CN107557710B - Hot galvanizing composite zinc liquid iron remover and use method thereof - Google Patents
Hot galvanizing composite zinc liquid iron remover and use method thereof Download PDFInfo
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- CN107557710B CN107557710B CN201710778289.3A CN201710778289A CN107557710B CN 107557710 B CN107557710 B CN 107557710B CN 201710778289 A CN201710778289 A CN 201710778289A CN 107557710 B CN107557710 B CN 107557710B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 114
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 109
- 239000011701 zinc Substances 0.000 title claims abstract description 109
- 239000007788 liquid Substances 0.000 title claims abstract description 72
- 238000005246 galvanizing Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title abstract description 11
- 239000000843 powder Substances 0.000 claims description 54
- 239000012188 paraffin wax Substances 0.000 claims description 38
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 25
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021538 borax Inorganic materials 0.000 claims description 9
- 239000004328 sodium tetraborate Substances 0.000 claims description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 9
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 56
- 239000002893 slag Substances 0.000 abstract description 26
- 238000007747 plating Methods 0.000 abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 abstract description 17
- 230000003213 activating effect Effects 0.000 abstract description 13
- 239000004088 foaming agent Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 32
- 239000000203 mixture Substances 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229940099259 vaseline Drugs 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 8
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910000599 Cr alloy Inorganic materials 0.000 description 5
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 5
- 239000000788 chromium alloy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000012629 purifying agent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to a hot galvanizing composite zinc liquid iron remover and a using method thereof, wherein the iron remover comprises the following components in percentage by mass: 10-50% of foaming agent; 2-15% of a moisture-proof forming agent; 2-20% of a reducing agent; 7-30% of an activating agent; 10-40% of slagging agent. The hot galvanizing composite zinc liquid iron remover can effectively remove iron in zinc liquid, and the iron removal rate reaches over 35 percent; meanwhile, more than 80% of suspended slag and iron-containing zinc slag in the zinc liquid can be removed. The hot galvanizing composite zinc liquid iron remover can also improve the fluidity of the zinc liquid, improve the surface quality of a plated part, reduce zinc slip on the surface of the plated part, enable the surface of the plated part to be more smooth, reduce the zinc feeding amount, enable the thickness of a plating layer to be reduced by at least 25%, and save the hot galvanizing cost. The method is simple, the product has high use efficiency, and the product has the functions of moisture resistance, long storage time and the like, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of hot dipping, in particular to a hot-dip galvanizing composite zinc liquid iron remover and a using method thereof.
Background
Hot dip galvanizing, that is, hot galvanizing, is a method of obtaining a zinc coating by immersing a metal product such as steel or cast iron in a molten zinc bath. When hot galvanizing is carried out, firstly, a zinc ingot is put in a zinc pot to be heated and melted, then, the pretreated steel product is soaked in molten zinc liquid at about 450 ℃, and a zinc-iron reaction is carried out for a short time to form a zinc coating on the surface of a plated piece, thereby playing the roles of corrosion resistance and corrosion resistance.
In the batch hot galvanizing process, the diffusion between a zinc pot and the zinc liquid, the melting of the steel matrix, iron ions in the plating assistant agent and iron salts on the surface of the matrix can increase the iron content in the zinc liquid. When the iron content in the zinc liquid reaches or exceeds 0.02 percent, on one hand, zinc slag is formed in the zinc liquid, so that zinc accumulation and small zinc slag particles appear on the surface of a plated part, the surface of a plated layer becomes rough and uneven, the corrosion resistance is reduced, the fluidity of the zinc liquid is reduced, the plated layer becomes thicker, and the cost is increased due to the increase of zinc consumption; on the other hand, the zinc dross is increased along with the increase of the iron content in the zinc liquid, and the zinc materials wasted along with the continuous increase of the zinc dross are increased in the hot-dip galvanizing process, so that the waste of resources is caused, and the cost pressure of enterprises is increased.
With the attention of hot galvanizing industry to the surface quality and cost of products, the purification treatment of zinc liquid is also paid attention. For example, CN102418062A discloses a zinc liquid purifying agent, which comprises the following raw materials in percentage by weight: CaF240-72％、ZnCl23-15％、C6Cl63-5％、MgCl2·KCl 20-30％、MnO22 to 10 percent. However, the purifying agent only focuses on removing impurities and hot-dip melt treatment, cannot meet the requirements of hot-dip galvanizing enterprises on treating suspended slag and removing iron, and is easy to deliquesce and inconvenient to store for a long time. CN103060736A discloses a hot galvanizing zinc liquid purifying agent, which comprises the following components in percentage by weight: 15-50% of a decomposing agent; 10-30% of fluxing agent; 30-70% of adsorbent. The invention only focuses on the treatment of the suspended slag in the zinc liquid, can not meet the requirement of reducing the iron content in the production, and has the advantages of complex preparation, easy deliquescence and inconvenient preservation for a long time.
Therefore, in consideration of the above problems, the development of a novel hot dip galvanizing iron remover with more comprehensive and excellent performance is urgently needed in the hot dip galvanizing industry.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a hot galvanizing composite zinc liquid iron remover and a using method thereof, which can effectively control the iron content in the zinc liquid and remove suspended slag, the iron removal rate reaches more than 35%, the slag removal rate is more than 80%, the surface quality and corrosion resistance of a plated part are improved, the thickness of a plating layer is reduced by at least 25%, the zinc feeding amount is reduced, and the hot galvanizing cost is saved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a hot galvanizing composite zinc liquid iron remover, which comprises the following components in percentage by mass:
the compound zinc liquid iron remover provided by the invention comprises a foaming agent, a moisture-proof forming agent, a reducing agent, an activating agent and a slagging agent with specific contents.
The foaming agent is added into the hot galvanizing liquid to generate a large amount of gas, so that the contact area of a subsequent reducing agent, an activating agent, a slag former and the zinc liquid is increased, and sustainable power is provided for subsequent reaction and removal of zinc slag in the original zinc liquid; the addition of the moisture-proof forming agent enables the composite zinc liquid iron remover to have a new moisture-proof function on the basis of easy briquetting forming, and the storage time is prolonged; the reducing agent is used for reacting with free iron dissolved in the zinc liquid and iron-zinc compounds in the iron-containing zinc slag to generate compounds with specific gravity smaller than that of the zinc liquid, so that the compounds are conveniently taken out of the surface of the zinc liquid under the power of a porous slag body generated by a slag former and a foaming agent; the activating agent increases the dispersibility and the fluidity of the compound zinc liquid iron remover and improves the utilization rate of the iron remover; after the slag former is added into the zinc liquid, a porous slag body with the specific gravity smaller than that of the zinc liquid is quickly formed, and compounds generated by the reaction of the reducing agent and the solid-dissolved free iron, iron-containing zinc slag in the zinc liquid and other impurities are carried.
The moisture-proof forming agent is the key of the invention, can play the roles of enabling the molten zinc iron remover to be easy to form, facilitating transportation, enhancing moisture resistance and prolonging storage time, and can increase the heat release of the whole molten zinc iron remover through combustion supporting after being immersed in the molten zinc. The moisture-proof forming agent can be rapidly melted into a liquid state when being put into the zinc liquid, and covers the surface of the zinc liquid to further prevent the volatilization of the iron removing agent of the zinc liquid, thereby prolonging the reaction time, improving the product utilization rate and improving the iron removing rate to a certain extent. A large number of experiments show that the reaction duration of the iron remover added with the moisture-proof forming agent in the zinc liquid is prolonged by 1.5min compared with the reaction duration of the iron remover without the moisture-proof forming agent, and the iron removal rate is improved by more than 5%.
The moisture-proof forming agent plays an indispensable role in the compound zinc liquid iron remover, but the addition amount is controlled within a reasonable range, if the dosage of the moisture-proof iron remover is too large, large zinc slag which is difficult to treat is formed after reaction, the difficulty of fishing the zinc slag is improved when the reaction slag is fished, and the zinc liquid is brought out of a zinc pot to cause extra economic loss; if the dosage of the added moisture-proof forming agent is too small, the zinc liquid and zinc liquid iron remover is difficult to be formed by pressing blocks, the moisture resistance is poor, and the storage time is shortened.
In the invention, the reducing agent is added to react with free iron dissolved in the zinc liquid and iron-zinc compounds in the iron-containing zinc slag to generate compounds with specific gravity smaller than that of the zinc liquid, so that the compounds are conveniently brought out of the surface of the zinc liquid under the power of a porous slag body and a foaming agent generated by a slag former. The addition of the activating agent reduces the melting point of the compound type iron remover and increases the dispersibility and the fluidity of the compound type zinc liquid iron remover. The inventor finds that when the reducing agent and the activating agent are added into the iron remover at the same time, the fluidity and the dispersity of the iron remover are improved, the iron content in the zinc liquid is reduced, and the utilization rate of the reducing agent and the iron removal rate of the iron remover are greatly improved. According to researches, when no activating agent is added into the compound zinc liquid iron remover, the iron removing effect of adding 10% of reducing agent is consistent with the iron removing effect of adding 0.5% of activating agent and 4% of reducing agent. The reducing agent and the activating agent are added into the compound zinc liquid iron remover at the same time, and the reducing agent and the activating agent have the effects of improving the iron removal rate and the utilization rate of the activating agent and reducing the cost of the iron remover. Thus, the reducing agent and the activating agent have a certain synergistic effect in the present invention.
According to the invention, the content of the foaming agent in the iron remover is 10-50% by mass, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, and the specific values between the above values are limited by space and for the sake of brevity, and are not exhaustive.
According to the invention, the content of the moisture-proof forming agent in the iron remover is 2-15% by mass, and can be, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, and the specific values between the above values are limited by space and for the sake of brevity and are not exhaustive.
According to the present invention, the content of the reducing agent in the iron remover according to the present invention is 2-20% by mass, for example, 2%, 4%, 6%, 8%, 10%, 12%, 14%, 16%, 18% or 20%, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
According to the invention, the content of the activator in the iron remover according to the invention is 7-30% by mass, for example, 7%, 9%, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 28% or 30%, and the specific values between the above values, which are limited by space and for the sake of brevity, are not exhaustive.
According to the invention, the content of the slag former in the iron remover is 10-40% by mass, for example, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, 33%, 35%, 37% or 40%, and the specific values between the above values are not exhaustive for reasons of space and simplicity.
As a preferred technical scheme, the iron removing agent comprises the following components in percentage by mass:
as a further preferable technical scheme, the iron removing agent comprises the following components in percentage by mass:
according to the invention, the frother is (NH4)2CO3、(NH4)2SO4、NH4Cl、Na2SO4、NaHCO3、Ca(HCO3)2、Li2CO3、Ca(NO3)2Or H2C2O4Any one or a combination of at least two of; for example, can be (NH4)2CO3、(NH4)2SO4、NH4Cl、Na2SO4、NaHCO3、Ca(HCO3)2、Li2CO3、Ca(NO3)2Or H2C2O4A typical but non-limiting combination of any of: (NH4)2CO3And (NH4)2SO4；NH4Cl and Na2SO4；Ca(HCO3)2And Ca (NO)3)2；Na2SO4And NaHCO3；Li2CO3And Ca (NO)3)2；(NH4)2CO3、(NH4)2SO4And NH4Cl, etc., are not exhaustive for the invention, but are limited to space and for the sake of brevity.
According to the invention, the moisture-proof forming agent is any one or combination of at least two of paraffin powder, vaseline or glycerol; for example, the solvent may be any one of paraffin powder, vaseline or glycerol, and a typical but non-limiting combination is as follows: paraffin powder and vaseline; paraffin powder and glycerin; petrolatum and glycerin; paraffin powder, vaseline and glycerol.
According to the invention, the reducing agent is any one or the combination of at least two of active aluminum powder, active magnesium powder, magnesium-aluminum alloy, aluminum-nickel alloy, aluminum-chromium alloy, borax or acetic acid; for example, the alloy can be any one of activated aluminum powder, activated magnesium powder, magnesium aluminum alloy, aluminum nickel alloy, aluminum chromium alloy, borax or acetic acid, and the typical but non-limiting combination is as follows: active aluminum powder and active magnesium powder; magnesium-aluminum alloys and aluminum-nickel alloys; aluminum-nickel alloys and aluminum-chromium alloys; borax and acetic acid; magnesium-aluminum alloys, aluminum-nickel alloys, aluminum-chromium alloys, and the like, are not exhaustive for purposes of space and brevity.
According to the invention, the particle size of the active aluminum powder is 300 meshes; the particle size of the active magnesium powder is 200 meshes.
According to the invention, the activator is AlF3、NaF、SnCl2、CeCl3Or ZnCl2Any one or a combination of at least two of; for example, AlF can be used3、NaF、SnCl2、CeCl3Or ZnCl2A typical but non-limiting combination of any of: AlF3And NaF; SnCl2And CeCl3；SnCl2And ZnCl2；AlF3NaF and SnCl2Etc., are not exhaustive for the invention, but are for brevity and clarity.
According to the invention, the slagging agent is B2O3Bentonite, MnO2、CaO、Fe2O3Or ZnO or a combination of at least two of the foregoing; for example, may be B2O3Bentonite, MnO2、CaO、Fe2O3And ZnO; typical but non-limiting combinations are: b is2O3And bentonite; MnO2And CaO; fe2O3And ZnO; b is2O3、MnO2And ZnO, etc., are not exhaustive for the invention, limited by space and for the sake of brevity.
In a second aspect, the present invention provides a method for using the hot dip galvanizing compound zinc liquid iron remover according to the first aspect, the method comprising: the foaming agent, the moisture-proof forming agent, the reducing agent, the activating agent and the slag former are completely mixed according to the formula amount, the iron removing agent is obtained after uniform mixing, water accounting for 5-6% of the weight of the iron removing agent is added, the mixture is uniformly stirred, then a block product is directly pressed by a briquetting machine, and the product is pressed into zinc liquid for removing iron.
According to the invention, if the moisture-proof forming agent in the formula contains paraffin powder and/or vaseline, the paraffin powder and/or vaseline are heated to 70-80 ℃ after water is added into the iron-removing agent and the mixture is uniformly stirred, and then the paraffin powder and/or vaseline is melted and pressed into a block product by using a briquetting machine.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the hot galvanizing composite zinc liquid iron remover obtained by the invention has excellent performance, the iron removal rate reaches more than 35%, suspended slag and iron-containing zinc slag in zinc liquid with more than 80% can be removed, and the thickness of a coating is reduced by at least 25%.
(2) The hot galvanizing composite zinc liquid iron remover obtained by the invention can improve the fluidity of the zinc liquid, improve the surface quality of a plated part, reduce zinc slip on the surface of the plated part, make the surface of the plated part smoother, reduce the zinc feeding amount and save the hot galvanizing cost.
(3) The iron remover disclosed by the invention is simple in preparation method, high in product use efficiency, has new functions of moisture prevention and long storage time, and has a good application prospect.
Drawings
FIG. 1 is an external view of a plated article obtained by hot dip plating after removing iron from a molten zinc bath with an iron remover obtained in example 1 of the present invention;
FIG. 2 is an external view of a plated article obtained by hot dip plating after removing iron from a molten zinc bath with an iron remover obtained in example 2 of the present invention;
FIG. 3 is an external view of a plated article obtained by hot dip plating directly in a zinc bath containing 0.025 wt% of iron without using an iron remover;
FIG. 4 is an external view of a plated article obtained by hot dip plating directly in a zinc bath having an iron content of 0.035 wt% without using an iron remover;
FIG. 5 is a plot of the dot distribution of the thickness of the plating layer of the test plated article.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: na (Na)2SO415％；(NH4)2SO415 percent; 6 percent of paraffin powder; 13% of active Al powder; 4% of active Mg powder; AlF320 percent; 12% of bentonite; 15% of CaO. The particle size of the active Al powder is 300 meshes, and the particle size of the active Mg powder is 200 meshes.
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 5 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 70 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine. The product can be directly used for selling, transporting and storing and can be used for removing iron from the zinc liquid.
Example 2
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: NaHCO 2330 percent; 8% of active Al powder; CH (CH)3COOH 5 percent; 8% of paraffin powder; 2% of glycerol; AlF312％；CeCl35％；MnO28％；B2O312 percent; 10% of CaO; the particle size of the active Al powder is-300 meshes.
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 5 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 75 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Example 3
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: NH (NH)4Cl14％；Ca(NO3)218 percent; 8% of paraffin powder; 4% of glycerol; 2% of borax; 12% of active Mg powder; SnCl26％；CeCl319％；MnO214 percent; 3 percent of CaO; the particle size of the active Mg powder is 200 meshes.
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 5 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 75 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Example 4
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: na (Na)2SO416％；(NH4)2SO411％；Li2CO35 percent; 6 percent of paraffin powder; 5% of aluminum-nickel alloy; CH (CH)3COOH 7％；NaF312％；ZnCl29％；B2O37％；CaO 22％。
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 75 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Example 5
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: h2C2O420 percent; 7% of glycerol; 2% of aluminum-chromium alloy; 10% of active Mg powder; AlF326 percent; 35% of CaO; the particle size of the active Mg powder is 200 meshes.
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring, and pressing into a blocky product by a briquetting machine.
Example 6
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by massThe formula is as follows: na (Na)2SO412％；Ca(NO3)230 percent; 8% of vaseline; 3% of paraffin powder; 4% of aluminum-nickel alloy; ZnCl28％；AlF37％；CaO22％；ZnO 6％。
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 80 ℃ to melt paraffin powder and vaseline, and pressing the mixture into a blocky product by using a briquetting machine.
Example 7
The hot galvanizing composite zinc liquid iron remover comprises the following components in percentage by mass: NH (NH)4Cl 34%; 13% of paraffin powder; 16% of borax; AlF311％；ZnO 26％。
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 80 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Comparative example 1
The iron removing agent for the zinc liquid comprises the following components in percentage by mass: NH (NH)4Cl 40 percent; 16% of borax; AlF315 percent; 29 percent of ZnO. (i.e., no moisture resistance-forming agent was added as compared with example 7)
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring, and pressing into a blocky product by a briquetting machine.
Comparative example 2
The iron removing agent for the zinc liquid comprises the following components in percentage by mass: NH (NH)4Cl 40 percent; 15% of paraffin powder; 16% of borax; 29 percent of ZnO. (i.e. without addition of activator in comparison with example 7)
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 80 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Comparative example 3
The iron removing agent for the zinc liquid comprises the following components in percentage by mass: NH (NH)4Cl 40 percent; 18% of paraffin powder; AlF311 percent; 31% of ZnO. (i.e. without addition of reducing agent compared to example 7)
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 80 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
Comparative example 4
The iron removing agent for the zinc liquid comprises the following components in percentage by mass: NH (NH)4Cl 40 percent; 15% of paraffin powder; 16% of borax; AlF30.1 percent; 28.9 percent of ZnO. (i.e. only a small amount of activator is added compared to example 7)
Weighing the raw materials according to the formula, putting the raw materials into a beaker, completely and uniformly mixing the raw materials, adding water accounting for 6 percent of the total mass of the iron removing agent, uniformly stirring the mixture, heating the mixture in a constant-temperature heating furnace to 80 ℃ to melt paraffin powder, and pressing the melted paraffin powder into a blocky product by using a briquetting machine.
And (3) performance testing:
under the same experimental conditions and according to the same addition ratio, the iron remover products obtained in the examples 1 to 7 and the comparative examples 1 to 4 of the invention are put into zinc liquid with the iron content of 0.035 wt% for removing iron, and then the plated piece is subjected to hot dip plating at 460 ℃. The iron removal rate was measured in accordance with GB/T12689.5-2004 "determination of iron content by chemical analysis method of Zinc and Zinc alloy", and the test results are shown in Table 1.
TABLE 1
From the above examples 1-7, it can be seen that the iron removing rate of the iron remover is above 35%,
FIG. 1 is an external view (iron content in molten zinc: 0.035 wt%) of a plated article obtained by hot dip plating after iron removal and purification of molten zinc using the iron remover obtained in example 1 of the present invention, and FIG. 2 is an external view (iron content in molten zinc: 0.035 wt%) of a plated article obtained by hot dip plating after iron removal and purification of molten zinc using the iron remover obtained in example 2 of the present invention. As can be seen from the figures 1 and 2, the surface of the plated part is flat and uniform, the defects of plating leakage, pinholes, shedding, zinc nodules and the like are not generated, and the surface quality is good.
FIG. 3 is an external view of a plated article obtained by direct hot dip plating without using a deferrization agent (molten zinc iron content: 0.025 wt.%), and FIG. 4 is an external view of a plated article obtained by direct hot dip plating without using a deferrization agent (molten zinc iron content: 0.035 wt.%). As can be seen from fig. 3 and 4, the zinc nodules and residues are distributed on the surface of the plated part, the plating layer is not uniform, and the surface quality is extremely poor. As is clear from comparison with FIGS. 1 and 2, the iron remover of the present invention can significantly improve the surface quality of the plated article after purifying the zinc bath.
Coating thickness measuring instrument for the plated part in FIG. 1 measures the plating thickness of each point according to the point-taking distribution given in FIG. 5, namely, the surface of the plated part is divided according to a 3 x 3 matrix, one point in each divided block is taken as a plating thickness measuring point, and the points are sequentially marked from left to right and from top to bottom according to FIG. 5 as follows: point 1, point 2, point 3, point 4, point 5, point 6, point 7, point 8, point 9. The results are shown in Table 2.
TABLE 2
The plated article in FIG. 2 was measured for the thickness of the plated layer at each point by a coating thickness meter in accordance with the point-taking distribution given in FIG. 5, and the results are shown in Table 3.
TABLE 3
The plated article in FIG. 3 was measured for the thickness of the plated layer at each point by a coating thickness meter in accordance with the point-taking distribution given in FIG. 5, and the results are shown in Table 4.
TABLE 4
The plated article in FIG. 4 was measured for the thickness of the plated layer at each point by a coating thickness meter in accordance with the point-taking distribution given in FIG. 5, and the results are shown in Table 5.
TABLE 5
It can be seen from the comparison of tables 2 and 3 with tables 4 and 5 that, under the same experimental conditions, after the compound liquid zinc iron remover is added, the plated part has uniform plating, the thickness of the plating is reduced by more than 25%, the zinc feeding amount is reduced within a certain range, and the hot galvanizing cost is reduced.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (1)
1. The hot galvanizing composite zinc liquid iron remover is characterized by comprising the following components in percentage by mass:
NaHCO330 percent; 8% of active Al powder; CH (CH)3COOH 5 percent; 8% of paraffin powder; 2% of glycerol; AlF312％；CeCl35％；MnO28％；B2O312 percent; 10% of CaO; the particle size of the active Al powder is 300 meshes;
or Na2SO416％；(NH4)2SO411％；Li2CO35 percent; 6 percent of paraffin powder; 5% of aluminum-nickel alloy; CH (CH)3COOH 7％；NaF312％；ZnCl29％；B2O37％；CaO 22％；
Or Na2SO415％；(NH4)2SO415 percent; 6 percent of paraffin powder; 13% of active Al powder; 4% of active Mg powder; AlF320 percent; 12% of bentonite; 15% of CaO; the particle size of the active Al powder is 300 meshes, and the particle size of the active Mg powder is 200 meshes;
or NH434% of Cl; 13% of paraffin powder; 16% of borax; AlF311％；ZnO 26％。
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