CN114230050B - Cold rolling pickling wastewater treatment method and system - Google Patents
Cold rolling pickling wastewater treatment method and system Download PDFInfo
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- CN114230050B CN114230050B CN202111683763.7A CN202111683763A CN114230050B CN 114230050 B CN114230050 B CN 114230050B CN 202111683763 A CN202111683763 A CN 202111683763A CN 114230050 B CN114230050 B CN 114230050B
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- 238000005097 cold rolling Methods 0.000 title claims abstract description 84
- 238000005554 pickling Methods 0.000 title claims abstract description 78
- 238000004065 wastewater treatment Methods 0.000 title claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 236
- 229910052742 iron Inorganic materials 0.000 claims abstract description 137
- 239000002253 acid Substances 0.000 claims abstract description 95
- 239000002351 wastewater Substances 0.000 claims abstract description 91
- 238000001728 nano-filtration Methods 0.000 claims abstract description 87
- 238000001471 micro-filtration Methods 0.000 claims abstract description 58
- 239000000706 filtrate Substances 0.000 claims abstract description 47
- -1 iron ions Chemical class 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000012466 permeate Substances 0.000 claims abstract description 34
- 238000006722 reduction reaction Methods 0.000 claims abstract description 30
- 230000008929 regeneration Effects 0.000 claims abstract description 29
- 238000011069 regeneration method Methods 0.000 claims abstract description 29
- 150000005837 radical ions Chemical class 0.000 claims abstract description 22
- 239000012141 concentrate Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012530 fluid Substances 0.000 claims abstract description 13
- 230000000149 penetrating effect Effects 0.000 claims abstract description 13
- 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 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- 229960002089 ferrous chloride Drugs 0.000 claims description 12
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- 239000013618 particulate matter Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 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
- 230000008569 process Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 4
- 238000010586 diagram Methods 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
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 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
- 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
- 230000000694 effects Effects 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
- 238000002360 preparation method 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical group [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 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
- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 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
Classifications
-
- 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
Landscapes
- 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 wastewater, which comprises the following steps of: carrying out microfiltration on cold rolling pickling wastewater to remove particulate matters so as to obtain a first filtrate; nanofiltration is carried out on the first filtrate, so that acid radical ions and iron ions are separated, and a first permeate and a first concentrate are obtained; nanofiltration is carried out on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid; adding scrap iron edge 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 (3) 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, iron and acid are obtained, and other pollutants needing to be treated again are avoided, so that the method is more environment-friendly and has lower treatment cost. Correspondingly, the invention also provides a system for treating 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 acid-wash the surface of the steel before cold rolling or before coating the surface of the steel so as to remove the iron scale on the surface of the steel. After the pickling, the steel surface is rinsed with pure water to clean the acid solution remaining on the steel surface. Thus, the method forms a large amount of acid washing wastewater containing iron ions. For the acid washing wastewater, the conventional method is to neutralize the acid washing wastewater by using an alkali neutralizer in a wastewater treatment station and treat the acid washing wastewater to form aqueous ferric hydroxide (metal sludge) and sodium chloride solution so as to meet the environmental protection emission standard and realize the standard emission of the acid washing wastewater.
The acid washing wastewater is treated by consuming a large amount of alkali neutralizer, generating a large amount of metal sludge, requiring subsequent treatment, and being relatively high in running cost and not friendly to the environment. Thus, there is a need for a low cost and efficient treatment method and system that can recycle the pickling wastewater.
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 containing particulate matter, acid radical ions and iron ions, comprising:
Carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters and obtain a first filtrate;
Nanofiltration is carried out on the first filtrate, so that the acid radical ions and the iron ions are separated, and a first permeate and a first concentrate are obtained;
nanofiltration is carried out on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
adding scrap iron selvedge yarns 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 (3) 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 recycled for use in a cold rolling pickling line or for neutralizing alkaline wastewater.
Optionally, the method for treating cold rolling pickling wastewater further comprises the following steps:
carrying out microfiltration on the first iron-containing solution to remove particles generated by the reduction reaction, thereby obtaining a second filtrate;
nanofiltration is carried out on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
And (3) carrying out 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 cold rolling pickling wastewater, which comprises:
A wastewater tank for containing cold rolling pickling wastewater containing particulate matter, acid radical ions and iron ions;
The first microfiltration device is connected with the wastewater tank and is used for carrying out microfiltration on the cold-rolled pickling wastewater to remove the particulate matters so as to obtain a first filtrate;
The first water storage tank is connected with the first micro-filtration device and is used for storing the first filtrate;
The first nanofiltration device is connected with the first water storage tank and is used for nanofiltration of the first filtrate so as to separate the acid radical ions from the iron ions, thereby obtaining a first permeate and a first concentrate;
the second water storage tank is connected with the first nanofiltration device and is used for storing the first concentrated solution;
The second nanofiltration device is connected with the second water storage tank and is used for nanofiltration of the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
The reduction tower is connected with the second nanofiltration device and is used for carrying out reduction reaction on the second concentrated solution and the scrap iron edge wire so as 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 cold rolling pickling wastewater treatment system further comprises:
the third water storage tank is connected with the reduction tower and is used for storing the first iron-containing solution;
the second microfiltration device is connected with 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 micro-filtration device and is 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 permeate;
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 tubular microfiltration membranes.
Optionally, the first nanofiltration device, the second nanofiltration device and the third nanofiltration device are acid-resistant nanofiltration membranes.
Optionally, the front ends of the first micro-filtration device, the second micro-filtration device, the first nano-filtration device, the second nano-filtration device and the third nano-filtration device are all provided with booster pumps.
Optionally, an exhaust fan is arranged on the reduction tower.
In the sewage treatment method provided by the invention, cold rolling pickling wastewater contains particles, acid radical ions and iron ions, and the cold rolling pickling wastewater is subjected to microfiltration to remove the particles, 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, thereby obtaining a first permeate and a first concentrate. And carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid. And adding scrap iron edge 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 (3) 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 needing to be treated again exist, so that the cold rolling pickling wastewater is more environment-friendly. This also has lower processing costs than conventional processing methods. In addition, the scrap iron edge wires are added into the second concentrated solution, so that the corrosiveness of the second concentrated solution can be reduced, the scrap iron edge wires generated in the cold rolling operation can be consumed, and solid wastes are further consumed, so that the cold rolling process is more environment-friendly. Correspondingly, the invention also provides a system for treating cold rolling pickling wastewater.
Drawings
FIG. 1 is a first flow chart of a method for treating cold rolling pickling wastewater in an embodiment of the present invention;
FIG. 2 is a second flow chart of a method of treating cold rolling pickling wastewater in an embodiment of the present invention;
FIG. 3 is a first schematic diagram of a system for treating cold rolling pickling wastewater in an embodiment of the present invention;
FIG. 4 is a second schematic diagram of a system for treating cold rolling pickling wastewater in an embodiment of the present invention;
wherein, the reference numerals are as follows:
101-a waste water 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-a reduction tower; 108-a third water storage tank; 109-a second microfiltration device; 110-fourth water storage tank; 111-a third nanofiltration device; 112-a fifth water storage tank;
A-a booster pump; b-exhaust fan; a C-acid regeneration device; d-lift pump.
Detailed Description
Specific embodiments of the present application will be described in more detail below with reference to the drawings. The advantages and features of the present application will become more apparent from the following description. It should be noted that the drawings are in a very simplified form and are all to a non-precise scale, merely for convenience and clarity in aiding in the description of embodiments of the application. 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 specification 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 or all possible combinations of one or more of the associated listed items. It should be understood that although the terms first, second, third, etc. may be used herein to describe various information, these information should not be limited by these terms. These terms are only used to distinguish one type of information from another. For example, a first device could also be termed a second device, and, similarly, a second device could also be termed a first device, without departing from the scope of the present application.
The cold rolling and pickling wastewater is wastewater obtained by cleaning steel on a cold rolling production line by acid, and a large amount of iron ions are generated after the steel on the cold rolling production line is cleaned by acid, wherein the iron ions comprise ferrous ions and ferric ions. In addition, the waste water obtained after cleaning the steel materials in the cold rolling production line also contains a certain amount of particulate matters and acid radical ions. Therefore, the cold rolling pickling wastewater contains particles, acid radical ions and iron ions.
In the embodiment of the invention, hydrochloric acid is used for cleaning the steel, specifically for cleaning the carbon steel, so that acid radical ions are hydrochloride radicals, namely negative chloride ions. It should be noted that in practice, sulfuric acid, hydrofluoric acid, or the like may be used to clean the steel material in a cold-rolled carbon steel production line, and in this case, the acid radical ion contained in the cold-rolled pickling wastewater is sulfate ion or fluoride ion. Thus, the type of acid ion is related to the type of acid used in the cleaning. In the present invention, the type of acid used in the cold rolling line is not particularly limited herein.
At present, when cold rolling pickling wastewater is treated, lime or sodium hydroxide is adopted as an alkali neutralizer in the traditional treatment method in the industry, and after the cold rolling pickling wastewater is neutralized, the cold rolling pickling wastewater is discharged after reaching the standard. The traditional treatment method in the industry consumes a large amount of alkali neutralizer, generates a large amount of metal sludge and requires subsequent treatment, so that the traditional treatment method has higher operation cost and is not friendly to the environment.
Based on the method, the invention provides a treatment method of cold rolling pickling wastewater. Has lower treatment cost and is more environment-friendly.
FIG. 1 is a first flow chart of a method for treating cold rolling pickling wastewater in an embodiment of the present invention. As shown in fig. 1, in the method for treating cold rolling pickling wastewater according to the present invention, the cold rolling pickling wastewater contains particulate matter, acid radical ions and iron ions, and comprises the steps of:
Step S101: and carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters, thereby obtaining a first filtrate.
Step S102: and carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions, thereby obtaining a first permeate and a first concentrate.
Step S103: nanofiltration is carried out on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
Step S104: adding scrap iron selvedge yarns into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with a certain concentration of iron ions;
step S105: and (3) carrying out acid regeneration reaction on the first iron-containing solution to obtain iron and acid.
In the method for treating cold rolling pickling wastewater, iron and acid are obtained after the cold rolling pickling wastewater is treated, and other pollutants needing to be treated again are avoided, so that the method is more environment-friendly. This also has lower processing costs than conventional processing methods. In the method for treating cold rolling pickling wastewater of the present invention, particulate matter in the cold rolling pickling wastewater is removed by microfiltration, and a first permeate, a first concentrate, a second concentrate, and a second permeate are obtained by nanofiltration. The method has high treatment efficiency, so that the treatment method of the cold rolling pickling wastewater has higher treatment efficiency, and the treatment cost is further reduced. In addition, the scrap iron edge wires are added into the second concentrated solution, so that the corrosiveness of the second concentrated solution can be reduced, the scrap iron edge wires generated in the cold rolling operation can be consumed, and solid wastes are further consumed, so that the cold rolling process is more environment-friendly.
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 concentrate is subjected to nanofiltration again, so as to obtain a second concentrate and a second permeate. Nanofiltration is known as a membrane separation technique based on nanofiltration membranes, which have pore sizes in the range of a few nanometers, driven by pressure to effect separation of substances. The separation mechanism of the nanofiltration membrane is that sieving and dissolution diffusion coexist, and meanwhile, the nanofiltration membrane has a charge rejection effect, so that divalent and multivalent ions can be effectively removed, and 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 should be appreciated that the particulate matter in the cold rolling pickling wastewater damages the nanofiltration membrane during the nanofiltration process, and thus the particulate matter in the cold rolling pickling wastewater needs to be removed and then nanofiltration is performed, so that the service life of the filtration membrane can be prolonged. Based on this, in step S101, the cold rolling pickling wastewater is subjected to microfiltration to remove the particulate matter. In this embodiment, the cold rolling pickling wastewater is microfiltered using a tubular microfilter system. The tubular micro-filtration system is an assembled water treatment device and occupies a small area. The core of the tubular microfiltration system is a tubular microfiltration membrane made of ultra-high molecular polymer, the aperture range 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 certain pressure, so that particles in the cold-rolling pickling wastewater can be separated.
Optionally, when nanofiltration is performed on the first filtrate, membrane separation is performed on the first filtrate by using an acid-resistant nanofiltration membrane.
It should be appreciated that when the first filtrate and the first concentrate are nanofiltration, most of the free hydrochloric acid radicals penetrate the nanofiltration membrane to the water-producing side, and the iron ions are blocked. The main components of the solution on the water producing side (namely, the first penetrating fluid and the second penetrating fluid) are small amount of free hydrochloric acid and trace iron ions, the solution can be directly reused in a cold rolling and pickling production line for acid preparation, and the acid preparation process is that dilute hydrochloric acid is mixed with concentrated hydrochloric acid to prepare acid for cleaning. Typically, the amount of the first permeate will be relatively large, and therefore, an excess portion of the first permeate will also be used to neutralize the alkaline waste water produced by cold rolling. Based on this, the first permeate and the second permeate are recycled for use in cold rolling pickling lines or for neutralizing alkaline wastewater.
In step S105, the first iron-containing solution is subjected to an acid regeneration reaction to obtain iron and acid. It should be appreciated that since in embodiments of the present invention hydrochloric acid is used to clean carbon steel, 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 contains ferric chloride and ferrous chloride as main components and small amount of free hydrochloric acid. At this time, the first concentrated solution is subjected to nanofiltration, and further concentration is performed, so that the concentration of ferric chloride and ferrous chloride in the first concentrated solution can be further increased, and a second concentrated solution is obtained. And placing the scrap iron edge wire into the second concentrated solution for reduction reaction, and further improving the concentration of ferrous chloride in the second concentrated solution to obtain the first iron-containing solution, so that the concentration of ferrous chloride in the first iron-containing solution reaches a certain value. The ferrous chloride solution is introduced into a final concentrate tank, and is sent to a cold rolling acid regeneration system through a lifting pump D for 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 flow chart of a method for treating cold rolling pickling wastewater in an embodiment of the present invention. As shown in FIG. 2, the treatment method of cold rolling pickling wastewater provided by the invention further comprises the following steps:
step S106: carrying out microfiltration on the first iron-containing solution to remove particles generated by the reduction reaction, thereby obtaining a second filtrate;
step S107: nanofiltration is carried out on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid;
step S108: and (3) carrying out 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 to remove particles generated by the reduction reaction, thereby obtaining a second filtrate. The scrap iron edge wire is thus added to the second concentrate to remove the reduced corrosiveness of the second concentrate. This also results in the resulting first iron-containing solution containing fines carried in by the scrap iron edge wires. Thus, the particles are removed by microfiltration in order to avoid damaging the nanofiltration membrane by the particles.
Further, the second filtrate is subjected to nanofiltration to obtain a second iron-containing solution and a third permeate. In this way, the concentration of iron ions in the obtained second iron-containing solution is further increased. In this example, the ferrous chloride concentration was greater than 10% when acid regeneration was 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 appreciated that the third permeate is a water-producing permeate subjected to three-stage nanofiltration, so that the content of iron ions in the third permeate is relatively high, and therefore, the third permeate can be introduced into the first filtrate and then subjected to nanofiltration treatment, so that the loss of iron ions is avoided, and the economic benefit can be further improved.
Based on the same inventive concept, the invention also provides a treatment system of cold rolling pickling wastewater.
FIG. 3 is a schematic diagram of a system for treating cold rolling pickling wastewater in an embodiment of the invention. As shown in fig. 3, the treatment system for cold rolling pickling wastewater comprises:
A wastewater tank 101 for accommodating cold rolling pickling wastewater containing particulate matter, acid radical ions and iron ions;
The first micro-filtration device 102 is connected with the wastewater tank 101 and is used for micro-filtering the cold-rolled pickling wastewater to remove the particulate matters and obtain a first filtrate;
a first water storage tank 103 connected to the first micro-filtration device 102 for storing the first filtrate;
The first nanofiltration device 104 is connected to the first water storage tank 103 and is used for nanofiltration of the first filtrate, so that the acid radical ions and the iron ions are separated to obtain a first permeate and a first concentrate;
a second water storage tank 105 connected to the first nanofiltration device 104 for storing the first concentrate;
The second nanofiltration device 106 is connected to the second water storage tank 105 and is used for nanofiltration of the first concentrated solution to obtain a second concentrated solution and a second permeate;
A reduction tower 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 plastic water tanks or stainless steel water tanks, or any materials 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 cylinder or a rectangular parallelepiped, 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 wastewater in an embodiment of the present invention. As shown in fig. 4, the treatment system for cold rolling pickling wastewater further comprises:
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, for microfiltration of the first iron-containing solution to remove particles generated by the reduction reaction, thereby obtaining a second filtrate;
a fourth water storage tank 110 connected to the second micro-filtration device 109 for storing the second filtrate;
a third nanofiltration device 111 for concentrating 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. Thus, 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 the 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 appreciated that the first microfiltration device 102 and the second microfiltration device 109 can alternatively employ tubular microfiltration membranes of the same size, allowing the tubular microfiltration membranes to be commonly used, as will be appreciated by those skilled in the art. The tubular microfiltration membranes with different sizes can also be selected according to the amount of cold rolling pickling wastewater 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 cold rolling pickling wastewater contains acid radical ions to be acidic, and therefore, the acid-resistant nanofiltration membrane can be more suitable for the cold rolling pickling wastewater.
Further, the front ends of the first micro-filtration device 102, the second micro-filtration device 109, the first nano-filtration device 104, the second nano-filtration device 106 and the third nano-filtration device 111 are all provided with a booster pump a. For pressurizing the liquid passing through the first, second, first, second and third micro-filtration devices 102, 109, 104, 106, 111.
Further, an exhaust fan B is disposed on the reduction tower 107, and is configured to pump the reduction tower 107 to a 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 cold rolling pickling wastewater treatment system, 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 radical ions and iron ions, and the method for treating cold-rolling pickling wastewater includes: and carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters, thereby obtaining a first filtrate. And carrying out nanofiltration on the first filtrate to separate the acid radical ions from the iron ions, thereby obtaining a first permeate and a first concentrate. And carrying out nanofiltration on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid. And adding scrap iron edge 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 (3) 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 needing to be treated again exist, so that the cold rolling pickling wastewater is more environment-friendly. This also has lower processing costs than conventional processing methods. In addition, the scrap iron edge wires are added into the second concentrated solution, so that the corrosiveness of the second concentrated solution can be reduced, the scrap iron edge wires generated in the cold rolling operation can be consumed, and solid wastes are further consumed, so that the cold rolling process is more environment-friendly. Correspondingly, the invention also provides a system for treating cold rolling pickling wastewater.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art will make any equivalent substitution or modification to the technical solution and technical content disclosed in the invention without departing from the scope of the technical solution of the invention, and the technical solution of the invention is not departing from the scope of the invention.
Claims (8)
1. A method for treating cold-rolled acid-washing wastewater containing particulate matter, acid ions, and iron ions including ferrous ions and ferric ions, comprising:
Carrying out microfiltration on the cold rolling pickling wastewater to remove the particulate matters and obtain a first filtrate;
Nanofiltration is carried out on the first filtrate, so that the acid radical ions and the iron ions are separated, and a first permeate and a first concentrate are obtained;
nanofiltration is carried out on the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
adding scrap iron selvedge yarns into the second concentrated solution, and carrying out reduction reaction to obtain a first iron-containing solution with a certain concentration of iron ions;
carrying out microfiltration on the first iron-containing solution to remove particles generated by the reduction reaction, thereby obtaining a second filtrate;
nanofiltration is carried out on the second filtrate to obtain a second iron-containing solution and a third penetrating fluid, wherein the concentration of ferrous chloride in the second iron-containing solution is more than 10%;
Carrying out acid regeneration reaction on the second iron-containing solution to obtain iron and acid;
And introducing the third permeate into the first filtrate, and then carrying out nanofiltration.
2. The method for treating cold-rolled pickling wastewater as claimed in 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-rolled acid-washing wastewater as claimed in claim 1, wherein the first permeate and the second permeate are reused in a cold-rolled acid-washing production line or for neutralizing alkaline wastewater.
4. A system for treating cold rolling pickling wastewater, comprising:
a wastewater tank for containing cold rolling pickling wastewater containing particulate matter, acid radical ions and iron ions, the iron ions including ferrous ions and ferric ions;
The first microfiltration device is connected with the wastewater tank and is used for carrying out microfiltration on the cold-rolled pickling wastewater to remove the particulate matters so as to obtain a first filtrate;
The first water storage tank is connected with the first micro-filtration device and is used for storing the first filtrate;
The first nanofiltration device is connected with the first water storage tank and is used for nanofiltration of the first filtrate so as to separate the acid radical ions from the iron ions, thereby obtaining a first permeate and a first concentrate;
the second water storage tank is connected with the first nanofiltration device and is used for storing the first concentrated solution;
The second nanofiltration device is connected with the second water storage tank and is used for nanofiltration of the first concentrated solution to obtain a second concentrated solution and a second penetrating fluid;
The reduction tower is connected with the second nanofiltration device and is used for carrying out reduction reaction on the second concentrated solution and the scrap iron edge wire so as to generate a first iron-containing solution;
the third water storage tank is connected with the reduction tower and is used for storing the first iron-containing solution;
the second microfiltration device is connected with 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 micro-filtration device and is 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 permeate, wherein the concentration of ferrous chloride in the second iron-containing solution is more than 10%;
A fifth water storage tank connected to the third nanofiltration device for storing the second iron-containing solution;
and the acid regeneration device is used for carrying out acid regeneration reaction on the second iron-containing solution to obtain iron and acid.
5. The cold-rolled acid cleaning wastewater treatment system as claimed in claim 4, wherein the first microfiltration device and the second microfiltration device are tubular microfiltration membranes.
6. The cold-rolled acid cleaning wastewater treatment system according to claim 4, wherein the first nanofiltration device, the second nanofiltration device and the third nanofiltration device are acid-resistant nanofiltration membranes.
7. The cold-rolled pickling wastewater treatment system as claimed in claim 4, wherein the front ends of the first micro-filtration device, the second micro-filtration device, the first nano-filtration device, the second nano-filtration device and the third nano-filtration device are provided with booster pumps.
8. The cold-rolling pickling wastewater treatment system as claimed in claim 4, wherein an exhaust fan is arranged on the reduction tower.
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