CN110894113A

CN110894113A - A kind of desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment

Info

Publication number: CN110894113A
Application number: CN201911310585.6A
Authority: CN
Inventors: 陈彤
Original assignee: Zhenjiang Zerun Environmental Technology Co Ltd
Current assignee: Zhenjiang Zerun Environmental Technology Co ltd; Beijing Huaneng Changjiang Environmental Protection Technology Research Institute Co Ltd
Priority date: 2019-12-18
Filing date: 2019-12-18
Publication date: 2020-03-20

Abstract

The invention discloses a desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment. It comprises the following steps: A. firstly adding acid to the desulfurization wastewater to adjust the pH value to 0.5-4 and then stirring and mixing with the liquid resin; B. the mixture is separated in a separation chamber; C. after the separation, the liquid resin enters the liquid resin buffer tank , the separated desulfurization wastewater enters the next stage reactor for further treatment; D. The treatment process repeats steps A, B and C and enters the air flotation degreasing device to remove the liquid resin dissolved in water. The desulfurization wastewater is used as reuse water, and the liquid resin brought out by the bubbles is transported to the resin buffer tank. The advantages are: the equipment investment is small, the operating cost is low, the water produced after the chloride ion removal can meet the reuse of industrial water, no waste is generated during the treatment process, the reaction process realizes real-time adsorption and real-time regeneration, and can achieve 100% removal of chloride ions, The whole process runs continuously without waiting and delay, and the production efficiency is high.

Description

Desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment

Technical Field

The invention relates to an industrial (desulfurization) wastewater treatment technology, in particular to a desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment.

Background

In order to protect resource environment and meet the requirement of environmental protection, the industrial production needs to perform desulfurization treatment on the generated wastewater, and in the prior art, the following two processes are generally adopted to treat the industrial wastewater:

firstly, adopting a three-header, softening, concentrating, evaporating and crystallizing process for desulfurization wastewater

It has the problems that:

1. the membrane method is adopted for concentration treatment, so that the requirements on the total salt content of the desulfurization wastewater and the content of calcium and magnesium ions are high, the pollution and blockage recovery of the membrane is the most important work in the actual operation process, and the maintenance amount of the membrane is increased;

2. because the types of membranes are different, the membranes required to be used in the system comprise microfiltration, ultrafiltration, reverse osmosis, high-pressure reverse osmosis and the like, the system is complex to maintain, the equipment investment is large, and the operating cost is high;

3. the steam quality and the steam quantity have higher requirements when the terminal evaporation crystallization is carried out;

4. the end product is salt, the power plant has no qualification of salt preparation by salt sale, and the partial product can only be treated as solid waste and dangerous waste, so the treatment cost is high.

Secondly, adopting a pretreatment and flue evaporation process for the desulfurization wastewater:

it has the problems that:

1. the treatment method has requirements on the amount of flue gas, and the amount of flue gas is 9000-10000Nm for treating 1 ton of desulfurization wastewater in a normal state³Meanwhile, the flue gas amount for treating the desulfurization wastewater is 5-6% of the total flue gas amount, the treated fly ash has salt shell effect, the moisture is difficult to be fully evaporated, the defect of high moisture content of the fly ash is likely to occur, and the follow-up pipeline and dust removal equipment are easy to corrode;

2. a set of desulfurization waste water bypass flue evaporation device is arranged behind each unit, so that the system is complex; the maintenance is increased, and the equipment investment is large;

3. because the generated fly ash is high-salt fly ash, when the fly ash enters the electric dust collector, part of the fly ash stays on the electrode under the action of electrostatic attraction, and the corona electrode is corroded greatly, so that electric dust removal failure or partial failure is easily caused, and the flue gas quality at the rear end is adversely affected;

4. when the method is used on a 300MW unit, the thermal efficiency of the boiler is generally reduced by about 0.4 percent due to the influence on the thermal efficiency of the boiler caused by the reduction of the temperature of the flue gas behind the air preheater;

5. the diameter of liquid drops sprayed by the double-fluid spraying device is small, generally 20-30 mu, the hot flue gas has high liquid drop treatment efficiency, the diameter of a nozzle of the nozzle is generally smaller than 2mm, and in order to ensure that the flue gas nozzle does not generate pollution blockage, a pretreatment working section is required to be arranged at the front section of desulfurization wastewater treatment to reduce the mud content of the desulfurization wastewater;

6. because desulfurization wastewater treatment system sets up on boiler flue gas handles the workshop section, the influence of every unit actual operation operating mode to desulfurization wastewater treatment device is big, and unit operation and desulfurization wastewater treatment device will realize being correlated with, lead to control system more complicated, and the device can't the water after the recovery processing when handling, and water waste is serious.

The analysis shows that the desulfurization wastewater is the tail end wastewater of industrial production or power plants and belongs to wastewater which is difficult to treat, wherein the most difficult to treat is the problem that the concentration of chloride ions is too high, the treatment difficulty is high, and the removal of the chloride ions in the wastewater is difficult to solve in the current world.

In addition, the conventional ion exchange resin is suitable for being used under the condition of low solution salinity, the ion exchange resin has weak chloride ion adsorption capacity and low saturation, cannot meet the treatment requirement of high-concentration chlorine-containing wastewater, is usually suitable for the condition that the chloride ion concentration is below 1000mg/l, is usually used for treating the produced water after reverse osmosis treatment in the power plant environment and is used as a supplementing process of boiler supplemented water, but when the salinity is increased and the chloride ion concentration is higher than 5000mg/l, the conventional ion exchange resin cannot meet the requirement, when the conventional ion exchange resin is used reluctantly, the resin regeneration period is greatly reduced, and strong acid and strong base required by regeneration and waste treatment and high operation cost caused by the strong acid and strong base become the biggest problems in use.

Disclosure of Invention

The invention aims to solve the technical problem of providing a desulfurization wastewater dechlorination treatment method and desulfurization wastewater treatment equipment which have the advantages of low investment cost, simple operation process, low operation and maintenance cost, capability of freely selecting the category of final products, realization of water production recycling, effective recycling of products and no generation of solid waste and hazardous waste in the whole process.

In order to solve the technical problem, the dechlorination treatment method of the desulfurization wastewater comprises the following steps:

A. firstly, adding acid into the desulfurization wastewater to adjust the pH value to 0.5-4, and then feeding the desulfurization wastewater into a stirring chamber of a primary dechlorination reactor to be stirred and mixed with liquid resin;

B. b, separating the mixture stirred and mixed in the step A in a separation chamber through the density difference between the desulfurization wastewater and the liquid resin, and adsorbing chloride ions of the separated desulfurization wastewater into the liquid resin;

C. the separated liquid resin with chloride ions absorbed enters a liquid resin buffer tank, and the separated desulfurization wastewater enters a stirring chamber of a next-stage reactor for further treatment;

D. a, B, C steps are repeated in the treatment process, chloride ions in the desulfurization wastewater after the multi-stage reaction are completely removed or enter the air floatation oil removal device to remove liquid resin dissolved in water on the premise of reaching a set treatment value, PH is adjusted to 6-9 before the air floatation oil removal device, the desulfurization wastewater after air floatation treatment and PH adjustment is used as reuse water, and the liquid resin brought out by air bubbles in the air floatation oil removal device is scraped by a scraping process and is conveyed into a resin buffer tank.

Liquid resin which is directly distributed and added from a resin storage tank is added into a stirring chamber of each stage of dechlorination reactor.

The precipitate that produces among the separation process is handled through adjusting sour settling tank between first order dechlorination reactor and the second grade dechlorination reactor or between the second grade dechlorination reactor and the tertiary dechlorination reactor to get rid of partial calcium ion and sulfate ion, the precipitate makes through the supernatant fluid entering next level dechlorination reactor of clarification sedimentation after adjusting sour settling tank and clarifying the sedimentation treatment, and the precipitate through clarification sedimentation treatment passes through the mud pump and carries desulfurization system.

The liquid resin entering the liquid resin buffer tank continuously enters a regeneration reactor stirring chamber of a resin regeneration process section, a regeneration medicament is added into the regeneration reactor stirring chamber to be stirred and mixed, chloride ions in the liquid resin are released into the regeneration medicament, the chloride ions react with the regeneration medicament to generate a chloride solution, a mixed solution of the chloride solution and the liquid resin generated after mixing and stirring enters a separation chamber of the process section, the separation is carried out through the specific gravity difference between the liquid resin and the regeneration medicament, the separated liquid resin enters a resin acidification tank to be acidified, and the liquid resin after being acidified flows back to a resin storage tank.

Chlorine salt solution generated by the reaction of chloride ions and the regeneration medicament enters a regeneration medicament storage tank, the chlorine salt solution is crystallized and separated after being continuously increased and concentrated in the regeneration medicament storage tank to reach supersaturated concentration, the separated crystal is chlorine salt crystal formed under the supersaturated concentration, the chlorine salt crystal is discharged out of the regeneration medicament storage tank, meanwhile, new regeneration medicament with the same volume is added into the regeneration medicament storage tank, and the regeneration medicament mixed liquid in the regeneration medicament storage tank circularly enters a regeneration reactor stirring chamber.

The regenerated chemical is alkaline earth metal hydroxide solution or ammonia water, and the regenerated product is corresponding alkaline earth metal chloride or ammonium chloride.

In the process of crystallization precipitation of the chlorine salt solution in the regeneration agent storage tank, a salting-out mode is adopted to promote the crystallization precipitation.

Adding alkali to adjust the pH value to 6-9 before the air-flotation oil removal device, and introducing the desulfurization wastewater subjected to air-flotation treatment and alkali addition adjustment into a clean water tank to serve as reuse water.

The liquid resin is prepared by mixing one or more organic chemicals of ethers, lipids, phenols, hydrocarbons, alcohols, aldehydes, amines, oil organic compounds, crosslinking agents and the like.

A desulfurization wastewater treatment device comprises a plurality of stages of dechlorination reactors which are mutually connected in series and are provided with a resin inlet, a resin outlet and a sulfuric acid inlet, wherein the resin inlets of the dechlorination reactors at all stages are simultaneously connected with resin storage tanks which can add liquid resin into the dechlorination reactors at all stages in a distributed manner, the resin outlets of the dechlorination reactors at all stages are simultaneously connected with resin buffer tanks, the sulfuric acid inlets of the dechlorination reactors at all stages are connected with sulfuric acid storage tanks which are used for adding sulfuric acid into the dechlorination reactors at all stages, the last stage of the dechlorination reactor is connected with an air floatation oil removal device 8 and can enable desulfurization wastewater after reaction at all stages to enter the air floatation oil removal device, the air flotation oil removing device is connected with the resin buffer storage tank and can enable liquid resin carried out by air bubbles in the air flotation oil removing device to be scraped and conveyed into the resin buffer tank, and the air flotation oil removing device can recycle the treated reuse water.

The first-stage dechlorination reactor is connected with a waste water storage tank.

An acid regulating sedimentation tank capable of treating sediments generated in the separation process is arranged between the primary reactor and the secondary reactor or between the secondary reactor and the tertiary reactor, the sediments are subjected to clarification and sedimentation treatment through the acid regulating sedimentation tank, then supernatant subjected to clarification and sedimentation treatment enters the next-stage dechlorination reactor, and the sediments subjected to clarification and sedimentation treatment are conveyed to a desulfurization system through a sludge discharge pump.

The liquid resin buffer tank is connected with a regeneration reactor and can make liquid resin in the liquid resin buffer tank enter into a regeneration reactor stirring chamber, the regeneration reactor is provided with an input port, an output port and a separation port, the input port of the regeneration reactor is connected with the output port of a regeneration agent storage tank capable of injecting regeneration agents into the regeneration reactor, the output port of the regeneration reactor is connected with the input port of the regeneration agent storage tank, the separation port of the regeneration reactor is connected with an inlet of a resin acidification tank, and an outlet of the resin acidification tank is connected with the resin storage tank and can reflux the liquid resin after the acidification treatment to the resin storage tank.

The dechlorination reactors at all levels comprise dechlorination reaction tanks and dechlorination stirring chambers and dechlorination separation chambers which are arranged in the dechlorination reaction tanks and are separated by partition boards, a waste water storage tank 18 is connected at the bottom of a first-level dechlorination reactor, the dechlorination separation chamber of the dechlorination reactor at the front level is connected with the dechlorination stirring chamber of the dechlorination reactor at the rear level in series, a resin inlet is arranged at the bottom of the dechlorination stirring chamber of the dechlorination reactor at all levels, the dechlorination separation chamber of the dechlorination reactor at the last level is connected with an inlet of an air floatation oil removing device, a resin outlet is arranged at the upper part of the dechlorination separation chamber of the dechlorination reactor at all levels, and the dechlorination separation chambers of the dechlorination reactors at all levels are connected.

The regeneration reactor comprises a regeneration reaction tank, and a regeneration stirring chamber and a regeneration separation chamber which are arranged in the regeneration reaction tank and are separated by a partition plate, wherein an input port of the regeneration reactor is arranged at the bottom of the regeneration stirring chamber, an output port of the regeneration reactor is arranged at the bottom of the regeneration separation chamber, and a resin separation port of the regeneration reactor is arranged at the middle upper part.

All be provided with VOC gas collection processing apparatus on each level reactor, air supporting deoiling device, resin storage tank, the resin buffer tank, collect the adsorption filtration processing through this VOC gas collection processing apparatus to the VOC gas that liquid resin produced, the gas after the processing discharges in the air, reaches the filler of saturation and carries out regeneration treatment or mixes to burn as the fuel in the buggy.

A multi-impeller stirrer is arranged in a dechlorination stirring chamber 16 of each dechlorination reactor.

The resin acidification tank comprises a tank body and a stirrer arranged in the tank body, a sulfuric acid inlet connected with a sulfuric acid storage tank and a resin inlet connected with a regeneration reactor are arranged at the bottom of the tank body, and an outlet connected with the resin storage tank is arranged at the upper part of the tank body.

The invention has the advantages that:

1. the reaction of the whole process is only the steps of stirring, mixing and separating, the process is simple, the system connection is convenient, the operation and maintenance are convenient and simple, the on-line monitoring can be realized, and the on-site unattended operation is realized; the equipment investment is small, the operation cost is low, the produced water after the chloride ions are removed can meet the requirement of industrial water recycling, no waste is generated in the treatment process, the real-time adsorption and real-time regeneration are realized in the reaction process, the whole process is continuously operated, waiting and delaying are not needed, and the production efficiency is high;

2. due to the reasonable design of the whole process steps, the whole process has strong treatment capacity, the efficiency of removing chloride ions is more than 99%, the chloride ions can be removed by 100% on the premise of process requirements, in addition, the hardness in the wastewater is also better removed, and the method is a better choice for realizing zero discharge of the desulfurization wastewater;

3. the liquid resin is prepared by mixing one or more organic chemicals of phenols, alcohols, aldehydes, amines, organic oil, cross-linking agents and the like, has strong adsorption capacity and large saturated adsorption capacity, can adsorb chloride ions more than 15 ten thousand mg/l, has strong selectivity to chloride ions, and only adsorbs chloride ions and has no adsorption effect on sulfate ions when chloride ions and sulfate ions simultaneously exist in the desulfurization wastewater; the resin can contain more chloride ions, the chloride ions can be completely removed through multi-stage treatment, and the reaction stages can be set as required, so that low-cost operation is realized;

4. the raw materials of the resin formula are conventional products in the market, the raw materials are used without limitation, large-scale production and transportation can be realized, the loss of the liquid resin in the operation is very little, the annual operation loss rate is very low, the operation condition can be met by adding a very small amount (not more than 0.5%) of the liquid resin every year, and the operation cost is low; the regeneration medicament used for resin regeneration is also a conventional medicament, the price is low, and the overall production cost is low;

5. for the whole set of equipment, the blocking design can be prized, the modular assembly is realized, the treatment capacity is not limited, the equipment is a low-pressure system, all reactions are finished at normal temperature and normal pressure, the heating and pressurizing treatment is not needed, and the operation cost is low;

6. the equipment is arranged outside a main system of a factory, can independently operate, has no influence on the operation of a boiler, has low investment cost per ton of water, is far lower than the cost of the traditional evaporative crystallization and bypass flue evaporation process, and different products are selected as end products according to the needs of the owner, so that the water recycling is realized, the products are effectively recycled, the value of the final product is high, and no solid waste or hazardous waste is generated in the whole process.

Drawings

FIG. 1 is a flow chart of a dechlorination treatment method of desulfurization waste water according to the present invention.

Detailed Description

The desulfurization waste water dechlorination treatment method and the desulfurization waste water treatment equipment of the present invention will be further described in detail with reference to the accompanying drawings and the specific embodiments.

The first embodiment is as follows:

as shown in the figure, the dechlorination treatment method of the desulfurization waste water of the embodiment is taken as a basic treatment means, and comprises the following steps:

A. firstly adding acid into the desulfurization waste water which is taken from a cyclone or taken from a triple box to adjust the pH value to 0.5-4, then leading the desulfurization waste water to enter a stirring chamber of a primary dechlorination reactor to be stirred and mixed with liquid resin, stirring the mixture for 1-10 minutes and then leading the mixture to enter a corresponding separation chamber in the step, namely leading the desulfurization waste water to be pretreated by a triple box before the desulfurization waste water enters the stirring chamber of the primary dechlorination reactor, wherein calcium ions are recommended to be removed in the pretreatment, sodium carbonate is added into a triple box reaction tank to remove most of the calcium ions in the waste water, and then taking water from a clear water tank after the triple box treatment, wherein the selected liquid resin is formed by mixing one or more organic chemicals such as ethers, lipids, phenols, hydrocarbons, alcohols, aldehydes, amines, oil organic compounds, cross-linking agents and the like, and is characterized in that the method can selectively complex the chloride ions in the waste water, the device has no complexing ability or weak complexing ability on other negative inorganic ions, the single-stage complexing ability of chloride ions is more than 80%, the removing ability of chloride ions after multi-stage treatment reaches more than 98%, the stirring chamber of the first-stage dechlorination reactor and the corresponding separation chamber in the step can adopt a split structure or an integrated structure, the integrated structure is that the stirring chamber and the separation chamber are directly arranged on the first-stage dechlorination reactor, the split structure is that the separation chamber is independently used as a part connected with the first-stage dechlorination reactor, and the subsequent dechlorination reactors at all stages can also adopt the same structure;

C. the separated liquid resin with chloride ions absorbed enters a liquid resin buffer tank to complete the first-stage reaction, and the separated desulfurization wastewater is added with acid to adjust the pH value to 0.5-4 and enters a stirring chamber of a next-stage reactor for further treatment;

D. a, B, C steps are repeated in the treatment process (the difference lies in that no water is taken from a cyclone or new sulfuric acid is taken from a triple box, but the desulfurization wastewater separated from the previous stage is adopted as a treatment raw material), all chloride ions in the desulfurization wastewater after several stages of reactions are removed or enter an air flotation oil removing device to remove trace dissolved liquid resin in the desulfurization wastewater on the premise of reaching a set treatment value (0-2000mg/l), the PH is adjusted to 6-9 before the air flotation oil removing device, the desulfurization wastewater after air flotation treatment and PH adjustment is used as reuse water, for example, the reuse water can be directly reused in a water inlet process section of a conventional desulfurization process, the liquid resin brought out by bubbles floating up in the air flotation oil removing device is scraped by a scraping process and conveyed into a resin buffer tank for continuous treatment, and practice proves that the desulfurization wastewater with the concentration of less than 30000mg/l can be treated to 300mg by three-stage reaction The concentration of chloride ions can be reduced to 0-100mg/l by further treatment below l, and the calcium hardness in the desulfurization wastewater is greatly removed;

it should be noted that the liquid resin distributed from the resin storage tank is directly added into the stirring chamber of each stage of dechlorination reactor, preferably, alkali is added to adjust the pH value to 6-9 before the air-flotation oil removing device, and the desulfurization waste water after air-flotation treatment and alkali addition adjustment enters the clean water tank as reuse water.

And further, the desulfurization wastewater separated in the step B is subjected to precipitation in the treatment process because chloride ions in the original desulfurization wastewater are adsorbed into liquid resin, and precipitates are generated in the treatment process, so that the precipitates generated in the separation process are treated through an acid regulating settling tank between a first-stage dechlorination reactor and a second-stage dechlorination reactor or between the second-stage dechlorination reactor and a third-stage dechlorination reactor, redundant calcium ions and sulfate ions are removed, the precipitates are subjected to clarification and precipitation treatment through the acid regulating settling tank, supernatant subjected to clarification and precipitation treatment enters a next-stage dechlorination reactor, and the precipitates subjected to clarification and precipitation treatment are conveyed to a desulfurization system vacuum belt conveyor through a sludge discharge pump for further treatment or are directly conveyed outside after being compressed through a filter press for treatment.

Example two:

the embodiment is a technical scheme which is further improved on the basis of the first embodiment, and can realize better treatment functions, specifically, liquid resin entering a liquid resin buffer tank continuously enters a resin regeneration process section, the regeneration process section is also an important program for realizing zero emission industrialization of desulfurization wastewater, a regeneration medicament is added into a regeneration reactor stirring chamber of the resin regeneration process section while the liquid resin entering the liquid resin buffer tank continuously enters the regeneration reactor stirring chamber of the resin regeneration process section, chloride ions in the liquid resin are released into the regeneration medicament, the chloride ions react with the regeneration medicament to generate a chloride solution, a mixed solution of the chloride solution and the liquid resin generated after mixing and stirring enters a separation chamber of the process section, the separation is carried out through the specific gravity difference between the liquid resin and the regeneration medicament, the separated liquid resin enters a resin acidification tank for acidification treatment, the liquid resin after acidification treatment flows back to the resin storage tank, chlorine salt solution generated by reaction of chloride ions and the regeneration medicament enters the regeneration medicament storage tank, the chlorine salt solution is crystallized and precipitated after being continuously increased and concentrated in the regeneration medicament storage tank to reach supersaturated concentration, the precipitated crystal is chlorine salt crystal formed under the supersaturated concentration, the chlorine salt crystal is discharged out of the regeneration medicament storage tank, meanwhile, new regeneration medicament with the same volume is added into the regeneration medicament storage tank, and the regeneration medicament mixed liquid in the regeneration medicament storage tank circularly enters a stirring chamber of the regeneration reactor.

Wherein, the regeneration medicament that selects for use in this embodiment is alkaline earth's hydroxide solution or aqueous ammonia, configures the solution of different concentrations as required, and the regeneration product has formed corresponding alkaline earth's chloride or ammonium chloride owing to absorbed the chloride ion, for example: when the regeneration agent is sodium hydroxide, calcium hydroxide and ammonia water, the partial crystal is sodium chloride, calcium chloride and ammonium chloride, wherein the sodium chloride can be used as a salt chemical raw material, the ammonium chloride can be used as a landscaping raw material, a fertilizer plant raw material, an electroplating plant reducing agent, and the calcium chloride can be used as a snow melting agent or a drying agent, so that the comprehensive utilization of the product is realized.

Further, in the process of crystallization precipitation of the chlorine salt solution in the regeneration agent storage tank, a salting-out mode is adopted to promote the crystallization precipitation.

Example three:

the desulfurization wastewater treatment equipment of the embodiment comprises a plurality of stages of dechlorination reactors 4 which are connected in series and are provided with a resin inlet 1, a resin outlet 2 and a sulfuric acid inlet 3 (generally called as a connecting port), wherein the multistage dechlorination reactor 4 comprises N-stage dechlorination reactors such as a first-stage dechlorination reactor, a second-stage dechlorination reactor, a third-stage dechlorination reactor and a fourth-stage dechlorination reactor, only the first-stage dechlorination reactor is connected with a wastewater storage tank 18 through a wastewater feeding pump, in the embodiment, each stage of the dechlorination reactor 4 comprises a dechlorination reaction tank 15 and a dechlorination stirring chamber 16 and a dechlorination separation chamber 17 which are arranged in the dechlorination reaction tank and are separated by a partition plate, a multi-impeller stirrer is arranged in the dechlorination stirring chamber 16 of each stage of the dechlorination reactor, the wastewater storage tank 18 is connected to the bottom of the dechlorination stirring chamber 16 of the first-stage dechlorination reactor, the dechlorination separation chamber 17 of the previous-, the resin inlet 1 is arranged at the bottom of a dechlorination stirring chamber of each level of dechlorination reactor, the resin inlets of the dechlorination reactors 4 are simultaneously connected with a liquid resin storage tank 5 which can distribute and add liquid resin into the dechlorination reactors 4, the liquid resin storage tank 5 is connected with the resin inlets of the dechlorination reactors 4 through a new resin feeding pump, a resin outlet 2 is arranged at the upper part of a dechlorination separation chamber 17 of the dechlorination reactors 4, the dechlorination separation chamber 17 of the dechlorination reactors 4 is respectively connected with a resin buffer tank 6 through the resin outlet 2, the sulfuric acid inlet 3 of the dechlorination reactor is arranged on stirring chamber 16, the sulfuric acid inlet 3 of the dechlorination reactor is connected with a sulfuric acid storage tank 7 which is used for adding sulfuric acid into the dechlorination reactor through a sulfuric acid dosing pump, the dechlorination separation chamber 17 of the last dechlorination reactor is connected with an inlet of an air floatation oil removing device 8 and can enable the desulfurized wastewater after reacting in several levels to enter the air floatation oil removing device 8, the air flotation oil removing device 8 is composed of an air flotation reaction tank, a Venturi jet flow generator and a corresponding pump valve, the air flotation oil removing device is connected with the resin buffer storage tank 6 and can enable liquid resin carried out by bubbles in the air flotation oil removing device to be scraped and conveyed into the resin buffer tank 6, and the air flotation oil removing device 8 can recycle the treated reuse water.

Furthermore, precipitation is generated during the treatment process of the first-stage dechlorination reactor or the second-stage dechlorination reactor, an acid regulating sedimentation tank capable of treating the precipitate generated in the separation process is arranged between the first-stage dechlorination reactor and the second-stage dechlorination reactor or between the second-stage dechlorination reactor and between the third-stage dechlorination reactors, the precipitate is subjected to clarification and sedimentation treatment by the acid regulating sedimentation tank, supernatant subjected to clarification and sedimentation treatment enters the next-stage dechlorination reactor, and the precipitate subjected to clarification and sedimentation treatment is conveyed to the desulfurization system by a sludge discharge pump.

Example four:

in this embodiment, a regeneration reactor 9 is connected to the liquid resin buffer tank 6 through a buffer resin feed pump, and the liquid resin in the liquid resin buffer tank can be fed into a regeneration reactor stirring chamber, the regeneration reactor 9 has an input port 10, an output port 11 and a separation port 12, which are collectively referred to as connection ports, the regeneration reactor 9 in this embodiment includes a regeneration reaction tank 21, and a regeneration stirring chamber 19 and a regeneration separation chamber 20 which are provided in the regeneration reaction tank and partitioned by a partition plate, the input port of the regeneration reactor 9 is provided at the bottom of the regeneration stirring chamber 19, the output port of the regeneration reactor 9 is provided at the bottom of the regeneration separation chamber 20, the resin separation port of the regeneration reactor 9 is provided at the middle upper part of the regeneration separation chamber 20, the input port of the regeneration reactor 9 is connected to an output port of a regeneration agent storage tank 13 which can inject the regeneration agent into the regeneration reactor, an output port of the regeneration reactor 9 is connected with an input port of a regeneration agent storage tank 13, a separation port of the regeneration reactor 9 is connected with an inlet of a resin acidification tank 14, and an outlet of the resin acidification tank 14 is connected with the resin storage tank 5 and can return liquid resin after acidification treatment to the resin storage tank 5.

In addition, liquid resin can generate odor in the using process, VOC gas collecting and processing devices are arranged on each stage of reactor, air floatation oil removing device, resin storage tank and resin buffer tank, activated carbon particles or activated carbon fiber yarns are used as adsorption filler, VOC gas generated by the liquid resin is collected, adsorbed and filtered by the VOC gas collecting and processing devices, the processed gas is discharged into the air, and the saturated filler is regenerated or mixed into coal powder as fuel to be co-combusted; furthermore, the resin acidification tank comprises a tank body and an acidification stirrer arranged in the tank body, the bottom of the tank body is provided with a sulfuric acid inlet connected with a sulfuric acid storage tank and a resin inlet connected with a regeneration reactor, and the upper part of the tank body is provided with an outlet connected with the resin storage tank.

Finally, as for the dechlorination reactors 4 and the regeneration reactor 9 of each stage, in addition to the integrated structure design in the third and fourth embodiments, a split structure can be adopted, wherein the split structure of the dechlorination reactors 4 of each stage means that the separation chamber is separately used as a part connected with the dechlorination reactors of each stage, and the split structure of the regeneration reactor 9 means that the separation chamber is separately used as a part connected with the regeneration reactor.

Through the structural design, all levels of dechlorination reactors 4 are connected in series, liquid resin is conveyed in parallel, the liquid resin enters all levels of dechlorination reactors 4 from a resin storage tank respectively and then is treated for desulfurization wastewater, and the treated liquid resin enters a resin buffer tank for centralized storage and then is conveyed from the buffer tank to a regeneration process section for centralized regeneration; before entering the stirring chamber of each stage of dechlorination reactor 4, quantitative inorganic acid is required to be added to adjust the pH value, sulfate ions of the desulfurized wastewater are slightly increased after the desulfurized wastewater is treated, and the improvement of the desulfurization efficiency is facilitated.

The principle of the technology is as follows, which mainly comprises two stages:

1. removal stage

Adding concentrated sulfuric acid into the desulfurization wastewater, wherein the aqueous solution contains a large amount of monatomic ions such as H ions and Cl ions under the acidic condition that the pH value reaches 0.5-4; after the liquid resin is added, the resin uses lone pair electrons on atoms in the medicament and proton coordinated water molecules to compete for monoatomic ions, and the resin firstly competes with H⁺Then the chlorine ions are separated by chemical replacement because of the small molecular and high ionization degree of the chlorine ionsNow the chloride ions are removed.

The chemical reaction equation is as follows:

H₂SO₄→2H⁺+SO₄ ^2-······(1)

R+nH⁺+nCl^-→R·(HCl)n······(2)

wherein R is an organic component in the resin, Cl^-Is chloride ion in the wastewater.

2. Regeneration phase

The complex formed by the chloride ions and the resin has small binding force, so that the tail end is easy to separate. Under alkaline condition, the complex of chloride ion and resin reacts with alkali, the resin is regenerated, corresponding chloride is produced, and the cost of the medicament is comprehensively considered, and the priority is to adopt calcium hydroxide Ca (OH)₂As a regenerant, the reaction equation at this time is as follows:

2R·(HCl)n+nCa(OH)₂→2R+nCaCl₂+nH₂O······(3)

by combining the above 3 reaction equations, it can be seen that the resin is only the carrier and is not consumed, and the combined reaction equation is: h₂SO₄+2Cl^-+Ca(OH)₂→

SO₄ ^2-+CaCl₂+H₂O······(4)

Wherein, CaCl₂Crystallizing out at high concentration.

Pilot test is carried out on the desulfurization wastewater dechlorination treatment method

At present, the liquid resin method desulfurization wastewater dechlorination recycling technology is still mainly in a laboratory research stage, and a field full-flow test is still to be developed, so a pilot test system is planned to be built in a power plant to develop a full-system test research.

The maximum processing capacity of the pilot test device reaches 500L/h, the aim of achieving that the concentration of the effluent chloride ions is lower than 500mg/L is achieved, field PLC control is achieved, and the test research of not less than 2000 hours is completed.

A subsystem of the test apparatus is described below:

(1) waste water is extracted from a clean water tank behind a desulfurization waste water triple box, the waste water is lifted into a waste water buffer tank, the waste water buffer tank is arranged according to the treatment capacity of 6 hours, and the volume of the waste water buffer tank is 3m³The material is carbon steel lining rubber, the bottom is provided with a sludge discharge device, and the discharged sludge flows back to the slurry pool.

(2) The reaction device adopts a six-header device and consists of a 1-level, a 2-level, a 3-level dechlorination reaction tank, a first-level acid regulating settling tank, a regeneration reaction tank and a resin acidification regeneration reaction tank, all tank bodies are designed according to 160L, the tank bodies are made of UPVC, the dechlorination reaction tank consists of a stirring chamber and a separation chamber (see attached drawing), a bypass system is arranged behind the 2-level dechlorination reaction tank, the treated wastewater can be directly conveyed to an air floatation device for oil removal treatment, the 3-level reaction tank system is arranged to ensure that different treatment requirements are met, the actual requirement can be met by 2-level treatment, and the concentration of the chloride ions in the wastewater is 11000mg/L to be lower than 500 mg/L.

① dechlorination stirring chamber

The stirring time is set to be 2.5 minutes, a stirring device is arranged in the stirring device, an acid adding device is configured, concentrated sulfuric acid is added according to the water inlet volume of 1%, the PH value is adjusted to be 0.5-2, the rotating speed of the stirring device is set according to 400-600 rpm, two connectors are arranged at the bottom of the stirring device, and the connectors are set to be DN 50.

10L of resin and 20L of desulfurization wastewater in a stirring chamber of the single-stage dechlorination reaction tank.

② dechlorination separation chamber

The dechlorination separation chamber is provided with: the separation time is 2 minutes when the pilot test, for guaranteeing separation effect and furthest reduction aquatic contains resin and resin moisture content, dechlorination separating chamber volume sets up according to 8 minutes capacity, and the bottom is the slope awl end, sets up the connector, DN50, sets up the overflow mouth in separation resin liquid level 0.1m below the top, and the overflow mouth sets up according to DN 50.

The resin in the separation chamber of the single-stage dechlorination reaction tank is 42L, and the desulfurization waste water is 84L.

③ resin storage tank

The resin storage tank is arranged according to 2 times of the resin amount required by the system, and the resin storage tank is 2m³1.5m of resin in the initial state³Normal run time systemThe interior ensures that 500L of the resin is operated in the subsystem, and more than 1000L of the resin is kept in the resin storage tank.

④ sulfuric acid storage tank

Acid storage tank according to 5m³The arrangement ensures that the acid storage amount in the storage tank can ensure the amount of sulfuric acid required by more than one week of production, and the acid tank is made of carbon steel; the system is arranged according to four-stage treatment, the concentration of chloride ions is below 500mg/l after 2-stage treatment, the dosage of acid for the system treatment can be calculated according to 3% of the wastewater amount, the daily wastewater treatment amount is 12 tons, the daily consumption of sulfuric acid is 360kg, and the acid storage amount can be maintained for 10 days.

⑤ settling tank

A settling tank is arranged behind the stage 1 reaction tank, calcium sulfate precipitation can be generated after the first-stage dechlorination reaction tank or the second-stage dechlorination reaction tank due to calcium ions in the wastewater, and calcium ions and sulfate ions in the water are removed at the same time, so the settling tank is arranged behind the first-stage dechlorination reaction tank or the second-stage dechlorination reaction tank, the supernatant after settlement enters subsequent treatment, and the calcium sulfate deposited at the bottom returns to the traditional desulfurization system;

(3) regenerated medicament storage tank

The capacity of a regenerated medicament storage tank (calcium hydroxide solution) is 5m³The material is carbon steel lining rubber.

(4) Selection of delivery pumps

The desulfurization waste water lift pump is set to be 1t/h, the lift is 10m, the overflowing part is made of an anti-corrosion material, and the pump is small in capacity, so that the pump adopts a diaphragm dosing pump.

A resin delivery pump, a wastewater delivery pump and a regenerative medicament delivery pump in the system are all 1-500L (adjustable) diaphragm medicament feeding pumps, an overflowing part is made of an anticorrosive material, the flow rate is variable in frequency, and the lift is 5 m.

The acid-base dosing pump adopts a 0-10L/h electromagnetic metering pump, the frequency conversion is adjustable, and the overflowing part is made of an anticorrosive material.

(5) Air-float oil-removing and PH regulating tank

The concentration of chloride ions in the wastewater after the 2-stage treatment is below 500mg/l, and the PH of the wastewater is adjusted to 6-9 by adding calcium hydroxide to meet the requirement of the subsequent PH treatment; contain trace resin in the waste water, the resin is oily liquid, need handle through the air supporting and reach the deoiling purpose, the air supporting generator is venturi fluidic device, produce nanometer air supporting, tiny oil drips in the waste water from aquatic come-up to air supporting pond surface and strike off through the load effect of microbubble, the air supporting pond adopts integrated equipment, the resin that strikes off contains water, it stores to get into the air supporting waste water tank, the waste water in the waste water tank after the separation of standing, the resin after the separation flows back to the resin buffer tank, waste water flows back to the air supporting pond and intakes the end, waste water after PH adjusts is handled through the air supporting and is got into the clear water tank and store and go into the retrieval and.

(6) Alkali storage tank

The alkali (regeneration agent) storage tank is filled with calcium hydroxide solution, the pH value of the solution is 14, the alkali storage tank is connected with an alkali dosing pump, and the alkali liquor and the wastewater are uniformly mixed under the action of air flotation.

(7) Clean water tank

The clear water tank is set to be 1m³The water storage capacity of 2 hours is met, the material is carbon steel lining rubber, and the treated wastewater enters a clear water tank for storage and is ready to be recycled.

A float flowmeter and a PH meter are arranged on the pipeline as required; valves, pipe fittings local control boxes are arranged according to requirements, and contact terminals, contactors and the like are contained in the boxes.

The equipment list is as follows.

Running cost of test stage

The pilot plant test apparatus was operated for 2000 hours, and the estimated amounts and costs of the acid and base reagents were as follows:

the operation is carried out for 2000 hours, the treated water amount in 2000 hours is 1000t according to 500L of treated water amount per hour, the content of chloride ions in wastewater is 11000mg/L, the chloride ions are all removed to be below 500mg/L, 2-stage reaction is needed, 1% of sulfuric acid is added in each stage of reaction, 2% of sulfuric acid is needed to be added in the 2-stage reaction, 1% of sulfuric acid is needed to be added in resin acidification, the total amount of sulfuric acid added is 3% of the treated water amount, 11.7 tons of calcium hydroxide are needed to be added when the produced water is neutralized to 6-9, and 12.5 tons of calcium hydroxide are needed to be added for resin regeneration, so the total amount of the required calcium hydroxide is; when the maximum loss rate of the resin is not more than 0.5%, the maximum loss amount is 1.5 × 0.5% — 0.0075 ton.

The ton water treatment cost is shown in the following table:

unit: yuan/ton water

Name of medicament	Medicine adding amount (ton)	Univalent (Yuan/t)	Price per ton of water
				Concentrated sulfuric acid	30	800	24
Calcium hydroxide	24.5	480	11.76
				Resin loss	0.0075	180000	1.35
Total amount of drug			37.11
					Total power consumption (kwh)	Station service (Yuan/kwh)
Electric charge	23800	0.4	9.52
				Running cost totalization			46.63

Wherein, the system electric power is estimated to be 11.9kW, and the statistics are shown in the following table:

serial number	Name (R)	Unit of	Number of	Single machine power/kW	Power/kW
						1	Water pump	Table (Ref. Table)	18	0.55	9.9
2	Acid-base dosing pump	Table (Ref. Table)	3	0.1	0.3
						3	Stirrer	Table (Ref. Table)	4	0.4	1.6
4	Air floatation device	Sleeve	1	1.1	1.1
							Power summing				11.9

In conclusion, the estimated direct cost of wastewater treatment is 46.63 yuan/ton of water, and because the addition amount of the medicament is based on laboratory data and part of the addition amount of the medicament is excessive, the addition amount of part of the medicament in actual production is reduced to a certain extent, and the production cost is possibly reduced. In addition, in order to clearly express the effect thereof, the inventors provided the following experimental reports:

the desulfurization wastewater treatment test reports of the power plant are as follows:

in 2019, experiments of zero emission of desulfurization wastewater were carried out from 22 days of 10 months to power generation limited company, and the concentration of raw water chloride ions in the desulfurization wastewater of the plant is 13661mg/l

Test time and test personnel

Year 2019, month 10, day 22, half a day; luscious environment, power generation, laboratory personnel;

adopts the process flow

Three-stage reaction and one-stage regeneration are adopted for processing, and sampling and assay are carried out after the processing.

The test condition

The test is an incomplete working condition and is only carried out aiming at water taking under the current condition;

description of the test procedure:

taking 200l of desulfurized wastewater for testing, treating the desulfurized wastewater according to the ratio of 1:1 of liquid resin to treated water, adding 1% of inorganic acid into the water to adjust the pH value before treatment, mixing the wastewater after the pH value adjustment with the liquid resin, placing the mixture in a stirrer for stirring at the stirring speed of about 350rpm for 4 minutes, placing the mixture in a liquid separation bottle for separation after the stirring is finished, performing secondary treatment after the separated water sample is subjected to filtration treatment, and performing three-stage circulation of the process, wherein each stage of sampling is performed for assay; except that the first stage adds acid and is 1%, each level of later processing adds the acid quantity and is 0.5%, carries out regeneration treatment with liquid resin after the processing is accomplished, and regeneration liquid resin is 25% sodium hydroxide solution, and liquid resin needs to carry out acidizing after regeneration, adds 1% inorganic acid and enters the storage tank and stores after stirring.

6. Test knot

1) After the three-stage reaction treatment, the concentration of chloride ions is 209.4mg/l, and the chloride ions can directly enter a water inlet process section of the desulfurization water process;

2) precipitate exists in the produced water after the reaction, and the precipitate is calcium salt precipitate; the removal rate of the chloride ions is close to 100 percent, the ratio of the liquid resin to water can be reduced in subsequent tests, the usage amount of the liquid resin is reduced, and the treatment efficiency is improved;

3) the liquid resin after acidification treatment enters a storage state so as to carry out next-stage treatment.

4) Liquid resin brought by the stage on site is recycled by dozens of stages, and the properties of the liquid resin are not obviously changed, so that the requirement of recycling treatment is met;

7. to summarize:

the desulfurization wastewater of the power generation Limited company is treated by adopting a liquid resin treatment process to remove chloride ions, the removal efficiency is higher than 98 percent, and meanwhile, the desulfurization wastewater also has a certain effect on removing calcium ions;

the desulfurization waste water adopts a liquid resin treatment process for dechlorination and decalcification, so that unattended operation can be realized, the direct operation cost is lower than 30 yuan/ton of water, the total equipment investment is not more than 700 million calculated according to 10 tons/H of desulfurization waste water of deep energy power generation limited company, the operation cost is far lower than that of an evaporative crystallization and flue evaporation process, water is recycled in a produced water recycling and desulfurization process section, the water taking cost can be greatly reduced, the desulfurization efficiency can be greatly improved, and the method is the best process selection at present for zero emission treatment of desulfurization waste water.

The report made on the desulfurization wastewater dechlorination treatment test in the hebei thermoelectric test is as follows:

dechlorination experiment of the desulfurized wastewater is carried out from Zhenjiang environmental science and technology Limited to Hebei by thermoelectricity in 10 months and 25 months in 2019, and the concentration of chloride ions in the raw water of the desulfurized wastewater is about 22000 mg/l.

Test time and test personnel

10 and 25 months in 2019, half a day. Moist environment, hebei thermoelectric laboratory personnel;

adopts the process flow

The test condition

description of the test procedure:

taking 200l of desulfurization wastewater for testing, treating the desulfurization wastewater according to the ratio of 1:2 of liquid resin to treated water, adding 1% of inorganic acid into the water to adjust the pH value before the first-stage treatment, mixing the wastewater after the pH adjustment with the liquid resin, placing the mixture in a stirrer for stirring at the stirring speed of about 350rpm for 4 minutes, placing the mixture in a liquid separation bottle for separation after the stirring is finished, performing second-stage treatment after the separated water sample is subjected to filtration treatment, circulating the process for three stages, and sampling each stage for testing; except that the first stage adds acid and is 1%, each level of later processing adds the acid quantity and is 0.5%, carries out regeneration treatment with liquid resin after the processing is accomplished, and regeneration liquid resin is 25% sodium hydroxide solution, and liquid resin needs to carry out acidizing after regeneration, adds 1% inorganic acid and enters the storage tank and stores after stirring.

Test knot

1) After the three-stage reaction treatment, the concentration of chloride ions is 170mg/l, the water inlet requirement of the desulfurization wastewater process is met, and the wastewater can directly enter a desulfurization water process water inlet process section;

to summarize:

the desulfurization wastewater produced by performing test production on Hebei and thermoelectricity is treated by a liquid resin treatment process to remove chloride ions, the treatment process is three-stage reaction plus first-stage regeneration, the removal efficiency of the chloride ions is 99.2%, and meanwhile, the removal effect on calcium ions is also certain;

the method has the advantages that the thermoelectricity desulfurization waste water in Hebei can realize unattended operation by adopting a liquid resin treatment process for dechlorination and decalcification, the direct operation cost is lower than 30 yuan/ton of water, the total equipment investment is not more than 700 million calculated according to 10 tons/H of thermoelectricity desulfurization waste water in Tangshan of Hebei construction, the total equipment investment is far lower than that of the thermoelectricity desulfurization waste water in Hebei construction, the method adopts evaporative crystallization and flue evaporation processes, water production recycling and water inlet of a desulfurization process section, the water taking cost can be greatly reduced, the desulfurization efficiency can be greatly improved, and the method is the best process selection for zero emission treatment of the desulfurization waste.

The report of the dechlorination treatment test of the production recycle water by Binzhou chemical industry is as follows:

10 and 30 months in 2019, which is half a day. Moist environment, chemical plant length, chemical laboratory personnel;

1. adopts the process flow

The first-stage reaction and the first-stage regeneration are adopted for processing, and sampling and testing are carried out after the processing.

2. The test condition

3. description of the test procedure:

taking 200L of chemical circulating water for testing, treating according to 1:2 of liquid resin and treated water, adding 1% of inorganic acid into the water to adjust the PH before the first-stage treatment, mixing the wastewater after the PH adjustment with the liquid resin, placing the mixture in a stirrer for stirring at the stirring speed of about 350rpm for 4 minutes, separating after the stirring is finished, taking a water sample for testing after the separation, and testing by adopting a raw water sample test and a test after 20 times of dilution; and after the treatment is finished, carrying out regeneration treatment on the liquid resin, wherein the regenerated liquid resin is 25% sodium hydroxide solution, the liquid resin needs to be acidified after being regenerated, and 1% inorganic acid is added to be stirred and then enters a storage tank for storage.

6. Test knot

1) After treatment, the concentration of chloride ions is 0.2mg/l, the chloride ions are almost completely removed, and the produced water can directly enter a water inlet process section of a circulating water process;

2) precipitate exists in the produced water after the reaction, and the precipitate is calcium salt precipitate; for the circulating water, the removal rate of chloride ions is close to 100%, the ratio of liquid resin to water can be reduced in subsequent tests, the use amount of the liquid resin is reduced, and the treatment efficiency is improved;

the circulating water is subjected to dechlorination and decalcification processes by adopting a liquid resin treatment process, so that unattended operation can be realized, the direct operation cost is lower than 3 yuan/ton of water, the production process and the production cost can be further optimized in a later test, the actual cost is verified in the project design, the produced water can be directly recycled, the water taking cost is greatly reduced, the circulating water heat exchange efficiency can be greatly improved, and the method is the best process selection for circulating water zero-discharge treatment at present.

Claims

1. A desulfurization wastewater dechlorination treatment method, comprising the following steps:

A. First add acid to the desulfurization wastewater to adjust the pH value to 0.5-4 and then enter the stirring chamber of the first-stage dechlorination reactor to stir and mix with the liquid resin;

B, the mixture after stirring and mixing in step A is separated in the separation chamber by the density difference between the desulfurization wastewater and the liquid resin, and the chloride ion of the separated desulfurization wastewater is adsorbed into the liquid resin;

C, the liquid resin adsorbed with chloride ions after separation enters the liquid resin buffer tank, and the separated desulfurization wastewater enters the stirring chamber of the next stage reactor for further processing;

D. Repeat steps A, B, and C in the treatment process. After several stages of reaction, the chloride ions in the desulfurization wastewater are completely removed or enter the air flotation degreasing device to remove the liquid resin dissolved in water under the premise of reaching the set treatment value. , before the air flotation degreasing device, adjust the pH to 6-9, and the desulfurization wastewater treated by air flotation and pH adjusted is used as reuse water. removed and transported to the resin buffer tank.

2 . The method for dechlorination of desulfurization wastewater according to claim 1 , wherein the liquid resin directly distributed from the resin storage tank is added into the stirring chambers of the dechlorination reactors at all levels. 3 .

3. according to the described desulfurization wastewater dechlorination treatment method of claim 1 and 2, it is characterized in that: between one-level dechlorination reactor and two-level dechlorination reactor or between two-level dechlorination reactor and three-level dechlorination reactor Between the chlorine reactors, the precipitates produced in the separation process are treated by the acid-conditioning settling tank to remove part of calcium ions and sulfate ions. The supernatant liquid enters the next-stage dechlorination reactor, and the sediment after clarification and precipitation is transported to the desulfurization system through the sludge pump.

4. according to the desulfurization wastewater dechlorination treatment method of claim 3, it is characterized in that: the liquid resin entering the liquid resin buffer tank continues to enter into the regeneration reactor stirring chamber of the resin regeneration process section, and simultaneously stirs the regeneration reactor The regeneration agent is added to the room for stirring and mixing, the chloride ions in the liquid resin are released into the regeneration agent, and the chloride ions react with the regeneration agent to form a chloride salt solution. After mixing and stirring, the mixture of the chloride salt solution and the liquid resin enters here In the separation chamber of the process section, the liquid resin is separated by the difference in specific gravity between the liquid resin and the regeneration agent. The separated liquid resin enters the resin acidification tank for acidification treatment, and the acidified liquid resin returns to the resin storage tank.

5. The desulfurization wastewater dechlorination treatment method according to claim 4, characterized in that: the chloride salt solution generated by the reaction of chloride ions and the regeneration agent enters the regeneration agent storage tank, and the chloride salt solution passes through the regeneration agent storage tank continuously. After increasing the concentration to supersaturated concentration, crystallization occurs, and the precipitated crystals are chloride salt crystals formed under supersaturated concentration. The chloride salt crystals are discharged from the regeneration agent storage tank, and at the same time, a new regeneration agent of the same volume is added to the regeneration agent storage tank. , the regeneration agent mixture in the regeneration agent storage tank is circulated into the stirring chamber of the regeneration reactor.

6. according to the described desulfurization wastewater dechlorination treatment method of claim 4 or 5, it is characterized in that: described regeneration agent is the hydroxide solution of alkaline earth metal or ammoniacal liquor, and the regeneration product is the chloride or ammonium chloride of corresponding alkaline earth metal .

7. The method for dechlorination of desulfurization wastewater according to claim 5, characterized in that: in the process of crystallization and precipitation of chlorine salt solution in the regenerating agent storage tank, a salting-out method is adopted to promote crystallization.

8. according to the desulfurization wastewater dechlorination treatment method described in claim 1,2,4,5 or 7, it is characterized in that: before the air flotation degreasing device, first add alkali to adjust pH to 6-9, and by air flotation treatment and The desulfurization wastewater adjusted by adding alkali enters the clean water tank as reuse water.

9. The method for dechlorination of desulfurization wastewater according to claim 8, wherein the liquid resin is composed of ethers, lipids, phenols, hydrocarbons, alcohols, aldehydes, amines, oil organic compounds , Cross-linking agent and one or more organic chemicals are mixed.

10. A desulfurization wastewater treatment equipment, characterized in that it comprises a multi-stage dechlorination reactor (4) connected in series with a resin inlet (1), a resin outlet (2) and a sulfuric acid inlet (3). The resin inlets of the dechlorination reactors (4) are simultaneously connected to the resin storage tanks (5) capable of distributing and adding liquid resin to the dechlorination reactors of all levels, and the resin outlets of the dechlorination reactors of all levels are simultaneously connected to the resin buffer tanks. (6), the sulfuric acid inlets of the dechlorination reactors at all levels are connected with sulfuric acid storage tanks (7) for adding sulfuric acid to the dechlorination reactors at all levels, and the dechlorination reactors at the last level are connected to the air flotation reactor. The degreasing device (8) is connected and can make the desulfurization wastewater after several stages of reaction enter into the air flotation degreasing device (8), which is connected with the resin buffer storage tank (6) and can make the air flotation degreasing device (8). The liquid resin carried by the floating bubbles in the degreasing device is scraped off and transported to the resin buffer tank (6). The air flotation degreasing device (8) is capable of reusing the treated water.

11. The desulfurization wastewater treatment facility according to claim 10, wherein: between the primary dechlorination reactor and the secondary dechlorination reactor or between the secondary dechlorination reactor and the tertiary dechlorination reactor There is an acid-conditioning settling tank that can process the precipitate produced in the separation process. The precipitate is clarified and precipitated by the acid-conditioning settling tank, and the supernatant liquid after the clarification and settling process is entered into the next stage of dechlorination. In the reactor, the sediment after clarification and precipitation treatment is transported to the desulfurization system through the sludge pump.

12. The desulfurization wastewater treatment equipment according to claim 11, characterized in that: the liquid resin buffer tank (6) is connected with a regeneration reactor (9) and enables the liquid resin in the liquid resin buffer tank to enter the regeneration reaction Inside the stirring chamber of the reactor, the regeneration reactor (9) has an input port (10), an output port (11) and a separation port (12), and the input port of the regeneration reactor (9) is connected to a The output port of the regeneration agent storage tank (13) into which the regeneration agent is injected, the output port of the regeneration reactor (9) is connected with the input port of the regeneration agent storage tank (13), and the separation port of the regeneration reactor (9) is connected with a The inlet of the resin acidification tank (14), the outlet of the resin acidification tank (14) is connected to the resin storage tank (5) and can return the acidified liquid resin to the resin storage tank (5).

13 . The desulfurization wastewater treatment equipment according to claim 12 , wherein the dechlorination reactors ( 4 ) at all levels include a dechlorination reaction tank ( 15 ) and a separator provided in the dechlorination reaction tank. 14 . The dechlorination stirring chamber (16) and the dechlorination separation chamber (17) are separated, and the waste water storage tank (18) is connected to the bottom of the first stage dechlorination reactor, and the dechlorination separation of the dechlorination reactor in the previous stage The chamber (17) is connected in series with the dechlorination stirring chamber (16) of the dechlorination reactor of the next stage, and the resin inlet (1) is arranged at the bottom of the dechlorination stirring chamber of the dechlorination reactor of the last stage. The dechlorination separation chamber (17) of the dechlorination reactor is connected to the inlet of the air flotation degreasing device, and the resin outlet (2) is arranged at the upper part of the dechlorination separation chamber (17) of the dechlorination reactors (4) at all levels , the dechlorination separation chambers (17) of the dechlorination reactors (4) at each stage are connected to the resin buffer tank (6) through the resin outlet (2).