CN114230050A - Method and system for treating cold rolling pickling wastewater - Google Patents
Method and system for treating cold rolling pickling wastewater Download PDFInfo
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- CN114230050A CN114230050A CN202111683763.7A CN202111683763A CN114230050A CN 114230050 A CN114230050 A CN 114230050A CN 202111683763 A CN202111683763 A CN 202111683763A CN 114230050 A CN114230050 A CN 114230050A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 102
- 238000005097 cold rolling Methods 0.000 title claims abstract description 98
- 238000005554 pickling Methods 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 242
- 229910052742 iron Inorganic materials 0.000 claims abstract description 141
- 239000002253 acid Substances 0.000 claims abstract description 93
- 238000001728 nano-filtration Methods 0.000 claims abstract description 89
- 238000001471 micro-filtration Methods 0.000 claims abstract description 62
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- -1 iron ions Chemical class 0.000 claims abstract description 45
- 230000008929 regeneration Effects 0.000 claims abstract description 32
- 238000011069 regeneration method Methods 0.000 claims abstract description 32
- 239000012530 fluid Substances 0.000 claims abstract description 31
- 230000000149 penetrating effect Effects 0.000 claims abstract description 30
- 238000006722 reduction reaction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000005837 radical ions Chemical class 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000003860 storage Methods 0.000 claims description 33
- 239000012528 membrane Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000012466 permeate Substances 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 12
- 229960002089 ferrous chloride Drugs 0.000 claims description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000013618 particulate matter Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for treating cold rolling pickling waste water, which contains particulate matters, acid radical ions and iron ions, and comprises the following steps: carrying out microfiltration on the cold rolling pickling wastewater to remove particles so as to obtain a first filtrate; carrying out nanofiltration on the first filtrate to separate acid radical ions from iron ions to obtain a first penetrating fluid and a first concentrated solution; carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid; adding scrap iron wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with iron ions with a certain concentration; and carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid. In the invention, after the cold rolling pickling wastewater is treated, the obtained iron and acid have no other pollutants needing to be treated again, so the method is more environment-friendly and has lower treatment cost. Correspondingly, the invention also provides a treatment system for the cold rolling pickling wastewater.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method and a system for treating cold rolling pickling wastewater.
Background
At present, hydrochloric acid is generally adopted in the industry to carry out acid pickling on the surface of steel before cold rolling or coating the surface of the steel so as to remove iron oxide scales on the surface of the steel. After pickling, the surface of the steel material needs to be washed with pure water to clean the acid solution remaining on the surface of the steel material. Therefore, the method forms a large amount of pickling waste water containing iron ions. For the pickling wastewater, the conventional method is to neutralize the pickling wastewater by using an alkali neutralizing agent in a wastewater treatment station and form hydrous ferric hydroxide (metal sludge) and a sodium chloride solution after treatment so as to meet the environmental protection discharge standard and realize the standard discharge of the pickling wastewater.
The treatment of the pickling wastewater needs to consume a large amount of alkali neutralizing agent, and simultaneously generates a large amount of metal sludge to be subsequently treated, so that the pickling wastewater has high operating cost and is not environment-friendly. Therefore, a low-cost and efficient treatment method and system capable of recycling the pickling wastewater are needed.
Disclosure of Invention
The invention aims to provide a method and a system for treating cold rolling pickling wastewater, which have lower treatment cost and higher treatment efficiency.
In order to achieve the above object, the present invention provides a method for treating cold rolling pickling wastewater, wherein the cold rolling pickling wastewater contains particulate matter, acid ions and iron ions, and the method comprises:
carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters to obtain a first filtrate;
carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions to obtain a first penetrating fluid and a first concentrated solution;
carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
adding scrap iron scrap wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with iron ions with a certain concentration;
and carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
Optionally, the acid is hydrochloric acid, and the first iron-containing solution is a ferrous chloride solution.
Optionally, the first permeate and the second permeate are reused in a cold rolling and pickling production line or used for neutralizing alkaline wastewater.
Optionally, the treatment method of the cold rolling pickling wastewater further comprises the following steps:
carrying out microfiltration on the first iron-containing solution, and removing particles generated by the reduction reaction to obtain a second filtrate;
carrying out nanofiltration on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
carrying out an acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
Optionally, the third permeate is introduced into the first filtrate, and then nanofiltration is performed.
Optionally, the concentration of iron ions in the second iron-containing solution is greater than 10%.
Correspondingly, the invention also provides a treatment system of the cold rolling pickling waste water, which comprises the following components:
the waste water tank is used for containing cold rolling pickling waste water, and the cold rolling pickling waste water contains particulate matters, acid radical ions and iron ions;
the first microfiltration device is connected to the wastewater tank and is used for carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters so as to obtain a first filtrate;
the first water storage tank is connected with the first microfiltration device and used for storing the first filtrate;
the first nanofiltration device is connected to the first water storage tank and used for carrying out nanofiltration on the first filtrate so as to separate the acid radical ions from the iron ions and obtain a first penetrating fluid and a first concentrated solution;
the second water storage tank is connected with the first nanofiltration device and used for storing the first concentrated solution;
the second nanofiltration device is connected to the second water storage tank and is used for carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
the reduction tower is connected to the second nanofiltration device and is used for carrying out reduction reaction on the second concentrated solution and the waste iron scrap wire to generate a first iron-containing solution;
and the acid regeneration device is used for carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
Optionally, the treatment system for cold rolling pickling waste water further comprises:
a third water storage tank connected to the reduction tower for storing the first iron-containing solution;
the second microfiltration device is connected to the third water storage tank and is used for carrying out microfiltration on the first iron-containing solution and removing particles generated by the reduction reaction to obtain a second filtrate;
the fourth water storage tank is connected with the second microfiltration device and used for storing the second filtrate;
the third nanofiltration device is used for concentrating the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
a fifth water storage tank connected to the third nanofiltration device, for storing the second iron-containing solution;
the acid regeneration device is used for carrying out acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
Optionally, the first microfiltration device and the second microfiltration device are both tubular microfiltration membranes.
Optionally, the first nanofiltration device, the second nanofiltration device and the third nanofiltration device are acid-resistant nanofiltration membranes.
Optionally, the first microfiltration device, the second microfiltration device, the first nanofiltration device, the second nanofiltration device and the third nanofiltration device are all provided with booster pumps at the front ends thereof.
Optionally, an exhaust fan is arranged on the reduction tower.
According to the sewage treatment method provided by the invention, cold rolling pickling wastewater contains particulate matters, acid radical ions and iron ions, and the cold rolling pickling wastewater is subjected to microfiltration to remove the particulate matters, so that a first filtrate is obtained. And carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions to obtain a first penetrating fluid and a first concentrated solution. And carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid. And adding scrap iron scrap wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with a certain concentration of iron ions. And carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid. In the embodiment of the invention, after the cold rolling pickling wastewater is treated, iron and acid are obtained, and no other pollutants need to be treated again, so that the method is more environment-friendly. This also has a lower processing cost relative to conventional processing methods. In addition, the scrap iron edge wire is added into the second concentrated solution, so that not only can the corrosivity of the second concentrated solution be removed and reduced, but also the scrap iron edge wire generated in the cold rolling operation can be consumed, the solid waste is further consumed, and the environment-friendly effect is achieved. Correspondingly, the invention also provides a treatment system for the cold rolling pickling wastewater.
Drawings
FIG. 1 is a first flowchart of a method for treating cold rolling pickling waste water according to an embodiment of the present invention;
FIG. 2 is a second flowchart of the method for treating cold rolling pickling waste water according to the embodiment of the present invention;
FIG. 3 is a first schematic diagram of a system for treating cold rolling pickling waste water according to an embodiment of the present invention;
FIG. 4 is a second schematic diagram of a system for treating cold rolling pickling waste water according to an embodiment of the present invention;
wherein the reference numbers are as follows:
101-a wastewater tank; 102-a first microfiltration device; 103-a first water storage tank; 104-a first nanofiltration device; 105-a second water storage tank; 106-a second nanofiltration device; 107-reduction column; 108-a third water storage tank; 109-a second microfiltration device; 110-a fourth water storage tank; 111-a third nanofiltration device; 112-a fifth water storage tank;
a-a booster pump; b-an exhaust fan; a C-acid regeneration unit; d-lift pump.
Detailed Description
The following describes in more detail embodiments of the present invention with reference to the schematic drawings. The advantages and features of the present invention will become more apparent from the following description. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items. It is to be understood that although the terms first, second, third, etc. may be used herein to describe various information, such information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, a first apparatus may also be referred to as a second apparatus, and similarly, a second apparatus may also be referred to as a first apparatus, without departing from the scope of the present application.
The cold rolling pickling wastewater is wastewater obtained by cleaning steel on a cold rolling production line by using acid, and a large amount of iron ions are generated after the steel on the cold rolling production line is cleaned by using the acid, wherein the iron ions comprise ferrous ions and ferric ions. In addition, the waste water after cleaning the steel material on the cold rolling line also contains a certain amount of particulate matter and acid radical ions. Therefore, the cold rolling and pickling wastewater contains particulate matters, acid radical ions and iron ions.
In the embodiment of the invention, hydrochloric acid is adopted to clean steel, in particular to clean carbon steel, so that acid radical ions are hydrochloric acid radicals, namely negative chloride ions. It should be noted that, in practice, the steel may be cleaned by using sulfuric acid or hydrofluoric acid, etc. on a carbon steel cold rolling production line, and in this case, the acid radical ions contained in the cold rolling pickling wastewater are sulfate radical ions or fluorine ions. Thus, the type of acid ion is related to the type of acid used in the washing. In the present invention, the type of acid used in the cold rolling line is not particularly limited.
At present, when cold rolling pickling wastewater is treated, the conventional treatment method in the industry adopts lime or sodium hydroxide as an alkali neutralizer, and the cold rolling pickling wastewater is neutralized and then is discharged after reaching the standard. Because the traditional treatment method in the industry needs to consume a large amount of alkali neutralizing agent, simultaneously generates a large amount of metal sludge and needs subsequent disposal, the traditional treatment method has higher operation cost and is not environment-friendly.
Based on the method, the invention provides a method for treating cold rolling pickling waste water. Has lower treatment cost and is more environment-friendly.
FIG. 1 is a first flowchart of a method for treating cold rolling pickling waste water according to an embodiment of the present invention. As shown in FIG. 1, in the method for treating cold rolling pickling waste water of the present invention, the cold rolling pickling waste water contains particulate matter, acid ions and iron ions, comprising the steps of:
step S101: and carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters, so as to obtain a first filtrate.
Step S102: and carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions to obtain a first penetrating fluid and a first concentrated solution.
Step S103: carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
step S104: adding scrap iron scrap wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with iron ions with a certain concentration;
step S105: and carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
In the method for treating the cold rolling pickling waste water, the cold rolling pickling waste water is treated to obtain iron and acid, and other pollutants needing to be treated again do not exist, so the method is more environment-friendly. This also has a lower processing cost relative to conventional processing methods. In addition, in the method for treating the cold rolling pickling wastewater, particulate matters in the cold rolling pickling wastewater are removed through microfiltration, and a first penetrating fluid, a first concentrated solution, a second concentrated solution and a second penetrating fluid are obtained through nanofiltration. The method has high treatment efficiency, so that the method for treating the cold rolling pickling waste water has higher treatment efficiency, and further reduces the treatment cost. In addition, the scrap iron edge wire is added into the second concentrated solution, so that not only can the corrosivity of the second concentrated solution be removed and reduced, but also the scrap iron edge wire generated in the cold rolling operation can be consumed, the solid waste is further consumed, and the environment-friendly effect is achieved.
In step S102, the first filtrate is subjected to nanofiltration, so that acid ions and iron ions are separated, and a first permeate and a first concentrate are obtained. In step S103, the first concentrated solution is subjected to nanofiltration again to obtain a second concentrated solution and a second permeate. It is known that nanofiltration is a membrane separation technique based on nanofiltration membranes with pore sizes in the range of a few nanometers, driven by pressure to achieve separation of substances. The separation mechanism of the nanofiltration membrane is the coexistence of screening and dissolution diffusion, and simultaneously has a charge repulsion effect, so that divalent and multivalent ions can be effectively removed, and therefore, the acid radical ions and the iron ions can be separated. The concentration of the iron ions in the first concentrated solution can be improved, and the second concentrated solution with higher concentration of the iron ions can be obtained.
It is known that the particulate matter in the cold-rolling pickling wastewater damages the nanofiltration membrane during the nanofiltration process, so that the particulate matter in the cold-rolling pickling wastewater needs to be removed and then nanofiltration needs to be performed, and thus, the service life of the filtration membrane can be prolonged. Based on this, in step S101, the cold rolling pickling waste water is subjected to microfiltration to remove the particulate matter. In the embodiment, the cold rolling pickling wastewater is subjected to microfiltration by using a tubular microfiltration system. The tubular microfiltration system is an assembled water treatment device and occupies small area. The core of the tubular microfiltration system is a tubular microfiltration membrane made of ultra-high molecular polymer, the pore size of the tubular microfiltration membrane is 0.1-1.0 micron, and the cold rolling pickling wastewater flows through the tubular microfiltration membrane under the drive of a certain pressure, so that particles in the cold rolling pickling wastewater can be separated out.
Optionally, when the first filtrate is subjected to nanofiltration, an acid-resistant nanofiltration membrane is used for performing membrane separation on the first filtrate.
It should be noted that when the first filtrate and the first concentrate are subjected to nanofiltration, most of the free hydrochloride will penetrate the nanofiltration membrane and enter the water producing side, and the iron ions will be intercepted. The main components of the solutions (namely, the first penetrating fluid and the second penetrating fluid) on the water production side are small amount of free hydrochloric acid and a trace amount of iron ions, and the solutions contain small amount of free hydrochloric acid and a trace amount of iron ions, and can be directly reused for acid preparation in a cold rolling and acid washing production line. Generally, the amount of the first permeate will be relatively large, and therefore, the excess of the first permeate will also be used for neutralizing alkaline waste water generated in the cold rolling. Based on this, the first permeate and the second permeate are reused for a cold rolling and pickling line or for neutralizing alkaline waste water.
In step S105, the first iron-containing solution is subjected to an acid regeneration reaction to obtain iron and acid. It will be appreciated that since in the examples of the invention the carbon steel is cleaned with hydrochloric acid, the first iron-containing solution is a ferrous chloride solution. In step S102, the first filtrate is subjected to nanofiltration, so that the acid ions and the iron ions are separated, and a first permeate and a first concentrate are obtained. The concentrated first concentrated solution mainly comprises ferric chloride, ferrous chloride and a small amount of free hydrochloric acid. At this time, the first concentrated solution is subjected to nanofiltration and further concentrated, so that the concentrations of ferric chloride and ferrous chloride in the first concentrated solution can be further increased to obtain a second concentrated solution. And (3) placing the waste iron scrap wire into the second concentrated solution for reduction reaction, and further increasing the concentration of ferrous chloride in the second concentrated solution to obtain the first iron-containing solution, so that the concentration of the ferrous chloride in the first iron-containing solution reaches a certain value. And (3) introducing the ferrous chloride solution into a final concentrated solution tank, and conveying the ferrous chloride solution into a cold rolling acid regeneration system through a lifting pump D to carry out regeneration reaction, such as heating or ionization, so that the ferrous chloride solution can be reacted to produce iron powder and hydrochloric acid.
FIG. 2 is a second flowchart of the method for treating cold rolling pickling waste water according to the embodiment of the present invention. As shown in FIG. 2, the method for treating cold rolling pickling wastewater provided by the invention further comprises the following steps:
step S106: carrying out microfiltration on the first iron-containing solution, and removing particles generated by the reduction reaction to obtain a second filtrate;
step S107: carrying out nanofiltration on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
step S108: carrying out an acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
Specifically, the first iron-containing solution is subjected to microfiltration, and particles generated by the reduction reaction are removed to obtain a second filtrate. Therefore, waste iron scrap is added to the second concentrated solution to remove and reduce the corrosiveness of the second concentrated solution. This also results in the resulting first iron-containing solution containing particulates carried in by the scrap iron scrap wire. The particles are therefore removed by microfiltration in order to avoid the particles damaging the nanofiltration membrane.
And further, carrying out nanofiltration on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid. In this way, the concentration of iron ions in the second iron-containing solution obtained is further increased. In this example, the ferrous chloride concentration is greater than 10% when acid regeneration is performed. That is, in the present invention, the concentration of iron ions in the second iron-containing solution is greater than 10%.
Optionally, the third permeate is introduced into the first filtrate, and then nanofiltration is performed. It should be noted that the third penetrating fluid is a water-producing penetrating fluid subjected to three-stage nanofiltration, and therefore, the content of iron ions in the third penetrating fluid is high, and therefore, the third penetrating fluid can be introduced into the first filtering fluid and then subjected to nanofiltration treatment to avoid the loss of iron ions, and thus, the economic benefit can be further improved.
Based on the same invention idea, the invention also provides a treatment system for the cold rolling pickling wastewater.
FIG. 3 is a schematic diagram of a treatment system for cold rolling pickling waste water in an embodiment of the invention. As shown in fig. 3, the treatment system for cold rolling pickling waste water comprises:
the waste water tank 101 is used for containing cold rolling pickling waste water, and the cold rolling pickling waste water contains particulate matters, acid radical ions and iron ions;
the first microfiltration device 102 is connected to the wastewater tank 101 and is used for carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters so as to obtain a first filtrate;
a first water storage tank 103 connected to the first microfiltration device 102 for storing the first filtrate;
a first nanofiltration device 104 connected to the first water storage tank 103 and configured to perform nanofiltration on the first filtrate so as to separate the acid ions from the iron ions, thereby obtaining a first permeate and a first concentrate;
a second water storage tank 105 connected to the first nanofiltration device 104 for storing the first concentrated solution;
a second nanofiltration device 106 connected to the second water storage tank 105, and configured to perform nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second permeate;
a reduction column 107 connected to the second nanofiltration device 106 for performing a reduction reaction on the second concentrated solution and the scrap iron edge wire to generate a first iron-containing solution;
and the acid regeneration device C is used for carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
Specifically, the waste water tank 101, the first water storage tank 103 and the second water storage tank 105 may be a plastic water tank or a stainless steel water tank, or any material selected according to the experience of those skilled in the art. The shape of the wastewater tank 101, the first water storage tank 103 and the second water storage tank 105 may be a cylindrical shape or a rectangular parallelepiped shape, or any shape according to the experience of those skilled in the art.
FIG. 4 is a second schematic diagram of a system for treating cold rolling pickling waste water according to an embodiment of the present invention. As shown in fig. 4, the treatment system for cold rolling pickling waste water further includes:
a third water storage tank 108 connected to the reduction tower 107 for storing the first iron-containing solution;
a second microfiltration device 109 connected to the third water storage tank 108, configured to microfiltration the first iron-containing solution, and remove particles generated by the reduction reaction, so as to obtain a second filtrate;
a fourth water storage tank 110 connected to the second microfiltration device 109 for storing the second filtrate;
a third nanofiltration device 111, configured to concentrate the second filtrate to obtain a second iron-containing solution and a third permeate;
a fifth water storage tank 112 connected to the third nanofiltration device 111, for storing the second iron-containing solution;
and the acid regeneration device C is used for carrying out acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
Further, the acid regeneration device C adopts a heating or ionization mode to react the first iron-containing solution or the second iron-containing solution to produce iron powder and acid. Therefore, the acid regeneration device C may be a reaction furnace having a heating function, or the acid regeneration device C may be an electrolytic furnace. The acid regeneration device C may also be other types of reaction devices used by those skilled in the art, such as a reaction kettle, etc., and is not limited herein.
Further, the front end of the acid regeneration device C is also provided with a lifting pump D, and the lifting pump D is used for sending a second iron-containing solution into the cold-rolling acid regeneration system.
Further, the first microfiltration device 102 and the second microfiltration device 109 are both tubular microfiltration membranes. It should be understood that the first microfiltration device 102 and the second microfiltration device 109 may be selected to use tubular microfiltration membranes of the same size according to the experience of those skilled in the art, so that the tubular microfiltration membranes can be used universally. Tubular microfiltration membranes of different sizes can also be selected according to the amount of the cold rolling pickling waste water and the amount of the first iron-containing solution.
Further, the first nanofiltration device 104, the second nanofiltration device 106 and the third nanofiltration device 111 are acid-resistant nanofiltration membranes. It is known that the cold rolling pickling waste water contains acid ions and is acidic, and therefore, the acid-resistant nanofiltration membrane can be more suitable for the cold rolling pickling waste water.
Further, the front ends of the first microfiltration device 102, the second microfiltration device 109, the first nanofiltration device 104, the second nanofiltration device 106 and the third nanofiltration device 111 are all provided with a booster pump a. For pressurizing the liquid passing through the first microfiltration device 102, the second microfiltration device 109, the first nanofiltration device 104, the second nanofiltration device 106 and the third nanofiltration device 111.
Further, an exhaust fan B is arranged on the reduction tower 107 and is used for pumping the reduction tower 107 to negative pressure, so that gas generated when the first iron-containing solution reacts with the scrap iron edge wire can be timely exhausted out of the reduction tower 107. Excessive accumulation of combustible gas in the reduction column 107 is avoided.
Furthermore, in the whole treatment process of the treatment system for the cold rolling pickling wastewater, the control process of each process section is automatically completed by a PLC.
In summary, the present invention provides a method for treating cold rolling pickling wastewater, where the cold rolling pickling wastewater contains particulate matter, acid ions, and iron ions, and the method includes: and carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters, so as to obtain a first filtrate. And carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions to obtain a first penetrating fluid and a first concentrated solution. And carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid. And adding scrap iron scrap wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with a certain concentration of iron ions. And carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid. In the embodiment of the invention, after the cold rolling pickling wastewater is treated, iron and acid are obtained, and no other pollutants need to be treated again, so that the method is more environment-friendly. This also has a lower processing cost relative to conventional processing methods. In addition, the scrap iron edge wire is added into the second concentrated solution, so that not only can the corrosivity of the second concentrated solution be removed and reduced, but also the scrap iron edge wire generated in the cold rolling operation can be consumed, the solid waste is further consumed, and the environment-friendly effect is achieved. Correspondingly, the invention also provides a treatment system for the cold rolling pickling wastewater.
The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any way. It will be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (12)
1. A treatment method of cold rolling pickling waste water, wherein the cold rolling pickling waste water contains particulate matters, acid radical ions and iron ions, and is characterized by comprising the following steps:
carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters to obtain a first filtrate;
carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions to obtain a first penetrating fluid and a first concentrated solution;
carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
adding scrap iron scrap wires into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with iron ions with a certain concentration;
and carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
2. The method for treating cold rolling pickling wastewater according to claim 1, wherein the acid is hydrochloric acid and the first iron-containing solution is a ferrous chloride solution.
3. The method for treating cold rolling pickling waste water according to claim 1, wherein said first permeate and said second permeate are reused for a cold rolling pickling line or for neutralizing alkaline waste water.
4. The method for treating cold rolling pickling waste water according to claim 1, further comprising:
carrying out microfiltration on the first iron-containing solution, and removing particles generated by the reduction reaction to obtain a second filtrate;
carrying out nanofiltration on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
carrying out an acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
5. The method for treating cold rolling pickling waste water according to claim 4, wherein said third permeate is introduced into said first filtrate and then subjected to nanofiltration.
6. The method of treating cold rolling pickling wastewater of claim 4 wherein the concentration of iron ions in said second iron-containing solution is greater than 10%.
7. A treatment system for cold rolling pickling waste water is characterized by comprising:
the waste water tank is used for containing cold rolling pickling waste water, and the cold rolling pickling waste water contains particulate matters, acid radical ions and iron ions;
the first microfiltration device is connected to the wastewater tank and is used for carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters so as to obtain a first filtrate;
the first water storage tank is connected with the first microfiltration device and used for storing the first filtrate;
the first nanofiltration device is connected to the first water storage tank and used for carrying out nanofiltration on the first filtrate so as to separate the acid radical ions from the iron ions and obtain a first penetrating fluid and a first concentrated solution;
the second water storage tank is connected with the first nanofiltration device and used for storing the first concentrated solution;
the second nanofiltration device is connected to the second water storage tank and is used for carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
the reduction tower is connected to the second nanofiltration device and is used for carrying out reduction reaction on the second concentrated solution and the waste iron scrap wire to generate a first iron-containing solution;
and the acid regeneration device is used for carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
8. The system for treating cold rolling pickling waste water according to claim 7, further comprising:
a third water storage tank connected to the reduction tower for storing the first iron-containing solution;
the second microfiltration device is connected to the third water storage tank and is used for carrying out microfiltration on the first iron-containing solution and removing particles generated by the reduction reaction to obtain a second filtrate;
the fourth water storage tank is connected with the second microfiltration device and used for storing the second filtrate;
the third nanofiltration device is used for concentrating the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
a fifth water storage tank connected to the third nanofiltration device, for storing the second iron-containing solution;
the acid regeneration device is used for carrying out acid regeneration reaction on the second iron-containing solution to obtain the iron and the acid.
9. The system for treating cold rolling pickling waste water according to claim 8, wherein said first microfiltration device and said second microfiltration device are both tubular microfiltration membranes.
10. The cold rolling pickling wastewater treatment system of claim 8 wherein said first nanofiltration device, said second nanofiltration device and said third nanofiltration device are acid-resistant nanofiltration membranes.
11. The cold rolling pickling wastewater treatment system of claim 7, wherein the first microfiltration device, the second microfiltration device, the first nanofiltration device, the second nanofiltration device and the third nanofiltration device are provided with booster pumps at the front ends thereof.
12. The system for treating cold rolling pickling waste water according to claim 7, wherein an exhaust fan is provided in said reduction tower.
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