CN114940906B - Efficient corrosive agent suitable for multiphase metal minerals and preparation method thereof - Google Patents
Efficient corrosive agent suitable for multiphase metal minerals and preparation method thereof Download PDFInfo
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- CN114940906B CN114940906B CN202210523131.2A CN202210523131A CN114940906B CN 114940906 B CN114940906 B CN 114940906B CN 202210523131 A CN202210523131 A CN 202210523131A CN 114940906 B CN114940906 B CN 114940906B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The application discloses a high-efficiency corrosive agent suitable for multiphase metal minerals, which comprises 30-50 parts by weight of deionized water, 12-14 parts by weight of sulfamic acid, 2-4 parts by weight of ammonium bifluoride, 2-4 parts by weight of citric acid, 0.5-2 parts by weight of ammonium chloride, 20-40 parts by weight of DMF and 0.4-0.6 part by weight of sodium hypochlorite. In the application, the corrosive agent adopts a water-DMF mixed solution, a small amount of sodium hypochlorite is added after the corrosive agent is fully dissolved, chlorine gas is generated and dissolved in DMF, the chlorine gas and ionized hydrogen ions in the water are utilized to etch metal, other components such as citric acid, chloride ions, fluoride ions and ammonium ions can carry out efficient complexation on the metal ions, so that the surface of the metal is exposed, the reaction is carried out, and the complexing agent has no other pollutants except for trace chlorine gas and trace volatilized DMF, and has greater safety guarantee and environmental protection effect compared with the traditional metal corrosive agent.
Description
Technical Field
The application relates to the technical field of technical corrosive agents, in particular to a high-efficiency corrosive agent suitable for multiphase metal minerals and a preparation method thereof.
Background
In the mine production process, the separation of mineral water in ore pulp is a very important ring, and only the concentrate after water removal can be subjected to subsequent treatment. The ceramic filter plate has enough strength to resist the pressure of mineral water separation, has longer service life and lower price, is widely applied to mines at present, but the ceramic filter plate is easily blocked by tiny concentrate particles in the water absorption process due to the non-uniform particle size of the concentrate particles, so that the service life of the ceramic filter plate is reduced, and therefore, a solvent is needed to corrode and dissolve the plugs in the ceramic filter plate. The metal mineral structure and the complexity thereof, the high-efficiency metal dissolvants at present comprise strong acid such as nitric acid and the like, organic complex such as cyanide and the like, and the dissolvants can be corroded efficiently, but nitric acid is difficult to purchase, concentrated nitric acid has extremely strong corrosiveness and volatility and can generate great harm to field instruments and personnel, and meanwhile, the application and limitation of cyanide and other organic solvents are caused by the high toxicity of cyanide and other organic solvents, and along with the continuous enhancement of environmental protection policies, the two large dissolvants are not accepted by the market.
Therefore, the application provides a high-efficiency corrosive agent suitable for multiphase metal minerals and a preparation method thereof.
Disclosure of Invention
The application aims at: in order to solve the problems, a high-efficiency corrosive agent suitable for multiphase metal minerals and a preparation method thereof are provided.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a high-efficiency corrosive agent suitable for multiphase metal minerals comprises 30-50 parts by weight of deionized water, 12-14 parts by weight of sulfamic acid, 2-4 parts by weight of ammonium bifluoride, 2-4 parts by weight of citric acid, 0.5-2 parts by weight of ammonium chloride, 20-40 parts by weight of DMF and 0.4-0.6 part by weight of sodium hypochlorite.
A preparation method of a high-efficiency corrosive agent suitable for multiphase metal minerals comprises the following steps:
s1, taking 30-50 parts by weight of deionized water, adding 12-14 parts by weight of sulfamic acid and 2-4 parts by weight of ammonium bifluoride, and stirring to fully dissolve the sulfamic acid and the ammonium bifluoride to obtain a mixed solution A;
s2, adding 2-4 parts by weight of citric acid and 0.5-2 parts by weight of ammonium chloride into the mixed solution A, and stirring to fully dissolve the mixture to obtain mixed solution B;
s3, adding 20-40 parts by weight of DMF into the mixed solution B to obtain mixed solution C;
s4, dissolving 0.4-0.6 part by weight of sodium hypochlorite in 30-50 parts by weight of deionized water to obtain a D mixed solution, adding the D mixed solution into the C mixed solution, and rapidly stirring to enable chlorine to escape into the C mixed solution;
s5, standing for 10min to enable the solution to react completely, and obtaining a corrosive solution sample.
Preferably, the solution reaction formula in the step S1 is: h 2 NSO 3 H+H 2 O＝NH 4 HSO 4 。
Preferably, the solution reaction formula in the step S4 is:
2NaC l O+4NH 4 HSO 4 +2NH 4 C l＝2C l 2 +2H 2 O+3(NH 4 ) 2 SO 4 +Na 2 SO 4 ；
C l 2 +H 2 O＝HCl O+HCl；
HCl and DMF produce highly efficient complexing agents.
Preferably, the chemical structural formula of the efficient complexing agent is:
in summary, due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
in the application, the corrosive agent adopts a water-DMF mixed solution, citric acid, sulfamic acid, ammonium bifluoride and ammonium chloride are fully dissolved in a water phase, a small amount of sodium hypochlorite is added to generate chlorine gas and dissolve in DMF, the chlorine gas and ionized hydrogen ions in water are utilized to etch metal, other components such as citric acid, chloride ions, fluoride ions and ammonium ions can carry out efficient complexation on the metal ions, thereby exposing the metal surface and leading the reaction to be carried out, and the complexing agent has no other pollutants except trace chlorine gas and trace volatilized DMF which are generated, and has greater safety guarantee and environmental protection effect compared with the traditional metal corrosive agent.
Drawings
FIG. 1 shows a schematic diagram of a process for providing acid etching of metals in accordance with an embodiment of the present application;
FIG. 2 illustrates a schematic diagram of an etching process for providing an etchant to a pure metal lattice in accordance with an embodiment of the present application;
FIG. 3 shows a schematic diagram of a corrosion process for providing corrosive agents to metal compounds (minerals such as oxides, sulfides, etc.) in accordance with an embodiment of the present application;
fig. 4 shows a comparative graph of cleaning effect provided according to an embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Referring to fig. 1-4, the present application provides a technical solution:
a high-efficiency corrosive agent suitable for multiphase metal minerals comprises 30-50 parts by weight of deionized water, 12-14 parts by weight of sulfamic acid, 2-4 parts by weight of ammonium bifluoride, 2-4 parts by weight of citric acid, 0.5-2 parts by weight of ammonium chloride, 20-40 parts by weight of DMF and 0.4-0.6 part by weight of sodium hypochlorite.
A preparation method of a high-efficiency corrosive agent suitable for multiphase metal minerals comprises the following steps:
s1, taking 30-50 parts by weight of deionized water, adding 12-14 parts by weight of sulfamic acid and 2-4 parts by weight of ammonium bifluoride, and stirring to fully dissolve the sulfamic acid and the ammonium bifluoride to obtain a mixed solution A;
s2, adding 2-4 parts by weight of citric acid and 0.5-2 parts by weight of ammonium chloride into the mixed solution A, and stirring to fully dissolve the mixture to obtain mixed solution B;
s3, adding 20-40 parts by weight of DMF into the mixed solution B to obtain mixed solution C;
s4, dissolving 0.4-0.6 part by weight of sodium hypochlorite in 30-50 parts by weight of deionized water to obtain a D mixed solution, adding the D mixed solution into the C mixed solution, and rapidly stirring to enable chlorine to escape into the C mixed solution;
s5, standing for 10min to enable the solution to react completely, and obtaining a corrosive solution sample.
Specifically, the solution reaction formula in step S1 is: h 2 NSO 3 H+H 2 O＝NH 4 HSO 4 。
Specifically, the solution reaction formula in step S4 is:
2NaC l O+4NH 4 HSO 4 +2NH 4 C l＝2C l 2 +2H 2 O+3(NH 4 ) 2 SO 4 +Na 2 SO 4 ；
C l 2 +H 2 O＝HCl O+HCl；
HCl and DMF produce highly efficient complexing agents.
Specifically, the chemical structural formula of the efficient complexing agent is as follows:
specifically, taking a sample of 100g etchant solution as an example:
s1, taking 40g of deionized water, adding 13g of sulfamic acid and 3g of ammonium bifluoride, and stirring to fully dissolve the mixture to obtain a mixed solution A;
s2, adding 3g of citric acid and 1g of ammonium chloride into the mixed solution A, and stirring to fully dissolve the mixture to obtain mixed solution B;
s3, adding 30g of DMF (dimethyl formamide) into the mixed solution B to obtain mixed solution C, and not stirring so as to facilitate subsequent chlorine absorption;
s4, dissolving 0.5g of sodium hypochlorite in 10g of deionized water to obtain a D mixed solution, adding the D mixed solution into the C mixed solution, and rapidly stirring to enable chlorine to escape into the C mixed solution;
s5, standing for 10min to enable the solution to react completely, and obtaining a corrosive solution sample.
The mixed mineral sample is subjected to cleaning test through a corrosive solution sample, and the specific cleaning steps are as follows:
samples of the etchant solutions in the examples were taken at 1:3, mixing the solution with distilled water through an acid pump after the solution is diluted in proportion, diluting by 50 times, injecting the solution into a ceramic filter plate, pressurizing and cleaning, placing a pressure gauge between the water pump and the ceramic filter plate, and because the blockage of the ceramic filter plate is dissolved, the gap is enlarged and increased, thereby reducing the system pressure, and reflecting the residual quantity of the blocked mineral sample through comparing the pressure change before and after cleaning, thereby reflecting the effect of corrosive agents.
The metal mineral has very complex constitution and contains various components such as metal, metal oxide, metal sulfide, metal-metal compound, complex silicate and the like, so that a ceramic filter plate blocked by a mixed mineral sample (sulfur concentrate, iron concentrate, copper concentrate and zinc concentrate) is used as a test material, micropores in the ceramic filter plate are dredged, the water permeability of the filter plate under the same pressure is increased, and the mixed mineral sample comprises the following elements:
| element(s) | Content (%) |
| Fe | 33.25 |
| Cu | 24.76 |
| Zn | 22.14 |
| S | 5.03 |
| Si | 4.28 |
| Ca | 3.25 |
| Mg | 4.98 |
| Pb | 1.02 |
| Cd | 0.51 |
| Mn | 0.78 |
The data before and after cleaning the ceramic filter plates are:
the pressure under the same flow represents the number of pressure gauges under the same water supply amount, and the flow under the same pressure represents the water inlet and outlet of the system under the same pressure before and after cleaning;
at the same time, 50% nitric acid was used for cleaning, and 1:3 is replaced by 50% nitric acid, the cleaning process is repeated, and the comparison graph of the effect obtained is shown in fig. 4.
In summary, the high-efficiency etchant for multiphase metal minerals provided in this embodiment has a stable and soluble complex formed by citric acid for three metals Ca, mg, and Fe, C l-DMF-HCl, a stable and soluble complex formed by A l, cr, co, cu, fe, pb, mn, N i, P, S, sn, T i, and other metals, ammonium groups, a stable and soluble complex formed by V, cr, zn, hg, fe, pd, pt, and ammonium bifluoride, and the generated fluoride ions can perform high-efficiency etching for silicon compounds and refractory ferric salt crystals, compared with the conventional etchant, the etchant has a relatively strong dissolving capacity for most metals (iron, copper, zinc, sulfur, gold, phosphorus, and the like) and their compounds (sulfides, oxides, silicates, and the like), can achieve a cleaning effect of nitric acid with a concentration of 90-95%, has a low application value, and has a wide application range, and has higher safety and environmental friendliness.
The previous description of the embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. The preparation method of the efficient corrosive agent suitable for the multiphase metal minerals is characterized by comprising the following steps of:
s1, taking 30-50 parts by weight of deionized water, adding 12-14 parts by weight of sulfamic acid and 2-4 parts by weight of ammonium bifluoride, and stirring to fully dissolve the sulfamic acid and the ammonium bifluoride to obtain a mixed solution A;
s2, adding 2-4 parts by weight of citric acid and 0.5-2 parts by weight of ammonium chloride into the mixed solution A, and stirring to fully dissolve the mixture to obtain mixed solution B;
s3, adding 20-40 parts by weight of DMF into the mixed solution B to obtain mixed solution C;
s4, dissolving 0.4-0.6 part by weight of sodium hypochlorite in 30-50 parts by weight of deionized water to obtain a D mixed solution, adding the D mixed solution into the C mixed solution, and rapidly stirring to enable chlorine to escape into the C mixed solution;
s5, standing for 10min to enable the solution to react completely, and obtaining a corrosive solution sample.
2. The method for preparing the high-efficiency corrosive agent applicable to the multiphase metal minerals according to claim 1, wherein the solution reaction formula in the step S1 is as follows: h 2 NSO 3 H+H 2 O＝NH 4 HSO 4 。
3. The method for preparing the high-efficiency corrosive agent applicable to the multiphase metal minerals according to claim 1, wherein the solution reaction formula in the step S4 is as follows:
2NaClO+4NH 4 HSO 4 +2NH 4 Cl＝2Cl 2 +2H 2 O+3(NH 4 ) 2 SO 4 +Na 2 SO 4 ；
Cl 2 +H 2 O＝HClO+HCl；
HCl and DMF produce highly efficient complexing agents.
4. The method for preparing the efficient etchant for multiphase metal minerals as recited in claim 3, wherein the efficient complexing agent has a chemical structural formula as follows:
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070298991A1 (en) * | 2006-06-14 | 2007-12-27 | Premier Dental Products Company | Denture cleanser composition |
| WO2018168641A1 (en) * | 2017-03-15 | 2018-09-20 | 栗田工業株式会社 | Cleaning fluid, detergent, and cleaning method for water-contact member |
| CN113462484A (en) * | 2021-06-28 | 2021-10-01 | 新疆水处理工程技术研究中心有限公司 | Cleaning agent for mine ceramic plate and preparation method and application thereof |
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| JP5835967B2 (en) * | 2011-06-29 | 2015-12-24 | 伯東株式会社 | Slime stripping agent and slime stripping method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070298991A1 (en) * | 2006-06-14 | 2007-12-27 | Premier Dental Products Company | Denture cleanser composition |
| WO2018168641A1 (en) * | 2017-03-15 | 2018-09-20 | 栗田工業株式会社 | Cleaning fluid, detergent, and cleaning method for water-contact member |
| CN113462484A (en) * | 2021-06-28 | 2021-10-01 | 新疆水处理工程技术研究中心有限公司 | Cleaning agent for mine ceramic plate and preparation method and application thereof |
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