CN101338353A - High sulfur coarse nickel iron refining desulphurization method - Google Patents
High sulfur coarse nickel iron refining desulphurization method Download PDFInfo
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- CN101338353A CN101338353A CNA2008100587960A CN200810058796A CN101338353A CN 101338353 A CN101338353 A CN 101338353A CN A2008100587960 A CNA2008100587960 A CN A2008100587960A CN 200810058796 A CN200810058796 A CN 200810058796A CN 101338353 A CN101338353 A CN 101338353A
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- refining
- nickel iron
- high sulfur
- lime
- soda ash
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 45
- 238000007670 refining Methods 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 38
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000002893 slag Substances 0.000 claims abstract description 22
- 230000006698 induction Effects 0.000 claims abstract description 16
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000010436 fluorite Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 9
- 230000004907 flux Effects 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 5
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 64
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 28
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 28
- 239000004571 lime Substances 0.000 claims description 28
- 239000005864 Sulphur Substances 0.000 claims description 25
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 25
- 235000017550 sodium carbonate Nutrition 0.000 claims description 25
- 238000006477 desulfuration reaction Methods 0.000 claims description 19
- 230000023556 desulfurization Effects 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 235000003599 food sweetener Nutrition 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000003765 sweetening agent Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
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- Treatment Of Steel In Its Molten State (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Abstract
The invention provides a method for the desulphurization of high sulfur crude-nickel iron by refining; a desulfurizing agent of calcined soda or/ and calcareousness with 3 to 10 percent of the quality of the crude-nickel iron and flux fluorite with 0 to 2 percent of the quality of the crude-nickel iron are added in the melt high sulfur crude-nickel iron in a middle-frequency induction furnace; under the effect of electromagnetic stirring and under the condition with a temperature of 1330 to 1630 DEG C, the sulfur in the crude-nickel iron is led to generate action with the calcined soda or the calcareousness for slagging; after refining for 5 to 20 minutes, the slag is removed to obtain the nickel iron the sulfur content of which is less than 0.05 percent and meets the demands for stainless steel smelting; the direct yield of nickel is equal to or more than 97.8 percent. The method of the invention has a simple technique and low energy consumption; the production scale can be flexibly adjusted; besides, the method of the invention is easy to realize industrial production.
Description
Technical field
The present invention relates to a kind of method of high sulfur coarse nickel iron refining desulphurization, belong to non-ferrous metal and technical field of iron alloy production.
Technical background
Industrial, nickel is mainly used to produce stainless steel, Special Alloy Steel and is applied to fields such as nickel plating, ceramic, battery, catalyzer.At present, the nickel product is from sulphide ores more than 60% in the world, but all being present in the red soil nickel ore more than 60% of world's nickel resources total amount.Along with the minimizing gradually of nickel sulfide ore resource in the world, the development and use red soil nickel ore is extremely important to the nickel industrial expansion.
Handle the ferronickel that obtains behind the red soil nickel ore with blast furnace or electric furnace reduction melting, promptly can be used for producing stainless steel through after the refining.Be used to produce stainless steel with ferronickel as the substitute of electrolytic nickel, can reduce the consumption of metallic nickel, increase the source of nickel element, reduce stainless smelting cost, to obtain good economic benefit.
In the thick ferronickel of output,,, will have a strong impact on stainless use properties at blast furnace or electrosmelting red soil nickel ore as not carrying out refining treatment owing to contain impurity such as sulphur, phosphorus, carbon, silicon.But especially sulphur complete miscibility in liquid steel, but solubleness is very little in solid-state iron and steel, adds " hot-short " that easily causes steel or alloy man-hour at metal fever, and therefore, the industrial sulphur content that should as far as possible reduce in steel or the alloy finished product is to reduce the damaging effect of sulphur.Thick ferronickel needs to be used further to stainless production behind the refining desulfuration.
At present, sweetening agents such as soda ash, lime, synthetic slag, carbide of calcium, magnesium are generally adopted in thick ferronickel desulfurization, carry out in the many stoves of ladle, electric furnace, open hearth, converter or Ka Er.The assorted nickel of Ukraine's Pabuk factory uses light ash etc. to carry out secondary desulfurization in steamed stuffed bun, when the soda ash consumption be ferronickel weight 1.0~1.7% the time, the sulphur content of thick ferronickel can be able to be reduced to 0.07~0.10% by 0.2%.When adopting soda ash-magnesium integrated process desulfurization, can make the ferronickel sulphur content reduce to 0.01~0.015% from~0.15%, desulfurization degree improves 20~28% than the method with soda ash or magnesium separately.Muscovite one tame factory uses synthetic lime aluminium slag (CaO 53% and Al in 25 tons cast steel bag
2O
343%) ferronickel has been carried out the secondary desulfurization test, can make the sulphur content of thick ferronickel reduce to 0.015~0.09% by 0.08~0.29%.Patent CN101082095A adopts lime desulfurization, with thick ferronickel in 10 tons of converters in 1500~1620 ℃ by being blown into oxygen and C
3H
8, the sulphur content of thick ferronickel can be reduced to below 0.05% by 0.1~0.5%.Patent CN101139642A adopts yellow soda ash, lime etc. to carry out desulfurization in the many stoves of Ka Er thick ferronickel, and sulphur content is reduced to below 0.02%.Though can the sulphur in the thick ferronickel is near below 0.05% in the many stoves of ladle, electric furnace, open hearth, converter or Ka Er, the oxidizing atmosphere of converter desulfurization is strong, so the quantity of slag is big, and nickel is bigger with the loss of slag, reduces the direct yield of nickel.The stirring intensity of melt is low when ladle, electric furnace, open hearth and the desulfurization of many stoves of Ka Er, causes the desulphurization reaction speed of melt slow, and production efficiency is lower.
Summary of the invention
The present invention is directed to the deficiency that exists in the above-mentioned high sulfur coarse nickel iron refining desulphurization method, the method for the coarse nickel iron refining desulphurization that a kind of technology is simple, flow process short, the ferronickel direct yield is high is provided.
The present invention finishes by following technical proposal: a kind of method of high sulfur coarse nickel iron refining desulphurization is characterized in that through following process steps:
A, in medium-frequency induction furnace, the sweetening agent soda ash that adds thick ferronickel quality 3~10% in the fused high sulfur coarse nickel iron is or/and the flux fluorite of lime and thick ferronickel quality 0~2%, sweetening agent and flux is fusing rapidly at high temperature;
B, be under 1330~1630 ℃ of conditions in function composite by electromagnetic stirring and temperature, sulfur-bearing coarse nickel iron refining 5~20 minutes makes sulphur in the thick ferronickel and soda ash, lime rapid reaction and slag making, after skimming the desulfurization ferronickel.
The refining desulfuration of described thick ferronickel also is applicable in line frequency furnace and carries out.
The thick ferronickel of sulfur-bearing that the present invention is used, its main chemical is: 8.68~10.42%Ni, 80.37~84.58%Fe, 0.56~3.87%Si, 2.03~3.87%C, 0.10~0.15%P, 0.52~1.03%S, 0.53~0.64%Cr.
The reaction formula of sulfur method of the present invention is:
(FeS)+(CaO)=(CaS)+(FeO)
(FeS)+(Na
2CO
3)=(Na
2S)+(FeO)+CO
2
When using lime as sweetening agent, also need to add thick ferronickel quality 1~2% the flux fluorite to reduce the viscosity of slag.But reinforcing desulfuration reaction process under the effect of induction stirring is removed after making the sulphur slag making in the thick ferronickel, obtains sulfur-bearing less than 0.05% ferronickel.
When independent use soda ash desulfurization, best refining time of the present invention is 5 minutes, and best refining temperature is 1360 ℃, and the optimum amount of soda ash is thick ferronickel quality 4%; When independent use lime desulfurization, best refining time of the present invention is 10 minutes, and best refining temperature is 1550 ℃, and it is 7% and 1.5% of thick ferronickel quality that the optimum amount of lime and fluorite is respectively; When using soda ash and lime composite desulfurizing agent, best refining time of the present invention is 7 minutes, and best refining temperature is 1510 ℃, and the optimum amount of soda ash, lime and fluorite is respectively thick ferronickel quality 2%, 4% and 1%.
When described use soda ash and lime composite desulfurizing agent, both mass ratioes are any ratio in the thick ferronickel quality 3~10%.
The present invention compared with prior art has following advantage and effect: adopt such scheme, promptly adopt the intermediate frequency or the line frequency induction furnace of prior art to carry out contactless heating, can make molten metal keep clean, the side effect of having avoided thermal source to produce, the used quantity of slag is few, the contact area of metal and slag is little, under the effect of induction stirring, the even temperature of molten metal, make that each element is evenly distributed very soon in the molten metal, accelerate physical reaction speed between phase interface, help spreading desulfurization and non-metallic inclusion come-up, thereby improve the dynamic conditions etc. of physical-chemical reaction, obtain sulfur-bearing less than 0.05% ferronickel, the direct yield of nickel is greater than 98%, and the ferronickel sulphur content meets stainless smelting ferronickel requirement.Technology of the present invention is simple, and energy consumption is low, and industrial scale can be adjusted flexibly, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the present invention's process flow sheet;
Fig. 2 is another process flow sheet of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
With main chemical is that the high sulfur coarse nickel iron of 8.68%Ni, 84.58%Fe and 0.86%S adds in the medium-frequency induction furnace and is heated to fusing, when temperature reaches 1330 ℃, the soda ash that in stove, is added thick ferronickel quality 3% in the high sulfur coarse nickel iron of induction stirring, soda ash is fusing and react and slag making with sulphur in the thick ferronickel rapidly at high temperature, refining after 10 minutes removes slag, get the refining ferronickel of sulfur-bearing 0.046%, the direct yield of nickel is 98.7%, and the ferronickel sulphur content meets the requirement of stainless steel smelting with ferronickel.
Embodiment 2
With main chemical is that the high sulfur coarse nickel iron of 9.32%Ni, 82.73%Fe and 0.52%S adds in the medium-frequency induction furnace and is heated to fusing, when temperature reaches 1360 ℃, the soda ash that in stove, is added thick ferronickel quality 4% in the high sulfur coarse nickel iron of induction stirring, soda ash is fusing and react and slag making with sulphur in the thick ferronickel rapidly at high temperature, refining after 5 minutes removes slag, ferronickel sulfur-bearing 0.037%, the direct yield of nickel is 98.9%, and the ferronickel sulphur content meets the requirement of stainless steel smelting with ferronickel.
Embodiment 3
With main chemical is that the high sulfur coarse nickel iron of 9.84%Ni, 83.67%Fe and 1.03%S adds in the medium-frequency induction furnace and is heated to fusing, when temperature reaches 1550 ℃, in stove, added the lime of thick ferronickel quality 7% and 1.5% fluorite in the high sulfur coarse nickel iron of induction stirring, lime and fluorite be fusing rapidly at high temperature, sulphur in lime and the thick ferronickel reacts and slag making, refining after 10 minutes removes slag, ferronickel sulfur-bearing 0.041%, the direct yield of nickel is 98.1%, and the ferronickel sulphur content meets the requirement of stainless steel smelting with ferronickel.
Embodiment 4
With main chemical is that the high sulfur coarse nickel iron of 10.42%Ni, 80.37%Fe and 0.72%S adds in the medium-frequency induction furnace and is heated to fusing, when temperature reaches 1630 ℃, in stove, added the lime of thick ferronickel quality 10% and 2% fluorite in the high sulfur coarse nickel iron of induction stirring, lime and fluorite be fusing rapidly at high temperature, sulphur in lime and the thick ferronickel reacts and slag making, refining after 20 minutes removes slag, ferronickel sulfur-bearing 0.029%, the direct yield of nickel is 97.8%, and the ferronickel sulphur content meets the requirement of stainless steel smelting with ferronickel.
Embodiment 5
With main chemical is 9.67%Ni, the high sulfur coarse nickel iron of 81.43%Fe and 0.91%S adds in the medium-frequency induction furnace and is heated to fusing, when temperature reaches 1510 ℃, the soda ash that in stove, is added thick ferronickel quality 2% in the high sulfur coarse nickel iron of induction stirring, 4% lime and 1% fluorite, soda ash, lime and fluorite be fusing rapidly at high temperature, soda ash, sulphur in lime and the thick ferronickel reacts and slag making, refining after 7 minutes removes slag, ferronickel sulfur-bearing 0.038%, the direct yield of nickel is 98.4%, and the ferronickel sulphur content meets the requirement of stainless steel smelting with ferronickel.
Claims (5)
1, a kind of method of high sulfur coarse nickel iron refining desulphurization is characterized in that through following process steps:
A, in medium-frequency induction furnace, the sweetening agent soda ash that adds thick ferronickel quality 3~10% in the fused high sulfur coarse nickel iron is or/and the flux fluorite of lime and thick ferronickel quality 0~2%, sweetening agent and flux is fusing rapidly at high temperature;
B, under function composite by electromagnetic stirring and temperature be under 1330~1630 ℃ the condition, refining 5~20 minutes, sulphur in the thick ferronickel and soda ash or lime react and slag making, remove to obtain sulphur content behind the slag and meet stainless steel smelting requirement ferronickel.
2, the method for a kind of high sulfur coarse nickel iron refining desulphurization according to claim 1 is characterized in that best refining time is 5 minutes when using the soda ash desulfurization separately, and best refining temperature is 1360 ℃, and the optimum amount of soda ash is thick ferronickel quality 4%; When independent use lime desulfurization, best refining time is 10 minutes, and best refining temperature is 1550 ℃, and it is 7% and 1.5% of thick ferronickel quality that the optimum amount of lime and fluorite is respectively; When using soda ash and lime composite desulfurizing agent, best refining time is 7 minutes, and best refining temperature is 1510 ℃, and the optimum amount of soda ash, lime and fluorite is respectively thick ferronickel quality 2%, 4% and 1%.
3, the method for a kind of high sulfur coarse nickel iron refining desulphurization according to claim 1, when it is characterized in that described use soda ash and lime composite desulfurizing agent, both mass ratioes are any ratio in the thick ferronickel quality 3~10%.
4, the method for a kind of high sulfur coarse nickel iron refining desulphurization according to claim 1 is characterized in that the main chemical of high sulfur coarse nickel iron is: 8.68~10.42%Ni, 80.37~84.58%Fe, 0.56~3.87%Si, 2.03~3.87%C, 0.10~0.15%P, 0.52~1.03%S, 0.53~0.64%Cr.
5, the method for a kind of high sulfur coarse nickel iron refining desulphurization according to claim 1 is characterized in that the refining desulfuration process of high sulfur coarse nickel iron also is adapted to carry out in line frequency furnace.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102061358A (en) * | 2011-01-17 | 2011-05-18 | 中国恩菲工程技术有限公司 | Desulfuration refining process of high-sulfur crude ferronickel |
CN102108428A (en) * | 2011-01-17 | 2011-06-29 | 中国恩菲工程技术有限公司 | Refining process of crude nickel iron |
CN112708714A (en) * | 2020-12-18 | 2021-04-27 | 邢台德勤工矿工程有限公司 | Ferronickel refining process |
-
2008
- 2008-08-08 CN CNA2008100587960A patent/CN101338353A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102061358A (en) * | 2011-01-17 | 2011-05-18 | 中国恩菲工程技术有限公司 | Desulfuration refining process of high-sulfur crude ferronickel |
CN102108428A (en) * | 2011-01-17 | 2011-06-29 | 中国恩菲工程技术有限公司 | Refining process of crude nickel iron |
CN102061358B (en) * | 2011-01-17 | 2012-12-26 | 中国恩菲工程技术有限公司 | Desulfuration refining process of high-sulfur crude ferronickel |
CN102108428B (en) * | 2011-01-17 | 2013-04-03 | 中国恩菲工程技术有限公司 | Refining process of crude nickel iron |
CN112708714A (en) * | 2020-12-18 | 2021-04-27 | 邢台德勤工矿工程有限公司 | Ferronickel refining process |
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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