment; the total amount of the solution is reduced by concentration, and since the solubility of the organic acid (mainly benzoic acid and phthalic acid) therein is fixed, it will precipitate when it exceeds the saturated solubility after concentration, and the inorganic salt is concentrated through the concentration process, so the proportion of inorganic matter in the total amount is increased, and the proportion of organic acid precipitation is reduced, thereby achieving separation of organic acid and inorganic salt;

[0045] Or the organic matter elimination equipment is a concentration equipment I, a cooler I, and a solid-liquid separator III, the outlet of the concentration equipment I is connected to the inlet of the cooler I, the outlet of the cooler I is connected to the inlet of the solid-liquid separator III, the inlet of the concentration equipment I is the inlet of the organic matter elimination equipment, and the liquid outlet of the solid-liquid separator III is the outlet of the organic matter elimination equipment; the amount of the overall solution is reduced by concentration, and since the solubility of the organic acid (mainly benzoic acid and phthalic acid) therein is fixed, it will precipitate when it exceeds the saturated solubility after concentration, and the inorganic salt is concentrated through the concentration process, so the proportion of inorganic matter in the total amount is increased, and the proportion of organic acid precipitation is reduced, thereby achieving separation of organic acid and inorganic salt; and the solubility of the organic acid can be further reduced by the cooler I, so that the organic acid concentration in the obtained inorganic salt is lower;

[0046] Or the organic matter elimination device is an extraction device, the extraction device is further provided with an extractant addition port, and the inlet and aqueous solution outlet of the extraction device are the inlet and outlet of the organic matter elimination device; or the organic matter elimination device is an extraction device and a static stratification device, the extraction device is further provided with an extractant addition port, the outlet of the extraction device is connected to the inlet of the static stratification device, the inlet of the extraction device is the inlet of the organic matter elimination device, and the aqueous solution outlet of the static stratification device is the outlet of the organic matter elimination device;

[0047] Or the organic matter elimination device includes an electrodialysis device and an organic matter adsorption device, the ion concentrate outlet of the electrodialysis device is connected to the inlet of the organic matter adsorption device, the organic matter adsorption device is filled with a filler that has an adsorption effect on organic matter, the inlet of the electrodialysis device is the inlet of the organic matter elimination device, and the outlet of the organic matter adsorption device is the outlet of the organic matter elimination device; that is, the organic matter adsorption device is used to remove the small amount of organic acid still contained in the inorganic salt aqueous solution after the organic acid (mainly benzoic acid and phthalic acid) has been removed once by the electrodialysis device;

[0048] Or the organic matter elimination equipment includes a concentrator I, a solid-liquid separator III, and an organic matter adsorption equipment, the outlet of the concentrator I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the organic matter adsorption equipment, the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentrator I is the inlet of the organic matter elimination equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; that is, the organic matter adsorption equipment is used to remove the small amount of organic acid still contained in the inorganic salt aqueous solution after the organic acid (mainly benzoic acid and phthalic acid) has been removed once by the concentrator I and the solid-liquid separator III;

[0049] Or the organic matter elimination equipment includes a concentrator I, a cooler I, a solid-liquid separator III, and an organic matter adsorption equipment, the outlet of the concentrator I is connected to the inlet of the cooler I, the outlet of the cooler I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the organic matter adsorption equipment, the interior of the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentrator I is the inlet of the organic matter elimination equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; that is, the organic matter adsorption equipment is used to remove the small amount of organic acid still contained in the inorganic salt aqueous solution after the organic acid (mainly benzoic acid and phthalic acid) has been removed once by the concentrator I, the cooler I, and the solid-liquid separator III;

[0050] Or the organic matter elimination equipment includes an extraction equipment and an organic matter adsorption equipment, the extraction equipment is further provided with an extractant addition port, the inlet of the extraction equipment is the inlet of the organic matter elimination equipment, the aqueous solution outlet of the extraction equipment is connected to the inlet of the organic matter adsorption equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; or the organic matter elimination equipment is an extraction equipment, a static stratification equipment and an organic matter adsorption equipment, the extraction equipment is further provided with an extractant addition port, the inlet of the extraction equipment is the inlet of the organic matter elimination equipment, the outlet of the extraction equipment is connected to the inlet of the static stratification equipment, the aqueous solution outlet of the static stratification equipment is connected to the inlet of the organic matter adsorption equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; that is, the small amount of organic acid still contained in the inorganic salt aqueous solution after the organic acid (mainly benzoic acid and phthalic acid) has been removed once by the extraction equipment using the organic matter adsorption equipment;

[0051] Or the organic matter elimination device includes a concentration device I, a solid-liquid separator III, an electrodialysis device and an organic matter adsorption device, the outlet of the concentration device I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the electrodialysis device, the ion concentrate outlet of the electrodialysis device is connected to the inlet of the organic matter adsorption device, the organic matter adsorption device is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentration device I is the inlet of the organic matter elimination device, and the outlet of the organic matter adsorption device is the outlet of the organic matter elimination device;

[0052] Or the organic matter elimination device comprises a concentrator I, a cooler I, a solid-liquid separator III, an electrodialysis device and an organic matter adsorption device, the outlet of the concentrator I is connected to the inlet of the cooler I, the outlet of the cooler I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the electrodialysis device, the ion concentrate outlet of the electrodialysis device is connected to the inlet of the organic matter adsorption device, the organic matter adsorption device is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentrator I is the inlet of the organic matter elimination device, and the outlet of the organic matter adsorption device is the outlet of the organic matter elimination device;

[0053] Or the organic matter elimination equipment includes an extraction equipment, an electrodialysis equipment and an organic matter adsorption equipment, the extraction equipment is further provided with an extractant addition port, the inlet of the extraction equipment is the inlet of the organic matter elimination equipment, the aqueous solution outlet of the extraction equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic matter adsorption equipment, the interior of the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; or the organic matter elimination equipment includes an extraction equipment, a static stratification equipment, an electrodialysis equipment and an organic matter adsorption equipment, the extraction equipment is further provided with an extractant addition port, the inlet of the extraction equipment is the inlet of the organic matter elimination equipment, the outlet of the extraction equipment is connected to the inlet of the static stratification equipment, the aqueous solution outlet of the static stratification equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic matter adsorption equipment, the interior of the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment;

[0054] Or the organic matter elimination equipment includes a concentration equipment I, a solid-liquid separator III, an extraction equipment, an electrodialysis equipment and an organic matter adsorption equipment, the outlet of the concentration equipment I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the extraction equipment, the extraction equipment is also provided with an extractant addition port, the aqueous solution outlet of the extraction equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic matter adsorption equipment, the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentration equipment I is the inlet of the organic matter elimination equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; or the organic matter elimination equipment includes a concentration equipment Preparation I, solid-liquid separator III, extraction equipment, stratification equipment, electrodialysis equipment and organic adsorption equipment, the outlet of the concentration equipment I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the extraction equipment, the extraction equipment is further provided with an extractant addition port, the outlet of the extraction equipment is connected to the inlet of the static stratification equipment, the aqueous solution outlet of the static stratification equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic adsorption equipment, the organic adsorption equipment is filled with a filler having an adsorption effect on organic matter, the inlet of the concentration equipment I is the inlet of the organic elimination equipment, and the outlet of the organic adsorption equipment is the outlet of the organic elimination equipment;

[0055] Or the organic matter elimination equipment includes a concentration equipment I, a cooler I, a solid-liquid separator III, an extraction equipment, an electrodialysis equipment and an organic matter adsorption equipment, the outlet of the concentration equipment I is connected to the inlet of the cooler I, the outlet of the cooler I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the extraction equipment, the extraction equipment is also provided with an extractant addition port, the aqueous solution outlet of the extraction equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic matter adsorption equipment, the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentration equipment I is the inlet of the organic matter elimination equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; or the organic matter elimination equipment includes a concentration equipment I, a cooler I, a solid-liquid separator III, an extraction equipment III, a solid-liquid separator III, an extraction equipment III, an extraction agent addition port, the aqueous solution outlet of the extraction equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic matter adsorption equipment, the organic matter adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentration equipment I is the inlet of the organic matter elimination equipment, and the outlet of the organic matter adsorption equipment is the outlet of the organic matter elimination equipment; Concentration equipment I, cooler I, solid-liquid separator III, extraction equipment, electrodialysis equipment and organic adsorption equipment, the outlet of the concentration equipment I is connected to the inlet of the cooler I, the outlet of the cooler I is connected to the inlet of the solid-liquid separator III, the liquid outlet of the solid-liquid separator III is connected to the inlet of the extraction equipment, the extraction equipment is also provided with an extractant addition port, the outlet of the extraction equipment is connected to the inlet of the static stratification equipment, the aqueous solution outlet of the static stratification equipment is connected to the inlet of the electrodialysis equipment, the ion concentrate outlet of the electrodialysis equipment is connected to the inlet of the organic adsorption equipment, the organic adsorption equipment is filled with a filler that has an adsorption effect on organic matter, the inlet of the concentration equipment I is the inlet of the organic elimination equipment, and the outlet of the organic adsorption equipment is the outlet of the organic elimination equipment.

[0056] Based on the above technical solution, preferably, the interior of the organic matter adsorption device is filled with a filler having an adsorption effect on organic matter, and the filler is preferably a resin having an adsorption effect on organic matter.

[0057] Based on the above technical solution, preferably, the organic adsorption equipment is filled with a filler that has an adsorption effect on organic matter. The filler is preferably a resin that has an adsorption effect on organic matter. The resin is preferably a resin that has an adsorption effect on terephthalic acid, benzoic acid, and its corresponding acid radicals.

[0058] Based on the above technical solution, preferably, the organic adsorption equipment is further provided with an inlet and an outlet for the regeneration liquid.

[0059] Based on the above technical solution, preferably, the organic adsorption equipment is further provided with an inlet and an outlet for a regeneration liquid, and the regeneration liquid is preferably a sodium hydroxide aqueous solution.

[0060] Based on the above technical solution, preferably, the organic matter adsorption equipment is further provided with an inlet and an outlet for a water washing liquid.

[0061] Based on the above technical solution, preferably, the organic adsorption equipment is further provided with an inlet and an outlet for the pickling liquid.

[0062] Based on the above technical solution, preferably, the organic adsorption equipment is further provided with an inlet and an outlet for a pickling solution, and the pickling is preferably performed with an HBr aqueous solution and / or an acetic acid aqueous solution.

[0063] Based on the above technical solution, preferably, the electrodialysis device is a device that can attract inorganic ions in the influent water to the other side of the membrane. It can attract inorganic ions due to the charge attraction, but has no adsorption effect on organic molecules (mainly phthalic acid and benzoic acid) because they are almost non-conductive; it has an attraction to organic anions (mainly phthalic acid anions and benzoic acid anions) but because the organic anions have a weak charge, the attraction is weak. Therefore, under the action of the electric field, it can mainly attract organic anions with a strong charge from a mixed aqueous solution containing inorganic ions, organic ions, and organic molecules. The inorganic ions are transferred to the other side of the membrane, and an aqueous solution mainly containing inorganic ions and a relatively small amount of organic anions can be extracted (called concentrated water of the electrodialysis device). From the aqueous solution containing inorganic ions, organic anions, and organic molecules, an aqueous solution mainly containing inorganic ions can be obtained by electric field attraction (called ion concentrated solution outlet, i.e. concentrated water), while the aqueous solution with reduced inorganic ion concentration is absorbed away, and the aqueous solution in which the organic anion concentration and organic molecule concentration do not change much (called ion dilute solution outlet, i.e., the inorganic matter in the original inlet water of the electrodialysis device is absorbed away, called dilute water).

[0064] Based on the above technical solution, preferably, an extractant that has a dissolving effect on benzoic acid and / or phthalic acid but is insoluble in water is added to the extractant addition port of the extraction equipment.

[0065] Based on the above technical solution, preferably, the extractant adding port of the extraction equipment adds an extractant that has a dissolving effect on benzoic acid and / or phthalic acid but is insoluble in water. The extractant is preferably solvent oil, ethers, alcohols, carbon tetrachloride, chloroform, etc.

[0066] Based on the above technical solution, preferably, the extractant outlet of the extraction equipment, or the extractant outlet of the static stratification equipment, that is, the extractant containing benzoic acid and / or phthalic acid extracted, is discharged; or the extractant is evaporated and recovered for reuse (for example, in an evaporation tower or a distillation tower, etc.); or an acid or an acid solution is added, at which time the benzoic acid and / or phthalic acid will precipitate into a solid, so that the extractant is separated from the precipitated solid, and the extractant can be used again.

[0067] Based on the above technical solution, preferably, the extractant outlet of the extraction equipment, or the extractant outlet of the static stratification equipment, refers to the extractant containing benzoic acid and / or phthalic acid, and acid or acid solution is added. At this time, benzoic acid and / or phthalic acid will precipitate into solids, and water + extractant phase and solid organic acid phase (mainly containing benzoic acid and / or phthalic acid) can be obtained through solid-liquid separation.

[0068] Based on the above technical solution, preferably, the extractant outlet of the extraction equipment, or the extractant outlet of the static stratification equipment, refers to the extractant containing benzoic acid and / or phthalic acid, and acid or acid solution is added. At this time, benzoic acid and / or phthalic acid will precipitate into solids, and water + extractant phase and solid organic acid phase (mainly containing benzoic acid and / or phthalic acid) can be obtained through solid-liquid separation. The water + extractant phase can be separated and the extract can be obtained again for extraction and use.

[0069] Based on the above technical solution, preferably, the process of adding liquid to the PTA oxidation residue for slurrying (the equipment used is the mixing tank I) is cooled at the same time; or the process of adding liquid to the PTA oxidation residue for slurrying is first cooled, and then solid-liquid separation is performed through the solid-liquid separator I.

[0070] Based on the above technical solution, preferably, the mixing tank I is equipped with a cooling device; or a cooling device is provided between the outlet of the mixing tank I and the inlet of the solid-liquid separator I. The purpose of the cooling device is to lower the temperature, reduce the solubility of the organic acid (mainly phthalic acid and benzoic acid), and precipitate it and separate it from the aqueous solution.

[0071] Based on the above technical solution, preferably, the mixing tank I is equipped with a cooling device, preferably a negative pressure vacuum cooling device.

[0072] Based on the above technical solution, preferably, a cold water addition point is designed between the outlet of the mixing tank I and the inlet of the solid-liquid separator I for adding cold water. Lowering the water temperature is more beneficial to reducing the solubility of benzoic acid and phthalic acid and causing them to precipitate, and then the solid-liquid separator I is used to separate them as solids.

[0073] Based on the above technical solution, preferably, the filtrate of the solid-liquid separator I is subjected to organic matter elimination treatment to remove organic matter, and then first undergoes iron removal treatment (named iron removal equipment) to remove iron ions, and then undergoes cobalt and manganese recovery treatment to remove and recover the cobalt and manganese ions therein;

[0074] Alternatively, the filtrate from the solid-liquid separator I is first subjected to an iron removal treatment (named an iron removal device) to remove iron ions, and then subjected to an organic matter elimination treatment to remove organic matter.

[0075] Based on the above technical solution, preferably, the outlet of the organic matter elimination equipment is first connected to the inlet of the iron removal equipment, and the liquid outlet of the iron removal equipment is connected to the inlet of the cobalt and manganese recovery equipment;

[0076] Alternatively, the liquid outlet of the solid-liquid separator I is first connected to the inlet of the iron removal device, and the liquid outlet of the iron removal device is connected to the inlet of the organic matter elimination device.

[0077] Based on the above technical solution, preferably, the iron removal equipment includes a mixing tank V and a solid-liquid separator V, and the mixing tank V is also provided with a dosing port. The outlet of the mixing tank V is connected to the inlet of the solid-liquid separator V, and the inlet of the mixing tank V is the inlet of the iron removal equipment, and the liquid outlet of the solid-liquid separator V is the outlet of the iron removal equipment.

[0078] Based on the above technical solution, preferably, the iron removal treatment is to add an alkaline substance to the aqueous solution and control the pH to filter out the iron ions into insoluble matter.

[0079] Based on the above technical solution, preferably, the mixing tank V is further provided with a dosing port for adding alkaline substances to convert the iron ions therein into insoluble substances and separate them from the aqueous solution. However, it should be noted that cobalt and manganese ions do not want to form insoluble substances, so the pH is controlled at 4.5-6.5, at which time most of the cobalt and manganese ions are still dissolved.

[0080] Based on the above technical solution, preferably, the mixing tank IV is further provided with a dosing port for adding alkaline substances, preferably sodium carbonate or sodium hydroxide.

[0081] Based on the above technical solution, preferably, the aqueous solution after the cobalt and manganese recovery treatment to remove cobalt and manganese ions is first treated by nanofiltration system I, and the fresh water obtained by the nanofiltration system I is then collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0082] Alternatively, the aqueous solution after the cobalt and manganese ions are removed through the cobalt and manganese recovery treatment is first evaporated and concentrated, and then solid-liquid separation is performed using a solid-liquid separator II. The resulting filtrate is then collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank.

[0083] Based on the above technical solution, preferably, the liquid outlet of the cobalt-manganese recovery equipment is first connected to the inlet of the nanofiltration system I, and the fresh water outlet of the nanofiltration system I is connected to the inlet of the collection tank, the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis equipment or the inlet of the evaporation tank;

[0084] Or the liquid outlet of the cobalt-manganese recovery device is first connected to the inlet of the heating evaporation device II, the outlet of the heating evaporation device II is connected to the inlet of the solid-liquid separator II, and the liquid outlet of the solid-liquid separator II is connected to the inlet of the collection tank, the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis device or the inlet of the evaporation tank.

[0085] Based on the above technical solution, preferably, the aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first evaporated and concentrated (the corresponding equipment is called heating evaporation equipment II), then cooled, and then solid-liquid separation is performed using solid-liquid separator II;

[0086] or the filtrate of the solid-liquid separator II is treated by the nanofiltration system II, and the fresh water of the nanofiltration system II is collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0087] Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first evaporated and concentrated (the corresponding equipment is called heating evaporation equipment II), then cooled, and then subjected to solid-liquid separation using solid-liquid separator II. The resulting filtrate is treated by nanofiltration system II, and the fresh water from the nanofiltration system II is then collected, heated and crystallized into a solid product, and treated using a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated using an evaporation tank.

[0088] Based on the above technical solution, preferably, the outlet of the heating evaporation device II is first connected to the inlet of the cooler II, the outlet of the cooler II is then connected to the inlet of the solid-liquid separator II, and the liquid outlet of the solid-liquid separator II is connected to the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis device, the inlet of the collection tank or the inlet of the evaporation tank;

[0089] Or the outlet of the heating evaporation device II is connected to the inlet of the solid-liquid separator II, the liquid outlet of the solid-liquid separator II is connected to the inlet of the nanofiltration system II, and the fresh water outlet of the nanofiltration system II is connected to the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis device, the inlet of the collection tank or the inlet of the evaporation tank;

[0090] Or the outlet of the heating evaporation device II is first connected to the inlet of the cooler II, the outlet of the cooler II is then connected to the inlet of the solid-liquid separator II, the liquid outlet of the solid-liquid separator II is connected to the inlet of the nanofiltration system II, and the fresh water outlet of the nanofiltration system II is connected to the inlet of the heating crystallizer II, the inlet of the bipolar membrane electrodialysis device, the inlet of the collection tank or the inlet of the evaporation tank.

[0091] Based on the above technical solution, preferably, the aqueous solution after the cobalt and manganese ions are removed by the cobalt and manganese recovery treatment is first subjected to alkali addition to adjust the pH (the corresponding alkali addition pipeline is called alkali addition pipeline I), and then is treated by the nanofiltration system I;

[0092] Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first heated (the corresponding equipment is referred to as heating equipment I) to convert bicarbonate into carbonate, and then is treated by nanofiltration system I;

[0093] Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove cobalt and manganese ions is first heated (the corresponding equipment is referred to as heating equipment I) to convert bicarbonate into carbonate, and then cooled and then processed by nanofiltration system I;

[0094] Alternatively, the aqueous solution after the cobalt-manganese recovery treatment to remove the cobalt-manganese ions is first subjected to alkali addition to adjust the pH (the corresponding alkali addition pipeline is called the alkali addition pipeline I), and then subjected to evaporation and concentration (i.e., the heating evaporation equipment II), and then subjected to solid-liquid separation in the solid-liquid separator II after the evaporation and concentration, or the evaporation and concentration are then cooled and then subjected to solid-liquid separation in the solid-liquid separator II;

[0095] Alternatively, the aqueous solution after the cobalt-manganese recovery treatment to remove cobalt-manganese ions is first heated (the corresponding equipment is referred to as heating equipment I) to convert bicarbonate into carbonate, and then evaporated and concentrated (i.e., the heating evaporation equipment II), and then passed through the solid-liquid separator II for solid-liquid separation after the evaporation and concentration, or the evaporation and concentration are then cooled and then passed through the solid-liquid separator II for solid-liquid separation.

[0096] Based on the above technical solution, preferably, an alkali adding pipeline I or a heating device I is further provided;

[0097] The alkali adding pipeline I is connected between the liquid outlet of the cobalt-manganese recovery equipment and the inlet of the nanofiltration system I, and the connection position is called the connection point a;

[0098] Or the liquid outlet of the cobalt-manganese recovery device is connected to the inlet of the heating device I, and the outlet of the heating device I is connected to the inlet of the nanofiltration system I;

[0099] Or the liquid outlet of the cobalt-manganese recovery device is connected to the inlet of the heating device I, the outlet of the heating device I is connected to the inlet of the cooler III, and the outlet of the cooler III is connected to the inlet of the nanofiltration system I;

[0100] Or the alkali adding pipeline I is connected between the liquid outlet of the cobalt-manganese recovery device and the inlet of the heating evaporation device II, and the connection position is called the connection point a;

[0101] Or the liquid outlet of the cobalt-manganese recovery device is connected to the inlet of the heating device I, and the outlet of the heating device I is connected to the inlet of the heating evaporation device II;

[0102] The purpose of adding alkali is to react bicarbonate in the aqueous solution with sodium hydroxide to form sodium carbonate, and heating is to decompose bicarbonate in the aqueous solution to form sodium carbonate + carbon dioxide (which escapes into the air). The ultimate goal is to convert sodium bicarbonate in the aqueous solution into sodium carbonate. Generally, the temperature needs to be controlled before entering the nanofiltration membrane. Too high a temperature will damage the membrane.

[0103] Sodium carbonate is separated from sodium bromide using the nanofiltration system I, that is, the aqueous solution containing sodium carbonate and sodium bromide is treated by the nanofiltration system I, and the obtained nanofiltration fresh water is an aqueous solution mainly containing sodium bromide, and the nanofiltration concentrated water is an aqueous solution mainly containing sodium carbonate, thereby achieving the separation of monovalent bromide ions and secondary carbonate ions;

[0104] Sodium carbonate is crystallized using the heating evaporation device II to obtain sodium carbonate solid, which is then separated from the sodium bromide aqueous solution (filtrate). Sodium carbonate has a lower solubility and sodium bromide has a higher solubility. Sodium carbonate and sodium bromide are separated using a method based on their different solubilities.

[0105] Based on the above technical solution, preferably, the fresh water in the nanofiltration system I is first acidified (the corresponding pipeline is called acidification pipeline I) to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0106] Alternatively, the fresh water in the nanofiltration system I is first acidified (the corresponding pipeline is called acidification pipeline I) to adjust the pH to react carbonate and bicarbonate to generate carbon dioxide, which is then removed by a decarbonization tower and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0107] Alternatively, the filtrate from the solid-liquid separator II is first subjected to acid addition (the corresponding pipeline is called acid addition pipeline I) to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0108] Alternatively, the filtrate from the solid-liquid separator II is first subjected to acid addition (the corresponding pipeline is called acid addition pipeline I) to adjust the pH to react carbonate and bicarbonate to generate carbon dioxide, and then passes through a decarbonization tower to remove the carbon dioxide, and then is collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0109] Alternatively, the fresh water in the nanofiltration system II is first acidified (the corresponding pipeline is called acidification pipeline I) to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank;

[0110] Alternatively, the fresh water in the nanofiltration system II is first acidified (the corresponding pipeline is called the acidification pipeline I) to adjust the pH to react carbonate and bicarbonate to generate carbon dioxide, and the carbon dioxide is removed by passing through a decarbonization tower. The carbon dioxide is then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank.

[0111] Based on the above technical solution, preferably, an acid addition pipeline I is further provided;

[0112] The acid addition line I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the heating crystallizer II, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the bipolar membrane electrodialysis device, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the collection tank, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the evaporation tank, and the connection position is called the connection point b;

[0113] Or a decarbonization tower I is provided, and the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system I and the inlet of the heating crystallizer II, and the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the decarbonization tower I, and the connection position is called connection point b; or a decarbonization tower I is provided, and the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system I and the inlet of the bipolar membrane electrodialysis device, and the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the decarbonization tower I, and the connection position is called connection point b. Connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system I and the inlet of the collection tank, the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the decarbonization tower I, and the connection position is called connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system I and the inlet of the evaporation tank, the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system I and the inlet of the decarbonization tower I, and the connection position is called connection point b;

[0114] Or the acid addition line I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the heating crystallizer II, and the connection position is called the connection point b; or the acid addition line I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the bipolar membrane electrodialysis device, and the connection position is called the connection point b; or the acid addition line I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the collection tank, and the connection position is called the connection point b; or the acid addition line I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the evaporation tank, and the connection position is called the connection point b;

[0115] Or a decarbonization tower I is provided, the decarbonization tower I is provided between the liquid outlet of the solid-liquid separator II and the inlet of the heating crystallizer II, the acid addition pipeline I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the decarbonization tower I, and the connection position is called connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the liquid outlet of the solid-liquid separator II and the inlet of the bipolar membrane electrodialysis device, the acid addition pipeline I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the decarbonization tower I, and the connection position is called connection point b. Connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the liquid outlet of the solid-liquid separator II and the inlet of the collecting tank, the acid addition pipeline I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the decarbonization tower I, and the connection position is referred to as connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the liquid outlet of the solid-liquid separator II and the inlet of the evaporation tank, the acid addition pipeline I is connected between the liquid outlet of the solid-liquid separator II and the inlet of the decarbonization tower I, and the connection position is referred to as connection point b;

[0116] Or the acid addition line I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the heating crystallizer II, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the bipolar membrane electrodialysis device, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the collection tank, and the connection position is called the connection point b; or the acid addition line I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the evaporation tank, and the connection position is called the connection point b;

[0117] Or a decarbonization tower I is provided, and the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system II and the inlet of the heating crystallizer II, and the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the decarbonization tower I, and the connection position is called the connection point b; or a decarbonization tower I is provided, and the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system II and the inlet of the bipolar membrane electrodialysis device, and the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the decarbonization tower I, and the connection position is called the connection point b. Connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system II and the inlet of the collection tank, the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the decarbonization tower I, and the connection position is called connection point b; or a decarbonization tower I is provided, the decarbonization tower I is provided between the fresh water outlet of the nanofiltration system II and the inlet of the evaporation tank, the acid addition pipeline I is connected between the fresh water outlet of the nanofiltration system II and the inlet of the decarbonization tower I, and the connection position is called connection point b;

[0118] The purpose of adding acid in the acid addition line I is to react with a small amount of carbonate and bicarbonate remaining in the water body, control the pH to 3-5, and generate carbon dioxide that escapes into the air. This can be beneficial in that: carbonate and bicarbonate are removed from the influent of the heating crystallizer II, resulting in a higher purity of the obtained sodium bromide solid; carbonate and bicarbonate are removed from the influent of the bipolar membrane electrodialysis device, the total amount of ions that need to be processed by the bipolar membrane electrodialysis device is reduced, the efficiency of the bipolar membrane electrodialysis device is improved, and damage to the membrane caused by carbon dioxide gas generated in the bipolar membrane electrodialysis device is avoided; carbonate and bicarbonate are removed from the collection tank, resulting in a higher purity of the obtained sodium bromide aqueous solution; carbonate and bicarbonate are removed from the influent of the evaporation tank, which is beneficial to the subsequent conversion into HBr.

[0119] Based on the above technical solution, preferably, the acid added in the acid addition line I is preferably HBr and / or acetic acid.

[0120] Based on the above technical solution, preferably, the filtrate of the solid-liquid separator II is first treated with alkali (the corresponding pipeline is called alkali adding pipeline II), and then treated by the nanofiltration system II;

[0121] Alternatively, the filtrate from the solid-liquid separator II is first heated (the corresponding device is referred to as heating device II) to convert bicarbonate into carbonate, and then is processed by the nanofiltration system II;

[0122] Alternatively, the filtrate from the solid-liquid separator II is first heated (the corresponding device is referred to as heating device II) to convert bicarbonate into carbonate, then cooled, and then processed by the nanofiltration system II;

[0123] Alternatively, the aqueous solution after the cobalt and manganese ions are removed through the cobalt and manganese recovery treatment is first evaporated and concentrated, then acidified (the corresponding pipeline is called acidification pipeline II), and then solid-liquid separation is performed using the solid-liquid separator II.

[0124] Based on the above technical solution, preferably, an alkali adding pipeline II, a heating device II or an acid adding pipeline II is further provided;

[0125] The alkali adding pipeline II is connected between the liquid outlet of the solid-liquid separator II and the inlet of the nanofiltration system II, and the connection position is called the connection point c;

[0126] Or the heating device II is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the nanofiltration system II;

[0127] Or the heating device II is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the nanofiltration system II, and then a cooler IV is further provided between the heating device II and the inlet of the nanofiltration system II;

[0128] The purpose of adding alkali and heating is also to convert bicarbonate into divalent carbonate, which is conducive to separation from sodium bromide;

[0129] Or the acid addition pipeline II is connected between the liquid outlet of the heating evaporation device II and the inlet of the solid-liquid separator II. The connection position is called connection point d. The purpose of adding acid is to convert sodium carbonate into sodium bicarbonate. Sodium bicarbonate has lower solubility and is more likely to form solid precipitation.

[0130] Based on the above technical solution, preferably, the solid in the solid-liquid separator I is also washed with water to produce a washing liquid;

[0131] or the solids in the solid-liquid separator I are slurried with water, and then separated into solid and liquid in the solid-liquid separator VI to produce a filtrate, i.e., a water washing liquid; or the solids in the solid-liquid separator I are slurried with water and separated into solid and liquid for multiple times, and then used for washing;

[0132] The washing liquid is discharged; or the washing liquid is reused in the process of adding liquid to the PTA oxidation residue as the added liquid, or the washing liquid is returned to the iron removal process for treatment, or the washing liquid is returned to the cobalt and manganese recovery process for treatment, or the washing liquid is treated by the nanofiltration system III, or the washing liquid is returned to the organic matter elimination process for treatment;

[0133] Alternatively, the solid in the solid-liquid separator VI is added with an alkaline substance and solid-liquid separation is performed using a solid-liquid separator VII, and the resulting filtrate, i.e., the water washing liquid, is refluxed to the nanofiltration system I for treatment; or the filtrate, i.e., the water washing liquid, is refluxed to the evaporation and concentration front section for evaporation and concentration, and then treated using the solid-liquid separator II, or discharged.

[0134] Based on the above technical solution, preferably, the solid-liquid separator I is further provided with a water washing liquid inlet and an outlet;

[0135] Or the solid outlet of the solid-liquid separator I is connected to the inlet of the mixing tank VI, the mixing tank VI is further provided with a wash liquid inlet, and the outlet of the mixing tank VI is connected to the inlet of the solid-liquid separator VI;

[0136] That is, the solid in the solid-liquid separator I is washed to remove the metals therein, mainly cobalt and manganese;

[0137] There are one or more mixing tanks VI; there are one or more solid-liquid separators VI;

[0138] The above-mentioned mixing tank VI + solid-liquid separator VI is used for washing once, or the washing can be repeated multiple times to further reduce the amount of cobalt and manganese ions in the solid.

[0139] Based on the above technical solution, preferably, the water washing liquid outlet of the solid-liquid separator I is connected to the inlet of the mixing tank I, the inlet of the mixing tank V, the inlet of the cobalt and manganese recovery equipment, the inlet of the nanofiltration system III, or the inlet of the organic matter elimination equipment;

[0140] Based on the above technical solution, preferably, the liquid outlet of the solid-liquid separator VI is discharged; or the liquid outlet of the solid-liquid separator VI is connected to the inlet of the mixing tank I, the inlet of the mixing tank V, the inlet of the cobalt and manganese recovery equipment, the inlet of the nanofiltration system III, or the inlet of the organic matter elimination equipment;

[0141] Based on the above technical solution, preferably, a mixing tank VII is further provided, the liquid outlet of the solid-liquid separator VI is connected to the inlet of the mixing tank VII, the mixing tank VII also has a dosing port, and the liquid outlet of the mixing tank VII is connected to the inlet of the nanofiltration system I, the inlet of the heating evaporation equipment II, the connection point a, the connection point b or the inlet of the heating equipment I, or discharge.

[0142] Based on the above technical scheme, preferably, the solid obtained by the solid-liquid separator I is incinerated (referred to as incineration equipment IV); or the solid obtained by the solid-liquid separator VI is incinerated (referred to as incineration equipment IV); or the solid obtained by the solid-liquid separator VI is subjected to a benzoic acid and phthalic acid separation process for separation; or the solid obtained by the solid-liquid separator I is subjected to a benzoic acid and phthalic acid separation process for separation; or the solid obtained by the solid-liquid separator I is subjected to an esterification reaction to generate an ester product; or the solid obtained by the solid-liquid separator VI is subjected to an esterification reaction to generate an ester product; or the solid obtained by the solid-liquid separator VI is subjected to a benzoic acid and phthalic acid separation process for separation, and the obtained benzoic acid and phthalic acid are subjected to an esterification reaction respectively to generate an ester product; or the solid obtained by the solid-liquid separator I is subjected to a benzoic acid and phthalic acid separation process for separation, and the obtained benzoic acid and phthalic acid are subjected to an esterification reaction respectively to generate an ester product.

[0143] Based on the above technical solution, preferably, the solid outlet of the solid-liquid separator I is connected to the inlet of the incineration equipment IV; or the solid outlet of the solid-liquid separator VI is connected to the inlet of the incineration equipment IV; or the solid outlet of the solid-liquid separator VI is connected to the inlet of the benzoic acid and phthalic acid separation equipment; or the solid outlet of the solid-liquid separator I is connected to the inlet of the benzoic acid and phthalic acid separation equipment; or the solid outlet of the solid-liquid separator I is connected to the inlet of the esterification reactor; or the solid outlet of the solid-liquid separator VI is connected to the inlet of the esterification reactor; or the solid outlet of the solid-liquid separator VI is connected to the inlet of the esterification reactor. Connect to the inlet of the benzoic acid and phthalic acid separation equipment, connect the benzoic acid outlet of the benzoic acid and phthalic acid separation equipment to the inlet of the esterification reactor', and / or connect the phthalic acid outlet of the benzoic acid and phthalic acid separation equipment to the inlet of the esterification reactor"; or connect the solid outlet of the solid-liquid separator I to the inlet of the benzoic acid and phthalic acid separation equipment, connect the benzoic acid outlet of the benzoic acid and phthalic acid separation equipment to the inlet of the esterification reactor', and / or connect the phthalic acid outlet of the benzoic acid and phthalic acid separation equipment to the inlet of the esterification reactor".

[0144] Based on the above technical solution, preferably, the incineration refers to burning organic matter.

[0145] Based on the above technical solution, preferably, the incineration also requires an external fuel inlet, and / or the incineration also generates steam, and the steam is used to recover the calorific value.

[0146] Based on the above technical solution, preferably, the incineration equipment IV is further provided with a fuel inlet, and / or the incineration equipment is further provided with a steam generating drum;

[0147] The steam generating drum can generate steam, which is equivalent to the recovery of calorific value, that is, the steam generating drum is a waste heat boiler, which is a device for generating steam by preheating.

[0148] Based on the above technical solution, preferably, the ash and slag after incineration are subjected to a reduction reaction with a reducing agent. The purpose of the reduction is that since the imported materials of the incineration equipment IV contain cobalt manganese ions, they will be partially oxidized into trivalent cobalt manganese ions with increased valence after incineration, and the PTA industry requires divalent cobalt manganese ions as an oxidation catalyst, so the trivalent cobalt manganese ions need to be reduced to divalent cobalt manganese ions.

[0149] Based on the above technical solution, preferably, the solid outlet after incineration of the incineration equipment IV is connected to the inlet of the reduction equipment. The purpose of reduction is that since the inlet material of the incineration equipment IV contains cobalt manganese ions, they will be partially oxidized into trivalent cobalt manganese ions with increased valence after incineration, and the PTA industry requires divalent cobalt manganese ions as an oxidation catalyst, so the trivalent cobalt manganese ions need to be reduced to divalent cobalt manganese ions.

[0150] Based on the above technical solution, preferably, the solid outlet after incineration in the incineration equipment IV is connected to the inlet of the reduction equipment, and the reduction equipment also has a reducing agent addition port.

[0151] Based on the above technical solution, preferably, the solid outlet after incineration of the incineration equipment IV is connected to the inlet of the reduction equipment, and the reduction equipment also has a reducing agent addition port and a heating device to facilitate the occurrence of the reduction reaction.

[0152] Based on the above technical solution, preferably, the reducing agent is a gaseous reducing agent such as hydrogen, carbon monoxide, and / or a solid reducing agent such as sodium sulfite, sodium bisulfite, or sodium formate.

[0153] Based on the above technical solution, preferably, the reducing agent is preferably a gas reducing agent such as hydrogen, carbon monoxide, etc., and the trivalent cobalt manganese ions are reduced by flowing through the airflow.

[0154] Based on the above technical solution, preferably, the reducing agent is a solid reducing agent such as sodium sulfite, sodium bisulfite, or sodium formate, which can be dissolved and reduced with trivalent cobalt manganese ions.

[0155] Based on the above technical solution, preferably, the reducing agent is preferably a solid reducing agent of sodium sulfite, sodium bisulfite, or sodium formate, which can be mixed with the trivalent cobalt manganese ion solid and heated for the reduction reaction to occur.

[0156] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation process adopts a sublimation process (the corresponding equipment is called a sublimation device), and the separation is achieved by utilizing the different sublimation temperatures of benzoic acid and phthalic acid; or adopts an extraction process (the corresponding equipment is called an extraction device), and the benzoic acid in the mixture is dissolved by an extractant to achieve separation from phthalic acid.

[0157] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is a sublimation equipment or an extraction equipment'.

[0158] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is a sublimation equipment, which uses the principle that benzoic acid has a low sublimation point (about 100°C) and phthalic acid has not sublimated at this temperature for separation.

[0159] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is a sublimation equipment, which uses the principle that benzoic acid has a low sublimation point (about 100°C) and phthalic acid has not yet sublimated at this temperature for separation. The outlet of the sublimation equipment is then connected to a cooling equipment to cool the benzoic acid vapor into a benzoic acid product for recovery.

[0160] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment', and the extraction equipment' is further provided with an extraction agent addition port, and the extraction is performed with water.

[0161] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment, and the extraction is performed with water, and the water is hot water. The solubility of benzoic acid in hot water is higher, while the solubility of phthalic acid in hot water is reduced, and is used for separation.

[0162] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment ', the extraction is performed with water, and the water is hot water. The solubility of benzoic acid in hot water is higher, while the solubility of phthalic acid in hot water is reduced, and is used for separation. The liquid outlet of the extraction equipment ' is connected to a cooling device, and the outlet of the cooling device is connected to the inlet of a filter, and the filter is filtered to obtain benzoic acid solid.

[0163] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment ', the extraction is performed with water, and the water is hot water. The solubility of benzoic acid in hot water is higher, while the solubility of phthalic acid in hot water is reduced, and is used for separation. The solid outlet of the extraction equipment ' (the solid outlet is a slurry outlet) is connected to the inlet of the filter ', and the filter ' filters to obtain phthalic acid solid.

[0164] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment ', the extraction is performed with water, and the water is hot water. The solubility of benzoic acid in hot water is higher, while the solubility of phthalic acid in hot water is reduced, and is used for separation. The liquid outlet of the extraction equipment ' is connected to a cooling device, the outlet of the cooling device is connected to the inlet of the filter, and the filtrate outlet of the filter is connected to the extractant addition port of the extraction equipment ', and is used for extraction again.

[0165] Based on the above technical solution, preferably, the benzoic acid and phthalic acid separation equipment is an extraction equipment ', the extraction is performed with water, and the water is hot water. The solubility of benzoic acid in hot water is higher, while the solubility of phthalic acid in hot water is reduced, and is used for separation. The solid outlet of the extraction equipment ' (the solid outlet is a slurry outlet) is connected to the inlet of the filter ', and the filtrate outlet of the filter ' is connected to the extractant addition port of the extraction equipment ', and is used for extraction again.

[0166] Based on the above technical solution, preferably, the esterification reactor further includes an alcohol inlet, and the esterification reaction occurs during the delivery to the esterification reactor.

[0167] Based on the above technical solution, preferably, the esterification reactor further adds an esterification catalyst and ensures various reaction conditions for the esterification reaction.

[0168] Based on the above technical solution, preferably, the filtrate outlet of the filter is connected to the inlet of the heater, and the outlet of the heater is connected to the extractant addition port of the extraction device for further extraction.

[0169] Based on the above technical solution, preferably, the filtrate outlet of the filter' is connected to the inlet of the heater, and the outlet of the heater is connected to the extractant addition port of the extraction device' for extraction again.

[0170] Based on the above technical solution, preferably, the aqueous solution after passing through the organic matter elimination equipment is first concentrated and then subjected to the cobalt and manganese recovery treatment;

[0171] or the aqueous solution after the cobalt and manganese recovery treatment is first concentrated and then treated by the nanofiltration system I;

[0172] or the aqueous solution after the cobalt and manganese recovery treatment is first concentrated and then subjected to the evaporation concentration treatment;

[0173] or the aqueous solution after the cobalt and manganese recovery treatment is first concentrated and then subjected to the heating treatment;

[0174] or the aqueous solution after the cobalt and manganese recovery treatment is first concentrated and then subjected to the alkali treatment;

[0175] or the heated aqueous solution is first concentrated and then processed by the nanofiltration system I;

[0176] or the aqueous solution after adding alkali is first concentrated and then processed by the nanofiltration system I;

[0177] or the heated aqueous solution is first concentrated and then subjected to the evaporation concentration treatment;

[0178] or the aqueous solution after adding alkali is first concentrated and then subjected to the evaporation concentration treatment;

[0179] Or the fresh water from the nanofiltration system I is first concentrated and then processed in the collection tank;

[0180] Or the fresh water from the nanofiltration system I is first concentrated and then processed by the heating crystallizer II;

[0181] or the fresh water from the nanofiltration system I is first concentrated and then subjected to the bipolar membrane electrodialysis treatment;

[0182] Or the fresh water from the nanofiltration system I is first concentrated and then processed by the evaporation tank;

[0183] Or the fresh water from the nanofiltration system I is first concentrated and then subjected to the acidification treatment;

[0184] or the acidified aqueous solution is first concentrated and then processed in the collection tank;

[0185] or the acidified aqueous solution is first concentrated and then treated in a heating crystallizer II;

[0186] or the acidified aqueous solution is first concentrated and then subjected to the bipolar membrane electrodialysis treatment;

[0187] or the acidified aqueous solution is first concentrated and then processed in the evaporation tank;

[0188] Or the filtrate of the solid-liquid separator II is first concentrated and then processed in the collection tank;

[0189] or the filtrate of the solid-liquid separator II is first concentrated and then processed by the heating crystallizer II;

[0190] or the filtrate of the solid-liquid separator II is first concentrated and then subjected to the bipolar membrane electrodialysis treatment;

[0191] Or the filtrate of the solid-liquid separator II is first concentrated and then processed by the evaporation tank;

[0192] or the filtrate of the solid-liquid separator II is first concentrated and then subjected to the acid treatment;

[0193] Or the fresh water from the nanofiltration system II is first concentrated and then processed in the collection tank;

[0194] Or the fresh water from the nanofiltration system II is first concentrated and then processed by the heating crystallizer II;

[0195] or the fresh water of the nanofiltration system II is first concentrated and then subjected to the bipolar membrane electrodialysis treatment;

[0196] Or the fresh water from the nanofiltration system II is first concentrated and then processed by the evaporation tank.

[0197] Based on the above technical solution, preferably, at least one of the concentration equipment II, the concentration equipment III, and the concentration equipment IV is further provided;

[0198] The concentration device II is arranged between the outlet of the organic matter elimination device and the inlet of the cobalt and manganese recovery device;

[0199] Or the concentration device III is arranged between the liquid outlet of the cobalt and manganese recovery device and the inlet of the nanofiltration system I;

[0200] Or the concentration device III is arranged between the liquid outlet of the cobalt and manganese recovery device and the inlet of the heating evaporation device II;

[0201] Or the concentration device III is arranged between the liquid outlet of the cobalt and manganese recovery device and the connection point a;

[0202] or the concentration device III is arranged between the liquid outlet of the cobalt-manganese recovery device and the inlet of the heating device I;

[0203] Or the concentration device III is arranged between the connection point a and the inlet of the nanofiltration system I;

[0204] Or the concentration device III is arranged between the outlet of the heating device I and the inlet of the nanofiltration system I;

[0205] or the concentration device III is arranged between the connection point a and the inlet of the heating evaporation device II;

[0206] Or the concentration device III is arranged between the outlet of the heating device I and the inlet of the heating evaporation device II;

[0207] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system I and the inlet of the collection tank;

[0208] Or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system I and the inlet of the heating crystallizer II;

[0209] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system I and the inlet of the bipolar membrane electrodialysis;

[0210] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system I and the inlet of the evaporation tank;

[0211] Or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system I and the connection point b;

[0212] or the concentration device IV is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the collection tank;

[0213] Or the concentration device IV is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the heating crystallizer II;

[0214] Or the concentrating device IV is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the bipolar membrane electrodialysis;

[0215] or the concentration device IV is arranged between the liquid outlet of the solid-liquid separator II and the inlet of the evaporation tank;

[0216] Or the concentration device IV is arranged between the liquid outlet of the solid-liquid separator II and the connection point b;

[0217] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system II and the inlet of the collection tank;

[0218] Or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system II and the inlet of the heating crystallizer II;

[0219] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system II and the inlet of the bipolar membrane electrodialysis;

[0220] or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system II and the inlet of the evaporation tank;

[0221] Or the concentration device IV is arranged between the fresh water outlet of the nanofiltration system II and the connection point b;

[0222] or the concentration device IV is arranged between the connection point b and the inlet of the collection tank;

[0223] or the concentrating device IV is arranged between the connection point b and the inlet of the heating crystallizer II;

[0224] or the concentrating device IV is arranged between the connection point b and the inlet of the bipolar membrane electrodialysis;

[0225] Or the concentration device IV is arranged between the connection point b and the inlet of the evaporation tank.

[0226] Based on the above technical solution, preferably, the concentration process is at least one of evaporation concentration, electrodialysis concentration, and reverse osmosis concentration.

[0227] Based on the above technical solution, preferably, the concentration device I, concentration device II, concentration device III or concentration device IV is at least one of an evaporation concentration device, an electrodialysis concentration device, and a reverse osmosis concentration device.

[0228] Based on the above technical solution, preferably, the concentrated water (mainly an aqueous solution of sodium carbonate) of the nanofiltration system I provides alkaline substances for the iron removal process, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas scrubber of the PTA plant, or is used as an alkaline substance;

[0229] or evaporating and crystallizing the concentrated water from the nanofiltration system I to obtain a solid product (i.e., sodium carbonate) (the corresponding equipment is called a heating evaporation crystallizer III);

[0230] Or the concentrated water (mainly an aqueous solution of sodium carbonate) of the nanofiltration system II provides alkaline substances for the iron removal process, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas scrubber of the PTA plant, provides alkaline substances for the evaporation and concentration, or is used as an alkaline substance;

[0231] or evaporating and crystallizing the concentrated water from the nanofiltration system II to obtain a solid product (i.e., sodium carbonate) (the corresponding equipment is called a heating evaporation crystallizer III);

[0232] Or the solid from the solid-liquid separator II provides alkaline substances for the iron removal process, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas scrubber of the PTA plant, and is dried (to obtain dry sodium carbonate) (the corresponding equipment is called drying equipment I), or is dried and then incinerated (to further remove organic matter in the dry sodium carbonate and completely incinerate it) (the corresponding equipment is called drying equipment II).

[0233] Based on the above technical solution, preferably, the concentrated water outlet of the nanofiltration system I is connected to the dosing port of the mixing tank V, the dosing port of the mixing tank IV, the dosing port of the mixing tank VII or the oxidation tail gas scrubber of the PTA plant;

[0234] Alternatively, a heating evaporation crystallizer III is provided, and the concentrated water outlet of the nanofiltration system I is connected to the inlet of the heating evaporation crystallizer III;

[0235] Or the concentrated water outlet of the nanofiltration system II is connected to at least one of the dosing port of the mixing tank V, the dosing port of the mixing tank IV, the dosing port of the mixing tank VII, the oxidation tail gas scrubber of the PTA plant, the inlet of the heating evaporation equipment II, or the inlet of the heating evaporation crystallizer III;

[0236] Alternatively, a heating evaporation crystallizer III is provided, and the concentrated water outlet of the nanofiltration system II is connected to the inlet of the heating evaporation crystallizer III;

[0237] Or the solid outlet of the solid-liquid separator II (or the form that needs to be dissolved into an aqueous solution first) is connected to at least one of the dosing port of the mixing tank V, the dosing port of the mixing tank IV, the dosing port of the mixing tank VII, the oxidation tail gas washing tower of the PTA plant, or the inlet of the drying equipment I.

[0238] Based on the above technical solution, preferably, the solid product obtained by the evaporative crystallization (i.e., the heated evaporative crystallizer III) is dried (to obtain dry sodium carbonate) (the corresponding equipment is called drying equipment II).

[0239] Or the solid product obtained by the evaporation crystallization (i.e., the heated evaporation crystallizer III) is dried (the corresponding equipment is called drying equipment II), and then the solid is incinerated (to further remove organic matter in the dry sodium carbonate and completely incinerate it) (the corresponding equipment is called incineration equipment I).

[0240] Based on the above technical solution, preferably, the solid outlet of the heating evaporation crystallizer III is connected to the inlet of the drying equipment II.

[0241] Or the solid outlet of the heating evaporation crystallizer III is connected to the inlet of the drying equipment II, and the solid outlet of the drying equipment II is connected to the inlet of the incineration equipment I;

[0242] Or the solid outlet of the drying equipment I is connected to the inlet of the incineration equipment II.

[0243] Based on the above technical solution, preferably, after the electrodialysis device extracts the aqueous solution containing inorganic matter with a relatively small proportion of organic matter, the remaining aqueous solution containing a relatively small proportion of inorganic matter, i.e., the fresh water of the electrodialysis device, is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or is treated together with the nanofiltration system III; or is treated with the nanofiltration system IV; or an alkaline substance is added and solid-liquid separation is performed using the solid-liquid separator VIII;

[0244] or the fresh water from the concentration device I is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying;

[0245] or the fresh water from the concentration device II is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying;

[0246] or the fresh water from the concentration device III is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying;

[0247] or the fresh water from the concentration device IV is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying;

[0248] or the brine of the bipolar membrane electrodialysis device is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying;

[0249] Or the organic matter adsorption equipment needs to be regenerated after adsorption saturation;

[0250] Or the solid-liquid separator IV is used in the oxidation reactor of the PTA plant after adding acid;

[0251] Or the solid-liquid separator VII is added with acid and then used in the oxidation reactor of the PTA plant;

[0252] Alternatively, the cobalt-manganese ion adsorption device needs to be regenerated after adsorption saturation, and the liquid obtained after regeneration carries the cobalt-manganese ions and is used in the oxidation reactor of the PTA plant.

[0253] Based on the above technical solution, preferably, the ion dilute liquid outlet of the electrodialysis device is connected to the liquid adding port of the mixing tank I; or the ion dilute liquid outlet of the electrodialysis device is connected to the inlet of the nanofiltration system III; or the ion dilute liquid outlet of the electrodialysis device is connected to the inlet of the nanofiltration system IV; the ion dilute liquid outlet of the electrodialysis device also contains a small amount of cobalt and manganese ions, and the nanofiltration system III is used to intercept the small amount of cobalt and manganese ions and transfer them to the concentrated water of the nanofiltration system III;

[0254] Alternatively, a mixing tank VIII and a solid-liquid separator VIII are further provided, the ion dilute liquid outlet of the electrodialysis device is connected to the inlet of the mixing tank VIII, the mixing tank VIII is further provided with a dosing port, the outlet of the mixing tank VIII is connected to the inlet of the solid-liquid separator VIII, the ion dilute liquid outlet of the electrodialysis device also contains a small amount of cobalt and manganese ions, and a sodium carbonate aqueous solution is added through the dosing port of the mixing tank VIII to precipitate and recover the cobalt and manganese ions;

[0255] or the fresh water outlet of the concentrating device I is connected to the liquid filling port of the mixing tank I;

[0256] or the fresh water outlet of the concentration device II is connected to the liquid filling port of the mixing tank I;

[0257] or the fresh water outlet of the concentrating device III is connected to the liquid filling port of the mixing tank I;

[0258] or the fresh water outlet of the concentrating device IV is connected to the liquid filling port of the mixing tank I;

[0259] Or the bipolar membrane electrodialysis equipment is further provided with a salt water tank, and the salt water tank of the bipolar membrane electrodialysis is connected to the liquid filling port of the mixing tank I;

[0260] Or the organic matter adsorption device is further provided with a regeneration liquid inlet and an outlet, and the regeneration liquid outlet is discharged;

[0261] Alternatively, the solid-liquid separator IV is further provided with an acid addition port and an acid liquid outlet, and the acid liquid outlet of the solid-liquid separator IV is connected to an oxidation reactor of a PTA plant; that is, the carbonate precipitate of cobalt and manganese is dissolved with acid and then returned to the oxidation reactor of the PTA plant for reuse as a catalyst;

[0262] Alternatively, the solid-liquid separator VII is further provided with an acid addition port and an acid liquid outlet, and the acid liquid outlet of the solid-liquid separator VII is connected to an oxidation reactor of a PTA plant; that is, the cobalt and manganese carbonate precipitates are dissolved with acid and then returned to the oxidation reactor of the PTA plant for reuse as a catalyst;

[0263] Alternatively, the cobalt-manganese ion adsorption device is further provided with a regeneration liquid inlet and outlet, and the regeneration liquid outlet of the cobalt-manganese ion adsorption device is connected to the oxidation reactor of the PTA plant, that is, the cobalt-manganese ions are regenerated with acid and then returned to the oxidation reactor of the PTA plant for use as a catalyst again.

[0264] Based on the above technical solution, preferably, the filtrate of the solid-liquid separator VIII is discharged.

[0265] Based on the above technical solution, preferably, the evaporation tank is added with chemicals and heated, and the evaporated steam is collected by a collection tank; or the evaporated steam is absorbed by water.

[0266] Based on the above technical solution, preferably, the evaporation tank is further provided with a heater and a dosing port, and the gas phase outlet of the evaporation tank is connected to a collection tank or a water absorption acid generator; the dosing port of the evaporation tank has two types of chemical agents added:

[0267] One method is to add a non-volatile acid. This method utilizes the principle of producing a volatile acid from a non-volatile acid. A non-volatile acid (such as sulfuric acid or phosphoric acid) is added to the dosing port of the evaporation tank and heated to convert sodium bromide + sulfuric acid (or phosphoric acid) into hydrobromic acid, which is then heated and evaporated into a gas phase and then collected in the collection tank or passed through the water absorption acid generator and absorbed into water to form a hydrobromic acid aqueous solution.

[0268] Another method is to add an oxidant (such as chlorine, or sodium hypochlorite + hydrochloric acid, hydrogen peroxide, etc.) to oxidize the sodium bromide into bromine, and then evaporate it through heating to obtain bromine vapor, which is then collected in the collection tank (the gaseous bromine must first be cooled in a cooler to liquefy it).

[0269] Based on the above technical solution, preferably, the liquid obtained by absorption with water is heated, and the evaporated steam is collected by a "collection tank"; or the evaporated steam is absorbed with water.

[0270] Alternatively, the liquid obtained by the water absorption is added with chemicals and heated, and the evaporated steam is collected by a "collection tank"; or the evaporated steam is absorbed by water.

[0271] Based on the above technical solution, preferably, the liquid outlet of the water absorption acid generator is further provided with a heater, or the liquid outlet of the water absorption acid generator is connected to the inlet of the evaporation tank, the evaporation tank is provided with a heater, and the gas phase outlet of the evaporation tank is connected to the collection tank or the water absorption acid generator; or the liquid outlet of the water absorption acid generator is connected to the inlet of the evaporation tank, the evaporation tank is provided with a heater and a dosing port, and the gas phase outlet of the evaporation tank is connected to the collection tank or the water absorption acid generator;

[0272] When adding a non-volatile acid to the evaporation tank, the evaporated hydrobromic acid vapor may contain a small amount of non-volatile acid droplets (e.g., sulfuric acid) carried by the steam and water. The non-volatile acid droplets are heated and evaporated again in the evaporation tank and absorbed by the water-absorbing acid generator, thereby reducing the content of non-volatile acid droplets in the hydrobromic acid vapor and reducing impurities in the hydrobromic acid.

[0273] When adding a non-volatile acid to the evaporation tank, the evaporated hydrobromic acid vapor may contain a small amount of non-volatile acid droplets (e.g., sulfuric acid) entrained with soda and water. Adding a chemical (e.g., barium hydroxide) to the evaporation tank and heating and evaporating it again reduces the non-volatile acid droplet content in the hydrobromic acid vapor, resulting in fewer impurities in the hydrobromic acid. Note: The sulfuric acid in the hydrobromic acid solution reacts with the barium hydroxide to form barium sulfate, which has extremely low solubility. Further heating of the evaporation tank evaporates the hydrobromic acid vapor, which is then absorbed by the water-absorbing acid generator, significantly reducing the sulfuric acid content in the hydrobromic acid.

[0274] Based on the above technical solution, preferably, the filtrate of the solid-liquid separator I is first deoxidized and then subjected to the organic matter elimination treatment;

[0275] or the aqueous solution after the organic matter elimination treatment is first deoxidized and then subjected to the cobalt and manganese recovery treatment;

[0276] or the aqueous solution after the cobalt and manganese recovery treatment is first deoxidized and then treated by the nanofiltration system I;

[0277] or the aqueous solution after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the evaporation and concentration treatment (i.e., heating evaporation equipment II);

[0278] or the aqueous solution after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the alkali treatment;

[0279] or the aqueous solution after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the heating treatment;

[0280] or the aqueous solution after adding alkali is firstly deoxidized and then processed by the nanofiltration system I;

[0281] or the aqueous solution after adding alkali is first deoxidized and then subjected to the evaporation and concentration treatment (i.e., heating evaporation equipment II);

[0282] or the filtrate of the solid-liquid separator II is first deoxidized and then processed by the nanofiltration system II;

[0283] or the filtrate from the solid-liquid separator II is first deoxidized and then processed through the collection tank;

[0284] or the filtrate of the solid-liquid separator II is first deoxidized and then processed by the heating crystallizer II;

[0285] or the filtrate of the solid-liquid separator II is first deoxidized and then subjected to the bipolar membrane electrodialysis treatment;

[0286] or the filtrate from the solid-liquid separator II is first deoxidized and then processed through the evaporation tank;

[0287] or the filtrate of the solid-liquid separator II is first deoxidized and then subjected to the acid treatment;

[0288] or the acidified aqueous solution is first deoxidized and then processed in the collection tank;

[0289] or the acidified aqueous solution is first deoxidized and then treated in the heating crystallizer II;

[0290] or the acidified aqueous solution is first deoxidized and then subjected to the bipolar membrane electrodialysis treatment;

[0291] or the acidified aqueous solution is first deoxidized and then processed in the evaporation tank;

[0292] Based on the above technical solution, preferably, an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator I and the inlet of the organic matter elimination device, or between the outlet of the organic matter elimination device and the cobalt-manganese recovery device;

[0293] Or an oxidizing removal device is provided between the outlet of the cobalt-manganese recovery device and the inlet of the nanofiltration system I, between the outlet of the cobalt-manganese recovery device and the inlet of the heating evaporation device II, between the outlet of the cobalt-manganese recovery device and the connection point a, between the connection point a and the inlet of the nanofiltration system I, or between the connection point a and the inlet of the heating evaporation device II;

[0294] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the inlet of the nanofiltration system II;

[0295] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the inlet of the collecting tank;

[0296] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the inlet of the heating crystallizer II;

[0297] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the inlet of the bipolar membrane electrodialysis;

[0298] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the inlet of the evaporation tank;

[0299] Or an oxidizing removal device is provided between the liquid outlet of the solid-liquid separator II and the connection point b;

[0300] Or an oxidizing removal device is provided between the connection point b and the inlet of the collection tank;

[0301] Or an oxidizing removal device is provided between the connection point b and the inlet of the heating crystallizer II;

[0302] Or an oxidizing removal device is provided between the connection point b and the inlet of the bipolar membrane electrodialysis;

[0303] Or an oxidizing removal device is provided between the connection point b and the inlet of the evaporation tank.

[0304] Based on the above technical solution, preferably, the oxidizing removal equipment refers to equipment that can remove oxidizing agents in water, including reducing agent addition equipment or fixed bed oxidizing removal equipment or evaporation equipment or oxidizing adsorption equipment.

[0305] Based on the above technical solution, preferably, the oxidizing agent removal equipment refers to equipment that can remove oxidizing agents in water, including a reducing agent adding equipment, which adds a reducing agent, and the reducing agent includes an organic reducing agent or an inorganic reducing agent.

[0306] Based on the above technical solution, preferably, the organic reducing agent is such as formaldehyde, acetaldehyde, formic acid, sodium formate, etc.; the inorganic reducing agent is such as sodium bisulfite, etc.

[0307] Based on the above technical solution, preferably, the oxidizing removal equipment refers to evaporation equipment, which evaporates the oxidizing substances in the water into the gas phase to reduce the oxidizing properties of the water.

[0308] Based on the above technical solution, preferably, the oxidizing removal device refers to an oxidizing adsorption device, and the oxidizing adsorption device is filled with a filler that has an adsorption effect on oxidizing.

[0309] Based on the above technical solution, preferably, the oxidizing removal device refers to an oxidizing adsorption device, and the oxidizing adsorption device is filled with a filler that has an adsorption effect on oxidizing, and the filler is preferably activated carbon, molecular sieve or a resin that has an adsorption effect on oxidizing.

[0310] Based on the above technical solution, preferably, the oxidizing removal device refers to an oxidizing adsorption device, and the oxidizing adsorption device is filled with a filler that has an adsorption effect on oxidizing, and the filler is preferably activated carbon, molecular sieve or a resin that has an adsorption effect on oxidizing, and the oxidizing adsorption device is regenerated after adsorption saturation.

[0311] Based on the above technical solution, preferably, the oxidative adsorption device is regenerated after adsorption saturation, and the regeneration is preferably regenerated with an alkaline aqueous solution or steam.

[0312] Based on the above technical solution, preferably, the alkali generated by the bipolar membrane electrodialysis device is used for the alkali addition or as an alkaline substance;

[0313] or the acid produced by the bipolar membrane electrodialysis device is used for the acid addition, and / or is used in the oxidation reactor of the PTA plant;

[0314] Or the ash and slag after incineration are subjected to reduction reaction with a reducing agent.

[0315] Based on the above technical solution, preferably, the heating crystallizer I is a thin film evaporator;

[0316] Or the bipolar membrane electrodialysis equipment is provided with an acid production tank and an alkali production tank, the outlet of the acid production tank of the bipolar membrane electrodialysis equipment is connected to the acid addition pipeline I or the acid addition pipeline II, and the oxidation reactor of the PTA plant, and / or, the outlet of the alkali production tank of the bipolar membrane electrodialysis equipment is connected to the oxidation tail gas washing tower of the PTA plant, the alkali addition pipeline I or the alkali addition pipeline II.

[0317] Based on the above technical solution, preferably, the fresh water of the nanofiltration system III is used for washing the solid-liquid separator I, for beating the solid-liquid separator I, or is reused as the added liquid in the beating process of adding liquid to the PTA oxidation residue;

[0318] Or the fresh water of the nanofiltration system IV is used for washing the solid-liquid separator I, for beating the solid-liquid separator I, or is reused for adding liquid to the PTA oxidation residue in the beating process as the added liquid;

[0319] Or the concentrated water from the nanofiltration system III enters the organic matter elimination treatment;

[0320] Or the concentrated water from the nanofiltration system IV enters the organic matter elimination treatment.

[0321] Based on the above technical solution, preferably, the fresh water outlet of the nanofiltration system III is connected to the inlet of the mixing tank I and the inlet of the mixing tank VI.

[0322] Based on the above technical solution, preferably, the fresh water outlet of the nanofiltration system IV is connected to the inlet of the mixing tank I and the inlet of the mixing tank VI.

[0323] Based on the above technical solution, preferably, the concentrated water outlet of the nanofiltration system III is connected to the inlet of the organic matter elimination equipment.

[0324] Based on the above technical solution, preferably, the concentrated water outlet of the nanofiltration system IV is connected to the inlet of the organic matter elimination equipment.

[0325] Based on the above technical solution, preferably, the purpose of the nanofiltration system III is to intercept the cobalt and manganese ions in the influent of the nanofiltration system III to the concentrated water side, and then enter the organic matter elimination equipment, and the organic matter in the cobalt and manganese ions is removed by the organic matter elimination equipment, and then enters the cobalt and manganese recovery equipment to recover cobalt and manganese.

[0326] Based on the above technical solution, preferably, the alkaline substance is used to convert the cobalt and manganese ions into insoluble substances to facilitate subsequent solid-liquid separation.

[0327] Based on the above technical solution, preferably, the alkaline substance is used to convert the cobalt manganese ions into insoluble substances, preferably sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0328] Based on the above technical solutions, preferably, the nanofiltration system I, nanofiltration system II, nanofiltration system III or nanofiltration system IV include various forms such as single-stage nanofiltration, single-stage multi-stage nanofiltration, multi-stage multi-stage nanofiltration, and require a matching high-pressure pump; the reverse osmosis is the same; Note: Nanofiltration (or reverse osmosis) fresh water is then treated with nanofiltration (or reverse osmosis) and is called multi-stage, and nanofiltration (or reverse osmosis) concentrated water is then treated with nanofiltration (or reverse osmosis) and is called multi-stage.

[0329] Based on the above technical solution, preferably, filtering equipment is added as needed at any position required by the process to physically remove colloids, SS, etc. in the water to avoid subsequent clogging problems.

[0330] Based on the above technical solution, preferably, filtering equipment is added as needed at any position required by the process to physically remove colloids, SS, etc. in the water to avoid subsequent clogging problems. The filtering equipment is preferably ultrafiltration, bag filter, microfiltration, security filter or PP cotton filter, etc.

[0331] Based on the above technical solution, preferably, if there are other bromine-containing aqueous solutions, they can also be incorporated into this system for treatment, and the incorporation point can be at any position in this system.

[0332] Beneficial effects

[0333] The present invention provides a treatment method for resource recovery of PTA oxidation residue. The method is used to treat PTA oxidation residue to recover the value of bromine therein, turning waste into treasure. At the same time, a mixture of organic acids containing benzoic acid, phthalic acid and the like is separated and can be incinerated to generate steam and recover calorific value; or the separated mixed organic matter containing benzoic acid and phthalic acid is separated into two products, benzoic acid and phthalic acid, which can also generate value; or the separated mixed organic matter containing benzoic acid and phthalic acid is subjected to an esterification reaction to generate esters, which can also generate value; or the separated mixed organic matter containing benzoic acid and phthalic acid is separated into two products, benzoic acid and phthalic acid, which are subjected to esterification reactions to generate esters, which can also generate value. BRIEF DESCRIPTION OF THE DRAWINGS

[0334] Figure 1 This is a schematic diagram of Example 1.

[0335] Figure 2 This is a schematic diagram of Example 2.

[0336] Figure 3 This is a schematic diagram of Example 3.

[0337] Figure 4 This is a schematic diagram of Example 4.

[0338] Figure 5 This is a schematic diagram of Example 5.

[0339] Figure 6 This is a schematic diagram of Example 6.

[0340] Figure 7 This is a schematic diagram of Example 7.

[0341] Figure 8 This is a schematic diagram of Example 8.

[0342] Figure 9 This is a schematic diagram of Example 9.

[0343] legend:

[0344]

[0345] DETAILED DESCRIPTION

[0346] The following non-limiting examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.

[0347] Example 1

[0348] A processing system for resource recovery of PTA oxidation residue mainly includes a heating crystallizer I 001, a mixing tank I 002, a solid-liquid separator I 004, an organic matter elimination device (an organic matter adsorption device 013 filled with resin having adsorption effect on terephthalic acid, benzoic acid, and their corresponding acid radicals), a cobalt and manganese recovery device (including a mixing tank IV 014 and a solid-liquid separator IV 016), an oxidizing removal device 057, a nanofiltration membrane 022 of a nanofiltration system I, a concentration system III (using a reverse osmosis membrane 027 as an example), a collection tank 030 or a bipolar membrane electrodialysis device 031 or an evaporation tank 037 or a heating crystallizer II 051.

[0349] The solid outlet of the heating crystallizer Ⅰ001 is connected to the inlet of the mixing tank Ⅰ002, and the mixing tank Ⅰ002 is also provided with a liquid adding port 003 and a vacuum cooling device 007. The outlet of the mixing tank Ⅰ002 is connected to the inlet of the solid-liquid separator Ⅰ004, and the liquid outlet 006 of the solid-liquid separator Ⅰ004 is connected to the inlet of the organic adsorption device 013. The outlet of the organic adsorption device 013 is connected to the inlet of the mixing tank IV014. The mixing tank IV014 is also provided with a drug adding port 015. The outlet of the mixing tank IV014 is connected to the inlet of the solid-liquid separator IV016. The liquid outlet 018 of the solid-liquid separator IV016 is connected to the alkali adding stirring tank 019. The alkali adding stirring tank 019 is also provided with an alkali adding pipeline Ⅰ020.

[0350] The solid outlet 005 of the solid-liquid separator I 004 is connected to the inlet of the mixing tank VI 058, which is also provided with a washing liquid inlet 059. The outlet of the mixing tank VI 058 is connected to the inlet of the solid-liquid separator VI 060, the liquid outlet 062 of the solid-liquid separator VI 060 is connected to the liquid addition port 003 of the mixing tank I 002, and the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration device IV 008. The incineration device IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010.

[0351] The outlet of the alkali addition stirring tank 019 is connected to the inlet of the oxidizing removal device 057, the outlet of the oxidizing removal device 057 is connected to the inlet of the nanofiltration membrane 022 of the nanofiltration system I through the high-pressure pump 021 of the nanofiltration system I, the concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the dosing port 015 of the mixing tank IV 014, the fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the inlet of the buffer tank 025, the buffer tank 025 is connected to the reverse osmosis membrane 027 through the high-pressure pump 026 of the reverse osmosis membrane, the concentrated water outlet 028 of the reverse osmosis membrane 027 is connected to the inlet of the acid addition stirring tank 029, and the acid addition stirring tank 029 is also provided with an acid addition pipeline I 056;

[0352] There are four connection methods:

[0353] (1) The outlet of the acid adding stirring tank 029 is connected to the inlet of the collecting tank 030;

[0354] (2) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the bipolar membrane electrodialysis device 031. The bipolar membrane electrodialysis device 031 is further provided with an alkali-producing tank 032, an acid-producing tank 034, and a desalted brine tank 033. The outlet of the alkali-producing tank 032 is connected to the alkali-adding pipeline I 020 of the alkali-adding stirring tank 019. The outlet of the desalted brine tank 033 is connected to the inlet of the buffer tank 025. The outlet I 035 of the acid-adding stirring tank 034 is connected to the acid-adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 036 of the acid-generating tank 034 is connected to the oxidation system of the PTA device.

[0355] (3) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the evaporation tank 037. The evaporation tank 037 is also provided with a heater 038 and a dosing port 039. The gas phase outlet 040 of the evaporation tank 037 is connected to the inlet of the water absorption acid generator 041. The water absorption acid generator 041 is also provided with a water adding point 042. The liquid outlet of the water absorption acid generator 041 is connected to the inlet of the evaporation tank '043. The evaporation tank '043 is also provided with a heater '044 and a dosing port '045. The gas phase outlet 046 of the evaporation tank '043 is connected to the inlet of the water absorption acid generator '047. The water absorption acid generator '047 is also provided with a water adding point '048. The outlet I 049 of the water absorption acid generator '047 is connected to the acid adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 050 of the water absorption acid generator '047 is connected to the oxidation system of the PTA device.

[0356] (4) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the heating crystallizer II 051. The heating crystallizer II 051 is also provided with a heater 052. The outlet of the heating crystallizer II 051 is connected to the inlet of the centrifuge 053. The solid outlet of the centrifuge 053 is collected and the liquid outlet of the centrifuge 053 is connected to the inlet of the heating crystallizer II 051.

[0357] The above system operates as follows:

[0358] The target material processed in this embodiment is the oxidation residue of PTA. The target material processed in all embodiments of the present invention is the oxidation residue of PTA. The source of the oxidation residue of PTA is the heating crystallizer Ⅰ001 equipment.

[0359] The source of PTA oxidation residue is the heating crystallizer Ⅰ001 equipment. The solid outlet of the heating crystallizer Ⅰ001 is the oxidation residue of PTA, which enters the mixing tank Ⅰ002 and is added with water (the source is the liquid addition port 003, about five times the volume) for stirring and beating, and is vacuumed with the vacuum cooling equipment 007 to ensure that the temperature is about 35-40 ° C. After solid-liquid separation in the solid-liquid separator Ⅰ004, the liquid outlet 006 of the solid-liquid separator Ⅰ004 is mainly an aqueous solution containing inorganic ions (which still contains a small amount of benzoic acid, phthalic acid and its acid radical). The organic adsorption device 013 adsorbs benzoic acid, phthalic acid and its acid radicals, and then enters the mixer IV 014, and sodium carbonate aqueous solution is added to the mixer IV 014 (from the dosing port 015), and then the solid-liquid separation is carried out by the solid-liquid separator IV 016. After the filtrate of the solid-liquid separator IV 016 is adjusted by adding sodium hydroxide (sodium hydroxide aqueous solution is added through the alkali adding stirring tank 019 and the alkali adding pipeline I 020) to adjust the pH, it first passes through the deoxidizing device 057 (filled with adsorption filler: activated carbon) to remove the oxidizing properties, and then passes through the nanofiltration membrane 022 of the nanofiltration system I;

[0360] The solids from the solid-liquid separator I004 are washed with a mixing tank VI058. Water (approximately five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing. The solid and liquid are then separated using a solid-liquid separator VI060. The resulting liquid is circulated back to the mixer I002. The resulting solids are collected and incinerated using an incineration device IV008 and fuel is added (from the fuel inlet 009) for incineration. The steam generator drum 010 is used to generate steam for reuse of heat value.

[0361] The concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I flows back to the dosing port 015 of the mixer IV 014 to provide sodium carbonate. The fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I (mainly sodium bromide) is concentrated by the concentration system III (using the reverse osmosis membrane 027 as an example), and then acid is added to neutralize the sodium carbonate and hydrobromic acid (through the acid addition stirring tank 029 and the acid addition pipeline I 056, the acid addition pipeline I 056 is used to provide hydrobromic acid). There are four treatment methods:

[0362] (1) Collect with collection tank 030;

[0363] (2) The alkali obtained is treated by bipolar membrane electrodialysis equipment 031, and the alkali is circulated back to the alkali adding pipeline I020 of the alkali adding stirring tank 019 to provide sodium hydroxide; a part of the hydrobromic acid obtained is circulated back to the acid adding pipeline I056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device; the sodium bromide liquid of the light brine tank 033 is circulated back to the buffer tank 025, and after being concentrated by the reverse osmosis membrane again, it is circulated back to the bipolar membrane electrodialysis equipment 031 for further treatment;

[0364] (3) Treat with evaporation tank 037, add sulfuric acid from the dosing port 039 of evaporation tank 037, and heat with heater 038 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator 041 to form hydrobromic acid aqueous solution. Then the hydrobromic acid aqueous solution enters evaporation tank '043, and add barium hydroxide from the dosing port '045 of evaporation tank '043, and heat with heater '044 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator '047 to form hydrobromic acid aqueous solution. A part of the hydrobromic acid aqueous solution is recycled back to the acid adding pipeline Ⅰ 056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device;

[0365] (4) Evaporation and concentration are carried out in a heating crystallizer II 051, and a sodium bromide solid product is produced in a centrifuge 053. The filtrate of the centrifuge 053 is returned to the heating crystallizer II 051 for reheating, and a continuous cycle is carried out to produce a sodium bromide solid product.

[0366] Note: The nanofiltration membrane used in all embodiments of the present invention is DuPont brand FilmTec TMThe NF270-400 / 34i was used, and the bipolar membrane electrodialysis system was the EX-4S provided by Hangzhou Lanran Technology Co., Ltd. The reverse osmosis membrane used was the DuPont SW30HRLE-440i. The filter was a commercially available 5µm pore-size PP cotton filter element. All solid-liquid separators were centrifuges. The resin for adsorption of cobalt and manganese ions was a commercially available conventional cationic resin, and the resin for adsorption of organic matter (benzoic acid and its radicals, phthalic acid and its radicals) was the American Dusheng brand macroporous adsorption resin (organic adsorption resin) ADS-850FG. Experiments were run using the above system and method:

[0367] Sampling analysis from solid outlet 005 of solid-liquid separator I 004 showed: cobalt ion = 6513 ppm, manganese ion = 3535 ppm, bromide ion = 4003 ppm, and water content of approximately 50%;

[0368] Sampling analysis from the solid outlet 061 of the solid-liquid separator VI 060 showed: cobalt ion = 553 ppm, manganese ion = 297 ppm, bromide ion = 332 ppm, and water content of approximately 50%;

[0369] Sampling analysis was performed from the liquid outlet 006 of the solid-liquid separator I 004: benzoic acid and its acid radical (BA) = 6565 ppm, phthalic acid and its acid radical = 3821 ppm, cobalt ion = 6672 ppm, manganese ion = 3999 ppm, bromide ion = 4551 ppm;

[0370] Sampling analysis from the outlet of organic adsorption device 013: benzoic acid and its acid radical (BA) = 3 ppm, phthalic acid and its acid radical = 1.1 ppm;

[0371] Sampling analysis was performed from the liquid outlet 018 of the solid-liquid separation device IV 016: cobalt ion 1.3ppm, manganese ion 2.5ppm, bromide ion 4593ppm;

[0372] The pH of the effluent from the alkali-adding mixing tank 019 was controlled to be 11.5, the starch oxidizing property was tested to be 12 ppm by the potassium iodide method, and the oxidizing property at the outlet of the oxidizing removal device 057 was not tested;

[0373] Analysis of concentrated water outlet 023 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 51315 ppm, bromide 1077 ppm; analysis of fresh water outlet 024 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 2513 ppm, bromide 5032 ppm;

[0374] The pH of the acid addition stirring tank 029 was controlled to be 3.5, and the sodium bromide was controlled to be 81303 ppm.

[0375] There are four ways to handle it:

[0376] (1) Collecting the sodium bromide aqueous solution product;

[0377] (2) The acid production tank 034 of the bipolar membrane electrodialysis equipment 031 was sampled and analyzed as follows: hydrogen ion 1.01 mol / L, bromide ion 8.03%, sodium ion 71 ppm, proving that the product was hydrobromic acid;

[0378] (3) The liquid outlet sampling of water absorption acid generator 041 was analyzed as follows: hydrobromic acid content 28.8%, sulfate 337ppm; the liquid outlet sampling of water absorption acid generator '047 was analyzed as follows: hydrobromic acid content 31.1%, sulfate undetectable;

[0379] (4) The solid outlet 054 of the centrifuge 053 of the heating crystallizer II 051 was sampled and analyzed as follows: the sodium bromide content was 99.1%.

[0380] Conclusion: After processing by this system:

[0381] The solid outlet 005 of the solid-liquid separator I 004 is washed by the mixing tank VI 058 + solid-liquid separator VI 060, thereby reducing the total amount of cobalt and manganese ions in the solid and reducing the waste of cobalt and manganese ions. In addition, steam is generated through incineration, and the calorific value is recovered.

[0382] The liquid outlet 006 of the solid-liquid separator I 004 first passes through the organic matter elimination equipment 013 to remove benzoic acid, phthalic acid and its acid radicals, and then passes through the mixing tank IV 014 + solid-liquid separator IV 016 to remove cobalt and manganese ions (which is equivalent to recovering cobalt and manganese). After that, the sodium carbonate and sodium bromide are separated by the nanofiltration membrane 022. The separated sodium carbonate is returned for cobalt and manganese precipitation recovery. The obtained sodium bromide aqueous solution is concentrated and acidified to remove the sodium carbonate still contained therein, and can be treated in four ways:

[0383] (1) A sodium bromide aqueous solution can be collected;

[0384] (2) The hydrobromic acid product can be obtained by using bipolar membrane electrodialysis equipment 031;

[0385] (3) The evaporation tank 037 can be used in conjunction with the water absorption acid generator 041 to convert the hydrobromic acid product, but it contains a small amount of sulfuric acid. At the same time, the evaporation tank '043 can be used in conjunction with the water absorption acid generator '047 to convert the hydrobromic acid product without sulfuric acid;

[0386] (4) Treat with heating crystallizer II to obtain sodium bromide solid.

[0387] Example 2

[0388] A processing system for resource recovery of PTA oxidation residue mainly includes a heating crystallizer I001, a mixing tank I002, a solid-liquid separator I004, an organic matter elimination device (an organic matter adsorption device 013 filled with terephthalic acid, benzoic acid, and resins with adsorption effects on their corresponding acid radicals), a cobalt and manganese recovery device (including a mixing tank IV014 and a solid-liquid separator IV016), an oxidizing removal device 057, a heating evaporation device II011, a solid-liquid separator II063, a collecting tank 030 or a bipolar membrane electrodialysis device 031 or an evaporation tank 037 or a heating crystallizer II051.

[0389] The solid outlet of the heating crystallizer Ⅰ001 is connected to the inlet of the mixing tank Ⅰ002, and the mixing tank Ⅰ002 is also provided with a liquid adding port 003 and a vacuum cooling device 007. The outlet of the mixing tank Ⅰ002 is connected to the inlet of the solid-liquid separator Ⅰ004, and the liquid outlet 006 of the solid-liquid separator Ⅰ004 is connected to the inlet of the organic adsorption device 013. The outlet of the organic adsorption device 013 is connected to the inlet of the mixing tank IV014. The mixing tank IV014 is also provided with a drug adding port 015. The outlet of the mixing tank IV014 is connected to the inlet of the solid-liquid separator IV016. The liquid outlet 018 of the solid-liquid separator IV016 is connected to the alkali adding stirring tank 019. The alkali adding stirring tank 019 is also provided with an alkali adding pipeline Ⅰ020.

[0390] The solid outlet 005 of the solid-liquid separator I 004 is connected to the inlet of the mixing tank VI 058, which is also provided with a washing liquid inlet 059. The outlet of the mixing tank VI 058 is connected to the inlet of the solid-liquid separator VI 060, the liquid outlet 062 of the solid-liquid separator VI 060 is connected to the liquid addition port 003 of the mixing tank I 002, and the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration device IV 008. The incineration device IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010.

[0391] The outlet of the alkali adding stirring tank 019 is connected to the inlet of the oxidizing removal device 057, the outlet of the oxidizing removal device 057 is connected to the inlet of the heating evaporation device II 011, the heating evaporation device II 011 is further provided with a heater 012, the outlet of the heating evaporation device II 011 is connected to the inlet of the solid-liquid separator II 063, the liquid outlet 065 of the solid-liquid separator II 063 is connected to the inlet of the acid adding stirring tank 029, and the acid adding stirring tank 029 is further provided with an acid adding pipeline I 056;

[0392] There are four connection methods:

[0393] (1) The outlet of the acid adding stirring tank 029 is connected to the inlet of the collecting tank 030;

[0394] (2) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the bipolar membrane electrodialysis device 031. The bipolar membrane electrodialysis device 031 is further provided with an alkali-producing tank 032, an acid-producing tank 034, and a desalted brine tank 033. The outlet of the alkali-producing tank 032 is connected to the alkali-adding pipeline I 020 of the alkali-adding stirring tank 019. The outlet of the desalted brine tank 033 is connected to the inlet of the alkali-adding stirring tank 019. The outlet I 035 of the acid-adding tank 034 is connected to the acid-adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 036 of the acid-adding tank 034 is connected to the oxidation system of the PTA device.

[0395] (3) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the evaporation tank 037. The evaporation tank 037 is also provided with a heater 038 and a dosing port 039. The gas phase outlet 040 of the evaporation tank 037 is connected to the inlet of the water absorption acid generator 041. The water absorption acid generator 041 is also provided with a water adding point 042. The liquid outlet of the water absorption acid generator 041 is connected to the inlet of the evaporation tank '043. The evaporation tank '043 is also provided with a heater '044 and a dosing port '045. The gas phase outlet 046 of the evaporation tank '043 is connected to the inlet of the water absorption acid generator '047. The water absorption acid generator '047 is also provided with a water adding point '048. The outlet I 049 of the water absorption acid generator '047 is connected to the acid adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 050 of the water absorption acid generator '047 is connected to the oxidation system of the PTA device.

[0396] (4) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the heating crystallizer II 051. The heating crystallizer II 051 is also provided with a heater 052. The outlet of the heating crystallizer II 051 is connected to the inlet of the centrifuge 053. The solid outlet of the centrifuge 053 is collected and the liquid outlet of the centrifuge 053 is connected to the inlet of the heating crystallizer II 051.

[0397] The above system operates as follows:

[0398] The target material processed in this embodiment is the oxidation residue of PTA. The target material processed in all embodiments of the present invention is the oxidation residue of PTA. The source of the oxidation residue of PTA is the heating crystallizer Ⅰ001 equipment.

[0399] The source of PTA oxidation residue is the heating crystallizer Ⅰ001 equipment. The solid outlet of the heating crystallizer Ⅰ001 is the oxidation residue of PTA. It enters the mixing tank Ⅰ002 and adds water (the source is the liquid addition port 003, about five times the volume) to stir and slurry, and is vacuumed by the vacuum cooling equipment 007 to ensure the temperature is about 35-40℃. After solid-liquid separation in the solid-liquid separator Ⅰ004, the liquid outlet 006 of the solid-liquid separator Ⅰ004 is mainly an aqueous solution containing inorganic ions (which still contains a small amount of benzoic acid, phthalic acid and its acid radicals). The organic adsorption device 013 adsorbs benzoic acid, phthalic acid and its acid radicals, and then enters the mixer IV 014, and sodium carbonate aqueous solution is added to the mixer IV 014 (from the dosing port 015), and then the solid-liquid separation is carried out in the solid-liquid separator IV 016. The filtrate of the solid-liquid separator IV 016 is adjusted by adding sodium hydroxide (sodium hydroxide aqueous solution is added through the alkali stirring tank 019 and the alkali adding pipeline I 020) to adjust the pH, and then first passes through the deoxidizing device 057 (filled with adsorption filler: activated carbon) to remove the oxidizing properties, and then is treated by the heating evaporation device II 011;

[0400] The solids from the solid-liquid separator I004 are washed with a mixing tank VI058. Water (approximately five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing. The solid and liquid are then separated using a solid-liquid separator VI060. The resulting liquid is circulated back to the mixer I002. The resulting solids are collected and incinerated using an incineration device IV008 and fuel is added (from the fuel inlet 009) for incineration. The steam generator drum 010 is used to generate steam for reuse of heat value.

[0401] The evaporation equipment II011 is heated and the solid-liquid separation is carried out in the solid-liquid separator II063. The filtrate is then acidified to neutralize the sodium carbonate and hydrobromic acid (through the acid addition stirring tank 029 and the acid addition pipeline I056, which is used to provide hydrobromic acid). There are four subsequent treatment methods:

[0402] (1) Collect with collection tank 030;

[0403] (2) The alkali obtained is circulated back to the alkali adding pipeline Ⅰ020 of the alkali adding stirring tank 019 for treatment to provide sodium hydroxide; a portion of the hydrobromic acid obtained is circulated back to the acid adding pipeline Ⅰ056 of the acid adding stirring tank 029 for providing hydrobromic acid to neutralize the sodium carbonate therein, and the other portion is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device; the sodium bromide liquid of the desalted water tank 033 is circulated back to the alkali adding stirring tank 019, heated and concentrated again, and then circulated back to the bipolar membrane electrodialysis device 031 for further treatment;

[0404] (3) Treat with evaporation tank 037, add sulfuric acid from the dosing port 039 of evaporation tank 037, and heat with heater 038 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator 041 to form hydrobromic acid aqueous solution. Then the hydrobromic acid aqueous solution enters evaporation tank '043, and add barium hydroxide from the dosing port '045 of evaporation tank '043, and heat with heater '044 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator '047 to form hydrobromic acid aqueous solution. A part of the hydrobromic acid aqueous solution is recycled back to the acid adding pipeline Ⅰ 056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device;

[0405] (4) Evaporation and concentration are carried out in a heating crystallizer II 051, and a sodium bromide solid product is produced in a centrifuge 053. The filtrate of the centrifuge 053 is returned to the heating crystallizer II 051 for reheating, and a continuous cycle is carried out to produce a sodium bromide solid product.

[0406] Run experiments using the above systems and methods:

[0407] Sampling analysis from solid outlet 005 of solid-liquid separator I 004 showed: cobalt ion = 6513 ppm, manganese ion = 3535 ppm, bromide ion = 4003 ppm, and water content of approximately 50%;

[0408] Sampling analysis from the solid outlet 061 of the solid-liquid separator VI 060 showed: cobalt ion = 553 ppm, manganese ion = 297 ppm, bromide ion = 332 ppm, and water content of approximately 50%;

[0409] Sampling analysis was performed from the liquid outlet 006 of the solid-liquid separator I 004: benzoic acid and its acid radical (BA) = 6565 ppm, phthalic acid and its acid radical = 3821 ppm, cobalt ion = 6672 ppm, manganese ion = 3999 ppm, bromide ion = 4551 ppm;

[0410] Sampling analysis from the outlet of organic adsorption device 013: benzoic acid and its acid radical (BA) = 3 ppm, phthalic acid and its acid radical = 1.1 ppm;

[0411] Sampling analysis was performed from the liquid outlet 018 of the solid-liquid separation device IV 016: cobalt ion 1.3ppm, manganese ion 2.5ppm, bromide ion 4593ppm;

[0412] The pH of the effluent from the alkali-adding mixing tank 019 was controlled to be 11.5, the starch oxidizing property was tested to be 12 ppm by the potassium iodide method, and the oxidizing property at the outlet of the oxidizing removal device 057 was not tested;

[0413] Analysis of the liquid outlet 065 of the solid-liquid separator II 063: carbonate 83332 ppm, bromide ion 22%;

[0414] The pH of the acid addition stirring tank 029 was controlled to be 3.5, and the sodium bromide was controlled to be 45.1% ppm.

[0415] There are four ways to handle it:

[0416] (1) Collecting the sodium bromide aqueous solution product;

[0417] (2) The acid production tank 034 of the bipolar membrane electrodialysis equipment 031 was sampled and analyzed as follows: hydrogen ion 1.31 mol / L, bromide ion 10.5%, sodium ion 66 ppm, proving that the product was hydrobromic acid;

[0418] (3) The liquid outlet sampling of water absorption acid generator 041 was analyzed as follows: hydrobromic acid content 27.1%, sulfate 301ppm; the liquid outlet sampling of water absorption acid generator '047 was analyzed as follows: hydrobromic acid content 27.9%, sulfate undetectable;

[0419] (4) The solid outlet 054 of the centrifuge 053 of the heating crystallizer II 051 was sampled and analyzed as follows: the sodium bromide content was 98.2%.

[0420] Conclusion: After processing by this system:

[0421] The solid outlet 005 of the solid-liquid separator I 004 is washed by the mixing tank VI 058 + solid-liquid separator VI 060, thereby reducing the total amount of cobalt and manganese ions in the solid and reducing the waste of cobalt and manganese ions. In addition, steam is generated through incineration, and the calorific value is recovered.

[0422] The liquid outlet 006 of the solid-liquid separator I 004 first passes through the organic matter elimination equipment 013 to remove benzoic acid, phthalic acid and its acid radicals, and then passes through the mixing tank IV 014 + solid-liquid separator IV 016 to remove cobalt and manganese ions (which is equivalent to recovering cobalt and manganese). After that, it passes through the heating evaporation equipment II 011 + solid-liquid separator II 063 to separate sodium carbonate and sodium bromide. The obtained sodium bromide aqueous solution is concentrated and acidified to remove the sodium carbonate still contained therein, and can be treated in four ways:

[0423] (1) A sodium bromide aqueous solution can be collected;

[0424] (2) The hydrobromic acid product can be obtained by using bipolar membrane electrodialysis equipment 031;

[0425] (3) The evaporation tank 037 can be used in conjunction with the water absorption acid generator 041 to convert the hydrobromic acid product, but it contains a small amount of sulfuric acid. At the same time, the evaporation tank '043 can be used in conjunction with the water absorption acid generator '047 to convert the hydrobromic acid product without sulfuric acid;

[0426] (4) Treat with heating crystallizer II to obtain sodium bromide solid.

[0427] At the same time, it is proved that the nanofiltration membrane 022 of the nanofiltration system I and the mixing tank IV 014 + solid-liquid separator IV 016 can play the role of separating carbonic acid and sodium bromide, and the effect is the same.

[0428] Example 3

[0429] A processing system for resource recovery of PTA oxidation residue mainly includes a heating crystallizer I 001, a mixing tank I 002, a solid-liquid separator I 004, an organic matter elimination device (organic matter adsorption device 013, filled with terephthalic acid, benzoic acid, and resin with adsorption effect on corresponding acid radicals), an organic matter elimination device (electrodialysis device 066), a cobalt and manganese recovery device (including a mixing tank IV 014 and a solid-liquid separator IV 016), an oxidizing removal device 057, a nanofiltration membrane 022 of a nanofiltration system I, a concentration system III (using a reverse osmosis membrane 027 as an example), a collection tank 030 or a bipolar membrane electrodialysis device 031 or an evaporation tank 037 or a heating crystallizer II 051.

[0430] The solid outlet of the heating crystallizer Ⅰ001 is connected to the inlet of the mixing tank Ⅰ002. The mixing tank Ⅰ002 is also provided with a liquid adding port 003 and a vacuum cooling device 007. The outlet of the mixing tank Ⅰ002 is connected to the inlet of the solid-liquid separator Ⅰ004. The liquid outlet 006 of the solid-liquid separator Ⅰ004 is connected to the inlet of the electrodialysis device 066. The ion dilute liquid outlet 068 of the electrodialysis device 066 is connected to the inlet of the mixing tank Ⅷ 069. The outlet of the mixing tank Ⅷ 069 is connected to the inlet of the solid-liquid separator Ⅷ 071. The liquid outlet 073 of the solid-liquid separator Ⅷ 071 is discharged.

[0431] The ion concentrate outlet 067 of the electrodialysis device 066 is connected to the inlet of the organic adsorption device 013, the outlet of the organic adsorption device 013 is connected to the inlet of the mixing tank IV 014, the mixing tank IV 014 is also provided with a dosing port 015, the outlet of the mixing tank IV 014 is connected to the inlet of the solid-liquid separator IV 016, the liquid outlet 018 of the solid-liquid separator IV 016 is connected to the alkali addition stirring tank 019, and the alkali addition stirring tank 019 is also provided with an alkali addition pipeline I 020;

[0432] The solid outlet 005 of the solid-liquid separator I 004 is connected to the inlet of the mixing tank VI 058, which is also provided with a washing liquid inlet 059. The outlet of the mixing tank VI 058 is connected to the inlet of the solid-liquid separator VI 060, the liquid outlet 062 of the solid-liquid separator VI 060 is connected to the liquid addition port 003 of the mixing tank I 002, and the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration device IV 008. The incineration device IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010.

[0433] The outlet of the alkali addition stirring tank 019 is connected to the inlet of the oxidation removal device 057, the outlet of the oxidation removal device 057 is connected to the inlet of the nanofiltration membrane 022 of the nanofiltration system I through the high-pressure pump 021 of the nanofiltration system I, the concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the dosing port 015 of the mixing tank IV 014 and the dosing port 070 of the mixing tank VIII 069, the fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the inlet of the buffer tank 025, the buffer tank 025 is connected to the reverse osmosis membrane 027 through the high-pressure pump 026 of the reverse osmosis membrane, the concentrated water outlet 028 of the reverse osmosis membrane 027 is connected to the inlet of the acid addition stirring tank 029, and the acid addition stirring tank 029 is also provided with an acid addition pipeline I 056;

[0434] There are four connection methods:

[0435] (1) The outlet of the acid adding stirring tank 029 is connected to the inlet of the collecting tank 030;

[0436] (2) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the bipolar membrane electrodialysis device 031. The bipolar membrane electrodialysis device 031 is further provided with an alkali-producing tank 032, an acid-producing tank 034, and a desalted brine tank 033. The outlet of the alkali-producing tank 032 is connected to the alkali-adding pipeline I 020 of the alkali-adding stirring tank 019. The outlet of the desalted brine tank 033 is connected to the inlet of the buffer tank 025. The outlet I 035 of the acid-adding stirring tank 034 is connected to the acid-adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 036 of the acid-generating tank 034 is connected to the oxidation system of the PTA device.

[0437] (3) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the evaporation tank 037. The evaporation tank 037 is also provided with a heater 038 and a dosing port 039. The gas phase outlet 040 of the evaporation tank 037 is connected to the inlet of the water absorption acid generator 041. The water absorption acid generator 041 is also provided with a water adding point 042. The liquid outlet of the water absorption acid generator 041 is connected to the inlet of the evaporation tank '043. The evaporation tank '043 is also provided with a heater '044 and a dosing port '045. The gas phase outlet 046 of the evaporation tank '043 is connected to the inlet of the water absorption acid generator '047. The water absorption acid generator '047 is also provided with a water adding point '048. The outlet I 049 of the water absorption acid generator '047 is connected to the acid adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 050 of the water absorption acid generator '047 is connected to the oxidation system of the PTA device.

[0438] (4) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the heating crystallizer II 051. The heating crystallizer II 051 is also provided with a heater 052. The outlet of the heating crystallizer II 051 is connected to the inlet of the centrifuge 053. The solid outlet of the centrifuge 053 is collected and the liquid outlet of the centrifuge 053 is connected to the inlet of the heating crystallizer II 051.

[0439] The above system operates as follows:

[0440] The target material processed in this embodiment is the oxidation residue of PTA. The target material processed in all embodiments of the present invention is the oxidation residue of PTA. The source of the oxidation residue of PTA is the heating crystallizer Ⅰ001 equipment.

[0441] The source of PTA oxidation residue is the heating crystallizer Ⅰ001 equipment. The solid outlet of the heating crystallizer Ⅰ001 is the oxidation residue of PTA. It enters the mixing tank Ⅰ002 and is added with water (the source is the liquid addition port 003, about five times the volume) for stirring and beating. It is then vacuumed with the vacuum cooling device 007 to ensure the temperature is around 35-40℃. After solid-liquid separation in the solid-liquid separator Ⅰ004, the liquid outlet 006 of the solid-liquid separator Ⅰ004 is mainly an aqueous solution containing inorganic ions (which still contains a small amount of benzoic acid, phthalic acid and its acid radicals). After being processed by the electrodialysis device 066, an ion concentrate outlet 067 (mainly containing a liquid after the inorganic matter in the influent water is concentrated) containing mainly inorganic ions and an ion dilute liquid outlet 068 (because the ions in the influent water are adsorbed away (to the side of the ion concentrate outlet 067), the inorganic ion concentration therein is reduced, but the organic matter concentration remains almost unchanged). The ion dilute liquid outlet 068 still contains a small amount of cobalt and manganese ions to prevent their loss. Sodium carbonate aqueous solution is added through the mixing tank VIII 069 and the cobalt and manganese ions are recovered by precipitation through the solid-liquid separator VIII 071;

[0442] The ion concentrate outlet 067 (mainly containing the liquid obtained by concentrating the inorganic matter in the influent water) mainly contains inorganic ions and passes through the organic adsorption device 013 to deeply adsorb benzoic acid, phthalic acid and its acid radicals, and then enters the mixer IV 014, and sodium carbonate aqueous solution is added to the mixer IV 014 (from the dosing port 015), and then the solid-liquid separation is carried out by the solid-liquid separator IV 016. After the filtrate of the solid-liquid separator IV 016 is adjusted by adding sodium hydroxide (sodium hydroxide aqueous solution is added through the alkali adding stirring tank 019 and the alkali adding pipeline I 020) to adjust the pH, it first passes through the deoxidizing device 057 (filled with adsorption filler: activated carbon) to remove the oxidizing property, and then passes through the nanofiltration membrane 022 of the nanofiltration system I for treatment;

[0443] The solids from the solid-liquid separator I004 are washed with a mixing tank VI058. Water (approximately five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing. The solid and liquid are then separated using a solid-liquid separator VI060. The resulting liquid is circulated back to the mixer I002. The resulting solids are collected and incinerated using an incineration device IV008 and fuel is added (from the fuel inlet 009) for incineration. The steam generator drum 010 is used to generate steam for reuse of heat value.

[0444] The concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I flows back to the dosing port 015 of the mixer IV 014 and the dosing port 070 of the mixing tank VIII 069 to provide sodium carbonate. The fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I (mainly sodium bromide) is concentrated by the concentration system III (using the reverse osmosis membrane 027 as an example), and then acid is added to neutralize the sodium carbonate with hydrobromic acid (through the acid addition stirring tank 029 and the acid addition pipeline I 056, the acid addition pipeline I 056 is used to provide hydrobromic acid). There are four treatment methods:

[0445] (1) Collect with collection tank 030;

[0446] (2) The alkali obtained is treated by bipolar membrane electrodialysis equipment 031, and the alkali is circulated back to the alkali adding pipeline I020 of the alkali adding stirring tank 019 to provide sodium hydroxide; a part of the hydrobromic acid obtained is circulated back to the acid adding pipeline I056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device; the sodium bromide liquid of the light brine tank 033 is circulated back to the buffer tank 025, and after being concentrated by the reverse osmosis membrane again, it is circulated back to the bipolar membrane electrodialysis equipment 031 for further treatment;

[0447] (3) Treat with evaporation tank 037, add sulfuric acid from the dosing port 039 of evaporation tank 037, and heat with heater 038 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator 041 to form hydrobromic acid aqueous solution. Then the hydrobromic acid aqueous solution enters evaporation tank '043, and add barium hydroxide from the dosing port '045 of evaporation tank '043, and heat with heater '044 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator '047 to form hydrobromic acid aqueous solution. A part of the hydrobromic acid aqueous solution is recycled back to the acid adding pipeline Ⅰ 056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device;

[0448] (4) Evaporation and concentration are carried out in a heating crystallizer II 051, and a sodium bromide solid product is produced in a centrifuge 053. The filtrate of the centrifuge 053 is returned to the heating crystallizer II 051 for reheating, and a continuous cycle is carried out to produce a sodium bromide solid product.

[0449] Run experiments using the above systems and methods:

[0450] Sampling analysis from solid outlet 005 of solid-liquid separator I 004 showed: cobalt ion = 6513 ppm, manganese ion = 3535 ppm, bromide ion = 4003 ppm, and water content of approximately 50%;

[0451] Sampling analysis from the solid outlet 061 of the solid-liquid separator VI 060 showed: cobalt ion = 553 ppm, manganese ion = 297 ppm, bromide ion = 332 ppm, and water content of approximately 50%;

[0452] Sampling analysis was performed from the liquid outlet 006 of the solid-liquid separator I 004: benzoic acid and its acid radical (BA) = 6565 ppm, phthalic acid and its acid radical = 3821 ppm, cobalt ion = 6672 ppm, manganese ion = 3999 ppm, bromide ion = 4551 ppm;

[0453] Sampling of the ion dilute liquid outlet 068 of the electrodialysis device 066: benzoic acid and its acid radical (BA) = 6277 ppm, phthalic acid and its acid radical = 3903 ppm, cobalt ion = 772 ppm, manganese ion = 537 ppm, bromide ion = 289 ppm;

[0454] Sampling of the liquid outlet 073 of the solid-liquid separator VIII 071: cobalt ion 2.4ppm, manganese ion 1.9ppm;

[0455] Sampling of the ion concentrate outlet 067 of the electrodialysis device 066: benzoic acid and its acid radical (BA) = 614 ppm, phthalic acid and its acid radical = 411 ppm, cobalt ion = 3.1%, manganese ion = 2.2%, bromide ion = 2.7%;

[0456] Sampling analysis from the outlet of organic adsorption device 013: benzoic acid and its acid radical (BA) = 4 ppm, phthalic acid and its acid radical = 1.7 ppm;

[0457] Sampling analysis was performed from the liquid outlet 018 of the solid-liquid separation device IV 016: cobalt ion 2.6ppm, manganese ion 4.1ppm, bromide ion 2.6%;

[0458] The pH of the effluent from the alkali-adding mixing tank 019 was controlled to be 11.5, the starch oxidizing property was tested to be 15 ppm by the potassium iodide method, and the oxidizing property at the outlet of the oxidizing removal device 057 was not tested;

[0459] Analysis of concentrated water outlet 023 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 38891 ppm, bromide 5321 ppm; analysis of fresh water outlet 024 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 5613 ppm, bromide 2.6%;

[0460] The pH of the acid-adding stirring tank 029 was controlled to be 3.5, and the sodium bromide was 7.1%.

[0461] There are four ways to handle it:

[0462] (1) Collecting the sodium bromide aqueous solution product;

[0463] (2) The acid production tank 034 of the bipolar membrane electrodialysis equipment 031 was sampled and analyzed as follows: hydrogen ion 1.2 mol / L, bromide ion 9.6%, sodium ion 33 ppm, proving that the product was hydrobromic acid;

[0464] (3) The liquid outlet sampling analysis of water absorption acid generator 041 is as follows: hydrobromic acid content 23.5%, sulfate 413ppm; the liquid outlet sampling analysis of water absorption acid generator '047 is as follows: hydrobromic acid content 35.2%, sulfate undetectable;

[0465] (4) The solid outlet 054 of the centrifuge 053 of the heating crystallizer II 051 was sampled and analyzed as follows: the sodium bromide content was 98.7%.

[0466] Conclusion: After processing by this system:

[0467] The solid outlet 005 of the solid-liquid separator I 004 is washed by the mixing tank VI 058 + solid-liquid separator VI 060, thereby reducing the total amount of cobalt and manganese ions in the solid and reducing the waste of cobalt and manganese ions. In addition, steam is generated through incineration, and the calorific value is recovered.

[0468] The liquid outlet 006 of the solid-liquid separator I 004 is first processed by the electrodialysis device 066. The organic matter content of the obtained ion concentrate outlet 067 is already low. The liquid then passes through the organic adsorption device 013 to remove benzoic acid, phthalic acid and its acid radicals (the load of the organic adsorption device 013 is reduced). The liquid then passes through the mixing tank IV 014 + solid-liquid separator IV 016 to remove cobalt and manganese ions (which is equivalent to recovering cobalt and manganese). The sodium carbonate and sodium bromide are then separated by the nanofiltration membrane 022. The separated sodium carbonate is returned for cobalt and manganese precipitation recovery. The obtained sodium bromide aqueous solution is concentrated and acidified to remove the sodium carbonate still contained therein. It can then be treated in four ways:

[0469] (1) A sodium bromide aqueous solution can be collected;

[0470] (2) The hydrobromic acid product can be obtained by using bipolar membrane electrodialysis equipment 031;

[0471] (3) The evaporation tank 037 can be used in conjunction with the water absorption acid generator 041 to convert the hydrobromic acid product, but it contains a small amount of sulfuric acid. At the same time, the evaporation tank '043 can be used in conjunction with the water absorption acid generator '047 to convert the hydrobromic acid product without sulfuric acid;

[0472] (4) Treat with heating crystallizer II to obtain sodium bromide solid.

[0473] The electrodialysis equipment 066 processes the obtained ion dilute liquid outlet 068, and the small amount of cobalt and manganese ions contained therein are then recovered through the mixing tank VIII 069 + solid-liquid separator VIII 071.

[0474] Example 2 has proved that the nanofiltration membrane 022 of the nanofiltration system I and the mixing tank IV014 + solid-liquid separator IV016 can separate carbonic acid and sodium bromide, and the effect is the same. Therefore, it can be inferred that the nanofiltration system I in this embodiment can be replaced by the mixing tank IV014 + solid-liquid separator IV016 to achieve the same effect as this embodiment.

[0475] Example 4

[0476] A processing system for resource recovery of PTA oxidation residue mainly includes a heating crystallizer I 001, a mixing tank I 002, a solid-liquid separator I 004, an organic matter elimination device (organic matter adsorption device 013, filled with resin having adsorption effect on terephthalic acid, benzoic acid, and corresponding acid radicals), an organic matter elimination device (evaporation concentration device I 074, a cooler I 075, a solid-liquid separator III 076), a cobalt and manganese recovery device (including a mixing tank IV 014 and a solid-liquid separator IV 016), an oxidizing agent removal device 057, a nanofiltration membrane 022 of a nanofiltration system I, a concentration system III (using a reverse osmosis membrane 027 as an example), a collection tank 030 or a bipolar membrane electrodialysis device 031 or an evaporation tank 037 or a heating crystallizer II 051.

[0477] The solid outlet of the heating crystallizer Ⅰ001 is connected to the inlet of the mixing tank Ⅰ002, and the mixing tank Ⅰ002 is also provided with a liquid addition port 003 and a vacuum cooling device 007. The outlet of the mixing tank Ⅰ002 is connected to the inlet of the solid-liquid separator Ⅰ004, and the liquid outlet 006 of the solid-liquid separator Ⅰ004 is connected to the inlet of the evaporation concentration device Ⅰ074. The outlet of the evaporation concentration device Ⅰ074 is connected to the inlet of the cooler Ⅰ075, and the outlet of the cooler Ⅰ075 is connected to the solid-liquid separator The inlet of III076 and the liquid outlet 078 of the solid-liquid separator III076 are connected to the inlet of the organic adsorption device 013, the outlet of the organic adsorption device 013 is connected to the inlet of the mixing tank IV014, the mixing tank IV014 is also provided with a dosing port 015, the outlet of the mixing tank IV014 is connected to the inlet of the solid-liquid separator IV016, the liquid outlet 018 of the solid-liquid separator IV016 is connected to the alkali adding stirring tank 019, and the alkali adding stirring tank 019 is also provided with an alkali adding pipeline I020;

[0478] The solid outlet 005 of the solid-liquid separator I 004 is connected to the inlet of the mixing tank VI 058, which is also provided with a washing liquid inlet 059. The outlet of the mixing tank VI 058 is connected to the inlet of the solid-liquid separator VI 060, the liquid outlet 062 of the solid-liquid separator VI 060 is connected to the liquid addition port 003 of the mixing tank I 002, and the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration device IV 008. The incineration device IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010.

[0479] The outlet of the alkali addition stirring tank 019 is connected to the inlet of the oxidizing removal device 057, the outlet of the oxidizing removal device 057 is connected to the inlet of the nanofiltration membrane 022 of the nanofiltration system I through the high-pressure pump 021 of the nanofiltration system I, the concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the dosing port 015 of the mixing tank IV 014, the fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the inlet of the buffer tank 025, the buffer tank 025 is connected to the reverse osmosis membrane 027 through the high-pressure pump 026 of the reverse osmosis membrane, the concentrated water outlet 028 of the reverse osmosis membrane 027 is connected to the inlet of the acid addition stirring tank 029, and the acid addition stirring tank 029 is also provided with an acid addition pipeline I 056;

[0480] There are four connection methods:

[0481] (1) The outlet of the acid adding stirring tank 029 is connected to the inlet of the collecting tank 030;

[0482] (2) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the bipolar membrane electrodialysis device 031. The bipolar membrane electrodialysis device 031 is further provided with an alkali-producing tank 032, an acid-producing tank 034, and a desalted brine tank 033. The outlet of the alkali-producing tank 032 is connected to the alkali-adding pipeline I 020 of the alkali-adding stirring tank 019. The outlet of the desalted brine tank 033 is connected to the inlet of the buffer tank 025. The outlet I 035 of the acid-adding stirring tank 034 is connected to the acid-adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 036 of the acid-generating tank 034 is connected to the oxidation system of the PTA device.

[0483] (3) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the evaporation tank 037. The evaporation tank 037 is also provided with a heater 038 and a dosing port 039. The gas phase outlet 040 of the evaporation tank 037 is connected to the inlet of the water absorption acid generator 041. The water absorption acid generator 041 is also provided with a water adding point 042. The liquid outlet of the water absorption acid generator 041 is connected to the inlet of the evaporation tank '043. The evaporation tank '043 is also provided with a heater '044 and a dosing port '045. The gas phase outlet 046 of the evaporation tank '043 is connected to the inlet of the water absorption acid generator '047. The water absorption acid generator '047 is also provided with a water adding point '048. The outlet I 049 of the water absorption acid generator '047 is connected to the acid adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 050 of the water absorption acid generator '047 is connected to the oxidation system of the PTA device.

[0484] (4) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the heating crystallizer II 051. The heating crystallizer II 051 is also provided with a heater 052. The outlet of the heating crystallizer II 051 is connected to the inlet of the centrifuge 053. The solid outlet of the centrifuge 053 is collected and the liquid outlet of the centrifuge 053 is connected to the inlet of the heating crystallizer II 051.

[0485] The above system operates as follows:

[0486] The target material processed in this embodiment is the oxidation residue of PTA. The target material processed in all embodiments of the present invention is the oxidation residue of PTA. The source of the oxidation residue of PTA is the heating crystallizer Ⅰ001 equipment.

[0487] The source of PTA oxidation residue is the heating crystallizer Ⅰ001 equipment. The solid outlet of the heating crystallizer Ⅰ001 is the oxidation residue of PTA, which enters the mixing tank Ⅰ002 and is added with water (the source is the liquid addition port 003, which is about five times the volume) for stirring and slurrying, and is vacuumed with the vacuum cooling equipment 007 to ensure that the temperature is about 35-40°C, and is separated into solid and liquid by the solid-liquid separator Ⅰ004. The liquid outlet 006 of the solid-liquid separator Ⅰ004 is mainly an aqueous solution containing inorganic ions (which still contains a small amount of benzoic acid, phthalic acid and its acid radicals). After the evaporation concentration equipment Ⅰ074 reduces the hydraulic load, and is cooled by the cooler Ⅰ075, it is filtered out by the solid-liquid separator Ⅲ076 to remove the precipitated benzoic acid and phthalic acid, which is equivalent to the concentration of benzoic acid, phthalic acid and its acid radicals in the water body being fixed but the water The amount is reduced, that is, part of the benzoic acid and phthalic acid is precipitated into solid and filtered out by solid-liquid separator III 076. The benzoic acid, phthalic acid and their acid radicals still contained in the liquid outlet 078 of the solid-liquid separator III 076 are deeply adsorbed by the organic adsorption equipment 013, and then enter the mixer IV 014, and sodium carbonate aqueous solution is added to the mixer IV 014 (from the dosing port 015), and then the solid-liquid separation is carried out by solid-liquid separator IV 016. After the filtrate of the solid-liquid separator IV 016 is adjusted by adding sodium hydroxide (sodium hydroxide aqueous solution is added through the alkali adding stirring tank 019 and the alkali adding pipeline I 020) to adjust the pH, it is first passed through the deoxidizing equipment 057 (filled with adsorption filler: activated carbon) to remove the oxidizing property, and then processed by the nanofiltration membrane 022 of the nanofiltration system I;

[0488] The solids from the solid-liquid separator I004 are washed with a mixing tank VI058. Water (approximately five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing. The solid and liquid are then separated using a solid-liquid separator VI060. The resulting liquid is circulated back to the mixer I002. The resulting solids are collected and incinerated using an incineration device IV008 and fuel is added (from the fuel inlet 009) for incineration. The steam generator drum 010 is used to generate steam for reuse of heat value.

[0489] The concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I flows back to the dosing port 015 of the mixer IV 014 to provide sodium carbonate. The fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I (mainly sodium bromide) is concentrated by the concentration system III (using the reverse osmosis membrane 027 as an example), and then acid is added to neutralize the sodium carbonate and hydrobromic acid (through the acid addition stirring tank 029 and the acid addition pipeline I 056, the acid addition pipeline I 056 is used to provide hydrobromic acid). There are four treatment methods:

[0490] (1) Collect with collection tank 030;

[0491] (2) The alkali obtained is treated by bipolar membrane electrodialysis equipment 031, and the alkali is circulated back to the alkali adding pipeline I020 of the alkali adding stirring tank 019 to provide sodium hydroxide; a part of the hydrobromic acid obtained is circulated back to the acid adding pipeline I056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device; the sodium bromide liquid of the light brine tank 033 is circulated back to the buffer tank 025, and after being concentrated by the reverse osmosis membrane again, it is circulated back to the bipolar membrane electrodialysis equipment 031 for further treatment;

[0492] (3) Treat with evaporation tank 037, add sulfuric acid from the dosing port 039 of evaporation tank 037, and heat with heater 038 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator 041 to form hydrobromic acid aqueous solution. Then the hydrobromic acid aqueous solution enters evaporation tank '043, and add barium hydroxide from the dosing port '045 of evaporation tank '043, and heat with heater '044 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator '047 to form hydrobromic acid aqueous solution. A part of the hydrobromic acid aqueous solution is recycled back to the acid adding pipeline Ⅰ 056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device;

[0493] (4) Evaporation and concentration are carried out in a heating crystallizer II 051, and a sodium bromide solid product is produced in a centrifuge 053. The filtrate of the centrifuge 053 is returned to the heating crystallizer II 051 for reheating, and a continuous cycle is carried out to produce a sodium bromide solid product.

[0494] Run experiments using the above systems and methods:

[0495] Sampling analysis from solid outlet 005 of solid-liquid separator I 004 showed: cobalt ion = 6513 ppm, manganese ion = 3535 ppm, bromide ion = 4003 ppm, and water content of approximately 50%;

[0496] Sampling analysis from the solid outlet 061 of the solid-liquid separator VI 060 showed: cobalt ion = 553 ppm, manganese ion = 297 ppm, bromide ion = 332 ppm, and water content of approximately 50%;

[0497] Sampling analysis was performed from the liquid outlet 006 of the solid-liquid separator I 004: benzoic acid and its acid radical (BA) = 6565 ppm, phthalic acid and its acid radical = 3821 ppm, cobalt ion = 6672 ppm, manganese ion = 3999 ppm, bromide ion = 4551 ppm;

[0498] Sampling of the liquid outlet 078 of the solid-liquid separator III 076 showed the following: benzoic acid and its acid radical (BA) = 5946 ppm, phthalic acid and its acid radical = 3991 ppm, cobalt ion = 21074 ppm, manganese ion = 12451 ppm, bromide ion = 13582 ppm. The inorganic ion concentration increased significantly, while the organic matter concentration did not increase.

[0499] Sampling analysis from the outlet of organic adsorption device 013: benzoic acid and its acid radical (BA) = 2.5 ppm, phthalic acid and its acid radical = 1.5 ppm;

[0500] Sampling analysis was performed from the liquid outlet 018 of the solid-liquid separation device IV 016: cobalt ion 3.5ppm, manganese ion 2.6ppm, bromide ion 1.4%;

[0501] The pH of the effluent from the alkali-adding mixing tank 019 was controlled to be 11.5, the starch oxidizing property was tested with potassium iodide method to be 13 ppm, and the oxidizing property at the outlet of the oxidizing removal device 057 was not tested;

[0502] Analysis of concentrated water outlet 023 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 50334 ppm, bromide 2533 ppm; analysis of fresh water outlet 024 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 4139 ppm, bromide 1.3%;

[0503] Control the pH of acid addition stirring tank 029 to 3.5, sodium bromide = 9.3%.

[0504] There are four ways to handle it:

[0505] (1) Collecting the sodium bromide aqueous solution product;

[0506] (2) The acid production tank 034 of the bipolar membrane electrodialysis equipment 031 was sampled and analyzed as follows: hydrogen ion 1.5 mol / L, bromide ion 12.1%, sodium ion 38 ppm, proving that the product was hydrobromic acid;

[0507] (3) The liquid outlet sampling analysis of water absorption acid generator 041 is as follows: hydrobromic acid content 27.3%, sulfate 571ppm; the liquid outlet sampling analysis of water absorption acid generator '047 is as follows: hydrobromic acid content 32.2%, sulfate undetectable;

[0508] (4) The solid outlet 054 of the centrifuge 053 of the heating crystallizer II 051 was sampled and analyzed as follows: the sodium bromide content was 98.5%.

[0509] Conclusion: After processing by this system:

[0510] The solid outlet 005 of the solid-liquid separator I 004 is washed by the mixing tank VI 058 + solid-liquid separator VI 060, thereby reducing the total amount of cobalt and manganese ions in the solid and reducing the waste of cobalt and manganese ions. In addition, steam is generated through incineration, and the calorific value is recovered.

[0511] The liquid outlet 006 of the solid-liquid separator I 004 is first concentrated by the evaporation concentration device I 074 and cooled by the cooler I 075. The solid-liquid separator III 076 filters out benzoic acid and phthalic acid, which is equivalent to removing some of the organic matter. The liquid then passes through the organic adsorption device 013 to remove benzoic acid, phthalic acid and their acid radicals (the load of the organic adsorption device 013 is reduced). The liquid then passes through the mixing tank IV 014 + solid-liquid separator IV 016 to remove cobalt and manganese ions (which is also equivalent to recovering cobalt and manganese). The sodium carbonate and sodium bromide are then separated by the nanofiltration membrane 022. The separated sodium carbonate is returned for cobalt and manganese precipitation recovery. The obtained sodium bromide aqueous solution is concentrated and acidified to remove the sodium carbonate still contained therein. It can be treated in four ways:

[0512] (1) A sodium bromide aqueous solution can be collected;

[0513] (2) The hydrobromic acid product can be obtained by using bipolar membrane electrodialysis equipment 031;

[0514] (3) The evaporation tank 037 can be used in conjunction with the water absorption acid generator 041 to convert the hydrobromic acid product, but it contains a small amount of sulfuric acid. At the same time, the evaporation tank '043 can be used in conjunction with the water absorption acid generator '047 to convert the hydrobromic acid product without sulfuric acid;

[0515] (4) Treat with heating crystallizer II to obtain sodium bromide solid.

[0516] The electrodialysis equipment 066 processes the obtained ion dilute liquid outlet 068, and the small amount of cobalt and manganese ions contained therein are then recovered through the mixing tank VIII 069 + solid-liquid separator VIII 071.

[0517] Example 2 has proved that the nanofiltration membrane 022 of the nanofiltration system I and the mixing tank IV014 + solid-liquid separator IV016 can separate carbonic acid and sodium bromide, and the effect is the same. Therefore, it can be inferred that the nanofiltration system I in this embodiment can be replaced by the mixing tank IV014 + solid-liquid separator IV016 to achieve the same effect as this embodiment.

[0518] Example 5

[0519] A processing system for resource recovery of PTA oxidation residue mainly includes a heating crystallizer I 001, a mixing tank I 002, a solid-liquid separator I 004, an organic matter elimination device (organic matter adsorption device 013, filled with terephthalic acid, benzoic acid, and resin with adsorption effect on corresponding acid radicals), an organic matter elimination device (extraction device 079, static stratification device 081), a cobalt and manganese recovery device (including a mixing tank IV 014 and a solid-liquid separator IV 016), an oxidizing agent removal device 057, a nanofiltration membrane 022 of a nanofiltration system I, a concentration system III (using a reverse osmosis membrane 027 as an example), a collection tank 030 or a bipolar membrane electrodialysis device 031 or an evaporation tank 037 or a heating crystallizer II 051.

[0520] The solid outlet of the heating crystallizer Ⅰ001 is connected to the inlet of the mixing tank Ⅰ002, which is also provided with a liquid addition port 003 and a vacuum cooling device 007. The outlet of the mixing tank Ⅰ002 is connected to the inlet of the solid-liquid separator Ⅰ004, and the liquid outlet 006 of the solid-liquid separator Ⅰ004 is connected to the inlet of the extraction device 079. The extraction device 079 is also provided with an extractant addition port 080. The outlet of the extraction device 079 is connected to the inlet of the static stratification device 081, which is provided with a water The solution outlet 082 and the extractant outlet 083, the aqueous solution outlet 082 of the static stratification device 081 are connected to the inlet of the organic adsorption device 013, the outlet of the organic adsorption device 013 is connected to the inlet of the mixing tank IV 014, the mixing tank IV 014 is also provided with a dosing port 015, the outlet of the mixing tank IV 014 is connected to the inlet of the solid-liquid separator IV 016, the liquid outlet 018 of the solid-liquid separator IV 016 is connected to the alkali adding stirring tank 019, and the alkali adding stirring tank 019 is also provided with an alkali adding pipeline I 020;

[0521] The solid outlet 005 of the solid-liquid separator I 004 is connected to the inlet of the mixing tank VI 058, which is also provided with a washing liquid inlet 059. The outlet of the mixing tank VI 058 is connected to the inlet of the solid-liquid separator VI 060, the liquid outlet 062 of the solid-liquid separator VI 060 is connected to the liquid addition port 003 of the mixing tank I 002, and the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration device IV 008. The incineration device IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010.

[0522] The outlet of the alkali addition stirring tank 019 is connected to the inlet of the oxidizing removal device 057, the outlet of the oxidizing removal device 057 is connected to the inlet of the nanofiltration membrane 022 of the nanofiltration system I through the high-pressure pump 021 of the nanofiltration system I, the concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the dosing port 015 of the mixing tank IV 014, the fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I is connected to the inlet of the buffer tank 025, the buffer tank 025 is connected to the reverse osmosis membrane 027 through the high-pressure pump 026 of the reverse osmosis membrane, the concentrated water outlet 028 of the reverse osmosis membrane 027 is connected to the inlet of the acid addition stirring tank 029, and the acid addition stirring tank 029 is also provided with an acid addition pipeline I 056;

[0523] There are four connection methods:

[0524] (1) The outlet of the acid adding stirring tank 029 is connected to the inlet of the collecting tank 030;

[0525] (2) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the bipolar membrane electrodialysis device 031. The bipolar membrane electrodialysis device 031 is further provided with an alkali-producing tank 032, an acid-producing tank 034, and a desalted brine tank 033. The outlet of the alkali-producing tank 032 is connected to the alkali-adding pipeline I 020 of the alkali-adding stirring tank 019. The outlet of the desalted brine tank 033 is connected to the inlet of the buffer tank 025. The outlet I 035 of the acid-adding stirring tank 034 is connected to the acid-adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 036 of the acid-generating tank 034 is connected to the oxidation system of the PTA device.

[0526] (3) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the evaporation tank 037. The evaporation tank 037 is also provided with a heater 038 and a dosing port 039. The gas phase outlet 040 of the evaporation tank 037 is connected to the inlet of the water absorption acid generator 041. The water absorption acid generator 041 is also provided with a water adding point 042. The liquid outlet of the water absorption acid generator 041 is connected to the inlet of the evaporation tank '043. The evaporation tank '043 is also provided with a heater '044 and a dosing port '045. The gas phase outlet 046 of the evaporation tank '043 is connected to the inlet of the water absorption acid generator '047. The water absorption acid generator '047 is also provided with a water adding point '048. The outlet I 049 of the water absorption acid generator '047 is connected to the acid adding pipeline I 056 of the acid-adding stirring tank 029. The outlet II 050 of the water absorption acid generator '047 is connected to the oxidation system of the PTA device.

[0527] (4) The outlet of the acid-adding stirring tank 029 is connected to the inlet of the heating crystallizer II 051. The heating crystallizer II 051 is also provided with a heater 052. The outlet of the heating crystallizer II 051 is connected to the inlet of the centrifuge 053. The solid outlet of the centrifuge 053 is collected and the liquid outlet of the centrifuge 053 is connected to the inlet of the heating crystallizer II 051.

[0528] The above system operates as follows:

[0529] The target material processed in this embodiment is the oxidation residue of PTA. The target material processed in all embodiments of the present invention is the oxidation residue of PTA. The source of the oxidation residue of PTA is the heating crystallizer Ⅰ001 equipment.

[0530] The source of the PTA oxidation residue is the heating crystallizer Ⅰ001 equipment. The solid outlet of the heating crystallizer Ⅰ001 is the PTA oxidation residue, which enters the mixing tank Ⅰ002 and is added with water (the source is the liquid addition port 003, about five times the volume) for stirring and beating, and is vacuumed by the vacuum cooling equipment 007 to ensure the temperature is around 35-40 ° C. After the solid-liquid separation in the solid-liquid separator Ⅰ004, the liquid outlet 006 of the solid-liquid separator Ⅰ004 is mainly an aqueous solution containing inorganic ions (which still contains a small amount of benzoic acid, phthalic acid and its acid radicals). After the extraction equipment 079 and the addition of solvent oil as an extractant, and after the static stratification equipment 081 is layered, and the aqueous solution of the static layering device 081 is then passed through the organic adsorption device 013 to deeply adsorb benzoic acid, phthalic acid and its acid radicals, and then enters the mixer IV 014, and the sodium carbonate aqueous solution is added to the mixer IV 014 (from the dosing port 015), and then the solid-liquid separation is carried out by the solid-liquid separator IV 016. The filtrate of the solid-liquid separator IV 016 is added with sodium hydroxide (through the alkali stirring tank 019 and the alkali pipeline I 020 to add the sodium hydroxide aqueous solution) to adjust the pH, and then first passes through the deoxidizing device 057 (filled with adsorption filler: activated carbon) to remove the oxidizing property, and then passes through the nanofiltration membrane 022 of the nanofiltration system I for treatment;

[0531] The solids from the solid-liquid separator I004 are washed with a mixing tank VI058. Water (approximately five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing. The solid and liquid are then separated using a solid-liquid separator VI060. The resulting liquid is circulated back to the mixer I002. The resulting solids are collected and incinerated using an incineration device IV008 and fuel is added (from the fuel inlet 009) for incineration. The steam generator drum 010 is used to generate steam for reuse of heat value.

[0532] The concentrated water outlet 023 of the nanofiltration membrane 022 of the nanofiltration system I flows back to the dosing port 015 of the mixer IV 014 to provide sodium carbonate. The fresh water outlet 024 of the nanofiltration membrane 022 of the nanofiltration system I (mainly sodium bromide) is concentrated by the concentration system III (using the reverse osmosis membrane 027 as an example), and then acid is added to neutralize the sodium carbonate and hydrobromic acid (through the acid addition stirring tank 029 and the acid addition pipeline I 056, the acid addition pipeline I 056 is used to provide hydrobromic acid). There are four treatment methods:

[0533] (1) Collect with collection tank 030;

[0534] (2) The alkali obtained is treated by bipolar membrane electrodialysis equipment 031, and the alkali is circulated back to the alkali adding pipeline I020 of the alkali adding stirring tank 019 to provide sodium hydroxide; a part of the hydrobromic acid obtained is circulated back to the acid adding pipeline I056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device; the sodium bromide liquid of the light brine tank 033 is circulated back to the buffer tank 025, and after being concentrated by the reverse osmosis membrane again, it is circulated back to the bipolar membrane electrodialysis equipment 031 for further treatment;

[0535] (3) Treat with evaporation tank 037, add sulfuric acid from the dosing port 039 of evaporation tank 037, and heat with heater 038 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator 041 to form hydrobromic acid aqueous solution. Then the hydrobromic acid aqueous solution enters evaporation tank '043, and add barium hydroxide from the dosing port '045 of evaporation tank '043, and heat with heater '044 to generate hydrogen bromide gas, which is absorbed by water-absorbing acid generator '047 to form hydrobromic acid aqueous solution. A part of the hydrobromic acid aqueous solution is recycled back to the acid adding pipeline Ⅰ 056 of the acid adding stirring tank 029 to provide hydrobromic acid to neutralize the sodium carbonate therein, and the other part is used as the product hydrobromic acid of this device and is recycled to the oxidation system of the PTA device;

[0536] (4) Evaporation and concentration are carried out in a heating crystallizer II 051, and a sodium bromide solid product is produced in a centrifuge 053. The filtrate of the centrifuge 053 is returned to the heating crystallizer II 051 for reheating, and a continuous cycle is carried out to produce a sodium bromide solid product.

[0537] Run experiments using the above systems and methods:

[0538] Sampling analysis from solid outlet 005 of solid-liquid separator I 004 showed: cobalt ion = 6513 ppm, manganese ion = 3535 ppm, bromide ion = 4003 ppm, and water content of approximately 50%;

[0539] Sampling analysis from the solid outlet 061 of the solid-liquid separator VI 060 showed: cobalt ion = 553 ppm, manganese ion = 297 ppm, bromide ion = 332 ppm, and water content of approximately 50%;

[0540] Sampling analysis was performed from the liquid outlet 006 of the solid-liquid separator I 004: benzoic acid and its acid radical (BA) = 6565 ppm, phthalic acid and its acid radical = 3821 ppm, cobalt ion = 6672 ppm, manganese ion = 3999 ppm, bromide ion = 4551 ppm;

[0541] Sampling of the aqueous solution outlet 082 of the stationary stratification device 081: benzoic acid and its acid radical (BA) = 798 ppm, phthalic acid and its acid radical = 2513 ppm, cobalt ion = 6564 ppm, manganese ion = 3856 ppm, bromide ion = 4499 ppm;

[0542] Sampling analysis from the outlet of organic adsorption device 013: benzoic acid and its acid radical (BA) = 4.4 ppm, phthalic acid and its acid radical = 2.3 ppm;

[0543] Sampling analysis was performed from the liquid outlet 018 of the solid-liquid separation device IV 016: cobalt ion 1.5ppm, manganese ion 2.9ppm, bromide ion 4538ppm;

[0544] The pH of the effluent from the alkali-adding mixing tank 019 was controlled to be 11.5, the starch oxidizing property was tested to be 13 ppm by potassium iodide method, and the oxidizing property at the outlet of the oxidizing removal device 057 was not tested;

[0545] Analysis of concentrated water outlet 023 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 51145 ppm, bromide 1109 ppm; analysis of fresh water outlet 024 of nanofiltration membrane 022 of nanofiltration system I 020: carbonate 3889 ppm, bromide 5011 ppm;

[0546] The pH of the acid-adding stirring tank 029 was controlled to be 3.5, and the sodium bromide was controlled to be 9.7%.

[0547] There are four ways to handle it:

[0548] (1) Collecting the sodium bromide aqueous solution product;

[0549] (2) The acid production tank 034 of the bipolar membrane electrodialysis equipment 031 was sampled and analyzed as follows: hydrogen ion 1.1 mol / L, bromide ion 8.9%, sodium ion 23 ppm, proving that the product was hydrobromic acid;

[0550] (3) The liquid outlet sampling of water absorption acid generator 041 was analyzed as follows: hydrobromic acid content 25.5%, sulfate 501ppm; the liquid outlet sampling of water absorption acid generator '047 was analyzed as follows: hydrobromic acid content 28.8%, sulfate undetectable;

[0551] (4) The solid outlet 054 of the centrifuge 053 of the heating crystallizer II 051 was sampled and analyzed as follows: the sodium bromide content was 98.0%.

[0552] Conclusion: After processing by this system:

[0553] The solid outlet 005 of the solid-liquid separator I 004 is washed by the mixing tank VI 058 + solid-liquid separator VI 060, thereby reducing the total amount of cobalt and manganese ions in the solid and reducing the waste of cobalt and manganese ions. In addition, steam is generated through incineration, and the calorific value is recovered.

[0554] The liquid outlet 006 of the solid-liquid separator I 004 first passes through the extraction device 079 to extract some organic matter, then passes through the organic adsorption device 013 to remove benzoic acid, phthalic acid and its acid radicals (the load of the organic adsorption device 013 is reduced), and then passes through the mixing tank IV 014 + solid-liquid separator IV 016 to remove cobalt and manganese ions (which is equivalent to recovering cobalt and manganese). After that, the sodium carbonate and sodium bromide are separated by the nanofiltration membrane 022. The separated sodium carbonate is returned for cobalt and manganese precipitation recovery. The obtained sodium bromide aqueous solution is concentrated and acidified to remove the sodium carbonate still contained therein, and can be treated in four ways:

[0555] (1) A sodium bromide aqueous solution can be collected;

[0556] (2) The hydrobromic acid product can be obtained by using bipolar membrane electrodialysis equipment 031;

[0557] (3) The evaporation tank 037 can be used in conjunction with the water absorption acid generator 041 to convert the hydrobromic acid product, but it contains a small amount of sulfuric acid. At the same time, the evaporation tank '043 can be used in conjunction with the water absorption acid generator '047 to convert the hydrobromic acid product without sulfuric acid;

[0558] (4) Treat with heating crystallizer II to obtain sodium bromide solid.

[0559] The electrodialysis equipment 066 processes the obtained ion dilute liquid outlet 068, and the small amount of cobalt and manganese ions contained therein are then recovered through the mixing tank VIII 069 + solid-liquid separator VIII 071.

[0560] Example 2 has proved that the nanofiltration membrane 022 of the nanofiltration system I and the mixing tank IV014 + solid-liquid separator IV016 can separate carbonic acid and sodium bromide, and the effect is the same. Therefore, it can be inferred that the nanofiltration system I in this embodiment can be replaced by the mixing tank IV014 + solid-liquid separator IV016 to achieve the same effect as this embodiment.

[0561] Example 6

[0562] A processing system for resource recovery of PTA oxidation residue, based on Example 1, replaces "the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the incineration equipment IV 008, and the incineration equipment IV 008 is also provided with a fuel inlet 009 and a steam generation drum 010" with "the solid outlet 061 of the solid-liquid separator VI 060 is connected to the inlet of the sublimation equipment 084, and the sublimation equipment 084 is also provided with a heater 085, and the gas phase outlet 086 of the sublimation equipment 084 is connected to the inlet of the cooling equipment 087 of the sublimation equipment 084, and the outlet of the cooling equipment 087 of the sublimation equipment 084 is collected".

[0563] The above system operates as follows:

[0564] On the basis of Example 1, “the solid in the solid-liquid separator I004 is washed with a mixing tank VI058, water (about five times the volume) is added to the washing liquid inlet 059 of the mixing tank VI058 for washing, and then the solid-liquid separation is carried out by the solid-liquid separator VI060, and the obtained liquid is circulated back to the mixer I002, and the obtained solid is collected by the incineration equipment IV008 and fuel is added (from the fuel inlet 009) for incineration, and the steam is generated by the steam generating drum 010 for recycling the heat value” is replaced by “the solid in the solid-liquid separator I004 is washed with a mixing tank VI058, water (about The liquid is five times the volume) for washing, and then the solid-liquid separation is carried out by solid-liquid separator VI060, and the obtained liquid is circulated back to mixer I002, and the obtained solid is collected and heated by sublimation equipment 084 (using heater 085 of sublimation equipment 084 for heating) and sublimated (controlling temperature 90-150°C), and then the gas phase is cooled by cooling equipment 087 of sublimation equipment 084, and the cooling equipment 087 of sublimation equipment 084 is also provided with a wall-hanging pushing device, such as a spiral, and the outlet 088 of cooling equipment 087 of sublimation equipment 084 is collected as benzoic acid product; the bottom of sublimation equipment 084 is collected as phthalic acid product.

[0565] Run experiments using the above systems and methods:

[0566] Benzoic acid collected at outlet 088 of cooling device 087 of sublimation device 084 was tested to have a benzoic acid content of 98.3%.

[0567] The bottom sampling test of sublimation equipment 084 showed phthalic acid content of 91.1%.

[0568] Conclusion: After processing by this system:

[0569] Based on the conclusion of Example 1, the sublimation equipment 084 + cooling equipment 087 can be used to separate benzoic acid and phthalic acid to obtain two products, benzoic acid and phthalic acid.

[0570] Example 7

[0571] A processing system for resource recovery of PTA oxidation residue, based on Example 1, replaces "the solid outlet 061 of the solid-liquid separator VI060 is connected to the inlet of the incineration device IV008, and the incineration device IV008 is also provided with a fuel inlet 009 and a steam generation drum 010" with "the solid outlet 061 of the solid-liquid separator VI060 is connected to the water inlet of the extraction device '089, the extraction device '089 is also provided with an extractant addition port 090, the liquid outlet of the extraction device '089 is connected to the inlet of the cooling device 091 of the extraction device '089, and the outlet of the cooling device 091 of the extraction device '089 is connected to the extraction device '089 The inlet of the filter 092 of the extraction device '089, the liquid outlet 093 of the filter 092 of the extraction device '089 is connected to the inlet of the heater 098, and the solid outlet 094 of the filter 092 of the extraction device '089 is collected; the solid outlet of the extraction device '089 is connected to the inlet of the filter '095 of the extraction device '089, the liquid outlet 097 of the filter '095 of the extraction device '089 is connected to the extractant addition port 090 of the extraction device '089, and the solid outlet 096 of the filter '095 of the extraction device '089 is collected; the outlet of the heater 098 is connected to the extractant addition port 090 of the extraction device '089".

[0572] The above system operates as follows:

[0573] On the basis of Example 1, “the solid in the solid-liquid separator Ⅰ004 is washed with a mixing tank Ⅵ058, water (about five times the volume) is added to the washing liquid inlet 059 of the mixing tank Ⅵ058 for washing, and then the solid-liquid separation is carried out by the solid-liquid separator Ⅵ060, and the obtained liquid is circulated back to the mixer Ⅰ002, and the obtained solid is collected by the incineration equipment Ⅳ008 and fuel is added (from the fuel inlet 009) for incineration, and the steam is generated by the steam generating drum 010 for recycling the heat value” is replaced by “the solid in the solid-liquid separator Ⅰ004 is washed with a mixing tank Ⅵ058, water (about five times the volume) is added to the washing liquid inlet 059 of the mixing tank Ⅵ058 for washing, and then the solid-liquid separation is carried out by the solid-liquid separator Ⅵ060, and the obtained liquid is The liquid is circulated back to the mixer Ⅰ002, and the solid obtained is collected and extracted with the extraction device '089. The extraction agent (90-150℃ hot water is used as the extraction agent) is added from the extraction agent addition port 090 of the extraction device '089. The extracted liquid is then cooled (cooled to 0-50℃) by the cooling device 091 of the extraction device '089 and filtered by the filter 092. The solid obtained by filtering with the filter 092 is the benzoic acid product. The filtrate of the filter 092 is heated (90-150℃) and then used as the extraction agent for re-extraction. The extracted solid (i.e., slurry) is filtered by the filter '095 of the extraction device '089. The solid obtained is the phthalic acid product, and the filtrate is used as the extraction agent for re-extraction.

[0574] Run experiments using the above systems and methods:

[0575] Benzoic acid test of the solid collected at the solid outlet 094 of the filter 092 of the extraction device '089: benzoic acid content 95.1%;

[0576] The solids collected at the solid outlet 096 of the filter '095 of the extraction device '089 were tested for phthalic acid: phthalic acid content 94.4%;

[0577] Conclusion: After processing by this system:

[0578] Based on the conclusion of Example 1, the extraction device '089+filter 092+filter '095 can be used to separate benzoic acid and phthalic acid to obtain two products, benzoic acid and phthalic acid.

[0579] Example 8

[0580] A processing system for resource recovery of PTA oxidation residue, based on Example 6, wherein a gas phase outlet 086 of a sublimation device 084 is connected to an inlet of a cooling device 087 of the sublimation device 084, an outlet 088 of the cooling device 087 of the sublimation device 084 is connected to an inlet of an esterification reactor '100, and the esterification reactor '100 is further provided with an alcohol addition inlet 102; a solid phase outlet 104 of the sublimation device 084 is connected to an inlet of an esterification reactor '101, and the esterification reactor '101 is further provided with an alcohol addition inlet 103;

[0581] The above system operates as follows:

[0582] Based on Example 6, the sublimation device 084 evaporates benzoic acid into benzoic acid vapor, which is then cooled by the cooling device 087. The benzoic acid vapor then enters the esterification reactor 100 and reacts with the alcohol (e.g., octanol) added from the alcohol inlet 102 to produce octanol benzoate.

[0583] Sublimation equipment 084 evaporates benzoic acid into benzoic acid vapor. The remaining solid, mainly phthalic acid, enters esterification reactor 101 and undergoes an esterification reaction with alcohol (e.g., ethylene glycol) added from alcohol inlet 103 to produce ethylene glycol phthalate.

[0584] Embodiment 9

[0585] A processing system for resource recovery of PTA oxidation residue, based on Example 7, wherein the solid outlet 094 of the filter 092 of the extraction device ' is connected to the inlet of the esterification reactor '100, and the esterification reactor '100 is further provided with an alcohol addition inlet 102; the solid outlet 096 of the filter '095 of the extraction device ' is connected to the inlet of the esterification reactor '101, and the esterification reactor '101 is further provided with an alcohol addition inlet 103;

[0586] The above system operates as follows:

[0587] Based on Example 7, the benzoic acid filtered out of the filter 092 of the extraction device enters the esterification reactor 100 and undergoes an esterification reaction with the alcohol (e.g., octanol) added from the alcohol inlet 102 to produce octanol benzoate.

[0588] The phthalic acid filtered out by the filter '095' of the extraction device enters the esterification reactor '101' and undergoes an esterification reaction with the alcohol (eg, ethylene glycol) added from the alcohol addition port 103 to produce ethylene glycol phthalate.

Claims

1. A method for recycling PTA oxidation residue, characterized in that: The processing method includes the following process: Liquid is added to the PTA oxidation residue for slurrying, and then solid-liquid separation is performed in a solid-liquid separator I. The obtained filtrate is subjected to an organic matter elimination treatment to remove organic matter, and then subjected to a cobalt-manganese recovery treatment to remove cobalt and manganese ions therein. The aqueous solution after the cobalt-manganese recovery treatment to remove cobalt and manganese ions is collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; The cobalt-manganese recovery treatment is to add an alkaline substance to the aqueous solution after the organic matter is removed by the organic matter elimination treatment, solidify the cobalt-manganese ions, and then remove the solidified substance of the cobalt-manganese ions through a solid-liquid separator IV and recover them; or the cobalt-manganese recovery treatment is to use a cobalt-manganese ion adsorption device to adsorb the cobalt-manganese ions in the aqueous solution after the organic matter is removed by the organic matter elimination treatment.

2. The method according to claim 1, characterized in that The organic matter elimination treatment includes at least one of the following methods: Adsorbing organic matter using an organic matter adsorption device, wherein the organic matter adsorption device is filled with a filler having an adsorption effect on the organic matter; Or use electrodialysis equipment to treat and obtain concentrated water from the electrodialysis equipment, and the content of organic matter in the concentrated water is reduced; Or concentration treatment can reduce the amount of water, which will cause the organic matter to form insoluble matter and precipitate, and then be removed by solid-liquid separation; Or concentrate to reduce the amount of water, and cool to reduce the solubility of organic matter, so that the organic matter therein forms insoluble matter and precipitates, and then removes it by solid-liquid separation; Or remove the organic matter in the aqueous solution by extraction; For example, when the organic matter elimination treatment adopts a combination of ≥2 of the above methods, the adopted methods can be combined and implemented in any order to deeply remove the organic matter.

3. The method according to claim 1 or 2, characterized in that The liquid is added to the PTA oxidation residue for beating and the mixture is cooled simultaneously; or the liquid is added to the PTA oxidation residue for beating and the mixture is cooled first, and then the mixture is passed through the solid-liquid separator I for solid-liquid separation.

4. The method according to claim 1 or 2, characterized in that The filtrate obtained from the solid-liquid separator I is subjected to an organic matter elimination treatment to remove organic matter, and then to an iron removal treatment to remove iron ions, and then to a cobalt and manganese recovery treatment to remove and recover cobalt and manganese ions therein; Alternatively, the filtrate from the solid-liquid separator I is first subjected to an iron removal treatment to remove iron ions, and then subjected to an organic matter elimination treatment to remove organic matter.

5. The method according to claim 1, 2, 3 or 4, characterized in that The aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first treated by the nanofiltration system I, and the fresh water obtained by the nanofiltration system I is collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the aqueous solution after the cobalt and manganese ions are removed through the cobalt and manganese recovery treatment is first evaporated and concentrated, and then solid-liquid separation is performed using a solid-liquid separator II. The resulting filtrate is then collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank.

6. The method according to claim 4, characterized in that The iron removal treatment is to add alkaline substances and control the pH to remove the iron ions by filtering and forming insoluble matter.

7. The method according to claim 5, characterized in that The aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first evaporated and concentrated, then cooled, and then solid-liquid separation is performed using a solid-liquid separator II; or the filtrate obtained from the solid-liquid separator II is treated by the nanofiltration system II, and the fresh water obtained from the nanofiltration system II is collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first evaporated and concentrated, then cooled, and then subjected to solid-liquid separation using a solid-liquid separator II. The resulting filtrate is treated by a nanofiltration system II, and the fresh water obtained from the nanofiltration system II is collected, heated and crystallized into a solid product, and treated using a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated using an evaporation tank.

8. The method according to claim 5 or 7, characterized in that The aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first alkali-added to adjust the pH, and then processed by the nanofiltration system I; Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove cobalt and manganese ions is first heated to convert bicarbonate into carbonate, and then processed by the nanofiltration system I; Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove cobalt and manganese ions is first heated to convert bicarbonate into carbonate, and then cooled and then processed by the nanofiltration system I; Alternatively, the aqueous solution after the cobalt and manganese recovery treatment to remove the cobalt and manganese ions is first subjected to alkali adjustment for pH, and then evaporated and concentrated, and then passed through a solid-liquid separator II for solid-liquid separation, or the evaporation and concentration are then cooled and then passed through a solid-liquid separator II for solid-liquid separation; Alternatively, the aqueous solution after the cobalt-manganese recovery treatment to remove the cobalt-manganese ions is first heated to convert bicarbonate into carbonate, and then evaporated and concentrated. After the evaporation and concentration, the aqueous solution is passed through a solid-liquid separator II for solid-liquid separation, or the aqueous solution is evaporated and concentrated and then cooled and then passed through a solid-liquid separator II for solid-liquid separation.

9. The method according to claim 5, 7 or 8, characterized in that The fresh water in the nanofiltration system I is first acidified to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the fresh water in the nanofiltration system I is first acidified to adjust the pH so that carbonate and bicarbonate react to generate carbon dioxide, which is then removed by a decarbonization tower. The carbon dioxide is then collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the filtrate from the solid-liquid separator II is first subjected to acid addition to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the filtrate from the solid-liquid separator II is first subjected to acid addition to adjust the pH to react carbonate and bicarbonate to generate carbon dioxide, which is then removed by a decarbonization tower and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the fresh water in the nanofiltration system II is first acidified to adjust the pH to remove carbon dioxide generated by the reaction of carbonate and bicarbonate, and then collected, heated and crystallized into a solid product, treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank; Alternatively, the fresh water in the nanofiltration system II is first acidified to adjust the pH so that carbonate and bicarbonate react to generate carbon dioxide, which is then removed by a decarbonization tower. The carbon dioxide is then collected, heated and crystallized into a solid product, and treated with a bipolar membrane electrodialysis device to obtain hydrobromic acid, or treated with an evaporation tank.

10. The method according to claim 5 or 7, characterized in that The filtrate from the solid-liquid separator II is first treated with alkali and then processed by the nanofiltration system II; Alternatively, the filtrate from the solid-liquid separator II is first heated to convert bicarbonate into carbonate, and then processed by the nanofiltration system II; Or the filtrate of the solid-liquid separator II is first heated to convert bicarbonate into carbonate, then cooled, and then processed by the nanofiltration system II; Alternatively, the aqueous solution after the cobalt and manganese ions are removed through the cobalt and manganese recovery treatment is first evaporated and concentrated, then acidified, and then solid-liquid separated using the solid-liquid separator II.

11. The method according to any one of claims 1 to 10, characterized in that The solid obtained from the solid-liquid separator I is also washed with water to produce a washing liquid; Alternatively, the solid obtained from the solid-liquid separator I is slurried with water, and then passed through a solid-liquid separator VI for solid-liquid separation to produce a filtrate, i.e., a water washing liquid; or the solid obtained from the solid-liquid separator I is slurried with water and subjected to solid-liquid separation multiple times to thoroughly wash the cobalt and manganese ions in the solid obtained from the solid-liquid separator I; Discharging of the washing liquid; or the water washing liquid is reused as the added liquid in the process of adding liquid to the PTA oxidation residue for slurrying, or the water washing liquid is refluxed to the iron removal process, or the water washing liquid is refluxed to the cobalt and manganese recovery process, or the water washing liquid is treated by the nanofiltration system III, or the water washing liquid is refluxed to the organic matter elimination process; or adding alkaline substance to the solid in the solid-liquid separator VI and performing solid-liquid separation in the solid-liquid separator VII, and the obtained filtrate is the water washing liquid; The washing liquid is discharged, or the washing liquid is returned to the nanofiltration system I for treatment; or the washing liquid is returned to the evaporation and concentration system for evaporation and concentration, and then treated by the solid-liquid separator II.

12. The method according to claim 1 or 11, characterized in that The solid obtained from the solid-liquid separator I is incinerated; or the solid obtained from the solid-liquid separator VI is incinerated; or the solid obtained from the solid-liquid separator VI is separated through a benzoic acid and phthalic acid separation process; or the solid obtained from the solid-liquid separator I is separated through a benzoic acid and phthalic acid separation process; or the solid obtained from the solid-liquid separator I is subjected to an esterification reaction to generate an ester product; or the solid obtained from the solid-liquid separator VI is subjected to an esterification reaction to generate an ester product; or the solid obtained from the solid-liquid separator VI is separated through a benzoic acid and phthalic acid separation process, and the obtained benzoic acid and phthalic acid are subjected to an esterification reaction respectively to generate an ester product; or the solid obtained from the solid-liquid separator I is separated through a benzoic acid and phthalic acid separation process, and the obtained benzoic acid and phthalic acid are subjected to an esterification reaction respectively to generate an ester product.

13. The method according to claim 12, characterized in that The incineration requires external fuel, and / or the incineration also generates steam.

14. The method according to any one of claims 1 to 13, characterized in that The aqueous solution obtained after the organic matter elimination treatment is first concentrated and then subjected to the cobalt and manganese recovery treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first concentrated and then treated by the nanofiltration system I; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first concentrated and then subjected to the evaporation concentration treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first concentrated and then subjected to the heating treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first concentrated and then subjected to the alkali treatment; or the aqueous solution obtained after the heating is first concentrated and then processed by the nanofiltration system I; or the aqueous solution obtained after adding the alkali is first concentrated and then processed by the nanofiltration system I; or the aqueous solution obtained after the heating is first concentrated and then subjected to the evaporation concentration treatment; or the aqueous solution obtained after adding the alkali is first concentrated and then subjected to the evaporation concentration treatment; Or the fresh water from the nanofiltration system I is first concentrated and then processed in the collection tank; Or the fresh water from the nanofiltration system I is first concentrated and then processed by the heating crystallizer II; or the fresh water from the nanofiltration system I is first concentrated and then subjected to the bipolar membrane electrodialysis treatment; Or the fresh water from the nanofiltration system I is first concentrated and then processed by the evaporation tank; Or the fresh water from the nanofiltration system I is first concentrated and then subjected to the acidification treatment; or the aqueous solution obtained after the acid addition is first concentrated and then processed in the collection tank; or the aqueous solution obtained after the acid addition is first concentrated and then treated in a heating crystallizer II; or the aqueous solution obtained after the acid addition is first concentrated and then subjected to the bipolar membrane electrodialysis treatment; or the aqueous solution obtained after the acid addition is first concentrated and then processed in the evaporation tank; or the filtrate obtained from the solid-liquid separator II is first concentrated and then processed in the collection tank; or the filtrate obtained from the solid-liquid separator II is first concentrated and then processed by the heating crystallizer II; or the filtrate obtained from the solid-liquid separator II is first concentrated and then subjected to the bipolar membrane electrodialysis treatment; Or the filtrate obtained from the solid-liquid separator II is first concentrated and then processed in the evaporation tank; or the filtrate obtained from the solid-liquid separator II is first concentrated and then subjected to the acid treatment; Or the fresh water from the nanofiltration system II is first concentrated and then processed in the collection tank; Or the fresh water from the nanofiltration system II is first concentrated and then processed by the heating crystallizer II; or the fresh water of the nanofiltration system II is first concentrated and then subjected to the bipolar membrane electrodialysis treatment; Or the fresh water from the nanofiltration system II is first concentrated and then processed by the evaporation tank.

15. The method according to claim 2 or 14, characterized in that The concentration is at least one of evaporation concentration, electrodialysis concentration, and reverse osmosis concentration.

16. The method according to any one of claims 1 to 15, characterized in that The concentrated water obtained by the nanofiltration system I provides alkaline substances for the iron removal treatment, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas scrubber of the PTA plant, or is used as alkaline substances; or evaporating and crystallizing the concentrated water obtained from the nanofiltration system I to obtain a solid product; Or the concentrated water obtained by the nanofiltration system II provides alkaline substances for the iron removal treatment, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas scrubber of the PTA plant, provides alkaline substances for the evaporation and concentration, or is used as alkaline substances; or evaporating and crystallizing the concentrated water obtained by the nanofiltration system II to obtain a solid product; Or the solid obtained from the solid-liquid separator II provides alkaline substances for the iron removal treatment, provides alkaline substances for the solidification of cobalt and manganese ions, provides alkaline substances for the water wash liquid to solidify the cobalt and manganese ions therein, provides alkaline substances for the oxidation tail gas washing tower of the PTA plant, is dried, or is dried and then incinerated.

17. The method according to claim 16, characterized in that The solid product obtained by the evaporation and crystallization is dried. Or the solid product obtained by evaporation and crystallization is dried, and then the solid is incinerated.

18. The method according to any one of claims 1 to 16, characterized in that The fresh water obtained from the electrodialysis device is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or is treated together with the nanofiltration system III; or is treated with the nanofiltration system IV; or an alkaline substance is added and solid-liquid separation is performed using the solid-liquid separator VIII; or the fresh water from the concentration device I is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or the fresh water from the concentration device II is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or the fresh water from the concentration device III is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or the fresh water from the concentration device IV is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; or the brine of the bipolar membrane electrodialysis device is reused in the process of adding liquid to the PTA oxidation residue as the liquid for adding liquid to the PTA oxidation residue for slurrying; Or the organic matter adsorption equipment needs to be regenerated after adsorption saturation; Or the solid-liquid separator IV is used in the oxidation reactor of the PTA plant after adding acid; Or the solid-liquid separator VII is added with acid and then used in the oxidation reactor of the PTA plant; Alternatively, the cobalt-manganese ion adsorption device needs to be regenerated after adsorption saturation, and the liquid obtained after regeneration carries the cobalt-manganese ions and is used in the oxidation reactor of the PTA plant.

19. The method according to any one of claims 1 to 18, characterized in that Chemicals are added to the evaporation tank and heated, and the evaporated steam is collected by a collection tank or absorbed by water.

20. The method according to claim 19, characterized in that The liquid obtained by the water absorption is heated, and the evaporated steam is collected in a "collection tank" or absorbed again with water. Alternatively, the liquid obtained by the water absorption is added with chemicals and heated, and the evaporated steam is collected in a "collection tank" or absorbed again with water.

21. The method according to any one of claims 1 to 18, characterized in that The filtrate obtained from the solid-liquid separator I is first deoxidized and then subjected to the organic matter elimination treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first deoxidized and then treated by the nanofiltration system I; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the evaporation and concentration treatment; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then processed by the nanofiltration system II; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then processed through the collection tank; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then treated in the heating crystallizer II; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then subjected to the bipolar membrane electrodialysis treatment; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then processed through the evaporation tank; or the aqueous solution obtained after the organic matter elimination treatment is first deoxidized and then subjected to the cobalt and manganese recovery treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the alkali treatment; or the aqueous solution obtained after the cobalt and manganese recovery treatment is first deoxidized and then subjected to the heating treatment; or the aqueous solution obtained after adding the alkali is first deoxidized and then processed by the nanofiltration system I; or the aqueous solution obtained after adding the alkali is first deoxidized and then subjected to the evaporation and concentration treatment; or the filtrate obtained from the solid-liquid separator II is first deoxidized and then subjected to the acid treatment; or the aqueous solution obtained after the acid addition is first deoxidized and then processed in the collection tank; or the aqueous solution obtained after the acid addition is first deoxidized and then treated in the heating crystallizer II; or the aqueous solution obtained after the acid addition is first deoxidized and then subjected to the bipolar membrane electrodialysis treatment; Or the aqueous solution obtained after the acid addition is first deoxidized and then processed in the evaporation tank.

22. The method according to any one of claims 1 to 21, characterized in that The alkali produced by the bipolar membrane electrodialysis device is used in the alkali addition process or as an alkaline substance; Or the acid produced by the bipolar membrane electrodialysis device is used in the acid addition process, and / or used in the oxidation reactor of the PTA plant; Alternatively, the solid incinerated by the incineration equipment IV is subjected to a reduction reaction to reduce the high-valence cobalt and manganese produced during the incineration process into divalent cobalt and manganese to serve as a catalyst for the PTA oxidation reaction.

23. The method according to any one of claims 1 to 22, characterized in that Process in at least one of the following ways: The fresh water of the nanofiltration system III is used for washing the solid-liquid separator I, for pulping the solid-liquid separator I, or is reused as the added liquid in the liquid pulping process of the PTA oxidation residue; Or the fresh water of the nanofiltration system IV is used for washing the solid-liquid separator I, for beating the solid-liquid separator I, or is reused in the beating process of adding liquid to the PTA oxidation residue as added liquid; or the concentrated water of the nanofiltration system III is subjected to the organic matter elimination treatment; Or the concentrated water of the nanofiltration system IV is subjected to the organic matter elimination treatment.

24. The method according to claim 12, wherein The benzoic acid and phthalic acid separation process adopts a sublimation process or an extraction process.

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