CN211545970U - System for producing nano zinc oxide by industrially recycling zinc - Google Patents
System for producing nano zinc oxide by industrially recycling zinc Download PDFInfo
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Abstract
The utility model discloses a system for zinc production nanometer zinc oxide is retrieved in industrialization belongs to chemical industry metallurgical technology field, and this system is provided with rotary hearth furnace, demineralizer, ammonia process leaching reactor, purification reactor, crystallization reactor, calcification reactor, rinsing jar, drying device and calcining device according to the production order of retrieving zinc. The system produces the secondary zinc oxide by putting the secondary zinc-containing material into a rotary hearth furnace to carry out primary zinc recovery and extraction; then zinc hypoxide produced by the rotary hearth furnace and a zinc-containing material are leached by an ammonia method for secondary zinc recovery and refining to produce zinc-ammonia complex solution; purifying, carbonizing and crystallizing the zinc-ammonia complex liquid to produce a zinc oxide precursor; then the zinc oxide precursor is rinsed, dried and calcined to form a nano zinc oxide product. The utility model discloses a combination of ammonia process and rotary hearth furnace technology carries out alternately joint deep level to the zinc in the zinciferous material and retrieves, thoroughly retrieves the zinc in the zinciferous material, produces the zinciferous product that the grade is up to more than 95%.
Description
Technical Field
The utility model belongs to the technical field of chemical industry metallurgy, concretely relates to system for retrieve zinc and come production nanometer zinc oxide from zinciferous material. Namely, the zinc is recovered by combining a rotary hearth furnace and an ammonia leaching process to produce the nano zinc oxide (containing high-purity zinc oxide).
Background
In the production process of industries such as steel, nonferrous metallurgy, chemical engineering and the like, a large amount of zinc-containing materials are generated, the materials are rich in elements such as iron, carbon and the like with recovery and utilizable values, and the zinc content of various materials is different, so that the zinc and iron are difficult to be comprehensively recovered by a single production process to generate zinc-containing and iron-containing products with high added value and high utilization value.
At present, two main methods for industrially recycling zinc-containing materials are available:
one is a wet process, which mainly comprises ammonia process and acid process leaching, wherein the acid process leaching is to completely dissolve zinc-containing materials by using sulfuric acid and the like, and to produce zinc ingots by electrolysis after purification treatment. The method has the main defects of high purification cost and serious environmental pollution caused by waste acid. The ammonia extraction method mainly comprises selectively extracting zinc from zinc-containing material with mixed solution of ammonia and ammonia salt (such as mixed solution of ammonia and ammonium chloride, mixed solution of ammonia and ammonium bicarbonate, etc.), recovering zinc from the material in form of zinc-ammonia complex, purifying the zinc-ammonia complex solution, and performing ammonia evaporation crystallization to obtain basic zinc carbonate or electrolyzing to obtain high-purity zinc product (such as high-purity zinc oxide or zinc ingot, etc.), rinsing, drying, and calcining to obtain basic zinc carbonateThe zinc-containing product, a large amount of ammonia vapor generated in the ammonia distillation process can not be completely recovered through a tail gas treatment device, the volatilized ammonia gas causes the severe working environment, and the basic zinc carbonate can generate a large amount of CO in the calcination process2，CO2The random discharge of the zinc can cause air pollution, and the method has the main advantages that the leaching of the zinc belongs to selective leaching, and the purification cost of the leaching solution is low; the main disadvantages are that the zinc recovery is not complete, about 2% of the zinc in the residual residue is to be further recovered, and the iron and carbon rich residue produced by the method cannot be directly returned to production and utilization.
The other is a fire recovery process mainly using a rotary hearth furnace or a rotary kiln, the process utilizes simple substance carbon in materials as a reducing agent, zinc in the materials is reduced into a simple substance zinc at high temperature, the simple substance zinc enters a flue gas treatment system along with flue gas, the simple substance zinc is re-oxidized into zinc oxide in the flue gas treatment system, secondary zinc oxide is obtained by recovery, iron in the materials is reduced into simple substance iron, the simple substance iron is recovered in the form of metallized pellets or metallized powder, and the simple substance carbon is recycled as an iron-making raw material. The method has the advantages that: the dezincification rate is high (generally more than 90 percent), the zinc content in the residual metallized pellets is less than 0.5 percent, and the pellets can be directly returned to production for recycling. The biggest defect is that only zinc-containing materials with low zinc content (zinc content is less than 10%) can be treated, and because elements such as potassium, sodium, chlorine, lead and the like can escape along with zinc in the pyrogenic treatment process, the grade of the zinc hypoxide product is low, the zinc oxide content is usually less than or equal to 60%, and good economic benefit cannot be realized.
SUMMERY OF THE UTILITY MODEL
In view of this, the utility model aims at providing a system for zinc production nanometer zinc oxide is retrieved in industrialization for solve in the current ammonia process leaching technology recovery of zinc not thorough, the unable recycle of valuable elements such as iron in the residue, salt divides in the material to lead to the system operation not smooth, the secondary zinc oxide low grade of rotary hearth furnace production, economic benefits subalternation problem.
The utility model discloses a realize through following technical scheme:
the utility model provides a system for zinc production nanometer zinc oxide is retrieved in industrialization, the system is provided with rotary hearth furnace, demineralizer, ammonia process leaching reactor, purification reactor, crystallization reactor, calcification reactor, rinsing jar, drying device and calcining device according to the production order of retrieving zinc, rotary hearth furnace is used for carrying out zinc recovery to two types of zinciferous materials that zinc content is less than 5% and refines and obtain secondary zinc oxide and metallization product, demineralizer is used for carrying out desalination treatment to one type of zinciferous material that zinc content is more than or equal to 5% and the secondary zinc oxide that rotary hearth furnace produced and obtains first solid and desalinized water, ammonia process leaching reactor is used for carrying out secondary zinc recovery to first solid and refines and obtain zinc ammine complex liquid, purification reactor is used for purifying and edulcorating zinc ammine complex liquid, crystallization reactor is used for carrying out carbonization crystallization to the zinc ammine complex liquid after the purification and obtains zinc oxide raffinate and crystallization, the rinsing tank, the drying device and the calcining device are used for sequentially and respectively rinsing, drying and calcining the zinc oxide precursor to obtain a nano zinc oxide product, and the calcification reactor is used for carrying out calcification treatment on the crystallization residual liquid to obtain calcium carbonate.
The system further comprises a filter press I, a filter press II, a filter press III, a filter press IV, a filter press V and a filter press VI which are respectively arranged behind the ammonia process leaching reactor, the purification reactor, the crystallization reactor, the rinsing tank, the calcification reactor and the desalination device and used for solid-liquid separation; leaching slag generated by the filter press I and purification slag generated by the filter press II return to the rotary hearth furnace through the conveying device respectively; the crystallization residual liquid generated by the filter press III enters a calcification reactor; the rinsing liquid generated by the filter press IV returns to the desalting device; adding calcified residual liquid generated by the filter press V as an extracting agent and water into an ammonia extraction reactor; the desalted water produced by the filter press VI is directly used for cooling the steel-making slag.
Further, the system also comprises a liquid charging tank which is connected with the ammonia process leaching reactor and used for providing leaching agent for the ammonia process leaching reactor, and a liquid storage tank which is connected with the liquid charging tank and used for providing water for the liquid charging tank, wherein the liquid storage tank is also connected with a filter press IV and a filter press V; the lixiviant is a mixed solution of ammonia and ammonium salt, wherein the concentration of the ammonia is 3-10 mol/L, and the concentration of the ammonium salt is 1-4 mol/L.
Further, the zinc-containing materials with the zinc content of more than or equal to 5 percent and the zinc hypoxide produced by the rotary hearth furnace are mixed and stirred with water in a desalting device, and the pH value of the mixed solution is adjusted: and 8-10, grinding and desalting.
Further, in the zinc-ammonia complex solution before purification: the concentration of zinc oxide is more than 20 g/L; in the purified zinc-ammonia complex solution: the total concentration of heavy metal ions except zinc is less than 10 mg/L.
Further, the carbonization crystallizing agent of the zinc-ammonia complex solution adopts industrial carbon dioxide, and the crystallization endpoint is the pH value of the crystallization residual liquid: 6.5 to 8.0.
Further, the heat source of the drying device is derived from a heat recovery device for recovering waste heat of the flue gas of the rotary hearth furnace, and the heat recovery device comprises, but is not limited to, a waste heat boiler, a plate heat exchanger and a heating furnace.
The utility model has the advantages that:
1. the utility model discloses the two advantage and disadvantage of ammonia process leaching and rotary hearth furnace technology is considered multipurposely, at first according to the height of zinc content with original zinciferous material classification planning, and then adopt the method that ammonia process leaching and rotary hearth furnace jointly dealt with to carry out alternately joint deep recovery to the zinc in the zinciferous material, get strong and short, thoroughly retrieve the zinc in the zinciferous material, with the nanometer zinc oxide (high-purity zinc oxide) product of production high-grade, iron in the zinciferous material of fully retrieving again simultaneously produces the metallization product, produce bigger dual economic benefits.
2. The utility model discloses still utilize industry carbon dioxide as the crystallization agent, the zinc oxide precursor is produced in the carbonization crystallization, has improved the crystallization efficiency of zinc oxide precursor, handles through the crystallization raffinate to the carbonization simultaneously, and the by-product goes out the calcium carbonate product, has further improved economic benefits.
3. The utility model discloses a get into the rotary hearth furnace production purification with the low-grade raw materials and obtain after the medium-grade zinc oxide product, reentrant ammonia process leaching acquires the high-grade zinc oxide product, still leaches the zinciferous material that sediment and purification slag collected with the ammonia process simultaneously and returns the rotary hearth furnace again, further carries out recycle to zinciferous material and iron element etc. so cyclic synthesis utilizes for solid waste handles rationally, and recycle rate is high.
4. The utility model also directly uses the desalted water after the desalting treatment for cooling the steel-making slag; the calcification residual liquid after the calcification treatment is used as an extracting agent and added with water for recycling; the rinsing liquid after rinsing treatment is used as an extracting agent and added with water for recycling and/or used as desalting and added with water for recycling, so that water resources are recycled, and zero discharge of wastewater is realized.
5. The utility model discloses still with the flue gas that the rotary hearth furnace produced waste heat behind the heat recovery as dry heat source cycle and use for the industry waste heat is used multipurposely, promotes economic value.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and/or combinations particularly pointed out in the appended claims.
Drawings
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail with reference to the accompanying drawings, in which:
fig. 1 is a schematic diagram of the system of the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The present invention can also be implemented or applied through other different specific embodiments, and various details in the present specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the features in the following embodiments and examples may be combined with each other without conflict.
Of the system of the present disclosureThe application range is not particularly limited, and the zinc-containing material can be widely applied to the utilization of various zinc-containing materials. The zinc-containing material comprises but is not limited to lead zinc ore, metallurgical zinc-containing dust sludge, water treatment sediment, waste catalysts, medical waste zinc-containing intermediate and the like, and the zinc component in the zinc-containing material can exist in one or more forms of but not limited to zinc oxide, zinc carbonate, zinc silicate and the like, is classified and recycled according to the zinc content, and is combined with ammonia leaching and rotary hearth furnace process to carry out cross combined deep recovery on the zinc in the zinc-containing material, so that the zinc in the zinc-containing material is recycled to the maximum extent; in particular, the zinc-bearing material is classified as: the zinc-containing materials comprise zinc materials with the zinc content of more than or equal to 5 percent and zinc materials with the zinc content of less than 5 percent; in particular, the intermediate zinc oxide precursor of the present disclosure is basic zinc carbonate [ Zn ]2(OH)2CO3]Zinc hydroxide [ Zn (OH) ]2]And zinc carbonate (ZnCO)3]Or a combination thereof; in particular, the metalized product of the present disclosure is a metalized pellet, a metalized powder or a ceramsite mainly containing iron element; in particular, heavy metal ions other than zinc of the present disclosure include, but are not limited to, iron, cadmium, manganese, lead, chromium, mercury, arsenic, and the like; in particular, the ammonia salts of the present disclosure include, but are not limited to, ammonium chloride, ammonium bicarbonate, and the like; in particular, "optional" in the present disclosure means that the subsequently described step may or may not be performed, or is otherwise substituted, and that the expression includes instances where the subsequently described step is performed, instances where the subsequently described step is not performed, and instances where the subsequently described step is otherwise substituted.
As shown in fig. 1, the system for producing nano zinc oxide by industrially recovering zinc in the embodiment is provided with a rotary hearth furnace, a desalting device, an ammonia leaching reactor, a purifying reactor, a crystallizing reactor, a calcification reactor, a rinsing tank, a drying device and a calcining device according to the production sequence of recovered zinc; wherein:
the rotary hearth furnace carries out primary zinc recovery and extraction on a second class of zinc-containing materials with the zinc content of less than 5 percent to produce secondary zinc oxide and a metalized product, namely the second class of zinc-containing materials react in the rotary hearth furnace to generate the metalized product and generate a large amount of smoke, the metalized product is directly recycled, the large amount of smoke sequentially passes through the heat recovery device and the dust removal device to remove dust, and then secondary zinc oxide-containing dust is collected and can be conveyed by a tank car and mixed with the first class of zinc-containing materials.
The desalting device is used for desalting a zinc-containing material with the zinc content of more than or equal to 5 percent and zinc hypoxide produced by the rotary hearth furnace to produce a first solid and desalted water, and a filter press VI used for solid-liquid separation of the first solid and the desalted water is arranged behind the desalting device. Because the salt in the zinc-containing materials (various zinc-containing ash, dust and slag) of the steel plant mainly exists in the forms of KCl and NaCl, the aim of desalting is fulfilled by washing the zinc-containing solid waste with water, dissolving the salt in the water and carrying away the salt in the zinc-containing solid waste through the water. Specifically, the second type zinc-containing material and zinc hypoxide are mixed with water, wet grinding is carried out (grinding time is not limited, selection is carried out according to actual needs, and 30min is preferred), then solid-liquid separation is carried out by a filter press VI, so as to obtain a first solid (namely the desalted zinc-containing material) and desalted water, and the desalted water can be directly used for cooling the steelmaking slag. In the process, the pH value of the mixed liquid of the secondary zinc-containing material, the zinc hypoxide and water is adjusted to 8-10, so that zinc dissolved in water in the desalting process is precipitated in the first solid in the form of zinc hydroxide and is not taken away by desalted water. Namely, in the desalting process, the zinc-containing material simultaneously contains ZnCl2，ZnCl2Can be dissolved in water in the water washing process and is taken away by desalted water, thus causing the loss of zinc. Therefore, in the desalting process, the solution pH is controlled to be preferably 9, so that Zn in water is obtained2+With Zn (OH)2Is precipitated in the desalted first solid. Of course, in various embodiments, the desalted water may be further processed, such as: the desalted water is recycled for desalting treatment, and after the total salt content is accumulated to be more than 10%, evaporative crystallization (including multi-effect evaporation or Mechanical Vapor Recompression (MVR) technology) is carried out on the desalted water to obtain mixed salt. The condensed water obtained by evaporation and crystallization is used as the rinsing water of the zinc oxide precursor. Thus, the desalting device is adopted to carry out desalting treatment on the second class zinc-containing material and the zinc hypoxide, thereby not only recovering the mixed salt in the material, but also ensuring the smooth operation of the leaching recovery by the ammonia process, and reducingCorrosion of the equipment occurs.
The ammonia leaching reactor is used for carrying out secondary zinc recovery refining on the first solid to produce zinc-ammonia complex liquid; a filter press I for solid-liquid separation of leaching slag and leaching liquid (namely zinc ammine complex liquid) is arranged behind an ammonia leaching reactor, namely, the first solid obtained in the desalting treatment step is mixed and stirred with a leaching agent (namely mixed liquid of ammonia and ammonium bicarbonate, wherein the molar concentration of ammonia is 5mol/L, and the molar concentration of ammonium bicarbonate is 2mol/L) for 2 hours by the ammonia leaching reactor, wet grinding is carried out (the grinding time is not limited, the selection is carried out according to actual needs, and the optimization is carried out for 2 hours), then, the solid-liquid separation is carried out by the filter press I to obtain the leaching slag (namely zinc-containing material residue after zinc recovery) and the leaching liquid (namely zinc ammine complex liquid), the leaching liquid is recycled for ammonia leaching, and the next purification treatment process is carried out after the content of zinc oxide in the leaching liquid is accumulated to be more than 20 g/L. And mixing and stirring the leaching residue and water (the stirring time is not limited, the selection is carried out according to actual needs, and the preferable time is 30min), washing to remove the leaching agent carried in the leaching residue, then carrying out solid-liquid separation, recovering the leaching agent, and returning the leaching agent to the ammonia leaching process for recycling. And (4) feeding the washed leaching slag into a rotary hearth furnace to produce a metalized product as an iron-making raw material. In the process, an ammonia process leaching reactor is adopted to carry out ammonia process leaching on the first solid to obtain zinc-ammonia complex liquid, and zinc in the first solid mainly comprises ZnO and ZnSiO3The ammonia process leaching process mainly comprises the following chemical reactions:
ZnO+(n-1)NH3+NH4HCO3＝[Zn(NH3)n]CO3+H2O
ZnSiO3+nNH3+2NH4HCO3→[Zn(NH3)n]CO3+SiO2·H2O+(NH4)2CO3
Zn(OH)2+(n-1)NH3+NH4HCO3→[Zn(NH3)n]Co3+H2O
wherein n is 1 to 4, ZnO, ZnSiO3、Zn(OH)2Most of the copper, cadmium, mercury and the like are leached through the reactionSimilar chemical reactions take place into solution.
Due to Mn in the ammonia leaching process2+、Mn4+、Pb2+、Pb4+、Fe2+、Fe3+Reaction with water to form Mn (OH)2、Mn(OH)4、Pb(OH)2、Pb(OH)4、Fe(OH)2、Fe(OH)3And (4) precipitating. Therefore, some insoluble compounds are left in the leaching residue in the ammonia leaching process to precipitate out, and the leaching solution (i.e. the second filtrate) is subjected to deep impurity removal through subsequent purification.
The purification reactor purifies and removes impurities from the zinc ammine complex solution, and a filter press II for solid-liquid separation of purified slag and the purified zinc ammine complex solution is arranged behind the purification reactor. Adopting an optional purification method, such as sequentially purifying with potassium permanganate and zinc powder to make the total concentration of heavy metal ions except zinc in the purified zinc-ammonia complex solution less than 10 mg/L; the heavy metal ions include, but are not limited to, iron, cadmium, manganese, lead, chromium, mercury, arsenic. In the process, the residual impurities in the zinc-ammonia complex solution comprise Fe2+、Mn2+、AsO3-、Pb2+、Cu2+、Cd2+、Ni2+、Hg2+Etc., need to be removed by further purification schemes; the zinc ammine complex solution obtained by ammonia extraction is purified and decontaminated by a purification reactor, and in the process, when solid substances are generated in the purified and decontaminated zinc ammine complex solution, solid-liquid separation is carried out by a filter press II to obtain purified slag, and the purified slag is returned to a rotary hearth furnace to produce metallized products as iron-making raw materials. The reaction equation for purification is as follows:
3Fe2++MnO4 -+7H2O→MnO2↓+3Fe(OH)3↓+5H+
3AsO3 3-+2MnO4 -+H2O→2MnO2↓+3AsO4 3-+2OH-
AsO4 3-+Fe3-→FeAsO4↓
M2++Zn→M↓+Zn2+
m comprises：Pb2+、Cu2+、Cd2+、Ni2+、Hg2+And (3) plasma.
And a crystallization reactor is used for carbonizing and crystallizing the purified zinc ammine complex liquid to produce a zinc oxide precursor and a crystallization residual liquid, namely carbon dioxide gas is introduced into the purified zinc ammine complex liquid for carbonization and crystallization, and a filter press III which is respectively connected with a rinsing tank and a calcification reactor and used for solid-liquid separation of the zinc oxide precursor and the crystallization residual liquid is arranged behind the crystallization reactor. In the process, (1) a crystallization reactor is adopted to carry out carbonization crystallization on the purified zinc-ammonia complex liquid, and the crystallization end point is the pH value of the crystallization residual liquid: 6.5-8.0, and stopping introducing carbon dioxide after the crystallization end point is reached. (2) And introducing the carbon dioxide into the purified zinc-ammonia complex liquid through an aeration device, wherein the carbon dioxide must have certain pressure when being introduced into the purified second filtrate, and the pressure is ensured to be 2-3 times of the sum of the static pressure of the carbon dioxide at the inlet of the crystallization reactor, the pressure loss of the carbon dioxide through the aeration device in the crystallization reactor and the pressure loss of a pipeline system. (3) Carbon dioxide is introduced in two stages: the first stage is as follows: controlling the flow of carbon dioxide gas to ensure that the ratio of the molar concentration of the carbon dioxide introduced into the solution to the molar concentration of the total ammonia in the zinc-ammonia complex solution is 1.25 until the pH value of the crystallization residual liquid reaches 8.5; and a second stage: after the pH value of the crystallization residual liquid reaches 8.5, controlling the flow of carbon dioxide gas to ensure that the ratio of the molar concentration of the carbon dioxide introduced into the solution to the molar concentration of the total ammonia in the zinc-ammonia complex solution is 2.5, and until the crystallization end point is reached, the pH value of the crystallization residual liquid is as follows: 6.5 to 8.0. Fully analyze the reaction efficiency of carbonization crystallization in this process, the carbon dioxide gas that adopts divide into two stages and lets in the second filtrating, has utilized velocity of flow and molar quantity relation between carbon dioxide gas and the second filtrating, promotes carbonization crystallization effect, has reduced the loss of carbon dioxide. The crystallization reactor for carbonization crystallization is a static pressure closed structure, including but not limited to a reaction kettle, a reaction tank and the like, wherein the gas above the zinc ammine complex liquid is discharged into another treatment process through a pipeline, and an aeration device for uniformly distributing carbon dioxide to participate in the carbonization crystallization reaction is arranged in the zinc ammine complex liquid, and comprises but not limited to a micropore diffuser, a middle bubble diffuser, a big bubble diffuser, a jet diffuser and a fixed spiral diffuser, namely the aeration device distributes the carbon dioxide gas in a distributed manner, so that the granularity of the carbonization crystallization meets the production of nano-scale zinc oxide; the device is provided with a compressor used for pressurizing industrial carbon dioxide to enter a crystallization reactor, an ultrasonic device acting on the crystallization reactor and used for assisting the zinc ammine complex liquid to carry out carbonization crystallization, and a seed crystal feeding port used for promoting the zinc ammine complex liquid to carry out carbonization crystallization, wherein the seed crystal fed into the crystallization from the seed crystal feeding port is one or more of basic zinc carbonate, zinc hydroxide, zinc carbonate or zinc oxide.
The main chemical reactions of the crystallization process are:
CO2+2NH3·H2O→(NH4)2CO3+H2O
6Zn(NH3)nCO3+(3n-4)CO2+(6n+8)H2O→2[ZnCO3·2Zn(OH)2·H2O]+3n(NH4)2CO3
and a calcification reactor is used for carrying out calcification treatment on the crystallization residual liquid to obtain a byproduct calcium carbonate, and a filter press V for solid-liquid separation of calcium carbonate and calcification residual liquid is arranged behind the calcification reactor. Namely, after the crystallization reaches the process design end point, the crystallization residual liquid contains a large amount of CO3 2-Simultaneously due to large amount of NH4+The existence of the carbon dioxide leads the pH value to be close to neutral, so that the crystallization raffinate needs to be treated to remove excessive CO in the raffinate3 2-Removing CO from the residue3 2-After the concentration is adjusted to the concentration required by the leaching solution, the leaching solution returns to the leaching process for recycling, and the project design adopts quicklime (CaO) or lime milk to treat the crystallized residual liquid. The main chemical reactions for the treatment of the crystallization residual liquid are as follows:
adding quicklime or lime milk into the crystallization residual liquid obtained by carbonization and crystallization, mixing and stirring for calcification treatment, then carrying out solid-liquid separation by using a filter press V to obtain calcification residual liquid and calcium carbonate, and returning the calcification residual liquid to the ammonia process leaching procedure to be used as a leaching agent and added with water for recycling. In the process, the amount of the added quicklime or lime milk is 100 to 150 percent of the sum of the molar concentrations of carbonate and carbonate in the crystallized residual liquid, and the quicklime or lime milk is utilized for calcification treatment to produce a calcium carbonate product as a byproduct, so that the economic benefit is further improved; the calcification residual liquid is recycled, so that water resources can be saved on one hand, and unreacted zinc components in the calcification residual liquid can be further recovered on the other hand.
And the rinsing tank is used for rinsing and removing impurities from the zinc oxide precursor, a filter press IV for solid-liquid separation is arranged behind the rinsing tank, and the generated rinsing liquid returns to the desalting device. Namely, rinsing the zinc oxide precursor by using a rinsing tank, wherein the rinsing agent is condensed water obtained by evaporation and crystallization in desalination treatment; namely, the rinsing agent of the rinsing tank is tap water or pure water, the rinsing form is internal unidirectional circulation, the times are 2-4, namely, the rinsing liquid after the next rinsing is used for the previous rinsing; and the rinsing liquid after rinsing in the rinsing tank enters a desalting treatment process so as to be reused. In this case, three rinses are used, wherein the rinse liquid after the third rinse is used for the second rinse, the rinse liquid after the second rinse is used for the first rinse, and the rinse liquid after the first rinse is used for desalting and adding water. Thus, the utilization rate of water resources is improved and the recovery of zinc in the rinsing liquid is facilitated. In different embodiments, the rinsing agent is condensed water obtained by evaporation and crystallization in desalination treatment, and in the process, the zinc oxide precursor can be further desalted and purified to achieve the purpose of purification.
And the drying device is used for drying the rinsed zinc oxide precursor. Drying is carried out at the temperature of 150-220 ℃, preferably 180-200 ℃, and the heat source of the drying device is a heat recovery device for recovering the waste heat of the flue gas of the rotary hearth furnace, wherein the heat recovery device comprises but is not limited to a waste heat boiler, a plate heat exchanger and a heating furnace.
And calcining the dried zinc oxide precursor by using a calcining device to produce nano zinc oxide with the grade of not less than 95%, and packaging and selling the nano zinc oxide by using a zinc oxide packaging machine. Calcining for 2 hours at the temperature of 220-440 ℃, preferably 320-370 ℃. The main chemical reactions in this process are:
ZnCO3·2Zn(OH)2·H2O→3ZnO+CO2+2H2O。
by adopting the scheme, the system carries out cross joint deep treatment on the tailings which are generated by the ammonia process and cannot be directly utilized and the secondary zinc oxide product generated by the rotary hearth furnace in the process, makes up for the deficiencies of the tailings and supplements each other, more reasonably and efficiently recovers the zinc in the zinc-containing material, the grade of the produced nano zinc oxide is not less than 95 percent, the iron in the zinc-containing material is fully recovered while the nano zinc oxide is produced, the metallized product is produced, and double economic benefits are generated; meanwhile, calcium carbonate is also produced as a byproduct, and water resources and waste heat resources are comprehensively utilized.
In this embodiment, the leaching residue generated by the filter press i and the purification residue generated by the filter press ii are connected to the rotary hearth furnace through the conveying device, that is, the residue of the ammonia leaching reactor after the production of the zinc ammine complexing solution and the residue generated during the purification of the zinc ammine complexing solution are both recycled into the rotary hearth furnace through the conveying device to recover valuable elements such as residual zinc and iron, so as to produce zinc hypoxide and metallized products.
The system in the embodiment also comprises a liquid charging tank connected to the ammonia leaching reactor and used for providing leaching agent for the ammonia leaching reactor, and a liquid storage tank connected to the liquid charging tank and used for providing water for the liquid charging tank, wherein the storage capacity in the liquid storage tank can be ensured by introducing industrial fresh water, the leaching agent is a mixed solution of ammonia and ammonium salt, such as a mixed solution of ammonia and ammonium chloride, a mixed solution of ammonia and ammonium bicarbonate and the like, the concentration of ammonia is 3-10 mol/L, and the concentration of ammonium salt is 1-4 mol/L. Rinsing liquid after rinsing can also enter a liquid storage tank, and is used for adding water into an extracting agent of a liquid adding tank and returning the extracting agent to the ammonia extraction process through the liquid adding tank for recycling, so that the utilization rate of water resources is improved, and the recovery of zinc components in the rinsing liquid is facilitated; meanwhile, the calcification residual liquid also enters the liquid storage tank for storage so as to be reused. In different embodiments, it is also possible to dispense with a liquid storage tank and to allow the calcification residual liquid and the rinsing liquid to directly enter the liquid mixing tank.
The process of the system comprises the following steps:
s1, feeding a second zinc-containing material with the zinc content less than 5% into a rotary hearth furnace for primary zinc recovery and extraction to produce secondary zinc oxide and a metalized product;
s2, sequentially desalting a zinc-containing material with the zinc content of more than or equal to 5% and secondary zinc recovery and refining of secondary zinc produced by a rotary hearth furnace, carrying out ammonia leaching and purification to produce a zinc-ammonia complex solution; directly using desalted water after desalting treatment for cooling steel-making slag, and returning leached slag after ammonia leaching and purified slag after purification treatment into a rotary hearth furnace;
s3, introducing carbon dioxide gas into the purified zinc ammonia complex solution for carbonization and crystallization to produce a zinc oxide precursor; and calcium oxide is utilized to carry out calcification treatment on the crystallization residual liquid after carbonization and crystallization, and calcium carbonate is a byproduct; the calcification residual liquid after the calcification treatment is used as an extracting agent and added with water for recycling;
s4, rinsing, drying and calcining the zinc oxide precursor to produce a nano zinc oxide product; the rinsing liquid after rinsing treatment is used as an extracting agent and added with water for recycling and/or used as desalination and added with water for recycling; the waste heat of the flue gas generated by the rotary hearth furnace after heat recovery is used as a drying heat source for recycling.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and it is obvious that those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (5)
1. The system for producing the nano-zinc oxide by industrially recovering the zinc is characterized by comprising a rotary hearth furnace, a desalting device, an ammonia process extraction reactor, a purification reactor, a crystallization reactor, a calcification reactor, a rinsing tank, a drying device and a calcining device according to the production sequence of recovered zinc, wherein the rotary hearth furnace is used for carrying out primary zinc recovery and refining on two types of zinc-containing materials with the zinc content of less than 5% to obtain secondary zinc oxide and a metalized product, the desalting device is used for carrying out desalting treatment on one type of zinc-containing materials with the zinc content of more than or equal to 5% and the secondary zinc oxide produced by the rotary hearth furnace to obtain a first solid and desalted water, the ammonia process extraction reactor is used for carrying out secondary zinc recovery and refining on the first solid to obtain a zinc-ammonia complex solution, the purification reactor is used for purifying and removing impurities from the zinc-ammonia complex solution, the crystallization reactor is used for carrying out carbonization and crystallization on the purified zinc-ammonia complex solution to obtain a zinc oxide precursor and a residual liquid, the rinsing tank, the drying device and the calcining device are used for sequentially and respectively rinsing, drying and calcining the zinc oxide precursor to obtain a nano zinc oxide product, and the calcification reactor is used for carrying out calcification treatment on the crystallization residual liquid to obtain calcium carbonate.
2. The system for producing nano-zinc oxide by industrially recovering zinc according to claim 1, further comprising a filter press I, a filter press II, a filter press III, a filter press IV, a filter press V and a filter press VI which are respectively arranged behind the ammonia leaching reactor, the purification reactor, the crystallization reactor, the rinsing tank, the calcification reactor and the desalting device and used for solid-liquid separation; leaching slag generated by the filter press I and purification slag generated by the filter press II return to the rotary hearth furnace through the conveying device respectively; the crystallization residual liquid generated by the filter press III enters a calcification reactor; the rinsing liquid generated by the filter press IV returns to the desalting device; adding calcified residual liquid generated by the filter press V as an extracting agent and water into an ammonia extraction reactor; the desalted water produced by the filter press VI is directly used for cooling the steel-making slag.
3. The system for producing nano-zinc oxide by industrially recovering zinc according to claim 2, further comprising a liquid charging tank connected to the ammonia leaching reactor and used for providing leaching agent thereto, and a liquid storage tank connected to the liquid charging tank and used for providing water thereto, wherein the liquid storage tank is further connected with a filter press IV and a filter press V.
4. The system for producing nano-zinc oxide by industrially recovering zinc according to claim 1, wherein the carbonized crystallizing agent of the zinc ammine complexing liquid is industrial carbon dioxide.
5. The system for producing nano zinc oxide by industrially recovering zinc according to claim 1, wherein the heat source of the drying device is a heat recovery device for recovering waste heat of the flue gas of the rotary hearth furnace, and the heat recovery device comprises a waste heat boiler, a plate heat exchanger or a heating furnace.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110775998A (en) * | 2019-10-31 | 2020-02-11 | 重庆赛迪热工环保工程技术有限公司 | System and method for producing nano zinc oxide by industrially recycling zinc |
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