CN106435188A - Treatment method and system for hot metallized pellets - Google Patents
Treatment method and system for hot metallized pellets Download PDFInfo
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- CN106435188A CN106435188A CN201610787189.2A CN201610787189A CN106435188A CN 106435188 A CN106435188 A CN 106435188A CN 201610787189 A CN201610787189 A CN 201610787189A CN 106435188 A CN106435188 A CN 106435188A
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- grinding
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- thermal state
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
- C21B13/0046—Making spongy iron or liquid steel, by direct processes making metallised agglomerates or iron oxide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a treatment method and system for hot metallized pellets. The treatment method for the hot metallized pellets is disclosed firstly, an alkaline water quenching solution is prepared from a tin stripping waste liquid and carbide slag, and the metallized pellets are subjected to a replacement reaction to generate metallic tin and ferrous ions by the aid of sensible heat produced when the hot metallized pellets are subjected to water quenching in the alkaline water quenching solution; the ferrous ions react with the carbide slag to generate ferrous hydroxide sediment; and subsequently, metallic iron/iron alloy particles, iron oxide red and metallic tin are obtained through treatment such as grinding, magnetic separation, gravity concentration, calcination and the like. The system for implementing the treatment method is further disclosed and comprises a water quenching device for the hot metallized pellets, a grinding device, a magnetic separation device, a gravity concentration grading device, a calcination device and a gravity concentration separating device. With the treatment method and system for the hot metallized pellets, the hot metallized pellets, the carbide slag and the tin stripping waste liquid are utilized comprehensively, and high-quality iron products, the high-quality iron oxide red and the high-quality metallic tin are produced.
Description
Technical field
The present invention relates to the processing method of a kind of thermal state metal pellet, further relate to the process of a kind of thermal state metal pellet
System, belongs to metallurgical technology field.
Background technology
Metallized pellet refers generally to the roasted product that ferrous material pelletizing obtains after direct-reduction, and wherein iron is mainly with gold
Presented in belonging to iron or ferroalloy (in ferroalloy, iron exists) by metallic iron form, therefore its degree of metalization is typically up to 60%
～95%.At present, metallized pellet many employings two ways is processed, and a kind of mode is that thermal state metal pellet is sent directly into
In smelting furnace, after separating, obtain molten point of iron/ferroalloy and melting slag through fusing；Another mode is that metallized pellet is first through water
Quench, crush, then after ore grinding, magnetic separation separation, obtain metallic iron/ferroalloy particles and mine tailing.Wherein, fusing separate mode is used
When, energy consumption is higher, but can obtain molten point of iron/ferroalloy of high-grade；When using ore grinding, magnetic separation mode to process, thermal state metal
After pelletizing need to first pass through cooling, then carry out ore grinding, magnetic separation, although cost is relatively low, but the grinding particle size because requiring is thin, therefore ore grinding
The energy consumption of process and water consumption occupy bigger proportion in production cost, and the sensible heat of thermal state metal pellet is not obtained by,
Cause the waste of heat.
With the increase of the development of information industry and electronic product demand, printed circuit board industry is flourish.But in print
The manufacturing process of circuit board processed can produce substantial amounts of waste liquid, and tin removal waste liquor is one of maximum waste liquid of generation amount, Qi Zhonghan
Have a large amount of acid and tin element etc..Currently neutralisation, chemical precipitation method, electrolysis, diffusion there is is to ooze the processing method of tin removal waste liquor
Isolating sub-film electrodeposition group technology etc., but said method limiting because of raw material, power consumption etc., production cost is all of a relatively high.
Chinese patent application publication No. CN 103956487 A discloses one and utilizes rotary hearth furnace metallized pellet to prepare phosphorus
The method of acid iron lithium, metallized pellet is carried out crush, grinding, magnetic separation, the multiple operation process such as grinding and secondary magnetic separation, then will
Ferrous alloy is used, and technological process is longer；And this invention uses metallized pellet grinding wet magnetic separation to mix
Material drying and sintering technique, material is successively through high temperature low temperature high temperature and dry method Wet-dry method process, energy consumption
Higher, thus high expensive；Obtained by LiFePO4 be also possible to the impurity brought into because of ferrous alloy and affect its product quality.
Chinese patent application publication No. CN 101200320A discloses a kind of high-carbonaceous metallized pellet for processing waste water and preparation
Method, prepares high-carbonaceous metallized pellet with carbonaceous material and iron-bearing material for raw material, and the method is only applicable to process electrolysis
Filtrate, and need to be in the acidic electrolyte bath aqueous solution, with carbon, iron as anode and cathode, use Fe2+Realize heavy metal with the reduction of carbon
And the reduction recovery of organic pollution, therefore its treatment effect and production cost are all undesirable, and can not realize valuable element
Reclaim, therefore economic benefit is poor.Chinese patent application publication No. CN 104986892A discloses the process side of a kind of tin removal waste liquor
Method, including in tin removal waste liquor add sulfate, regulation pH value to 1.0-1.5, add polyacrylamide flocculant reclaim tin,
The ammoniacal liquor adding concentration to be 18～25% in copper-containing wastewater is neutralized to reclaim copper, then is further processed waste water；
I.e. in different acid-base value systems, the form difference existing due to metal ion makes it separate, and can reclaim tin removal waste liquor step by step
In tin, copper, make full use of the resource in tin removal waste liquor；But this invention is reclaimed the metal obtaining and is existed with hydroxide form,
Its value of the product is relatively low, and needs to carry out under conditions of strong acid, and is repeatedly neutralized precipitation, the therefore requirement to equipment
Higher.
It would therefore be highly desirable to develop processing method and the system of a kind of new thermal state metal pellet, can be by thermal state metal ball
The utilization of group's sensible heat, and realize the comprehensive utilization of thermal state metal pellet and tin removal waste liquor, reduce being processed into of metallized pellet
This.
Content of the invention
First technical problem to be solved by this invention is to provide the processing method of a kind of thermal state metal pellet, the party
Method is capable of the comprehensive utilization of thermal state metal pellet, carbide slag and tin removal waste liquor, output high-quality iron product, iron oxide red
And metallic tin.
Another technical problem to be solved by this invention is to provide the processing system of a kind of thermal state metal pellet.
For solving above-mentioned technical problem, the technical solution used in the present invention is：
First the present invention discloses the processing method of a kind of thermal state metal pellet, comprises the following steps：(1) useless to moving back tin
Liquid adds carbide slag, obtains alkalescence shrend solution；(2) thermal state metal pellet addition alkalescence shrend solution will carry out water
Quench, obtain metallized pellet and alkalescence sensible heat solution；Metallized pellet and alkalescence sensible heat solution reaction, obtain mixed material；(3)
Mixed material carried out grinding and completes reaction further, obtaining grinding slip；(4) grinding slip is carried out magnetic separation separation,
To magnetic material and non-magnetic material；Wherein said magnetic material includes metallic iron/ferroalloy particles and ferrous hydroxide；(5)
Magnetic material is carried out gravity treatment classification, obtains ferrous hydroxide slip, metallic iron/ferroalloy particles；(6) by hydroxide iron charge
Slurry is calcined, and obtains iron oxide red；(7) non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
Wherein, step (1) adds excessive carbide slag in tin removal waste liquor, in order to the pH value obtaining alkalescence shrend solution is
7-9, preferably 8-9.Tin ion content >=the 50mg/L of the described tin removal waste liquor of step (1)；Wherein, described tin removal waste liquor is for printing
The waste liquid producing in circuit boards, containing a large amount of acid and tin element etc.；Described carbide slag is that calcium carbide smelts the waste residue producing, and has
Effect composition is calcium hydroxide.The described thermal state metal pellet of step (2) is the heat that ferrous material pelletizing obtains after direct-reduction
State product of roasting, its temperature is 800-1000 DEG C；Preferably, according to mass percentage, the gold of described thermal state metal pellet
Belonging to rate is 60%-95%, rich in iron granule or ferroalloy in more preferably 80%-95%, and thermal state metal pellet
Particle；Mol ratio >=10 of tin ion in metallic iron and tin removal waste liquor in step (2) control metallized pellet：1, preferably 10-
1000：1.The temperature of step (2) described alkalescence sensible heat solution is 70-100 DEG C, preferably 90-100 DEG C.According to mass percent
Meter, in the described grinding slip of step (3), the particle of fineness≤0.074mm accounts for more than 70%；Tin ion in described grinding slip
Concentration ＜ 4mg/L.Metallic iron/ferroalloy particles of the present invention refers to one of iron granule or ferroalloy particles.
The temperature of thermal state metal pellet is generally 800-1000 DEG C, can be carried for displacement reaction by Water Quenching
For sensible heat solution.Utilize thermal state metal pellet sensible heat, tin removal waste liquor and carbide slag prepare pH value be 7-9, temperature be 70-
In the alkaline sensible heat solution of 100 DEG C, the metallic iron/ferroalloy particles in metallized pellet easily occurs displacement anti-with tin removal waste liquor
Should, generating metallic tin and ferrous ion, metallic tin is wrapped on metallized pellet, can be separated by follow-up grinding process；And
The ferrous ion generating then continues to react generation ferrous hydroxide precipitation with excessive carbide slag (active ingredient is calcium hydroxide),
And can be reclaimed by follow-up magnetic separation separating technology, thus obtain mixed material.In follow-up grinding process, in mixed material
Metallic iron/ferroalloy particles gradually levigate, and with alkalescence sensible heat solution be fully contacted, promote displacement reaction further
With completing of precipitation reaction, and with the generation of displacement reaction, grinding of metallic iron/ferroalloy particles also can be improved further
Property, reduce the iron content in ferroalloy particles, thus be conducive to improving grinding efficiency, it is thus achieved that more high-grade alloy product.
The present invention is found by great many of experiments, and in tin removal waste liquor, tin ion concentration is at more than 50mg/L, by control metal
Pellet and the ratio of tin removal waste liquor so that mol ratio >=10 of tin ion in metallic iron and tin removal waste liquor in metallized pellet：
1, preferably 10-1000：1, it can be ensured that tin ion can farthest be displaced by the metallic iron in metallized pellet so that
Tin ion concentration in follow-up waste liquid is less than 4mg/L, reaches the environmental requirement of industrial wastewater discharge.
The present invention adds carbide slag in tin removal waste liquor, and obtaining pH value is 8-9 alkalescence shrend solution, thus can promote metal
Fully there is displacement reaction in iron and tin ion, and makes the ferrous ion generating all generate ferrous hydroxide precipitation, further
Promote the generation of reduction reaction.If pH value is less than 8, then displacement reaction occurs not exclusively, and ferrous ion precipitation is also incomplete；If
PH value is more than 9, and excessive carbide slag can affect pulp density, thus is unfavorable for the carrying out of grinding process, affects the ore grinding of material
Fineness.
The present invention further discloses a kind of system implementing described processing method, including：Thermal state metal pellet shrend
Device, grinding device, magnetic separating device, gravity treatment grading plant, calciner plant and Gravity separation device.
Wherein, described thermal state metal pellet granulating unit is provided with tin removal waste liquor entrance, carbide slag entrance, thermal state metal
Pelletizing entrance and mixed material outlet；Described grinding device is provided with mixed material entrance and grinding slurry outlet；Described magnetic separation divides
It is provided with grinding slurry inlet, magnetic material outlet and non-magnetic material outlet from device；Described gravity treatment grading plant is provided with magnetic
Material inlet, metallic iron/ferroalloy particles outlet and ferrous hydroxide slurry outlet；Described calciner plant is provided with ferrous hydroxide
Slurry inlet and iron oxide red outlet；Described Gravity separation device is provided with non-magnetic material entrance, metallic tin outlet and mine tailing and goes out
Mouthful.
It is further preferred that the mixed material outlet of described thermal state metal pellet granulating unit and described grinding device
Mixed material entrance is connected；The grinding slurry inlet phase of the grinding slurry outlet of described grinding device and described magnetic separating device
Even；The magnetic material outlet of described magnetic separating device is connected with the magnetic material entrance of described gravity treatment grading plant；Described heavy
The ferrous hydroxide slurry outlet of grading plant is selected to be connected with the ferrous hydroxide slurry inlet of described calciner plant；Described magnetic separation
The non-magnetic material outlet of separator is connected with the non-magnetic material entrance of described Gravity separation device.Wherein, described grinding
Device can be ball mill.
" being connected " of the present invention can be fixing connection, it is also possible to is to removably connect；Can be to be mechanically connected, it is possible to
To be electrical connection；Can be to be directly connected to, it is also possible to be to be indirectly connected to by intermediary.
In present system, thermal state metal pellet granulating unit is used for thermal state metal pellet at alkalescence shrend solution
In carry out shrend, obtain metallized pellet and alkalescence sensible heat solution, and metallized pellet be molten with alkaline sensible heat during shrend
Liquid starts displacement reaction and precipitation reaction, increasingly generates ferrous hydroxide precipitation and metallic tin, obtains mixture further
Material；Described grinding device, for mixed material carrying out grinding and completing displacement reaction and precipitation reaction further, obtains grinding
Slip；Described magnetic separating device, for grinding slip is carried out magnetic separation separation, obtains magnetic material and non-magnetic material, wherein
Magnetic material includes metallic iron/ferroalloy particles and ferrous hydroxide；Described gravity treatment grading plant is for carrying out magnetic material
Gravity treatment is classified, and obtains ferrous hydroxide slip, metallic iron/ferroalloy particles；Described calciner plant is for by hydroxide iron charge
Slurry is calcined, and obtains iron oxide red；Described Gravity separation device, for non-magnetic material is carried out Gravity separation, obtains metal
Tin and mine tailing.
Technical solution of the present invention compared with prior art, has the advantages that：
The present invention, on the premise of not changing metallized pellet existing main body process technique, substitutes with thermal state metal pellet
Straight iron powder or iron filings, and by using the sensible heat that tin removal waste liquor and carbide slag produce during shrend and alkaline condition, and nothing
The ancillary method such as need to stir, shrend and grinding process can complete displacement reaction and precipitation reaction, improve metallization ball
The grindability of group, reduce further shrend water consumption, ore grinding water consumption and ore grinding energy consumption, thus significantly reduces thermal state metal ball
Group, the processing cost of tin removal waste liquor, good in economic efficiency, and tin ion concentration of emission can reach environmental protection and wants in waste water after treatment
Ask.The processing method of thermal state metal pellet of the present invention and system, it is achieved that thermal state metal pellet, carbide slag and tin removal waste liquor
Comprehensive utilization, output high-quality metallic iron/ferroalloy particles, iron oxide red and metallic tin.
Brief description
Fig. 1 is the structural representation of the processing system of thermal state metal pellet of the present invention；
Fig. 2 is the flow chart of the processing method of thermal state metal pellet of the present invention.
Detailed description of the invention
Further describe the present invention below in conjunction with specific embodiment, advantages of the present invention and feature will be with describe and
Apparent.It should be understood that described embodiment is only exemplary, any restriction is not constituted to the scope of the present invention.This area
Skilled artisans appreciated that, lower without departing from the spirit and scope of the present invention can to the details of technical solution of the present invention and
Form is modified or replaces, but these modifications or replacement each fall within protection scope of the present invention.
As it is shown in figure 1, the invention provides the processing system of a kind of thermal state metal pellet, including：Thermal state metal ball
Group's granulating unit the 1st, grinding device the 2nd, magnetic separating device the 3rd, gravity treatment grading plant the 4th, calciner plant 5 and Gravity separation device 6.
Wherein, thermal state metal pellet granulating unit 1 is provided with tin removal waste liquor entrance, carbide slag entrance, thermal state metal ball
Group's entrance and mixed material outlet；Grinding device 2 is provided with mixed material entrance and grinding slurry outlet；Magnetic separating device 3 sets
Have grinding slurry inlet, magnetic material outlet and non-magnetic material outlet；Gravity treatment grading plant 4 is provided with magnetic material entrance, gold
Belong to iron/ferroalloy particles outlet and ferrous hydroxide slurry outlet；Calciner plant 5 is provided with ferrous hydroxide slurry inlet and oxidation
Iron oxide red exports；Gravity separation device 6 is provided with non-magnetic material entrance, metallic tin outlet and mine tailing outlet.
Further, the mixed material outlet of thermal state metal pellet granulating unit 1 and the mixed material of grinding device 2 enter
Mouth is connected；The grinding slurry outlet of grinding device 2 is connected with the grinding slurry inlet of magnetic separating device 3；Magnetic separating device 3
Magnetic material outlet be connected with the magnetic material entrance of gravity treatment grading plant 4；The ferrous hydroxide slip of gravity treatment grading plant 4
Outlet is connected with the ferrous hydroxide slurry inlet of calciner plant 5；The non-magnetic material outlet of magnetic separating device 3 divides with gravity treatment
Non-magnetic material entrance from device 6 is connected.
" being connected " of the present invention can be fixing connection, it is also possible to is to removably connect；Can be to be mechanically connected, it is possible to
To be electrical connection；Can be to be directly connected to, it is also possible to be to be indirectly connected to by intermediary.
The processing system of thermal state metal pellet of the present invention, tin removal waste liquor and carbide slag pass through thermal state metal pellet respectively
The tin removal waste liquor entrance of granulating unit 1, carbide slag entrance enter thermal state metal pellet granulating unit 1, are mixed to get wherein
Alkalescence shrend solution；Thermal state metal pellet adds through the thermal state metal pellet entrance of thermal state metal pellet granulating unit 1
In alkalescence shrend solution, thermal state metal pellet carries out shrend in alkalescence shrend solution, obtains metallized pellet and alkalescence shows
Hot solution, and during shrend, metallized pellet and alkalescence sensible heat solution start displacement reaction and precipitation reaction, generate
Ferrous hydroxide precipitation and metallic tin, obtain mixed material further.Mixed material enters through the mixed material entrance of grinding device 2
Enter grinding device 2, through grinding and complete displacement reaction and precipitation reaction further, obtain grinding slip.Grinding slip is through magnetic separation
The grinding slurry inlet of separator 3 enters magnetic separating device 3, carries out magnetic separation separation, obtains magnetic material and nonmagnetics
Material, wherein magnetic material includes metallic iron/ferroalloy particles and ferrous hydroxide.Magnetic material is through the magnetic of gravity treatment grading plant 4
Property material inlet enter gravity treatment grading plant 4, magnetic material is carried out gravity treatment classification, obtain ferrous hydroxide slip, metallic iron/
Ferroalloy particles.Ferrous hydroxide slip enters calciner plant 5 through the ferrous hydroxide slurry inlet of calciner plant 5, by hydrogen-oxygen
Change ferrous slip to calcine, obtain iron oxide red.Grinding slip is through the nonmagnetics of magnetic separating device 3 magnetic separation isolated
Material, enters Gravity separation device 6 through the non-magnetic material entrance of Gravity separation device 6, non-magnetic material is carried out Gravity separation,
Obtain metallic tin and mine tailing.
Embodiment one
[1] join tin removal waste liquor in granulating unit, then be that the tin removal waste liquor of 500g/L adds to tin ion concentration
Excessive carbide slag waste liquid, (the process flow figure of thermal state metal pellet is shown in figure to obtain the alkaline shrend solution that pH value is 8
2)；
[2] will obtain closing rich in ferronickel after " lateritic nickel ore joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT
Gold grain, degree of metalization are the thermal state metal pellet that the 80%th, temperature is 800 DEG C, are directly thrown in granulating unit, obtain temperature
Degree is the alkaline sensible heat solution of 100 DEG C, by the ratio of control metallized pellet and tin removal waste liquor so that in dilval particle
Metallic iron is 10 with the mol ratio of tin ion in stanniferous waste water：1, the dilval particle in metallized pellet gradually with move back tin give up
Liquid generation displacement reaction, generates metallic tin and ferrous ion, and metallic tin is wrapped on metallized pellet, obtains shrend metallization
Pelletizing, ferrous ion then continues to react generation ferrous hydroxide precipitation with carbide slag, obtains being precipitated by ferrous hydroxide and shrend
The mixed material of metallized pellet composition；
[3] mixed material is sent into ball mill grinding, ore grinding time 40min, with the carrying out of grinding process, complete further
Displacement reaction and precipitation reaction, and to finally give fineness be that below 0.074mm accounts for more than 70%, tin ion concentration is less than 4mg/L
Grinding slip；
[4] grinding slip being carried out magnetic separation separation, obtaining magnetic material and non-magnetic material, wherein magnetic material is ferronickel
Alloying pellet and ferrous hydroxide, non-magnetic material is metallic tin and mine tailing；
[5] magnetic material is carried out gravity treatment classification, obtain the high ferronickel that nickel grade is that the 9.73%th, Iron grade is 63.02%
Alloying pellet, and ferrous hydroxide slip；
[6] ferrous hydroxide slip is calcined, obtain iron oxide red product；
[7] non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
Embodiment two
[1] join tin removal waste liquor in granulating unit, then be that the tin removal waste liquor of 5g/L added to tin ion concentration
The carbide slag waste liquid of amount, obtains the alkaline shrend solution that pH value is 8.5；
[2] will obtain rich in low ferronickel after " nickel fibers slag joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT
Alloying pellet, degree of metalization are the thermal state metal pellet that the 85%th, temperature is 900 DEG C, are directly thrown in granulating unit, obtain
Temperature is the alkaline sensible heat solution of 80 DEG C, by the ratio of control metallized pellet and tin removal waste liquor so that low dilval
In Li, metallic iron and the mol ratio of tin ion in stanniferous waste water are 100：1, the low dilval particle in metallized pellet is gradually
With tin removal waste liquor generation displacement reaction, generating metallic tin and ferrous ion, metallic tin is wrapped on metallized pellet, obtains water
Quenching metallized pellet, ferrous ion then continues to react generation ferrous hydroxide precipitation with carbide slag, obtains being sunk by ferrous hydroxide
Form sediment the mixed material with shrend metallized pellet composition；
[3] mixed material is sent into ball mill grinding, ore grinding time 30min, with the carrying out of grinding process, complete further
Displacement reaction and precipitation reaction, and to finally give fineness be that below 0.074mm accounts for more than 80%, tin ion concentration is less than 4mg/L
Grinding slip；
[4] grinding slip being carried out magnetic separation separation, obtaining magnetic material and non-magnetic material, wherein magnetic material is ferronickel
Alloying pellet and ferrous hydroxide, non-magnetic material is metallic tin and mine tailing；
[5] magnetic material is carried out gravity treatment classification, obtain the low dilval of Iron grade the 90.19%th, nickel content 1.96%
Particle, and ferrous hydroxide slip；
[6] ferrous hydroxide slip is calcined, obtain iron oxide red product；
[7] non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
Embodiment three
[1] join tin removal waste liquor in granulating unit, then be that the tin removal waste liquor of 50mg/L adds to tin ion concentration
Excessive carbide slag waste liquid, obtains the alkaline shrend solution that pH value is 9；
[2] will obtain rich in metallic iron after " iron ore concentrate joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT
Grain, degree of metalization are the thermal state metal pellet that the 95%th, temperature is 1000 DEG C, are directly thrown in granulating unit, obtain temperature
It is the alkaline sensible heat solution of 70 DEG C, by the ratio of control metallized pellet and tin removal waste liquor so that metal in metallized pellet
Iron is 1000 with the mol ratio of tin ion in stanniferous waste liquid：1, the iron granule in metallized pellet is gradually sent out with tin removal waste liquor
Raw displacement reaction, generates metallic tin and ferrous ion, and metallic tin is wrapped on metallized pellet, obtains shrend metallization ball
Group, ferrous ion then continues to react generation ferrous hydroxide precipitation with carbide slag, obtains by ferrous hydroxide precipitation and shrend gold
Belong to the mixed material of pellet composition；
[3] mixed material is sent into ball mill grinding, ore grinding time 20min, with the carrying out of grinding process, complete further
Displacement reaction and precipitation reaction, and to finally give fineness be that below 0.074mm accounts for more than 90%, tin ion concentration is less than 4mg/L
Grinding slip；
[4] grinding slip being carried out magnetic separation separation, obtaining magnetic material and non-magnetic material, wherein magnetic material is metal
Iron particle and ferrous hydroxide, non-magnetic material is metallic tin and mine tailing；
[5] magnetic material is carried out gravity treatment classification, obtain the iron granule of TFe grade 90.97%, and hydroxide
Iron charge is starched；
[6] ferrous hydroxide slip is calcined, obtain iron oxide red product；
[7] non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
Embodiment four
[1] join tin removal waste liquor in granulating unit, then be that the tin removal waste liquor of 50g/L added to tin ion concentration
The carbide slag waste liquid of amount, obtains the alkaline shrend solution that pH value is 7；
[2] will obtain closing rich in ferronickel after " lateritic nickel ore joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT
Gold grain, degree of metalization are the thermal state metal pellet that the 60%th, temperature is 800 DEG C, are directly thrown in granulating unit, obtain temperature
Degree is the alkaline sensible heat solution of 90 DEG C, by the ratio of control metallized pellet and tin removal waste liquor so that in dilval particle
Metallic iron is 10 with the mol ratio of tin ion in stanniferous waste water：1, the dilval particle in metallized pellet gradually with move back tin give up
Liquid generation displacement reaction, generates metallic tin and ferrous ion, and metallic tin is wrapped on metallized pellet, obtains shrend metallization
Pelletizing, ferrous ion then continues to react generation ferrous hydroxide precipitation with carbide slag, obtains being precipitated by ferrous hydroxide and shrend
The mixed material of metallized pellet composition；
[3] mixed material is sent into ball mill grinding, ore grinding time 45min, with the carrying out of grinding process, complete further
Displacement reaction and precipitation reaction, and to finally give fineness be that below 0.074mm accounts for more than 80%, tin ion concentration is less than 4mg/L
Grinding slip；
[4] grinding slip being carried out magnetic separation separation, obtaining magnetic material and non-magnetic material, wherein magnetic material is ferronickel
Alloying pellet and ferrous hydroxide, non-magnetic material is metallic tin and mine tailing；
[5] magnetic material is carried out gravity treatment classification, obtain the high ferronickel that nickel grade is that the 10.24%th, Iron grade is 61.41%
Alloying pellet, and ferrous hydroxide slip；
[6] ferrous hydroxide slip is calcined, obtain iron oxide red product；
[7] non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
Contrast test one
Will be after " lateritic nickel ore joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT, obtaining degree of metalization is 80%
Thermal state metal pellet, after shrend send into ball mill grinding, ore grinding time 50min, obtaining fineness is that below 0.074mm accounts for
The grinding slip of more than 70%, grinding slip separates through magnetic separation, obtains nickel grade 6.03%, and the ferronickel of Iron grade 65.57% closes
Gold grain.
Contrast test two
Will be after " nickel fibers slag joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT, obtaining degree of metalization is 85%
Thermal state metal pellet, after shrend send into ball mill grinding, ore grinding time 40min, obtaining fineness is that below 0.074mm accounts for
The grinding slip of more than 70%, grinding slip separates through magnetic separation, obtains the low ferronickel of nickel grade the 0.89%th, Iron grade 92.35%
Alloying pellet.
Contrast test three
Will be after " iron ore concentrate joins the direct-reduction of carbon pellets rotary hearth furnace " PROCESS FOR TREATMENT, obtaining degree of metalization is 90%
Thermal state metal pellet, sends into ball mill grinding after shrend, and ore grinding time 30min, obtaining fineness is that below 0.074mm accounts for
The grinding slip of more than 70%, grinding slip separates through magnetic separation, obtains the iron granule of Iron grade 92.86%.
Claims (10)
1. the processing method of a thermal state metal pellet, it is characterised in that comprise the following steps：
(1) in tin removal waste liquor, add carbide slag, obtain alkalescence shrend solution；
(2) by thermal state metal pellet addition alkalescence shrend solution carries out shrend, obtain metallized pellet and alkalescence sensible heat is molten
Liquid；Metallized pellet and alkalescence sensible heat solution reaction, obtain mixed material；
(3) mixed material is carried out grinding, obtain grinding slip；
(4) grinding slip is carried out magnetic separation separation, obtain magnetic material and non-magnetic material；
(5) magnetic material is carried out gravity treatment classification, obtain ferrous hydroxide slip, metallic iron/ferroalloy particles；
(6) ferrous hydroxide slip is calcined, obtain iron oxide red；
(7) non-magnetic material is carried out Gravity separation, obtain metallic tin and mine tailing.
2. according to the processing method described in claim 1, it is characterised in that：Step (1) adds the electricity of excess in tin removal waste liquor
Rock ballast, in order to the pH value obtaining alkalescence shrend solution is 7-9, preferably 8-9.
3. according to the processing method described in claim 1, it is characterised in that：The tin ion content of the described tin removal waste liquor of step (1)
≥50mg/L；
Wherein, described tin removal waste liquor is the waste liquid producing during printed circuit board；Described carbide slag is that calcium carbide smelts generation
Waste residue.
4. according to the processing method described in claim 1, it is characterised in that：The described thermal state metal pellet of step (2) is iron content
The hot product of roasting that material pelletizing obtains after direct-reduction, its temperature is 800-1000 DEG C；Preferably, according to percent mass
Than meter, the degree of metalization of described thermal state metal pellet is 60%-95%, more preferably 80%-95%；
Mol ratio >=10 of tin ion in metallic iron and tin removal waste liquor in step (2) control metallized pellet：1, preferably 10-
1000：1.
5. according to the processing method described in claim 1, it is characterised in that：The temperature of step (2) described alkalescence sensible heat solution is
70-100 DEG C, preferably 90-100 DEG C.
6. according to the processing method described in claim 1, it is characterised in that：According to mass percent, the described grinding of step (3)
In slip, the particle of fineness≤0.074mm accounts for more than 70%；The concentration ＜ 4mg/L of tin ion in described grinding slip.
7. the system implementing processing method described in claim 1 to 6 any one, it is characterised in that include：Thermal state metal
Pellet granulating unit, grinding device, magnetic separating device, gravity treatment grading plant, calciner plant and Gravity separation device.
8. according to the system described in claim 7, it is characterised in that：Described thermal state metal pellet granulating unit be provided with move back tin give up
Liquid entrance, carbide slag entrance, thermal state metal pellet entrance and mixed material outlet；
Described grinding device is provided with mixed material entrance and grinding slurry outlet；
Described magnetic separating device is provided with grinding slurry inlet, magnetic material outlet and non-magnetic material outlet；
Described gravity treatment grading plant is provided with magnetic material entrance, metallic iron/ferroalloy particles outlet and ferrous hydroxide slip and goes out
Mouthful；
Described calciner plant is provided with ferrous hydroxide slurry inlet and iron oxide red outlet；
Described Gravity separation device is provided with non-magnetic material entrance, metallic tin outlet and mine tailing outlet.
9. according to the system described in claim 8, it is characterised in that：The mixed material of described thermal state metal pellet granulating unit
Outlet is connected with the mixed material entrance of described grinding device；
The grinding slurry outlet of described grinding device is connected with the grinding slurry inlet of described magnetic separating device；
The magnetic material outlet of described magnetic separating device is connected with the magnetic material entrance of described gravity treatment grading plant；
The ferrous hydroxide slurry inlet phase of the ferrous hydroxide slurry outlet of described gravity treatment grading plant and described calciner plant
Even；
The non-magnetic material outlet of described magnetic separating device is connected with the non-magnetic material entrance of described Gravity separation device.
10. according to the system described in claim 7, it is characterised in that：Described grinding device is ball mill.
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| GB1278207A (en) * | 1970-02-18 | 1972-06-21 | Woodall Duckham Ltd | Improvements trlating to the extracton of tin from its ores |
| CN86105223A (en) * | 1986-08-16 | 1988-03-02 | 戴元宁 | The medium tin ore hydrometallurgy is produced spongy tin and pink salt |
| GB2261443A (en) * | 1991-11-15 | 1993-05-19 | Compeq Manufacturing Co Limite | Process for recovering tin from a waste liquid containing tin recovered from printed circuit boards |
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