WO2019144631A1

WO2019144631A1 - Stainless steel pickling wastewater treatment system

Info

Publication number: WO2019144631A1
Application number: PCT/CN2018/105804
Authority: WO
Inventors: 余章军
Original assignee: 福建欣宇卫浴科技股份有限公司
Priority date: 2018-01-26
Filing date: 2018-09-14
Publication date: 2019-08-01
Also published as: CN108046480A

Abstract

A stainless steel pickling wastewater treatment system (1), comprising a mixed acid pickling wastewater treatment system and a sulfuric acid pickling wastewater treatment system. The sulfuric acid pickling wastewater treatment system comprises a first filtering device (103), a first pH conditioning tank (104), a first concentration membrane device (105), a first demanganization reaction tank (106), a second demanganization reaction tank (107), a second concentration membrane device (108), a second pH conditioning tank (113), a third concentration membrane device (114), and a first collection tank (117) that are sequentially communicated; the mixed acid pickling wastewater treatment system comprises a second filtering device (203), a third pH conditioning tank (204), a fourth concentration membrane device (205), a third demanganization reaction tank (206), a fourth demanganization reaction tank (207), a fifth concentration membrane device (208), a fourth pH conditioning tank (209), a sixth concentration membrane device (210), a defluorination reaction tank (211), a seventh concentration membrane device (212), and a resin adsorption and purification device (222) that are sequentially communicated. The stainless steel pickling wastewater treatment system (1) can completely recycle metallic ions from pickling wastewater of different kinds of stainless steel, and use same in a stainless steel production process, thereby effectively solving the problem of resource waste.

Description

Stainless steel pickling wastewater treatment system

Cross-reference to related applications

The present application claims priority to Chinese Patent Application No. 201810076987.3, entitled "Stainless Steel Pickling Wastewater Treatment System", filed on Jan. 26, 2018, the entire contents of which is incorporated herein by reference.

Technical field

The present application relates to the field of wastewater treatment technology, and in particular to a stainless steel pickling wastewater treatment system.

Background technique

Stainless steel is widely used for its excellent corrosion resistance and good appearance. In the production process, stainless steel is inevitably subjected to annealing, normalizing, quenching, welding and other processes, and the surface often produces black scale. The scale not only affects the appearance quality of the stainless steel, but also adversely affects the subsequent processing of the product. Therefore, it must be removed by surface treatment such as pickling or polishing before subsequent processing.

Iron oxide scale is formed on the surface of stainless steel, and its main components are FeO, Fe ₂ O ₃ , NiO, Cr ₂ O ₃ , Fe ₃ O ₄ , FeO·Cr ₂ O ₃ , Ni·Fe ₂ O ₃ , FeO·Cr ₂ O ₃ - a dense oxide such as Fe ₂ O ₃ , MnO or Mn ₂ O ₃ . These oxides have strong adhesion. In the treatment process of shot blasting, high-temperature alkali etching, molten salt electrolysis, mixed acid pickling, multi-stage rinsing, etc., it is inevitable to discharge neutral salt wastewater, acid-containing wastewater, and A plurality of pickling and rinsing wastewaters such as fluoro mixed acid wastewater.

In the pickling process of stainless steel, the surface of the scale is generally firstly washed with sulfuric acid to remove the scale, and then pickled with 90-160 g/L of nitric acid and 50-60 g/L of hydrofluoric acid mixed acid. Nitric acid with strong oxidizing properties can oxidize metals and metal oxides to form Cr ³⁺ , Fe ³⁺ , Fe ²⁺ and/or Mn ³⁺ , Mn ^{2+ ,} etc. These metal ions (especially Cr ³⁺ , Fe) ²⁺ , Fe ³⁺ , Mn ^{2+ ,} and Mn ^{3+ ,} etc.) and nitric acid and hydrofluoric acid form stable compounds. During the multi-stage rinsing process, the above acid and metal ions enter the rinsing water to form pickling wastewater.

For the treatment of such pickling wastewater, the most common one is lime neutralization single-step precipitation. The neutralization method is simple and easy, but there are problems such as unstable and high fluoride ion concentration in the effluent, large sludge volume, and high treatment cost.

Under normal circumstances, the sludge produced by the existing wastewater treatment facilities has a water content of about 50%. Of the 50% of the solid materials remaining after removing the water, the effective components account for about 65%, and the ineffective components of the waste materials. About 35%. If these solid waste materials are recycled into the stainless steel production process, not only waste energy, waste of raw materials, waste of production line capacity, waste of manpower, reduction of production line output rate, but also adverse effects on production processes and product quality.

Application content

In view of this, the stainless steel pickling wastewater treatment system provided by the present application can at least better overcome the problems and defects of the prior art described above, and is safe, stable, simple to operate, and convenient to manage stainless steel pickling wastewater treatment. The system can be processed at the same time by separating the acid pickling wastewater and the sulfuric acid pickling wastewater, or it can be treated separately according to the actual production conditions, and the metal ions in the series of stainless steels of 200, 300 and 400 can reach 100. % recycling, F ^- ion can also be recycled, and reduce environmental pollution, and make wastewater resources, solve the problem of recycling of stainless steel pickling wastewater, achieve the effect of "comprehensive comprehensive management", and reduce the production cost of enterprises.

A stainless steel pickling wastewater treatment system, comprising a sulfuric acid pickling wastewater treatment system and a mixed acid pickling wastewater treatment system;

The sulfuric acid pickling wastewater treatment system comprises a first filtering device, a first pH adjusting tank, a first concentration membrane device, a first manganese removal reaction tank, a second manganese removal reaction tank, a second concentration membrane device, and a first communication device. a second pH adjusting tank, a third concentrated membrane device and a first collecting tank, wherein the fresh water outlet of the first concentrated membrane device is in communication with the first manganese removal reaction tank, and the concentrated water outlet of the first concentrated membrane device is connected to the first a filter press, the sludge outlet of the first filter press is connected to the first calciner, the water clear of the second concentrated membrane device is in communication with the second pH adjusting tank, and the second concentrated membrane device is thick The nozzle is connected to the second filter press, the sludge outlet of the second filter press is connected to the second calciner, and the water outlet of the third concentrated membrane device is in communication with the first collection tank, the third condensation The concentrated water inlet of the membrane device is connected to a third filter press, and the sludge outlet of the third filter press is connected to the third calciner;

The mixed acid pickling wastewater treatment system comprises a second filtering device, a third pH adjusting tank, a fourth concentrated membrane device, a third manganese removal reaction tank, a fourth manganese removal reaction tank, a fifth concentrated membrane device, and a second a fourth pH adjusting tank, a sixth concentrated membrane device, a fluorine removal reaction tank, a seventh concentration membrane device, a resin adsorption purification device and a second collection tank, the water outlet of the fourth concentration membrane device and the third manganese removal reaction tank Connected, the concentrated water port of the fourth concentrated membrane device is connected to the fourth filter press, the sludge outlet of the fourth filter press is connected to the fourth calciner, the fresh water port of the fifth concentrated membrane device is The fourth pH adjusting tank is connected, the concentrated water port of the fifth concentrated membrane device is connected to the fifth filter press, the sludge outlet of the fifth filter press is connected to the fifth calcining furnace, and the sixth concentrated membrane device is a clear water port is connected to the fluorine removal reaction tank, a concentrated water port of the sixth concentration membrane device is connected to a sixth filter press, and a sludge outlet of the sixth filter press is connected to a sixth calciner, The clear water port of the seven concentrated membrane device is adsorbed with the resin Communication means, said seventh concentrated concentrated water outlet communicated to the seventh membrane filter apparatus, the filter press sludge outlet communicating to the seventh seventh calciner.

Further, the first pH adjusting tank is provided with a first dosing device, and the first dosing device is configured to add an alkaline substance to the first pH adjusting tank;

The first manganese removal reaction tank is provided with a second dosing device and a first aeration device, and the second dosing device is configured to add an acidic substance to the first manganese removal reaction tank, the first ventilation device Configuring to pass ozone into the first manganese removal reaction tank;

The second manganese removal reaction tank is provided with a third dosing device, and the third dosing device is configured to add potassium permanganate to the second manganese removal reaction tank;

The second pH adjusting tank is provided with a fourth dosing device configured to add an alkaline substance to the second pH adjusting tank.

Further, the third pH adjusting tank is provided with a fifth dosing device, and the fifth dosing device is configured to add an alkaline substance to the third pH adjusting tank;

The third manganese removal reaction tank is provided with a sixth dosing device and a second aeration device, and the sixth dosing device is configured to add an acidic substance to the third manganese removal reaction tank, the second aeration device Configuring to pass ozone into the third manganese removal reaction tank;

The fourth manganese removal reaction tank is provided with a seventh dosing device, and the seventh dosing device is configured to add potassium permanganate to the fourth manganese removal reaction tank;

The fourth pH adjusting tank is provided with an eighth dosing device, and the eighth dosing device is configured to add an alkaline substance to the fourth pH adjusting tank;

The fluorine removal reaction tank is provided with a ninth dosing device and a tenth dosing device, and the ninth dosing device is configured to add an alkaline substance to the defluoridation reaction tank, and the tenth dosing device is configured A fluorine removal material is added to the fluorine removal reaction tank.

Further, the first pH adjusting tank is provided with a first pH monitoring device, and the first pH monitoring device is connected to the first medicating device;

The first manganese removal reaction tank is provided with a second pH monitoring device, and the second pH monitoring device is connected to the second dosing device;

The second pH adjusting tank is provided with a third pH monitoring device, and the third pH monitoring device is connected to the fourth dosing device.

Further, the third pH adjusting tank is provided with a fourth pH monitoring device, and the fourth pH monitoring device is connected to the fifth dosing device;

The third demineralization reaction tank is provided with a fifth pH monitoring device, and the fifth pH monitoring device is connected to the sixth dosing device;

The fourth pH adjusting tank is provided with a sixth pH monitoring device, and the sixth pH monitoring device is connected to the eighth dosing device;

The fluorine removal reaction tank is provided with a seventh pH monitoring device, and the seventh pH monitoring device is connected to the ninth dosing device.

Further, the water outlet of the first filter press is in communication with the first pH adjustment tank; the water outlet of the second filter press is in communication with the second manganese removal reaction tank.

Further, the water outlet of the fourth filter press is in communication with the third pH adjustment tank; the water outlet of the fifth filter press is in communication with the fourth manganese removal reaction tank; The water outlet of the machine is in communication with the fluorine removal reaction tank.

Further, a membrane separation device is disposed at a communication between the water outlet of the seventh concentration membrane device and the resin adsorption purification device; a water outlet of the membrane separation device is in communication with the resin adsorption purification device, and the membrane separation device The sludge outlet is in communication with the seventh filter press.

Further, the sulfuric acid pickling wastewater treatment system further includes a sulfuric acid pickling wastewater storage tank, and the sulfuric acid pickling wastewater storage tank is connected to the first filtering device through a first lift pump;

The mixed acid pickling wastewater treatment system further includes a mixed acid pickling wastewater storage tank, and the mixed acid pickling wastewater storage tank is in communication with the second filtering device through a second lift pump.

Further, the resin adsorption purification device is further connected to the fluorine removal reaction tank.

Further, the first dosing device comprises a first funnel, and the top and bottom of the first funnel are respectively provided with openings, and the opening of the bottom of the first funnel is in communication with the first pH adjusting tank.

Further, the first dosing device comprises a first tank, the first tank is installed above the first pH adjusting tank, and the first tank and the first pH adjusting tank pass through the pipeline Connected.

Further, the pipeline is provided with a shut-off valve and a flow regulating valve, the side wall of the first tank is provided with a sight glass, and one side of the sight glass is provided with a scale line, and the first box body is A feeding port is arranged on the top surface, and the feeding port is provided with a material door, and the material door is detachably connected to the feeding port.

Further, the first dosing device comprises a first tank, the first tank is disposed at one side of the first pH adjusting tank, and the first tank and the first pH adjusting tank pass The pipeline is connected, and a pump is arranged on the pipeline.

Further, a weighing device is disposed under the first box body, a side mirror is disposed on a sidewall of the first box body, and a feeding port is disposed on a top surface of the first box body, the feeding A door is provided on the mouth, and the door is hinged to the feeding port.

Further, the first pH monitoring device includes a first pH sensor and a first controller;

The first pH sensor is disposed in the first pH adjustment tank, the first controller is coupled to the first pH sensor, and the first controller is configured to control activation of the first dosing device.

Further, the first ventilation device comprises a gas cylinder, and an outlet of the gas cylinder is connected to the first manganese removal reaction tank through a pipeline, and the pipeline is provided with a shut-off valve and a flow regulating valve.

Compared with the prior art, the stainless steel pickling wastewater treatment system of the present application has at least the following advantages:

(1) The stainless steel pickling wastewater treatment system of the present application separates the mixed acid pickling wastewater and the sulfuric acid pickling wastewater, and the two processing systems can be processed simultaneously, or can be separately processed according to actual production conditions, not only for 200, 300 And the metal ions in the 400 series stainless steel pickling wastewater are 100% recycled, F ^- ion can also be recycled, and the sludge produced in the system is calcined to become recyclable material, 100% is the active ingredient. The waste material has zero ineffective components, 100% recycled in the stainless steel production process, which effectively reduces the sludge treatment cost and load, and solves the problem of resource waste; on the other hand, it increases by removing fluoride from the fluorine removal tank and adding slaked lime. The resin adsorption purification device further adsorbs fluoride ions through the resin, so that the concentration of the fluoride ion in the final effluent is greatly reduced, and the precipitate after the reaction in the fluorine removal reaction tank is recovered by pressure filtration and calcination to obtain high-purity CaF ₂ (99% content). Therefore, turning waste into treasure, avoiding the subsequent mixing and recycling, the production of stainless steel is caused by inaccurate addition. Adverse effects and reduced environmental pollution.

(2) The stainless steel pickling wastewater treatment system of this application is safe, stable, simple to operate, easy to manage, stainless steel pickling wastewater treatment system, and the waste water resources to solve the recycling problem of stainless steel pickling wastewater, to achieve "comprehensive comprehensive management The effect of reducing the production cost of the enterprise.

The above described objects, features, and advantages of the present invention will become more apparent from the following description.

DRAWINGS

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings to be used in the embodiments will be briefly described below. It should be understood that the following drawings show only certain embodiments of the present application, and therefore It should be seen as a limitation on the scope, and those skilled in the art can obtain other related drawings according to these drawings without any creative work.

1 is a schematic structural view of a stainless steel pickling wastewater treatment system of the present application;

2 is a schematic structural view of a first dosing device having a first funnel in the stainless steel pickling wastewater treatment system of the present application;

3 is a schematic structural view of a first dosing device having a first tank in the stainless steel pickling wastewater treatment system of the present application;

4 is a schematic structural view of a first dosing device having a first tank and a pump in the stainless steel pickling wastewater treatment system of the present application;

FIG. 5 is a schematic structural view of a first pH monitoring device in a stainless steel pickling wastewater treatment system of the present application.

The main component symbol description:

1-stainless steel pickling wastewater treatment system; 101-sulfate pickling wastewater storage tank; 102-first lift pump; 103-first filter device; 104-first pH regulating tank; 1041-first dosing device; 10411- First funnel; 10412-first box; 10413-scope; 10414-tick line; 10415-stop valve; 10416-flow regulating valve; 10417-pump; 1042-first pH monitoring device; 10421-first pH sensor 10422-first controller; 105-first concentrated membrane device; 106-first manganese removal reaction cell; 1061-second dosing device; 1062-second pH monitoring device; 1063-first aeration device; Second manganese removal reaction tank; 1071-third dosing device; 108-second concentration membrane device; 109-first filter press; 110-first calciner; 111-second filter press; 112-second Calciner; 113-second pH adjusting tank; 1131-fourth dosing device; 1132-third pH monitoring device; 114-third concentrated membrane device; 115-third filter press; 116-third calciner; 117-first collection tank; 118-clear water recovery treatment device; 201-mixed acid pickling wastewater storage tank; 202-second lift pump; 203-second filter device; 204-third pH adjustment tank; Device; 2042 - fourth pH monitoring device; 205 - fourth concentrated membrane device; 206 - third manganese removal reaction cell; 2061 - sixth dosing device; 2062 - second aeration device; 2063 - fifth pH monitoring device; 207-fourth manganese removal reaction tank; 2071-seventh dosing device; 208-fifth concentration membrane device; 209-fourth pH adjustment tank; 2091-eighth dosing device; 2092-sixth pH monitoring device; - sixth concentrated membrane device; 211 - fluorine removal reaction cell; 2111 - ninth dosing device; 2112 - tenth dosing device; 2113 - seventh pH monitoring device; 212 - seventh concentrated membrane device; Filter press; 214 - fourth calciner; 215 - fifth filter press; 216 - fifth calciner; 217 - sixth filter press; 218 - sixth calciner; 219 - seventh filter press; - seventh calciner; 221 - membrane separation device; 222 - resin adsorption purification device; 223 - second collection tank; 3- weighing device.

Detailed ways

To facilitate an understanding of the present application, a stainless steel pickling wastewater treatment system will now be described more fully with reference to the associated drawings. A preferred embodiment of a stainless steel pickling wastewater treatment system is given in the drawings. However, the stainless steel pickling wastewater treatment system can be implemented in many different forms and is not limited to the embodiments described herein. Rather, the purpose of providing these embodiments is to make the disclosure of the stainless steel pickling wastewater treatment system more thorough and comprehensive.

In the description of the present application, it is to be understood that the terms "longitudinal", "transverse", "upper", "lower", "front", "back", "left", "right", "vertical", The orientation or positional relationship of the indications of "horizontal", "top", "bottom", "inside", "outside", etc. is based on the orientation or positional relationship shown in the drawings, only for the convenience of describing the present application and simplifying the description. It is not intended or implied that the device or component that is referred to has a particular orientation, is constructed and operated in a particular orientation, and therefore is not to be construed as limiting. Moreover, the terms "first", "second", "third", and the like are used merely to distinguish a description, and are not to be construed as indicating or implying a relative importance.

In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the application. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

In the description of the present application, unless otherwise specified and limited, it should be noted that the terms "installation", "connected", and "connected" are to be understood broadly, and may be, for example, mechanically or electrically connected, or The internal communication of the components may be directly connected or indirectly connected through an intermediate medium. For those skilled in the art, the specific meanings of the above terms may be understood according to specific circumstances.

Referring to Figure 1, the present application provides a stainless steel pickling wastewater treatment system 1, comprising a sulfuric acid pickling wastewater treatment system and a mixed acid pickling wastewater treatment system;

The sulfuric acid pickling wastewater treatment system comprises a first filtering device 103, a first pH adjusting tank 104, a first concentration membrane device 105, a first manganese removal reaction tank 106, a second manganese removal reaction tank 107, and a second, which are sequentially connected. The concentrated membrane device 108, the second pH adjusting tank 113, the third concentrated membrane device 114, and the first collection tank 117.

The first filtering device 103, the first pH adjusting tank 104, the first concentration membrane device 105, the first manganese removal reaction tank 106, the second manganese removal reaction tank 107, the second concentration membrane device 108, and the second pH adjustment tank 113. The third concentrated membrane device 114 and the first collecting tank 117 are respectively connected by a pipeline, and a shut-off valve may be arranged on the pipeline to adjust the opening and closing of the pipeline, and a flow regulating valve may also be disposed on the pipeline to adjust the flow downward. The flow of a part.

The fresh water outlet of the first concentrated membrane device 105 is in communication with the first manganese removal reaction tank 106, and the concentrated water outlet of the first concentrated membrane device 105 is further connected to the first filter press 109, the first filter press The sludge outlet of 109 is connected to the first calciner 110. The water clearing port of the second concentrated membrane device 108 is in communication with the second pH adjusting tank 113, and the concentrated water port of the first concentrated membrane device 105 is further connected to the second filter press 111, and the second filter press 111 The sludge outlet is connected to the second calciner 112. The water clearing port of the third concentrated membrane device 114 is in communication with the first collecting tank 117. The concentrated water port of the third concentrated membrane device 114 is connected to the third filter press 115, and the sludge outlet of the third filter press 115 is connected to the third calcining furnace 116.

Wherein, the first concentration membrane device 105 and the first filter press 109, the first filter press 109 and the first calciner 110, the second concentration membrane device 108 and the second filter press 111, the second filter press 111, and The second calcining furnace 112, the third concentrated membrane device 114 and the third filter press 115, and the third filter press 115 and the third calcining furnace 116 are respectively connected by a pipeline, and a shut-off valve may be disposed on the pipeline to adjust the pipe The flow path can also be set on the pipeline to regulate the flow to the next component.

The various components in the sulfuric acid pickling wastewater treatment system are connected by pipelines to isolate the sulfuric acid pickling wastewater from being transported between the various components to prevent the sulfuric acid pickling wastewater from overflowing or reacting with external substances, thereby improving the stability of the treatment. And security.

The mixed acid pickling wastewater treatment system comprises a second filtering device 203, a third pH adjusting tank 204, a fourth concentrated membrane device 205, a third manganese removing reaction tank 206, a fourth manganese removing reaction tank 207, and a fifth. The concentrated membrane device 208, the fourth pH adjusting tank 209, the sixth concentrated membrane device 210, the fluorine removal reaction tank 211, the seventh concentration membrane device 212, the resin adsorption purification device 222, and the second collection tank 223.

The water outlet of the fourth concentration membrane device 205 is in communication with the third manganese removal reaction tank 206, and the concentrated water outlet of the fourth concentration membrane device 205 is connected to the fourth filter press 213, and the fourth filter press 213 The sludge outlet is connected to the fourth calciner 214. The fresh water outlet of the fifth concentration membrane device 208 is in communication with the fluorine removal reaction tank 211, and the concentrated water outlet of the fifth concentration membrane device 208 is connected to the fifth filter press 215, and the fifth filter press 215 is dirty. A fifth calciner 216 is connected to the mud outlet. The fresh water outlet of the sixth concentrated membrane device 210 is in communication with the fluorine removal reaction tank 211, and the concentrated water outlet of the sixth concentrated membrane device 210 is connected to the sixth filter press 217, and the sixth filter press 217 is dirty. The mud outlet is connected to a sixth calciner 218. The water clearing port of the seventh concentration film device 212 is in communication with the resin adsorption purification device 222, and the concentrated water port of the seventh concentration film device 212 is connected to the seventh filter press 219, and the seventh filter press 219 is dirty. The mud outlet is connected to the seventh calciner 220.

Among them, the various components in the mixed acid pickling wastewater treatment system are connected by pipelines, and a shut-off valve can be arranged on the pipeline to adjust the on-off of each pipeline, and a flow regulating valve can also be provided to regulate the flow rate to the next component.

The various components in the sulfuric acid pickling wastewater treatment system are connected by pipelines to isolate the mixed acid pickling wastewater from being transported between the various components to prevent the mixed acid pickling wastewater from overflowing or reacting with external substances, thereby improving the stability of the treatment. And security.

It should be noted that the 300 series stainless steel, the main components of iron, chromium, nickel, such as 304 stainless steel, its main components are iron 73%, chromium 18%, nickel 8%. 400 series stainless steel, the main components of iron, chromium, such as 430 stainless steel, its main components are iron 83%, chromium 16%. 200 series stainless steel, the main components of iron, chromium, manganese, such as 201 stainless steel, its main components are iron 74%, chromium 14%, manganese 10%, nickel 1%.

The utility model provides a stainless steel pickling wastewater treatment system 1 which is integrated, modularized, fully automatic operation, safe and stable in operation, simple in operation and convenient in management, and separates the mixed acid pickling wastewater and the sulfuric acid pickling wastewater in the front stage. Treatment, the two treatment systems can be processed at the same time, or can be processed separately according to the actual production situation, not only can the metal ions in the 200, 300 and 400 series stainless steel pickling wastewater reach 100% recycling, especially 200 series stainless steel Mn ²⁺ and / or Mn ³⁺ , F ^- ions in pickling wastewater can also be recycled, and reduce environmental pollution, make wastewater resources, solve the recycling problem of stainless steel pickling wastewater, and achieve "comprehensive comprehensive management" The effect is to reduce the production cost of the enterprise.

It should be understood that the above filtering device is used for filtering out impurities such as solid particles in the stainless steel pickling wastewater to avoid affecting the membrane separation performance in the subsequent concentrated membrane device. The filter device may be exemplified by a quartz sand filter, an activated carbon filter, a ceramic filter, a multi-media filter, or a fiber filter.

The first pH adjusting tank 104 and the first pH adjusting tank 104 are adjusted to pH 7 by adding a basic substance such as sodium hydroxide, and at the same time, with heavy metal ions (Cr ³⁺ , Fe ²⁺ and Fe ³⁺ in the wastewater). The reaction) forms a hydroxide precipitate.

In the first manganese removal reaction tank 106 and the third manganese removal reaction tank 206, the pH is adjusted to 7.0, and ozone is kept, so that Mn ²⁺ and/or Mn ³⁺ in the wastewater is oxidized to precipitate MnO ₂ . The second manganese removal reaction tank 107 and the fourth manganese removal reaction tank 207 are further retained in the wastewater after the first manganese removal reaction tank 106 and the third manganese removal reaction tank 206 are precipitated by adding potassium permanganate. Mn ²⁺ or Mn ^{3+ is} oxidized to precipitate MnO ₂ .

The fluorine removal reaction tank 211 reacts with fluoride ions in the pickling wastewater by adding slaked lime to form a CaF ₂ precipitate.

The stainless steel pickling wastewater treatment system of the present application converts the sludge generated in the system into a recyclable material by being calcined, 100% is an effective component, the waste material has zero invalid component, and 100% is recycled for use in the stainless steel production process. The utility model effectively reduces the sludge treatment cost and load, and solves the problem of waste of resources; on the other hand, by adding the slaked lime in the fluorine removal reaction tank 211 to remove the fluorine, the resin adsorption purification device 222 is further added, and the fluorine ion is further adsorbed by the resin to finally The effluent fluoride ion concentration is greatly reduced, and the precipitate after the reaction of the fluorine removal reaction tank 211 is recovered by pressure filtration and calcination to obtain high-purity CaF ₂ (99% content), thereby turning waste into treasure and avoiding the subsequent mixing treatment and recovery. Due to the inaccurate addition, the stainless steel production process is adversely affected and environmental pollution is reduced.

Preferably, the first pH adjusting tank 104 is provided with a first dosing device 1041 for adding an alkaline substance to the first pH adjusting tank 104.

The first dosing device 1041 may include a first funnel 10411. The top and bottom of the first funnel 10411 are respectively provided with openings, and the bottom opening of the first funnel 10411 communicates with the first pH adjusting cell 104 to The top opening of a funnel 10411 is placed in the first funnel 10411, i.e., alkaline material can be introduced into the first pH adjusting cell 104 from the bottom of the first funnel 10411.

The first dosing device 1041 may also include a first tank 10412, the first tank 10412 is installed above the first pH adjusting tank 104, and the first tank 10412 communicates with the first pH adjusting tank 104 through a pipeline. A shut-off valve 10415 is provided. The first tank 10412 is provided with an alkaline substance. When the shut-off valve 10415 is opened, the alkaline substance in the first tank 10412 can provide alkali to the first pH adjusting tank 104 under the action of gravity. In addition, a flow regulating valve 10416 may be disposed on the pipeline, and the flow regulating valve 10416 may adjust the flow rate of the alkaline substance in the first tank 10412 to the first pH adjusting tank 104.

The side wall of the first box 10412 may be provided with a sight glass 10413 for observing the state of the alkaline substance in the first box 10412, and one side of the sight glass 10413 is provided with a scale line 10414, which can be obtained by the scale line 10414. The remaining amount of the alkaline substance in the first tank 10412.

The top surface of the first box body 10412 may be provided with a feeding port, the alkaline material is replenished into the first box body 10412 through the feeding port, and the material door is provided with a material door, and the material door is detachably connected with the feeding port (click or Threaded connection, etc., the door can close or open the feed port.

The first dosing device 1041 may further include a first case 10412, the first case 10412 is installed at one side of the first pH adjusting tank 104, and the first case 10412 is connected to the first pH adjusting pool 104 through a pipe. A pump 10417 is disposed on the road, and the first tank 10412 is provided with an alkaline substance. When the pump 10417 is opened, the alkaline substance in the first tank 10412 can supply the alkaline substance to the first pH adjusting tank 104.

A weighing device may be disposed under the first box 10412 for detecting the weight of the first box 10412 to obtain the weight of the alkaline substance in the first box 10412. A speculum 10413 may be disposed on the sidewall of the first case 10412 for observing the state of the alkaline substance in the first case 10412. The top surface of the first case 10412 may be provided with a feeding port, and the first port is provided through the feeding port. The tank body 10412 is filled with alkaline substances, and a material door can be provided with a material door, and the material door is hinged with the feeding port, and the material door can close or open the feeding port.

Further, the first pH adjusting device 104 is provided with a first pH monitoring device 1042, and the first pH monitoring device 1042 is connected to the first medicating device 1041.

Specifically, the first pH monitoring device 1042 includes a first pH sensor 10421 and a first controller 10422. The first pH sensor 10421 is disposed in the first pH adjusting tank 104 and is in contact with the wastewater in the first pH adjusting tank 104, thereby The pH of the wastewater in the first pH adjusting tank 104 is detected, and the first pH sensor 10421 can send the pH value of the wastewater in the first pH adjusting tank 104 to the first controller 10422, and the first controller 10422 is in the first pH adjusting tank. When the pH of the wastewater in 104 is less than the first preset value, the first dosing device 1041 is controlled to be activated to add alkaline substances to the first pH adjusting cell 104, and the first controller 10422 is in the first pH adjusting cell 104. When the pH of the wastewater is greater than or equal to the second predetermined value, the first dosing device 1041 is controlled to stop adding the alkaline substance to the first pH adjusting cell 104.

It should be noted that in order to ensure the best effect of the reaction in the first pH adjusting tank 104, the alkaline substance completely reacts with metal ions such as Cr ³⁺ , Fe ²⁺ , Fe ³⁺ to form Cr(OH) ₃ and Fe ( OH) ₃ , Fe(OH) _2, etc., the pH in the reaction cell needs to be adjusted to 5.6-7.5. Therefore, in the embodiment of the present application, the first pH monitoring device 1042 is configured to monitor the pH value of the wastewater in the first pH adjusting tank 104 in real time. When the monitored pH value is less than 5.6, the first pH monitoring device 1042 automatically controls the The first dosing device 1041 adds an alkaline substance to the first pH adjusting tank 104; when the monitored pH value is greater than or equal to 7.5, the first pH monitoring device 1042 automatically controls the first dosing device 1041 to adjust to the first pH. The addition of alkaline substances in the pool 104 is stopped.

The first manganese removal reaction tank 106 is provided with a second dosing device 1061 and a first ventilation device 1063, and the second dosing device 1061 is configured to add an acidic substance to the first manganese removal reaction cell 106. The first aeration device 1063 is configured to introduce ozone into the first manganese removal reaction cell 106.

Wherein, the second dosing device 1061 may include a second funnel, the top and the bottom of the second funnel are respectively provided with openings, and the bottom opening of the second funnel is in communication with the second dosing device 1061, and the acidic substance is from the top of the second funnel The opening is placed in the second funnel so that the acidic material can enter the first manganese removal reaction cell 106 from the bottom of the second funnel.

The second dosing device 1061 may also include a second tank, the second tank is installed above the first manganese removal reaction tank 106, and the second tank is connected to the first manganese removal reaction tank 106 through a pipeline, and the pipeline is arranged The shut-off valve is used for setting the acidic substance in the second tank. When the shut-off valve is opened, the acidic substance in the second tank can supply the acidic substance to the first manganese removal reaction tank 106 under the action of gravity, and the pipeline can also be used. A flow regulating valve is provided, and the flow regulating valve can adjust the flow rate of the acidic substance in the second tank to the first manganese removing reaction tank 106.

The side wall of the second box may be provided with a sight glass 10413 for observing the state of the acidic substance in the second box body, and a scale line 10414 is disposed on one side of the sight glass 10413, and the second box body may be obtained through the scale line 10414. The remaining amount of acidic substances.

The top surface of the second box body may be provided with a feeding port, the acid material is added to the second box body through the feeding port, and the material door can be provided with a material door, and the material door is detachably connected with the feeding port (clamping or screwing, etc.) The door can close or open the feed port.

The second dosing device 1061 may further include a second tank, the second tank is installed on the side of the first manganese removal reaction tank 106, and the second tank is connected to the first manganese removal reaction tank 106 through the pipeline. A pump is provided, and the second tank is used for setting an acidic substance. When the pump is turned on, the acidic substance in the second tank can supply the acidic substance to the first manganese removal reaction tank 106.

Wherein, a weighing device may be disposed under the second box for detecting the weight of the second box to obtain the weight of the acidic substance in the second box. A side mirror 10413 may be disposed on the side wall of the second box for observing the state of the acidic substance in the second box body, and a feeding port may be disposed on the top surface of the second box body, and the acidic substance is added to the second box body through the feeding port. And the material door can be provided with a material door, the material door is hinged with the feeding port, and the material door can close or open the feeding port.

The first venting device 1063 may include a gas cylinder in which ozone is disposed. As an embodiment, compressed oxygen is disposed in the gas cylinder, and the outlet of the gas cylinder is connected to the first manganese removal reaction tank 106 through a pipeline, and the pipeline is closed. Valve and flow regulating valve, when the shut-off valve is opened, the gas cylinder inputs ozone into the first manganese removal reaction tank 106. When the shut-off valve is closed, the gas cylinder stops inputting ozone into the first manganese removal reaction tank 106, and the flow regulating valve regulates the gas. The bottle enters the flow rate of ozone into the first manganese removal reaction tank 106; as another embodiment, the atmospheric pressure ozone is set in the gas cylinder, and the outlet of the gas cylinder is connected with the first manganese removal reaction tank 106 through the pipeline, and the pipeline is arranged. When the gas pump, the shut-off valve and the flow regulating valve are opened, the gas cylinder inputs ozone into the first manganese removal reaction tank 106 when the shut-off valve and the air pump are turned on, and the gas cylinder stops inputting to the first manganese removal reaction tank 106 when the shut-off valve and the air pump are closed. The ozone and flow regulating valve regulates the flow rate of the input ozone into the first demineralization reaction tank 106 of the gas cylinder.

Further, the first manganese removal reaction tank 106 is provided with a second pH monitoring device 1062, and the second pH monitoring device 1062 is connected to the second medicating device 1061.

Specifically, the second pH monitoring device 1062 includes a second pH sensor and a second controller, and the second pH sensor is disposed in the first manganese removal reaction tank 106 and is in contact with the wastewater in the first manganese removal reaction tank 106, thereby detecting The pH of the wastewater in the first manganese removal reaction tank 106, the second pH sensor can send the pH value of the wastewater in the first manganese removal reaction tank 106 to the second controller, and the second controller is in the first manganese removal reaction tank 106. When the pH of the internal wastewater is less than the third preset value, the second dosing device 1061 is controlled to be activated to add the acidic substance to the first manganese removal reaction tank 106, and the second controller is in the first demineralization reaction tank 106. When the pH value is greater than or equal to the fourth predetermined value, the second dosing device 1061 is controlled to stop the addition of the acidic substance to the first manganese removal reaction cell 106.

It should be noted that in order to ensure the best effect of the reaction in the first manganese removal reaction tank 106, ozone completely oxidizes Mn ²⁺ and/or Mn ³⁺ in the wastewater to MnO ₂ precipitation, and at the same time, Fe ²⁺ The oxidation to Fe ^{3+ is} converted to Fe(OH) ₃ and the pH in the reaction cell is adjusted to 7-7.5. Therefore, in the embodiment of the present application, the second pH monitoring device 1062 is configured to monitor the pH value of the wastewater in the first manganese removal reaction tank 106 in real time. When the monitored pH value is greater than 7.5, the second pH monitoring device 1062 automatically controls the The second dosing device 1061 adds an acidic substance to the first manganese removal reaction tank 106; when the monitored pH value is less than or equal to 7, the second pH monitoring device 1062 automatically controls the second dosing device 1061 to the first division The addition of the acidic substance is stopped in the manganese reaction cell 106.

The second manganese removal reaction tank 107 is provided with a third dosing device 1071 for adding potassium permanganate to the second manganese removal reaction tank 107.

The structure of the third dosing device 1071 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again.

Preferably, the second pH adjusting tank 113 is provided with a fourth dosing device 1131 for adding an alkaline substance to the second pH adjusting tank 113.

The structure of the fourth dosing device 1131 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again.

Further, the second pH adjusting tank 113 is provided with a third pH monitoring device 1132, and the third pH monitoring device 1132 is connected to the fourth dosing device 1131.

Specifically, the third pH monitoring device 1132 includes a third pH sensor and a third controller, and the third pH sensor is disposed in the second pH adjusting tank 113 and is in contact with the wastewater in the second pH adjusting tank 113, thereby detecting the second The pH of the wastewater in the pH adjusting tank 113, the third pH sensor is capable of transmitting the pH value of the wastewater in the second pH adjusting tank 113 to the third controller, and the pH value of the wastewater in the second pH adjusting tank 113 of the third controller When the value is less than the fifth preset value, the fourth dosing device 1131 is controlled to be activated to add the alkaline substance to the second pH adjusting pool 113, and the pH of the wastewater in the second pH adjusting pool 113 of the third controller is greater than or equal to At the sixth preset value, the fourth dosing device 1131 is controlled to stop the addition of the alkaline substance to the second pH adjusting tank 113.

It should be noted that the second pH adjusting tank 113 is used for further removing Ni ²⁺ , Mn ²⁺ and Fe ²⁺ which may remain in the sulfuric acid pickling wastewater, so as to ensure the best reaction in the second pH adjusting tank 113. The effect is that the alkaline substance reacts completely with metal ions such as Ni ²⁺ , Mn ²⁺ and Fe ²⁺ to form Ni(OH) ₂ , Mn(OH) ₃ and Fe(OH) _{2 ,} etc., and the pH value in the reaction tank needs to be Adjust to 10.5-11. Therefore, in the embodiment of the present application, the third pH monitoring device 1132 is configured to monitor the pH value of the wastewater in the second pH adjusting tank 113 in real time. When the monitored pH value is less than 10.5, the third pH monitoring device 1132 automatically controls the The fourth dosing device 1131 adds an alkaline substance to the second pH adjusting tank 113; when the monitored pH value is greater than or equal to 11, the third pH monitoring device 1132 automatically controls the fourth dosing device 1131 to adjust to the second pH. The addition of alkaline substances in the pool 113 is stopped.

The third pH adjusting tank 204 is provided with a fifth dosing device 2041 for adding an alkaline substance to the third pH adjusting tank 204.

The structure of the fifth dosing device 2041 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again.

Further, the third pH adjusting tank 204 is provided with a fourth pH monitoring device 2042, and the fourth pH monitoring device 2042 is connected to the fifth dosing device 2041.

The structure of the fourth pH monitoring device 2042 is the same as that of the first pH monitoring device 1042 or the second pH monitoring device 1062, and details are not described herein again.

It should be noted that in order to ensure the best effect of the reaction in the third pH adjusting tank 204, the alkaline substance completely reacts with metal ions such as Cr ³⁺ , Fe ²⁺ , Fe ³⁺ to form Cr(OH) ₃ and Fe ( OH) ₃ , Fe(OH) _2, etc., the pH in the reaction cell needs to be adjusted to 5.6-7.5. Therefore, in the embodiment of the present application, the first pH monitoring device 1042 is configured to monitor the pH value of the wastewater in the third pH adjusting tank 204 in real time. When the monitored pH value is less than 5.6, the fourth pH monitoring device 2042 automatically controls the The fifth dosing device 2041 adds an alkaline substance to the third pH adjusting tank 204; when the monitored pH value is greater than or equal to 7.5, the fourth pH monitoring device 2042 automatically controls the fifth dosing device 2041 to adjust to the third pH. The addition of alkaline substances in the pool 204 is stopped.

The third manganese removal reaction tank 206 is provided with a sixth dosing device 2061 and a second aeration device 2062, and the sixth dosing device 2061 is configured to add an acidic substance to the third manganese removal reaction cell 206. The second aeration device 2062 is configured to introduce ozone into the third manganese removal reaction tank 206.

The structure of the sixth dosing device 2061 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again. The structure of the second ventilation device 2062 is the same as that of the first ventilation device 1063, and details are not described herein again.

Further, the third manganese removal reaction tank 206 is provided with a fifth pH monitoring device 2063, and the fifth pH monitoring device 2063 is connected to the sixth medicating device 2061.

The structure of the fifth pH monitoring device 2063 is the same as that of the first pH monitoring device 1042 or the second pH monitoring device 1062, and details are not described herein again.

It should be noted that in order to ensure the best effect of the reaction in the third manganese removal reaction tank 206, ozone completely oxidizes Mn ²⁺ and/or Mn ³⁺ in the wastewater to MnO ₂ precipitation, and at the same time, Fe ²⁺ The oxidation to Fe ^{3+ is} converted to Fe(OH) ₃ and the pH in the reaction cell is adjusted to 7-7.5. Therefore, in the embodiment of the present application, the fifth pH monitoring device 2063 is configured to monitor the pH value of the wastewater in the third manganese removal reaction tank 206 in real time. When the monitored pH value is greater than 7.5, the fifth pH monitoring device 2063 automatically controls the The sixth dosing device 2061 adds an acidic substance to the third manganese removing reaction tank 206; when the monitored pH value is less than or equal to 7, the fifth pH monitoring device 2063 automatically controls the sixth dosing device 2061 to the third dividing The addition of acidic substances in the manganese reaction cell 206 is stopped.

The fourth manganese removal reaction tank 207 is provided with a seventh dosing device 2071 for adding potassium permanganate to the fourth manganese removal reaction tank 207.

The structure of the seventh dosing device 2071 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again.

The fourth pH adjusting tank 209 is provided with an eighth dosing device 2091 for adding an alkaline substance to the fourth pH adjusting tank 209.

The structure of the eighth dosing device 2091 is the same as that of the first dosing device 1041 or the second dosing device 1061, and details are not described herein again.

The fourth pH adjusting tank 209 is provided with a sixth pH monitoring device 2092, and the sixth pH monitoring device 2092 is connected to the eighth dosing device 2091.

The structure of the sixth pH monitoring device 2092 is the same as that of the first pH monitoring device 1042 or the second pH monitoring device 1062, and details are not described herein again.

It should be noted that the fourth pH adjusting tank 209 is used for further removing Ni ²⁺ , Mn ²⁺ and Fe ²⁺ which may remain in the mixed acid pickling wastewater, so as to ensure the best reaction in the fourth pH adjusting tank 209. The effect is that the alkaline substance reacts completely with metal ions such as Ni ²⁺ , Mn ²⁺ and Fe ²⁺ to form Ni(OH) ₂ , Mn(OH) ₃ and Fe(OH) _{2 ,} etc., and the pH value in the reaction tank needs to be Adjust to 10.5-11. Therefore, in the embodiment of the present application, the sixth pH monitoring device 2092 is configured to monitor the pH value of the wastewater in the fourth pH adjusting tank 209 in real time. When the monitored pH value is less than 10.5, the sixth pH monitoring device 2092 automatically controls the The eighth dosing device 2091 adds an alkaline substance to the fourth pH adjusting tank 209; when the monitored pH value is greater than or equal to 11, the sixth pH monitoring device 2092 automatically controls the eighth dosing device 2091 to adjust to the fourth pH. The addition of alkaline substances in the tank 209 was stopped.

The fluorine removal reaction tank 211 is provided with a ninth dosing device 2111 and a tenth dosing device 2112, and the ninth dosing device 2111 is configured to add an alkaline substance to the defluoridation reaction tank 211, the first The dosing device 2112 is for adding a defluorinating substance to the fluorine removing reaction tank 211, and the defluorinating substance may be exemplified by slaked lime Ca(OH) ₂ or CaCl ₂ .

The structures of the ninth dosing device 2111 and the tenth dosing device 2112 are the same as those of the first dosing device 1041 or the second dosing device 1061, respectively, and are not described herein again.

Further, the fluorine removal reaction tank 211 is provided with a seventh pH monitoring device 2113, and the seventh pH monitoring device 2113 is connected to the ninth dosing device 2111.

The structure of the seventh pH monitoring device 2113 is the same as that of the first pH monitoring device 1042 or the second pH monitoring device 1062, and details are not described herein again.

It should be noted that in order to ensure the best effect of the reaction in the fluorine removal reaction tank 211, the fluorine-removing hydrated lime Ca(OH) ₂ or CaCl ₂ reacts with the F+ in the wastewater to form a CaF ₂ precipitate, which is in the reaction tank. The pH should be adjusted to 8. Therefore, in the embodiment of the present application, the seventh pH monitoring device 2113 is configured to monitor the pH value of the wastewater in the fluorine removal reaction tank 211 in real time. When the monitored pH value is less than 8, the seventh pH monitoring device 2113 automatically controls the first The nine-dosing device 2111 adds an alkaline substance to the fluorine removal reaction tank 211; when the monitored pH value is greater than or equal to 8, the seventh pH monitoring device 2113 automatically controls the ninth dosing device 2111 to the fluorine removal reaction tank 211. Stop adding alkaline substances.

Preferably, the water outlet of the first filter press 109 is in communication with the first pH adjusting tank 104; the water outlet of the second filter press 111 is in communication with the second manganese removing reaction tank 107.

The water outlet of the first filter press 109 communicates with the first pH adjusting tank 104 through a pipeline, and suitable components such as a shut-off valve, a flow regulating valve and a flow meter may be disposed on the pipeline, and the water outlet of the first filter press 109 flows out. waste water can flow into a first pH-adjusting tank 104 to continue the processing, can be better recovered in the waste water metal ions and F ^- ions, increase the recovery rate, reduce pollution.

The water outlet of the second filter press 111 communicates with the second manganese removal reaction tank 107 through a pipeline, and suitable components such as a shut-off valve, a flow regulating valve and a flow meter may be disposed on the pipeline, and the water outlet of the second filter press 111 flows out. waste water can flow into the second addition of manganese in the reaction tank 107 to continue the processing, better able to recover metal ions in wastewater and F ^- ions, increase the recovery rate, reduce pollution.

The water outlet of the fourth filter press 213 is in communication with the third pH adjusting tank 204; the water outlet of the fifth filter press 215 is in communication with the fourth manganese removal reaction tank 207; The water outlet of the filter 219 is in communication with the fluorine removal reaction tank 211.

The water outlet of the fourth filter press 213 is connected to the third pH adjusting tank 204 through a pipeline. The pipeline may be provided with suitable components such as a shut-off valve, a flow regulating valve and a flow meter, and the outlet of the fourth filter press 213 flows out. pH adjusted wastewater can flow into the third pool 204 continues processing, better able to recover metal ions in wastewater and F ^- ions, increase the recovery rate, reduce pollution.

The water outlet of the seventh filter press 219 is connected to the fluorine removal reaction tank 211 through a pipeline, and a suitable component such as a shut-off valve, a flow regulating valve and a flow meter may be disposed on the pipeline, and the wastewater flowing out of the water outlet of the seventh filter press 219 The treatment can be continued in the fluorine removal reaction tank 211, and the F ^- ion in the wastewater can be recovered well, and the recovery rate can be improved and the pollution can be reduced.

Preferably, a membrane separation device 221 is disposed at a communication between the water outlet of the seventh concentration membrane device 212 and the resin adsorption purification device 222; a water outlet of the membrane separation device 221 is in communication with the resin adsorption purification device 222, The sludge outlet of the membrane separation device 221 is in communication with the seventh filter press 219.

The water outlet of the seventh concentration membrane device 212 and the membrane separation device 221, the water outlet of the membrane separation device 221 and the resin adsorption purification device 222, and the sludge outlet of the membrane separation device 221 and the seventh filter press 219 are connected by a pipe. Suitable components such as a shut-off valve, a flow regulating valve, and a flow meter can be provided on the pipeline.

The membrane separation device 221 can be exemplified by a reverse osmosis membrane, a microfiltration membrane or an ultrafiltration membrane. Since the pore size of the membrane is small, fine particles and other contaminants in the waste liquid can be trapped, and further solid-liquid separation and wastewater purification can be performed. . The solid matter obtained by the membrane separation is transported from the sludge outlet of the membrane separation device 221 to the seventh filter press 219, and the cleaned water after the membrane separation is directly discharged from the outlet of the membrane separation device 221 to the resin adsorption purification device 222 for treatment.

Wherein, the sulfuric acid pickling wastewater can directly flow into the first filtering device 103, and the mixed acid pickling wastewater can directly flow into the second filtering device 203.

Preferably, the mixed sulfuric acid pickling wastewater treatment system further includes a sulfuric acid pickling wastewater storage tank 101 that communicates with the first filtering device 103 through a first lift pump 102.

The mixed acid pickling wastewater treatment system further includes a mixed acid pickling wastewater storage tank 201 that communicates with the second filtering device 203 through a second lift pump 202.

The sulfuric acid pickling wastewater is stored in the sulfuric acid pickling wastewater storage tank 101, and is sent to the first filtering device 103 through the first lift pump 102 when it is needed for treatment; the mixed acid pickling wastewater is stored in the mixed acid pickling wastewater storage tank 201, When treatment is required, it is delivered to the second filter device 203 by the second lift pump 202.

The first lift pump 102 and the second lift pump 202 may be a variable frequency pump to adjust the flow rate of the sulfuric acid pickling wastewater into the first filtering device 103 and the flow rate of the mixed acid pickling wastewater into the second filtering device 203.

Preferably, the resin adsorption purification device 222 is further in communication with the fluorine removal reaction cell 211. The purified water purified by the resin adsorption purification device 222 is discharged into the second collection tank 223, and the concentrated water produced by the regeneration is returned to the fluorine removal reaction tank 211 for further processing. It can be better recovered in the wastewater F ^- ions, increase the recovery rate, reduce pollution.

Preferably, the first collection tank 117 and the second collection pool may each be connected with a clean water recovery treatment device for separately recycling and recycling the finally recovered wastewater.

The first collection tank 117 is connected to the clean water recovery treatment device through a pipeline, and any suitable components such as a shut-off valve, a flow regulating valve and a flow meter may be disposed on the pipeline, and the second collection tank is connected to the clean water recovery treatment device through the pipeline, and the pipeline is connected. Any suitable components such as a shut-off valve, a flow regulating valve, and a flow meter can be provided.

Adsorption purification apparatus 222 described above using a fluororesin (e.g., strongly basic anion exchange resin, chelating resin) having a high specific fluoride ion selective adsorption properties of the water F ^- and OH on the resin ^- are exchanged, F ^- Adsorbed by the resin, OH ^- is exchanged into water, through exchange to achieve the purpose of further reducing the F ^- concentration of the effluent, to meet the higher and more stringent pickling wastewater recovery standards.

It should be noted that the above-mentioned concentrated membrane device can be exemplified by a high pressure reverse osmosis roll membrane or a high pressure reverse osmosis disc membrane or a vibrating membrane or a forward osmosis membrane, and of course, it can also be enumerated as a nanofiltration membrane, an ultrafiltration membrane, and a microfiltration membrane. The film or the general filter element or the like is separated by a membrane in the concentrated membrane device, and the precipitated particles such as hydroxide or manganese dioxide in the concentrated water are further concentrated, aggregated, and thickened to form a clear and turbid separation.

As shown in Figure 1, the process flow of the stainless steel pickling wastewater treatment system 1 is:

The sulfuric acid pickling wastewater in the sulfuric acid pickling wastewater storage tank 101 is pumped into the first filtering device 103 through the first lifting pump 102 to filter out solid foreign particles in the waste liquid, and the filtered sulfuric acid pickling wastewater enters the first pH adjusting tank. In 104, the pH of the sulfuric acid pickling wastewater is adjusted to 5.6-7.5 by adding an alkali solution (such as sodium hydroxide), and simultaneously reacting with heavy metal ions (Cr ³⁺ , Fe ³⁺ , Fe ^{2+ ,} etc.) in the wastewater. Forming precipitates of hydroxides such as Cr(OH) ₃ , Fe(OH) ₃ and Fe(OH) ₂ ; the pickling wastewater after adjusting the pH passes through the first concentration membrane device 105 to concentrate and aggregate the hydroxide precipitate particles. Large, and form a clear turbid separation, the obtained clean water is directly discharged into the first manganese removal reaction tank 106, and the concentrated water is pumped to the first filter press 109 by a sludge pump (not shown) to produce the mud. The cake is sent to the first calcining furnace 110 for high-temperature calcination to obtain a metal oxide such as chromium oxide or iron oxide, and the filtrate is recovered into the first pH adjusting tank 104 to continue the secondary treatment. The waste liquid entering the first manganese removal reaction tank 106 is oxidized to MnO _{2 by} oxidizing Mn ²⁺ and/or Mn ³⁺ in the wastewater by adjusting the pH to 7-7.5, and simultaneously, Fe ^{2 +} oxidized to Fe ³⁺ to Fe(OH) ₃ , and then sent to the second manganese removal reaction tank 107, and potassium permanganate is added to further oxidize residual Mn ²⁺ or Mn ³⁺ into MnO _{2 .} Precipitating, and then passing through the second concentration membrane device 108, the granules such as MnO ₂ and Fe(OH) ₃ are concentrated and aggregated to increase and thicken, and the turbidity separation is formed, and the concentrated water obtained is passed through the sludge pump (not shown) It is shown that it is pumped to the second filter press 111, and the generated mud cake is sent into the second calcining furnace 112 for high-temperature calcination, and the filtrate is recovered into the second manganese removal reaction tank 107; the obtained fresh water is directly Discharge into the second pH adjusting tank 113, and adjust the pH of the sulfuric acid pickling wastewater to 10.5-11 by adding an alkali solution (such as sodium hydroxide), and simultaneously with the residual metal ions (Ni ²⁺ , Mn ^{2 in the} wastewater). ⁺ and Fe ^2+, etc. react to form hydroxide precipitates such as Ni(OH) ₂ , Mn(OH) ₃ and Fe(OH) ₂ ; the pickling wastewater after pH adjustment passes through the third concentration membrane device 114 to oxidize Object The concentrated particles are concentrated and aggregated to increase and form a clear and turbid separation, and the obtained clean water is directly discharged into the first collection tank 117, and the concentrated water is pumped to the third filter press 115 by a sludge pump (not shown). After filtration, the produced mud cake is sent to the third calcining furnace 116 for high-temperature calcination to recover metal oxide, and the filtrate is recovered to the second pH adjusting tank 113 for secondary treatment.

The sulfuric acid pickling wastewater in the mixed acid pickling wastewater storage tank 201 is pumped into the second filtering device 203 through the second lift pump 202 to filter out the solid impurity particles in the waste liquid, and the filtered sulfuric acid pickling wastewater enters the third pH adjusting tank. In 204, the pH of the sulfuric acid pickling wastewater is adjusted to 5.6-7.5 by adding an alkali solution (such as sodium hydroxide), and simultaneously reacting with heavy metal ions (Cr ³⁺ , Fe ³⁺ , Fe ^{2+ ,} etc.) in the wastewater. Forming precipitates of hydroxides such as Cr(OH) ₃ , Fe(OH) ₃ and Fe(OH) ₂ ; the pickling wastewater after adjusting the pH passes through the fourth concentration membrane device 205 to concentrate and aggregate the hydroxide precipitate particles. Large, and form a clear turbid separation, the obtained clean water is directly discharged into the third manganese removal reaction tank 206, and the concentrated water is pumped to the fourth filter press 213 by a sludge pump (not shown) to produce the mud. The cake is sent to the fourth calciner 214 for high-temperature calcination to obtain metal oxides such as chromium oxide and iron oxide, and the filtrate is recovered to the third pH adjusting tank 204 for secondary treatment.

The waste liquid entering the third manganese removal reaction tank 206 is oxidized to MnO _{2 by} oxidizing Mn ²⁺ and/or Mn ³⁺ in the wastewater by adjusting the pH to 7-7.5, and simultaneously, Fe ^{2 +} oxidized to Fe ³⁺ to Fe(OH) ₃ , and then sent to the fourth manganese removal reaction tank 207, and potassium permanganate is added to further oxidize residual Mn ²⁺ or Mn ³⁺ into MnO _{2 .} Precipitating, and then passing through the fifth concentration membrane device 208, the precipitate particles such as MnO ₂ and Fe(OH) ₃ are concentrated and aggregated to increase and thicken, and the turbidity separation is formed, and the concentrated water obtained is passed through the sludge pump (not shown) It is shown that it is pumped to the fifth filter press 215, and the resulting cake is sent to the fifth calciner 216 for high-temperature calcination and recovered.

The obtained fresh water is directly discharged into the fourth pH adjusting tank 209, and the pH of the sulfuric acid pickling wastewater is adjusted to 10.5-11 by adding an alkali solution (such as sodium hydroxide), and simultaneously with the residual metal ions (Ni ^{2 in the} wastewater). ⁺ , Mn ²⁺ and Fe ²⁺ etc. react to form hydroxide precipitates such as Ni(OH) ₂ , Mn(OH) ₃ and Fe(OH) ₂ . Then, after passing through the sixth concentration membrane device 210, the hydroxide precipitation particles are concentrated and aggregated to increase and thicken, and a turbid separation is formed, and the obtained concentrated water is pumped to the sixth pressure filter through a sludge pump (not shown). The machine 217 is press-filtered, and the generated mud cake is sent into the sixth calcining furnace 218 for high-temperature calcination to recover metal oxide, and the filtrate is recovered to the fourth pH adjusting tank 209 for further secondary treatment, and the clean water is directly discharged into the defluoridation reaction tank. 211, adding slaked lime Ca (OH) ₂ or CaCl ₂ and other fluorine-removing substances, reacting with fluoride ions in the wastewater to form a CaF ₂ precipitate, and then passing through the seventh concentrated membrane device 212, the CaF ₂ precipitated particles are concentrated and aggregated to increase and increase. And the turbidity separation is formed, and the obtained concentrated water is pumped to the seventh filter press 219 by a sludge pump (not shown), and the generated mud cake is automatically sent to the seventh filter press 219 for high-temperature calcination or After the standing, the calcination treatment is intermittently performed to obtain a high-purity CaF ₂ powder, and the filtrate is recovered to the fluorine removal reaction tank 211 to continue the secondary treatment. The resulting fresh water is again solid-liquid separated by the membrane separation device 221. The filtrate separated by the membrane separation device 221 is discharged into the seventh filter press 219, and the filtrate enters the resin adsorption purification device 222 for ion adsorption exchange, and the purified water discharged through the resin adsorption purification device 222 is discharged into the second collection tank 223. The resin regeneration wastewater generated at the same time is recovered into the fluorine removal reaction tank 211 to continue the secondary treatment.

In summary, the stainless steel pickling wastewater treatment system 1 provided by the embodiments of the present application has at least the following advantages:

(1) The stainless steel pickling wastewater treatment system provided by the embodiment of the present application can be processed simultaneously by separating the mixed acid pickling wastewater and the sulfuric acid pickling wastewater, or can be separately processed according to actual production conditions, not only for 200, 300 and The metal ions in the 400 series stainless steel pickling wastewater are 100% recycled, and the fluoride ions can also be recycled. The sludge produced in the system is calcined and turned into recyclable materials, 100% is the active ingredient, and the waste material is used. The invalid component is zero, 100% is recycled in the stainless steel production process, which effectively reduces the sludge treatment cost and load, and solves the problem of waste of resources; on the other hand, it increases the resin adsorption after removing fluoride from the fluorine removal tank and slaked lime. The purification device further adsorbs the fluoride ion through the resin, so that the concentration of the fluoride ion in the final effluent is greatly reduced, and the precipitate after the reaction in the fluorine removal reaction tank is recovered by pressure filtration and calcination to obtain high-purity CaF ₂ (99% content), thereby changing Waste is a treasure, avoiding the subsequent mixing and recycling, resulting in stainless steel production process due to inaccurate addition Adverse effects and reduced environmental pollution.

Although the term structure is used more frequently, such as "acid washing wastewater storage tank", "fluorine removal reaction tank", "resin adsorption purification device", etc., the possibility of using other terms is not excluded. These terms are only used to more easily describe and explain the nature of the application; any of these additional limitations are inconsistent with the spirit of the application.

The foregoing is only a specific embodiment of the present application, but the scope of protection of the present application is not limited thereto, and any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed in the present application. It should be covered by the scope of protection of this application.

Industrial applicability

The stainless steel pickling wastewater treatment system provided by the embodiment of the present invention reduces the sludge treatment cost and load, solves the problem of resource waste, reduces environmental pollution, is safe and stable in operation, simple in operation and convenient in management.

Claims

A stainless steel pickling wastewater treatment system, comprising: a mixed acid pickling wastewater treatment system and a sulfuric acid pickling wastewater treatment system;

The sulfuric acid pickling wastewater treatment system comprises a first filtering device, a first pH adjusting tank, a first concentration membrane device, a first manganese removal reaction tank, a second manganese removal reaction tank, a second concentration membrane device, and a first communication device. a second pH adjusting tank, a third concentrated membrane device and a first collecting tank, wherein the fresh water outlet of the first concentrated membrane device is in communication with the first manganese removal reaction tank, and the concentrated water outlet of the first concentrated membrane device is connected to the first a filter press, the sludge outlet of the first filter press is connected to the first calciner, the water clear of the second concentrated membrane device is in communication with the second pH adjusting tank, and the second concentrated membrane device is thick The nozzle is connected to the second filter press, the sludge outlet of the second filter press is connected to the second calciner, and the water outlet of the third concentrated membrane device is in communication with the first collection tank, the third condensation The concentrated water inlet of the membrane device is connected to a third filter press, and the sludge outlet of the third filter press is connected to the third calciner;

The mixed acid pickling wastewater treatment system comprises a second filtering device, a third pH adjusting tank, a fourth concentrated membrane device, a third manganese removal reaction tank, a fourth manganese removal reaction tank, a fifth concentrated membrane device, and a second a fourth pH adjusting tank, a sixth concentrated membrane device, a fluorine removal reaction tank, a seventh concentration membrane device, a resin adsorption purification device and a second collection tank, the water outlet of the fourth concentration membrane device and the third manganese removal reaction tank Connected, the concentrated water port of the fourth concentrated membrane device is connected to the fourth filter press, the sludge outlet of the fourth filter press is connected to the fourth calciner, the fresh water port of the fifth concentrated membrane device is The fourth pH adjusting tank is connected, the concentrated water port of the fifth concentrated membrane device is connected to the fifth filter press, the sludge outlet of the fifth filter press is connected to the fifth calcining furnace, and the sixth concentrated membrane device is a clear water port is connected to the fluorine removal reaction tank, a concentrated water port of the sixth concentration membrane device is connected to a sixth filter press, and a sludge outlet of the sixth filter press is connected to a sixth calciner, The clear water port of the seven concentrated membrane device is adsorbed with the resin Communication means, said seventh concentrated concentrated water outlet communicated to the seventh membrane filter apparatus, the filter press sludge outlet communicating to the seventh seventh calciner.
The stainless steel pickling wastewater treatment system according to claim 1, wherein the first pH adjusting tank is provided with a first dosing device, and the first dosing device is configured to be toward the first pH adjusting tank. Adding alkaline substances;

The first manganese removal reaction tank is provided with a second dosing device and a first aeration device, and the second dosing device is configured to add an acidic substance to the first manganese removal reaction tank, the first ventilation device Configuring to pass ozone into the first manganese removal reaction tank;

The second manganese removal reaction tank is provided with a third dosing device, and the third dosing device is configured to add potassium permanganate to the second manganese removal reaction tank;

The second pH adjusting tank is provided with a fourth dosing device configured to add an alkaline substance to the second pH adjusting tank.
The stainless steel pickling wastewater treatment system according to claim 2, wherein the third pH adjusting tank is provided with a fifth dosing device, and the fifth dosing device is configured to be directed to the third pH adjusting tank. Adding alkaline substances;

The third manganese removal reaction tank is provided with a sixth dosing device and a second aeration device, and the sixth dosing device is configured to add an acidic substance to the third manganese removal reaction tank, the second aeration device Configuring to pass ozone into the third manganese removal reaction tank;

The fourth manganese removal reaction tank is provided with a seventh dosing device, and the seventh dosing device is configured to add potassium permanganate to the fourth manganese removal reaction tank;

The fourth pH adjusting tank is provided with an eighth dosing device, and the eighth dosing device is configured to add an alkaline substance to the fourth pH adjusting tank;

The fluorine removal reaction tank is provided with a ninth dosing device and a tenth dosing device, and the ninth dosing device is configured to add an alkaline substance to the defluoridation reaction tank, and the tenth dosing device is configured A fluorine removal material is added to the fluorine removal reaction tank.
The stainless steel pickling wastewater treatment system according to claim 2 or 3, wherein the first pH adjusting tank is provided with a first pH monitoring device, the first pH monitoring device and the first dosing device connection;

The first manganese removal reaction tank is provided with a second pH monitoring device, and the second pH monitoring device is connected to the second dosing device;

The second pH adjusting tank is provided with a third pH monitoring device, and the third pH monitoring device is connected to the fourth dosing device.
The stainless steel pickling wastewater treatment system according to claim 3, wherein the third pH adjusting tank is provided with a fourth pH monitoring device, and the fourth pH monitoring device is connected to the fifth dosing device;

The third demineralization reaction tank is provided with a fifth pH monitoring device, and the fifth pH monitoring device is connected to the sixth dosing device;

The fourth pH adjusting tank is provided with a sixth pH monitoring device, and the sixth pH monitoring device is connected to the eighth dosing device;

The fluorine removal reaction tank is provided with a seventh pH monitoring device, and the seventh pH monitoring device is connected to the ninth dosing device.
The stainless steel pickling wastewater treatment system according to any one of claims 1 to 5, wherein a water outlet of the first filter press is in communication with the first pH adjusting tank; the second pressure filter The water outlet of the machine is in communication with the second manganese removal reaction tank.
The stainless steel pickling wastewater treatment system according to any one of claims 1 to 6, wherein a water outlet of the fourth filter press is in communication with the third pH adjusting tank; the fifth pressure filter The water outlet of the machine is in communication with the fourth manganese removal reaction tank; the water outlet of the seventh filter press is in communication with the fluorine removal reaction tank.
The stainless steel pickling wastewater treatment system according to any one of claims 1 to 7, wherein a membrane separation device is disposed at a communication portion between the water clearing port of the seventh concentration membrane device and the resin adsorption purification device; The water outlet of the membrane separation device is in communication with the resin adsorption purification device, and the sludge outlet of the membrane separation device is in communication with the seventh filter press.
The stainless steel pickling wastewater treatment system according to any one of claims 1 to 8, wherein the sulfuric acid pickling wastewater treatment system further comprises a sulfuric acid pickling wastewater storage tank, and the sulfuric acid pickling wastewater storage tank passes a first lift pump is in communication with the first filter device;

The mixed acid pickling wastewater treatment system further includes a mixed acid pickling wastewater storage tank, and the mixed acid pickling wastewater storage tank is in communication with the second filtering device through a second lift pump.
The stainless steel pickling wastewater treatment system according to any one of claims 1 to 9, wherein the resin adsorption purification device is further connected to the fluorine removal reaction tank.
The stainless steel pickling wastewater treatment system according to any one of claims 2 to 5, wherein the first dosing device comprises a first funnel, and the top and bottom of the first funnel are respectively provided with openings, An opening of the bottom of the first funnel is in communication with the first pH adjusting tank.
The stainless steel pickling wastewater treatment system according to any one of claims 2 to 5, wherein the first dosing device comprises a first tank, and the first tank is installed at the first pH Above the conditioning tank, the first tank is in communication with the first pH regulating tank through a pipeline.
The stainless steel pickling wastewater treatment system according to claim 12, wherein the pipeline is provided with a shut-off valve and a flow regulating valve, and the side wall of the first casing is provided with a sight glass, the sight glass One side of the first box body is provided with a mark line, and a feeding port is arranged on the top surface of the first box body, and the material feeding door is provided with a material door, and the material door is detachably connected with the feeding port.
The stainless steel pickling wastewater treatment system according to any one of claims 2 to 5, wherein the first dosing device comprises a first tank, and the first tank is disposed at the first pH One side of the adjustment tank is connected to the first pH adjustment tank through a pipeline, and the pipeline is provided with a pump.
The stainless steel pickling wastewater treatment system according to claim 14, wherein a weighing device is disposed below the first casing, and a side mirror is disposed on a side wall of the first casing. A feeding port is arranged on a top surface of a box body, and a feeding door is arranged on the feeding port, and the material door is hinged with the feeding port.
The stainless steel pickling wastewater treatment system according to claim 4, wherein said first pH monitoring device comprises a first pH sensor and a first controller;

The first pH sensor is disposed in the first pH adjustment tank, the first controller is coupled to the first pH sensor, and the first controller is configured to control activation of the first dosing device.
The stainless steel pickling wastewater treatment system according to any one of claims 2 to 5, wherein the first aeration device comprises a gas cylinder, and an outlet of the gas cylinder and the first manganese removal reaction tank pass The pipeline is connected, and the pipeline is provided with a shut-off valve and a flow regulating valve.