CN104004913A - Method for removing iron from iron-containing zinc sulfate solution - Google Patents
Method for removing iron from iron-containing zinc sulfate solution Download PDFInfo
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- CN104004913A CN104004913A CN201410225014.3A CN201410225014A CN104004913A CN 104004913 A CN104004913 A CN 104004913A CN 201410225014 A CN201410225014 A CN 201410225014A CN 104004913 A CN104004913 A CN 104004913A
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- deironing
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- zinc sulfate
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- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a method for removing iron from an iron-containing zinc sulfate solution. The method comprises the following steps: supplying the iron-containing zinc sulfate solution to a vertical reaction kettle, and introducing steam and oxygen into the vertical reaction kettle so as to perform primary iron removal treatment in the vertical reaction kettle to obtain first iron-removed slurry; supplying the first iron-removed slurry to a horizontal reaction kettle, and introducing steam and oxygen to the horizontal reaction kettle so as to perform secondary iron removal treatment in the horizontal reaction kettle to obtain second iron-removed slurry. According to the method of removing iron from the iron-containing zinc sulfate solution disclosed by the embodiment of the invention, the vertical reaction kettle and the horizontal reaction kettle are combined for use so as to effectively solve the production interruption caused by the problems of scaling in the kettles in the iron removal process and ensure the continuous and stable operation of production, thereby significantly improving the iron removal efficiency and the equipment utilization rate.
Description
Technical field
The invention belongs to chemical industry and field of metallurgy, particularly, the present invention relates to a kind of method of iron content solution of zinc sulfate being carried out to deironing.
Background technology
Iron conventionally can enter solution with impurity form in the wet smelting process such as zinc, in order to obtain purer zinc product, in smelting process, can before product recovery process, the iron precipitation in solution be removed, conventionally the method adopting has neutralisation, siderotil method, goethite process and iron oxide process, neutralisation wherein, siderotil method, separation of iron in goethite form slag iron content is all lower, scum enters tailings reservoir for piling conventionally, the product that iron oxide process obtains is because iron content is higher, can be used as cement, the raw material of ironmaking or production iron oxide red product, not only can solve problem of environmental pollution, can also effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.Yet because iron oxide process is carried out under High Temperature High Pressure, make the continous-stable of producing affect very large on production cost.
Therefore, existing iron removal technology is further improved.
Summary of the invention
The present invention is intended at least solve one of technical problem existing in prior art.For this reason, one object of the present invention is to propose a kind of method of iron content solution of zinc sulfate being carried out to deironing, the method can effectively solve the production causing due to problems such as foulings and interrupt, guarantee the continuous and steady operation of producing, and significantly improve the utilization ratio of equipment, not only can effectively solve the occupation of land of scum Tailings Dam and problem of environmental pollution, but also can effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit simultaneously.
In one aspect of the invention, the present invention proposes a kind of method of iron content solution of zinc sulfate being carried out to deironing, the method comprises:
Iron content solution of zinc sulfate is supplied in vertical response still, and introduces steam and oxygen in described vertical response still, to carry out the first deironing processing in described vertical response still, and obtain the first deironing rear slurry; And
Described the first deironing rear slurry is supplied in horizontal reacting still, and introduces steam and oxygen in described horizontal reacting still, to carry out the second deironing processing in described horizontal reacting still, and obtain the second deironing rear slurry.
According to the method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention by vertical response still and horizontal reacting still are combined to use, can effectively solve the interior scale problems of still in iron removal, thereby significantly improve de-ironing efficiency and plant factor in iron content solution of zinc sulfate, not only can effectively solve scum Tailings Dam takes up an area and problem of environmental pollution simultaneously, but also can effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.
In addition, the method that iron content solution of zinc sulfate is carried out to deironing according to the above embodiment of the present invention can also have following additional technical characterictic:
In some embodiments of the invention, in described iron content solution of zinc sulfate zinc concentration not higher than 100g/L.
In some embodiments of the invention, in described iron content solution of zinc sulfate is supplied to vertical response still before, in advance described iron content solution of zinc sulfate is heated to 80～100 degrees Celsius, preferably 90 degrees Celsius.Thus, can significantly improve the first deironing processing efficiency.
In some embodiments of the invention, to process be to be to carry out completing for 0.5～1 hour under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature in described the first deironing.Thus, can further improve the first deironing processing efficiency.
In some embodiments of the invention, to process be to be to carry out completing for 2～3 hours under 170-200 degree Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature in described the second deironing.Thus, can significantly improve the second deironing processing efficiency.
In some embodiments of the invention, the described method that iron content solution of zinc sulfate is carried out to deironing further comprises: described the second deironing rear slurry is carried out to the processing of flash distillation decrease temperature and pressure, and obtain the second deironing rear slurry of processing through flash distillation; And described the second deironing rear slurry of processing through flash distillation is carried out to filtration washing, to obtain respectively iron oxide product and the solution after deironing purifies.Thus, can realize the effective separated of iron oxide product and solution.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Accompanying drawing explanation
Above-mentioned and/or additional aspect of the present invention and advantage accompanying drawing below combination obviously and is easily understood becoming the description of embodiment, wherein:
Fig. 1 carries out the method flow schematic diagram of deironing according to an embodiment of the invention to iron content solution of zinc sulfate;
Fig. 2 is the method flow schematic diagram that iron content solution of zinc sulfate is carried out to deironing of another embodiment according to the present invention;
Fig. 3 be implement one embodiment of the invention iron content solution of zinc sulfate is carried out to the system architecture schematic diagram of the method for deironing;
Fig. 4 be implement another embodiment of the present invention iron content solution of zinc sulfate is carried out to the system architecture schematic diagram of the method for deironing.
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has the element of identical or similar functions from start to finish.Below by the embodiment being described with reference to the drawings, be exemplary, be intended to for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, it will be appreciated that, term " first ", " second " be only for describing object, and can not be interpreted as indication or hint relative importance or the implicit quantity that indicates indicated technical characterictic.Thus, one or more these features can be expressed or impliedly be comprised to the feature that is limited with " first ", " second ".In description of the invention, the implication of " a plurality of " is two or more, unless otherwise expressly limited specifically.
In the present invention, unless otherwise clearly defined and limited, the terms such as term " installation ", " being connected ", " connection ", " fixing " should be interpreted broadly, and for example, can be to be fixedly connected with, and can be also to removably connect, or connect integratedly; Can be mechanical connection, can be to be also electrically connected to; Can be to be directly connected, also can indirectly be connected by intermediary, can be the connection of two element internals.For the ordinary skill in the art, can understand as the case may be above-mentioned term concrete meaning in the present invention.
In one aspect of the invention, the present invention proposes a kind of method of iron content solution of zinc sulfate being carried out to deironing.Below with reference to Fig. 1-2, the method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention is described in detail.According to embodiments of the invention, the method comprises:
S100: the first deironing is processed
According to embodiments of the invention, iron content solution of zinc sulfate is supplied in vertical response still, and introduces steam and oxygen in vertical response still, to carry out the first deironing processing in vertical response still, thereby can obtain the first deironing rear slurry.According to a particular embodiment of the invention, in iron content solution of zinc sulfate, zinc concentration can be higher than 100g/L.According to embodiments of the invention, the condition that the first deironing is processed is also not particularly limited, according to a particular embodiment of the invention, to process to be to carry out 0.5～1 hour under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature in the first deironing.In this step, concrete, the iron in iron content solution of zinc sulfate enters solid phase with ferric oxide, generates sulfuric acid simultaneously, and sulfuric acid can return and leach operation continuation utilization, and the main reaction equation occurring is: 2FeSO
4+ 0.5O
2+ 2H
2o=Fe
2o3+2H
2sO
4.
S200: the second deironing is processed
According to embodiments of the invention, above-mentioned resulting the first deironing rear slurry is supplied in horizontal reacting still, and introduce steam and oxygen in horizontal reacting still, to carry out the second deironing processing in horizontal reacting still, thereby can obtain the second deironing rear slurry.According to embodiments of the invention, the condition that the second deironing is processed is also not particularly limited, and according to a particular embodiment of the invention, it can be to carry out 2～3 hours under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature that the second deironing is processed.In this step, same, iron enters solid phase with ferric oxide, generates sulfuric acid simultaneously, and sulfuric acid can return and leach operation continuation utilization.
According to the method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention by vertical response still and horizontal reacting still are combined to use, can effectively solve the production stage casing that in iron removal, in still, scale problems causes, guarantee the continuous and steady operation of producing, thereby significantly improve de-ironing efficiency and plant factor, the quantity of slag that the method produces is little, iron level is high, carry other valuable metal amounts secretly few, slag is without storing up, can be used as by-product sale, not only can solve problem of environmental pollution, can also effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.
Below with reference to Fig. 2, the method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention is described further.According to embodiments of the invention, the method further comprises:
S300: thermal pretreatment
According to embodiments of the invention, in iron content solution of zinc sulfate is supplied to vertical response still before, iron content solution of zinc sulfate is carried out to thermal pretreatment.According to embodiments of the invention, iron content solution of zinc sulfate is carried out the temperature of thermal pretreatment and is not particularly limited, according to a particular embodiment of the invention, before in iron content solution of zinc sulfate is supplied to vertical response still, iron content solution of zinc sulfate can be preheated to 80～100 degrees Celsius, for example, iron content solution of zinc sulfate can be preheated to 90 degrees Celsius.Contriver finds, before iron content solution of zinc sulfate is supplied to vertical response still, iron content solution of zinc sulfate is carried out to thermal pretreatment to this temperature range and can significantly improve follow-up the first deironing processing efficiency.
S400: flash distillation is processed
According to embodiments of the invention, above-mentioned resulting the second deironing rear slurry is carried out to the processing of flash distillation decrease temperature and pressure, thereby can obtain the second deironing rear slurry through flash distillation processing.In this step, High Temperature High Pressure slurries are down to 100 degrees Celsius of normal pressures, generate a large amount of secondary steams simultaneously, secondary steam can be used as thermal source and recycles.
S500: filtration washing
According to embodiments of the invention, above-mentioned resulting the second deironing rear slurry of processing through flash distillation is carried out to filtration washing, thereby can obtain respectively iron oxide product and the solution after deironing purifies, wherein, iron oxide product can be used as cement, steel-making or produces the raw material use of iron oxide red product, not only can solve problem of environmental pollution, can also effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.
For convenient, understand, the system that iron content solution of zinc sulfate is carried out to the method for deironing of implementing the embodiment of the present invention below with reference to Fig. 3-4 pair is described in detail.According to embodiments of the invention, this system comprises:
Vertical response still 100: according to embodiments of the invention, this vertical response still 100 has vertical response body 10.According to embodiments of the invention, in vertical response still body 10, limit the first deironing reaction compartment, for carrying out the first deironing processing at the first deironing reaction compartment, thereby can obtain the first deironing rear slurry.According to a particular embodiment of the invention, in iron content solution of zinc sulfate, zinc concentration can be higher than 100g/L.According to embodiments of the invention, the condition that the first deironing is processed is also not particularly limited, according to a particular embodiment of the invention, to process to be to carry out 0.5～1 hour under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature in the first deironing.In this step, concrete, the iron in iron content solution of zinc sulfate enters solid phase with ferric oxide, generates sulfuric acid simultaneously, and sulfuric acid can return and leach operation continuation utilization, and the main reaction equation occurring is: 2FeSO
4+ 0.5O
2+ 2H
2o=Fe
2o
3+ 2H
2sO
4.
According to embodiments of the invention, vertical response still body 10 is provided with iron content solution of zinc sulfate supplying opening 11, the first steam-ins 12, the first oxygen intake 13 and the first deironing rear slurry outlet 14.According to a particular embodiment of the invention, iron content solution of zinc sulfate supplying opening 11 is for being supplied to iron content solution of zinc sulfate the first deironing reaction compartment, the first steam-in 12 is for by steam supply to the first deironing reaction compartment, the first oxygen intake 13 is for oxygen being supplied to described the first deironing reaction compartment, and the first deironing rear slurry outlet 14 is for discharging the first deironing reaction compartment by resulting the first deironing rear slurry.
Horizontal reacting still 200: according to embodiments of the invention, horizontal reacting still 200 has horizontal reacting still body 20.According to embodiments of the invention, in horizontal reacting still body 20, limit the second deironing reaction compartment, at the second deironing reaction compartment, the first deironing rear slurry being carried out to the second deironing processing, and obtain the second deironing rear slurry.According to embodiments of the invention, the condition that the second deironing is processed is also not particularly limited, and according to a particular embodiment of the invention, it can be to carry out 2～3 hours under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature that the second deironing is processed.In this step, same, iron enters solid phase with ferric oxide, generates sulfuric acid simultaneously, and sulfuric acid can return and leach operation continuation utilization.
According to embodiments of the invention, horizontal reacting still body 20 is provided with the first deironing rear slurry supplying opening 21, the second steam-in 22 and the second oxygen intake 23.According to a particular embodiment of the invention, the first deironing rear slurry supplying opening 21 is connected with the first deironing rear slurry outlet 14.According to a particular embodiment of the invention, the first deironing rear slurry supplying opening 21 is for being supplied to iron content solution of zinc sulfate the second deironing reaction compartment, the second steam-in 22 is for by steam supply to the second deironing reaction compartment, and the second oxygen intake 23 is for being supplied to oxygen the second deironing reaction compartment.
Implement the system of method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention by vertical response still and horizontal reacting still are combined to use, can effectively solve the production stage casing that in iron removal, in still, scale problems causes, guarantee the continuous and steady operation of producing, thereby significantly improve iron content solution of zinc sulfate de-ironing efficiency and plant factor, the quantity of slag that the method produces is simultaneously little, iron level is high, carry other valuable metal amounts secretly few, slag is without storing up, can be used as by-product sale, not only can effectively solve scum Tailings Dam takes up an area and problem of environmental pollution, but also can effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.
Below with reference to Fig. 4, to implementing the system that iron content solution of zinc sulfate is carried out to the method for deironing of the embodiment of the present invention, be described further.According to embodiments of the invention, this system further comprises:
Primary heater unit 300: according to embodiments of the invention, primary heater unit 300 is connected with iron content solution of zinc sulfate supplying opening 11, for before iron content solution of zinc sulfate is supplied to vertical response still, in advance iron content solution of zinc sulfate is carried out to thermal pretreatment.According to embodiments of the invention, iron content solution of zinc sulfate is carried out the temperature of thermal pretreatment and is not particularly limited, according to a particular embodiment of the invention, before in iron content solution of zinc sulfate is supplied to vertical response still, iron content solution of zinc sulfate can be preheated to 80～100 degrees Celsius, for example, iron content solution of zinc sulfate can be preheated to 90 degrees Celsius.
Flash distillation treatment unit 400: according to embodiments of the invention, flash distillation treatment unit 400 is connected with horizontal reacting still 200, for the second deironing rear slurry is carried out to the processing of flash distillation decrease temperature and pressure, and obtains the second deironing rear slurry through flash distillation processing.In this step, High Temperature High Pressure slurries are down to 100 degrees Celsius of normal pressures, generate a large amount of secondary steams simultaneously, secondary steam can be used as thermal source and recycles.
Filtration washing device 500: according to embodiments of the invention, filtration washing device 500 is connected with flash distillation treatment unit 400, for the second deironing rear slurry of processing through flash distillation is carried out to filtration washing, to obtain respectively iron oxide product and the iron content solution of zinc sulfate through purifying, wherein, iron oxide product can be used as cement, steel-making or produces the raw material use of iron oxide red product, not only can solve problem of environmental pollution, can also effectively improve the rate of recovery of metallic zinc, increase Business Economic Benefit.
According to embodiments of the invention, the system that iron content solution of zinc sulfate is carried out to the method for deironing of implementing the embodiment of the present invention can comprise a plurality of vertical response stills and a plurality of horizontal reacting still, wherein, each horizontal reacting still is connected with at least one vertical response still respectively, and between vertical response still and described horizontal reacting still, be provided with by-pass valve control, for the connected sum of controlling between vertical response still and described horizontal reacting still, close.
Below with reference to specific embodiment, present invention is described, it should be noted that, these embodiment are only descriptive, and do not limit the present invention in any way.
Embodiment
Utilize the method that iron content solution of zinc sulfate is carried out to deironing of the embodiment of the present invention to process iron content solution of zinc sulfate:
Wherein, this iron content solution of zinc sulfate is liquid after the heavy indium of zinc smelting.
In 1m
3vertical response still and 3m
3in horizontal reacting still, with 1m
3the flow of/h adds iron content solution of zinc sulfate, and solution is containing zinc 100g/L, and iron content 30g/L is (with Fe
2+meter), pH value is 3, maintains 185 ℃ of temperature of reaction, after heavy iron solution through flash distillation, filtration washing, liquid (filtrate) after acquisition iron-containing product (precipitation) and heavy iron, and will sink liquid retrieval system after iron and recycle.
By mensuration, draw containing iron oxide product iron content 60～68%, containing zinc <0.5%, sulfur-bearing <0.8%, it can be used as cement, iron oxide red product is sold or further produced to iron ore.
In the description of this specification sheets, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the feature of this embodiment or example description.In this manual, the schematic statement of above-mentioned term is not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or feature can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that not departing from principle of the present invention and aim, can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (6)
1. iron content solution of zinc sulfate is carried out to a method for deironing, it is characterized in that, comprising:
Iron content solution of zinc sulfate is supplied in vertical response still, and introduces steam and oxygen in described vertical response still, to carry out the first deironing processing in described vertical response still, and obtain the first deironing rear slurry; And
Described the first deironing rear slurry is supplied in horizontal reacting still, and introduces steam and oxygen in described horizontal reacting still, to carry out the second deironing processing in described horizontal reacting still, and obtain the second deironing rear slurry.
2. method according to claim 1, is characterized in that, in described iron content solution of zinc sulfate, zinc concentration is not higher than 100g/L.
3. method according to claim 1, is characterized in that, in described iron content solution of zinc sulfate is supplied to vertical response still before, in advance described iron content solution of zinc sulfate is heated to 80～100 degrees Celsius, preferably 90 degrees Celsius.
4. method according to claim 1, is characterized in that, it is to be to carry out completing for 0.5～1 hour under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature that described the first deironing is processed.
5. method according to claim 1, is characterized in that, it is to be to carry out completing for 2～3 hours under 170～200 degrees Celsius, the oxygen partial pressure condition that is 0.2～0.4MPa in temperature that described the second deironing is processed.
6. method according to claim 1, is characterized in that, further comprises:
Described the second deironing rear slurry is carried out to the processing of flash distillation decrease temperature and pressure, and obtain the second deironing rear slurry through flash distillation processing; And
Described the second deironing rear slurry of processing through flash distillation is carried out to filtration washing, to obtain iron oxide product and the solution after deironing purifies.
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Inventor after: Liu Cheng Inventor after: Dong Aiguo Inventor after: Yin Shuyan Inventor after: Wu Xiao Inventor after: Wang Hongzhen Inventor after: Shen Meiling Inventor after: Fu Jianguo Inventor before: Dong Aiguo Inventor before: Yin Shuyan Inventor before: Wu Xiao Inventor before: Wang Hongzhen Inventor before: Shen Meiling Inventor before: Fu Jianguo |