System and method for removing multi-characteristic water pollutants difficult to biochemically degrade

Abstract

The invention provides a system and a method for removing multi-characteristic water pollutants difficult to biochemically degrade. The removal system comprises a combined treatment unit, the acid adjusting part is used for pre-adjusting the pH value in the raw water storage lifting unit to a first interval and adjusting the pH value in the hydroxyl production oxidation unit to a second interval; the active catalyst feeding part comprises a first catalyst feeding part communicated to the hydroxyl-producing oxidation unit, a second catalyst feeding part communicated to the degassing coupling adsorption fading unit and third catalyst feeding devices respectively arranged in the hydroxyl-producing oxidation unit; the oxidant feeding part comprises a main material oxidant part and an auxiliary material oxidant part; the alkali adjusting part is used for adjusting and neutralizing the pH in the degassing coupling adsorption fading unit to a third interval; the adsorption complexing feeding part comprises an adsorbent part and a multi-calcium material part; and a coagulant feeding part. According to the removal system provided by the invention, the enhanced removal efficiency of specific pollutants in water can be enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of water treatment, and in particular to a system and method for removing multi-characteristic water pollutants that are difficult to biodegrade. Background Art

[0002] Characteristic pollutants refer to the representative parts of pollutants emitted by a certain industry, which can show the pollution degree of this industry. They can generally be understood as pollutants with higher emissions from the perspective of emission volume and total emission, such as organic pollutants and inorganic pollutants that are difficult to biochemically degrade in the pharmaceutical industry. In the same industry, due to different production processes and products, water pollutants may be different, and the difficulty of degradation treatment may also vary.

[0003] In the process of implementing the present invention, the inventors found that there are at least the following problems in the prior art:

[0004] The existing industrial wastewater, special industry wastewater, mixed industrial wastewater, cross-type characteristic organic pollutants (such as aromatic compounds, heterocyclic compounds, etc.), using conventional Fenton oxidation, quasi-Fenton oxidation, or ozone-aerated biological filter combined with existing degradation technology means, the removal rate of long-chain functional groups that are difficult to biodegrade (CODnb, COD ofnon-biodegration) is often less than 45%, it is difficult to ensure that the overall effluent is better than the Class A discharge standard or the reuse water standard, COD often exceeds 50mg / L, chromaticity far exceeds 30mg / L, and total phosphorus also exceeds 0.5mg / L, which is difficult to effectively degrade through biochemical pathways, and the removal efficiency is low, resulting in soluble COD, chromaticity, difficult-to-degrade total phosphorus, emerging water pollutants (such as POPs-persistent organic pollutants, PPCPs-Pharmaceutical and Personal Care Products antibiotics, EDCs-endocrine disruptors, PFAS-perfluorinated and polyfluoroalkyl substances), fluoride and other characteristic pollutants have high residual concentrations, and it is difficult to stably meet the pollutant indicators in the tail water, so it is difficult to ensure the ultimate quality of the tail water, and it is difficult to achieve the demand for resource reuse of the tail water. In addition, the infrastructure investment is large, the energy consumption, material and drug consumption, water consumption and periodic maintenance costs are high, and the greenhouse gas carbon dioxide equivalent emissions are large, making it difficult to achieve significant synergistic benefits of environmental, economic and social benefits.

[0005] Therefore, a system and method for removing multi-characteristic water pollutants that are difficult to biodegrade are needed to at least partially solve the above technical problems. Summary of the invention

[0006] The embodiments of the present invention provide a system and method for removing multi-characteristic water pollutants that are difficult to biodegrade, which can enhance the removal efficiency of residual characteristic pollutants such as COD and TP in water that are difficult to degrade through biochemical pathways.

[0007] In a first aspect, an embodiment of the present invention provides a system for removing multi-characteristic water pollutants that are difficult to biodegrade, the removal system comprising:

[0008] The combined treatment unit comprises a raw water storage and lifting unit, a hydroxyl group-generating oxidation unit, a degassing coupled adsorption and fading unit, a condensation reaction unit and a precipitation and separation unit which are sequentially connected; wherein the hydroxyl group-generating oxidation unit and the degassing coupled adsorption and fading unit respectively have a meandering separation reaction and diversion corridor (or partition wall) formed by spaced partition plates;

[0009] Acid adjustment components are connected to the raw water storage and lifting unit and the hydroxyl group-producing oxidation unit, respectively, and are used to pre-adjust the pH in the raw water storage and lifting unit to a first interval and to adjust the pH in the hydroxyl group-producing oxidation unit to a second interval;

[0010] The active catalyst feeding component comprises a first catalyst feeding component connected to the inlet proximal end of the hydroxyl group oxidation unit, a second catalyst feeding component connected to the inlet proximal end of the degassing coupling adsorption fading unit, and a third catalyst feeding device respectively arranged in the hydroxyl group oxidation unit; wherein the first catalyst feeding component and the second catalyst feeding component are used to feed a catalyst activator liquid with a preset flow ratio, and the third catalyst feeding device is used to feed a solid catalytic active granular material;

[0011] An oxidant feeding component, comprising a main material oxidant component and an auxiliary material oxidant component, each of which is connected to the inlet proximal end of the hydroxyl group oxidation unit through pipelines, and the main material oxidant component and the auxiliary material oxidant component are used to feed a first oxidant liquid and a second oxidant liquid respectively;

[0012] Alkali adjustment components are connected to the front middle point and the middle rear point of the degassing coupling adsorption fading unit respectively, and are used to adjust and neutralize the pH in the degassing coupling adsorption fading unit to a third interval;

[0013] An adsorption complex feeding component, comprising an adsorbent component and a multi-calcium material component each connected to the proximal end gallery of the degassing coupled adsorption fading unit, wherein the adsorbent component and the multi-calcium material component are used to feed an adsorbent solution and a calcium powder multi-material solution respectively; and

[0014] The coagulant feeding component is connected to the inlet head end of the coagulant reaction unit and is used for feeding the coagulant.

[0015] According to the removal system of the present invention, it includes a combined treatment unit, an acid adjustment component, an active catalyst feeding component, an oxidant feeding component, an alkali adjustment component, an adsorption complex feeding component, and a coagulant feeding component, etc., and the active catalyst feeding component and the oxidant feeding component are coupled with isotopic reactions, and the optimal reaction pH acid-base environment adjustment of the acid adjustment component and the alkali adjustment component is linked to achieve strong removal of characteristic organic pollutants (such as aromatic compounds, heterocyclic compounds, etc.) that are difficult to biodegrade. Through the strong input of the adsorption complex feeding component, the coordinated physical and chemical removal of characteristic multi-pollutants with low microbial biochemical degradation removal efficiency such as soluble COD, chromaticity, difficult-to-degrade total phosphorus, emerging water pollutants, fluoride, etc. can be further strengthened. It also greatly reduces infrastructure investment, saves energy consumption, material and drug consumption, water consumption, and periodic maintenance costs, and reduces greenhouse gas carbon dioxide equivalent emissions.

[0016] In a second aspect, an embodiment of the present invention further provides a method for removing multi-characteristic water pollutants that are difficult to biodegrade, and a removal system based on the above technical solution.

[0017] The degassing coupling adsorption fading unit adopts the first operation mode and the second operation mode to cyclically alternately control.

[0018] The first operating mode: the second controllable switch is started, the third controllable switch is closed, the fourth controllable switch is turned on, and the adsorbent component and the multi-calcium material component are in a shutdown state. Under this condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area - pre-degassing zone - post-neutralization reaction zone";

[0019] The second operating mode: the second controllable switch is closed, the third controllable switch is opened, the fourth controllable switch is closed, and the adsorbent component and the multi-calcium material component are in the operating state. Under this condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area - neutralization and degassing zone - adsorption and multi-calcium complexation feeding reaction zone".

[0020] According to the removal method of the present invention, the degassing coupled adsorption fading unit adopts the first operating mode and the second operating mode for cyclic alternating regulation, which can greatly reduce the consumption of reagents and save energy. The combined process can further enhance the removal efficiency of residual characteristic pollutants such as COD, TP, and emerging pollutants (such as POPs, PPCPs, EDCs, PFAS) that are difficult to degrade through biochemical pathways.

[0021] In a third aspect, an embodiment of the present invention further provides a method for removing multi-characteristic water pollutants that are difficult to biodegrade, and a removal system based on the above technical solution.

[0022] Among them, the pH value in the raw water storage and lifting unit is adjusted to 3.0-4.5 by adding an acid regulator, which is used as a pre-adjustment of the acidity to provide an acidic environment for the hydroxyl oxidation unit; the pH value in the hydroxyl oxidation unit is adjusted to 2.5-3.5 by adding an acid regulator, which is used as the main adjustment of the acidity to further ensure that the pH value in the one-third area near the inlet head end of the degassing coupled adsorption fading unit can still maintain a slightly acidic pH range of 3.5-4.8, thereby continuing the acidic reaction environment of the one-third area near the inlet head end of the degassing coupled adsorption fading unit to continue to participate in the Fenton oxidation reaction II stage; Among them,

[0023] Mode of pre-adjusting acidity: the acid storage agent dosing component of the first acid adjustment component is linked with the first pH meter to control the amount of acid adjustment agent, and the pH value range is adjusted by PID;

[0024] Mode of main acidity adjustment: the acid storage and dosing component of the second acid adjustment component is linked with the second pH meter and the third pH meter to control the amount of acid regulator adjustment, the second pH meter feedforward controls the frequency conversion frequency of the acid storage and dosing component of the second acid adjustment component to adjust the delivery amount, the third pH meter feedback assists in monitoring and correcting the frequency conversion frequency of the acid storage and dosing component of the second acid adjustment component, and PID is used for adjustment within the pH value range.

[0025] According to the removal method of the present invention, the drug delivery frequency of the acid storage agent dosing component of the first acid adjustment component and the pumping component of the acid storage agent dosing component of the second acid adjustment component can be accurately achieved.

[0026] Additional advantages, purposes, and features of the present invention will be described in part in the following description, and will become apparent to those skilled in the art after studying the following, or may be learned from the practice of the present invention. The purposes and other advantages of the present invention may be achieved and obtained by the structures specifically indicated in the specification and the accompanying drawings.

[0027] Those skilled in the art will appreciate that the objectives and advantages that can be achieved with the present invention are not limited to the above specific description, and the above and other objectives that can be achieved by the present invention will be more clearly understood from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The drawings described herein are used to provide a further understanding of the present invention, constitute a part of this application, and do not constitute a limitation of the present invention. The components in the drawings are not drawn to scale, but are only for illustrating the principles of the present invention. In order to facilitate the illustration and description of some parts of the present invention, the corresponding parts in the drawings may be enlarged, that is, they may become larger relative to other components in the exemplary device actually manufactured according to the present invention. In the drawings:

[0029] Figure 1is a schematic diagram of a removal system according to an embodiment of the present invention;

[0030] Figure 2 is a schematic diagram of a degassing coupled adsorption fading unit in a removal method according to an embodiment of the present invention when the unit is in a first operation mode;

[0031] Figure 3 is a schematic diagram of a degassing coupled adsorption fading unit in a removal method according to an embodiment of the present invention when the degassing coupled adsorption fading unit is in a second operation mode; and

[0032] Figure 4 It is a schematic diagram of the removal efficiency improvement effect of the removal system according to one embodiment of the present invention on the residual refractory COD.

[0033] Description of reference numerals:

[0034] 100. Removal system;

[0035] 11. Raw water storage and lifting unit; 12. Hydroxyl production and oxidation unit; 13. Degassing coupling adsorption and fading unit; 14. Coagulation reaction unit; 15. Sedimentation and separation unit;

[0036] 21. Acid storage agent dosing components; 23. Acid storage agent dosing components; 22. Dosing pipeline components; 24. Dosing pipeline components;

[0037] 31. Catalyst dosing component; 32. Catalyst dosing pipeline; 33. Catalyst dosing pipeline; 3a', solid particle catalyst head-end interception device; 3b', solid particle catalyst end interception device; 3', solid catalytic active particle material;

[0038] 41. Main material oxidant component; 42. Auxiliary material oxidant component;

[0039] 51. Alkali storage agent dosing components and dosing main pipeline; 52. Branch pipeline; 53. Branch pipeline;

[0040] 61. Adsorbent component; 62. Multi-calcium material component;

[0041] 7. Coagulant feeding parts;

[0042] 81. first stirring component; 82. second stirring component; 83. aeration component; 84. third stirring component; 85. mud scraping and suction component;

[0043] 91. a first pH meter; 92. a second pH meter; 93. a third pH meter; 94. a fourth pH meter;

[0044] 121, reaction liquid reflux pipeline; 121a, reflux pump component;

[0045] 131. Separate the reaction diversion corridor;

[0046] 151a, sludge return pipeline; 151b, sludge discharge pipeline; 151a1, pumping component; 151b1, pumping component;. DETAILED DESCRIPTION

[0047] By referring to the exemplary embodiments, the objects and functions of the present invention and the methods for achieving these objects and functions will be explained. However, the present invention is not limited to the exemplary embodiments disclosed below; it can be implemented in different forms. The essence of the description is only to help those skilled in the relevant art to comprehensively understand the specific details of the present invention.

[0048] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should also be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, wholes, steps, operations, elements and / or components, but does not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or combinations thereof.

[0049] Ordinal numbers such as "first" and "second" cited in the present invention are merely identifications and do not have any other meanings, such as a specific order, etc. Moreover, for example, the term "first component" itself does not imply the existence of the "second component", and the term "second component" itself does not imply the existence of the "first component".

[0050] It should be noted that the terms "upper", "lower", "front", "back", "left", "right", "inside", "outside" and similar expressions used in this document are for illustrative purposes only and are not limiting.

[0051] The embodiment of the present invention provides a system 100 for removing multi-characteristic water pollutants that are difficult to biodegrade. Figure 1 The removal system 100 may include a combined treatment unit, an acid adjustment component, an active catalyst feeding component, an oxidant feeding component, an alkali adjustment component, an adsorption complex feeding component, a coagulant feeding component 7, a power component and a pH measuring instrument component.

[0052] Specifically, the combined treatment unit may include a raw water storage and lifting unit 11, a hydroxyl group oxidation unit 12, a degassing coupled adsorption and fading unit 13, a coagulation reaction unit 14 and a precipitation separation unit 15. The raw water storage and lifting unit 11 is connected to the sewage to be treated through a pipeline. Among them: acid pre-adjustment is performed in unit 11 to provide an acidic environment for the subsequent oxidation of unit 12, and its hydraulic retention time is 20 to 40 minutes. Units 12 and 13 are the main units of the physicochemical reaction (with a separation reaction diversion corridor 131, such as 131 in unit 13), wherein the hydraulic retention time of unit 12 is 3 to 6 hours. The hydraulic retention time of unit 13 is 2 to 4 hours. Unit 14 promotes the modification and coagulation of colloids, particulate pollutants and suspended matter through electrical neutralization, flocculation and coagulation, adsorption and bridging, etc. Unit 15 performs gravity separation on the reaction precipitate and sewage, and its hydraulic retention time is 1 to 3 hours. A reaction liquid reflux pipeline 121 (with a reflux pump component 121a) can be provided at the inner end of the self-unit 12, and the reaction liquid can be refluxed to its own inflow head end, and the reflux ratio is 3% to 10% according to the processing volume, so that the residual liquid that has not reacted completely can be recirculated to the unit 12 system, reducing the loss of chemical agents such as acids, catalysts, and oxidants, and improving the utilization rate of the agents. Unit 15 can be equipped with a bottom sludge conveying system 151, including a sludge reflux pipeline 151a and a sludge discharge pipeline 151b, and correspondingly provided with pumping components 151a1 and 151b1. A small amount of the bottom sludge of unit 15 is circulated back to the middle and rear points of unit 13 through 151a, and the reflux ratio is 5% to 12% according to the processing volume. Excess sludge in unit 15 is discharged to the sludge storage unit to be dehydrated through 151b for subsequent sludge dehydration treatment to limit the depth of the bottom sludge layer in unit 15 and ensure that there is enough clean water protection layer on the top of the sludge layer (the upper clean water layer is not less than 1.0m). Figure 1 Not shown.

[0053] The acid adjustment component may include pipeline components 21 to 24. Among them: 21 and 23 are acid storage agent dosing components, which mainly contain a drug storage tank and a liquid acid-resistant pumping component. The pumping component is an intelligent pump that adjusts the drug delivery through frequency conversion precision. 21 can be interlocked with 91 (mentioned below) to control the amount of drug adjustment, and 23 can be interlocked with 92 (mentioned below) to control the amount of drug adjustment. 22 and 24 are dosing pipeline components (the pipeline is provided with a controllable switch for opening and closing / adjusting the flow, such as a valve). The acid regulator can be concentrated sulfuric acid or dilute sulfuric acid, and the pH in the control unit 11 is adjusted to 3.0 to 4.5. 91 can be interlocked with the liquid acid-resistant pumping component of 21, and the pH value range is adjusted by PID. When the value is lower than the lower limit of the threshold, the pump is stopped; when the value is higher than the upper limit of the threshold, the pump is started to pre-adjust the acidity. The pH in the control unit 12 is adjusted to 2.5-3.5. 92 can be interlocked with the acid-resistant pumping component of the liquid medicine 23. The pH value range is adjusted by PID. When the value is lower than the lower threshold, the pump is stopped; when the value is higher than the upper threshold, the pump is started. 92 feedforward controls the frequency conversion frequency of the acid-resistant pumping component of the liquid medicine 23 to adjust the amount of medicine delivered, while 93 feedback assists in monitoring and appropriately corrects and controls the frequency conversion frequency of the acid-resistant pumping component of the liquid medicine 23, thereby realizing the feedforward main control + feedback monitoring / correction control of the precise frequency of the acid-resistant pumping component of the liquid medicine 23 through 92&93, which is the main acid adjustment. After the pH range of unit 12 is adjusted to 2.5-3.5, it can be further ensured that the pH in the front one-third area of ​​the space near the inlet head end of unit 13 can still be maintained in the acidic range of 3.5-4.8, thereby continuing the acidic reaction environment of the near one-third area of ​​the head end of unit 13 to continue to participate in the Fenton oxidation reaction II stage.

[0054] The active catalyst feeding component is a Fenton oxidation stage I, and may include components 31 to 33 and a solid particle catalyst head-end interception device 3a' and a solid particle catalyst tail-end interception device 3b' respectively arranged at the head and tail ends of the inflow in unit 12. The interception devices 3a' and 3b' may be configured to include mesh boxes each filled with solid catalytic active particles 3'. Among them: 31 is a catalyst dosing component (mainly containing a dissolving medicine storage tank and a liquid medicine pumping component) and a dosing main pipeline. 32 and 33 are catalyst feeding pipelines for dosing into the near-head end of the inflow of units 12 and 13 respectively (the pipelines are provided with controllable switches for opening and closing / adjusting the flow, and the one on 33 is the second controllable switch). The flow adjustment ratio of the branch liquid entering units 12 and 13 is (0.9~0.95): (0.05~0.1). The catalytic activator of 31 is preferably ferrous salt (Fe 2+ ) is mainly composed of ferrous sulfate, supplemented by ferrous chloride and magnetic powder Fe 3 O 4The mass ratio of the three can be in the range of 1-3:1:0.2-0.5, and the dry powder can be mixed and dissolved in water. The powder can be prepared into a 2%-10% liquid dilution with tap water or clean water from unit 15 and then transported. The solid catalytic active particle material 3' can be made of activated alumina, molecular sieve and titanium dioxide (TiO 2 ) are mixed and proportioned, and the mass ratio is 1-3:1:0.2-0.5, and the volume filling ratio in the unit 12 is 5%-15%. The solid catalytic active particles 3' are arranged in a fixed mesh box. The pores of the mesh box device are smaller than the particle size of the active particles, ensuring that water can pass through while the active particles are blocked in the mesh box. 2+ ), magnetic powder (Fe-II, Fe-III iron-based bivalent state), activated alumina, molecular sieve and titanium dioxide (TiO 2 ), forming a heterogeneous catalytic reaction system.

[0055] The oxidant feeding component may include a main material oxidant component 41 and an auxiliary material oxidant component 42, both of which are fed to the inlet near the head end of the unit 12. Among them: 41 and 42 both contain a drug storage tank and a drug liquid pumping component. 41 feeds hydrogen peroxide (generally 27.5% or lower content). 42 feeds potassium persulfate (tap water or clean water from unit 15, the powder can be configured into a 2% to 10% liquid dilution and then transported). Sulfate free radicals and hydroxyl free radicals can be generated by oxidative decomposition of persulfate. These two oxidant components 41 and 42 are set, in the aforementioned ferrous salt (Fe 2+ ), magnetic powder (divalent Fe-II, trivalent Fe-III iron-based bivalent state), activated alumina, molecular sieve and titanium dioxide (TiO 2 ) coupling, a heterogeneous mixed catalytic activation-persulfate-Fenton co-oxidation system of sulfate radicals and hydroxyl radicals (·OH) is formed.

[0056] The alkali adjustment component may include pipeline components 51 to 53. Among them: 51 is an alkali storage agent dosing component and a dosing main pipeline, which mainly contains a dissolved medicine storage tank and a liquid alkali-resistant pumping component. The pumping component is an intelligent pump that adjusts the drug delivery through frequency conversion accuracy, and it is interlocked with 93 or 94 (mentioned below) to control the amount of drug adjustment. 52 and 53 are branch pipelines for drug delivery into the front middle point and the middle and rear points of the unit 13 respectively. The pipeline is provided with a controllable switch for opening and closing / adjusting the flow, wherein a third controllable switch is provided on 52, and a fourth controllable switch is provided on 53. The alkali regulator can be liquid sodium hydroxide, and the pH in the neutralization control unit 13 is adjusted to 7.0 to 8.5. 93 or 94 is interlocked with the liquid alkali-resistant pumping component 51, and the pH value range is adjusted by PID. When the value is lower than the lower limit of the threshold, the pump is started; when the value is higher than the upper limit of the threshold, the pump is stopped.

[0057] Among them, the connection position between the 52 branch pipeline and the unit 13 is separated from the head end corridor of the unit 13 by at least one corridor.

[0058] The adsorption complex feeding component may include an adsorbent component 61 and a multi-calcium material component 62, both of which are added to the near-end corridor of unit 13. Among them: 61 and 62 both contain a dissolving medicine storage tank and a liquid medicine pumping component. 61 is activated carbon for coal-based sewage (its iodine adsorption value is not less than 750 mg / g, and its methylene blue adsorption value is not less than 110 mg / g), and is supplemented with an adsorption resin mixed ratio (the mass ratio of activated carbon to resin is 1-3:0.3-0.6). 62 is a mixed ratio calcium powder multi-material, which is mixed and proportioned with calcium aluminate, calcium hydroxide, calcium chloride and calcium carbonate, wherein the total amount of the mixed material: the mass proportion of calcium aluminate is about 70% to 80%, the mass proportion of calcium hydroxide is about 10% to 20%, and the mass proportion of calcium chloride and calcium carbonate is about 2.5% to 5% respectively. Tap water or clean water from unit 15 can be used to prepare the mixed powder into a 2% to 10% liquid dilution and then transported. 61 is used to further remove the organic pollutants, emerging pollutants (such as POPs, PPCPs, EDCs, PFAS), total phosphorus (such as phytic acid, phytate phosphorus substituents), colored functional groups and other complex pollutants that remain in the wastewater as soluble and difficult-to-degrade components after heterogeneous oxidation in 12, by means of enhanced dual adsorption. 62 can assist 61, and with the total phosphorus, fluoride, and colored functional groups of the aforementioned organic or inorganic phosphorus components that are difficult to be oxidized and degraded, through iron (Fe-III) and calcium metal ions, calcium fluoride, and complex insoluble substances such as phosphorus iron and phosphorus calcium are formed, and the characteristic pollutants are transferred from the water phase to the solid phase for co-adsorption flocculation and precipitation separation for removal.

[0059] The coagulant feeding component 7 is fed to the corridor near the head end of the unit 14, and may include a dissolving medicine storage tank and a medicine liquid pumping component. The coagulant is a mixed ingredient, and anionic PAM (polyacrylamide) and sodium alginate are mixed and proportioned. Among the total amount of the mixture: PAM accounts for about 70% to 85% by weight, and sodium alginate accounts for about 15% to 30% by weight. The mixed powder can be prepared into a liquid dilution of 0.8‰ to 2.0‰ with tap water or clean water from the unit 15 and then transported.

[0060] The power component may include a first stirring component 81, a second stirring component 82, an aeration component 83, a third stirring component 84 and a sludge scraping and sucking component 85. 81 to 84 provide stirring or aeration power to units 11, 12, 13 and 14 one by one. 85 performs solid-liquid separation of mud and water in unit 15 to ensure that the upper clear liquid with the expected purification efficiency is discharged and the bottom sludge is regularly discharged from the system.

[0061] The pH measuring instrument components may include 91 (i.e., a first pH meter) installed in unit 11, a second pH meter 92 installed in unit 12, a third pH meter 93 installed in the inlet head end area of ​​unit 13, and a fourth pH meter 94 installed in the inlet tail end area, which are respectively used to monitor the pH of the reaction liquid at the installation position points of the corresponding units.

[0062] In summary, according to the removal system 100 of the present invention, the active catalyst feeding component and the oxidant feeding component are coupled with isotopic reactions, and the optimal reaction pH acid-base environment adjustment of the acid adjustment component and the alkali adjustment component are linked to achieve strong removal of characteristic organic pollutants (such as aromatic compounds, heterocyclic compounds, etc.) that are difficult to biodegrade. Through the strong input of the adsorption complex feeding component and the reasonable reflux of the circulating liquid, the coordinated physical and chemical removal of characteristic multi-pollutants with low microbial biodegradation efficiency such as soluble COD, chromaticity, difficult-to-degrade total phosphorus, emerging water pollutants, fluoride, etc. can be further enhanced. For example, the COD index of stubborn organic pollutants with long-chain functional groups that are difficult to biodegrade (COD nb ) is the removal target, compared with the existing degradation technology means (COD nb The removal rate is 30% to 45%), which can further ensure a significant increase in removal efficiency of 20% to 40%, and greatly reduce infrastructure investment, save energy consumption, material and water consumption and periodic maintenance costs, and reduce greenhouse gas carbon dioxide equivalent emissions. Significant environmental benefits: After the wastewater is treated by secondary biodegradation, the COD (COD nb ) mass concentration still remains in the range of 80-110 mg / L, the coupled enhanced technology can be used to regulate and remove, which can ensure that the overall effluent is better than Class A, and the COD reaches 30-50 mg / L or lower concentration range (such as Figure 4 Example). At the same time, it can ensure that the chromaticity is reduced to less than 30mg / L. When the total phosphorus in the raw water that is difficult to biodegrade or coagulate and precipitate is in the range of 0.3-1.2mg / L, the total phosphorus can be reduced to 0.15-0.40mg / L through the regulation and removal of this technical means, of which orthophosphate is reduced to less than 0.05mg / L. It also has a good oxidation removal effect on emerging pollutants in water.

[0063] In a second aspect, the present invention further provides a removal method of the removal system 100 based on the above embodiment.

[0064] The following will be based on Figure 2 and Figure 3 , briefly describing the process of the removal method of an embodiment of the present invention.

[0065] Figure 2 , Figure 3The two main control timing alternating modes of unit 13 adopt cascade cycle control (after the first operation mode, the second operation mode continues, and then returns to the first operation mode, and this cycle is repeated), wherein the operating time of the first operation mode is 0 to 30 minutes, and the preset time T1 parameter is adjustable; the second operation mode continues the first operation mode, and the operating time is also 0 to 30 minutes, and the preset time T2 parameter is adjustable.

[0066] For example, when T1 and T2 are set to 30 minutes, after running in the first operating mode for 30 minutes, it can be switched to the second operating mode for 30 minutes, and then switched to the first operating mode, and so on. Such alternating operation can greatly reduce the consumption of reagents and save energy. The combined process can also enhance the removal efficiency of residual characteristic pollutants such as COD, TP, and emerging pollutants (such as POPs, PPCPs, EDCs, and PFAS) that are difficult to degrade through biochemical pathways.

[0067] The first operating mode: the second controllable switch and the corresponding pumping components are started, the third controllable switch is closed, the fourth controllable switch and the corresponding pumping components are turned on, and the adsorbent component and the multi-calcium material component are in a shutdown state. Under this operating condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area-pre-degassing zone-post-neutralization reaction zone".

[0068] The second operating mode: the second controllable switch and the corresponding pumping components are closed, the third controllable switch and the corresponding pumping components are turned on, the fourth controllable switch is closed, and the adsorbent component and the multi-calcium material component are in the operating state. Under this operating condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area-neutralization and degassing zone-adsorption and multi-calcium complex feeding reaction zone".

[0069] In a third aspect, the present invention further provides a removal method of the removal system 100 based on the above embodiment.

[0070] Among them, the pH in the raw water storage and lifting unit is adjusted to 3.0-4.5 by adding an acid regulator, which is used as a pre-adjustment of the acidity to provide an acidic environment for the hydroxyl oxidation unit. The pH in the hydroxyl oxidation unit is adjusted to 2.5-3.5 by adding an acid regulator, which is used as the main adjustment of the acidity to further ensure that the pH in the one-third area near the inlet head end of the degassing coupled adsorption fading unit can still be maintained in the acidic range of pH 3.5-4.8, thereby continuing the acidic reaction environment of the one-third area near the inlet head end of the degassing coupled adsorption fading unit to continue to participate in the Fenton oxidation reaction II stage.

[0071] Among them, the mode of pre-adjusting acidity: the acid storage agent dosing component (pumping component) of the first acid adjustment component and the first pH meter are linked to control the amount of acid adjustment agent, and the pH value range is adjusted by PID.

[0072] Mode of main acidity adjustment: the acid storage and dosing component of the second acid adjusting component is linked with the second pH meter and the third pH meter to control the amount of acid regulator adjustment, the second pH meter feedforward controls the frequency conversion frequency of the acid storage and dosing component (pumping component) of the second acid adjusting component to adjust the delivery amount, the third pH meter feedback assists in monitoring and correcting the frequency conversion frequency of the acid storage and dosing component (pumping component) of the second acid adjusting component, and the pH value range is adjusted by PID.

[0073] Other embodiments of the present invention will be readily apparent to those skilled in the art from the description and practice of the invention disclosed herein. The description and embodiments are to be considered exemplary only, and the true scope and spirit of the present invention are to be limited by the claims.

Claims

1. A system for removing multi-characteristic water pollutants that are difficult to biodegrade, characterized in that: The removal system comprises: The combined treatment unit comprises a raw water storage and lifting unit, a hydroxyl group-generating oxidation unit, a degassing coupled adsorption and fading unit, a condensation reaction unit and a precipitation and separation unit which are sequentially connected; wherein the hydroxyl group-generating oxidation unit and the degassing coupled adsorption and fading unit respectively have a winding and extending separation reaction and diversion corridor formed by spaced partition plates; Acid adjustment components are connected to the raw water storage and lifting unit and the hydroxyl group-producing oxidation unit, respectively, and are used to pre-adjust the pH in the raw water storage and lifting unit to a first interval and to adjust the pH in the hydroxyl group-producing oxidation unit to a second interval; The active catalyst feeding component comprises a first catalyst feeding component connected to the inlet proximal end of the hydroxyl group oxidation unit, a second catalyst feeding component connected to the inlet proximal end of the degassing coupling adsorption fading unit, and a third catalyst feeding device respectively arranged in the hydroxyl group oxidation unit; wherein the first catalyst feeding component and the second catalyst feeding component are used to feed a catalyst activator liquid with a preset flow ratio, and the third catalyst feeding device is used to feed a solid catalytic active granular material; An oxidant feeding component, comprising a main material oxidant component and an auxiliary material oxidant component, each of which is connected to the inlet proximal end of the hydroxyl group oxidation unit through pipelines, and is used to feed a first oxidant liquid and a second oxidant liquid respectively; Alkali adjustment components are connected to the front middle point and the middle rear point of the degassing coupling adsorption fading unit respectively, and are used to adjust and neutralize the pH in the degassing coupling adsorption fading unit to a third interval; Adsorption complex feeding components, including adsorbent components and multi-calcium material components each connected to the near-end gallery of the degassing coupled adsorption fading unit, for respectively feeding adsorbent liquid and calcium powder multi-material liquid; and The coagulant feeding component is connected to the inflow head end of the coagulant reaction unit and is used for feeding the coagulant.

2. The removal system according to claim 1, characterized in that The removal system is constructed as follows: The acid adjustment component includes a first acid adjustment component with a controllable switch connected to the raw water storage and lifting unit through a pipeline and a second acid adjustment component with a controllable switch connected to the hydroxyl-producing oxidation unit through a pipeline, wherein the first acid adjustment component is used to pre-adjust the pH in the raw water storage and lifting unit to 3.0-4.5, and the second acid adjustment component is used to adjust the pH in the hydroxyl-producing oxidation unit to 2.5-3.5; Wherein, the first acid adjustment component and the second acid adjustment component each include a connected acid storage agent dosing component and a dosing pipeline component with a controllable switch.

3. The removal system according to claim 1, characterized in that The first catalyst feeding component comprises a first catalyst feeding pipeline with a controllable switch connected to the catalyst feeding component; The second catalyst dosing component comprises a second catalyst dosing pipeline connected to the catalyst dosing component and having a second controllable switch; The third catalyst feeding device comprises an interception device with mesh arranged at the inlet head and tail ends of the hydroxyl oxidation unit to prevent the filler from escaping from the hydroxyl oxidation unit, and solid catalytic active granular material filled in the interception device; Wherein, the catalytic activator is a powder dissolved in water to form a 2% to 10% liquid diluent, wherein the components of the powder include ferrous sulfate, ferrous chloride and magnetic powder Fe3O4 of ferrous salts, and the mass ratio of each is 1 to 3:1:0.2 to 0.5; the components of the solid catalytic active granular material include activated alumina, molecular sieve and titanium dioxide, and the mass ratio is 1 to 3:1:0.2 to 0.5, and the volume filling ratio of the solid catalytic active granular material in 12 units is 5% to 15%; and / or The flow rate ratio of the catalyst activator liquid added by the first catalyst feeding component and the second catalyst feeding component is (0.9-0.95): (0.05-0.1).

4. The removal system according to claim 1, characterized in that The main material oxidant component and the auxiliary material oxidant component each include a solution storage tank and a liquid pumping component, and the first main material oxidant liquid and the second auxiliary material oxidant liquid are hydrogen peroxide and potassium persulfate dilution respectively.

5. The removal system according to claim 1, characterized in that The alkali adjustment component includes a first alkali adjustment dosing pipeline component with a third controllable switch and a second alkali adjustment dosing pipeline component with a fourth controllable switch, which are respectively connected to the front middle point and the middle rear point of the degassing coupling adsorption fading unit through pipelines, wherein the alkali adjuster is a sodium hydroxide solution.

6. The removal system according to claim 1, characterized in that The adsorbent liquid is a liquid obtained by mixing activated carbon for coal-based sewage and adsorption resin in a mass ratio of 1 to 3:0.3 to 0.6, wherein the iodine adsorption value of the activated carbon for coal-based sewage is not less than 750 mg / g, and the methylene blue adsorption value is not less than 110 mg / g; The calcium powder multi-material liquid is a 2% to 10% liquid dilution prepared by dissolving calcium powder multi-material in water, wherein the components of the calcium powder multi-material include calcium aluminate, calcium hydroxide, calcium chloride and calcium carbonate, wherein: the mass proportion of calcium aluminate is about 70% to 80%, the mass proportion of calcium hydroxide is about 10% to 20%, and the mass proportions of calcium chloride and calcium carbonate are about 2.5% to 5% respectively.

7. The removal system according to claim 1, characterized in that Also includes: The power component includes a first stirring component, a second stirring component, an aeration component, a third stirring component and a sludge scraping component which are respectively arranged in the raw water storage and lifting unit, the hydroxyl group oxidation unit, the degassing coupling adsorption fading unit, the condensation reaction unit and the precipitation separation unit; and / or The pH measuring instrument components include a first pH meter arranged in the raw water storage and lifting unit, a second pH meter arranged in the hydroxyl group oxidation unit, and a third pH meter and a fourth pH meter respectively arranged at the inlet head and tail ends of the degassing coupled adsorption and fading unit, which are used to monitor the pH of the reaction liquid at corresponding positions.

8. The removal system according to claim 1, characterized in that Also includes: A reaction liquid reflux pipeline is provided at the end of the self-produced hydroxyl oxidation unit to connect the inlet head and tail ends thereof, so as to realize the reaction liquid reflux according to the preset reflux ratio of the processing volume; wherein the preset reflux ratio of the processing volume is 3% to 10%, The pipeline is connected to the sludge conveying system at the bottom of the sedimentation separation unit, and the sludge conveying system includes: A sludge return pipeline component for returning the bottom sludge according to a preset return ratio of the processing volume to the middle and rear points of the degassing coupled adsorption fading unit, wherein the preset return ratio of the processing volume is 5% to 12%; and / or Sludge removal piping components used to discharge excess sludge from the bottom to limit the depth of the bottom sludge layer in the sedimentation separation unit.

9. A method for removing multi-characteristic water pollutants that are difficult to biodegrade, based on the removal system according to any one of claims 1 to 8, characterized in that: The degassing coupled adsorption fading unit adopts the first operation mode and the second operation mode to cyclically alternately control, wherein The first operating mode: the second controllable switch is started, the third controllable switch is closed, the fourth controllable switch is turned on, and the adsorbent component and the multi-calcium material component are in a shutdown state. Under this condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area - pre-degassing zone - post-neutralization reaction zone"; The second operating mode: the second controllable switch is closed, the third controllable switch is opened, the fourth controllable switch is closed, and the adsorbent component and the multi-calcium material component are in the operating state. Under this condition, the degassing coupled adsorption fading unit reaction zone forms a coupled spatial reaction partition of "Fenton oxidation reaction II level area - neutralization and degassing zone - adsorption and multi-calcium complex feeding reaction zone".

10. A method for removing multi-characteristic water pollutants that are difficult to biodegrade, based on the removal system according to any one of claims 1 to 8, characterized in that: The pH value in the raw water storage and lifting unit is adjusted to 3.0-4.5 by adding an acid regulator, which is used as a pre-adjustment of the acidity to provide an acidic environment for the hydroxyl oxidation unit; the pH value in the hydroxyl oxidation unit is adjusted to 2.5-3.5 by adding an acid regulator, which is used as the main adjustment of the acidity to further ensure that the pH value in the one-third area near the inlet head end of the degassing coupled adsorption fading unit can still be maintained in the acidic range of pH 3.5-4.8, thereby continuing the acidic reaction environment of the one-third area near the inlet head end of the degassing coupled adsorption fading unit to continue to participate in the Fenton oxidation reaction II; Mode of pre-adjusting acidity: the acid storage agent dosing component of the first acid adjustment component is linked with the first pH meter to control the amount of acid adjustment agent, and the pH value range is adjusted by PID; Mode of main acidity adjustment: the acid storage and dosing component of the second acid adjustment component is linked with the second pH meter and the third pH meter to control the amount of acid regulator adjustment, the second pH meter feedforward controls the frequency conversion frequency of the acid storage and dosing component of the second acid adjustment component to adjust the delivery amount, the third pH meter feedback assists in monitoring and correcting the frequency conversion frequency of the acid storage and dosing component of the second acid adjustment component, and PID is used for adjustment within the pH value range.

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