CN102094094B - Process for smelting ferronickel from red soil nickel ore - Google Patents
Process for smelting ferronickel from red soil nickel ore Download PDFInfo
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- CN102094094B CN102094094B CN2011100094310A CN201110009431A CN102094094B CN 102094094 B CN102094094 B CN 102094094B CN 2011100094310 A CN2011100094310 A CN 2011100094310A CN 201110009431 A CN201110009431 A CN 201110009431A CN 102094094 B CN102094094 B CN 102094094B
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Abstract
The invention discloses a method for smelting ferronickel from red soil nickel ore, which comprises the following steps of: 1) mixing the red soil nickel ore with coal dust or coke, and sintering for 2 to 8 hours to obtain sintered nickel ore; 2) smelting the sintered nickel ore, a flux and a reducing agent for 2 to 3 hours in an electric furnace to obtain a crude ferronickel melt; and 3) refining the crude ferronickel melt: a) ensuring that the melt temperature is higher than 1,450DEG C; b) adding a complex desulfurizer into the melt for desulfurization; c) detecting the sulfur content of the melt, stopping desulfurization when the sulfur content is lower than a preset value, detecting the melt temperature when the sulfur content is higher than the preset value, slagging off and raising the temperature of the melt and repeating the step b) until the sulfur content is lower than the preset value when the temperature is below 1,350DEG C, repeating the step b) until the sulfur content is smaller than the preset value when the temperature is higher than 1,350DEG C, and slagging off; d) adding a complex dephosphorization agent into the melt for dephosphorization; and e) casting and demolding to obtain the refined ferronickel alloy. The method has the advantages of simple process and low energy consumption.
Description
Technical field
The present invention relates to the chemical industry metallurgical technology field, especially relate to a kind of technique of smelting ferronickel from red soil nickel ore.
Background technology
As everyone knows, nickel is alloying element important in the metallurgy industry, because the nickel metal has unique performance, have very widely and use producing stainless steel, Special Alloy Steel and be applied to the various fields such as nickel plating, ceramic, cell catalyst, nickel alloy material all occupies very consequence in the development of the national economy and national defense and military construction.
Along with the widespread use of global stainless steel and special steel, cause the main element of metallurgical stainless steel and special steel-nickel metal short supply, cause that price skyrockets.At present, the nickel product is from sulphide ores more than 60% in the world, and all being present in the red soil nickel ore more than 60% of world's nickel resources.Process the ferronickel that red soil nickel ore obtains with blast furnace or electric furnace reduction melting, both can be used as the substitute of electrolytic nickel for the production of stainless steel through after the refining.
In the ferronickel that blast furnace or electric furnace reduction smelting red clay nickel ore obtain, contain the impurity such as sulphur, phosphorus, carbon, silicon.At present the nickel iron refining processing method that adopts of domestic and international large-scale nickel-iron smelting factory generally all is to change dephosphorization in the converter in electric furnace after the desulfurization over to, so complex procedures, energy consumption is high and direct yield ferronickel is low.And the removal of various impurity needs proceed step by step.
Application number is the method that discloses a kind of raw ferro nickel oxygen one-step impurity removing refining in 200810058736.9 the patent application, raw ferro nickel is put into refining furnace after metal charge all melts, or after directly being poured on electric furnace or blast-furnace smelting raw ferro nickel molten iron out in the refining furnace, adding is by yellow soda ash, Wingdale, prepare burden by a certain percentage compound slag making auxiliary agent and the reductive agent ferrosilicon of gained of fluorite blows, after dropping into compound slag making auxiliary agent and reductive agent 10-20 minute, in refining furnace, pass through top blast or bottom blowing mode delivering oxygen, 1450 ℃～1700 ℃ of blowing temperature are cast in the Rhometal liquid injection hot metal ladle that after 15-40 minute oxidation refining is made that blows.Although the method has proposed the concept of simultaneously desulfurization, dephosphorization, for the high thick ferronickel of sulphur content, high sulfur coarse nickel iron needs the amount of Wingdale very large, and disposable adding then is easy to cause the unstable of quality.
Summary of the invention
Purpose of the present invention is intended to solve at least one of above-mentioned technological deficiency, a kind of technique of smelting ferronickel from red soil nickel ore is particularly proposed, can effectively utilize the character of ferronickel self, the sulphur that can remove high-content can reduce power consumption again, simultaneously desulfurization and dephosphorization is finished in to the situation of the strict demand of ferronickel phosphorus content in a reaction vessel satisfying stainless steel production.
In order to achieve the above object, technique according to the smelting ferronickel from red soil nickel ore of the embodiment of the invention, comprise following operation: be that 90: 10～95: 5 ratio is mixed with red soil nickel ore and coal dust or coke according to weight ratio 1), after this utilize rotary kiln 600～1000 ℃ of lower sintering 2～8 hours, obtain the sintering nickel minerals; 2) described sintering nickel minerals, flux and reductive agent are put into electric furnace, under 200V～300V, smelted 2～3 hours, obtain thick ferronickel melt; And 3) described thick ferronickel melt is carried out refining.Wherein, described refining may further comprise the steps: a) initial temperature with the electrosmelting gained is that thick ferronickel melt is poured in the ferronickel tank by melt feeding device (not shown) more than 1450 ℃; B) add composite desulfurizing agent in the thick ferronickel melt in the described ferronickel tank with desulfurization and pass into high pressure gas by the bottom of described ferronickel tank and stir, contain the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described composite desulfurizing agent
2And the CaCO of 3wt%～7wt%; C) in desulfurization, detect termly the sulphur content of described thick ferronickel melt by the thermometric sampling unit, when the sulphur content of described thick ferronickel melt is that 0.03wt% stops desulfurization when following, when being higher than 0.03wt%, the sulphur content of described thick ferronickel melt detects the temperature of described thick ferronickel melt, when temperature be skim below 1350 ℃ the time and by repeating step b after in described melt, passing into oxygen and Al powder described thick ferronickel melt being heated up) until sulphur content be below the 0.03wt% till, repeating step b when temperature is higher than 1350 ℃) until sulphur content be below the 0.03wt% till, obtain Rhometal melt after the desulfurization after skimming; D) pass into oxygen in the Rhometal melt after the described desulfurization and add compound dephosphorization agent and pass into oxygen or rare gas element stirs with dephosphorization by the bottom, obtain Refining Nickel iron alloy liquid after skimming, described compound dephosphorization agent is comprised of slag former and solid oxidizing agent, contains the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described slag former
2And the CaCO of 3wt%～7wt%
3, described solid oxidizing agent is FeO; And e) described Refining Nickel iron alloy liquid is cast, obtain refining Rhometal after the cooling and demolding.
In addition, the technique of the smelting ferronickel from red soil nickel ore of the above embodiment of the present invention can also have following additional technical feature:
According to one embodiment of present invention, step 2) employed described flux is lime in, and described reductive agent is coke or coal, and described sintering nickel minerals: described lime: the weight ratio of described reductive agent is 1: (9～12): (5～7).
According to one embodiment of present invention, the sulphur content of described thick ferronickel is more than the 0.25wt%.
According to one embodiment of present invention, described composite desulfurizing agent also contains the Al powder of 1～10wt% and/or the C powder of 1～10wt%.
According to one embodiment of present invention, the particle diameter of described composite desulfurizing agent is below the 75 μ m.
According to one embodiment of present invention, described composite desulfurizing agent adds by the mode of top winding-up take pressurized gas as carrier.
According to one embodiment of present invention, described slag former adds by the mode of top winding-up take pressurized gas as carrier, and described solid oxidizing agent is powder or block, adds by mode of vibration.
Compared with prior art, the present invention has one of following advantages at least:
Technique according to smelting ferronickel from red soil nickel ore of the present invention, with the removal of impurities of in the ferronickel tank, directly jetting of the high sulfur coarse nickel iron of electric furnace output, reduce the process of tank switching, shorten the operating time, reduce thermal losses, and can be implemented in the removing process that carries out plurality of impurities in the same device.In addition, and existing technique simplified in comparison processing step, reduced investment, also capable of reducing energy consumption simultaneously.This Processes and apparatus is very flexible, can take corresponding removal of impurities measure according to the difference of red soil nickel ore composition.
According to the technique of smelting ferronickel from red soil nickel ore of the present invention, employed composite desulfurizing agent and lower, the convenient transportation of compound dephosphorization agent cost.In addition, the thick ferronickel of electric furnace output directly can be transported to the winding-up position in the ferronickel tank, thereby can reduce process, shortening operating time, the reduction thermal losses of tank switching.
And the sulphur content of handled nickel minerals can be up to more than 0.58%, and sulphur content reaches below 0.02% after processing, and can satisfy stainless steel plant's standard.And this technique has also solved the problem of temperature drop in the sweetening process, thereby can guarantee the quality of product after the refining.
The aspect that the present invention adds 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.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment below in conjunction with accompanying drawing, wherein:
Fig. 1 is the synoptic diagram of employed ferronickel refining system in the technique of smelting ferronickel from red soil nickel ore according to an embodiment of the invention; And
Fig. 2 is the schematic flow sheet of the technique of the smelting ferronickel from red soil nickel ore of the ferronickel refining system of use Fig. 1.
Embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings, and wherein identical or similar label represents identical or similar element or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, only be used for explaining the present invention, and can not be interpreted as limitation of the present invention.
Disclosing hereinafter provides many different embodiment or example to be used for realizing different structure of the present invention.In addition, the various specific technique that the invention provides and the example of material, but those of ordinary skills can recognize the property of can be applicable to of other techniques and/or the use of other materials.
I) ferronickel refining system
The employed ferronickel refining system of dephosphorization refinery practice of 1 pair of phosphorus-containing coarse nickel iron of the present invention is described at first, with reference to the accompanying drawings.Fig. 1 shows ferronickel refining system synoptic diagram according to an embodiment of the invention.
As shown in Figure 1, the ferronickel refining system according to the embodiment of the invention comprises ferronickel tank 1, melt feeding device (not shown), ferronickel tank running gear 2, solid oxidizing agent adding set 8, slag former adding set 9, top oxygen blowing device 7, bottom blowing device 12, temperature-detecting device, sampling unit and device for removing slag 11.
Particularly, described ferronickel tank 1 top is provided with opening and the bottom arranges bottom gas entrance.
Described melt feeding device links to each other with the opening of described ferronickel tank 1 and adds described ferronickel tank 1 for the thick ferronickel melt with melting.
Described ferronickel tank 1 is set with mobile and the described ferronickel tank 1 that tilts at described ferronickel tank running gear 2.
Described solid oxidizing agent adding set 8 links to each other with described opening in order to ferronickel tank 1 interior interpolation iron protoxide.In a concrete example, described solid oxidizing agent adding set 8 is vibration material feeding.Thus, can realize by solid oxidizing agent FeO the dephosphorization etc. of ferronickel melt.
Slag former adding set 9 links to each other with the opening of described ferronickel tank 1 and is used for to ferronickel tank 1 interior interpolation slag former.
Top oxygen blowing device 7 comprises oxygen canister 7a and is connected to the oxygen lance 7b of oxygen canister 7a below that described oxygen lance 7b is inserted in the ferronickel tank 1 for spray oxygen in the melt of ferronickel tank 1 from the described opening of ferronickel tank 1.
Bottom blowing device 12 links to each other to spray into gas from the bottom in described ferronickel tank 1 with the described bottom gas entrance of ferronickel tank 1.
Temperature-detecting device carries out skimming after the desulfurization or continuing desulfurization operations with detection for detection of the melt temperature in the ferronickel tank 1.
Thereby the melt sample that sampling unit is used for gathering in the ferronickel tank carries out dephosphorization or intensification desulfurization operations with the foreign matter content detection of measuring in the melt.
Device for removing slag 11 is used at the slag that removes after the desulfurization and behind the dephosphorization above the ferronickel tank 1 interior melt.
Thus, the character that can effectively utilize josephinite self removes the phosphorus of high-content when reducing electric energy loss.In addition, this system can also and realize desulfurization and dephosphorization in to the situation of the strict demand of ferronickel foreign matter content satisfying stainless steel production in a reaction vessel.In addition, this ferronickel refining system and existing system simplified in comparison equipment, reduced investment, also capable of reducing energy consumption simultaneously.And this ferronickel refining system is very flexible, can take corresponding removal of impurities measure according to the difference of thick ferronickel composition.In addition, the removal of impurities of the high sulfur coarse nickel iron of electric furnace output directly can being jetted in the ferronickel tank of this ferronickel refining system reduces the process of tank switching, shortens the operating time, reduces thermal losses.
Need to prove that solid oxidizing agent also can mix with slag former and add by slag former adding set 9, and solid oxidizing agent adding set 8 and slag former adding set 9 are arranged respectively just a preferred embodiment of the present invention.Because slag former itself namely has the slag making effect, also shown in following, can remove the impurity such as Si, S in the ferronickel melt, can carry out at first for the impurity content of ferronickel melt that the identical slag former of recycling carries out slag making in dephosphorization after desulfurization, the desiliconization and solid oxidizing agent adding set 8 and slag former adding set 9 arranged respectively, so setting then need not the slag former in the slag former hopper is changed and used same equipment can realize neatly the impurity removing refining of the ferronickel melt of the different impurity contents of different batches.
In addition, spill in the removal of impurities process in order to prevent melt, described ferronickel refining system can also comprise splash guard 3; And splash guard lifting device 31.Described splash guard lifting device 31 is connected with described splash guard 3 so that splash guard 3 movement between the second position of the first location of the opening that covers ferronickel tank 1 and the opening that leaves the ferronickel tank.
In some of them embodiment of the present invention in the employed ferronickel refining system, described ferronickel refining system can also comprise aluminium powder adding set 14, and described aluminium powder adding set 14 links to each other with described opening when being lower than sulphur content in preset temperature and the melt and being higher than preset value with the melt temperature in the ferronickel tank to ferronickel tank 1 interior interpolation aluminium powder.In a concrete example, described aluminium powder adding set 14 is vibration material feeding.Thus, can make itself and oxygen generation oxidizing reaction by adding aluminium powder when needed according to the variation of melt temperature in the removal of impurities process, thereby owing to this oxidizing reaction is that temperature reaction need not the temperature that heating installation can improve melt.
In some of them embodiment of the present invention in the employed ferronickel refining system, in order to prevent causing that powder disperses when adding aluminum oxide or iron protoxide powder etc., described ferronickel refining system can also comprise the dust gathering arrester 4 that is arranged on described splash guard 3 tops.
In some of them embodiment of the present invention in the employed ferronickel refining system, in the ferronickel refining system of some of them embodiment of the present invention, slag former adding set 9 comprises slag former hopper 9a, be connected to the slag former winding-up tank 9b of slag former hopper 9a lower end and be connected to the slag former spray gun 9c of slag former winding-up tank 9b lower end.Slag former spray gun 9c is used for slag former is sprayed into melt in the ferronickel tank in described opening is inserted into described ferronickel tank melt.Thus, by take dried compressed air or nitrogen as carrier joins slag former in the ferronickel melt, increased the dispersiveness of slag former in the ferronickel melt, thereby can when improving dust removal rate, improve impurity-eliminating effect.Sealed valve, control wearable valve can be set to control the winding-up of slag former before and after the slag former winding-up tank 9b.
In some of them embodiment of the present invention, in the employed ferronickel refining system, be provided with the screen cloth that the fineness of described slag former is controlled in the slag former hopper 9a, such as 200 orders (being that particle diameter is less than 75 μ m) or thinner screen cloth.Thus, be conducive to the dispersion of slag former in melt, can improve speed of response simultaneously.
In some of them embodiment of the present invention in the employed ferronickel refining system, the slag former adding set also comprises fluidizator (not shown), and described fluidizator is arranged between slag former hopper 9a and the slag former winding-up tank 9b so that described slag former fluidization.Thus, make described slag former be more convenient for carrying.
In some of them embodiment of the present invention, in the employed ferronickel refining system, be provided with the screen cloth that the fineness of described slag former is controlled in the slag former winding-up tank 9a, such as 200 orders (being that particle diameter is less than 75 μ m) or thinner screen cloth.Thus, be conducive to the dispersion of slag former in melt, can improve speed of response simultaneously.
In addition, described ferronickel refining system can also comprise waste residue recycling and processing device 13, and described waste residue recycling and processing device 13 and described ferronickel tank 1 adjacent setting are in order to reclaim and process the slag that is removed by described device for removing slag 11.Thus, by the slag that removes of recycling, thus various compositions to containing in the slag as required, such as Ca, Al, S, P, Si etc. recycles.
Preferably, temperature-detecting device and sampling unit are integrated into one and become thermometric sampling unit 10.Can make so the simpler compactness of ferronickel refining system, operability is stronger.
II) nickel iron refining technique
Below, the technique of the smelting ferronickel from red soil nickel ore of the ferronickel refining system that uses Fig. 1 is described with reference to figure 2.
Embodiment 1
Below with reference to the technique of Fig. 2 description according to the smelting ferronickel from red soil nickel ore of the embodiment of the invention 1, Fig. 1 shows the schematic flow sheet according to the technique of the smelting ferronickel from red soil nickel ore of present embodiment 1.
Step 1: be that 90: 10～95: 5 ratio is mixed with red soil nickel ore and coal dust or coke according to weight ratio, after this utilize rotary kiln 600～1000 ℃ of lower sintering 2～8 hours, obtain the sintering nickel minerals.
For example, be that 90: 10 ratio is mixed with red soil nickel ore and coal dust or coke powder according to weight ratio, after this utilize rotary kiln 800 ℃ of lower sintering 5 hours, obtain the sintering nickel minerals.
Step 2: after this, described sintering nickel minerals, flux and reductive agent are put into electric furnace under 200V～300V, smelted 1～3 hour, obtain thick ferronickel.
Step 3: then, pour the high sulfur coarse nickel iron of electric furnace output into the ferronickel tank, and carry out refining according to following steps, thereby obtain the refining ferronickel.
A): at first, it is the melt of the high sulfur coarse nickel iron more than 1450 ℃ that initial temperature is provided.Particularly, can use the melt of the thick ferronickel of Combustion in High Temperature High Sulfur that electrosmelting obtains, be that thick ferronickel melt is poured in the ferronickel tank 1 by melt feeding device (not shown) more than 1450 ℃ with the initial temperature of electrosmelting gained, the ferronickel tank 1 that after this by ferronickel tank running gear 2 thick ferronickel melt will be housed moves to the refining station.Thus can be directly the high sulfur coarse nickel iron of high temperature be carried out refining, thereby save the link such as heat, can energy efficient.
B): after this, above ferronickel tank 1, install successively splash guard 3 and dust gathering arrester 4 additional, and the cleaner spray gun 9b of cleaner adding set 9 is inserted into predetermined depth in the melt, add in the melt take pressurized gas as carrier and contain CaO, CaCO
3, CaF
2Composite desulfurizing agent to carry out desulfurization.Passing into high pressure gas by bottom blowing device 12 in the ferronickel tank 1 simultaneously stirs.Particularly, described high pressure gas can be compressed nitrogens or such as rare gas elementes such as argon gas.Because native system is provided with bottom blowing device 12, can overcome therefore that traditional electric furnace can't stir and the problem such as speed of response is slow, reaction efficiency is low.
C): the sulphur content by 10 pairs of described melts of thermometric sampling unit detects termly in desulfurization, when sulphur content is that preset value stops refining when following, when sulphur content is higher than preset value then according to melt temperature different continues stirring desulphurization or after skimming, heating up the continuation stirring desulphurization obtain thus Rhometal melt after the desulfurization until till sulphur content reaches product requirement.
Particularly, when temperature is (for example 1350 ℃ of preset temperatures, preferred 1400 ℃) stop refining when following and skim, and after skimming, in melt, add aluminium powder by aluminium powder adding set 14, and pass through oxygen lance 7 and in melt, jet oxygen so that melt heats up, after this proceed stirring, desulfurization.Described skimming removed splash guard 3 by splash guard lifting gear 31 particularly, the angle of utilizing ferronickel tank running gear 2 to make ferronickel tank 1 tilt to be scheduled to, and skim by device for removing slag 11, the slag that removes recycles by waste residue recycling and processing device 13.When being higher than preset temperature (for example 1350 ℃, preferred 1400 ℃), temperature continues stirring, desulfurization.
D): after this, add compound dephosphorization agent in the Rhometal melt after the described desulfurization, be blown into simultaneously oxygen from the top and pass into high pressure gas by the bottom and stir with dephosphorization, obtain Refining Nickel iron alloy liquid.Because native system is provided with bottom blowing device 12, can overcome therefore that traditional electric furnace can't stir and the problem such as speed of response is slow, reaction efficiency is low.
Particularly, described compound dephosphorization agent comprises slag former and solid oxidizing agent.Slag former described in the concrete example can be take pressurized gas as carrier in the melt winding-up add.Described solid oxidizing agent is iron protoxide (FeO), can add with mode of vibration by the solid oxidizing agent adding set.The described high pressure gas that passed into by the bottom can be compressed nitrogens or such as rare gas elementes such as argon gas.
Preferably, contain the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described slag former
2And the CaCO of 3wt%～7wt%
3Particularly, the usage quantity of slag former and solid oxidizing agent can be according to containing of ferronickel, assorted situation be different changes, by adding progressively until the impurity content of melt meet till the product requirement.
E): after dephosphorisation reaction finishes, skim, cast, obtain refining Rhometal after the cooling and demolding.
In the present embodiment, relate to following reaction:
1) desulfurization
Owing to be in reducing atmosphere from the thick ferronickel melt of electrosmelting gained, process so at first this melt is carried out desulfurization.
According to a preferred embodiment of the present invention, contain the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described composite desulfurizing agent
2And the CaCO of 3wt%～7wt%
3
In above-mentioned refining process, in sweetening process, relate to following reaction:
2S+2CaO＝2CaS+O
2 (1)
Si+O
2＝SiO
2 (2)
CaO+SiO
2＝CaSiO
3 (3)
Because the CaS that reaction (1) generates will directly enter in the slag.And by reaction formula (2) as can be known, in the situation that adds the composite desulfurizing agent take CaO as main component of the present invention, in desulfurization, can also remove silicon.
Because the SiO that contained impurity Si forms through oxidation in CaO and the thick ferronickel
2Generate CaSiO by above-mentioned reaction formula (3) reaction
3, and the CaSiO that generates
3For film like and be wrapped in the surface of CaO, therefore affected further desulfurization.Given this, by in composite desulfurizing agent, containing certain low-melting CaF
2, can destroy CaSiO
3Film.And on the other hand, add a certain amount of CaCO
3Then can improve by following reaction (4) flowability of melt, improve sweetening effectiveness.
CaCO
3＝CaO+CO
2 (4)
And according to a preferred embodiment of the present invention, can also contain Al and/or carbon dust in the composite desulfurizing agent.In the case, following reaction will occur:
2Al+3O
2＝Al
2O
3 (5)
2C+O
2＝2CO (6)
2CO+O
2＝2CO
2 (7)
Reaction (5), (7) can increase the flowability of melt on the one hand, thereby can compensate the caused calorific loss because cold burden is jetted because above-mentioned reaction is thermopositive reaction on the one hand.
Except above-mentioned reaction, also carry out following reaction in the melt:
2[P]+5[O]＝(P
2O
5) (8)
(P
2O
5)+4CaO＝4CaO·P
2O
5 (9)
Therefore, in desulfurization, its phosphorus content also decreases.
According to a preferred embodiment of the present invention, the granularity of described composite desulfurizing agent is controlled at below the 75 μ m.Be controlled at below the 75 μ m by the granularity with composite desulfurizing agent, can promote desulphurization reaction to carry out fast.
In sweetening process, because cold burden winding-up and the bottom ventilation in the winding-up process stir heat radiation, therefore can cause the loss of heat.Above-mentioned reaction (2) is thermopositive reaction, can compensate the cold burden caused calorific loss of jetting when silicon content is higher than 2wt%.And when the not enough 2wt% of silicone content in the ferronickel, need to solve the temperature drop problem by other intensification means.Drop to preset value (for example 1350 ℃, preferred 1400 ℃) when following in temperature, need to stop desulfurization and the rear further intensification of skimming, guarantee carrying out smoothly of sulfur removal technology when improving desulphurization reaction speed and reaction efficiency.According to a preferred embodiment of the present invention, can pass into oxygen or aluminium powder and make its oxidizing reaction that for example above-mentioned (2), (5), (7) occur to realize described intensification.
Through behind the aforesaid sulfur removal technology, can make the sulphur content of melt reach product requirement.
2) dephosphorization
According to the particular case of the contained phosphorus content of the thick ferronickel of raw material, behind desulfurizing and refining, further also carried out dephosphorization for wherein contained phosphorus impurities.
Because some is removed by reaction formula (8), (9) its contained phosphorus in sweetening process, in ensuing dephosphorizing process, except lime, Wingdale, fluorite, also further add iron protoxide powder or block.Therefore, in dephosphorizing process, following reaction except occuring, occurs also in (8), (9) reaction:
2P+5FeO+4CaO＝4CaO·P
2O
5+5Fe (10)
Particularly, contained impurity and content (weight content) thereof are as follows in the handled thick ferronickel sample:
| S | Si | P | C | Cr |
| 0.50％ | 0.4％ | 0.1％ | 1.9％ | 0.2％ |
After desulfurization and dephosphorization refining, the foreign matter content in the Rhometal of gained refining (weight content) is as follows:
| S | Si | P | C | Cr |
| 0.03％ | 0.02％ | 0.015％ | 0.03％ | 0.1％ |
Hence one can see that, according to the ferronickel refining system of the embodiment of the invention, the sulfur impurity in the ferronickel, phosphorus, carbon, silicon etc. can be reduced to and satisfy the desired level of Refining Nickel iron product.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment that scope of the present invention is by claims and be equal to and limit.
Claims (7)
1. the technique of a smelting ferronickel from red soil nickel ore is characterized in that, may further comprise the steps:
1) is that 90: 10～95: 5 ratio is mixed with red soil nickel ore and coal dust or coke according to weight ratio, after this utilizes rotary kiln 600～1000 ℃ of lower sintering 2～8 hours, obtain the sintering nickel minerals;
2) described sintering nickel minerals, flux and reductive agent are put into electric furnace, under 200V～300V, smelted 2～3 hours, obtain thick ferronickel melt; And
3) described thick ferronickel melt is carried out refining, described refining may further comprise the steps:
A) initial temperature with the electrosmelting gained is that thick ferronickel melt is poured in the ferronickel tank by the melt feeding device more than 1450 ℃;
B) add composite desulfurizing agent in the thick ferronickel melt in the described ferronickel tank with desulfurization and pass into high pressure gas by the bottom of described ferronickel tank and stir, contain the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described composite desulfurizing agent
2And the CaCO of 3wt%～7wt%
3
C) in desulfurization, detect termly the sulphur content of described thick ferronickel melt by the thermometric sampling unit,
When the sulphur content of described thick ferronickel melt is that 0.03wt% stops desulfurization when following,
When being higher than 0.03wt%, the sulphur content of described thick ferronickel melt detects the temperature of described thick ferronickel melt,
When temperature be skim below 1350 ℃ the time and by repeating step b after in described melt, passing into oxygen and Al powder described thick ferronickel melt being heated up) until sulphur content be below the 0.03wt% till,
Repeating step b when temperature is higher than 1350 ℃) until sulphur content be below the 0.03wt% till, obtain Rhometal melt after the desulfurization after skimming;
D) pass into oxygen in the Rhometal melt after the described desulfurization and add compound dephosphorization agent and pass into oxygen or rare gas element stirs with dephosphorization by the bottom, obtain Refining Nickel iron alloy liquid after skimming, described compound dephosphorization agent is comprised of slag former and solid oxidizing agent, contains the CaO of 82wt%～92wt%, the CaF of 2wt%～10wt% in the described slag former
2And the CaCO of 3wt%～7wt%
3, described solid oxidizing agent is FeO; And
E) described Refining Nickel iron alloy liquid is cast, obtain refining Rhometal after the cooling and demolding.
2. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1, it is characterized in that, step 2) employed described flux is lime in, described reductive agent is coke or coal, and described sintering nickel minerals: described lime: the weight ratio of described reductive agent is 1: (9～12): (5～7).
3. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1 is characterized in that, the sulphur content of described thick ferronickel is more than the 0.25wt%.
4. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1 is characterized in that, described composite desulfurizing agent also contains the Al powder of 1～10wt% and/or the C powder of 1～10wt%.
5. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1 is characterized in that, the particle diameter of described composite desulfurizing agent is below the 75 μ m.
6. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1 is characterized in that, described composite desulfurizing agent adds by the mode of top winding-up take pressurized gas as carrier.
7. the technique of smelting ferronickel from red soil nickel ore as claimed in claim 1 is characterized in that, described slag former adds by the mode of top winding-up take pressurized gas as carrier, and described solid oxidizing agent is powder or block, adds by mode of vibration.
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| CN103451457B (en) * | 2013-08-26 | 2015-08-26 | 江苏大学 | A kind of method preparing high-quality ferronickel |
| CN108220623B (en) * | 2017-12-21 | 2020-04-24 | 中南大学 | Method for reducing energy consumption of RKEF process ferronickel production |
| CN110616284B (en) * | 2019-10-24 | 2021-10-15 | 中南大学 | High-efficiency alkali metal carbonate double-salt flux for smelting ferronickel in laterite-nickel ore electric furnace |
| CN111910039B (en) * | 2020-07-28 | 2021-03-23 | 王平 | Method for treating surface layer ores of laterite-nickel ores by three-stage reduction method |
| CN112458227A (en) * | 2020-10-27 | 2021-03-09 | 扬州一川镍业有限公司 | Dephosphorization equipment for producing nickel pig iron by using laterite-nickel ore and using method thereof |
| CN112391570B (en) * | 2020-11-03 | 2021-08-24 | 福建三宝钢铁有限公司 | Steelmaking process of cold-rolled base material for deep drawing |
| CN112708714B (en) * | 2020-12-18 | 2021-08-17 | 邢台德勤工矿工程有限公司 | Ferronickel refining process |
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