CN111238290B - Method for cleaning manganese dioxide scale in zinc hydrometallurgy heat exchanger pipeline - Google Patents
Method for cleaning manganese dioxide scale in zinc hydrometallurgy heat exchanger pipeline Download PDFInfo
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- CN111238290B CN111238290B CN201811434505.3A CN201811434505A CN111238290B CN 111238290 B CN111238290 B CN 111238290B CN 201811434505 A CN201811434505 A CN 201811434505A CN 111238290 B CN111238290 B CN 111238290B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
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Abstract
The invention discloses a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline, which comprises the following steps: (1) preparing acid liquor containing ferrous ions; (2) in the process of preheating a zinc raw material leaching precursor by a heat exchanger, supplying the acid solution containing ferrous ions to the heat exchanger, and reacting the acid solution containing ferrous ions with manganese dioxide scale in a pipeline of the heat exchanger to dissolve the manganese dioxide scale. The method can clean the scaling substances in the pipeline when the heat exchanger operates normally, cannot influence the service life of the pipeline, cannot influence the normal operation of production, and can ensure the safe and stable operation of the pressurizing equipment.
Description
Technical Field
The invention belongs to the field of zinc smelting heat exchange equipment, and particularly relates to a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline.
Background
The zinc hydrometallurgy pressurized kettle heat exchanger is mainly used for preheating a leaching agent (waste electrolyte) of a zinc raw material, and ensures that the temperature of the leaching agent or electrolysis waste liquid entering the pressurized kettle reaches more than 80 ℃. However, in the actual production operation, along with the extension of the operation period, anode mud doped in the electrolytic waste liquid in the pipeline can be deposited and attached to the inner wall of the coil pipe to form scale, so that the flowing resistance of the solution in the pipeline is increased, and the pressure of the pressurizing equipment is increased. Therefore, the flow of the pressurizing equipment can not meet the production requirement, and more importantly, the operation of the pressurizing equipment and the pipeline thereof is brought with greater safety risk; secondly, heat transfer efficiency is seriously affected after the inner wall of the pipeline is scaled, preheating effect is poor, and heat loss is increased. In contrast, most manufacturers take down the heat exchanger and the coil pipe in the kettle after stopping, and remove the scale in the pipeline by manual strong knocking, cleaning and blowing and other methods. The method has the problems of high labor intensity, long time consumption, influence on normal production and the like, shortens the service life of the coil pipe, and increases the material cost. Therefore, how to clean the scale in the pipe is to be further improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline. The method can clean the scaling substances in the pipeline when the heat exchanger operates normally, cannot influence the service life of the pipeline, cannot influence the normal operation of production, and can ensure the safe and stable operation of the pressurizing equipment.
In one aspect of the invention, the invention provides a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline, which comprises the following steps:
(1) preparing acid liquor containing ferrous ions;
(2) in the process of preheating a zinc raw material leaching precursor by a heat exchanger, supplying the acid solution containing ferrous ions to the heat exchanger, and reacting the acid solution containing ferrous ions with manganese dioxide scale in a pipeline of the heat exchanger to dissolve the manganese dioxide scale.
According to the method for cleaning manganese dioxide scale in the pipeline of the zinc hydrometallurgy heat exchanger disclosed by the embodiment of the invention, the acid liquid containing ferrous ions is used as the leaching precursor in the process of directly preheating the zinc raw material leaching precursor in the heat exchanger, and the manganese dioxide deposited in the pipeline and the ferrous ions are subjected to chemical reaction by utilizing the reducibility of the ferrous ions in the acid liquid and are re-dissolved into the solution, so that the purpose of cleaning deposits in the heat exchanger is realized, the running resistance of pressurizing equipment in the zinc hydrometallurgy process is reduced, the normal supply of the leaching precursor and the safe running of the pressurizing equipment are ensured, and the heat exchange efficiency of the heat exchanger is improved. By adopting the method to clean the sediments in the heat exchanger pipeline, time and labor can be saved, the method is economical and convenient, the operability is strong, the service life of the heat exchanger pipeline cannot be influenced, and physical damage to the pipeline caused by physical impact can be effectively avoided.
In addition, the method for cleaning manganese dioxide scale in the zinc hydrometallurgy heat exchanger pipeline according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the present invention, in step (1), the ferrous ion-containing acid solution is obtained by mixing a dilute sulfuric acid solution with iron pieces. Thus, the pre-leaching agent can be supplemented with ferrous ions.
In some embodiments of the invention, in step (1), the dilute sulfuric acid solution is a spent electrolyte. Thus, the waste electrolyte can be recycled.
In some embodiments of the invention, in the step (1), the concentration of ferrous ions in the acid solution containing ferrous ions is not lower than 0.2 g/L. Therefore, the cleaning efficiency and the cleaning effect of the scaling substances in the heat exchanger pipeline are improved.
In some embodiments of the invention, in the step (1), the concentration of ferrous ions in the acid solution containing ferrous ions is 0.3-0.6 g/L. Therefore, the efficiency and effect of removing the fouling materials in the heat exchanger pipeline can be further improved.
In some embodiments of the present invention, in step (2), when the pressure of the pressurizing device of the heat exchanger is greater than 1.4MPa, the acid solution containing ferrous ions is introduced into the heat exchanger. Therefore, the scale in the heat exchanger pipeline can be removed in time, and the excessive load on the pressurizing equipment is avoided.
In some embodiments of the invention, in step (2), the flow rate of the pre-leaching agent for the zinc feed in the heat exchanger tubes is less than 5m3And h, introducing the acid solution containing the ferrous ions into the heat exchanger pipeline. Therefore, the scale in the heat exchanger pipeline can be removed in time, and the excessive load on the pressurizing equipment is avoided.
In some embodiments of the present invention, the method for cleaning manganese dioxide scale in the tube of the zinc hydrometallurgy heat exchanger further comprises: (3) and (3) adding sodium sulfite into the solution with the concentration of ferrous ions lower than 0.2g/L in the solution obtained in the step (2). Therefore, the ferric ions in the solution can be reduced into ferrous ions, and the cleaning of the scaling substances in the heat exchanger pipeline is further realized.
In some embodiments of the present invention, in step (3), the sodium sulfite is added in an amount such that the concentration of ferrous ions in the solution after the reaction is not less than 0.2 g/L. Therefore, ferric ions in the solution can be reduced, the cyclic utilization of ferrous ions is realized, and the removal efficiency of the scaling substances in the heat exchanger is further improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline according to one embodiment of the invention;
FIG. 2 is a schematic flow diagram of a method for cleaning manganese dioxide scale in the tube of a zinc hydrometallurgy heat exchanger according to yet another embodiment of the invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, the invention provides a method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline, and according to an embodiment of the invention, and referring to fig. 1, the method comprises the following steps:
s100: blending acid liquor containing ferrous ions
In the step, by preparing acid liquor containing ferrous ions, the ferrous ions can reduce manganese dioxide in the anode mud under an acidic condition, and granular manganese dioxide is reduced into manganese sulfate to be dissolved in the acid liquor, so that the manganese dioxide as a scaling substance is gradually dissolved into the solution from the inner wall of the heat exchanger pipeline. According to one embodiment of the invention, the ferrous ion-containing acid solution is obtained by mixing a dilute sulfuric acid solution with iron filings. Iron in the iron scraps is reacted with hydrogen ions in the dilute sulfuric acid solution to obtain ferrous ions and hydrogen, and further to obtain the acid solution containing the ferrous ions. According to another embodiment of the present invention, the dilute sulfuric acid solution can be a pre-leaching agent of zinc raw material preheated by an autoclave heat exchanger in a zinc hydrometallurgy process, namely, waste electricityAnd (3) electrolyte, wherein the waste electrolyte is generated in the zinc electrodeposition process in the zinc hydrometallurgy process. The acid solution containing ferrous ions can be formed by directly adding scrap iron into a zinc raw material leaching agent, or can be formed by mixing other dilute sulfuric acid and scrap iron and then adding the mixture into the zinc raw material leaching agent. According to still another embodiment of the present invention, the concentration of ferrous ions in the acid solution containing ferrous ions may be not less than 0.2 g/L. The inventor finds that if Fe is contained in the acid liquor2+Too low a concentration results in too slow a dissolution rate of the manganese dioxide foulant and may result in an insufficiently cleaned heat exchanger tube. Preferably, the concentration of the ferrous ions in the acid solution containing the ferrous ions can be 0.3-0.6 g/L. The inventors found that the Fe was supplemented in the zinc raw material pre-leaching agent2+The acid liquor with the concentration range has little influence on the iron content in the leached liquid of the zinc raw material on one hand, so that the method can be implemented in normal production and is convenient to operate; on one hand, the heat exchanger coil is beneficial to being cleaned thoroughly.
S200: in the process of preheating the pre-leaching agent of the zinc raw material by the heat exchanger, acid liquor containing ferrous ions is supplied to the heat exchanger
In the step, in the process of preheating the pre-leaching agent of the zinc raw material by the heat exchanger, acid liquor containing ferrous ions is supplied to the heat exchanger, and the acid liquor containing ferrous ions reacts with manganese dioxide scale in a pipeline of the heat exchanger, so that the manganese dioxide scale is dissolved. The inventor finds that the aim of cleaning deposits in the heat exchanger is fulfilled by adding acid liquor containing ferrous ions in the process of directly preheating the zinc raw material leaching precursor in the heat exchanger and utilizing the reducibility of the ferrous ions in the acid liquor to enable manganese dioxide deposited in a pipeline to chemically react with the ferrous ions and redissolve the ferrous ions into the solution, so that the running resistance of a pressurizing device in the wet zinc smelting process is reduced, the normal supply of the leaching precursor and the safe running of the pressurizing device are ensured, and the heat exchange efficiency of the heat exchanger is improved. Therefore, the method can realize the cleaning of the scaling substances in the pipeline when the heat exchanger operates normally, cannot influence the service life of the pipeline, cannot influence the normal operation of production, and can ensure the safe and stable operation of the pressurizing equipment.
According to one embodiment of the invention, the heat exchanger is provided withThe pressure of the pressing device is more than 1.4MPa, and acid liquor containing ferrous ions is introduced into the heat exchanger. Along with the operation of the heat exchanger, scaling substances can slowly appear in the pipeline, so that the flowing resistance of liquid in the pipeline is increased, and the pressure of a pressurizing device of the heat exchanger is increased. The inventor finds that in the zinc hydrometallurgy process, when the heat exchanger is not scaled, the pressure of a pressurizing device is about 1.3-1.4MPa, and when the pressure of the pressurizing device of the heat exchanger is more than 1.4MPa, manganese dioxide scaling substances in the heat exchanger need to be removed, and at the moment, acid liquor containing ferrous ions can be introduced into the heat exchanger. Under an acidic condition, ferrous ions can reduce scale-forming substance manganese dioxide in a heat exchanger pipeline, namely granular manganese dioxide can be reduced into manganese sulfate to be dissolved in acid liquor, so that the scale-forming substance manganese dioxide is gradually dissolved into solution from the inner wall of the pipeline, and a specific ion reaction equation is as follows: 2Fe2++MnO2+4H+＝2Fe3++Mn2++2H2And O. It should be noted that the above values are only obtained according to one embodiment of the present invention, and in the specific practical process, those skilled in the art can determine the above values according to the actually used heat exchanger and pressurizing device.
According to a further embodiment of the invention, the flow of the pre-leaching agent for the zinc raw material in the heat exchanger tubes is less than 5m3And h, introducing acid liquor containing ferrous ions into the heat exchanger pipeline. The inventor finds that with the operation of the heat exchanger, scaling substances can slowly appear in the pipeline, so that the liquid flow resistance in the pipeline is increased, and the flow of the zinc raw material leaching agent in the pipeline is reduced. When no scaling matter exists in the heat exchanger pipeline, the flow of the zinc raw material pre-leaching agent in the heat exchanger pipeline is about 12-14m3The flow of the agent before leaching the zinc raw material in the heat exchanger pipeline is lower than 5m3And h, indicating that the scale substances in the pipeline need to be removed, and introducing acid liquor containing ferrous ions into the pipeline of the heat exchanger. The main component of the scaling agent is manganese dioxide, ferrous ions can react with the manganese dioxide to generate ferric ions under the acidic condition, and the manganese is changed from solid manganese dioxide to liquid bivalent manganese ions, so that the scaling in the pipeline is removed. It should be noted that the above numerical values are only based on the present inventionAs will be appreciated by one of ordinary skill in the art, in particular practice, the values may be determined by one skilled in the art based on the heat exchanger actually used.
According to the embodiment of the invention, the method for cleaning manganese dioxide scale in the zinc hydrometallurgy heat exchanger pipeline has at least one of the following advantages:
according to one embodiment of the invention, by adopting the method to clean the scale in the heat exchanger pipeline, not only time and labor can be saved, but also more importantly, the safe and stable operation of the pressurizing equipment can be ensured;
according to another embodiment of the invention, the method is economical, convenient and fast, and has strong operability;
according to another embodiment of the invention, the method does not affect the service life of the pipeline, and can effectively avoid physical damage to the pipeline caused by physical impact.
According to the method for cleaning manganese dioxide scale in the zinc hydrometallurgy heat exchanger pipeline, disclosed by the embodiment of the invention, the acid liquid containing ferrous ions is directly added in the process of preheating the zinc raw material leaching precursor in the heat exchanger to serve as the leaching precursor, the manganese dioxide deposited in the pipeline and the ferrous ions are subjected to chemical reaction by utilizing the reducibility of the ferrous ions in the acid liquid and are re-dissolved into the solution, and then the purpose of cleaning deposits in the heat exchanger is realized, so that the running resistance of pressure equipment in the zinc hydrometallurgy process is reduced, the normal supply of the leaching precursor and the safe running of the pressure equipment are ensured, and the heat exchange efficiency of the heat exchanger is improved. By adopting the method to clean the sediments in the heat exchanger pipeline, time and labor can be saved, the method is economical and convenient, the operability is strong, the service life of the heat exchanger pipeline cannot be influenced, and physical damage to the pipeline caused by physical impact can be effectively avoided.
According to an embodiment of the present invention, referring to fig. 2, the method for cleaning manganese dioxide scale in the tube of the hydrometallurgical zinc heat exchanger further comprises:
s300: s200, adding sodium sulfite into the solution, wherein the concentration of ferrous ions in the solution is lower than 0.2g/L
At S200, with the progress of the reaction, ferrous ions in the acid solution react with manganese dioxide as a scaling substance in the pipeline to generate ferric ions and manganese ions, the concentration of the ferrous ions in the solution in the pipeline is gradually reduced, the concentration of the ferrous ions in the solution is lower than 0.2g/L, sodium sulfite is added into the solution, the ferric ions in the solution can be reduced into the ferrous ions after the sodium sulfite is dissolved, and the obtained ferrous ions can further react with the manganese dioxide as the scaling substance, so that the repeated washing of the pipeline is realized, and the pipeline resistance is reduced. The specific ion reaction equation is: 2Fe3++SO3 2-+H2O＝2Fe2++SO4 2-+2H+。
According to an embodiment of the present invention, the amount of sodium sulfite added is not particularly limited, and may be selected by those skilled in the art according to actual needs, so long as the added sodium sulfite can reduce ferric ions in the solution to ferrous ions, and the concentration of ferrous ions in the reduced solution is not less than 0.2 g/L. The inventor finds that if too much sodium sulfite is added, the raw material cost is increased, and the content of sodium ions in the zinc raw material leached liquid is increased, so that the production is influenced; if too little sodium sulfite is added, Fe in the solution cannot be made3+Reduction to Fe by sulfite ions2+And then, the concentration of ferrous ions in the solution is not lower than 0.2 g/L.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Examples
The phenomenon of scaling and blocking appear in the coil of the heat exchanger of the pressure kettle after long-time operation, the flow resistance of liquid in the pipeline is increased, the pressure of the pressure equipment reaches 1.5MPa, and the flow of the zinc raw material leaching agent in the pipeline is 5m3H is used as the reference value. Soaking iron filings in dilute sulfuric acid to obtain ferrous ion containing acid solution with ferrous ion concentration of 0.3-0.6 g/L. The ion reaction equation mainly involved is: fe +2H+＝Fe2++H2×) @. In the process of preheating the pre-leaching agent of the zinc raw material in a heat exchanger, adding the zinc raw material into the pre-leaching agentAnd (3) supplying the acid solution containing the ferrous ions to the heat exchanger, and reacting the acid solution containing the ferrous ions with manganese dioxide scale in the pipeline of the heat exchanger to dissolve the manganese dioxide scale. The ion reaction equation mainly involved is: 2Fe2++MnO2+4H+＝2Fe3++Mn2++2H2And O. Adding sodium sulfite into the solution, wherein the ferrous ion concentration in the solution is lower than 0.2g/L, and the adding amount of the sodium sulfite is 1kg/m3. Therefore, ferric ions in the solution can be reduced into ferrous ions, and the ferrous ions further react with scaling substances in the pipeline, so that the recycling of the ferric ions is realized. The ion reaction equation mainly involved is: 2Fe3++SO3 2-+H2O＝2Fe2++SO4 2-+2H+. Along with the removal of the scaling substances in the pipeline, the pressure of the pressurizing equipment is recovered to the normal range of 1.3-1.4MPa, and the flow of the agent before the leaching of the zinc raw material in the pipeline is also increased to 13-14m3/h。
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A method for cleaning manganese dioxide scale in a zinc hydrometallurgy heat exchanger pipeline is characterized by comprising the following steps:
(1) preparing acid liquor containing ferrous ions;
(2) in the process of preheating a zinc raw material leaching precursor by a heat exchanger, supplying the acid solution containing ferrous ions to the heat exchanger, and reacting the acid solution containing ferrous ions with manganese dioxide scale in a pipeline of the heat exchanger to dissolve the manganese dioxide scale;
(3) adding sodium sulfite into the solution with the ferrous ion concentration lower than 0.2g/L obtained in the step (2),
wherein the concentration of ferrous ions in the acid liquor containing ferrous ions is 0.3-0.6 g/L;
in the step (1), the acid solution containing ferrous ions is obtained by mixing a dilute sulfuric acid solution with scrap iron, wherein the dilute sulfuric acid solution is a waste electrolyte;
in the step (3), the sodium sulfite is added in an amount such that the concentration of ferrous ions in the solution after the reaction is not less than 0.2 g/L.
2. The method according to claim 1, wherein in the step (2), the pressure of the pressurizing device of the heat exchanger is more than 1.4MPa, and the acid solution containing ferrous ions is introduced into the heat exchanger.
3. The method of claim 1, wherein in step (2), the flow rate of the pre-leaching agent for the zinc raw material in the heat exchanger tube is less than 5m3And h, introducing the acid solution containing the ferrous ions into the heat exchanger pipeline.
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| JPS5641335A (en) * | 1979-08-31 | 1981-04-18 | Nippon Jiryoku Senko Kk | Separating and recovering method for useful mineral from electrically collected dust generated in reduced pellet manufacturing process |
| HUT35725A (en) * | 1983-11-18 | 1985-07-29 | Inst Chemii Przemyslowej | Preperation for the removal of miniral deposits, mainly of scale |
| CN102912138A (en) * | 2012-10-19 | 2013-02-06 | 湖南有色金属研究院 | Method of recycling zinc, manganese, lead and silver from zinc electrowinning anode mud |
| CN108239701A (en) * | 2016-12-26 | 2018-07-03 | 北京有色金属研究总院 | A kind of method of lead zinc in high mud carbonate-type lead-zinc of synthetical recovery |
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