CN108083392B - Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor - Google Patents
Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor Download PDFInfo
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- CN108083392B CN108083392B CN201711394257.XA CN201711394257A CN108083392B CN 108083392 B CN108083392 B CN 108083392B CN 201711394257 A CN201711394257 A CN 201711394257A CN 108083392 B CN108083392 B CN 108083392B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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Abstract
The invention relates to a device for preparing superfine iron oxide and regenerated pickling solution by using pickling waste liquor, belonging to the technical field of waste regeneration. The device comprises a stainless steel electrochemical reaction tank; the top end of the stainless steel electrochemical reaction tank is provided with a cathode water outlet, and the bottom end of the stainless steel electrochemical reaction tank is provided with a water inlet; a titanium micropore anode tube is arranged in the stainless steel electrochemical reaction tank; the top end of the titanium microporous anode tube is provided with an anode water outlet; and the adjustable direct current power supply is connected with the stainless steel electrochemical reaction tank. The invention successfully recovers the iron resource in the pickling waste liquid and obtains the regenerated pickling solution with low pH value.
Description
Technical Field
The invention relates to a device for preparing superfine iron oxide and regenerated pickling solution by using pickling waste liquor, belonging to the technical field of waste regeneration.
Background
In the production of metal building materials, surface cleaning is generally performed with a mixed acid in order to remove scale on the surface of the annealed metal, and this process is called pickling, and the mixed acid used is called pickling solution. In the pickling process, iron, chromium, nickel and the like are continuously dissolved out from the oxide scale or the metal material on the metal surface, so that the pickling solution is changed into a mixture of acid and metal, the concentration of the acid is reduced along with the pickling, the pickling effect is reduced, and the pickling solution cannot be reused to be changed into pickling waste liquid. The waste liquid has high yield, high acidity and high metal ion content, mainly takes iron (Fe) ions as main materials, also contains a small amount of other toxic pollutants (nickel, chromium, fluorine and the like), and belongs to the waste liquid which is difficult to treat. The main harm is that structures such as underground pipelines and reinforced concrete are corroded, and soil layer structures are damaged by entering surface water, so that the growth of crops is influenced.
At present, the method for treating the pickling waste liquid is a neutralization method generally in China, but the following problems exist: the treatment capacity of the waste liquid is limited, resources in the waste liquid cannot be effectively utilized, the sludge amount is large, the treatment is difficult, and secondary pollution is easily caused; meanwhile, the neutralization method needs more manpower, occupies a large area, and further solves the problems of waste residue stacking, transportation and the like. Therefore, people pay attention to the method for finding a more environment-friendly treatment method with recyclable resources, and the method not only has obvious economic benefits, but also brings corresponding social benefits.
Disclosure of Invention
The invention solves the problems of iron resource waste, environmental pollution and pickle liquor regeneration in the pickle liquor from the viewpoints of resource recycling and energy saving, and the invention uses a titanium microporous anode tube as an anode and a stainless steel electrochemical reaction tank as a cathode, and applies voltage to make anions and cations in the pickle liquor move under an electric field to generate electrochemical reaction, thereby realizing the recycling of iron resources and pickle liquor and achieving the purpose of recycling.
The invention provides a device for preparing superfine iron oxide and regenerated pickling solution by using pickling waste liquor, which comprises a stainless steel electrochemical reaction tank;
the top end of the stainless steel electrochemical reaction tank is provided with a cathode water outlet, and the bottom end of the stainless steel electrochemical reaction tank is provided with a water inlet;
a titanium micropore anode tube is arranged in the stainless steel electrochemical reaction tank;
the top end of the titanium microporous anode tube is provided with an anode water outlet;
and the adjustable direct current power supply is connected with the stainless steel electrochemical reaction tank.
The device of the invention preferably comprises a storage tank and a pump;
the inlet of the pump is connected with the storage tank, and the outlet of the pump is connected with the water inlet at the bottom end of the stainless steel electrochemical reaction tank;
a cathode water outlet at the top end of the stainless steel electrochemical reaction tank is connected with the storage tank;
and an anode water outlet at the top end of the titanium microporous anode tube is connected with the storage tank.
Another object of the present invention is to provide a method for preparing ultra-fine iron oxide and regenerated pickling solution using the above apparatus, the method comprising the steps of:
adding the pickle liquor into a storage tank, and circulating the pickle liquor between the storage tank and a stainless steel electrochemical reaction tank by using a pump;
starting an adjustable direct current power supply to enable anions and cations in the pickling waste liquid to respectively move towards the cathode and the anode under the action of an electric field, and Fe2+Losing electron at anode and oxidizing to obtain Fe3+And Fe recycled to the stainless steel electrochemical reaction tank2+、Fe3+Converting into ferric hydroxide at the cathode;
and (3) dehydrating the ferric hydroxide precipitated on the cathode at high temperature to obtain superfine ferric oxide, and reducing the pH value of the solution in the storage tank to 1-2 to obtain regenerated pickling solution.
The voltage of the adjustable direct current power supply is preferably 12-24V.
The principle of the method for preparing the superfine ferric oxide and the regenerated pickling solution by using the device is as follows:
①Fe2+-e-→Fe3+；
②Fe3++3OH-→Fe(OH)3；
③Fe(OH)3→α(β)FeOOH→Fe3O4(Fe2O3)。
the device for preparing the superfine ferric oxide and the regenerated pickling solution by using the pickling waste solution comprises a stainless steel electrochemical reaction tank, wherein the top end of the stainless steel electrochemical reaction tank is provided with a cathode water outlet, and the bottom end of the stainless steel electrochemical reaction tank is provided with a water inlet; a titanium micropore anode tube is arranged in the stainless steel electrochemical reaction tank, and the top end of the stainless steel electrochemical reaction tank is provided with an anode water outlet; and the adjustable direct current power supply is connected with the stainless steel electrochemical reaction tank. The invention successfully recovers the iron resource in the pickling waste liquid and obtains the regenerated pickling solution with low pH value.
Drawings
In the figure 3 of the attached drawings of the invention,
FIG. 1 is an XRD spectrum of the ultrafine iron oxide prepared in example 2;
FIG. 2 is an SEM photograph of the ultra-fine iron oxide prepared in example 2;
FIG. 3 is a schematic structural diagram of an apparatus for preparing ultra-fine iron oxide and regenerating pickling solution from pickling waste liquid in example 1;
the device comprises a stainless steel electrochemical reaction tank, a water inlet of the stainless steel electrochemical reaction tank, a cathode water outlet of the stainless steel electrochemical reaction tank, a titanium microporous anode tube, an anode water outlet of the titanium microporous anode tube, 2 an adjustable direct current power supply, 3 a pump, 4 and a storage tank.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
A device for preparing superfine ferric oxide and regenerated pickling solution by using pickling waste liquor comprises a stainless steel electrochemical reaction tank 1, an adjustable direct-current power supply 2, a pump 3 and a storage tank 4;
the top end of the stainless steel electrochemical reaction tank 1 is provided with a cathode water outlet 12, and the bottom end of the stainless steel electrochemical reaction tank 1 is provided with a water inlet 11;
a titanium micropore anode tube 13 is arranged in the stainless steel electrochemical reaction tank 1;
an anode water outlet 14 is formed in the top end of the titanium microporous anode tube 13;
the adjustable direct current power supply 2 is connected with the stainless steel electrochemical reaction tank 1;
the inlet of the pump 3 is connected with the storage tank 4, and the outlet of the pump 3 is connected with the water inlet 11 at the bottom end of the stainless steel electrochemical reaction tank 1;
a cathode water outlet 12 at the top end of the stainless steel electrochemical reaction tank 1 is connected with the storage tank 4;
and an anode water outlet 14 at the top end of the titanium microporous anode tube 13 is connected with the storage tank 4.
The device has the advantages of small manpower demand, small occupied area, low energy consumption, small environmental pollution, simple and convenient operation, long service life and low operating cost.
Example 2
A method of preparing ultra fine iron oxide and regenerating pickling solution using the apparatus of example 1, the method comprising the steps of:
adding the pickling waste liquid into a storage tank 4, and circulating the pickling waste liquid between the storage tank 4 and a stainless steel electrochemical reaction tank 1 by using a pump 3;
starting the adjustable DC power supply 2, adjusting the voltage to 24V, so that the anions and the cations in the pickling waste liquid respectively move to the cathode and the anode under the action of an electric field, and Fe2+Losing electron at anode and oxidizing to obtain Fe3+And Fe recycled to the stainless steel electrochemical reaction tank 1 again2+、Fe3+Converting into ferric hydroxide at the cathode;
and (3) dehydrating the ferric hydroxide precipitated on the cathode at high temperature to obtain superfine ferric oxide, and reducing the pH value of the solution in the storage tank 4 to 1.5 to obtain regenerated pickling solution.
The method can successfully recover the iron resource in the pickling waste liquid and obtain the low-pH regenerated pickling liquid.
Claims (1)
1. A method for preparing superfine ferric oxide and regenerated pickling solution by using pickling waste liquid is characterized by comprising the following steps: the method uses an apparatus comprising a stainless steel electrochemical reaction tank, a storage tank, a pump; the top end of the stainless steel electrochemical reaction tank is provided with a cathode water outlet, and the bottom end of the stainless steel electrochemical reaction tank is provided with a water inlet; a titanium micropore anode tube is arranged in the stainless steel electrochemical reaction tank; the top end of the titanium microporous anode tube is provided with an anode water outlet; the inlet of the pump is connected with the storage tank, and the outlet of the pump is connected with the water inlet at the bottom end of the stainless steel electrochemical reaction tank; a cathode water outlet at the top end of the stainless steel electrochemical reaction tank is connected with the storage tank; an anode water outlet at the top end of the titanium microporous anode tube is connected with the storage tank; the adjustable direct current power supply is connected with the stainless steel electrochemical reaction tank;
the method comprises the following steps:
adding the pickle liquor into a storage tank, and circulating the pickle liquor between the storage tank and a stainless steel electrochemical reaction tank by using a pump;
starting an adjustable direct current power supply, wherein the voltage of the adjustable direct current power supply is 12-24V, so that anions and cations in the pickling waste liquid respectively move to the cathode and the anode under the action of an electric field, and Fe2+Losing electron at anode and oxidizing to obtain Fe3+And Fe recycled to the stainless steel electrochemical reaction tank2+、Fe3+Converting into ferric hydroxide at the cathode;
and (3) dehydrating the ferric hydroxide precipitated on the cathode at high temperature to obtain superfine ferric oxide, and reducing the pH value of the solution in the storage tank to 1-2 to obtain regenerated pickling solution.
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| CN201711394257.XA CN108083392B (en) | 2017-12-21 | 2017-12-21 | Device and method for preparing superfine iron oxide and regenerating pickling solution by using pickling waste liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103754957A (en) * | 2013-12-31 | 2014-04-30 | 上海宝钢磁业有限公司 | Method and device of preparing high quality ferric oxide powder by adopting chlorohydric acid pickling waste liquor |
| CN105399187A (en) * | 2015-11-20 | 2016-03-16 | 扬州祥发资源综合利用有限公司 | Method for resource utilization of steel wire rope pickling waste liquor |
| CN105463490A (en) * | 2015-12-23 | 2016-04-06 | 无锡市瑞思科环保科技有限公司 | Method for reclaiming copper and recycling sulfuric acid through copper pipe pickling wastewater |
| CN106396002A (en) * | 2016-11-09 | 2017-02-15 | 大连交通大学 | Bypass electrolysis device and method for removing chloridion in water solution |
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| JPH04128396A (en) * | 1990-09-17 | 1992-04-28 | Sumitomo Metal Ind Ltd | Method for recovering iron oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103754957A (en) * | 2013-12-31 | 2014-04-30 | 上海宝钢磁业有限公司 | Method and device of preparing high quality ferric oxide powder by adopting chlorohydric acid pickling waste liquor |
| CN105399187A (en) * | 2015-11-20 | 2016-03-16 | 扬州祥发资源综合利用有限公司 | Method for resource utilization of steel wire rope pickling waste liquor |
| CN105463490A (en) * | 2015-12-23 | 2016-04-06 | 无锡市瑞思科环保科技有限公司 | Method for reclaiming copper and recycling sulfuric acid through copper pipe pickling wastewater |
| CN106396002A (en) * | 2016-11-09 | 2017-02-15 | 大连交通大学 | Bypass electrolysis device and method for removing chloridion in water solution |
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Effective date of registration: 20220228 Address after: 116600 No.1-1, Xinhui South Road, Dalian Free Trade Zone, Liaoning Province Patentee after: DALIAN BONDED AREA JINBAOZHI ELECTRONICS CO.,LTD. Address before: 116028 No. 794, the Yellow River Road, Shahekou District, Liaoning, Dalian Patentee before: Dalian Jiaotong University |
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Denomination of invention: A device and method for preparing ultrafine iron oxide and regenerating pickling solution using pickling wastewater Effective date of registration: 20230919 Granted publication date: 20210416 Pledgee: Bank of China Limited Dalian Jinpu New Area Branch Pledgor: DALIAN BONDED AREA JINBAOZHI ELECTRONICS CO.,LTD. Registration number: Y2023980057481 |