Cold rolling wastewater treatment agent and wastewater treatment method thereof

Abstract

The invention provides a cold rolling wastewater treatment agent and a sewage treatment method thereof, and is applied to the field of cold rolling wastewater treatment. The cold rolling wastewater treatment agent comprises an adsorption carrier, a coagulation core, a chelating agent, a demulsifying agent and a bridging flocculating agent. Compared with existing common coagulants and flocculants, the cold rolling wastewater treatment agent can effectively destroy stable oil-in-water emulsion in cold rolling wastewater; the components of the agent can generate chelation reaction with zinc, chromium, nickel and other heavy metal ions existing in the wastewater in a dissolved state; by introducing a magnetic component as a core, the problems of slow sedimentation and low solid-liquid separation efficiency caused by loose and light floc of the existing medicament can be effectively solved.

Description

Technical Field

[0001] This invention relates to the technical field of cold rolling wastewater treatment, and more specifically, to a cold rolling wastewater treatment agent and a wastewater treatment method thereof. Background Technology

[0002] Wastewater treatment in the cold rolling process of the steel industry faces numerous challenges. Current technologies using ordinary inorganic coagulants or simple organic flocculants as wastewater treatment agents suffer from poor treatment effects and unstable operation. Specifically, the technical drawbacks are as follows: 1) Oils in cold rolling wastewater mainly exist in a highly stable oil-in-water (O / W) emulsion form. The oil droplets are small in size and negatively charged, forming a stable dispersion system. Existing agents have weak demulsification targeting, resulting in persistently excessive oil content in the effluent. 2) For the existing suspended solids in the wastewater, the flocs formed by existing agents are often lightweight, loosely structured, and small in size. These flocs settle slowly under static conditions and are easily carried out by the water flow in sedimentation tanks or clarification equipment where there is an upward flow velocity, resulting in extremely low solid-liquid separation efficiency. Therefore, existing agents cannot form dense flocs, causing sludge to float and run off, resulting in high turbidity in the effluent. 3) Cold rolling wastewater is usually highly acidic, which severely inhibits the hydrolysis process of conventional coagulants, preventing them from forming effective flocs. This leads to a sharp decline in efficacy or even complete ineffectiveness, and poses a risk of acid corrosion to equipment. Additionally, it contains dissolved heavy metal ions such as zinc, chromium, and nickel that cannot be removed.

[0003] Therefore, there is an urgent need for a highly efficient cold rolling wastewater treatment agent. Summary of the Invention

[0004] In view of the above problems, the purpose of this invention is to provide a cold rolling wastewater treatment agent and a wastewater treatment method thereof to solve at least one problem existing in the prior art.

[0005] In a first aspect, the present invention provides a cold rolling wastewater treatment agent, comprising, by weight parts, the following components: adsorption carrier: 400-600 parts; coagulation nuclei: 50-100 parts; chelating agent: 30-60 parts; demulsifier: 10-25 parts; bridging flocculant: 2-5 parts.

[0006] In addition, an optional technical solution is that the adsorption carrier is one of acid-modified fly ash, acid-modified red mud, or acid-modified blast furnace slag.

[0007] In addition, an optional technical solution is that the condensation nucleus is one of iron tetroxide nanoparticles, cobalt ferrite nanoparticles, or nickel ferrite nanoparticles.

[0008] In addition, an optional technical solution is that the chelating agent is waste cation exchange resin powder or modified regenerated carbon powder. It should be noted that the chelating agent is at least one of the following: physically activated or chemically modified waste activated carbon powder or waste biochar powder; activation treatment, performed at high temperature of 750-1000℃ under a protective atmosphere to restore and reconstruct its pore structure; chemical modification, through impregnation, precipitation, or other methods, loading metal oxides onto its surface or introducing specific functional groups to enhance its targeted adsorption capacity for specific pollutants.

[0009] In addition, an optional technical solution is that the demulsifier is a nonionic or cationic demulsifier; and / or the bridging flocculant is a cationic polyacrylamide. It should be noted that the bridging flocculant is a cationic polyacrylamide with a molecular weight of 5 million to 15 million and a cationicity of 20% to 60%. The demulsifier is selected from at least one of polyether-modified polysiloxane and polyquaternary ammonium salt.

[0010] Secondly, this invention provides a wastewater treatment method for treating cold rolling wastewater. The method comprises the following components of a cold rolling wastewater treatment agent, obtained by weight: 400-600 parts of an adsorbent carrier, 50-100 parts of a coagulation nucleus, 30-60 parts of a chelating agent, and 10-25 parts of a demulsifier. After adjusting the pH of the cold rolling wastewater to be treated to 6-8, the cold rolling wastewater treatment agent is added and mixed. Then, 2-5 parts of a bridging flocculant are added and mixed until flocs are formed in the cold rolling wastewater. The floc-forming cold rolling wastewater is then precipitated to complete solid-liquid separation. It should be noted that this wastewater treatment method effectively reduces water quality indicators such as turbidity, oil content, and heavy metal ion concentration.

[0011] Alternatively, an optional technical solution is to apply a pressurized integrated wastewater purification device to treat cold rolling wastewater. The method includes obtaining the following components of a cold rolling wastewater treatment agent by weight: 400-600 parts of adsorbent carrier, 50-100 parts of coagulation nuclei, 30-60 parts of chelating agent, and 10-25 parts of demulsifier; adjusting the pH of the cold rolling wastewater to be treated to 6-8; adding the cold rolling wastewater treatment agent to the pressurized integrated wastewater purification device in the primary reaction zone for a primary reaction; the primary reaction zone includes a water flow path from the swirling primary sedimentation chamber to the primary flocculation reaction chamber; adding 2-5 parts of bridging flocculant to the pressurized integrated wastewater purification device in the secondary reaction zone, mixing and reacting it with the cold rolling wastewater after the primary reaction until flocs are formed in the cold rolling wastewater; the secondary reaction zone includes a water flow path for the secondary flocculation reaction chamber; and then settling the floc-forming cold rolling wastewater to complete solid-liquid separation.

[0012] In addition, an optional technical solution is that, in the primary reaction zone, the cold rolling wastewater treatment agent is added at the vortex primary sedimentation chamber; and in the secondary reaction zone, the bridging flocculant is added at the hydraulic circulation clarification chamber of the secondary flocculation reaction chamber.

[0013] In addition, optional technical solutions include: the adsorption carrier is one of acid-modified fly ash, acid-modified red mud, or acid-modified blast furnace slag; and / or the condensation nucleus is one of iron oxide nanoparticles, cobalt ferrite nanoparticles, or nickel ferrite nanoparticles; and / or the chelating agent is waste cation exchange resin powder or modified regenerated carbon powder; and / or the demulsifier is a nonionic or cationic demulsifier; and / or the bridging flocculant is cationic polyacrylamide.

[0014] Alternatively, an optional technical solution is to precipitate the cold rolling wastewater that forms flocs in a clarification and sedimentation zone; the clarification and sedimentation zone includes a hydraulic circulation clarification chamber and an inclined tube three-stage sedimentation zone.

[0015] This invention discloses a cold rolling wastewater treatment agent and a wastewater treatment method thereof. Compared with existing common coagulants and flocculants, the cold rolling wastewater treatment agent of this invention has the following beneficial effects: 1) It can effectively destroy the stable oil-in-water (O / W) emulsion in cold rolling wastewater. Through targeted demulsification and charge neutralization, it destabilizes and aggregates the fine oil droplets, significantly reducing the oil content in the effluent and solving the problem of its continuous exceeding of standards.

[0016] 2) The reagent components can chelate with heavy metal ions such as zinc, chromium, and nickel that exist in dissolved state in wastewater to form insoluble products, thereby achieving efficient removal of heavy metals.

[0017] 3) By introducing a magnetic component as the core, the resulting flocs have a dense internal structure and high specific gravity. These flocs settle quickly, effectively overcoming the problems of slow settling and low solid-liquid separation efficiency caused by the loose and lightweight nature of existing reagent flocs.

[0018] 4) It can maintain stable chemical properties under strong acidic wastewater conditions, and its hydrolysis and flocculation are not severely inhibited, ensuring treatment efficiency under typical pH conditions of cold rolling wastewater, while reducing the risk of equipment acid corrosion caused by improper pH adjustment.

[0019] Furthermore, the cold rolling wastewater treatment agent of the present invention, when applied to a pressurized integrated wastewater purification device for wastewater treatment, has the following beneficial effects: 1) By adopting a multi-point, step-by-step dosing method in the pressurized integrated sewage purification device, the demulsification, heavy metal chelation and flocculation sedimentation functions of the reagent are completed sequentially and efficiently in the matching hydraulic flow field, thus optimizing the reaction process.

[0020] 2) This combined process enables the integrated unit to effectively treat cold rolling wastewater containing emulsified oil, which was previously difficult to handle. The resulting supergravity flocs settle extremely rapidly, ensuring complete solid-liquid separation within the limited residence time of the unit, thereby significantly improving the quality of the effluent.

[0021] 3) It has solved the technical obstacles of the equipment in treating cold rolling wastewater, greatly expanding its application scope. At the same time, the improved treatment efficiency and stable compliance of effluent quality help reduce overall operating costs, resulting in significant economic and environmental benefits.

[0022] To achieve the foregoing and related objectives, one or more aspects of the invention include the features that will be described in detail below. The following description details certain exemplary aspects of the invention. However, these aspects indicate only a few of the various ways in which the principles of the invention can be used. Furthermore, the invention is intended to include all such aspects and their equivalents. Detailed Implementation

[0023] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the claims of the present invention.

[0024] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0025] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventional meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents, and instruments shall be performed according to the manufacturer's instructions and parameters.

[0026] References to "one embodiment" or "some embodiments" as described in this specification mean that one or more embodiments of this application include a specific feature, structure, or characteristic described in connection with that embodiment. Therefore, the phrases "in one embodiment," "in some embodiments," "in other embodiments," "in still other embodiments," etc., appearing in different parts of this specification do not necessarily refer to the same embodiment, but rather mean "one or more, but not all, embodiments," unless otherwise specifically emphasized. The terms "comprising," "including," "having," and variations thereof mean "including but not limited to," unless otherwise specifically emphasized.

[0027] Example 1 Experimental materials: fly ash was purchased from Anhui Chuangneng Environmental Protection Materials Co., Ltd.; iron oxide nanoparticles with an average particle size of 50nm were purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.; waste cation exchange resin powder was purchased from Langfang Anheng Energy Saving Technology Co., Ltd.; polyether-modified polysiloxane demulsifier was purchased from Zhengzhou Rongmao Water Purification Materials Factory; cationic polyacrylamide (CPAM) with a molecular weight of 12 million and a cationicity of 40% was purchased from Daqian Environmental Protection Technology Co., Ltd.; other materials were commercially available.

[0028] The wastewater to be treated is emulsified wastewater discharged from the cold rolling section of a steel plant. Its main water quality indicators are: pH=3.5, oil content=350mg / L, chemical oxygen demand (COD)=800mg / L, suspended solids (SS)=150mg / L, Zn 2+ =25mg / L, Cr 3+ =10mg / L.

[0029] S1. According to the mass fractions, obtain the following components of the cold rolling wastewater treatment agent: 500 parts of fly ash as the adsorption carrier, 80 parts of iron oxide nanoparticles as the coagulation nucleus, 40 parts of waste cation exchange resin powder as the chelating agent, 15 parts of polyether-modified polysiloxane demulsifier as the demulsifier, and 3 parts of cationic polyacrylamide (CPAM) as the bridging flocculant.

[0030] It should be noted that after weighing each component of the above-mentioned cold rolling wastewater treatment agent, the reagent pretreatment should be carried out as follows: Specifically, the adsorbent carrier, coagulation nucleus, and chelating agent should be dry-premixed evenly in a mixer to prepare the main functional powder A. 15 parts of polyether-modified polysiloxane demulsifier should be prepared into a 10% aqueous solution as demulsifier solution B. 3 parts of cationic polyacrylamide (CPAM) with a molecular weight of 12 million and a cationicity of 40% should be weighed and prepared into a 0.1% aqueous solution as bridging flocculant solution C.

[0031] S2. After adjusting the pH value of the cold rolling wastewater to be treated to 6.8, add the adsorbent carrier, coagulation nucleus, chelating agent and demulsifier from the cold rolling wastewater treatment agent and carry out a mixed reaction.

[0032] Take 1L of cold-rolling wastewater and adjust the pH from 3.5 to 6.8 by adding lime slurry. Place the pH-adjusted 1L of wastewater in a beaker and start the stirrer, stirring rapidly at 200 rpm for 2 minutes. Then, add the main functional powder A at 0.6 g / L and the demulsifier solution B at 0.03 g / L simultaneously. Continue stirring rapidly for 3 minutes to ensure thorough mixing of the agents, completing the demulsification of emulsified oil, adsorption of oil stains, and chelation of heavy metals, forming micro-composite floc cores.

[0033] S3. Add bridging flocculant and mix until flocs are formed in the cold rolling wastewater.

[0034] Reduce the stirring speed to 50 rpm, add bridging flocculant solution C at 0.005 g / L, and stir slowly for 10 minutes to allow the tiny flocs to bridge and grow, forming macroscopic supergravity magnetic flocs.

[0035] S4. After sedimentation, the cold rolling wastewater that forms flocs is separated into solid and liquid phases.

[0036] Turn off the stirring and let it stand for 15 minutes to settle.

[0037] After settling, a dense sludge layer formed at the bottom of the beaker, and the supernatant was clear. Sampling and testing showed a significant improvement in effluent quality: oil content <3 mg / L, COD <80 mg / L, SS <15 mg / L, and Zn <10 mg / L. 2+ Removal rate > 85%, Cr 3+ Removal rate > 88%. Fast settling speed; within 15 minutes, the sludge volume is reduced to less than 10% of the total water volume.

[0038] Example 2 Experimental materials: The adsorption carrier was acid-modified red mud purchased from Shandong Aluminum Co., Ltd.; the coagulation nucleus was cobalt ferrite nanoparticles purchased from Zhongke Yannuo (Beijing) Technology Co., Ltd.; the chelating agent was modified recycled carbon purchased from Hunan Yujie New Material Technology Co., Ltd.; the demulsifier was polyquaternary ammonium salt demulsifier purchased from Langfang Sairui Beda Technology Co., Ltd.; and the bridging flocculant was nonionic polyacrylamide purchased from Gongyi Lanyu Water Purification Materials Co., Ltd.

[0039] The wastewater to be treated is emulsified wastewater discharged from the cold rolling section of a steel plant. Its main water quality indicators are: pH=3.5, oil content=350mg / L, chemical oxygen demand (COD)=800mg / L, suspended solids (SS)=150mg / L, Zn 2+ =25mg / L, Cr 3+ =10mg / L.

[0040] S1. According to the mass fractions, obtain the following components of the cold rolling wastewater treatment agent: 400 parts of acid-modified red mud as the adsorption carrier, 50 parts of cobalt ferrite nanoparticles as the coagulation nucleus, 40 parts of modified regenerated carbon as the chelating agent, 10 parts of polyquaternary ammonium salt demulsifier as the demulsifier, and 2 parts of nonionic polyacrylamide as the bridging flocculant.

[0041] It should be noted that after weighing the various components of the above-mentioned cold rolling wastewater treatment agent, the reagent pretreatment is carried out as follows: Specifically, the adsorbent carrier, coagulation nucleus, and chelating agent are dry-premixed evenly in a mixer to prepare the main functional powder A. A 10% aqueous solution of polyquaternary ammonium salt demulsifier is prepared as demulsifier solution B. A 0.1% aqueous solution of nonionic polyacrylamide with a molecular weight of 12 million and a cationicity of 40% is prepared as bridging flocculant solution C. The modification of the modified regenerated carbon is an activation treatment, performed at high temperature (750-1000℃) under a protective atmosphere to restore and reconstruct its pore structure.

[0042] S2. After adjusting the pH of the cold rolling wastewater to be treated to 6, add the adsorbent carrier, coagulation nucleus, chelating agent and demulsifier from the cold rolling wastewater treatment agent and carry out a mixed reaction.

[0043] Take 1L of cold-rolling wastewater and adjust the pH from 3.5 to 6 by adding lime slurry. Place the pH-adjusted 1L of wastewater in a beaker and start the stirrer, stirring rapidly at 200 rpm for 2 minutes. Then, add the main functional powder A at 0.6 g / L and the demulsifier solution B at 0.03 g / L simultaneously. Continue stirring rapidly for 3 minutes to ensure thorough mixing of the agents, completing the demulsification of emulsified oil, adsorption of oil stains, and chelation of heavy metals, forming micro-composite floc cores.

[0044] S3. Add bridging flocculant and mix until flocs are formed in the cold rolling wastewater.

[0045] Reduce the stirring speed to 50 rpm, add bridging flocculant solution C at 0.005 g / L, and stir slowly for 10 minutes to allow the tiny flocs to bridge and grow, forming macroscopic supergravity magnetic flocs.

[0046] S4. After sedimentation, the cold rolling wastewater that forms flocs is separated into solid and liquid phases.

[0047] Turn off the stirring and let it stand for 15 minutes to settle.

[0048] After settling, a dense sludge layer formed at the bottom of the beaker, and the supernatant was clear. Sampling and testing showed a significant improvement in effluent quality: oil content <3 mg / L, COD <80 mg / L, SS <15 mg / L, and Zn <10 mg / L. 2+Removal rate > 85%, Cr 3+ Removal rate > 88%. Fast settling speed, the sludge volume is reduced to less than 10% of the total water volume within 15 minutes, which greatly improves wastewater treatment efficiency and significantly reduces sludge disposal load.

[0049] Example 3 Experimental materials: The adsorption carrier was acid-modified blast furnace slag purchased from Shijiazhuang Xuhan New Material Technology Co., Ltd.; the coagulation nucleus was nickel ferrite nanoparticles purchased from Shandong Changxin Nanotechnology Co., Ltd.; the chelating agent was modified waste biochar; the demulsifier was polyquaternary ammonium salt demulsifier purchased from Langfang Sairui Beda Technology Co., Ltd.; and the bridging flocculant was cationic polyacrylamide (CPAM) purchased from Gongyi Lanyu Water Purification Materials Co., Ltd.

[0050] The wastewater to be treated is emulsified wastewater discharged from the cold rolling section of a steel plant. Its main water quality indicators are: pH=3.5, oil content=350mg / L, chemical oxygen demand (COD)=800mg / L, suspended solids (SS)=150mg / L, Zn 2+ =25mg / L, Cr 3+ =10mg / L.

[0051] S1. According to the mass fractions, obtain the following components of the cold rolling wastewater treatment agent: 600 parts of acid-modified blast furnace slag as the adsorption carrier, 100 parts of nickel ferrite nanoparticles as the coagulation nucleus, 60 parts of modified waste biochar as the chelating agent, 25 parts of polyquaternary ammonium salt demulsifier as the demulsifier, and 5 parts of cationic polyacrylamide (CPAM) as the bridging flocculant.

[0052] It should be noted that after weighing the various components of the above-mentioned cold rolling wastewater treatment agent, the reagent pretreatment is carried out as follows: Specifically, the adsorbent carrier, coagulation nucleus, and chelating agent are dry-premixed evenly in a mixer to prepare the main functional powder A. A 10% aqueous solution of polyether-modified polysiloxane demulsifier is prepared as demulsifier solution B. A 0.1% aqueous solution of cationic polyacrylamide (CPAM) with a molecular weight of 12 million and a cationicity of 40% is prepared as bridging flocculant solution C. The modification of the modified regenerated carbon is an activation treatment, performed at high temperature (750-1000℃) under a protective atmosphere to restore and reconstruct its pore structure.

[0053] S2. After adjusting the pH value of the cold rolling wastewater to be treated to 6, add the adsorbent carrier, coagulation nucleus, chelating agent and demulsifier from the cold rolling wastewater treatment agent and carry out a mixed reaction.

[0054] Take 1L of cold-rolling wastewater and adjust the pH from 3.5 to 6 by adding lime slurry. Place the pH-adjusted 1L of wastewater in a beaker and start the stirrer, stirring rapidly at 200 rpm for 2 minutes. Then, add the main functional powder A at 0.6 g / L and the demulsifier solution B at 0.03 g / L simultaneously. Continue stirring rapidly for 3 minutes to ensure thorough mixing of the agents, completing the demulsification of emulsified oil, adsorption of oil stains, and chelation of heavy metals, forming micro-composite floc cores.

[0055] S3. Add bridging flocculant and mix until flocs are formed in the cold rolling wastewater.

[0056] Reduce the stirring speed to 50 rpm, add bridging flocculant solution C at 0.005 g / L, and stir slowly for 10 minutes to allow the tiny flocs to bridge and grow, forming macroscopic supergravity magnetic flocs.

[0057] S4. After sedimentation, the cold rolling wastewater that forms flocs is separated into solid and liquid phases.

[0058] Turn off the stirring and let it stand for 15 minutes to settle.

[0059] After settling, a dense sludge layer formed at the bottom of the beaker, and the supernatant was clear. Sampling and testing showed a significant improvement in effluent quality: oil content <3 mg / L, COD <80 mg / L, SS <15 mg / L, and Zn <10 mg / L. 2+ Removal rate > 85%, Cr 3+ Removal rate > 88%. Fast settling speed, the sludge volume is reduced to less than 10% of the total water volume within 15 minutes, which greatly improves wastewater treatment efficiency and significantly reduces sludge disposal load.

[0060] Example 4 The core of this invention lies in deeply coupling the aforementioned multifunctional cold-rolling wastewater treatment composite agent with the internal structure and hydraulic characteristics of a pressurized integrated wastewater purification device (Authorization Announcement No.: CN 102010088 A; Authorization Announcement Date: 2012.09.05). Through a refined step-by-step dosing method, this device is upgraded from one primarily relying on physical sedimentation to a highly efficient chemical-physical reactor integrating chemical demulsification, adsorption, chelation, flocculation, and rapid gravity sedimentation. The fundamental problems faced by existing integrated devices in treating cold-rolling wastewater are: 1) the device itself lacks the ability to destroy stable emulsions; 2) even if the emulsion is destroyed, the resulting oil-containing flocs have too low a specific gravity to effectively settle in the rising flow field of the device; 3) the device has no ability to remove dissolved heavy metal ions. The cold-rolling wastewater treatment agent and wastewater treatment method of this invention precisely solve all the above problems. The structure of the pressurized integrated wastewater purification device is shown in Figure 1 of CN102010088 A. Experimental materials: fly ash was purchased from Anhui Chuangneng Environmental Protection Materials Co., Ltd.; iron oxide nanoparticles with an average particle size of 50nm were purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.; waste cation exchange resin powder was purchased from Langfang Anheng Energy Saving Technology Co., Ltd.; polyether-modified polysiloxane demulsifier was purchased from Zhengzhou Rongmao Water Purification Materials Factory; cationic polyacrylamide (CPAM) with a molecular weight of 12 million and a cationicity of 40% was purchased from Daqian Environmental Protection Technology Co., Ltd.; other materials were commercially available.

[0061] The wastewater to be treated is emulsified wastewater discharged from the cold rolling section of a steel plant. Its main water quality indicators are: pH=3.5, oil content=350mg / L, chemical oxygen demand (COD)=800mg / L, suspended solids (SS)=150mg / L, Zn 2+ =25mg / L, Cr 3+ =10mg / L.

[0062] S1. The following components of the cold rolling wastewater treatment agent are as follows, by mass: 500 parts of fly ash as the adsorption carrier, 80 parts of iron oxide nanoparticles as the coagulation nucleus, 40 parts of waste cation exchange resin powder as the chelating agent, 15 parts of polyether-modified polysiloxane demulsifier as the demulsifier, and 3 parts of cationic polyacrylamide (CPAM) as the bridging flocculant.

[0063] It should be noted that after weighing each component of the above-mentioned cold rolling wastewater treatment agent, the reagent pretreatment should be carried out as follows: Specifically, the adsorbent carrier, coagulation nucleus, and chelating agent should be dry-premixed evenly in a mixer to prepare the main functional powder A. 15 parts of polyether-modified polysiloxane demulsifier should be prepared into a 10% aqueous solution as demulsifier solution B. 3 parts of cationic polyacrylamide (CPAM) with a molecular weight of 12 million and a cationicity of 40% should be weighed and prepared into a 0.1% aqueous solution as bridging flocculant solution C.

[0064] S2. Add lime slurry to the equalization tank before it enters the pressurized integrated sewage purification device to adjust the pH value from 3.5 to 6.8.

[0065] S3. In the primary reaction zone, the main functional powder A and demulsifier solution B of the cold rolling wastewater treatment agent are added to the pressurized integrated wastewater purification device to carry out the primary reaction; the primary reaction zone includes a water flow path from the swirling primary sedimentation chamber to the primary flocculation reaction chamber. The cold rolling wastewater treatment agent is added to the swirling primary sedimentation chamber within the primary reaction zone.

[0066] In the specific implementation process, the influent pump is started to pump the pH-adjusted wastewater into the integrated device. Simultaneously, the main functional powder A is added at a specific rate to the suction well of the vortex primary sedimentation chamber at the bottom of the device via a screw feeder; and the demulsifier solution B is injected into the same location via a metering pump. The reagents and wastewater are thoroughly mixed under the vigorous agitation of the pump impeller and the vortex chamber. As the wastewater rises through the primary flocculation reaction chamber, the demulsifier rapidly breaks down the emulsified oil, the precipitated oil droplets are adsorbed by the fly ash, and heavy metal ions are chelated by the resin, all encapsulating on microflocs with iron oxide nanoparticles as their core.

[0067] S4. In the secondary reaction zone, 2-5 parts of bridging flocculant are added to the pressurized integrated wastewater purification device and mixed with the cold rolling wastewater after the primary reaction until flocs are formed in the cold rolling wastewater. The secondary reaction zone includes the water flow path of the secondary flocculation reaction chamber. In the secondary reaction zone, the bridging flocculant is added at the hydraulic circulation clarification chamber of the secondary flocculation reaction chamber.

[0068] As the wastewater is about to enter the hydraulic circulation clarification chamber, the bridging flocculant solution C is injected through the dosing pipe of the device. The long-chain molecules of CPAM rapidly bridge and sweep together the numerous micro-flocs formed in the first-stage reaction, forming large, dense magnetically weighted flocs.

[0069] S5. The cold rolling wastewater that forms flocs is subjected to sedimentation to complete solid-liquid separation. The cold rolling wastewater that forms flocs is then precipitated in a clarification and sedimentation zone; the clarification and sedimentation zone includes a hydraulic circulation clarification chamber and an inclined tube three-stage sedimentation zone.

[0070] In summary, the treatment process begins with cold-rolled emulsified wastewater, initially pH 3.5, containing oils and heavy metals. First, the pH is adjusted to the neutral range. Then, the wastewater enters the pump, pressurized, and flows under pressure. In the primary synergistic effect stage, the main functional material A and demulsifying liquid B are added for initial mixing. The water then enters the vortex primary sedimentation chamber, where primary sedimentation occurs using the vortex effect, simultaneously undergoing a delamination process to form magnetic polyurethane through emulsification-adsorption-binding. The water then enters the primary flocculation reaction chamber for general flocculation and flows to the secondary sedimentation chamber for secondary sedimentation. In the secondary precision effect stage, bridging flocculant solution C is added via a metering pump and then through a dosing pipe. The flocculant enters the secondary flocculation reaction chamber for bridging and growth, forming supergravity agglomerates. The water then enters the hydraulic circulation clarification chamber for further purification through vortex and clarification. Finally, it enters the inclined tube tertiary sedimentation chamber for circular separation and rapid supergravity settling. The final purified water produced has the following water quality indicators: oil content less than 1 mg / L, COD less than 50 mg / L, and suspended solids (SS) less than 10 mg / L, and is discharged through the top effluent pipe. The high-density sludge (high solids content) generated by sedimentation is discharged through the bottom drain pipe, enters the sludge tank, and is treated by a filter press to form sludge cake with a moisture content of less than 60%, which is then reused or discharged. The entire process employs a multi-stage sedimentation and flocculation reaction chamber design, including cyclone primary sedimentation, flocculation-guided secondary sedimentation, and inclined tube tertiary sedimentation, ensuring efficient purification and sludge concentration, while utilizing a pressurized integrated device to save energy.

[0071] Wastewater carrying heavy flocs enters the hydraulic circulation clarification chamber and the inclined tube three-stage sedimentation zone. Due to the extremely high specific gravity of the flocs and their excellent settling performance, they settle rapidly within the equipment, achieving efficient solid-liquid separation. The purified water is discharged through the top outlet pipe; the high-density sludge is discharged to the sludge tank through the bottom drain pipe and then pumped to the filter press for dewatering.

[0072] After treatment by the method of this invention, the effluent quality of the pressurized integrated device is stable, wherein: oil content <1mg / L, COD <50mg / L, SS <10mg / L, Zn 2+ Removal rate > 95%, Cr 3+ Removal rate > 96%. The device can handle a surface load of up to 20 m². 3 / (m 2 The efficiency (·h) is 33% higher than the design value. The discharged sludge has a high solids content, and the moisture content of the filter cake after pressing is less than 60%, and it has a certain recycling value.

[0073] Comparative Example 1 The same cold-rolling wastewater and pressurized integrated wastewater purification device as in Example 1 were used. The reagents used were a turbid circulating water purification composition of polyaluminum chloride (PAC) and polyacrylamide (PAM) disclosed in the prior art. Following conventional methods, PAC was added in the primary flocculation back-dosing stage of the device shown in Figure 1 of patent document CN 102010088 A, and PAM was added in the secondary flocculation reaction chamber.

[0074] Polyaluminum chloride (PAC) cannot effectively disrupt the stable emulsion system in cold-rolling wastewater under weakly acidic to neutral conditions, resulting in the inability to separate oil and water. Although flocs are formed, they are mainly composed of suspended solids from the raw water, are small in size, and contain a large number of undemulsified oil droplets, resulting in low overall density and stickiness. Inside the device, a large number of light, oily flocs cannot settle effectively and are carried by the water flow to the outlet. Observation shows that the final effluent from the pressurized integrated wastewater treatment device is turbid and the water quality is seriously substandard: oil content >30mg / L, SS >50mg / L, and has virtually no removal effect on dissolved heavy metal ions. To achieve the desired treatment effect, a significant increase in chemical consumption is required, and even then, stable compliance with effluent standards cannot be guaranteed.

[0075] The comparison between Example 4 and Comparative Example 1 fully demonstrates that the cold rolling wastewater treatment agent and the wastewater treatment method based on the pressurized integrated wastewater purification device provided by the present invention have unparalleled and groundbreaking technical advantages and beneficial effects in treating highly difficult cold rolling emulsified wastewater.

[0076] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and not restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be embraced within the present invention. Furthermore, it is clear that the word "comprising" does not exclude other elements or steps, and the singular does not exclude the plural.

[0077] However, those skilled in the art should understand that various modifications can be made to the cold rolling wastewater treatment agent and magnetoelasticity proposed in this invention without departing from the scope of the invention. Therefore, the scope of protection of this invention should be determined by the appended claims.

Claims

1. A cold rolling wastewater treatment agent, characterized by, According to the mass fraction, It includes the following components: Adsorption carrier: 400-600 parts; Condensed core: 50-100 parts; Chelating agent: 30-60 parts; Demulsifier: 10-25 parts; Bridge flocculant: 2-5 parts.

2. The cold rolling wastewater treatment agent according to claim 1, wherein the adsorption carrier is one of acid-modified fly ash, acid-modified red mud or acid-modified blast furnace slag.

3. The cold rolling wastewater treatment agent according to claim 1, wherein the condensed core is one of ferric oxide nanoparticles, cobalt ferrite nanoparticles or nickel ferrite nanoparticles.

4. The cold rolling wastewater treatment agent according to claim 1, wherein the chelating agent is waste cation exchange resin powder or modified regenerated carbon powder.

5. The cold rolling wastewater treatment agent according to claim 1, wherein the demulsifier is a non-ionic or cationic demulsifier; and / or the bridge flocculant is a cationic polyacrylamide.

6. A sewage treatment method for treating cold rolling wastewater, comprising the following steps: According to the mass fraction, the following components of the cold rolling wastewater treatment agent are obtained: 400-600 parts of adsorption carrier, 50-100 parts of condensed core, 30-60 parts of chelating agent, and 10-25 parts of demulsifier; After adjusting the PH value of the cold rolling wastewater to be treated to 6-8, the cold rolling wastewater treatment agent is added and mixed; 2-5 parts of bridge flocculant are added and mixed until the cold rolling wastewater forms flocculation; After the cold rolling wastewater forms flocculation, sedimentation is carried out to complete solid-liquid separation. The method for treating cold rolling wastewater by using a pressure type integrated sewage purification device, comprising: According to the mass fraction, the following components of the cold rolling wastewater treatment agent are obtained: 400-600 parts of adsorption carrier, 50-100 parts of condensed core, 30-60 parts of chelating agent, and 10-25 parts of demulsifier; The PH value of the cold rolling wastewater to be treated is adjusted to 6-8; In the primary reaction zone, the cold rolling wastewater treatment agent is added to the pressure type integrated sewage purification device for primary reaction; the primary reaction zone includes the water flow path from the cyclone primary sedimentation chamber to the primary flocculation reaction chamber; In the secondary reaction zone, 2-5 parts of bridge flocculant are added to the pressure type integrated sewage purification device for mixing reaction with the cold rolling wastewater after primary reaction until the cold rolling wastewater forms flocculation; the secondary reaction zone includes the water flow path of the secondary flocculation reaction chamber; 7. The method of sewage treatment according to claim 6, characterized in that, After the cold rolling wastewater forms flocculation, sedimentation is carried out to complete solid-liquid separation.

8. The sewage treatment method according to claim 7, wherein in the primary reaction zone, the addition position of the cold rolling wastewater treatment agent is the cyclone primary sedimentation chamber; and in the secondary reaction zone, the addition position of the bridge flocculant is the hydraulic circulation clarifier of the secondary flocculation reaction chamber.

9. The sewage treatment method according to claim 7, wherein the adsorption carrier is one of acid-modified fly ash, acid-modified red mud or acid-modified blast furnace slag. ​ ​ ​ ​ ​ ​ ​ ​ And / or, the condensed core is one of ferroferric oxide nanoparticles, cobalt ferrite nanoparticles or nickel ferrite nanoparticles; And / or, the chelating agent is waste cation exchange resin powder or modified regenerated carbon powder; And / or, the demulsifier is a non-ionic or cationic demulsifier; And / or, the bridging flocculant is a cationic polyacrylamide.

10. The method of sewage treatment according to claim 7, characterized in that, The flocculated cold rolling wastewater is precipitated in a clarification sedimentation zone; the clarification sedimentation zone comprises a hydraulic circulation clarification chamber and a three-stage sedimentation zone of inclined pipes.