CN116444364A

CN116444364A - Treatment process for mother liquor extract of refined terephthalic acid oxidation unit

Info

Publication number: CN116444364A
Application number: CN202211011056.8A
Authority: CN
Inventors: 李玉宽
Original assignee: Best Tech Water Treatment Environmental Technology Dalian Co ltd
Current assignee: Best Tech Water Treatment Environmental Technology Dalian Co ltd
Priority date: 2019-03-27
Filing date: 2019-07-02
Publication date: 2023-07-18
Also published as: CN109776307A; CN110128266A; CN110128266B

Abstract

The invention provides a treatment process for mother liquor extract of a purified terephthalic acid oxidation unit, which belongs to the field of industrial waste separation, recovery and reutilization, and comprises the following process flows: after passing through an acetic acid recovery unit, mother liquor extract is treated as follows: crystallizing and separating to obtain solid organic matters and separating liquid by adopting a temperature-reducing solid-liquid separation method, and separating and recovering the beneficial substances in the solid organic matters and separating liquid respectively; or adopting an esterification process to react most of organic matters to form esters and recycling, and recycling separation liquid generated by washing in the process; or dissolving with solvent, and recovering by solid-liquid separation, and recovering the washing solution generated by washing. After the improvement of the process, the economic value of a part of beneficial substances is recovered; the sewage treatment difficulty and the cost are reduced; the consumption of alkaline substances is reduced, the cost of enterprises is reduced as a whole, and the utilization rate is increased.

Description

Treatment process for mother liquor extract of refined terephthalic acid oxidation unit

The patent application of the invention is that the application date is 2019-07-02, and the application number is: 201910591654.9 and the invention name is: a divisional application of a treatment process for mother liquor extraction liquid of a refined terephthalic acid oxidation unit.

Technical Field

The invention belongs to the field of separation, recovery and reutilization of industrial waste, and particularly relates to a treatment process of mother liquor extract of an oxidation unit of a refined terephthalic acid (also called terephthalic acid) production device.

Background

Terephthalic acid is an important polyester production raw material, and thus has very wide industrial application. The main process for producing terephthalic acid is divided into two parts of oxidation and refining, wherein an oxidation unit can produce a mother liquor extract, and the mother liquor extract mainly contains phthalic acid (including ortho-position, meta-position and para-position, which are called phthalic acid in a general way unless otherwise specified), by-product benzoic acid, oxidation intermediate product p-methylbenzoic acid, oxidation intermediate product p-carboxybenzaldehyde, by-product anthraquinone fluorenone and other heterocyclic compounds, acetic acid and sodium ions, metal corrosion products (such as iron and chromium ions in the production process, wherein the metal corrosion products mainly contain iron ions according to concentration, and the concentration of chromium ions is relatively low compared with that of iron ions), bromine ions, cobalt ions and manganese ions.

The oxidation process mainly comprises the steps of reacting raw paraxylene with oxygen in air in a reactor to generate terephthalic acid, wherein elements of cobalt, manganese and bromine are additionally added in the reaction process to serve as catalysts, and acetic acid is used as a solvent.

In the prior art, one of the conventional methods for treating the mother liquor extract in the prior art is to remove a part of acetic acid and water from the mother liquor extract by evaporation or membrane method (recovery), pulping the rest of the mother liquor extract with water, controlling the temperature after pulping to precipitate and filter terephthalic acid (recovery), adding alkaline substances (generally using carbonate, bicarbonate and hydroxide) to the filtrate, filtering, adding alkaline substances (generally using carbonate, bicarbonate and hydroxide), filtering, discharging to the sewage treatment process, and adding alkaline substances for the first time to raise the PH (controlling the PH between about 3.0 and 7.5) and forming a part of metal corrosion products (such as iron and chromium ions) into solid matters; the purpose of the second alkaline material addition to raise the pH (to a pH of between about 7.5 and 14) is to recover cobalt and manganese: the solid matters formed by cobalt ions and manganese ions are collected in a filter, and are periodically dissolved by hydrobromic acid and then recycled to an oxidation reaction system (namely, cobalt, manganese, cobalt and bromine are recycled as catalysts of oxidation reaction).

The sewage discharged to the sewage plant after the treatment mainly contains heterocyclic compounds such as bromide ions, phthalic acid, byproduct benzoic acid, oxidation intermediate products of p-methylbenzoic acid, oxidation intermediate products of p-carboxybenzaldehyde, sodium ions, acetic acid which is not completely removed, byproduct anthraquinone fluorenone and the like.

However, in such treatment, the aqueous solution discharged to the sewage plant contains a certain amount of phthalic acid, benzoic acid and the like, and the treatment load and cost of sewage COD are high; simultaneously, the phthalic acid, the benzoic acid and the like are beneficial substances, and the economic value can be generated by separating and recycling or utilizing part of the phthalic acid, the benzoic acid and the like to form esters for recycling; then, the bromide ions enter a sewage plant at the later stage to influence biochemical sludge to reduce activity, so that biochemical effect is reduced, and bromine is also a beneficial substance, is one of catalysts for oxidation reaction, can be recycled to an oxidation reaction system to recover economic value, and reduces the addition amount of bromine elements in an oxidation process; in addition, a large amount of alkaline substances are consumed in the process of adding the alkaline substances, the operation cost is high, and the operation cost can be reduced by reducing the consumption of a part of alkaline substances.

The method has the advantages that beneficial substances (such as bromine, benzoic acid or phthalic acid) can be extracted from the discharged industrial waste from the source to change waste into valuable to generate economic value, meanwhile, the purposes of reducing COD load and operation cost of sewage treatment, reducing the consumption of alkaline substances (reducing the consumption of alkaline substances by a method for reducing the amount of benzene series in sewage, reducing the consumption of alkaline substances by a method for recovering cobalt and manganese ions by a cobalt and manganese adsorption resin instead of a method for adding alkaline substances to form solid substances by cobalt and manganese ions) are achieved, the operation cost of enterprises is reduced, and the environmental protection is facilitated.

Disclosure of Invention

The invention aims to solve the defects of high COD load, high cost, high valuable organic matters (benzoic acid, phthalic acid and the like) and serious bromide ion waste, high enterprise cost and resource waste caused by large alkaline matter consumption in a sewage plant in the prior art by a treatment process of mother liquor extract of an oxidation unit of a purified terephthalic acid (also called terephthalic acid) production device, comprising separation, recovery and reutilization treatment, and provides the following process route:

flow a: the mother liquor extract of the oxidation unit passes through an acetic acid recovery unit (such as an evaporation method or a membrane method) to remove part of acetic acid and water to obtain a residual mixture;

flow b: the remaining mixture of scheme a is processed in scheme b, which has 3 routes, alternatively, routes b-I, b-II, and b-III, respectively:

route b-I: carrying out solid-liquid separation treatment or temperature reduction and solid-liquid separation treatment on the rest mixture in the process a to obtain a solid I and a separation liquid I; the solid I is a mixture mainly comprising phthalic acid and benzoic acid; the separating liquid I mainly comprises sodium ions, bromine ions, metal corrosion products (such as iron and chromium ions, the metal corrosion products mainly comprise iron ions according to concentration, the concentration of the chromium ions is relatively low compared with that of the iron ions), cobalt ions, manganese ions, acetic acid, benzoic acid and phthalic acid which are still dissolved in water, and the like;

Another method for separating out and obtaining the solid I and the separating liquid I is to add acid to separate out and solid-liquid separation after the residual mixture of the flow a is subjected to the conventional process of adding alkaline substances to dissolve benzene series and recovering cobalt-manganese units. However, the method not only does not reduce the consumption of alkaline substances, but also increases the consumption of acid, which is relatively higher than the method of directly cooling the rest mixture in the process a and separating acid and alkali in solid-liquid separation, and has high consumption and high operation cost;

the separating liquid I is directly discharged; or the separation liquid I is treated according to the route b-I-1; or the separation liquid I is treated according to the route b-I-1-a;

route b-I-1: delivering to a impurity removal unit, filtering or precipitating to remove iron, chromium and other ions by adopting a method of adding alkaline substances to crystallize and separate iron and chromium ions, delivering the effluent of the impurity removal unit to a cobalt-manganese resin adsorption unit, adsorbing cobalt and manganese in the effluent, and taking the adsorbed effluent as an aqueous solution a; or adding alkaline substances into the effluent of the impurity removal unit to form solid substances of cobalt and manganese ions in the effluent, and precipitating and/or filtering to obtain an aqueous solution a ', wherein the aqueous solution a and/or the aqueous solution a' are directly discharged; or directly or filtering (removing broken resin) the aqueous solution a and/or the aqueous solution a' and then conveying to a bromine removing unit, adsorbing bromine by a bromine adsorption resin (the bromine adsorption resin is an adsorption resin which is selective to bromine), and directly discharging the effluent after adsorbing bromine to a sewage comprehensive treatment unit or filtering and then discharging to the sewage comprehensive treatment unit;

Route b-I-1-a: delivering to a impurity removing unit, filtering or precipitating to remove iron, chromium and other ions by adopting a method of adding alkaline substances to crystallize and separate iron and chromium ions, delivering the liquid to a bromine removing unit, and adsorbing bromine by a bromine adsorption resin (the bromine adsorption resin is an adsorption resin selective to bromine), wherein the effluent after adsorbing bromine is directly discharged; or directly or filtering the outlet water after bromine adsorption and then conveying the outlet water to a cobalt-manganese resin adsorption unit to adsorb cobalt and manganese in the outlet water, wherein the outlet water after adsorption is an aqueous solution b; or directly or filtering the outlet water after bromine adsorption, adding alkaline substances to form cobalt and manganese ions therein into solid matters, and precipitating and/or filtering to obtain an aqueous solution b ', wherein the aqueous solution b and/or the aqueous solution b' are directly discharged to a sewage comprehensive treatment unit; or filtering the aqueous solution b and/or the aqueous solution b 'and then discharging the filtered aqueous solution b and/or the filtered aqueous solution b' to a sewage comprehensive treatment unit;

the cobalt-manganese resin adsorption unit and the bromine removal unit can be implemented independently or in an interchangeable sequence;

the solid I is subjected to waste treatment; or the solid I is recycled; or the solid I is treated according to the route b-I-a;

route b-I-a: washing the solid I with water to obtain a solid I-1 and a washing liquid I-1, wherein the solid I-1 mainly comprises phthalic acid and benzoic acid, the solid I-1 is abandoned or the solid I-1 is recycled, the washing liquid I-1 mainly comprises sodium ions, bromine ions, metal corrosion products (such as iron ions and chromium ions), cobalt ions, manganese ions, acetic acid, benzoic acid still dissolved in water, phthalic acid and the like, the washing liquid I-1 is directly discharged, or the washing liquid I-1 is treated by b-I-1-a, or the washing liquid I-1 is treated by a route b-I-2, or the washing liquid I-1 is treated by b-I-2-a;

Route b-I-2: the washing liquid I-1 is conveyed to a cobalt-manganese resin adsorption unit to adsorb cobalt and manganese in the washing liquid I-1, and effluent after adsorption is an aqueous solution c; or adding alkaline substances into the washing liquid I-1 to form solid substances of cobalt and manganese ions therein, precipitating and/or filtering to obtain an aqueous solution c ', and directly discharging the aqueous solution c and/or the aqueous solution c'; or the aqueous solution c and/or the aqueous solution c' are directly or after being filtered and then are conveyed to a bromine removing unit, bromine is adsorbed by bromine adsorption resin, and effluent water after bromine adsorption is directly discharged to a sewage comprehensive treatment unit or is discharged to the sewage comprehensive treatment unit after being filtered;

route b-I-2-a: the washing liquid I-1 is conveyed to a bromine removal unit, bromine is adsorbed by an adsorption resin with selectivity to bromine, and effluent water after the bromine adsorption is directly discharged; or directly or after filtering, delivering the outlet water after bromine adsorption to a cobalt-manganese resin adsorption unit to adsorb cobalt and manganese in the outlet water, wherein the outlet water after adsorption is an aqueous solution d; or directly or after filtering the effluent after bromine adsorption, adding alkaline substances to form cobalt and manganese ions in the effluent into solid matters, precipitating and/or filtering to obtain an aqueous solution d ', and directly discharging the aqueous solution d and/or the aqueous solution d ' to a sewage comprehensive treatment unit or filtering and discharging the aqueous solution d and/or the aqueous solution d ' to the sewage comprehensive treatment unit;

The impurity removing unit adopts an alkaline substance, preferably hydroxide (such as sodium hydroxide, potassium hydroxide and the like), carbonate (such as sodium carbonate, potassium carbonate and the like) or bicarbonate (such as sodium bicarbonate, potassium bicarbonate and the like), and pH is controlled to be about 3.0-7.5, and the impurity removing means that metal corrosion products are formed into solid matters and filtered to be removed (the metal corrosion products such as iron ions and chromium ions, the metal corrosion products are mainly iron ions according to the concentration, and the concentration of the chromium ions is relatively low compared with that of the iron ions, so that the main purpose of removing the metal corrosion products is iron ions);

the alkaline substance is added to form cobalt and manganese ions into solid matters: the alkaline substance is preferably carbonate (such as sodium carbonate, potassium carbonate, etc.), bicarbonate (such as sodium bicarbonate, potassium bicarbonate, etc.), hydroxide (such as sodium hydroxide, potassium hydroxide, etc.), and raise the pH (control pH between about 7.5-14);

b-Ⅱ：

carrying out esterification reaction on the residual mixture in the process a and alcohols (methanol is taken as an example below), or carrying out esterification reaction on the residual mixture in the process a after water is removed and then the residual mixture in the process a and the alcohols (methanol is taken as an example below) to obtain an ester-containing mixture A, and carrying out advanced treatment; in the process, most of phthalic acid, benzoic acid, p-methylbenzoic acid (the relative concentration is far lower than that of phthalic acid and benzoic acid), p-carboxybenzaldehyde (the relative concentration is far lower than that of phthalic acid and benzoic acid), acetic acid and alcohols undergo esterification reaction to respectively form solid esters or liquid esters;

Route b-III:

directly or after dewatering the rest mixture of the process a, adding an organic solvent, and then carrying out solid-liquid separation to obtain solid and separation liquid, and treating the solid by discarding or recycling organic matters; the separated liquid is directly discharged or recycled.

Based on the above technical scheme, preferably, in the route b-I, the rest mixture in the process a is pulped with water and then cooled; cooling (for example, 0-90 ℃) and carrying out solid-liquid separation treatment to obtain a solid I and a separating liquid I; or cooling (for example, 0-90 ℃) and before solid-liquid separation, firstly passing through a terephthalic acid part recovery treatment unit (terephthalic acid is crystallized out by controlling the temperature of pulped slurry, filtered, separated, extracted and recovered), firstly recovering terephthalic acid, and then cooling (for example, 0-90 ℃) and solid-liquid separation are carried out on filtrate;

before the esterification reaction in the route b-II, the rest mixture in the process a is firstly pulped by water, terephthalic acid is firstly crystallized by controlling the temperature after pulping, and is filtered, separated, extracted and recovered, and then the residue is dehydrated and then subjected to the esterification reaction with alcohols; the esterification reaction comprises alcohol recovery, temperature adjusting units and other conventional esterification reaction factories.

Based on the above technical scheme, preferably, the treatment route b-I-a of the solid I is replaced by any one of routes b-I-b and b-I-c:

b-I-b: directly or after crushing, cleaning the solid I by hydrobromic acid solution and/or acetic acid solution, and carrying out solid-liquid separation after cleaning to obtain a solid I-2 and a washing liquid I-2; the solid I-2 is abandoned or the solid I-2 is recycled, and the washing liquid I-2 is directly discharged; or the washing liquid I-2 is recycled to the oxidation reaction system unit; or washing liquid I-2 is recycled;

b-I-c: directly or after crushing, cleaning the solid I by using other acid solutions (preferably sulfuric acid or hydrochloric acid or oxalic acid) except acetic acid or hydrobromic acid, and performing solid-liquid separation after cleaning to obtain a solid I-3 and a washing liquid I-3; the solid I-3 is abandoned or recycled, and the washing liquid I-3 is directly discharged; or the washing liquid I-3 passes through the cobalt-manganese recovery unit I, and the effluent of the cobalt-manganese recovery unit I is directly discharged; or washing liquid I-3 passes through a impurity removal unit, alkaline substances are added to precipitate and/or filter out metal corrosion products, and then the washing liquid I-3 passes through a cobalt-manganese recovery unit I, and effluent of the cobalt-manganese recovery unit I is directly discharged;

the purpose of washing the solid I with water, acetic acid or hydrobromic acid, and other types of acid except acetic acid or hydrobromic acid is to wash away various ions in the water of the solid I, and the washing liquid obtained by washing with acetic acid or hydrobromic acid can be directly recycled to the unit of the oxidation reaction system because the original oxidation reaction system needs to be added with acetic acid and hydrobromic acid, and the washing liquid obtained by washing with other types of acid except acetic acid or hydrobromic acid (preferably hydrochloric acid or sulfuric acid or oxalic acid) cannot be recycled to the oxidation reaction system because the ionic types which are not originally contained in the washing liquid cannot be introduced into the oxidation reaction system.

Based on the technical scheme, the route for recycling the solid I, the solid I-1 and the solid I-2 is preferably that the solid I, the solid I-1 and the solid I-2 are directly or after being dried and then are processed through any one of the routes b-I, b-I-II and b-I-III; the solid I-3 is recovered and treated directly or after washing and/or drying, the solid I-3 is treated by any one of routes b-I, b-I-II and b-I-III;

route b-I: adding alcohol solvent or crushing, adding alcohol solvent (such as methanol or ethanol as below) under stirring to dissolve part of the solid, and separating solid from liquid to obtain separating liquid I-1-1 and solid I-1-1, wherein isophthalic acid, phthalic acid and benzoic acid are easily dissolved in ethanol; terephthalic acid is not easy to dissolve in ethanol, the solid I-1-1 mainly contains terephthalic acid, and the solid I-1-1 is discarded; or the solid I-1-1 is directly recycled; or the solid I-1-1 is recovered or enters an oxidation reaction system after being washed and/or dried (drying refers to evaporating to remove ethanol) or crushed and then enters the oxidation reaction system; or the solid I-1-1 is dried or washed and dried and then is subjected to esterification reaction with alcohols to generate esters for recovery; the separating liquid I-1-1 is a mixture of alcohols (for example, ethanol) dissolved with main isophthalic acid, phthalic acid and benzoic acid, and the separating liquid I-1-1 is directly discharged; or the separating liquid I-1-1 is heated, evaporated and crystallized to separate out solid I-1-1-a, wherein the solid I-1-1-a mainly comprises isophthalic acid, phthalic acid and benzoic acid, and the solid I-1-1-a is abandoned; or the solid I-1-1-a is directly recovered; or the solid I-1-1-a is recovered after washing and/or drying; or drying the solid I-1-1-a or washing and drying the solid I-1-a, and then carrying out esterification reaction with alcohols to generate esters for recovery;

Scheme b-I-II: directly or after crushing, adding an ether solvent (such as diethyl ether) or a benzene solvent (such as toluene or xylene such as paraxylene) or an ester solvent (such as methyl acetate), stirring to dissolve a part of the solids and separating the solids from the liquid to obtain a separation liquid I-1-2 and a solid I-1-2, wherein the solid I-1-2 mainly contains phthalic acid, and the solid I-1-2 is discarded; or the solid I-1-2 is directly recycled; or the solid I-1-2 is recovered after washing and/or drying; or the solid I-1-2 is dried or washed and dried and then is subjected to esterification reaction with alcohols to generate esters for recovery; the separating liquid I-1-2 is mainly benzoic acid dissolved in a solvent, and the separating liquid I-1-2 is directly discharged; or the separating liquid I-1-2 is heated, evaporated, crystallized and separated out to obtain a solid I-1-2-a mainly containing benzoic acid, and the solid I-1-2-a is abandoned; or the solid I-1-2-a is directly recovered; or the solid I-1-2-a is recovered after washing and/or drying, and the economic value can be generated according to the takeout of the low-purity benzoic acid due to the higher solid I-1-2-a benzoic acid; or the solid I-1-2-a is dried or washed and dried and then is subjected to esterification reaction with alcohols to generate esters for recovery;

Scheme b-I-III: after drying, carrying out esterification reaction with alcohols to generate esters for recycling;

the solvent alcohols in the routes b-I can be cooled for recycling after evaporation, and the solvents in the routes b-I-II can be cooled for recycling after evaporation;

routes b-I, b-I-II may be practiced separately or in combination as: the solid material I-1-1-a obtained in the route b-1-I is subjected to the treatment in the route b-I-II; or the solid I-1-2 described in scheme b-I-II is dried or washed with water and then subjected to the treatment of scheme b-I.

Based on the above technical scheme, preferably, the step of carrying out advanced treatment on the mixture A containing esters in the route b-II comprises the following steps: the mixture A containing esters is subjected to washing, direct solid-liquid separation or cooling in sequence, then solid matters are recovered through solid-liquid separation, liquid esters are recovered through layered separation, and separation liquid is obtained; or the mixture A containing esters is subjected to solid-liquid separation or temperature reduction in sequence to recover solid matters through solid-liquid separation, and liquid ester is recovered through washing and layering separation to obtain a separation liquid; most of benzoic acid, phthalic acid, acetic acid, p-methyl benzoic acid and p-carboxyl benzaldehyde are subjected to esterification reaction, so that the esterification reaction is not easy to dissolve in water, anthraquinone fluorenone (the relative specific concentration is far lower than that of phthalic acid and benzoic acid) and is not easy to dissolve in water;

The above washing may be selected from any of the following 3 washing solutions:

washing with water to obtain separating liquid II-a; the separation liquid II-a mainly comprises: sodium ions, cobalt ions, manganese ions, metal corrosion products (e.g., iron, chromium ions), bromide ions, and benzoic acid, phthalic acid, acetic acid, p-methylbenzoic acid, p-carboxybenzaldehyde which are not completely reacted, as well as a small amount of methanol which is not completely removed after the esterification reaction; the separation liquid II-a is directly discharged or recycled to an oxidation reaction system unit or is recycled;

washing with acetic acid solution and/or hydrobromic acid solution to obtain separating liquid II-b; the separation liquid II-b mainly comprises: sodium ions, cobalt ions, manganese ions, metal corrosion products (such as iron and chromium ions, the metal corrosion products mainly contain iron ions according to the concentration, the concentration of the chromium ions is relatively low compared with that of the iron ions), acetic acid, bromide ions, benzoic acid, phthalic acid, p-methylbenzoic acid and p-carboxybenzaldehyde which are not completely reacted, and a small amount of methanol which is not completely removed after the esterification reaction; the separation liquid II-b is directly discharged or recycled to an oxidation reaction system unit or is recycled;

washing with other acid solution (preferably hydrochloric acid, sulfuric acid or oxalic acid) except acetic acid or hydrobromic acid to obtain separating liquid II-c; the separation liquid II-c mainly comprises: sodium ions, cobalt ions, manganese ions, metal corrosion products (such as iron and chromium ions, the metal corrosion products mainly contain iron ions according to the concentration, the concentration of chromium ions is relatively low compared with that of iron ions), bromide ions, benzoic acid, phthalic acid, acetic acid, p-methylbenzoic acid and p-carboxybenzaldehyde which are not completely reacted, a small amount of methanol which is not completely removed after esterification reaction and residual acid for cleaning; the separating liquid II-c is directly discharged; or the separating liquid II-c passes through a cobalt-manganese recovery unit II, and the effluent of the cobalt-manganese recovery unit II is discharged; or the separating liquid II-c firstly passes through a impurity removing unit, alkaline substances are added to precipitate and/or filter metal corrosion products (such as iron and chromium ions, the metal corrosion products mainly contain iron ions according to concentration, the concentration of the chromium ions is relatively low compared with that of the iron ions, so that the main purpose of removing the metal corrosion products is iron ions), and then the metal corrosion products pass through a cobalt-manganese recovery unit II, and the cobalt-manganese recovery unit II discharges water.

The impurity removing unit adopts an added alkaline substance, preferably hydroxide (such as sodium hydroxide, potassium hydroxide and the like), carbonate (such as sodium carbonate, potassium carbonate and the like) or bicarbonate (such as sodium bicarbonate, potassium bicarbonate and the like), and pH is controlled to be about 3.0-7.5, and impurity removing means that metal corrosion products are formed into solid matters and filtered and removed (the metal corrosion products such as iron ions and chromium ions are mainly used as the metal corrosion products according to the concentration, and the concentration of the chromium ions is relatively low compared with that of the iron ions, so that the main purpose of removing the metal corrosion products is iron ions);

based on the above technical scheme, preferably, in the route b-iii, before adding the solvent and performing solid-liquid separation, adding the solvent and performing solid-liquid separation after cooling and/or crushing; the solvent is an alcohol or ether or benzene solvent or an ester solvent;

solvents are selected from alcohols (e.g., methanol or ethanol, as exemplified below by ethanol), route b-III-1; the solvent is selected from ether (such as diethyl ether) or benzene solvent (such as toluene or xylene such as para-xylene) or ester solvent (such as methyl acetate), route b-III-2:

route b-III-1: adding alcohol (e.g. ethanol) solvent, stirring or crushing, adding alcohol (e.g. ethanol) solvent, stirring, and separating solid from liquid to obtain separating liquid III-1 and solid III-1, respectively, wherein isophthalic acid, phthalic acid and benzoic acid are easily dissolved in ethanol; terephthalic acid is not easy to dissolve in ethanol, benzene organic matters in the solid III-1 are mainly terephthalic acid, the solid III-1 is abandoned or the solid III-1 is recycled or the solid III-1 is washed, the separating liquid III-1 is directly discharged or the separating liquid III-1 is heated and crystallized to obtain the solid III-1-1, and the benzene organic matters in the solid III-1-1 are mainly isophthalic acid, phthalic acid and benzoic acid; discarding the solid III-1-1 or recycling the solid III-1-1 or washing the solid III-1-1;

Route b-III-2: adding an ether (e.g., diethyl ether) solvent or a benzene solvent (e.g., toluene or xylene such as para-xylene) or an ester solvent (e.g., methyl acetate) and stirring; or crushing, adding an ether (such as diethyl ether) solvent or a benzene solvent (such as toluene or xylene such as paraxylene) or an ester solvent (such as methyl acetate) and stirring, and then separating solid from liquid to obtain a separating liquid III-2 and a solid III-2 respectively, wherein the solid III-2 is discarded or the solid III-2 is recycled or the solid III-2 is washed, and the separating liquid III-2 is directly discharged; or separating liquid III-2 is heated and crystallized to obtain solid III-2-1, benzene series organic matters in the solid III-2-1 are mainly benzoic acid, and the solid III-2-1 is discarded or the solid III-2-1 is recycled or the solid III-2-1 is washed;

the solid III-1, the solid III-1-1, the solid III-2 and the solid III-2-1 are abandoned or recycled or washed, or the solid III-1, the solid III-1-1, the solid III-2 and the solid III-2-1 are dried and/or crushed before being washed; solid-liquid separation after washing; the purpose of the washing is to wash out ions in the solid, which can be chosen arbitrarily from the following 3 washing solutions:

washing with water, namely, for the solid III-1, the solid III-1-1, the solid III-2 or the solid III-2-1, washing solutions generated by solid-liquid separation after washing are respectively named as washing solution III-1-a, washing solution III-1-1-a, washing solution III-2-a and washing solution III-2-1-a according to the sequence, and the solid generated by solid-liquid separation after washing is respectively named as solid III-1-a, solid III-1-1-a, solid III-2-a and solid III-2-1-a according to the sequence; for the washing liquid III-1-a, the washing liquid III-1-1-a, the washing liquid III-2-a or the washing liquid III-2-1-a, directly discharging or recycling the washing liquid III-1-a to an oxidation reaction system unit or carrying out recycling treatment;

Washing with acetic acid solution and/or hydrobromic acid solution, namely, washing liquid generated by solid-liquid separation after washing the solid III-1, the solid III-1-1, the solid III-2 or the solid III-2-1 is respectively named as washing liquid III-1-b, washing liquid III-1-1-b, washing liquid III-2-b and washing liquid III-2-1-b according to the sequence, and the washed solid is respectively named as solid III-1-b, solid III-1-1-b, solid III-2-b and solid III-2-1-b according to the sequence; the washing liquid III-1-b, the washing liquid III-1-1-b, the washing liquid III-2-b or the washing liquid III-2-1-b is directly discharged or recycled to an oxidation reaction system unit or washing liquid for recycling treatment;

washing with other acid solutions (preferably hydrochloric acid, sulfuric acid or oxalic acid) except acetic acid or hydrobromic acid, namely washing solid III-1, solid III-1-1, solid III-2 or solid III-2-1, and performing solid-liquid separation to obtain washing solutions respectively named washing solutions III-1-c, III-1-1-c, III-2-c and III-2-1-c in the above order, and respectively named solid III-1-c, solid III-1-1-c, solid III-2-c and solid III-2-1-c in the above order; directly discharging the washing liquid III-1-c, the washing liquid III-1-1-c, the washing liquid III-2-c or the washing liquid III-2-1-c; or the washing liquid III-1-c, the washing liquid III-1-1-c, the washing liquid III-2-c or the washing liquid III-2-1-c is discharged through the cobalt manganese recovery unit III; or the washing liquid III-1-c, the washing liquid III-1-1-c, the washing liquid III-2-c or the washing liquid III-2-1-c is subjected to impurity removal unit, alkaline substances are added to precipitate and/or filter, then metal corrosion products (such as iron and chromium ions) are removed, and then the washing liquid III-1-c, the washing liquid III-2-c or the washing liquid III-2-1-c is subjected to cobalt-manganese recovery unit III, and effluent of the cobalt-manganese recovery unit III is discharged;

discarding the solid III-1-a or the solid III-1-b or the solid III-1-c; or the solid III-1-a, the solid III-1-b or the solid III-1-c is recycled or enters an oxidation reaction system unit or is subjected to esterification reaction with alcohols to generate esters for recycling; or the solid III-1-a, the solid III-1-b or the solid III-1-c is washed and/or dried before being recycled or entering an oxidation reaction system unit or being subjected to esterification reaction with alcohols to generate esters for recycling;

discarding the solid III-1-1-a or the solid III-1-1-b or the solid III-1-1-c or the solid III-2-a or the solid III-2-b or the solid III-2-c or the solid III-2-1-a or the solid III-2-1-b or the solid III-2-1-c; or the solid III-1-1-a or the solid III-1-1-b or the solid III-1-1-c or the solid III-2-a or the solid III-2-b or the solid III-2-c or the solid III-2-1-a or the solid III-2-1-b or the solid III-2-1-c is recovered or is subjected to esterification reaction with alcohols to generate esters for recovery; or the solid III-1-1-a or the solid III-1-1-b or the solid III-1-1-c or the solid III-2-a or the solid III-2-b or the solid III-2-c or the solid III-2-1-a or the solid III-2-1-b or the solid III-2-1-c is washed and/or dried before being recovered or being subjected to esterification reaction with alcohols to generate esters;

The steps can be carried out independently or in combination; the combination mode is as follows: solid III-1-1 or solid III-1-1-a or solid III-1-1-b or III-1-1-c is directly or after washing and/or drying treated by b-III-2 route; or solid III-2-a or solid III-2-b or solid III-2-c is directly or after washing and/or drying is carried out, and then b-III-1 treatment is carried out;

based on the above technical scheme, preferably, the treatment route b-I-1 or the alternative route of the route b-I-1-a is: any one of the routes c-I, c-II, c-III, c-IV, c-V, c-VI; the alternative route of the treatment route b-I-2 or route b-I-2-a is: any one of the routes c-I, c-II, c-III, c-IV, c-V, c-VI;

washing liquid I-2, separating liquid II-a, separating liquid II-b, washing liquid III-1-1-a, washing liquid III-1-1-b, washing liquid III-1-a, washing liquid III-1-b, washing liquid III-2-1-a, washing liquid III-2-1-b, washing liquid III-2-a or washing liquid III-2-b, wherein the recovery treatment is carried out by any one of the following 6 routes, namely, route c-I, route c-II, route c-III, route c-IV, route c-V and route c-VI;

The separation liquid I, the washing liquid I-1 or the washing liquid I-2 described in the route b-I; the separation liquid II-a and the separation liquid II-b in the route b-II; the washing solutions III-1-1-a, III-1-1-b, III-1-a, III-1-b, III-2-1-a, III-2-1-b, III-2-a or III-2-b in the routes b-III mainly contain sodium ions, cobalt ions, manganese ions, metal corrosion products (such as iron and chromium ions), bromide ions, acetic acid, benzoic acid, phthalic acid, p-methylbenzoic acid and p-carboxybenzaldehyde, and the separating solution II-a or II-b also contains alcohols (such as methanol) which are not completely removed;

cobalt ions, manganese ions, bromide ions and acetic acid are catalysts and solvents which are needed to be supplemented by the original oxidation reaction system, and can be recycled to the oxidation reaction system unit; sodium ions and metal corrosion products (such as iron and chromium ions, the metal corrosion products are mainly iron ions according to the concentration, the concentration of chromium ions is relatively low compared with that of iron ions) are not easy to recycle into an oxidation reaction system, and the concentration of sodium ions and metal corrosion products (such as iron and chromium ions, the metal corrosion products are mainly iron ions according to the concentration, and the concentration of chromium ions is relatively low compared with that of iron ions) in a mother solution of the oxidation reaction system can be increased; the phthalic acid can be returned to the oxidation reaction system; the benzoic acid is returned to the oxidation reaction system, and the concentration of the benzoic acid in the whole oxidation mother liquor can be balanced as long as the extraction amount of the oxidation mother liquor is increased (most of the benzoic acid in the mother liquor extraction liquid is separated and removed from the mother liquor extraction liquid in the form of solid matters in the steps b-I and b-III, and most of the benzoic acid in the mother liquor extraction liquid and alcohols form esters in the step b-II and are separated and removed from the mother liquor extraction liquid); the p-methylbenzoic acid and the p-carboxybenzaldehyde can be returned to an oxidation reaction system for re-oxidation to form terephthalic acid; a process in which methyl acetate is generated from methanol and oxidation reaction is not significantly affected (the oxidation mother liquor originally contains a certain concentration of methyl acetate);

Route c-I: directly recycled to the oxidation reaction system unit. However, the metal corrosion products (such as iron and chromium ions) are not removed, and sodium ions are not removed, so that the ion concentration of the oxidation mother liquor sodium ions and the metal corrosion products (such as iron and chromium ions) is increased, and the route is only applicable to a device which does not influence the production of terephthalic acid when the concentration of the oxidation mother liquor sodium ions and the metal corrosion products (such as iron and chromium ions) is increased;

route c-II: treated by a cobalt-manganese recovery unit IV (the effluent of the cobalt-manganese recovery unit IV mainly comprises benzoic acid, phthalic acid, p-methylbenzoic acid, p-carboxybenzaldehyde, acetic acid, bromide ions, sodium ions, separating liquid II-a or separating liquid II-b also comprises methanol which is not completely removed), and the effluent of the cobalt-manganese recovery unit IV is directly discharged; or the effluent of the cobalt manganese recovery unit IV enters an oxidation reaction system unit after cations such as sodium ions are removed through hydrogen type cationic resin, and is recovered to the oxidation reaction system unit, wherein the oxidation reaction system mainly contains benzoic acid, phthalic acid, p-toluic acid (which can be oxidized into terephthalic acid again), p-carboxybenzaldehyde (which can be oxidized into terephthalic acid again), acetic acid and bromide ions, and the separating liquid II-a or the separating liquid II-b also contains methanol which is not completely removed (methyl acetate can be generated through oxidation reaction and does not cause serious adverse effects on the oxidation process), so that the extraction amount of oxidation mother liquor can balance the concentration of benzoic acid in the mother liquor;

Route c-III: after being treated by hydrogen type cation resin, the mixture enters an oxidation reaction system unit, and the mixture is recycled to the oxidation reaction system unit, wherein the oxidation reaction system unit mainly contains benzoic acid, phthalic acid, p-toluic acid (which can be oxidized into terephthalic acid again), p-carboxybenzaldehyde (which can be oxidized into terephthalic acid again), acetic acid and bromide ions, and the separating liquid II-a or the separating liquid II-b also contains methanol which is not completely removed (methyl acetate can be generated through oxidation reaction and does not cause serious adverse effect on the oxidation process), so that the concentration of benzoic acid in the mother liquor can be balanced by increasing the extraction amount of oxidation mother liquor;

routes c-IV: after being treated by cobalt-manganese adsorption resin, the mixture is subjected to hydrogen type cation resin and then enters an oxidation reaction system unit, and the oxidation reaction system unit mainly contains benzoic acid, phthalic acid, p-methylbenzoic acid (which can be oxidized into terephthalic acid again), p-carboxybenzaldehyde (which can be oxidized into terephthalic acid again), acetic acid and bromide ions, the separating liquid II-a or the separating liquid II-b also contains incompletely removed methanol (esters of acetic acid can be generated through oxidation reaction, and serious adverse effects are not caused on an oxidation process), and the concentration of benzoic acid in the mother liquor can be balanced by increasing the extraction amount of oxidation mother liquor;

Route c-V: introducing the fresh water into a nanofiltration unit I, and allowing fresh water in the nanofiltration unit I to enter and be recycled into an oxidation reaction system unit; or fresh water of the nanofiltration unit I enters an oxidation reaction system unit after passing through hydrogen type cationic resin, and mainly contains benzoic acid (increasing the extraction amount of oxidation mother liquor and balancing the concentration of benzoic acid in the mother liquor), phthalic acid, p-methylbenzoic acid (being oxidized into terephthalic acid again), p-carboxybenzaldehyde (being oxidized into terephthalic acid again), acetic acid, bromide ions, separating liquid II-a or separating liquid II-b, and also contains methanol which is not completely removed (esters of acetic acid can be generated through oxidation reaction, so that serious adverse effects on an oxidation process are avoided);

route c-VI: routes c-VI include three routes, c-VI-a, c-VI-b and c-VI-c, respectively, optionally one:

route c-VI-a: the effluent of the cobalt-manganese recovery unit V is directly discharged through the cobalt-manganese recovery unit V; or the effluent of the cobalt-manganese recovery unit V is directly discharged after bromine ions are adsorbed by the bromine adsorption resin; or the effluent of the cobalt-manganese recovery unit V is filtered and directly discharged after bromine ions are adsorbed by bromine adsorption resin;

route c-VI-b: adsorbing bromine ions by a bromine adsorption resin, and directly discharging outlet water of the bromine adsorption resin; or directly filtering the effluent of the bromine adsorption resin or after filtering, passing through a cobalt-manganese recovery unit VI, and directly discharging the effluent of the cobalt-manganese recovery unit VI;

Route c-VI-c: the aqueous solution passes through a nanofiltration unit II, concentrated water of the nanofiltration unit II passes through a cobalt-manganese recovery unit VII, and effluent of the cobalt-manganese recovery unit VII is directly discharged;

based on the above technical scheme, preferably, the liquid processed by any one of the routes c-I, c-II, c-III, c-IV, c-V, c-VI is processed by any one of the ultrafiltration membrane, reverse osmosis membrane fresh water drain, reverse osmosis membrane concentrate entering route c-I, c-II, c-III, c-IV, c-V, and c-VI before entering the route c-I, c-II, c-IV, c-III, c-V, c-VI.

Based on the above technical solution, it is preferable,

in the route c-II, the inflow water of the route c-II firstly passes through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or metal corrosion products (such as iron and chromium ions) are removed by filtration to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit IV;

in the route c-III, the inlet water of the route c-III firstly passes through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or metal corrosion products (such as iron and chromium ions) are removed by filtration to obtain filtrate, and the filtrate enters an oxidation reaction system unit after being treated by hydrogen type cationic resin;

In the route c-VI-a, the inlet water of the route c-VI-a firstly passes through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added to precipitate and/or filter metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit V;

in the route c-VI-b, the inlet water of the route c-VI-b firstly passes through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added to precipitate and/or filter out metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate passes through bromine adsorption resin; or the inlet water of the route c-VI-b passes through bromine adsorption resin, the outlet water of the bromine adsorption resin passes through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added to precipitate and/or filter out metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit VI;

in the route c-VI-c, concentrated water of the nanofiltration unit II is firstly subjected to a impurity removal unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or filtration to remove metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is subjected to a cobalt-manganese recovery unit VII; the fresh water of the nanofiltration unit II is directly discharged; or the fresh water of the nanofiltration unit II is directly discharged after passing through the bromine adsorption resin; or the treatment route of the fresh water of the nanofiltration unit II is the same as that of the concentrated water of the nanofiltration unit II after the fresh water passes through the bromine adsorption resin.

Based on the above technical scheme, preferably, in the patent of the invention, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added to precipitate and/or filter out metal corrosion products (such as iron and chromium ions): the metal corrosion products are mainly iron ions according to the concentration, and the concentration of chromium ions is relatively low compared with that of iron ions, so that the metal corrosion products are mainly iron ions removed, and alkaline substances are preferably carbonates (such as sodium carbonate, potassium carbonate and the like), bicarbonates (such as sodium bicarbonate, potassium bicarbonate and the like) and hydroxides (such as sodium hydroxide, potassium hydroxide and the like), so that the PH is raised (the PH is controlled to be between about 3.0 and 7.5); adding alkaline substances to form cobalt and manganese ions into solid precipitates and/or filtering: the alkaline material is preferably selected from carbonates (e.g., sodium carbonate, potassium carbonate, etc.), bicarbonates (e.g., sodium bicarbonate, potassium bicarbonate, etc.), hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.), and raised to a pH (control pH between about 7.5-14).

Based on the above technical solution, it is preferable,

before the effluent water passing through the hydrogen type cationic resin in the route c-II enters the oxidation reaction system unit, filtering equipment (such as a filter) is arranged to filter broken resin and/or hydrobromic acid is added for emptying and stirring, and the hydrobromic acid is added for emptying and stirring to react residual carbonate or bicarbonate (such as carbonate or bicarbonate is added at the front end) to form carbon dioxide which is discharged and removed from the aqueous solution, so that the carbonate or bicarbonate is prevented from entering the oxidation reaction system;

Before the effluent water passing through the hydrogen type cationic resin in the route c-III enters the oxidation reaction system unit, filtering equipment (such as a filter) is arranged to filter broken resin and/or hydrobromic acid is added to blow down and stir;

before the effluent water passing through the hydrogen type cationic resin in the routes c-IV enters the oxidation reaction system unit, a filtering device (such as a filter) is arranged for filtering the crushed resin;

when the water solution adopted in the route c-V passes through the nanofiltration unit I, fresh water passes through the hydrogen type cationic resin, and effluent of the hydrogen type cationic resin enters and is recycled to the oxidation reaction system unit: the effluent water passing through the hydrogen type cation resin is provided with a filtering device (such as a filter) for filtering the crushed resin before being recycled to the oxidation reaction system unit.

Based on the above technical solution, it is preferable,

in said route b-I-1, in said route b-I-1-a, in said route b-1-2-a,

the cobalt-manganese adsorption resin is desorbed and regenerated by an acid solution (such as acetic acid and/or hydrobromic acid solution) or is washed after being regenerated after being adsorbed and saturated, and the regenerated solution of the cobalt-manganese adsorption resin (i.e. the solution after being desorbed and regenerated) enters an oxidation reaction system unit (such as an oxidation reactor) to be recycled; the water washing liquid is directly discharged or enters into an oxidation reaction system unit for recycling; or the regenerated liquid and the water washing liquid are provided with filtering equipment (such as a filter) for filtering the crushed resin before entering the oxidation reaction system unit;

After the bromine adsorption resin is adsorbed and saturated, any one or a mixed solution of any two substances or a mixed solution of three substances in an acetic acid solution, a cobalt acetate solution and a manganese acetate solution is subjected to desorption regeneration or water washing after regeneration; or the bromine adsorption resin is desorbed and regenerated by acetate (such as sodium acetate solution or potassium acetate solution) and/or alkaline solution (such as hydroxide solution, sodium hydroxide solution and the like) of other types than manganese acetate and cobalt acetate after being adsorbed and saturated, and then is washed by water; or the bromine adsorption resin is desorbed and regenerated through a salt solution (such as a chloride salt solution, a sodium chloride salt solution and the like) or is washed after regeneration after being adsorbed and saturated; the desorption regeneration is to recover the adsorption volume of the bromine adsorption resin and then to be adsorbed again for use;

after the bromine adsorption resin is adsorbed and saturated, regenerating by any one or a mixed solution of any two substances or a mixed solution of three substances of acetic acid solution, cobalt acetate solution and manganese acetate solution: the regenerated liquid is directly discharged or enters into an oxidation reaction system unit to be recycled; or the regenerated liquid is provided with filtering equipment (such as a filter) for filtering the crushed resin before being recycled to the oxidation reaction system unit;

The bromine adsorption resin is regenerated by acetate (such as sodium acetate solution or potassium acetate solution) and/or alkaline solution of other types than manganese acetate and cobalt acetate after being saturated by adsorption: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted and recycled into an oxidation reaction system unit (such as an oxidation reactor) by a bipolar membrane method (namely, bipolar membrane method electrodialysis, hydrogen ions and hydroxyl ions are respectively formed on two sides of the membrane under the action of a direct current electric field, and the bromine element is applied to the regeneration liquid or the water washing liquid to generate an aqueous solution of hydrobromic acid by combining the hydrogen ions and the bromine ions on one side of the membrane; or bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to an oxidation reaction system unit (such as an oxidation reactor); or the regenerated liquid passes through the hydrogen type cationic resin, the effluent of the hydrogen type cationic resin is directly discharged or enters into an oxidation reaction system unit or the effluent of the hydrogen type cationic resin is filtered and then enters into the oxidation reaction system unit, the hydrogen type cationic resin is regenerated by acid solution (such as sulfuric acid solution, hydrochloric acid solution, acetic acid solution and the like) after being adsorbed and saturated, and the regenerated liquid is directly discharged;

The bromine adsorption resin is regenerated with a salt solution (for example, a chloride salt solution, and a sodium chloride salt solution) after adsorption saturation: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted and recycled into an oxidation reaction system unit by a bipolar membrane method (namely, bipolar membrane method electrodialysis is performed, hydrogen ions and hydroxyl ions are respectively formed on two sides of the membrane under the action of a direct current electric field; or the bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to the oxidation reaction system unit;

in the adsorption process of the selective adsorption resin for bromine, most of organic matters such as benzene series are not adsorbed, and then the effluent of the resin enters the next step, namely, a small amount of organic matters such as benzene series are trapped on the resin, and the organic matters are desorbed and dissociated from the resin together with bromine in the desorption regeneration process of the desorption regeneration liquid when the alkaline solution is used for desorption, so that the resin is a process of extracting and concentrating the bromine and separating the bromine from most of organic matters such as benzene series, and the used desorption regeneration liquid is recovered and treated with bromine by a bipolar membrane method or an electrolytic method. Another method of bromine removal is to directly conduct a bipolar membrane process or an electrolytic process to recover bromine, but in contrast: the volume of desorption regeneration liquid of the selective adsorption resin for bromine is far smaller than the volume of sewage treated by one operation adsorption saturation period of the resin, namely the volume of desorption regeneration liquid to be treated is small, and the equipment of a bipolar membrane method or an electrolytic method is small and the operation cost is low; most of organic matters such as benzene series in the adsorption process of the bromine selective adsorption resin are not adsorbed, and directly enter the next step along with the resin effluent, namely the content of the organic matters such as total benzene series contained in the desorption regeneration liquid is smaller than the content of the organic matters such as total benzene series in sewage treated by the resin in one operation adsorption saturation period, and the organic matters such as benzene series have influence on the equipment operation of the bipolar membrane method or the electrolytic method, so the equipment influence on the bipolar membrane method or the electrolytic method by treating the desorption regeneration liquid is small.

In the route c-II, after adsorption saturation, regenerating by acid solution (such as hydrochloric acid solution and acetic acid solution) or washing after regeneration, and directly discharging regenerated liquid or washing liquid;

the hydrogen type cationic resin in the route c-III is regenerated by an acid solution (such as a hydrochloric acid solution and an acetic acid solution) or is washed after being regenerated after being adsorbed and saturated, and the regenerated solution or the washing solution mainly contains cobalt ions, manganese ions, sodium ions and the acid solution and is directly discharged after passing through a cobalt-manganese recovery unit VIII; or the regenerated liquid and the washing liquid firstly pass through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or filtration to remove metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is directly discharged after passing through a cobalt-manganese recovery unit VIII;

in the routes c-IV, the cobalt-manganese adsorption resin is regenerated by an acid solution (such as hydrochloric acid solution and acetic acid solution) or washed after regeneration after adsorption saturation, and the regenerated solution and the washed solution are directly discharged after passing through a cobalt-manganese recovery unit IX; or the regenerated liquid and the washing liquid firstly pass through a impurity removing unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or filtration to remove metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is directly discharged after passing through a cobalt-manganese recovery unit IX; the hydrogen type cation resin is regenerated by acid solution (such as hydrochloric acid solution and acetic acid solution) or washed after regeneration after being adsorbed and saturated, and the regenerated solution or the washing solution is directly discharged;

In the route c-V, the hydrogen type cationic resin is regenerated by an acid solution (such as hydrochloric acid solution and acetic acid solution) or washed after regeneration after adsorption saturation, and the regenerated solution, the washing solution or the concentrated water of the nanofiltration unit I is directly discharged after passing through the cobalt-manganese recovery unit X; or the waste liquid is subjected to a impurity removal unit before the waste liquid passes through a cobalt-manganese recovery unit X, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added to precipitate and/or filter metal corrosion products (such as iron and chromium ions) to obtain filtrate, and the filtrate is directly discharged after the filtrate passes through the cobalt-manganese recovery unit X; the nanofiltration concentrated water of the nanofiltration unit I mainly contains cobalt ions, manganese ions and products of metal corrosion (such as iron and chromium ions); and sodium ions, benzoic acid, phthalic acid, p-methylbenzoic acid, p-carboxybenzaldehyde, acetic acid, bromide ions, separating liquid II-a or separating liquid II-b which do not pass through the nanofiltration membrane also contain methanol which is not completely removed.

Based on the above technical solution, it is preferred that, in the route c-vi,

after the bromine adsorption resin is adsorbed and saturated, any one or a mixed solution of any two substances or a mixed solution of three substances in an acetic acid solution, a cobalt acetate solution and a manganese acetate solution is subjected to desorption regeneration or water washing after regeneration; or the bromine adsorption resin is desorbed and regenerated by acetate solution (such as sodium acetate solution or potassium acetate solution) and/or alkaline solution (such as hydroxide solution, sodium hydroxide solution for example) of other types than manganese acetate and cobalt acetate after being adsorbed and saturated, and then is washed by water; or the bromine adsorption resin is desorbed and regenerated by a salt solution (such as a chloride salt solution and a sodium chloride salt solution for example) after being adsorbed and saturated or is washed after being regenerated:

After the bromine adsorption resin is adsorbed and saturated, regenerating by any one or a mixed solution of any two substances or a mixed solution of three substances of acetic acid solution, cobalt acetate solution and manganese acetate solution: the regenerated liquid is directly discharged or enters into an oxidation reaction system unit to be recycled; or the regenerated liquid is provided with a filter to filter broken resin before entering the oxidation reaction system unit;

the bromine adsorption resin is regenerated by acetate solution (such as sodium acetate solution or potassium acetate solution) and/or alkaline solution of other types than manganese acetate and cobalt acetate after adsorption saturation: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted into hydrobromic acid by a bipolar membrane method to be recycled to an oxidation reaction system unit; or the bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to the oxidation reaction system unit; or the regenerated liquid passes through the hydrogen type cationic resin, the effluent of the hydrogen type cationic resin is directly discharged or the effluent of the hydrogen type cationic resin enters into the oxidation reaction system unit to be recovered, or the effluent of the hydrogen type cationic resin enters into the oxidation reaction system unit to be recovered after being filtered; the hydrogen type cation resin is regenerated by acid solution (such as sulfuric acid solution, hydrochloric acid solution, acetic acid solution, etc.) after being adsorbed and saturated, and the regenerated solution is directly discharged;

The bromine adsorption resin is regenerated with a salt solution (for example, a chloride salt solution, and a sodium chloride salt solution) after adsorption saturation: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted and recycled into an oxidation reaction system unit by a bipolar membrane method (namely, bipolar membrane method electrodialysis is performed, hydrogen ions and hydroxyl ions are respectively formed on two sides of the membrane under the action of a direct current electric field; or the bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to the oxidation reaction system unit.

Based on the above technical scheme, preferably, the hydrogen type cationic resin; or cobalt manganese adsorption resin; or a bromine adsorption resin which is desorbed and regenerated by any one or a mixed solution of any two substances or a mixed solution of three substances in acetic acid solution, cobalt acetate solution and manganese acetate solution; or the bromine adsorption resin regenerated by the salt solution is sequentially washed, regenerated and recovered by alkali lye after being polluted by the organic matters.

Based on the technical scheme, preferably, a nanofiltration unit III and a nanofiltration unit IV are arranged in the route c-III; before being treated by the hydrogen type cationic resin, the nanofiltration fresh water enters a nanofiltration unit III in the route c-III, and the nanofiltration fresh water of the nanofiltration unit III is treated by the hydrogen type cationic resin; the nanofiltration concentrated water of the nanofiltration unit III is treated by a cobalt-manganese recovery unit VIII; or the nanofiltration concentrated water of the nanofiltration unit III is firstly subjected to a impurity removal unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or metal corrosion products (such as iron and chromium ions) are removed by filtration to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit VIII;

the regenerated liquid or the washing liquid generated by the hydrogen type cationic resin in the route c-III is directly discharged through a nanofiltration unit IV and nanofiltration fresh water of the nanofiltration unit IV; the nanofiltration concentrated water of the nanofiltration unit IV is treated by a cobalt-manganese recovery unit VIII; or the nanofiltration concentrated water of the nanofiltration unit IV is firstly subjected to impurity removal unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or metal corrosion products (such as iron and chromium ions) are removed by filtration to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit VIII;

A nanofiltration unit V is arranged in the route c-IV, and the regenerated liquid or the water washing liquid generated by the cobalt-manganese adsorption resin in the route c-IV firstly enters the nanofiltration unit V, and the nanofiltration concentrated water generated by the nanofiltration unit V is treated by a cobalt-manganese recovery unit IX; or the nanofiltration concentrated water of the nanofiltration unit V is firstly subjected to impurity removal unit, alkaline substances (such as carbonate, bicarbonate and hydroxide) are added for precipitation and/or metal corrosion products (such as iron and chromium ions) are removed by filtration to obtain filtrate, and the filtrate is treated by the cobalt-manganese recovery unit IX; the nanofiltration fresh water generated by the nanofiltration unit V is directly discharged or is used for regenerating hydrogen type cation resin or cobalt-manganese adsorption resin adsorption saturation after acid is supplemented.

Based on the above technical scheme, preferably, the cobalt-manganese recovery units I, II, III, IV, V, VI, VII, VIII, IX and X are used for recovering cobalt ions and manganese ions, and the specific treatment routes of the cobalt-manganese recovery units are 2, and any one of the specific treatment routes can be selected, namely, route 1 and route 2:

route 1 is to add alkaline substances (generally using carbonates, bicarbonates, hydroxides, pH about 7.5-14) to form cobalt and manganese ions into solid substances, precipitate and/or filter, and then use the solid substances as the effluent of a cobalt and manganese recovery unit; intermittently cleaning filter residues with acetic acid solution and/or hydrobromic acid solution to dissolve cobalt ions and manganese ions to generate a dissolving solution, and recycling the dissolving solution to the oxidation reaction system unit, wherein a filtering unit can be optionally added before the dissolving solution is recycled to the oxidation reaction system unit;

The route 2 is that the cobalt-manganese adsorption resin is used as the effluent of the cobalt-manganese recovery unit after adsorbing cobalt ions and manganese ions, the cobalt-manganese adsorption resin is regenerated by acetic acid and/or hydrobromic acid solution after being saturated or is washed after being regenerated, and the regenerated liquid is recovered to the oxidation reaction system unit; the water washing liquid is directly discharged or recycled to the oxidation reaction system unit; or the regenerated liquid and the water washing liquid enter a facility filter before being recycled to the oxidation reaction system unit to filter broken resin; the cobalt-manganese adsorption resin is polluted by organic matters, and the organic matters are sequentially dissolved by alkali liquor for cleaning, washing, regenerating and recovering;

the route 2 can be directly used as a route 1 alternative route in the prior art of the background technology to be used independently, and the rest processes are unchanged, so that the consumption of alkaline substances can be saved.

Based on the technical scheme, preferably, the filter residue in the route 1 of the cobalt-manganese recovery units I, II, III, IV, V, VI, VII, VIII, IX and X is cleaned and dissolved by an acetic acid solution, and the dissolved solution is a mixed solution containing acetic acid, cobalt acetate and manganese acetate, and can be used for desorption regeneration after adsorption saturation of bromine adsorption resin.

Based on the technical scheme, preferably, the nanofiltration units I, II, III, IV and V are provided with ultrafiltration membranes and nanofiltration membranes, and the source aqueous solution enters the nanofiltration membranes after ultrafiltration; or the nanofiltration units I, II, III, IV and V are provided with ultrafiltration membranes, reverse osmosis membranes and nanofiltration membranes, the source aqueous solution enters the reverse osmosis membranes after ultrafiltration, reverse osmosis fresh water is discharged outwards, reverse osmosis concentrated water enters the nanofiltration membranes, and nanofiltration membranes are separated to generate nanofiltration fresh water (water and solute passing through the membrane holes of the nanofiltration membranes) and nanofiltration concentrated water (water and solute without passing through the membrane holes of the nanofiltration membranes in a barrel); the nanofiltration membrane unit and the reverse osmosis membrane unit are preferably selected, wherein a first-stage one-stage nanofiltration membrane unit or a reverse osmosis membrane unit can be designed, and a multi-stage or multi-stage nanofiltration membrane unit or a multi-stage reverse osmosis membrane unit can also be designed; description: the nanofiltration membrane through which the concentrated water of the nanofiltration membrane passes is called a two-stage nanofiltration membrane; the nanofiltration membrane through which the fresh water passes is called a secondary nanofiltration membrane; the reverse osmosis membrane through which the concentrated water of the reverse osmosis membrane passes is called a second-stage reverse osmosis membrane; the reverse osmosis membrane through which fresh water of the reverse osmosis membrane passes is called a secondary reverse osmosis membrane.

Based on the above technical scheme, preferably, the unit of the recycled oxidation reaction system is: directly enters an oxidation reaction system; or sequentially passing through an ultrafiltration membrane and a reverse osmosis membrane, wherein reverse osmosis membrane concentrated water enters the oxidation reaction system and is discharged outside of fresh water of the reverse osmosis membrane, and the reverse osmosis membrane at least comprises a first-stage reverse osmosis membrane and a first-stage reverse osmosis membrane; the oxidation reaction system is the feeding of an oxidation reactor of the terephthalic acid production process;

based on the above technical scheme, preferably, the whole process is convenient for the system to run stably, buffer tanks can be additionally arranged among units, or a plurality of buffer tanks can be arranged on the whole treatment process route according to actual conditions.

The purposes of different steps, routes, units and the like designed by the invention are different and mutually independent, and each step, route, unit and the like can be independently applied, can be selected and combined in different orders according to actual demands, and can be only selected and applied to a part of processes, steps, routes, units and the like, and are all within the scope of the patent protection of the invention.

The direct discharge of the invention is discharged from the process route of the invention after the treatment of the invention, and no matter what specific treatment method is adopted after the direct discharge (such as discharging to a sewage comprehensive treatment unit and the like), the protection of the invention is not affected.

The waste is treated as waste, and the specific treatment mode of the waste after the waste does not affect the protection of the content of the invention.

The recovery of the present invention does not affect the protection of the present invention, regardless of the specific disposal mode (including proper recovery of solids to the oxidation reaction system) that is employed after recovery.

Advantageous effects

Extracting and purifying and recycling most of organic matters in the extracted liquid of the oxidation mother liquor (phthalic acid, benzoic acid and the like) to generate economic value;

recovering bromine in the oxidation mother liquor extract to return to an oxidation reaction system or extracting hydrobromic acid generated by bromine in the oxidation mother liquor extract, purifying and recycling to generate economic value;

the useful substances such as cobalt, manganese, bromine and the like are recycled to the oxidation reaction system to generate economic value;

the concentration of bromide ions and COD (benzene series such as benzoic acid and phthalic acid) of the sewage is reduced, the adverse effect on the activity of biochemical sludge is avoided, the sewage treatment difficulty and the operation consumption are reduced, and the efficiency of the comprehensive treatment of the sewage in the later stage is improved;

the crystallization of the steps b-I and b-III separates most acidic organic matters (such as benzoic acid, phthalic acid and the like) which are originally needed to be added with alkaline matters for dissolution to form solid, so that the consumption of the alkaline matters is reduced; b-II, most acidic organic matters (such as benzoic acid, phthalic acid and the like) which are needed to be added with alkaline matters originally to be dissolved react to generate esters and are separated and removed, namely, the amount of the acidic organic matters which are needed to be neutralized in the aqueous solution is reduced, so that the consumption of the alkaline matters is greatly reduced, resources are saved, the enterprise cost is reduced, and the utilization rate is increased;

The method for recovering cobalt and manganese ions by using the cobalt-manganese adsorption resin replaces the method for recovering cobalt and manganese ions by adding alkaline substances to form solid substances, so that the consumption of the alkaline substances is greatly reduced, resources are saved, the enterprise cost is reduced, and the utilization rate is increased.

Drawings

FIG. 1 is a schematic of schemes a, b-I (excluding various alternative routes within b-I)

Fig. 2 shows a schematic diagram of the flow a and b.

Fig. 3 is a schematic diagram of flow c.

Fig. 4 is a schematic diagram of a cobalt manganese recovery unit.

Fig. 5 is a schematic diagram of a nanofiltration unit.

FIG. 6 is a schematic view of recovery to an oxidation reactor unit.

Detailed Description

Description: english symbols of the following test samples:

TA: phthalic acid and its acid radical; BA: benzoic acid and its acid radical; HAC: acetic acid and its acid radical; 4-CBA: p-carboxybenzaldehyde and acid radicals thereof; PT acid: p-methylbenzoic acid and its acid radical. In the drawings in the specification of the application, a route indicated by a broken line is a more preferable technical scheme.

The cobalt manganese adsorption resin, the hydrogen type cation resin and the bromine adsorption resin used in the invention can be selected from brands for producing the resin, such as Siemens Lan Xiao, dusheng brand Tulsion in the United states, jiangsu Jin Kai resin and the like, and cobalt manganese adsorption resin (chelate resin) LSC-500 of Siemens blue brand is selected in the embodiment to selectively mainly adsorb multivalent cations such as cobalt manganese and the like from cations, hydrogen type cation resin LSD-001 and bromine adsorption resin LX-950 can adsorb bromide ions.

Example 1

Route a+b-I and related tests:

experiment 1:

the experimental process comprises the following steps:

heating the extracted liquid of the oxidation mother liquor to remove HAC and water, pulping with water, controlling the temperature after pulping=100 ℃ for filter pressing, weighing filtrate (100 ℃) obtained after sampling and filter pressing to 73.96KG, cooling to 18 ℃, separating out solids in the cooling process, and carrying out suction filtration to obtain 33.62KG of filter cake 1 and 39.58KG of filtrate 1:

sampling 3KG of filter cake 1, heating to 105 ℃ for 24 hours to dry and weigh 0.71KG;

filtrate 1 analysis composition: TA12112ppm; BA6926ppm; PT acid 107ppm;4-CBA181ppm; HAC11310ppm; sodium ions 1426ppm; cobalt ion 3507ppm; manganese ions 3301ppm; 2616ppm of bromide; iron ions 3.78ppm; heterocyclic compound 0ppm. The filtrate 1 is the separating liquid I of the b-I flow.

Experiment 2:

the experimental process comprises the following steps: taking experiment 1 filter cake 1, sampling 4.60KG, washing with 4.6L pure water, suction filtering to obtain filtrate 2, calculating 4.42KG and filter cake 2, and analyzing the filtrate: TA8835ppm; BA4423ppm; PT acid 66.7ppm;4-CBA96.3ppm; HAC4959ppm; 808ppm of sodium ions; 1563ppm of cobalt ions; manganese ions 1420ppm; 1411ppm of bromide; iron ions 2.09ppm; heterocyclic compound 0ppm.

Experiment 3:

the experimental process comprises the following steps: taking a filter cake 1 of an experiment 1, sampling 4.60KG, pickling with 4.6L of hydrogen bromide containing 3% hydrogen bromide, carrying out suction filtration to obtain a filtrate 3, namely 4.67KG and a filter cake 3, and analyzing the filtrate: TA6214ppm; BA3503ppm; PT acid 51.2ppm;4-CBA81.2ppm; HAC4873ppm; 769ppm sodium ions; cobalt ion 1782ppm; manganese ion 1738ppm; 18832ppm of bromide; iron ions 4.45ppm; heterocyclic compound 0ppm.

Experiment 4:

the experimental process comprises the following steps: taking experiment 1 filter cake 1 to sample 4.6KG, washing with 4.6L of hydrochloric acid containing 3% of hydrogen chloride, suction filtering to obtain 4.52KG of filtrate 4 and filter cake 4, and analyzing the filtrate: TA6288ppm; BA3473ppm; PT acid 48.2ppm;4-CBA72.0ppm; HAC4899ppm; sodium ions 782ppm; cobalt ion 1795ppm; 1716ppm of manganese ions; 1456ppm of bromide; iron ions 4.31ppm; 17104ppm of chloride ions; heterocyclic compound 0ppm.

Experiment 5:

the experimental process comprises the following steps: heating the experiment 2 filter cake 2 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0612g, adding 80g of excessive absolute ethyl alcohol, stirring and dissolving for 0.5 hour, carrying out suction filtration, washing insoluble matters on filter paper by using 20g of absolute ethyl alcohol, respectively heating and evaporating the filter liquor and the filter paper to remove the ethanol, heating to 105 ℃ for 24 hours (the weight is unchanged), measuring 3.7431g of solid remained on the filter paper, and analyzing the terephthalic acid concentration to be 92.31%; after evaporation of the filtrate with ethanol, 6.2511g of solid (mainly comprising BA, isophthalic acid, phthalic acid) are precipitated.

The experimental process comprises the following steps: heating the filter cake 2 of the experiment 2 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0003g, adding 80g of excessive methanol, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on the filter paper by using 20g of methanol, respectively heating and evaporating the filtrate and the filter paper to remove the methanol, heating to 105 ℃ for 24 hours (the weight is unchanged), measuring 3.5826g of solid remained on the filter paper, and analyzing the concentration of terephthalic acid to be 91.88%; after evaporation of the filtrate methanol, 6.3576g of solid precipitated.

Conclusion of this experiment: the method of dissolving with ethanol and methanol can dissolve out BA, isophthalic acid and phthalic acid, separate solid organic matters, and the insoluble matter is mainly terephthalic acid, and the economic value of terephthalic acid can be recovered by re-returning the insoluble matter to the oxidation reaction system.

Experiment 6:

the experimental process comprises the following steps:

heating the experiment 2 filter cake 2 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0175g, adding 80g of excessive diethyl ether, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of diethyl ether, respectively heating and evaporating the filtrate and the filter paper to remove diethyl ether, heating to 105 ℃ for 24 hours (unchanged weight), absorbing diethyl ether steam by using ethanol, and measuring 4.7209g of solid remained on the filter paper; after evaporation of the filtrate from diethyl ether, 5.2607g of solid was precipitated, which was analyzed to give a BA concentration of 96.07%.

Heating the experiment 2 filter cake 2 to 105 ℃ for 24 hours until the mixture is dried, grinding and sampling 10.0005g, adding 80g of excessive toluene, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of toluene, respectively heating and evaporating the filtrate and the filter paper to remove the toluene, heating to 130 ℃ for 24 hours (the weight is unchanged), and measuring 4.6303g of solid remained on the filter paper; after evaporation of the filtrate toluene, 5.3843g of solid was precipitated, which was analyzed to give a BA concentration of 97.25%.

Heating the experiment 2 filter cake 2 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0037g, adding 240g of excess paraxylene, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 60g of paraxylene, respectively heating and evaporating the filtrate and the filter paper to remove the paraxylene, heating to 150 ℃ for 24 hours (the weight is unchanged), and measuring 4.5842g of solid remained on the filter paper; after evaporation of the filtrate paraxylene, 5.4113g of solid was precipitated, which was analyzed to give a BA concentration of 92.41%.

Heating the filter cake 2 of the experiment 2 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0151g, adding 80g of excessive methyl acetate, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of methyl acetate, respectively heating and evaporating the filtrate and the filter paper to remove the methyl acetate, heating to 105 ℃ for 24 hours (the weight is unchanged), and measuring 4.3421g of solid remained on the filter paper; the filtrate, methyl acetate, evaporated to yield 5.6253g of solid, which was analyzed to have a BA concentration of 98.11%.

Conclusion of this experiment: the method of dissolving diethyl ether, toluene, p-xylene and methyl acetate in solvent can separate solid organic matter, and the dissolved matter is mainly benzoic acid and may be taken out as crude benzoic acid.

Experiment 7:

the experimental process comprises the following steps: heating the filter cake 3 of experiment 3 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0002g, adding 80g of excessive absolute ethyl alcohol, stirring and dissolving for 0.5 hour, then carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of absolute ethyl alcohol, respectively heating and evaporating the filter liquor and the filter paper to remove the ethanol, heating to 105 ℃ for 24 hours (unchanged weight), measuring 3.7332g of solid remained on the filter paper, and analyzing the terephthalic acid concentration to be 90.15%; after evaporation of the filtrate with ethanol, 6.2428g of solid precipitated.

Conclusion of this experiment: as in experiment 5.

Experiment 8:

the experimental process comprises the following steps: heating the filter cake 3 of experiment 3 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0005g, adding 80g of excessive diethyl ether, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of diethyl ether, respectively heating and evaporating the filtrate and the filter paper to remove diethyl ether, heating to 105 ℃ for 24 hours (unchanged weight), absorbing diethyl ether steam by using ethanol, and measuring 4.7331g of solid remained on the filter paper; after evaporation of the filtrate from diethyl ether, 5.2107g of solid was precipitated, which was analyzed to give a BA concentration of 94.41%.

Conclusion of this experiment: as in experiment 6.

Experiment 9:

the experimental process comprises the following steps: heating the experiment 4 filter cake 4 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0008g, adding 80g of excessive absolute ethyl alcohol, stirring and dissolving for 0.5 hour, carrying out suction filtration, washing insoluble matters on filter paper by using 20g of absolute ethyl alcohol, respectively heating and evaporating the filter liquor and the filter paper to remove the ethanol, heating to 105 ℃ for 24 hours (the weight is unchanged), measuring 3.6889g of solid remained on the filter paper, and analyzing the concentration of terephthalic acid to be 93.16%; after evaporation of the filtrate with ethanol, 6.2897g of solid precipitated.

Conclusion of this experiment: as in experiment 5.

Experiment 10:

the experimental process comprises the following steps: heating the experiment 4 filter cake 4 to 105 ℃ for 24 hours until the filter cake is dried, grinding and sampling 10.0015g, adding 80g of excessive diethyl ether, stirring and dissolving for 0.5 hour, carrying out suction filtration, flushing insoluble matters on filter paper by using 20g of diethyl ether, respectively heating and evaporating the filtrate and the filter paper to remove diethyl ether, heating to 105 ℃ for 24 hours (unchanged weight), absorbing diethyl ether steam by using ethanol, and measuring 4.6633g of solid remained on the filter paper; after evaporation of the filtrate from diethyl ether, 5.2771g of solid was precipitated, which was analyzed to give a BA concentration of 97.17%.

Conclusion of this experiment: as in experiment 6.

Experiment 11:

sampling experiment 1 filtrate 1 to 5L, adding sodium carbonate and stirring to generate a large amount of bubbles, lifting the PH to 5.7, using 180.2g of sodium carbonate solid, measuring TA12050ppm after filtration, wherein the volume is not changed obviously; BA6987ppm; PT acid 105ppm;4-CBA184ppm; HAC10455ppm; 17031ppm of sodium ions; cobalt ion 3355ppm; manganese ion 3142ppm; 2602ppm of bromide; iron ion 0.52ppm, referred to as sample A.

Dividing into 2 routes:

route 1: sample A was taken 1L

Sodium carbonate was then added and ph=9.5 was raised, 35.1g of sodium carbonate was consumed, the volume was not significantly changed, and TA12001ppm was measured after filtration; BA6944ppm; PT acid 98ppm;4-CBA189ppm; HAC10146ppm; sodium ion 33031ppm; cobalt ion 0.02ppm; manganese ion 0.01ppm; bromide 2625ppm; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

And taking 0.9L of filtrate, passing through two stages of serially connected (the effluent after the first stage treatment passes through the second stage) hydrogen type cation resin columns (each stage of resin amount is 500g, the second stage of resin adsorbs sodium ions of the effluent of the first stage again), and controlling the flow rate of the effluent below the resin columns to be about 100 ml/hour. The sodium ion concentration of the effluent is shown in the following table, in ppm:

the residual water sample of the second-stage hydrogen type cationic resin is analyzed as follows: TA12088ppm; BA6991ppm; PT acid 103ppm;4-CBA169ppm; HAC10101ppm; sodium ion 0.11ppm; cobalt ion 0.03ppm; manganese ion 0.05ppm; 2612ppm of bromide; iron ion 0ppm.

The first stage hydrogen type cationic resin was regenerated with 1.5L of 10% hydrochloric acid after being liquid-removed by compressed air, and the regenerated liquid was tested as follows: sodium 17214ppm.

Route 2: sample A taken 1L

The effluent flow rate under the resin column is controlled to be about 150 ml/h through two stages of cobalt-manganese adsorption resins (100 g of resin amount per stage), and the concentration of cobalt and manganese ions in effluent is controlled as shown in the following table and is expressed in ppm

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: TA12088ppm; BA6955ppm; PT acid 97.1ppm;4-CBA171ppm; HAC root 10421ppm; sodium ion 17049ppm; cobalt ion 0.22ppm; manganese ion 0.11ppm; 2603ppm of bromide; iron ion 0ppm.

Sampling 0.5L of the second-stage cobalt-manganese adsorption resin water sample, passing through two stages of serial hydrogen-type cation resin columns (150 g of resin in each stage), controlling the flow rate to be about 50 ml/hour, and controlling the concentration of sodium ions in effluent to be as shown in the following table, wherein the unit ppm

Effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours	After 5 hours	After 6 hours	After 7 hours
								Sodium salt	2.56	12.3	38.2	68.9	245	896	1380

The second-stage hydrogen type cation effluent water sample is analyzed as follows: TA12018ppm; BA6921ppm; PT acid 91.3ppm;4-CBA192ppm; HAC10398ppm; sodium ion 0.21ppm; cobalt ion 0.03ppm; manganese ion 0.03ppm; 2593ppm of bromide; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 300ml of 23.75% hydrobromic acid is used for regeneration, and 10245ppm of cobalt ions are measured by the regenerated liquid; manganese ion 9571ppm; sodium ions 2.12ppm.

The first-stage hydrogen cation-adsorption resin was subjected to liquid removal by compressed air and then regenerated with 500ml of 10% hydrochloric acid, and the regenerated solution was measured for 15918ppm of sodium ions.

Conclusion of this experiment: the experiment is to simulate the treatment process of B-I separating liquid I in patent requirements through a c-II process route, wherein a cobalt-manganese recovery unit can recover a final water body (second-stage hydrogen type cation resin effluent) through hydrogen type cation resin to an oxidation reaction system unit no matter a method of adding alkaline substances for precipitation filtration or a method of adsorbing cobalt-manganese resin is selected: sodium ions and metallic corrosion product iron ions have been removed; TA, BA, PT acid, 4-CBA, HAC and bromide ions can enter the oxidation reaction system again; cobalt ions and manganese ions can be recovered in a cobalt-manganese recovery unit (2 methods) and intermittently dissolved in hydrobromic acid, so that the cobalt ions and the manganese ions can be recovered in an oxidation reaction system.

Meanwhile, the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions are not obviously changed through all experimental steps in the whole process of the c-II process, and only the concentrations of sodium ions, iron ions, cobalt ions and manganese ions are changed through all experimental steps, so that the concentrations and influences of the TA, BA, PT acid, 4-CBA, HAC and bromide ions can be not considered according to the c-II process.

Experiment 12:

sample experiment 11 sample A1L, through two-stage series connection hydrogen type cation resin column (each stage resin amount 400 g), controlling flow rate about 100 ml/hr, and effluent cobalt, manganese and sodium ion concentration in ppm as shown in the following table

Second-stage hydrogen-type cation resin effluent quality: TA12371ppm; BA6897ppm; PT acid 112ppm;4-CBA181ppm; HAC10159ppm; sodium ion 0.13ppm; cobalt ion 0.05ppm; manganese ion 0.01ppm; bromide 2654ppm; iron ion 0ppm.

The first stage hydrogen cationic resin was regenerated with 1.2L of 5% hydrochloric acid and the regeneration solution was analyzed as follows: cobalt 2535ppm, manganese 2389ppm, sodium 12848ppm, there are 2 routes of treatment for the regeneration solution:

route 1: taking 300ml of the first-stage hydrogen type cation resin regenerated liquid, adding sodium carbonate to raise the pH=9.5, generating a large amount of gas by 21.4g of sodium carbonate, and carrying out water sample analysis after filtering, wherein the volume of the gas is not changed obviously: cobalt 0.04ppm; manganese 0.01ppm; sodium 43720ppm, about half of the filter cake was fully soluble with 100ml of 47.5% hydrobromic acid.

Route 2: taking 600ml of the first-stage hydrogen type cation resin regenerated liquid, lifting PH=3.5 by sodium hydroxide, passing through two stages of cobalt-manganese adsorption resins (50 g of each stage of resin), controlling the flow rate to be about 100 ml/h, and controlling the concentration of cobalt ions and manganese ions in effluent to be as follows in unit ppm:

the water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: 38839ppm of sodium ions; cobalt ion 0.23ppm; manganese ion 0.21ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 150ml of 23.75% hydrobromic acid is used for regeneration, and 8991ppm of cobalt ions are measured by the regenerated liquid; manganese ion 8461ppm; sodium ions 5.11ppm.

Conclusion of this experiment: the experiment simulates the treatment process of B-I separating liquid I in patent requirements through a c-III process route, after alkaline substances are added into the separating liquid I and iron ions are removed through filtration, sodium ions, cobalt ions and manganese ions are removed through hydrogen type cation resin, and second-stage hydrogen type cation resin effluent can be recycled to an oxidation reaction system unit: sodium ions, cobalt ions, manganese ions and iron ions which are metal corrosion products are removed; TA, BA, PT acid, 4-CBA, HAC and bromide ions can enter the oxidation reaction system again;

The acid regeneration liquid of the hydrogen type cation resin can be recovered and intermittently dissolved in hydrobromic acid no matter the method of adding alkaline substances for precipitation and filtration or the method of adsorbing cobalt-manganese resin, and can be recovered to an oxidation reaction system.

Meanwhile, the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions are not obviously changed through all experimental steps in the whole process of the c-III process, and only the concentrations of sodium ions, iron ions, cobalt ions and manganese ions are changed through all experimental steps, so that the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions can be not considered according to the c-III process.

Experiment 13:

sample experiment 1 filtrate 1 was taken 1L, and through two stages of series cobalt-manganese adsorption resin (150 g per stage of resin), the flow rate was controlled at about 120 ml/hr, and the cobalt and manganese ion concentrations in water were as shown in the following table, in ppm:

the water sample result of the second-stage cobalt-manganese adsorption resin effluent is as follows: TA12312ppm; BA6904ppm; PT acid 108ppm;4-CBA189ppm; HAC11346ppm; 1425ppm sodium ions; cobalt ion 0.08ppm; manganese ion 0.05ppm; bromide 2621ppm; iron ion 0ppm.

Taking 0.8L of effluent of the second-stage cobalt-manganese adsorption resin, passing through two stages of serial hydrogen-type cation resin columns (50 g of resin in each stage), controlling the flow rate to be about 100 ml/hour, and controlling the concentration of sodium ions in the effluent to be as shown in the following table, wherein the unit ppm

Second-stage hydrogen type cation resin effluent water sample: TA12287ppm; BA6924ppm; PT acid 104ppm;4-CBA169ppm; HAC11309ppm; sodium ion 0.12ppm; cobalt ion 0.04ppm; manganese ion 0.08ppm; 2601ppm of bromide; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by using 500ml of 3% hydrochloric acid after the liquid is removed by compressed air, and the regenerated liquid is measured to be 6113ppm of cobalt ions; 5904ppm of manganese ions; sodium ions 4.04ppm; iron ions 7.12ppm.

The first stage hydrogen cation adsorption resin was subjected to liquid removal by compressed air and then regenerated with 200ml of 3% hydrochloric acid, and the regenerated liquid was found to have 5112ppm of sodium ions.

400ml of the first-stage cobalt-manganese adsorption resin regeneration liquid is sampled, sodium carbonate is added to raise the PH=5.7, the dosage of the sodium carbonate is 21.5g, and the filtered filtrate is tested as follows: cobalt ion 6033ppm; 5854ppm of manganese ions; 23378ppm of sodium ions; iron ions 0.22ppm. There are 2 routes:

route 1: taking 100ml of the filtrate, adding sodium carbonate to raise the PH=9.5, filtering with 2.1g of sodium carbonate, and obtaining water quality: cobalt ion 0.02ppm; manganese ion 0.02ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: 300ml of the filtrate is taken and passed through two-stage series-connected cobalt-manganese adsorption resin (50 g of resin quantity of each stage), the flow rate is controlled to be about 60 ml/hour, and the concentration of cobalt and manganese ions in water is shown in the following table, and the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	4.12	59.4	123.8	231.4
Manganese (Mn)	2.25	41.4	114.4	212.9
					Sodium salt	23326	23365	23318	23078

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.06ppm; manganese ion 0.03ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by 200ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and 8401ppm of cobalt ions are measured by the regenerated liquid; 8234ppm of manganese ions; sodium ion 2.13ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the B-I separating liquid I in the patent requirement through a c-IV process route, the separating liquid I absorbs cobalt ions, manganese ions and iron ions through cobalt-manganese resin and then absorbs sodium ions through hydrogen-type cation resin, namely, the cobalt ions, the manganese ions, the iron ions and the sodium ions are removed, and the separating liquid I can be recycled to an oxidation reaction system unit: TA, BA, PT acid, 4-CBA, HAC and bromide ions can enter the oxidation reaction system again;

the acid regeneration liquid of the cobalt-manganese adsorption resin is added with alkaline substances and filtered to remove iron ions, and then the alkaline substances are filtered, and the alkaline substances are precipitated and filtered or the cobalt-manganese adsorption resin is adsorbed by the cobalt-manganese recovery unit, so that cobalt ions and manganese ions can be recovered and intermittently dissolved in hydrobromic acid and can be recovered to an oxidation reaction system.

Meanwhile, the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions are not obviously changed through all experimental steps in the whole process of the c-IV process, and only the concentrations of sodium ions, iron ions, cobalt ions and manganese ions are changed through all experimental steps, so that the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions can be not considered according to the c-IV process.

Experiment 14:

sample experiment 1 filtrate 1 was measured at 20L and subjected to nanofiltration (fresh water amount: concentrate control=2:1), nanofiltration concentrate water sample analysis: TA12514ppm; BA7201ppm; PT acid 106ppm;4-CBA187ppm; HAC12889ppm; 1415ppm of sodium ions; cobalt ion 6679ppm; manganese ion 6036ppm; 2612ppm of bromide; iron ions 2.06ppm. Nanofiltration fresh water sample analysis: TA11121ppm; BA6321ppm; PT acid 101ppm;4-CBA171ppm; HAC9514ppm; 1456ppm of sodium ions; cobalt ion 2091ppm; 1904ppm of manganese ions; 2593ppm of bromide; iron ions 0.81ppm.

The nanofiltration fresh water is sampled and 2L is passed through two stages of serial hydrogen type cation resin columns (200 g of resin amount of each stage), the flow rate is controlled to be about 250 ml/hour, and the concentration of cobalt, manganese and sodium ions in effluent is as follows, the unit ppm:

second-stage hydrogen-type cation resin effluent quality: TA11171ppm; BA6312ppm; PT acid 102ppm;4-CBA181ppm; HAC root 9429ppm; sodium ion 0.31ppm; cobalt ion 0.09ppm; manganese ion 0.01ppm; 2604ppm of bromide; iron ion 0ppm.

Regenerating the first-stage hydrogen type cationic resin by 600ml of 5% hydrochloric acid, wherein the regenerated liquid contains 4389ppm of sodium ions; cobalt ion 6218ppm; 5689ppm of manganese ions; iron ions 2.43ppm.

1L of concentrated water is taken and mixed with 500ml of regeneration liquid, sodium carbonate is added to the obtained mixed liquid to raise the PH=5.7, the dosage of the sodium carbonate is 67.5g, and the filtrate is obtained by filtration, and the analysis is as follows: 22888ppm sodium ions; cobalt ion 6204ppm; 5731ppm of manganese ions; iron ion 0.47ppm. The filtrate had 2 routes:

route 1: the filtrate was sampled at 500ml, sodium carbonate was added to raise ph=9.5, sodium carbonate consumption was 23.5g, effluent quality: 43012ppm of sodium ions; cobalt ion 0.12ppm; manganese ion 0.01ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: sampling 0.9L of the filtrate, passing through two stages of cobalt-manganese adsorption resin (150 g of resin in each stage), controlling the flow rate to be about 200 ml/hr, and controlling the concentration of cobalt and manganese ions in the effluent to be expressed in ppm as shown in the following table

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	7.65	73.8	136	257
Manganese (Mn)	12.9	83.1	125	248
					Sodium salt	22774	22798	22704	22691

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.08ppm; manganese ion 0.11ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by 450ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and the regenerated liquid is measured to be 10873ppm of cobalt ions; 10004ppm of manganese ions; sodium ions 4.13ppm.

Conclusion of this experiment: the experiment simulates the treatment process of B-I separating liquid I in patent requirements through a c-V process route, nanofiltration fresh water firstly reduces the concentration of cobalt ions, manganese ions and iron ions, and after the nanofiltration fresh water is subjected to hydrogen type cation resin to adsorb the cobalt ions, the manganese ions, the iron ions and the sodium ions, the nanofiltration fresh water can be recycled to an oxidation reaction system unit: TA, BA, PT acid, 4-CBA, HAC and bromide ions can enter the oxidation reaction system again;

after alkaline substances are added into nanofiltration concentrated water and acid regeneration liquid of hydrogen type cation resin, and iron ions are removed through filtration, the alkaline substances are added into the acid regeneration liquid, and then the acid regeneration liquid passes through a cobalt-manganese recovery unit, wherein the cobalt-manganese recovery unit can recover cobalt ions and manganese ions and intermittently dissolve in hydrobromic acid no matter a method of precipitation filtration by adding alkaline substances or a method of adsorption by cobalt-manganese resin is selected, and the cobalt ions and the manganese ions can be recovered to an oxidation reaction system.

Meanwhile, the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions are not obviously changed through the c-V process route, and only the concentrations of sodium ions, iron ions, cobalt ions and manganese ions are changed through the experimental steps, so that the concentrations of TA, BA, PT acid, 4-CBA, HAC and bromide ions can be not considered according to the c-V process route.

Experiment 15:

taking 1L of filtrate 1 of experiment 1, passing through two-stage serial bromine adsorption resin (100 ml of resin in each stage), controlling the flow rate to be about 200 ml/hour, and controlling the concentration of cobalt and manganese ions in effluent to be shown in the following table, wherein the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	56.5	132	203	543

Second-stage bromine adsorption resin effluent quality: 1429ppm sodium ions; cobalt ion 3447ppm; manganese ion 3261ppm; bromide 1.89ppm; iron ions 3.66ppm.

Adding sodium carbonate and stirring to generate a large amount of bubbles, raising the pH to 5.7, using 14.3g of sodium carbonate solid, measuring 9129ppm of sodium ions after filtration, wherein the volume is not changed obviously; 3403ppm of cobalt ions; 3222ppm of manganese ions; bromide 1.33ppm; iron ions 0.21ppm.

Then, dividing into 2 routes:

route 1: taking 100ml

Sodium carbonate is added again and the PH=9.5 is raised, 3.4g of sodium carbonate is consumed, the volume is not changed obviously, and 24002ppm of sodium ions are measured after filtration; cobalt ion 0.03ppm; manganese ion 0.02ppm; bromide 1.65ppm; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: take 0.5L

The effluent flow rate under the resin column is controlled to be 75 ml/h by two stages of cobalt-manganese adsorption resins (50 g of resin amount per stage), and the concentration of cobalt and manganese ions in effluent is controlled as shown in the following table and is expressed in ppm

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: sodium ion 9118ppm; cobalt ion 0.13ppm; manganese ion 0.08ppm; bromide 1.72ppm; iron ion 0ppm.

Regeneration of first-stage bromine adsorption resin: after the primary bromine adsorption resin is subjected to liquid removal by compressed air pressure:

regenerating 20ml of bromine adsorption resin with 75ml of 1% sodium hydroxide, and measuring 6053ppm of bromide ions by using a regeneration liquid;

50ml of regeneration liquid is added into 100ml of hydrogen type cationic resin to be soaked for 2 hours, and water outlet test is carried out: bromide 6013ppm, sodium 3.72ppm;

taking 20ml of bromine adsorption resin, and regenerating with 75ml of 5% cobalt acetate solution, wherein the regenerated solution is used for measuring 6032ppm of bromide ions;

regenerating 20ml of bromine adsorption resin with 75ml of 5% manganese acetate solution, and measuring 6030ppm of bromide ions by using the regenerated solution;

regenerating 20ml of bromine adsorption resin with 75ml of mixed solution containing 5% cobalt acetate and 5% manganese acetate, and measuring 6072ppm of bromide ions by using the regenerated solution;

taking 20ml of bromine adsorption resin, taking 15g of filter cake collected in experiments 11-15, dissolving with 75ml of 25% acetic acid, taking supernatant as regeneration liquid to regenerate 20ml of bromine adsorption resin, and measuring 6008ppm of bromide ions in the regeneration liquid.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 150ml of 23.75% hydrobromic acid is used for regeneration, and 10368ppm of cobalt ions are measured by the regenerated liquid; 9873ppm of manganese ions; sodium ions 1.89ppm.

Conclusion of this experiment: the experiment is to simulate the treatment process of B-I separating liquid I in patent requirement through c-VI-B technological route, wherein bromine adsorbing resin can adsorb bromine and can be regenerated with sodium hydroxide solution; can be desorbed and regenerated by cobalt acetate and/or manganese acetate mixed solution; can be desorbed and regenerated by using a mixed solution of acetic acid, cobalt acetate and manganese acetate; then cobalt and manganese can be recovered no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt and manganese resin is selected;

meanwhile, after passing through the bromine adsorption resin, the concentration of bromide ions is reduced, and cobalt-manganese-iron is not changed obviously; from a large number of previous experiments, bromine ions are unchanged in the process of adding sodium carbonate to solid cobalt and manganese ions and in the process of adsorbing cobalt and manganese by using cobalt-manganese adsorption resin, so that the bromine adsorption resin has no obvious influence on cobalt ions, manganese ions and iron ions; the 2 methods of cobalt manganese removal have no significant effect on bromide ions, so it can be further deduced that it is possible to reverse the order of the bromine adsorption resin and the cobalt manganese removal process (including routes 1& 2) (i.e., c-vi-a).

The final water discharge in the process is realized without considering the concentration of TA, BA, PT acid, 4-CBA, HAC and the like.

Experiment 16: the nanofiltration fresh water 1L of the sampling experiment 14 is subjected to two-stage serial bromine adsorption resin (100 g of resin amount of each stage), the flow rate is controlled to be about 200 ml/hour, and the concentration of cobalt and manganese ions in effluent is shown in the following table, and the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	38.6	117	232	511

Second-stage bromine adsorption resin effluent quality: sodium ions 1448ppm; 2006ppm of cobalt ions; 1876ppm of manganese ions; 2.05ppm of bromide; iron ions 0.77ppm.

The first stage bromine adsorption resin was subjected to liquid removal by compressed air and then regenerated with 300ml of 4% sodium hydroxide, and the regenerated liquid was found to have a bromide ion of 7759ppm.

Conclusion of this experiment: the experiment is to simulate the treatment process of nanofiltration fresh water passing through a c-VI-c process route in the patent requirement, wherein the nanofiltration fresh water can adsorb bromine through a bromine adsorption resin and can be desorbed by sodium hydroxide solution; the mixed solution of the effluent treated by the bromine adsorption resin and the nanofiltration concentrated water can be deduced from the similar experiment before that sodium carbonate is added to remove iron ions of corrosion products, and then cobalt and manganese ions are solidified by adding sodium carbonate or removed by a method of cobalt-manganese adsorption resin and cobalt-manganese is recovered (see the treatment experiment of the mixed solution of the nanofiltration concentrated water and the hydrogen type cation resin regeneration liquid in experiment 14).

Experiment 17:

experiment 4 filtrate 4 was sampled 4L, sodium carbonate was added to raise ph=5.7, sodium carbonate consumption was 223.2g, filtered, and filtrate was measured: TA6212ppm; BA3488ppm; PT acid 46.1ppm;4-CBA76.3ppm; HAC4831ppm; 24674ppm of sodium ions; cobalt ion 1732ppm; manganese ions 1685ppm; 1426ppm bromide; iron ion 0.32ppm; chlorine ion 17306ppm. The filtrate has two treatment routes:

route 1: 1L of sodium carbonate is sampled, PH=9.5 is raised, the consumption of sodium carbonate is 38.4g, and the water quality of effluent is: 41498ppm of sodium ions; cobalt ion 0.02ppm; manganese ion 0.01ppm; iron ion 0ppm; chloride ion 16894ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: sampling 1L of the filtrate, passing through two-stage series-connected cobalt-manganese adsorption resin (100 g of resin in each stage), controlling the flow rate to be about 200 ml/hour, and controlling the concentration of cobalt and manganese ions in the effluent to be expressed in ppm as shown in the following table

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	1.04	14.3	39.1	51.4
Manganese (Mn)	7.12	5.51	24.5	47.2
					Sodium salt	24611	24698	24611	24688

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.51ppm; manganese ion 0.12ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, and then is regenerated by 300ml of 23.75% hydrobromic acid, wherein 5231ppm of cobalt ions are measured by the regenerated liquid; manganese ions 5019ppm; sodium ion 2.32ppm.

Conclusion of this experiment: the experiment is to simulate the hydrochloric acid washing liquid of the solid I of B-I in patent requirements, and a cobalt-manganese recovery unit (2 methods) can recover cobalt and manganese no matter whether the cobalt-manganese recovery unit adopts a method of adding alkaline substances for precipitation filtration or a method of adsorbing cobalt-manganese resin: cobalt ions and manganese ions can be recovered and intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recovery unit (2 methods), and can be recovered to an oxidation reaction system.

Example 1 summaries:

1. according to the planned b-I process route, the solid obtained by cooling, separating out and separating is dissolved in methanol or ethanol or diethyl ether or toluene, paraxylene and methyl acetate, so that solid organic matters can be separated to obtain purer organic matters, and the economic value of the purer organic matters can be recovered;

2. the separation liquid I of B-I (the experimental filtrate 1) can achieve the aim of recycling the treated water solution to the oxidation reaction system through c-II, III, IV and V, and the economic value of the water solution is recycled (c-I is directly recycled, c-II, III, IV and V are recycled to the oxidation reaction system after being treated, and c-VI is finally discharged after being treated);

3. c-II, III, IV, V and VI, the cobalt and manganese recovery units can recover cobalt and manganese no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt and manganese resin is selected: cobalt ions and manganese ions can be recycled and can be intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recycling unit (2 methods), and can be recycled to an oxidation reaction system;

4. The concentration of the separating liquid I of the B-I is not obviously changed through all experimental steps of c-II, III, IV, V, TA, BA, PT acid, 4-CBA, HAC and bromide ion, and only the concentration of sodium ion, iron ion, cobalt ion and manganese ion is changed through all experimental steps, so that the concentration of TA, BA, PT acid, 4-CBA, HAC and bromide ion can not be considered, the concentration of TA, BA, PT acid, 4-CBA, HAC and bromide ion can not be influenced, and the subsequent test does not consider and analyze TA, BA, PT acid, 4-CBA, HAC and bromide ion; the separation liquid I of B-I can separate bromine through c-VI, and the concentration of TA, BA, PT acid, 4-CBA, HAC and sodium ions is not needed to be considered because bromine is discharged after final water treatment.

5. The composition of the water washing liquid and hydrobromic acid washing liquid of the filter cake 1 is the same as that of the separation liquid I, but the concentration is different, so that the same experimental purpose can be deduced through c-II, III, IV, V and VI.

6. The hydrochloric acid washing liquid of the filter cake 1 can be used for recovering cobalt and manganese through a cobalt and manganese recovery unit, whether a method of adding alkaline substances for precipitation filtration or a method of adsorbing cobalt and manganese resin is selected: cobalt ions and manganese ions can be recycled and can be intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recycling unit (2 methods), and can be recycled to an oxidation reaction system.

Example 2

Route a+b-II and related tests:

experiment 1:

the experimental process comprises the following steps: the following samples were taken: heating the extracted liquid of the oxidation mother liquor to remove the mixture of HAC and water, carrying out esterification reaction on various organic carboxylic acids in the mixture and methanol, wherein cobalt and manganese in the mixture can be used as catalysts, and the methanol is excessive in the adding amount.

Adding 3.51KG mixture and 60KG methanol into a small reactor, designing a water absorbing device at the top of the reactor (filling calcium sulfate 3KG into filter cloth, placing the filter cloth in a glass tube water absorbing device, arranging a reflux cooler above the glass tube for cooling water, heating to 70 ℃ for 4 hours at the initial stage of the reaction process, controlling the temperature to 110-120 ℃ for 48 hours, continuously maintaining heating after the reaction is finished, and not recycling the methanol to the reactor after condensation, wherein substances in the reactor are the generated mixed ester mixture, and the mixture is named as a mixture A.

Experiment 2:

3KG of the mixture A of the experiment 1 is sampled, 20L of pure water is used for washing and suction filtration to obtain solid 1 and washing liquid 1, the washing liquid 1 is static for 12 hours and layered by a layering funnel to obtain 18.25L of an aqueous solution A, and the inorganic matter ion composition of the aqueous solution is analyzed as follows: 983ppm of sodium ions; cobalt ion 1731ppm; 1281ppm of manganese ions; 12.04ppm of iron ions and 1845ppm of bromide ions; heterocyclic compound 0ppm.

Experiment 3:

sampling 0.15KG of the experiment 1 mixture A, washing with 1L hydrobromic acid containing 3% of hydrogen bromide, carrying out suction filtration to obtain a solid 2 and a washing liquid 2, standing the washing liquid 2 for 12 hours by using a layering funnel for layering to obtain an aqueous solution, and analyzing the inorganic matter ion composition of the aqueous solution to be: sodium ions 955ppm; cobalt ion 1888ppm; 1389ppm of manganese ions; 14.77ppm of iron ions; heterocyclic compound 0ppm.

Experiment 4:

the mixture A of the experiment 1 is sampled to 0.15KG, washed with 1L hydrochloric acid containing 3% of hydrogen chloride and filtered by suction to obtain solid 3 and washing liquid 3, and the washing liquid 3 is kept static for 12 hours for layering by a layering funnel to obtain an aqueous solution B. The inorganic ion composition of the analysis aqueous solution is as follows: sodium ion 968ppm; cobalt ion 1895ppm; 1363ppm of manganese ions; 1652ppm of bromide; 14.34ppm of iron ions and 29893ppm of chloride ions; heterocyclic compound 0ppm.

Experiment 5:

sampling experiment 2 water solution A, counting 5L, adding sodium carbonate, stirring to generate a large amount of bubbles, raising the pH to 5.7, using 36.1g of sodium carbonate solid, measuring 4116ppm of sodium ions after filtration, wherein the volume is not changed obviously; cobalt ion 1698ppm; manganese ions 1235ppm; iron ion 0.67ppm, referred to as sample A.

Dividing into 2 routes:

route 1: sample A was taken 1L

Sodium carbonate was added again and ph=9.5 was raised, 7.0g of sodium carbonate was consumed, the volume was not significantly changed, and sodium ion 7159ppm was measured after filtration; cobalt ion 0.03ppm; manganese ion 0.01ppm; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

And 0.9L of filtrate is taken to pass through a two-stage serial (the effluent after the first-stage treatment passes through a second-stage) hydrogen type cationic resin column (the resin content of each stage is 150g, the second-stage resin adsorbs sodium ions of the effluent of the first stage again), and the effluent flow rate below the resin column is controlled to be about 100 ml/hour. The sodium ion concentration of the effluent is shown in the following table, in ppm:

the residual water sample of the second-stage hydrogen type cationic resin is analyzed as follows: sodium ion 0.03ppm; cobalt ion 0.01ppm; manganese ion 0.04ppm; iron ion 0ppm.

The first stage hydrogen type cation resin is regenerated by 450ml of 10% hydrochloric acid after being pressurized by compressed air to remove liquid, and the regenerated liquid is tested as follows: sodium 12889ppm.

Route 2: sample A taken 1L

The effluent flow rate under the resin column is controlled to be about 150 ml/h through two stages of cobalt-manganese adsorption resins (50 g of resin amount per stage), and the concentration of cobalt and manganese ions in effluent is controlled as shown in the following table and is expressed in ppm

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: 4107ppm of sodium ions; cobalt ion 0.11ppm; manganese ion 0.06ppm; iron ion 0ppm.

Sampling 0.5L of the second-stage cobalt-manganese adsorption resin water sample, passing through two stages of serial hydrogen-type cation resin columns (50 g of resin in each stage), controlling the flow rate to be about 50 ml/hour, and controlling the concentration of sodium ions in effluent to be as shown in the following table, wherein the unit ppm

Effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours	After 5 hours	After 6 hours	After 7 hours
								Sodium salt	1.41	25.6	22.4	54.2	68.9	227	325

The water sample analysis of the second-stage hydrogen type cationic resin effluent is as follows: sodium ion 0.08ppm; cobalt ion 0.04ppm; manganese ion 0.03ppm; iron ion 0ppm.

The first stage cobalt-manganese adsorption resin is regenerated by using 150ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and the regenerated liquid is measured to be 10782ppm of cobalt ions; 7892ppm of manganese ions; sodium ions 1.78ppm.

The first-stage hydrogen cation-adsorption resin was subjected to liquid removal by compressed air and then regenerated with 150ml of 10% hydrochloric acid, and the regenerated solution was found to have sodium ions of 12189ppm.

Conclusion of this experiment: the experiment is to simulate the treatment process of B-II separating liquid II in patent requirements through a c-II process route, wherein a cobalt-manganese recovery unit can recover a final water body (second-stage hydrogen type cation resin effluent) through hydrogen type cation resin to an oxidation reaction system unit no matter a method of adding alkaline substances for precipitation filtration or a method of adsorbing cobalt-manganese resin is selected: sodium ions and metallic corrosion product iron ions have been removed; cobalt ions and manganese ions can be recovered in a cobalt-manganese recovery unit (2 methods) and intermittently dissolved in hydrobromic acid, so that the cobalt ions and the manganese ions can be recovered in an oxidation reaction system.

Experiment 6:

sample experiment 5 sample A1L was subjected to two-stage series connection of hydrogen type cation resin column (150 g per stage resin), the flow rate was controlled at about 120 ml/hr, and the concentration of cobalt, manganese and sodium ions in water was measured in ppm as shown in the following table

Second-stage hydrogen type cation effluent quality: sodium ion 0.32ppm; cobalt ion 0.01ppm; manganese ion 0.07ppm; iron ion 0ppm.

The first-stage hydrogen cation resin was regenerated with 1L of 3% hydrochloric acid, and the regenerated solution was analyzed as follows: cobalt 1601ppm, manganese 1147ppm, sodium 3876ppm, 2 treatment routes for the regeneration liquor:

route 1: taking 300ml of the first-stage hydrogen type cation resin regenerated liquid, adding sodium carbonate to raise the pH=9.5, generating a large amount of gas by using 19.8g of sodium carbonate, and carrying out water sample analysis after filtering, wherein the volume of the gas is not changed obviously: cobalt 0.12ppm; manganese 0.04ppm; sodium 33043ppm, about half of the filter cake was fully soluble with 100ml of 47.5% hydrobromic acid.

first stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours	After 5 hours
						Cobalt (Co)	1.04	14.5	18.5	24.8	46.4
Manganese (Mn)	0.03	16.4	13.2	27.5	35.3
						Sodium salt	30011	29783	29668	29845	29872

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: 29804ppm of sodium ions; cobalt ion 0.17ppm; manganese ion 0.06ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, and then is regenerated by 150ml of 23.75% hydrobromic acid, wherein the regenerated liquid is used for measuring 5698ppm of cobalt ions; 4012ppm of manganese ions; sodium ions 2.12ppm.

Conclusion of this experiment: the experiment simulates the treatment process of B-II separating liquid II in patent requirements through a c-III process route, washing liquid II is subjected to alkaline substance addition and iron ion removal by filtration, sodium ions, cobalt ions and manganese ions are removed through hydrogen type cation resin, and second-stage hydrogen type cation resin effluent can be recycled to an oxidation reaction system unit: sodium ions, cobalt ions, manganese ions and iron ions which are metal corrosion products are removed; can reenter the oxidation reaction system;

Experiment 7:

sample experiment 2 aqueous solution a 1L was subjected to two stages of series cobalt-manganese adsorption resins (50 g per stage of resin) and the flow rate was controlled to about 120 ml/hr, and the cobalt and manganese ion concentrations in water were as shown in the following table, unit ppm:

the water sample result of the second-stage cobalt-manganese adsorption resin effluent is as follows: 978ppm of sodium ions; cobalt ion 0.06ppm; manganese ion 0.04ppm; iron ion 0ppm.

Second-stage hydrogen type cation resin effluent water sample: sodium ion 0ppm; cobalt ion 0.07ppm; manganese ion 0.04ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by using 300ml of 3% hydrochloric acid after the liquid is removed by compressed air, and the regenerated liquid is measured to be 5207ppm of cobalt ions; manganese ions 3843ppm; sodium ion 1.72ppm; iron ions 35.41ppm.

The first-stage hydrogen cation-adsorption resin was subjected to liquid removal by compressed air and then regenerated with 150ml of 3% hydrochloric acid, and the regenerated liquid was found to have sodium ion of 4767ppm.

The regenerated liquid of the first-stage cobalt-manganese adsorption resin is sampled to 200ml, sodium carbonate is added to raise the PH=5.7, the dosage of the sodium carbonate is 10.1g, and the test result is that: cobalt ion 5157ppm; manganese ions 3801ppm; sodium ions 21907ppm; iron ions 0.32ppm. The filtrate after filtration had 2 routes:

Route 1: 50ml of the filtrate was taken and added with sodium carbonate to raise the pH to 9.5, the sodium carbonate consumption was 0.9g and filtered, and the effluent water quality was: cobalt ion 0.03ppm; manganese ion 0.01ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: 150ml of the filtrate is taken and passed through two-stage series-connected cobalt-manganese adsorption resin (50 g of resin quantity of each stage), the flow rate is controlled to be about 30 ml/hr, and the concentration of cobalt and manganese ions in water is shown in the following table, and the unit ppm

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Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.03ppm; manganese ion 0.05ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 150ml of 23.75% hydrobromic acid is used for regeneration, and 4909ppm of cobalt ions are measured by the regenerated liquid; manganese ion 3657ppm; sodium ions 1.57ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the B-II separating liquid II in the patent requirement through a c-IV process route, wherein the washing liquid II is subjected to cobalt-manganese resin to adsorb cobalt ions, manganese ions and iron ions, and then is subjected to hydrogen-type cation resin to adsorb sodium ions, so that the cobalt ions, the manganese ions, the iron ions and the sodium ions are removed, and the washing liquid II can be recycled to an oxidation reaction system unit;

Experiment 8:

the aqueous solution a of sample experiment 2 was sampled to 10L and subjected to nanofiltration (fresh water amount: concentrate control=2:1), nanofiltration concentrate sample analysis: sodium ions 1015ppm; cobalt ion 2967ppm; manganese ions 2004ppm; iron ions 17.79ppm. Nanofiltration fresh water sample analysis: 941ppm of sodium ions; cobalt ion 1104ppm; manganese ions 886ppm; iron ions 8.81ppm.

second-stage hydrogen-type cation resin effluent quality: sodium ion 0.13ppm; cobalt ion 0.01ppm; manganese ion 0.06ppm; iron ion 0ppm.

Regenerating the first-stage hydrogen type cationic resin by 600ml of 5% hydrochloric acid, wherein the regenerated liquid contains 2859ppm of sodium ions; cobalt ion 3382ppm; manganese ion 2679ppm; iron ions 26.7ppm.

1L of concentrated water is taken and mixed with 500ml of regeneration liquid, sodium carbonate is added to the obtained mixed liquid to raise the PH=5.7, the dosage of the sodium carbonate is 58.4g, and the filtrate is obtained by filtration, and the analysis is as follows: sodium ions 18177ppm; cobalt ion 3005ppm; manganese ions 2189ppm; iron ion 0.31ppm. The filtrate had 2 routes:

route 1: the filtrate was sampled at 500ml, sodium carbonate was added to raise ph=9.5, sodium carbonate consumption was 18.2g, effluent quality: cobalt ion 0.06ppm; manganese ion 0.04ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: the filtrate was sampled at 0.9L, and passed through a two-stage series-connected cobalt-manganese adsorption resin (100 g per resin stage) at a controlled flow rate of about 200 ml/hr, and the cobalt and manganese ion concentrations in the effluent were as shown in the following table, in ppm:

first stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	0.17	28.9	87.4	113
Manganese (Mn)	3.45	32.3	65.4	98.7
					Sodium salt	18251	18087	18156	18199

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.04ppm; manganese ion 0.03ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, and then is regenerated by 300ml of 23.75% hydrobromic acid, and cobalt ions 8347ppm are measured by the regenerated liquid; manganese ion 6017ppm; sodium ion 0.78ppm.

Conclusion of this experiment: the experiment simulates the treatment process of B-II separating liquid II in the patent requirement through a c-V process route, nanofiltration fresh water firstly reduces the concentration of cobalt ions, manganese ions and iron ions, and the nanofiltration fresh water can be recycled to an oxidation reaction system unit after the nanofiltration fresh water is subjected to hydrogen type cation resin to adsorb the cobalt ions, the manganese ions, the iron ions and the sodium ions;

Experiment 9:

taking 1L of experiment 2 aqueous solution A, passing through two-stage serial bromine adsorption resin (100 g of resin in each stage), controlling the flow rate to be about 200 ml/hour, and controlling the concentration of cobalt and manganese ions in effluent to be shown in the following table, wherein the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	24.2	89.3	146	314

Second-stage bromine adsorption resin effluent quality: 997ppm of sodium ions; 1701ppm of cobalt ions; manganese ions 1226ppm; iron ion 11.58ppm and bromine ion 1.91ppm.

Adding sodium carbonate and stirring to generate a large amount of bubbles, raising the pH to 5.7, using 9.3g of sodium carbonate solid, measuring 6022ppm of sodium ions after filtration, wherein the volume is not changed obviously; cobalt ion 1658ppm; manganese ions 1189ppm; bromide 1.68ppm; iron ion 0.29ppm.

Then, dividing into 2 routes:

route 1: taking 100ml

Sodium carbonate was then added and ph=9.5 was raised, 2.6g of sodium carbonate was consumed, the volume was not significantly changed, and 17246ppm of sodium ions were measured after filtration; cobalt ion 0.01ppm; manganese ion 0.06ppm; 2.33ppm of bromide; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: take 0.5L

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: sodium ion 6037ppm; cobalt ion 0.17ppm; manganese ion 0.15ppm; 2.12ppm of bromide; iron ion 0ppm.

regenerating 20ml of bromine adsorption resin with 75ml of 1% sodium hydroxide, and measuring 4031ppm of bromide ions in the regenerated solution;

50ml of regeneration liquid is added into 100ml of hydrogen type cationic resin to be soaked for 2 hours, and water outlet test is carried out: 3937ppm of bromide ions and 4.53ppm of sodium ions;

taking 20ml of bromine adsorption resin, and regenerating with 75ml of 5% cobalt acetate solution, wherein the regenerated solution is measured to obtain 4211ppm of bromide ions;

regenerating 20ml of bromine adsorption resin with 75ml of 5% manganese acetate solution, and measuring 4156ppm of bromide ions in the regenerated solution;

regeneration of 20ml of bromine adsorption resin with 75ml of mixed solution containing 5% cobalt acetate and 5% manganese acetate, and detection of bromide ion 4148ppm by the regenerated solution

Taking 20ml of bromine adsorption resin, dissolving 15g of filter cake collected in experiments 5-9 with 75ml of 25% acetic acid, taking supernatant as regeneration liquid to regenerate 20ml of bromine adsorption resin, and measuring 3928ppm of bromide ions in the regeneration liquid;

the first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 150ml of 23.75% hydrobromic acid is used for regeneration, and 5125ppm of cobalt ions are measured by the regenerated liquid; manganese ion 3363ppm; sodium ion 1.03ppm.

Conclusion of this experiment: the experiment is to simulate the treatment process of the separation liquid II of B-II in the patent requirement through a c-VI-B process route, wherein bromine can be adsorbed by bromine adsorption resin, and can be desorbed and regenerated by sodium hydroxide solution, and can be desorbed and regenerated by cobalt acetate and/or manganese acetate solution; can be desorbed and regenerated by using a mixed solution of acetic acid, cobalt acetate and manganese acetate; the cobalt-manganese recovery unit can recover cobalt ions and manganese ions no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt-manganese resin is selected;

meanwhile, after passing through the bromine adsorption resin, the concentration of bromide ions is reduced, and cobalt-manganese-iron is not changed obviously; from a large number of previous experiments, bromine ions are unchanged in the process of adding sodium carbonate to solid cobalt and manganese ions and in the process of adsorbing cobalt and manganese by using cobalt-manganese adsorption resin, so that the bromine adsorption resin has no obvious influence on cobalt ions, manganese ions and iron ions; the 2 methods of cobalt manganese removal have no significant effect on bromide ions, so it can be further deduced that it is possible to reverse the order of the bromine adsorption resin and the cobalt manganese removal process (routes 1& 2) (i.e., c-vi-a).

Experiment 10:

sampling 1L of nanofiltration fresh water of experiment 8, measuring 1867ppm of bromide ions, passing through two-stage serial bromine adsorption resin (100 g of resin in each stage), controlling the flow rate to be about 200 ml/hour, and controlling the concentration of cobalt and manganese ions in effluent to be shown in the following table, wherein the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	12.4	46.8	101	269

Second-stage bromine adsorption resin effluent quality: 976ppm of sodium ions; cobalt ions 1085ppm; manganese ion 835ppm; bromide 0.86ppm; iron ions 7.42ppm.

The first stage bromine adsorption resin was subjected to liquid removal by compressed air and then regenerated with 300ml of 4% sodium hydroxide, and the regenerated liquid was measured as 5644ppm of bromide ions.

Conclusion of this experiment: the experiment is to simulate the treatment process of nanofiltration fresh water passing through a c-VI-c process route in the patent requirement, wherein the nanofiltration fresh water can adsorb bromine through a bromine adsorption resin and can be desorbed by sodium hydroxide solution; the mixed solution of the effluent treated by the bromine adsorption resin and the nanofiltration concentrated water can be deduced from the similar experiment before that sodium carbonate is added to remove iron ions of corrosion products, and then cobalt and manganese ions are solidified by adding sodium carbonate or removed by a method of cobalt-manganese adsorption resin and cobalt-manganese is recovered (see the treatment experiment of the mixed solution of the nanofiltration concentrated water and the hydrogen type cation resin regeneration liquid in experiment 8).

Experiment 11:

the aqueous solution B of experiment 4 was sampled at 0.9L, sodium carbonate was added to raise ph=5.7, the sodium carbonate consumption was 32.6g, and the filtrate was measured by filtration: 16720ppm of sodium ions; cobalt ions 1813ppm; manganese ions 1298ppm; iron ions 0.21ppm. The filtrate has two treatment routes:

route 1: sampling 0.3L, adding sodium carbonate, lifting PH=9.5, consuming 7.6g of sodium carbonate, and obtaining water quality: 27398ppm of sodium ions; cobalt ion 0.11ppm; manganese ion 0.04ppm; about half of the filter cake taken at 0ppm of iron ion and 29811ppm of chloride ion was fully dissolved at 100ml of 47.5% hydrobromic acid.

Route 2: sampling 0.5L of the filtrate, passing through two stages of cobalt-manganese adsorption resin (50 g of resin in each stage), controlling the flow rate to be about 100 ml/hr, and controlling the concentration of cobalt and manganese ions in the effluent to be expressed in ppm as shown in the following table

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	0.23	2.93	4.87	11.3
Manganese (Mn)	0.16	1.47	6.25	9.87
					Sodium salt	16548	16735	16771	16739

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.02ppm; manganese ion 0.23ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, and then is regenerated by 150ml of 23.75% hydrobromic acid, wherein 5468ppm of cobalt ions are measured by the regenerated liquid; manganese ions 3894ppm; sodium ion 1.25ppm.

Conclusion of this experiment: the experiment simulates hydrochloric acid washing liquid of a mixture A of B-II in patent requirements, and a cobalt-manganese recovery unit (2 methods), wherein the cobalt-manganese recovery unit can recover cobalt and manganese no matter whether an alkaline substance adding precipitation filtration method or a cobalt-manganese resin adsorption method is selected: cobalt ions and manganese ions can be recovered and intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recovery unit (2 methods), and can be recovered to an oxidation reaction system.

Example 2 summaries:

1. the separation liquid II of B-II (the water solution A of the experiment 2) can achieve the aim of recycling the treated water solution to the oxidation reaction system through c-II, III, IV and V, and the economic value of the water solution is recycled (c-I is directly recycled, and c-II, III, IV and V are recycled to the oxidation reaction system after being treated); after c-VI, bromine can be separated through testing, and the bromine is discharged after final water treatment;

2. c-II, III, IV, V and VI, the cobalt and manganese recovery units can recover cobalt and manganese no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt and manganese resin is selected: cobalt ions and manganese ions can be recycled and can be intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recycling unit (2 methods), and can be recycled to an oxidation reaction system;

the water washing liquid and hydrobromic acid washing liquid of the mixture A have the same material composition and only have different concentrations, so that the hydrobromic acid washing liquid can be inferred to achieve the same experimental purpose through c-II, III, IV, V and VI.

3. The hydrochloric acid washing liquid of the mixture A can be used for recovering cobalt and manganese through a cobalt and manganese recovery unit, and the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt and manganese resin can be selected: cobalt ions and manganese ions can be recycled and can be intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recycling unit (2 methods), and can be recycled to an oxidation reaction system.

Example 3

Route a+b-III and related tests:

experiment 1:

the experimental process comprises the following steps: the following samples were taken: the mixture of HAC and water is removed by heating the extracted liquid of the oxidation mother liquor, and 16.81KG is weighed and ground for later use, namely solid A.

Sampling the solid A for 10.00KG, adding 80KG ethanol, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on a filter cloth by 20KG ethanol to obtain a filter cake 16.56KG and a filtrate, keeping the temperature at 105 ℃ for 24 hours (unchanged weight), evaporating the filtrate to remove the ethanol, and obtaining a crystal 1, and weighing 6.82KG; the filter cake 1 obtained after heating the filter cake was weighed 3.62KG.

Sampling 10.0007g of solid A in experiment 1, adding 80g of methanol, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on a filter cloth by 20g of methanol to obtain a filter cake and filtrate, keeping the temperature at 105 ℃ for 24 hours (the weight is unchanged), evaporating the filtrate to remove the methanol, and weighing 6.7931g; the above cake was dried and weighed 3.2778g to analyze 91.32% terephthalic acid. Experiment 2:

sampling 80.0012g of the solid A in the experiment 1, adding 640g of diethyl ether, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on the filter cloth by 160g of diethyl ether to obtain 164.7336g of filter cake and filtrate, keeping the temperature at 105 ℃ for 24 hours (constant weight) and adsorbing diethyl ether by ethanol, evaporating the filtrate to remove diethyl ether to obtain crystals 2, and weighing 42.7982g; the above filter cake was heated to give filter cake 2 weighing 36.9932g.

Sampling 20.0007g of experiment 1 solid A, adding 160g of toluene, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on a filter cloth by 40g of toluene to obtain a filter cake and filtrate, keeping the temperature at 130 ℃ for 24 hours (the weight is unchanged), evaporating the filtrate to remove the toluene, weighing 10.5833g, and testing the BA content to be 95.07%; the above cake was dried and weighed 9.3889g.

Sampling 20.0082g of solid A in experiment 1, adding 480g of paraxylene, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on a filter cloth by 120g of paraxylene to obtain a filter cake and a filtrate, keeping the temperature at 150 ℃ for 24 hours (unchanged by weight), evaporating the filtrate to remove the paraxylene, weighing 10.1875g, and testing the BA content of 92.13%; the above cake was dried and weighed 9.8112g.

Sampling 20.0046g of experiment 1 solid A, adding 160g of methyl acetate, stirring, carrying out suction filtration by a suction filter, washing and suction filtration on the solid on the filter cloth by 40g of methyl acetate to obtain a filter cake and filtrate, keeping the temperature at 105 ℃ for 24 hours (unchanged weight), evaporating the filtrate to remove the methyl acetate, weighing 10.8877g, and testing the BA content to 96.31%; the above cake was dried and weighed 9.1114g.

Experiment 3:

sampling the crystallization 1 of experiment 1 to 6.00KG, adding 34L of pure water, stirring and suction filtering, and washing and suction filtering the solid on the filter cloth by 8L of pure water to obtain the solid again:

25.16KG of filter cake, heating the filter cake to 105 ℃ for 24 hours to dry, and weighing 5.98KG;

filtrate 22.01KG, analysis result: sodium ion 1407ppm; 2480ppm of cobalt ions; 1887ppm of manganese ions; 17.1ppm of iron ions; bromide 2588ppm; 0ppm of heterocyclic compound is called filtrate A. The filtrate A is the washing liquid III in the flow B-III.

Sample experiment 1 cake 1 20.0000g, add 110mL pure water and stir and suction filter, the solid on the filter cloth is washed with 30mL pure water and suction filtered again to obtain:

88.4869g of filter cake, which was heated to 105℃for 24 hours to dryness and weighed 20.3514g, analyzed for concentration: 91.54% of terephthalic acid;

filtrate analysis results: 433ppm of sodium ions; 779ppm of cobalt ions; manganese ions 571ppm; iron ions 5.12ppm; the method comprises the steps of carrying out a first treatment on the surface of the Heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using ethanol as solvent to dissolve can separate solid A solid organic matter, the insoluble matter is mainly terephthalic acid, and the economic value of terephthalic acid can be recovered after washing with pure water.

Experiment 4:

sample 20.0013g of experiment 1, add 110mL hydrobromic acid containing 3% hydrogen bromide, stir and suction filter, wash the solids on the filter cloth with 30mL hydrobromic acid containing 3% hydrogen bromide, suction filter again to get filter cake and filtrate, filtrate analysis: sodium ions 1344ppm; cobalt ion 2532ppm; 1898ppm of manganese ions; 18.3ppm of iron ions; heterocyclic compound 0ppm.

Sampling 20.0045g of experiment 1 filter cake 1, adding 110mL of hydrobromic acid containing 3% of hydrogen bromide, stirring and suction filtering, flushing and suction filtering the solid on the filter cloth by using 30mL of hydrobromic acid containing 3% of hydrogen bromide, obtaining a filter cake and filtrate again, heating the filter cake to 105 ℃ for 24 hours, and analyzing 90.04% of terephthalic acid after drying; filtrate analysis: 478ppm of sodium ions; 904ppm of cobalt ions; 597ppm of manganese ions; iron ions 6.34ppm; heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using ethanol as solvent to dissolve can separate solid A solid organic matter, the insoluble matter is mainly terephthalic acid, and the hydrobromic acid can recover the economic value of terephthalic acid after washing.

Experiment 5:

the crystallization 1 of experiment 1 is sampled by 0.5KG, 3L hydrochloric acid containing 3% hydrogen chloride is added for stirring and suction filtration, the solid on the filter cloth is washed and suction filtered by 0.5L hydrochloric acid containing 3% hydrogen chloride, a filter cake and a filtrate B are obtained again, and the filtrate is analyzed: 1510ppm of sodium ions; cobalt ion 2580ppm; 1904ppm of manganese ions; 18.8ppm of iron ions; chlorine ion 30189ppm; heterocyclic compound 0ppm.

Sampling 20.0089g of experiment 1 filter cake 1, adding 110mL of hydrochloric acid containing 3% hydrogen chloride, stirring and suction filtering, flushing and suction filtering the solid on the filter cloth by using 30mL of hydrochloric acid containing 3% hydrogen chloride, obtaining a filter cake and filtrate again, heating the filter cake to 105 ℃ for 24 hours, and then drying to analyze terephthalic acid 93.24%; filtrate analysis: sodium ions 498ppm; cobalt ion 798ppm; 573ppm of manganese ions; iron ions 5.87ppm; chloride 29911ppm; heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using ethanol as solvent to dissolve can separate solid A solid organic matter, the insoluble matter is mainly terephthalic acid, and the economic value of terephthalic acid can be recovered after hydrochloric acid washing.

Experiment 6:

sampling 20.0005g of the crystallization 2 of the experiment 2, adding 110ml of pure water, stirring, filtering, washing and filtering the solid on the filter cloth with 30ml of pure water, obtaining a filter cake and filtrate again, heating the filter cake to 105 ℃ for 24 hours, and analyzing BA=95.89% after drying; filtrate analysis: 1611ppm of sodium ions; 2859ppm of cobalt ions; manganese ions 2187ppm; 17.6ppm of iron ions; heterocyclic compound 0ppm.

Sample 20.0019g of experiment 2 filter cake 2, add 110ml of pure water, stir and suction filter, wash and suction filter the solid on the filter cloth with 30ml of pure water, get filter cake and filtrate again, filtrate analysis: 425ppm of sodium ions; cobalt ions 721ppm; manganese ion 545ppm; iron ions 5.13ppm; heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using diethyl ether as solvent can separate solid A solid organic matter, the dissolved matter is mainly benzoic acid, and the economic value of benzoic acid can be recovered after washing with pure water.

Experiment 7:

sample 20.0002g of experiment 2 crystal 2, add 110mL hydrobromic acid containing 3% hydrogen bromide, stir and suction filter, the solid on the filter cloth is washed and suction filtered with 30mL hydrobromic acid containing 3% hydrogen bromide, get filter cake and filtrate again, filter cake is heated to 105 ℃ and kept for 24 hours until it is dry, analyze ba=95.89%; filtrate analysis: sodium ions 1676ppm; cobalt ion 2912ppm; manganese ions 2199ppm; 18.3ppm of iron ions; heterocyclic compound 0ppm.

Sample experiment 2 cake 2 20.0000g, add 110mL hydrobromic acid containing 3% hydrogen bromide, stir and suction filter, the solid on the filter cloth is then rinsed and suction filtered with 30mL hydrobromic acid containing 3% hydrogen bromide, get cake and filtrate again, filtrate analysis: sodium ions 432ppm; 746ppm of cobalt ions; manganese ion 575ppm; iron ions 6.02ppm; heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using diethyl ether as solvent can separate solid A solid organic matter, the dissolved matter is mainly benzoic acid, and the economic value of benzoic acid can be recovered after hydrobromic acid is washed.

Experiment 8:

sample 20.0004g of the experiment 2 crystal 2, add 110mL hydrochloric acid containing 3% hydrogen chloride, stir and suction filter, wash and suction filter the solid on the filter cloth with 30mL hydrochloric acid containing 3% hydrogen chloride, get filter cake and filtrate again, heat the filter cake to 105 ℃ for 24 hours to reach analysis BA= 96.01% after drying; filtrate analysis: 1634ppm sodium ions; cobalt ion 2891ppm; manganese ion 2165ppm; 19.01ppm of iron ions; 30199ppm of chloride ions; heterocyclic compound 0ppm.

Sample experiment 2 cake 2 20.0000g, add 110mL hydrochloric acid containing 3% hydrogen chloride, stir and suction filter, the solid on the filter cloth is then washed with 30mL hydrochloric acid containing 3% hydrogen chloride and suction filter, get cake and filtrate again, filtrate analysis: sodium ions 467ppm; 788ppm of cobalt ions; 593ppm of manganese ions; iron ions 6.35ppm; chloride 2983 ppm; heterocyclic compound 0ppm.

Conclusion of this experiment: the method of using diethyl ether as solvent can separate solid A solid organic matter, the dissolved matter is mainly benzoic acid, and the economic value of benzoic acid can be recovered after hydrochloric acid is washed.

Experiment 9:

sampling filtrate A of experiment 3 to 5L, adding sodium carbonate and stirring to generate a large amount of bubbles, raising the pH to 5.7, using 144.7g of sodium carbonate solid, measuring sodium ions 13968ppm after filtration, wherein the volume of the sodium carbonate solid is not changed obviously; cobalt ion 2402ppm; manganese ion 1835ppm; iron ion 0.27ppm, referred to as sample A.

Dividing into 2 routes:

route 1: sample A was taken 1L

Sodium carbonate was then added and ph=9.5 was raised, 28.4g of sodium carbonate was consumed, the volume was not significantly changed, and 26017ppm of sodium ions were measured after filtration; cobalt ion 0.01ppm; manganese ion 0ppm; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Taking 0.9L of the filtrate, passing through two stages of serially connected (the effluent after the first stage treatment passes through the second stage) hydrogen type cation resin columns (the resin amount of each stage is 500g, the second stage resin adsorbs sodium ions of the effluent of the first stage again), and controlling the flow rate of the effluent below the resin columns to be about 100 ml/hour. The sodium ion concentration of the effluent is shown in the following table, in ppm:

the residual water sample of the second-stage hydrogen type cationic resin is analyzed as follows: sodium ion 0.35ppm; cobalt ion 0.02ppm; manganese ion 0.02ppm; iron ion 0ppm.

The first stage hydrogen type cation resin is regenerated by using 1500ml of 10% hydrochloric acid after being subjected to liquid removal by compressed air, and the regenerated liquid is tested as follows: sodium 14358ppm.

Route 2: sample A taken 1L

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours	After 5 hours	After 6 hours
							Cobalt (Co)	1.62	2.81	42.3	35.1	62.3	83.2
Manganese (Mn)	0.93	3.44	12.1	16.8	51.1	67.5
							Sodium salt	13987	14003	13925	13961	13988	13942

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: 13941ppm of sodium ions; cobalt ion 0.33ppm; manganese ion 0.27ppm; iron ion 0ppm.

The water sample analysis of the second-stage hydrogen type cationic resin effluent is as follows: sodium ion 0.12ppm; cobalt ion 0.01ppm; manganese ion 0.06ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 300ml of 23.75% hydrobromic acid is used for regeneration, and 7226ppm of cobalt ions are measured by the regenerated liquid; 5569ppm of manganese ions; sodium ions 1.17ppm.

The first-stage hydrogen cation-adsorption resin was subjected to liquid removal by compressed air and then regenerated with 500ml of 10% hydrochloric acid, and the regenerated solution was measured for 12895ppm of sodium ions.

Conclusion of this experiment: the experiment is to simulate the treatment process of the washing liquid III of B-III in the patent requirements through a c-II process route, wherein the cobalt-manganese recovery unit can recover the final water body (second-stage hydrogen type cationic resin effluent) of the hydrogen type cationic resin to the oxidation reaction system unit no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt-manganese resin is selected: sodium ions and metallic corrosion product iron ions have been removed; cobalt ions and manganese ions can be recovered in a cobalt-manganese recovery unit (2 methods) and intermittently dissolved in hydrobromic acid, so that the cobalt ions and the manganese ions can be recovered in an oxidation reaction system.

Experiment 10:

sample experiment 9 sample A1L was passed through a two-stage series-connected hydrogen type cation resin column (400 g each stage of resin), the flow rate was controlled to be about 100 ml/hr, and the concentration of cobalt, manganese and sodium ions in water was measured in ppm as shown in the following table

The water quality of the second-stage hydrogen type cation resin effluent contains 0.61ppm of sodium ions; cobalt ion 0ppm; manganese ion 0.02ppm; iron ion 0ppm.

The first stage hydrogen cationic resin was regenerated with 1.2L of 5% hydrochloric acid and the regeneration solution was analyzed as follows: cobalt 1825ppm, manganese 1403ppm, sodium 10998ppm, 2 treatment routes for the regeneration liquor:

Route 1: taking 300ml of the first-stage hydrogen type cation resin regenerated liquid, adding sodium carbonate to raise the pH=9.5, generating a large amount of gas by 26.5g of sodium carbonate, and carrying out water sample analysis after filtering, wherein the volume of the gas is not changed obviously: cobalt 0.09ppm; manganese 0.02ppm; sodium 49897ppm, about half of the filter cake was fully soluble with 100ml of 47.5% hydrobromic acid.

first stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours	After 5 hours
						Cobalt (Co)	1.34	6.45	12.1	18.8	56.8
Manganese (Mn)	1.88	4.33	8.89	12.7	34.6
						Sodium salt	41057	41078	41124	41002	41078

The water sample analysis of the second-stage cobalt-manganese resin effluent is as follows: 41049ppm of sodium ions; cobalt ion 0.06ppm; manganese ion 0.02ppm; iron ion 0ppm.

The first stage cobalt-manganese adsorption resin is regenerated by using 150ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and cobalt ions 6732ppm are measured by the regenerated liquid; 5250ppm of manganese ions; sodium ions 2.04ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the washing liquid III of B-III in the patent requirements through a c-III process route, after alkaline substances are added into the washing liquid III and iron ions are removed through filtration, sodium ions, cobalt ions and manganese ions are removed through hydrogen type cation resin, and the effluent of the second-stage hydrogen type cation resin can be recycled to an oxidation reaction system unit: sodium ions, cobalt ions, manganese ions and iron ions which are metal corrosion products are removed; can reenter the oxidation reaction system;

Experiment 11:

1L of filtrate A of sample experiment 3 is counted by two stages of cobalt-manganese adsorption resin (150 g of resin in each stage), the flow rate is controlled to be about 120 ml/hour, and the concentration of cobalt ions and manganese ions in effluent is as follows in the following table, and the unit ppm is as follows:

the water sample result of the second-stage cobalt-manganese adsorption resin effluent is as follows: sodium ions 1399ppm; cobalt ion 0.01ppm; manganese ion 0.06ppm; iron ion 0ppm.

Second-stage hydrogen type cation resin effluent water sample: sodium ion 0.03ppm; cobalt ion 0.06ppm; manganese ion 0.04ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by using 500ml of 3% hydrochloric acid after being subjected to liquid removal by compressed air, and the regenerated liquid is measured to be 4489ppm of cobalt ions; manganese ion 3431ppm; sodium ion 2.15ppm; iron ions 30.2ppm.

The first-stage hydrogen cation-adsorption resin was subjected to liquid removal by compressed air and then regenerated with 200ml of 3% hydrochloric acid, and the regenerated liquid was found to have a sodium ion of 5089ppm.

400ml of the first-stage cobalt-manganese adsorption resin regeneration liquid is sampled, sodium carbonate is added to raise the PH=5.7, the dosage of the sodium carbonate is 19.1g, and the test result is that: cobalt ions 4421ppm; manganese ion 3391ppm; 20782ppm of sodium ions; iron ion 0.25ppm. The filtrate after filtration had 2 routes:

route 1: taking 100ml of the filtrate, adding sodium carbonate to raise the PH=9.5, filtering the filtrate with the dosage of 2.0g, and obtaining water quality: cobalt ion 0.01ppm; manganese ion 0.07ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	2.15	24.5	64.2	111.3
Manganese (Mn)	2.25	21.7	43.8	89.3
					Sodium salt	20764	20731	20718	20743

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.02ppm; manganese ion 0.01ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is subjected to liquid removal by compressed air, 200ml of 23.75% hydrobromic acid is used for regeneration, and the regenerated liquid is used for measuring 6239ppm of cobalt ions; manganese ion 4791ppm; sodium ion 1.45ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the washing liquid III of B-III in the patent requirements through a c-IV process route, wherein the washing liquid III is subjected to cobalt-manganese resin to adsorb cobalt ions, manganese ions and iron ions, and then is subjected to hydrogen-type cation resin to adsorb sodium ions, so that the cobalt ions, the manganese ions, the iron ions and the sodium ions are removed, and the washing liquid III can be recycled to an oxidation reaction system unit;

Experiment 12:

taking filtrate a of experiment 3 to measure 12L, carrying out nanofiltration (fresh water amount: concentrated water amount control=2:1), and carrying out nanofiltration concentrated water sample analysis: sodium ions 1391ppm; cobalt ion 3725ppm; manganese ion 2813ppm; iron ions 26.9ppm. Nanofiltration fresh water sample analysis: sodium ions 1443ppm; cobalt ion 1879ppm; 1401ppm of manganese ions; iron ions 12.3ppm.

second-stage hydrogen-type cation resin effluent quality: sodium ion 0.02ppm; cobalt ion 0.01ppm; manganese ion 0.01ppm; iron ion 0ppm.

Regenerating the first-stage hydrogen type cationic resin by 600ml of 5% hydrochloric acid, wherein the regenerated liquid contains 4459ppm of sodium ions; cobalt ion 5891ppm; manganese ion 4389ppm; iron ion 35.1ppm.

1L of concentrated water is taken and mixed with 500ml of regeneration liquid, sodium carbonate is added to the obtained mixed liquid to raise the PH=5.7, the dosage of the sodium carbonate is 63.3g, and the filtrate is obtained by filtration, and the analysis is as follows: 19898ppm of sodium ions; 4401ppm of cobalt ions; 3287ppm of manganese ions; iron ions 0.24ppm. The filtrate had 2 routes:

route 1: the filtrate was sampled at 500ml, sodium carbonate was added to raise ph=9.5, sodium carbonate consumption was 20.4g, effluent quality: cobalt ion 0.01ppm; manganese ion 0.05ppm; iron ion 0ppm. About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.01ppm; manganese ion 0.05ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by 450ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and the regenerated liquid is measured to be 8203ppm of cobalt ions; manganese ion 6107ppm; sodium ion 2.03ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the washing liquid III of B-III in the patent requirement through a c-V process route, the concentration of cobalt ions, manganese ions and iron ions in nanofiltration fresh water is reduced firstly after nanofiltration, and the nanofiltration fresh water can be recycled to an oxidation reaction system unit after the cobalt ions, the manganese ions, the iron ions and the sodium ions are adsorbed by hydrogen type cation resin;

Experiment 13:

taking 1L of filtrate A of experiment 3, passing through two-stage serial bromine adsorption resin (100 g of resin in each stage), controlling flow rate to about 200 ml/hr, and controlling cobalt and manganese ion concentration of effluent to be shown in the following table, wherein the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	62.6	163	188	526

Second-stage bromine adsorption resin effluent quality: 1412ppm sodium ions; 2442ppm of cobalt ions; 1821ppm of manganese ions; 3.34ppm of bromide; iron ions 16.7ppm.

Adding sodium carbonate and stirring to generate a large amount of bubbles, raising the pH to 5.7, using 13.1g of sodium carbonate solid, measuring 8473ppm of sodium ions after filtration, wherein the volume of the sodium carbonate solid has no obvious change; cobalt ion 2398ppm; manganese ion 1788ppm; 2.59ppm of bromide; iron ion 0.37ppm.

Then, dividing into 2 routes:

route 1: taking 100ml

Sodium carbonate was then added and ph=9.5 was raised, 3.2g of sodium carbonate was consumed, the volume was not significantly changed, and 16246ppm of sodium ions were measured after filtration; cobalt ion 0.09ppm; manganese ion 0.06ppm; 3.44ppm of bromide; iron ion 0ppm.

About half of the filter cake was dissolved in 100ml of 47.5% hydrobromic acid.

Route 2: take 0.5L

The water sample analysis of the second-stage cobalt-manganese adsorption resin effluent is as follows: sodium ion 8437ppm; cobalt ion 0.15ppm; manganese ion 0.02ppm; 3.23ppm of bromide; iron ion 0ppm.

regenerating 20ml of bromine adsorption resin with 75ml of 1% sodium hydroxide, and measuring 5647ppm of bromide ions in the regenerated solution;

50ml of regeneration liquid is added into 100ml of hydrogen type cationic resin to be soaked for 2 hours, and water outlet test is carried out: 5623ppm of bromide ion and 6.64ppm of sodium ion;

taking 20ml of bromine adsorption resin, regenerating with 75ml of 5% cobalt acetate solution, and measuring 5699ppm of bromide ions from the regenerated solution;

regenerating 20ml of bromine adsorption resin with 75ml of 5% manganese acetate solution, and measuring 5615ppm of bromide ions by using the regenerated solution;

regenerating 20ml of bromine adsorption resin with 75ml of mixed solution containing 5% cobalt acetate and 5% manganese acetate, and measuring 5656ppm of bromine ions from the regenerated solution;

taking 20ml of bromine adsorption resin, dissolving 15g of filter cake collected in experiments 9-13 with 75ml of 25% acetic acid, taking supernatant as regeneration liquid to regenerate 20ml of bromine adsorption resin, and measuring 5528ppm of bromide ions in the regeneration liquid;

The first stage cobalt-manganese adsorption resin is regenerated by using 150ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and cobalt ions 7445ppm are measured by the regenerated liquid; 5655ppm of manganese ions; sodium ion 2.27ppm.

Conclusion of this experiment: the experiment simulates the treatment process of the washing liquid III of B-III in the patent requirement through a c-VI process route, wherein bromine can be adsorbed by bromine adsorption resin and can be desorbed and regenerated by sodium hydroxide solution; can be desorbed and regenerated by cobalt acetate and/or manganese acetate solution; can be desorbed and regenerated by using a mixed solution of acetic acid, cobalt acetate and manganese acetate; the cobalt-manganese recovery unit can recover cobalt ions and manganese ions no matter the method of adding alkaline substances for precipitation filtration or the method of adsorbing cobalt-manganese resin is selected;

Experiment 14: sampling 1L of nanofiltration fresh water of experiment 12, measuring 2581ppm of bromide ions, passing through two-stage serial bromine adsorption resin (100 g of resin in each stage), controlling the flow rate to be about 200 ml/hour, and controlling the concentration of cobalt and manganese ions in effluent to be shown in the following table, wherein the unit ppm

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Bromine	44.3	113	247	532

Second-stage bromine adsorption resin effluent quality: 1429ppm sodium ions; cobalt ion 1833ppm; 1335ppm of manganese ions; bromide 3.22ppm; iron ions 11.2ppm.

The first stage bromine adsorption resin was subjected to liquid removal by compressed air and then regenerated with 300ml of 4% sodium hydroxide, and 7569ppm of bromide was measured in the regenerated liquid.

Conclusion of this experiment: the experiment is to simulate the treatment process of nanofiltration fresh water passing through a c-VI-c process route in the patent requirement, wherein the nanofiltration fresh water can adsorb bromine through a bromine adsorption resin and can be desorbed by sodium hydroxide solution; the mixed solution of the effluent treated by the bromine adsorption resin and the nanofiltration concentrated water can be deduced from the similar experiment before that sodium carbonate is added to remove iron ions of corrosion products, and then cobalt and manganese ions are solidified by adding sodium carbonate or removed by a method of cobalt-manganese adsorption resin and cobalt-manganese is recovered (see the treatment experiment of the mixed solution of the nanofiltration concentrated water and the hydrogen type cation resin regeneration liquid in experiment 12).

Experiment 15:

experiment 5 filtrate B was sampled 1.2L, sodium carbonate was added to raise ph=5.7, the sodium carbonate consumption was 49.9g, and the filtrate was filtered to give filtrate: 19583ppm of sodium ions; cobalt ion 2521ppm; manganese ions 1867ppm; iron ion 0.39ppm; chlorine ion 30167ppm. The filtrate has two treatment routes:

route 1: sampling 0.2L of added sodium carbonate, raising PH=9.5, consuming 6.2g of sodium carbonate and yielding water quality: cobalt ion 0.01ppm; manganese ion 0.03ppm; iron ion 0ppm; chloride ion 30251ppm. The filter cake was fully soluble with 100ml of 47.5% hydrobromic acid.

First stage resin effluent quality	After 1 hour	After 2 hours	After 3 hours	After 4 hours
					Cobalt (Co)	3.15	31.2	65.3	89.3
Manganese (Mn)	4.24	20.0	46.9	87.2
					Sodium salt	19511	19213	19237	19563

Second-stage cobalt-manganese adsorption resin effluent quality: cobalt ion 0.11ppm; manganese ion 0.04ppm; iron ion 0ppm.

The first-stage cobalt-manganese adsorption resin is regenerated by 300ml of 23.75% hydrobromic acid after being subjected to liquid removal by compressed air, and the regenerated liquid is measured to be 7689ppm of cobalt ions; 5826ppm of manganese ions; sodium ion 2.98ppm.

Conclusion of this experiment: the experiment is to simulate the hydrochloric acid washing liquid of the B-III crystal 1 in patent requirements, and a cobalt-manganese recovery unit (2 methods) can recover cobalt and manganese no matter the cobalt-manganese recovery unit selects a method of adding alkaline substances for precipitation filtration or a method of adsorbing cobalt-manganese resin: cobalt ions and manganese ions can be recovered and intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recovery unit (2 methods), and can be recovered to an oxidation reaction system.

Example 3 summarises:

1. according to the planned b-III process route, the solid organic matters can be separated by dissolving the solid organic matters with methanol or ethanol or diethyl ether or toluene, paraxylene and methyl acetate to obtain purer organic matters, and the economic value of the purer organic matters can be recovered;

2. the washing solution III of B-III (filtrate A of experiment 3) can achieve the aim of recycling the treated water solution to the oxidation reaction system through c-II, III, IV and V, and the economic value of the water solution is recycled (c-I is directly recycled, and c-II, III, IV and V are recycled to the oxidation reaction system after being treated); after c-VI, bromine can be separated through testing, and the bromine is discharged after final water treatment;

the material compositions of the crystal water washing liquid and hydrobromic acid washing liquid are the same, and the concentration is only different, so that the inference can be made that the hydrobromic acid washing liquid can achieve the same experimental purpose through c-II, III, IV, V and VI.

4. The hydrochloric acid washing liquid of the crystal 1 can be used for recovering cobalt and manganese through a cobalt and manganese recovery unit, whether a method of adding alkaline substances for precipitation and filtration or a method of adsorbing cobalt and manganese resin is selected: cobalt ions and manganese ions can be recycled and can be intermittently dissolved in hydrobromic acid after entering a cobalt-manganese recycling unit (2 methods), and can be recycled to an oxidation reaction system.

Example 4:

experiments with bromine adsorption resins.

The mixture of the mother liquor extract after acetic acid removal is cooled and subjected to solid-liquid separation to obtain a separating liquid, alkaline substances (sodium carbonate is selected and the PH=5.5 is raised), and after iron and chromium ions are removed by filtration, 10L of filtrate is sampled after cobalt-manganese adsorption resin with the volume of 2L of resin is filled (the flow rate is 2L/H), the bromine content is 2612ppm, the volume of experimental resin is 100ml, and after the flow rate which is 2 times of the volume of resin passes through the adsorption resin (namely the flow rate is controlled to be 200 ml/H), the concentration of bromine in the effluent is as follows:

experiments prove that the water can absorb bromine normally and selectively by using the resin with selectivity to bromine. Soaking with 4% sodium hydroxide for 1 hr, washing with water to neutrality, and performing adsorption test at flow rate of 100ml/H:

sampling time	Water is discharged for 15 minutes	Water is discharged for 2 hours	Water is discharged for 3 hours	Water is discharged for 4 hours
					Treated water volume	0.25 times of resin	2 times of resin	3 times of resin	4 times of resin
Bromine concentration in effluent	433ppm	443ppm	673ppm	753ppm
					Sampling time	5 hours	For 6 hours	7 hours
Treated water volume	5 times of resin	6 times of resin	7 times of resin
					Bromine concentration in effluent	918ppm	1051ppm	1248ppm

Conclusion: first, the adsorption capacity of the resin increases after desorption regeneration, and the resin can be reused. The production design is to design the required resin amount according to the adsorption capacity of the resin after desorption and regeneration, and the actual operation process can be designed according to the adsorption capacity after desorption and regeneration.

Example 5:

sample 1: and the effluent of the sampling oxidation mother liquor is subjected to 0.23Kg of effluent sewage of an acetic acid recovery process and a terephthalic acid partial recovery process.

Sample 2: the effluent of the oxidation mother liquor extraction liquid is subjected to acetic acid recovery process and terephthalic acid partial recovery process, and then is subjected to cooling, filtering and solid-liquid separation to obtain a separation liquid, wherein the separation liquid is sampled by 0.23Kg, the PH=3.1, and the temperature of the separation liquid is reduced to 18 ℃ in a laboratory in this experiment.

Sodium carbonate was used as a 9% strength aqueous solution.

The first table is the consumption test of the alkaline substance used in sample 1, and the second table is the consumption test of the alkaline substance used in sample 2:

list one

Watch II

Conclusion:

from the above table, it can be seen that the consumption of alkaline substance for the separation liquid (sample 2) after the application of solid-liquid separation is significantly reduced as compared with that for sample 1.

Claims

1. A process for treating mother liquor extract of a purified terephthalic acid oxidation unit is characterized by sequentially comprising the following steps of:

flow a: the mother liquor extract of the oxidation unit passes through an acetic acid recovery unit to obtain a residual mixture;

flow b: the remaining mixture of scheme a is treated in a scheme b, which is optionally one of b-ii or b-iii:

b-II: carrying out esterification reaction on the rest mixture of the flow a and alcohols; or the rest mixture of the process a is dehydrated and then is subjected to esterification reaction with alcohols to obtain an ester-containing mixture A, and then is subjected to advanced treatment;

the step of carrying out advanced treatment on the ester-containing mixture A in the route b-II is as follows: separating the mixture A containing esters to obtain a separating liquid, wherein the process comprises washing, direct solid-liquid separation or solid-liquid separation after cooling to recover solid matters and layered separation to recover liquid esters; or the process comprises the steps of solid-liquid separation directly or after cooling, solid-liquid separation to recover solid, washing and layered separation to recover liquid ester;

when the washing process is: when washing with water: the obtained separating liquid is separating liquid II-a; the separation liquid II-a is recycled to an oxidation reaction system unit or is recycled;

When the washing process is: when the aqueous solution is washed by acetic acid solution and/or hydrobromic acid solution, the obtained separating liquid is separating liquid II-b; the separation liquid II-b is recycled to an oxidation reaction system unit or is recycled;

when the washing process is: when hydrochloric acid or sulfuric acid or oxalic acid is used for washing, the obtained separating liquid is separating liquid II-c; the separating liquid II-c passes through a cobalt-manganese recovery unit II, and effluent of the cobalt-manganese recovery unit II is discharged; or the separating liquid II-c is added with alkaline substances to precipitate and/or filter, and after removing metal corrosion products, the separating liquid II-c passes through a cobalt-manganese recovery unit II, and effluent of the cobalt-manganese recovery unit II is discharged;

b-III: directly or after dewatering the rest mixture of the process a, adding an organic solvent, and then carrying out solid-liquid separation to obtain solid and separation liquid, wherein the solid is discarded or the organic matters are recycled; recovering the separating liquid;

in the routes b-III, before the solvent is added and solid-liquid separation is carried out, the solvent is added and solid-liquid separation is carried out after cooling and/or crushing; the solvent is an alcohol or ether or benzene solvent or an ester solvent;

the solvent is selected from alcohols, and the route is a route b-III-1; the solvent is selected from ether or benzene series solvent or ester solvent, and the route is route b-III-2:

Route b-III-1: adding an alcohol solvent, stirring or crushing, adding the alcohol solvent, stirring, and then performing solid-liquid separation to obtain a separating liquid III-1 and a solid III-1 respectively, wherein the separating liquid III-1 is directly discharged; or heating and crystallizing the separating liquid III-1 to obtain a solid III-1-1;

route b-III-2: directly or after crushing, adding an ether solvent or a benzene solvent or an ester solvent, stirring, and then separating solid from liquid to obtain a separating liquid III-2 and a solid III-2 respectively, wherein the separating liquid III-2 is directly discharged; or heating and crystallizing the separating liquid III-2 to obtain a solid III-2-1;

the solid III-1, the solid III-1-1, the solid III-2 or the solid III-2-1 is abandoned or recycled or washed, or the solid III-1, the solid III-1-1, the solid III-2 and the solid III-2-1 are dried and/or crushed before being washed; solid-liquid separation after washing; the washing process is any one of the following processes;

washing with water: after the solid III-1 is washed, carrying out solid-liquid separation to generate a washing liquid III-1-a and a solid III-1-a; the solid III-1-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-1-1-a and a solid III-1-1-a; after the solid III-2 is washed, carrying out solid-liquid separation to generate a washing liquid III-2-a and a solid III-2-a; the solid III-2-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-2-1-a and a solid III-2-1-a; the washing liquid III-1-a, III-1-1-a, III-2-a or III-2-1-a is recycled to an oxidation reaction system unit or is subjected to recycling treatment;

Washing with acetic acid solution and/or hydrobromic acid solution: after the solid III-1 is washed, carrying out solid-liquid separation to generate a washing liquid III-1-b and a solid III-1-b; the solid III-1-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-1-1-b and a solid III-1-1-b; after the solid III-2 is washed, carrying out solid-liquid separation to generate a washing liquid III-2-b and a solid III-2-b; the solid III-2-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-2-1-b and a solid III-2-1-b; the washing liquid III-1-b, III-1-1-b, III-2-b or III-2-1-b is recycled to an oxidation reaction system unit or is subjected to recycling treatment;

washing with hydrochloric acid or sulfuric acid or oxalic acid: after the solid III-1 is washed, carrying out solid-liquid separation to generate a washing liquid III-1-c and a solid III-1-c; the solid III-1-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-1-1-c and a solid III-1-1-c; after the solid III-2 is washed, carrying out solid-liquid separation to generate a washing liquid III-2-c and a solid III-2-c; the solid III-2-1 is washed and then subjected to solid-liquid separation to generate a washing liquid III-2-1-c and a solid III-2-1-c; the washing liquid III-1-c, III-1-1-c, III-2-c or III-2-1-c passes through a cobalt-manganese recovery unit III, and the effluent of the cobalt-manganese recovery unit III is discharged; or the washing liquid III-1-c, III-1-1-c, III-2-c or III-2-1-c is added with alkaline substances to precipitate and/or filter and remove metal corrosion products, and then the washing liquid III-1-c, III-2-c or III-2-1-c is discharged through a cobalt-manganese recovery unit III;

The separation liquid II-a, the separation liquid II-b, the washing liquid III-1-1-a, the washing liquid III-1-1-b, the washing liquid III-1-a, the washing liquid III-1-b, the washing liquid III-2-1-a, the washing liquid III-2-1-b, the washing liquid III-2-a or the washing liquid III-2-b are subjected to recovery treatment, and any one of the following 6 routes is adopted as a route c-II, a route c-III, a route c-IV, a route c-V and a route c-VI;

route c-II: the effluent of the cobalt-manganese recovery unit IV is directly discharged or enters an oxidation reaction system unit after passing through hydrogen type cationic resin to be recovered after being treated by the cobalt-manganese recovery unit IV;

route c-III: the treated hydrogen type cation resin enters an oxidation reaction system unit for recycling; the hydrogen type cationic resin in the route c-III is regenerated by an acid solution or washed after regeneration after being adsorbed and saturated, and the regenerated liquid and the washed liquid are directly discharged after passing through a cobalt-manganese recovery unit VIII; or the regenerated liquid and the washing liquid are added with alkaline substances to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is directly discharged after passing through a cobalt-manganese recovery unit VIII; or the regenerated liquid or the washing liquid generated by the hydrogen type cationic resin in the route c-III is firstly subjected to a nanofiltration unit IV, and the nanofiltration fresh water of the nanofiltration unit IV is directly discharged; the nanofiltration concentrated water of the nanofiltration unit IV is treated by a cobalt-manganese recovery unit VIII; or the nanofiltration concentrated water of the nanofiltration unit IV is firstly added with alkaline substances for precipitation and/or filtered to remove metal corrosion products to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit VIII;

Routes c-IV: after being treated by cobalt-manganese adsorption resin, the catalyst is subjected to hydrogen type cation resin and then enters an oxidation reaction system unit for recycling;

route c-V: introducing the fresh water into a nanofiltration unit I, and allowing fresh water in the nanofiltration unit I to enter and be recycled into an oxidation reaction system unit; or the fresh water of the nanofiltration unit I enters the oxidation reaction system unit after passing through the hydrogen type cationic resin; in the route c-V, concentrated water of the nanofiltration unit I is directly discharged after passing through the cobalt-manganese recovery unit X; or adding alkaline substances to precipitate and/or filter to remove metal corrosion products to obtain filtrate before passing through the cobalt-manganese recovery unit X, and directly discharging the filtrate after passing through the cobalt-manganese recovery unit X;

route c-VI-a: the effluent of the cobalt-manganese recovery unit V is directly discharged through the cobalt-manganese recovery unit V; or the effluent of the cobalt-manganese recovery unit V is directly discharged after passing through bromine adsorption resin; or the effluent of the cobalt-manganese recovery unit V is filtered and then directly discharged after passing through bromine adsorption resin;

route c-VI-b: the aqueous solution passes through the bromine adsorption resin, and the effluent of the bromine adsorption resin is directly discharged; or directly filtering the effluent of the bromine adsorption resin or directly discharging the effluent of the cobalt-manganese recovery unit VI after filtering;

Route c-VI-c: the aqueous solution passes through a nanofiltration unit II, concentrated water of the nanofiltration unit II passes through a cobalt-manganese recovery unit VII, and effluent of the cobalt-manganese recovery unit VII is directly discharged; or in the route c-VI-c, adding alkaline substances into concentrated water of the nanofiltration unit II to precipitate and/or filter out metal corrosion products to obtain filtrate, and treating the filtrate by the cobalt-manganese recovery unit VII; or the fresh water of the nanofiltration unit II is directly discharged; or the fresh water of the nanofiltration unit II is directly discharged after passing through the bromine adsorption resin; or the fresh water of the nanofiltration unit II passes through bromine adsorption resin and then is treated by the same route as the concentrated water of the nanofiltration unit II;

the treatment route of the cobalt manganese recovery units II, III, IV, V, VI, VII, VIII and X is as follows:

the effluent is taken as effluent of a cobalt-manganese recovery unit after passing through the cobalt-manganese adsorption resin; the cobalt-manganese adsorption resin is regenerated by acetic acid and/or hydrobromic acid solution after being saturated in adsorption or is washed after being regenerated, and the regenerated solution of the cobalt-manganese adsorption resin enters an oxidation reaction system unit to be recycled; the water washing liquid is directly discharged or enters into an oxidation reaction system unit for recycling; or the regenerated liquid and the water washing liquid are filtered and crushed by a filtering device before entering the oxidation reaction system unit.

2. The process according to claim 1, wherein the esterification reaction in the route b-ii is preceded by beating the remaining mixture of the process a with water, crystallizing terephthalic acid by controlling the temperature after beating, filtering, separating, extracting and recovering terephthalic acid, and then dehydrating the residue and carrying out the esterification reaction with alcohols.

3. The process according to claim 1, wherein the treatment process is performed,

discarding the solid III-1-a, the solid III-1-b or the solid III-1-c; or the solid III-1-a, the solid III-1-b or the solid III-1-c is recycled or enters an oxidation reaction system unit or is subjected to esterification reaction with alcohols to generate esters for recycling; or the solid III-1-a, the solid III-1-b or the solid III-1-c is washed and/or dried before being recycled or entering an oxidation reaction system unit or being subjected to esterification reaction with alcohols to generate esters for recycling;

discarding the solid III-1-1-a, solid III-1-1-b, solid III-1-1-c, solid III-2-a, solid III-2-b, solid III-2-c, solid III-2-1-a, solid III-2-1-b or solid III-2-1-c; or the solid III-1-1-a, the solid III-1-1-b, the solid III-1-1-c, the solid III-2-a, the solid III-2-b, the solid III-2-c, the solid III-2-1-a, the solid III-2-1-b or the solid III-2-1-c is recovered or is subjected to esterification reaction with alcohols to generate esters for recovery; or the solid III-1-1-a, the solid III-1-1-b, the solid III-1-1-c, the solid III-2-a, the solid III-2-b, the solid III-2-c, the solid III-2-1-a, the solid III-2-1-b or the solid III-2-1-c is washed and/or dried before being recovered or being subjected to esterification reaction with alcohols to generate esters for recovery;

The steps can be carried out independently or in combination; the combination mode is as follows: solid III-1-1 or solid III-1-1-a or solid III-1-1-b or III-1-1-c is directly or after washing and/or drying treated by b-III-2 route; or solid III-2-a or solid III-2-b or solid III-2-c, and then is treated by b-III-1 directly or after washing and/or drying.

4. The process of claim 1 wherein the liquid treated in any of the routes c-ii, c-iii, c-iv, c-v, c-vi is treated in any of the routes c-ii, c-iii, c-iv, c-v, c-vi by passing through an ultrafiltration membrane followed by a reverse osmosis membrane, fresh water removal from the reverse osmosis membrane, and concentrated reverse osmosis membrane water entering the routes c-ii, c-iii, c-iv, c-v, c-vi.

5. A process according to claim 1, wherein,

in the route c-II, alkaline substances are added into the inflow water of the route c-II to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit IV;

in the route c-III, alkaline substances are added into the water fed in the route c-III to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is treated by hydrogen type cationic resin and then enters an oxidation reaction system unit for recycling;

In the route c-VI-a, alkaline substances are added into the inflow water of the route c-VI-a to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit V;

in the route c-VI-b, alkaline substances are added into the inflow water of the route c-VI-b to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate passes through bromine adsorption resin; or the inlet water of the route c-VI-b passes through bromine adsorption resin, alkaline substances are added into the outlet water of the bromine adsorption resin to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is treated by a cobalt-manganese recovery unit VI.

6. A process according to claim 1, wherein,

before the effluent water passing through the hydrogen type cationic resin in the route c-II enters into the oxidation reaction system unit, filtering the crushed resin by a filtering device and/or adding hydrobromic acid for emptying and stirring;

before the effluent water passing through the hydrogen type cationic resin in the route c-III enters into the oxidation reaction system unit, filtering the crushed resin by a filtering device and/or adding hydrobromic acid for emptying and stirring;

before the effluent water passing through the hydrogen type cationic resin in the routes c-IV enters into the oxidation reaction system unit, filtering equipment is arranged for filtering broken resin;

When the water solution adopted in the route c-V passes through the nanofiltration unit I, fresh water passes through the hydrogen type cationic resin, and effluent of the hydrogen type cationic resin enters and is recycled to the oxidation reaction system unit: and before the effluent water passing through the hydrogen type cationic resin enters the oxidation reaction system unit, filtering the crushed resin by a filtering device.

7. A process according to claim 1, 5 or 6, characterized in that,

in the route c-II, the hydrogen type cationic resin is regenerated by an acid solution or is washed after being regenerated after being saturated by adsorption, and the regenerated liquid or the washing liquid is directly discharged;

in the routes c-IV, the cobalt-manganese adsorption resin is regenerated by an acid solution or is washed after being regenerated after being adsorbed and saturated, and the regenerated liquid and the washing liquid are directly discharged after passing through a cobalt-manganese recovery unit IX; or the regenerated liquid and the washing liquid are added with alkaline substances to precipitate and/or filter and remove metal corrosion products to obtain filtrate, and the filtrate is directly discharged after passing through a cobalt-manganese recovery unit IX; regenerating the hydrogen type cation resin after being adsorbed and saturated by an acid solution or washing the hydrogen type cation resin after regeneration, and directly discharging regenerated liquid or washing liquid;

in the route c-V, the hydrogen type cationic resin is regenerated by an acid solution after being adsorbed and saturated or is washed after being regenerated, and the regenerated liquid and the washing liquid are directly discharged after passing through a cobalt-manganese recovery unit X; or adding alkaline substances to precipitate and/or filter to remove metal corrosion products to obtain filtrate before passing through the cobalt-manganese recovery unit X, and directly discharging the filtrate after passing through the cobalt-manganese recovery unit X;

In the course of the said routes c-vi,

after the bromine adsorption resin is adsorbed and saturated, any one or a mixed solution of any two substances or a mixed solution of three substances in an acetic acid solution, a cobalt acetate solution and a manganese acetate solution is subjected to desorption regeneration or water washing after regeneration; or the bromine adsorption resin is desorbed and regenerated by sodium acetate or potassium acetate solution and/or alkaline solution after being adsorbed and saturated, and then is washed by water; or the bromine adsorption resin is desorbed and regenerated by a salt solution after being adsorbed and saturated or is washed after being regenerated;

after the adsorption saturation, the bromine adsorption resin is regenerated by alkaline solution and/or sodium acetate or potassium acetate solution: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted into hydrobromic acid by a bipolar membrane method to be recycled to an oxidation reaction system unit; or the bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to the oxidation reaction system unit; or the regenerated liquid passes through the hydrogen type cationic resin, the effluent of the hydrogen type cationic resin is directly discharged or the effluent of the hydrogen type cationic resin enters into the oxidation reaction system unit to be recovered, or the effluent of the hydrogen type cationic resin enters into the oxidation reaction system unit to be recovered after being filtered; the hydrogen type cation resin is adsorbed and saturated and then is regenerated by acid solution, and the regenerated liquid is directly discharged;

After the adsorption saturation of the bromine adsorption resin, the bromine adsorption resin is regenerated by chloride salt solution: directly discharging the regenerated liquid; or the regenerated liquid is subjected to evaporative crystallization or membrane concentration evaporative crystallization to be used as solid waste treatment; or the bromine element of the regeneration liquid is extracted into hydrobromic acid by a bipolar membrane method to be recycled to an oxidation reaction system unit; or the bromine element of the regeneration liquid is extracted by an electrolysis method to form hydrobromic acid, and the hydrobromic acid is recycled to the oxidation reaction system unit.

8. The process according to claim 1 or 7, wherein nanofiltration units iii and iv are arranged in the routes c-iii; before being treated by the hydrogen type cationic resin, the nanofiltration fresh water enters a nanofiltration unit III in the route c-III, and the nanofiltration fresh water of the nanofiltration unit III is treated by the hydrogen type cationic resin; the nanofiltration concentrated water of the nanofiltration unit III is treated by a cobalt-manganese recovery unit VIII; or the concentrated nanofiltration water of the nanofiltration unit III is firstly added with alkaline substances for precipitation and/or filtered to remove metal corrosion products to obtain filtrate, and the filtrate is treated by the cobalt-manganese recovery unit VIII;

a nanofiltration unit V is arranged in the route c-IV, and the regenerated liquid or the water washing liquid generated by the cobalt-manganese adsorption resin in the route c-IV firstly enters the nanofiltration unit V, and the nanofiltration concentrated water generated by the nanofiltration unit V is treated by a cobalt-manganese recovery unit IX; or the nanofiltration concentrated water of the nanofiltration unit V is firstly added with alkaline substances for precipitation and/or filtered to remove metal corrosion products to obtain filtrate, and the filtrate is treated by the cobalt-manganese recovery unit IX; the nanofiltration fresh water generated by the nanofiltration unit V is directly discharged, or the nanofiltration fresh water generated by the nanofiltration unit V is used for regenerating hydrogen type cation resin or cobalt-manganese adsorption resin adsorption saturation after acid is supplemented.

9. The process according to claim 1, 5, 7 or 8, wherein the cobalt manganese recovery units ii, iii, iv, v, vi, vii, viii, ix and x comprise 2 routes, respectively route 1 and route 2:

route 1: adding alkaline substances to form cobalt and manganese ions into solid matters, precipitating and/or filtering, and then taking the solid matters as effluent of a cobalt-manganese recovery unit; intermittently cleaning and dissolving cobalt ions and manganese ions by using acetic acid and/or hydrobromic acid to generate a dissolving solution, and directly or filtering the dissolving solution and then feeding the dissolving solution into an oxidation reaction system unit;

route 2: the effluent is taken as effluent of a cobalt-manganese recovery unit after passing through the cobalt-manganese adsorption resin; the cobalt-manganese adsorption resin is regenerated by acetic acid and/or hydrobromic acid solution after being saturated in adsorption or is washed after being regenerated, and the regenerated solution of the cobalt-manganese adsorption resin enters an oxidation reaction system unit to be recycled; the water washing liquid is directly discharged or enters into an oxidation reaction system unit for recycling; or the regenerated liquid and the water washing liquid are filtered and crushed by a filtering device before entering the oxidation reaction system unit.

10. The process according to claim 1, 5, 6, 7 or 8, wherein the nanofiltration units i, ii, iii, iv, v are provided with ultrafiltration membranes and nanofiltration membranes, and the aqueous source solution enters the nanofiltration membranes after ultrafiltration; or the nanofiltration units I, II, III, IV and V are provided with ultrafiltration membranes, reverse osmosis membranes and nanofiltration membranes, the source aqueous solution enters the reverse osmosis membranes after ultrafiltration, the reverse osmosis membrane concentrated water enters the nanofiltration membranes and the reverse osmosis membrane fresh water is discharged, the water and solute passing through the nanofiltration membranes are nanofiltration fresh water, the water and solute not passing through the nanofiltration membranes are nanofiltration concentrated water, and the nanofiltration membranes and the reverse osmosis membranes at least comprise one-stage and one-stage nanofiltration membranes and reverse osmosis membranes.

11. The process of claim 1, 5, 6, 7, 8 or 9 wherein the recovery to oxidation reaction system unit is: directly enters an oxidation reaction system; or sequentially passing through an ultrafiltration membrane and a reverse osmosis membrane, wherein reverse osmosis membrane concentrated water enters the oxidation reaction system and is discharged outside of fresh water of the reverse osmosis membrane, and the reverse osmosis membrane at least comprises a first-stage reverse osmosis membrane and a first-stage reverse osmosis membrane; the oxidation reaction system is the feed to the oxidation reactor of the terephthalic acid production process.