CN113755852A - Treatment system and method for reducing acid consumption and reducing emission of red mud in steel acid pickling and rust removing process - Google Patents

Treatment system and method for reducing acid consumption and reducing emission of red mud in steel acid pickling and rust removing process Download PDF

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Publication number
CN113755852A
CN113755852A CN202111067157.2A CN202111067157A CN113755852A CN 113755852 A CN113755852 A CN 113755852A CN 202111067157 A CN202111067157 A CN 202111067157A CN 113755852 A CN113755852 A CN 113755852A
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pump
acid
tank
pickling
reducing
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CN113755852B (en
Inventor
杨伟芳
李世伟
王永强
尹少华
沈阳
邱涛
钭国光
胡辉辉
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Zhejiang Kingland Pipeline Technology Co ltd
Kunming University of Science and Technology
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Zhejiang Kingland Pipeline Technology Co ltd
Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00Apparatus for cleaning or pickling metallic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B13/00Accessories or details of general applicability for machines or apparatus for cleaning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00Cleaning by methods involving the use or presence of liquid or steam
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/081Iron or steel solutions containing H2SO4
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36Regeneration of waste pickling liquors

Abstract

The invention belongs to the technical field of steel corrosion prevention, and relates to a treatment system and a method for reducing acid consumption and reducing emission of red mud in a steel acid pickling and rust removing process. Compared with the traditional process, the novel process has no rinsing water treatment system, and has no acid-base neutralization reaction, thereby fundamentally avoiding the generation of red mud, greatly reducing the acid consumption and realizing the zero emission of the red mud.

Description

Treatment system and method for reducing acid consumption and reducing emission of red mud in steel acid pickling and rust removing process
Technical Field
The invention belongs to the technical field of steel corrosion prevention, and particularly relates to a treatment system and method for reducing acid consumption and reducing emission of red mud in a steel acid pickling and rust removing process.
Background
Steel has the advantages of high yield, good mechanical properties, low price and the like, so the steel is widely applied to industries such as machinery, buildings, household appliances and the like. However, ordinary steel is extremely easy to corrode in natural environment, the corrosion rate is higher in special environment occasions such as marine climate, high temperature and high humidity, and a large amount of steel is scrapped due to corrosion every year. The hot galvanizing can greatly slow down the corrosion of steel and prolong the service life of the steel, and has the advantages of low production cost, good mechanical property of a coating and the like, so the hot galvanizing is a common method for steel corrosion prevention. In the hot galvanizing production process, hydrochloric acid or sulfuric acid is generally adopted to chemically dissolve rust on the surface of a steel product, so that iron atoms in the steel product are exposed on the surface of the steel product, and necessary process conditions are created for subsequent hot galvanizing.
In the traditional sulfuric acid pickling process of hot galvanizing, in order to reduce the concentration of iron ions in rinsing water and reduce the amount of the iron ions brought into a plating assistant solution, the rinsing water is usually purified to generate a large amount of red mud (the main components are ferric hydroxide, zinc hydroxide and water).
The prior art pickling, spent acid treatment and rinse water treatment process is shown in figure 1. In the pickling process of the steel, pickling and rust removal are completed in a first-stage pickling tank, a second-stage pickling tank or a third-stage pickling tank, and a layer of sulfuric acid solution (mainly comprising water, sulfuric acid and ferrous sulfate) is adhered to the surface of the pickled steel. In the rinsing process, the pickled steel sequentially passes through a primary rinsing tank and a secondary rinsing tank, the sulfuric acid solution on the surface of the steel is washed into rinsing water, and the sulfuric acid and the iron ions in the secondary rinsing tank are low in concentration because the steel firstly passes through the primary rinsing tank and then passes through the secondary rinsing tank. However, as the rinsing process proceeds, the concentrations of sulfuric acid and iron ions in the secondary rinsing tank gradually increase, which leads to a decrease in pH and an increase in the concentration of iron ions in the subsequent processes, and finally causes an increase in the amount of zinc slag in the hot galvanizing process. Therefore, the rinse water in the secondary rinse tank must be subjected to online iron removal, the waste rinse water is continuously conveyed to the purification tank during the iron removal process, and meanwhile, alkali (generally sodium hydroxide) is added into the purification tank, so that the sulfuric acid is converted into sodium sulfate (causing high sulfuric acid consumption), and iron ions are converted into iron hydroxide (namely red mud). According to the regulations of the national records of dangerous wastes, red mud is a dangerous waste. According to the environmental prevention and control method of China: the enterprise and public institution should utilize the industrial solid waste produced by the enterprise and public institution according to economic and technical conditions; for those that are temporarily unused or unusable, it is necessary to construct storage facilities and sites according to the regulations of the administrative department of environmental protection of the state department, to store them in safe classification, or to take harmless measures. Because the main component of the red mud is ferric hydroxide and the zinc content is low, the disposal difficulty is high, and therefore, all hot galvanizing enterprises adopt a method of entrusting qualified third party disposal to treat the red mud, and the defects of high disposal cost and large environmental risk exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process and a treatment method based on the system.
The invention adopts the following technical scheme:
the utility model provides a reduce steel pickling rust cleaning in-process acid consumption and emission reduction red mud's processing system, including the descaling bath, with the one-level potcher of descaling bath intercommunication, with the second grade potcher of one-level potcher intercommunication and with the tertiary potcher of second grade potcher intercommunication and receipt the low temperature crystallization pond of descaling bath discharge liquid with be used for to the descaling bath provides the acid mixing groove of acidizing fluid, one-level potcher intercommunication the acid mixing groove, tertiary potcher passes through back flow reverse intercommunication the second grade potcher pass through back flow reverse intercommunication the one-level potcher, just tertiary potcher intercommunication has the running water supply pipe.
According to the scheme, the steel after acid washing is sequentially rinsed in the first-stage rinsing tank, the second-stage rinsing tank and the third-stage rinsing tank to realize three-stage rinsing, and the concentrations of sulfuric acid and iron ions are the largest in the first-stage rinsing tank, the concentrations of sulfuric acid and iron ions are the next lowest in the second-stage rinsing tank and the concentrations of sulfuric acid and iron ions are the lowest in the third-stage rinsing tank. In the acid preparation process, part of rinsing water in the primary rinsing tank is extracted, so that high-concentration sulfuric acid and iron ions in the primary rinsing tank are recycled. Meanwhile, part of the low-sulfuric-acid and iron-ion-concentration rinsing water in the secondary rinsing tank and tap water are respectively input into the primary rinsing tank (so that the concentration of sulfuric acid and iron ions in the rinsing water in the primary rinsing tank is reduced, and the rinsing capacity of the rinsing water is improved). Meanwhile, the rinse water in the third-level rinse tank is conveyed to the second-level rinse tank, tap water is conveyed to the third-level rinse tank, the concentration of sulfuric acid and iron ions of the rinse water in the second-level rinse tank and the concentration of the sulfuric acid and the iron ions of the rinse water in the third-level rinse tank are reduced, and the rinsing capacity of the rinse water is improved. Because a rinsing water treatment system in the traditional process is not provided, and acid-base neutralization reaction is not performed, the acid consumption can be greatly reduced, and the zero emission of red mud can be realized.
Preferably, the primary rinsing tank is communicated with a tap water supply pipe.
Preferably, the primary rinsing tank is communicated with the acid preparation tank through a first pump, a second pump is arranged on a tap water supply pipe communicated with the primary rinsing tank, and a third pump is arranged on a return pipe reversely communicated with the primary rinsing tank.
Preferably, the sum of the flow rates of the second and third pumps is equal to the flow rate of the first pump.
Preferably, the flow rate ratio of the second pump to the third pump is from 0:8 to 8: 0.
Preferably, a fourth pump is arranged on a return pipe of the three-stage rinsing tank which is reversely communicated with the two-stage rinsing tank, a fifth pump is arranged on a tap water supply pipe communicated with the three-stage rinsing tank, and the first pump, the second pump, the third pump, the fourth pump and the fifth pump are controlled by the same switch.
Preferably, the low-temperature crystallization tank is communicated with the acid preparation tank.
Preferably, the flow rates of the third pump, the fourth pump and the fifth pump are the same.
The processing method provided by the invention adopts the following technical scheme:
a treatment method for reducing acid consumption and reducing emission of red mud in a steel acid pickling and rust removing process comprises an acid pickling step of pickling steel, a three-stage rinsing step of rinsing the pickled steel, a low-temperature crystallization step of crystallizing discharged liquid in an acid pickling tank and an acid preparation step of preparing acid liquor for the acid pickling tank, wherein in the acid preparation step, a first pump is started to pump rinse water in part of a first-stage rinsing tank to the acid preparation tank, and a second pump, a third pump, a fourth pump and a fifth pump are started simultaneously.
Preferably, in the three-stage rinsing step, the time of each stage of rinsing is 1-15 min.
Preferably, the crystallization temperature of the low-temperature crystallization step is from-50 ℃ to 5 ℃.
Through the implementation of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
compared with the traditional process, the novel process has no rinsing water treatment system and no acid-base neutralization reaction, thereby fundamentally avoiding the generation of red mud, greatly reducing the acid consumption and realizing the zero emission of the red mud.
Drawings
FIG. 1 is a flow chart of a steel acid pickling rust removal system in the prior art;
FIG. 2 is a flow chart of the steel acid pickling rust removal system.
Detailed Description
For better understanding of the above technical solutions, the above technical solutions will be described in detail with reference to the drawings and specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
The utility model provides a reduce processing system that steel pickling rust cleaning in-process acid consumed and reduce discharging red mud, as shown in figure 2, including the descaling bath, with the one-level potcher of descaling bath intercommunication, with the second grade potcher of one-level potcher intercommunication and with the tertiary potcher of second grade potcher intercommunication and receipt the low temperature crystallizer of descaling bath discharge liquid with be used for to the descaling bath provides the acid mixing groove of acidizing fluid, one-level potcher intercommunication have the running water supply pipe with the acid mixing groove installs first pump B1 on communicating pipe with the acid mixing groove intercommunication, installs second pump B2 on the running water supply pipe. The tertiary rinsing tank is reversely communicated with the secondary rinsing tank through a return pipe, and a fourth pump B4 is arranged on the return pipe. The second-stage rinsing tank is reversely communicated with the first-stage rinsing tank through a return pipe, a third pump B3 is installed on the return pipe, the third-stage rinsing tank is communicated with a tap water supply pipe, and a fifth pump B5 is arranged on the tap water supply pipe.
According to the scheme, the steel after acid washing is sequentially rinsed in the first-stage rinsing tank, the second-stage rinsing tank and the third-stage rinsing tank to realize three-stage rinsing, and the concentrations of sulfuric acid and iron ions are the largest in the first-stage rinsing tank, the concentrations of sulfuric acid and iron ions are the next lowest in the second-stage rinsing tank and the concentrations of sulfuric acid and iron ions are the lowest in the third-stage rinsing tank. In the acid preparation process, part of rinsing water in the primary rinsing tank is extracted, so that high-concentration sulfuric acid and iron ions in the primary rinsing tank are recycled. Meanwhile, part of the low-sulfuric-acid and iron-ion-concentration rinse water in the secondary rinse tank and tap water are respectively input into the primary rinse tank (so that the concentration of sulfuric acid and iron ions in the rinse water in the primary rinse tank is reduced and the rinsing capacity of the rinse water is improved), and in the process, the sum of the flow rates of the second pump B2 and the third pump B3 is kept equal to the flow rate of the first pump B1. Meanwhile, the rinse water in the third-stage rinse tank is conveyed to the second-stage rinse tank, tap water is conveyed to the third-stage rinse tank, the concentration of sulfuric acid and iron ions of the rinse water in the second-stage rinse tank and the concentration of the sulfuric acid and the iron ions of the rinse water in the third-stage rinse tank are reduced, the rinse capacity of the rinse water is improved, and in the process, the flow rates of the third pump B3, the fourth pump B4 and the fifth pump B5 are the same. The first pump B1, the second pump B2, the third pump B3, the fourth pump B4 and the fifth pump B5 are controlled by the same switch to be turned on and off simultaneously. Because a rinsing water treatment system in the traditional process is not provided, and acid-base neutralization reaction is not performed, the acid consumption can be greatly reduced, and the zero emission of red mud can be realized.
Example 2:
the utility model provides a reduce processing system of steel pickling rust cleaning in-process acid consumption and emission reduction red mud, as shown in figure 2, including the descaling bath, with the one-level potcher of descaling bath intercommunication, with the second grade potcher of one-level potcher intercommunication and with the tertiary potcher of second grade potcher intercommunication and receipt the low temperature crystallizer of descaling bath discharge liquid with be used for to the descaling bath provides the pickling bath of acidizing fluid, the descaling bath sets up threely, one-level potcher intercommunication have the running water supply pipe with the pickling bath installs first pump B1 on communicating pipe with the pickling bath intercommunication, installs second pump B2 on the running water supply pipe. The tertiary rinsing tank is reversely communicated with the secondary rinsing tank through a return pipe, and a fourth pump B4 is arranged on the return pipe. The second-stage rinsing tank is reversely communicated with the first-stage rinsing tank through a return pipe, a third pump B3 is installed on the return pipe, the third-stage rinsing tank is communicated with a tap water supply pipe, and a fifth pump B5 is arranged on the tap water supply pipe.
The treatment method for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process based on the treatment system comprises an acid pickling step of pickling the steel, a three-stage rinsing step of rinsing the pickled steel, a low-temperature crystallization step of crystallizing the discharged liquid in the pickling tank and an acid preparation step of preparing acid liquor for the pickling tank. Firstly, the pickling is carried out in a three-stage pickling tank sequentially, the pickling time is 3-30 minutes, and the pickling is carried out for 15 minutes in the embodiment. And then, sequentially rinsing the pickled steel in a first-stage rinsing tank, a second-stage rinsing tank and a third-stage rinsing tank to realize three-stage rinsing, wherein the time of each stage of rinsing is 1-15min, the first-stage rinsing time is preferably longer than the second-stage rinsing time and longer than the third-stage rinsing time, and in the embodiment, the time is preferably 10 minutes, 6 minutes and 2 minutes sequentially. The sulfuric acid and iron ion concentrations are greatest in the primary rinse tank, next to the secondary rinse tank, and lowest in the tertiary rinse tank. In the acid preparation process, part of rinsing water in the primary rinsing tank is extracted, so that high-concentration sulfuric acid and iron ions in the primary rinsing tank are recycled. Meanwhile, part of the low-sulfuric-acid and iron-ion-concentration rinse water in the secondary rinse tank and tap water are respectively input into the primary rinse tank (so that the concentration of sulfuric acid and iron ions in the rinse water in the primary rinse tank is reduced and the rinsing capacity of the rinse water is improved), in the process, the sum of the flow rates of a second pump B2 and a third pump B3 is kept equal to the flow rate of a first pump B1, and the flow rate ratio of the second pump B2 to the third pump B3 is 0:8 to 8:0, and the embodiment is preferably 1: 3. Meanwhile, the rinse water in the third-stage rinse tank is conveyed to the second-stage rinse tank, tap water is conveyed to the third-stage rinse tank, the concentration of sulfuric acid and iron ions of the rinse water in the second-stage rinse tank and the concentration of the sulfuric acid and the iron ions of the rinse water in the third-stage rinse tank are reduced, the rinse capacity of the rinse water is improved, and in the process, the flow rates of the third pump B3, the fourth pump B4 and the fifth pump B5 are the same. The first pump B1, the second pump B2, the third pump B3, the fourth pump B4 and the fifth pump B5 are controlled by the same switch to be turned on and off simultaneously. Because a rinsing water treatment system in the traditional process is not provided, and acid-base neutralization reaction is not performed, the acid consumption can be greatly reduced, and the zero emission of red mud can be realized.
The waste acid after acid washing is treated by a low-temperature crystallization method to produce ferrous sulfate and mother liquor, wherein the crystallization temperature is minus 50 ℃ to 5 ℃, and the temperature is preferably zero to five ℃. The mother liquor enters an acid preparation tank and is prepared with the added sulfuric acid and the rinsing liquid of the primary rinsing tank.

Claims (10)

1. The utility model provides a reduce processing system of steel pickling rust cleaning in-process acid consumption and emission reduction red mud, including the descaling bath, with the one-level potcher of descaling bath intercommunication, with the second grade potcher of one-level potcher intercommunication and with the tertiary potcher of second grade potcher intercommunication and receipt the low temperature crystallizer of descaling bath discharge liquid with be used for to the descaling bath provides the acid mixing groove of acidizing fluid, a serial communication, the one-level potcher intercommunication the acid mixing groove, tertiary potcher passes through back flow reverse intercommunication the second grade potcher pass through back flow reverse intercommunication the one-level potcher, just tertiary potcher intercommunication has the running water supply pipe.
2. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process of claim 1, wherein the primary rinsing tank is communicated with a tap water supply pipe.
3. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process according to claim 1, wherein the primary rinsing tank is communicated with the acid preparation tank through a first pump, a second pump is arranged on a tap water supply pipe communicated with the primary rinsing tank, and a third pump is arranged on a return pipe reversely communicated with the primary rinsing tank.
4. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process of claim 1, wherein the sum of the flow rates of the second pump and the third pump is equal to the flow rate of the first pump.
5. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process of claim 1, wherein the flow rate ratio of the second pump to the third pump is 0:8 to 8: 0.
6. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process according to claim 1, wherein a fourth pump is arranged on a return pipe of the three-stage rinsing tank which is reversely communicated with the two-stage rinsing tank, a fifth pump is arranged on a tap water supply pipe communicated with the three-stage rinsing tank, and the first pump, the second pump, the third pump, the fourth pump and the fifth pump are controlled by the same switch.
7. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling rust removing process according to claim 1, wherein the low-temperature crystallizing pond is communicated with the acid preparation tank.
8. The treatment system for reducing acid consumption and reducing emission of red mud in the steel acid pickling and rust removing process of claim 1, wherein the flow rates of the third pump, the fourth pump and the fifth pump are the same.
9. The treatment method according to any one of claims 1 to 8, comprising a pickling step of pickling the steel material, a three-stage rinsing step of rinsing the pickled steel material, a low-temperature crystallization step of crystallizing the effluent in the pickling tank, and an acid preparation step of preparing the pickling tank with an acid solution, wherein in the acid preparation step, the first pump is started to pump a part of the rinse water in the primary rinse tank to the acid preparation tank, and the second pump, the third pump, the fourth pump, and the fifth pump are started at the same time.
10. The process train method of claim 8, wherein in the three rinsing steps, the time for each rinsing step is 1-15 min.
CN202111067157.2A 2021-09-13 2021-09-13 Treatment system and method for reducing acid consumption and reducing emission of red mud in steel acid pickling and rust removing process Active CN113755852B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114369780A (en) * 2022-01-13 2022-04-19 湖北汉唐电力器材有限公司 Hot galvanizing process for power iron accessory and photovoltaic solar bracket

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JPH04346684A (en) * 1991-05-22 1992-12-02 Sumitomo Metal Ind Ltd Discoloration preventing method and device for continuous pickling line
JPH07166383A (en) * 1993-12-13 1995-06-27 Nisshin Steel Co Ltd Method for recovering acid in apparatus for pickling metallic strip and apparatus therefor
CN111014315A (en) * 2019-12-20 2020-04-17 马钢(合肥)板材有限责任公司 Method for improving surface reflectivity of rolled hard coil strip steel

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JPH0369515A (en) * 1989-08-09 1991-03-25 Tetsugen:Kk Method for recovering high-purity iron sulfate from waste sulfuric acid pickling solution for stainless steel
JPH04346684A (en) * 1991-05-22 1992-12-02 Sumitomo Metal Ind Ltd Discoloration preventing method and device for continuous pickling line
JPH07166383A (en) * 1993-12-13 1995-06-27 Nisshin Steel Co Ltd Method for recovering acid in apparatus for pickling metallic strip and apparatus therefor
CN111014315A (en) * 2019-12-20 2020-04-17 马钢(合肥)板材有限责任公司 Method for improving surface reflectivity of rolled hard coil strip steel

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Publication number Priority date Publication date Assignee Title
CN114369780A (en) * 2022-01-13 2022-04-19 湖北汉唐电力器材有限公司 Hot galvanizing process for power iron accessory and photovoltaic solar bracket

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