CN101082095A - Method for extracting nickel iron alloy from laterite ore - Google Patents
Method for extracting nickel iron alloy from laterite ore Download PDFInfo
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Abstract
The present invention is ferronickel alloy produced with laterite as material, and through pre-treatment, adding flux and reductant, smelting at 1450-1550 deg.c for 45-60 min. The ferronickel alloy contains nickel in 6-18 wt%, impurity P less than 0.05 wt% and C, Si, S, etc. in required amount. The present invention makes it possible to utilize laterite reasonably, and is significant in improving nickel smelting technique, protecting nickel resource and protecting environment.
Description
Technical field the invention belongs to non-ferrous metal pyrometallurgy field.Relate to the method that a kind of laterite (nickel oxide ore) extracts Rhometal, particularly relate to the method for extracting Rhometal with pyrometallurgical smelting.
Background technology is present, and basis, world's nickel reserves (metal) is 5,630 ten thousand tons; Find out that resource surpasses 7,000 ten thousand tons (refer to ore nickeliferous＞1% resource); Wherein 20% is nickel sulfide ore, and 80% is laterite type mineral deposit (oxidized ore); But there is 60% product to come approximately in sulphide ores.The retained reserve of China's nickel is 785.31 ten thousand tons, and what still consumed accounts for about 67% of total reserves with existing production mine.The huge rock nickel minerals has entered middle and advanced stage, and the resource of Jinchuan nickel minerals 80% of reserves maximum concentrates on the deep, mining area, and the exploitation difficulty strengthens.
Because global sulphide ores resource is exhausted day by day, causes the nickel increase of production slow, but because demand increases fast, makes global nickel short supply, thereby caused the highest level since present nickel price is in nineteen ninety.Therefore, the degree of concern of nickel oxide ore is increased day by day, the development and use of nickel oxide ore are put on agenda.
At occurring in nature, the nickel oxide mineral deposit be nickeliferous peridotites in the torrid zone or the subtropics form through extensive long-term weathering leaching is rotten.The Yuanjiang River nickel minerals is the nickel oxide ore of domestic maximum.A large amount of magnesium, iron, silicon and a spot of nickel are contained in this ore deposit.This ore body has comprised the silicic acid nickel minerals (NiMg) of deep layer
6Si
4-O
10(OH)
8The limonite on (serpentine) and top layer (FeNi) O (OH) nH
2O two classes.According to geological prospecting, this upper strata, ore deposit is irony ore deposit (being commonly called as chapeau de fer), and the middle level is the femic ore deposit, and lower floor is magnesia ore deposit (serpentine ore).But because the change of the geology in mineral deposit, the irony ore deposit on top, mineral deposit and the garnirite of bottom usually can not remain on original ore bed, and several ore is everlasting and formation mixed type laterite is occurred in the same mineral deposit.
The processing technological flow of laterite mainly is wet process and firing method process.Wet process mainly contains wet method ammonia and soaks and pressurized acid leaching.
There are nickelic factory, India Su Jinda factory in the Ni Jialuo factory, the USBM of U.S. mineral bureau method flow process, Ya Bulu factory of Queensland ,Australia nickel company of Cuba, Brazilian Tuo Kantisi nickel company, the Soviet Union of Philippines Malin Du Ke mining company in the representative factory that wet method ammonia soaks; The used composition of ores of Ni Jialuo factory: Ni 1.4%, Co 0.06%, SiO
214%, MgO 10.3%, Fe 38%, H
2O 28 ~ 30%; Laterite is directly handled in the technical process that these factories all adopt reducing roasting-normal pressure ammonia to soak-make liquid-heavy nickel-electro deposited nickel (or producing nickel oxide), the shortcoming of this flow process is a long flow path, energy consumption height (45400 ~ 61700KW/t Ni), the rate of recovery of metallic nickel is low, and the metallic nickel rate of recovery of nickelic factory is 78% in the Soviet Union.
That adopts pressurized acid leaching in the wet processing has a Cuba hair A Niechang, handles iron, to bore content higher, contains the seldom ore deposit of (Mg content is low) of serpentine.Its main flow process is: laterite slurrying-pressurized acid leaching-heavy (Ni, Co) S-Ni, Co reclaims.This flow process consumes sour low because of Mg content in the raw material is low, this method should be handled nickeliferous height (＞1.5%), contain the low oxidized ore of magnesium, not so low, the acid consumption high pollution environment of the rate of recovery of nickel.
The method that nickel oxide ore is handled in pyrometallurgy has melting ferronickel and matte smelting abroad.As many Ni Anbo of New Caledonia smeltery, smeltery, metal company eight family, the Japanese Pacific Ocean, SUMITOMO CHEMICAL metal mining company's day to smeltery etc.The composition of ores of many Ni Anbo smeltery, New Caledonia is: Ni 2.5 ~ 2.9%, Fe14 ~ 15%, SiO
235 ~ 40%, MgO20 ~ 28%, H
2O20 ~ 30% adopts revolution-eaf process.The ore characteristics that these producers handle all are that nickel is of high grade, magnesium is high, iron is low.
On the other hand, nickel oxide ore is because minerogentic condition is different with rate of decay, and component difference is bigger, its physical properties difference is also very big, and to Powdered, containing surface water also can be from fluctuation between percentum to percent tens from hundreds of millimeters for its granularity, difference of specific gravity is also big, so treatment process is different.According to the data report, heterogeneity preparation of ore method is roughly divided and is seen Table 1:
Table 1 heterogeneity preparation of ore method
| Ni(％) | Fe(％) | MgO(％) | Treatment process | Remarks |
| ＜1.5 | ＞20~50 | ＜5 | Hydrometallurgy | |
| ＞1.5 | ＜20 | 5~45 | Pyrometallurgy | |
| 1.0± | ＞20 | ＞5 | The present invention | The Yuanjiang River laterite |
For low-grade laterite, and iron height, ore deposit that magnesium is high; Though during once studying and associate, various countries extract the method for nickel, cobalt, and few in industrial application technology flow process, domestic still blank.
As domestic first adopt the Yuanjiang River nickel industry company of wet processing flow processing laterite, through practice, laterite character is fully realized, low because of its composition nickel, iron is high, magnesium is high; Because of it is shaped as earthy, poor permeability, light specific gravity, many, the liquid-solid separation difficulty of suspended substance in the leach liquor; In dump leaching with stir in the process of soaking, the nickel leaching yield is low, the acid consumption is high, and big to environmental influence, comprehensive benefit is poor.So do not recommend to use pyrogenic process abroad for this, also should not be with the ore of wet method, though think that after deliberation its composition is complicated, but cobalt in the ore, copper content are low, and suitable slag making composition is arranged, as long as batching rationally, processing condition are suitable, and it is also suitable to handle with thermal process.
Still do not develop magnesia silicate-type nickel oxide ore resource in China, lack the experience of nickel oxide ore pyrometallurgical smelting process.
Summary of the invention the present invention at main raw material be laterite, its physical properties: outward appearance is brown, particulate, earthy; Little (the 1.1g/cm of proportion
3), surface water and crystal water total amount＞25%, igloss reaches 15%; Nickeliferous 0.99 ~ 1.35% (average out to 1.07%), Co 0.03%, Cu 0.011%, Fe
2O
325.8%, SiO
231.96%, Al
2O
36.9%, CaO 0.34%, MgO 19.7%, the nickel in the ore more than 99% are the silicate form and exist.
The present invention is to be raw material with a kind of laterite (nickel oxide ore), extracts the method for Rhometal with pyrometallurgical smelting.
The objective of the invention is to provides pyrogenic process to produce the method for Rhometal to the laterite of low nickel, high ferro, high magnesium, physical form difference, laterite is obtained nickeliferous 6 ~ 18% commodity Rhometal through pre-treatment-electric furnace reduction melting, and the rate of recovery of nickel is 93 ~ 97%; Slag is as the raw material of producing cement.
The electric furnace reduction smelting process is the main method of producing Rhometal.This method is made reductive agent with carbon, the reduction laterite is produced Rhometal, and furnace charge adds in the stove and with electrode and inserts in the furnace charge, heats material melting by the furnace charge arc heat that has a resistance by electric arc and electric current, molten metal accumulates in furnace bottom, and slag is then on alloy.Adopt the intermittent type smelting process in the testing laboratory, in large-scale commercial production, then adopt the continous way smelting process.Nickel, cobalt/cobalt oxide nearly all in electric furnace all are reduced into metal, and iron oxide reduction becomes the amount of metal by the reduction dosage decision that adds.
Raw material of the present invention, auxiliary material and batching are as table 2, table 3, table 4.
Main raw material is laterite (nickel oxide ore), and its chemical ingredients is: Ni 0.99 ~ 1.35% (average out to 1.07%), Co 0.03%, Cu 0.011%, Fe
2O
325.8%, SiO
231.96%, Al
2O
36.9%, CaO 0.34%, MgO 19.7%.
Auxiliary material comprises flux Wingdale, quartz, fluorite and reductive agent coke powder.
Table 3 raw materials pretreatment (drying) back melting ratio of components
| Raw materials pretreatment (drying) back melting proportion scheme | Main raw material | The mass percent of auxiliary material and main raw material (%) | ||
| Lime | Quartzy | Coke powder | ||
| (％) | 100 | 8~15 | 15~25 | 3~8 |
The direct melting ratio of components of table 2 raw material
| The direct melting proportion scheme of raw material | Main raw material | The mass percent of auxiliary material and main raw material (%) | ||
| Lime | Quartzy | Coke powder | ||
| (％) | 100 | 10~25 | 15~35 | 3~8 |
Table 4 raw materials pretreatment (sintering) back melting ratio of components
| Raw materials pretreatment (sintering) back melting proportion scheme | Main raw material | The mass percent of auxiliary material and main raw material (%) | ||
| Lime | Quartzy | Coke powder | ||
| (％) | 100 | 3~8 | 8~15 | 3~8 |
Method of the present invention comprises: laterite drying and dehydrating, sintering prereduction, electrosmelting obtain operations such as thick Rhometal, refining Rhometal, belong to non-ferrous metal pyrometallurgy field, and concrete steps are as follows:
(1) moisture laterite recited above is heated to 300 ℃ in process furnace, time 2 ~ 4h makes moisture content in the ore＜7%;
(2) dried material is allocated into 5 ~ 8% coke powder and in the sintering cellar for storing things, carried out sintering, 800 ~ 1200 ℃ of temperature, furnace charge sintering time in sintering oven is 4 ~ 6h;
(3) will be by gained sintered material and flux (lime, quartz) and reductive agent (coke powder) by following mixed: sintered material: lime: quartz: nut coke=100: 3 ~ 8: 8 ~ 15: 3 ~ 8, wherein the lime composition is: CaO＞85%, P＜0.02%, S＜0.2%, granularity 50～80mm; Quartzy composition is: SiO
2＞98%, P
2O
5＜0.02%, granularity 5～60mm; The coke powder composition is: C＞82%, S＜0.6%, P＜0.02～0.06, from powdery ~ 20mm;
(4) furnace charge that sinters is added the melting of electric arc furnace submerged arc.
Used electric arc furnace power is the 20KVA single-phase electricfurnace; Burner hearth specification: φ 250 * 350mm; Graphite Electrodes specification: 50 * 50 * 600mm; Specified commutating voltage: 20KW; Induction voltage regulator model: TSTA-100/0.5,
Operating process control condition: electric current: 200 ~ 400A; Voltage: 30 ~ 60V; Smelting temperature: 1450 ~ 1600 ℃; Smelting time: 40 ~ 60min; Process produces smoke content:＜0.5%, and after reclaiming, dust collecting system returns batching;
The gained alloy is nickeliferous: 6 ~ 18%; Slag contains Ni 0.01 ~ 0.1%, FeO 25 ~ 35%, CaO 5 ~ 10%, MgO 10 ~ 16%, Al
2O
35 ~ 12%, SiO
238 ~ 45%.
Main reduction reaction in the process
NiO+C＝Ni+CO↑
FeO+C＝Fe+CO↑
Main slag making reaction in the process
2FeO+SiO
2＝2FeO·SiO
2
MgO+SiO
2＝2MgO·SiO
2
Al
2O
3+CaO+SiO
2＝CaO·Al
2O
3·SiO
2
The refining of thick Rhometal
Nickeliferous 6 ~ 18% in the thick Rhometal of electrosmelting gained, its impurity C, Si, P, S promptly can make commodity ferronickel ingot casting and sell as meeting the requirement of refining the stainless steel plant; If C, Si, P, S (especially P) exceed standard, just need refining, refinery practice is as follows:
Add lime (or yellow soda ash) desulfurization in the cast steel bag, service temperature: 1550 ~ 1600 ℃, Si, P, C are taken off in oxygen blast in converter or converting furnace again, service temperature: 1650 ℃; The Rhometal after qualified of blowing casts 15 or the 22.5Kg/ piece, and the blowing slag returns electrosmelting and reclaims nickel.
The present invention's energy adaptive element complexity, various nickeliferous oxide compound ore or other material of composition fluctuation big (high silicon, high alumina, high ferro, high-moisture).Low-grade laterite is rationally utilized, produce positive effect improving and simplifying nickel smelting technology, protective development nickel resources, increase economic results in society and environment protection.
The present invention compares the advantage of existence with known technology:
1, at not only being not suitable for the pyrogenic process but also the laterite of handy wet processing not, finds a kind of suitable pyrometallurgical smelting process, nickel is effectively separated with impurity such as iron, silicon, calcium, magnesium, obtain thick Rhometal.Nickeliferous 6 ~ 18% in the alloy, reach the specification of quality of stainless steel industry to Rhometal.Whole process flow is simple and direct, reasonable.Metallic nickel rate of recovery height can reach 93 ~ 97% in the ore, is higher than the rate of recovery of wet processing far away, is easy to suitability for industrialized production.
2, impurity C, Si, P, the S in the thick Rhometal of gained of the present invention can rationally be controlled, and needn't refining just can do the sale of commodity ferronickel.Current stainless steel metallurgy industry to the great situation of metallic nickel demand under, market outlook are good.
3, dust rate＜0.5% that produces of the present invention, qualified discharge after gathering dust, and obnoxious flavour such as no sulfurous gas in the flue gas; Gained slag CaO, MgO, Al
2O
3, the FeO total amount is more than 98%, is the solid metallurgical slag that does not change, and can be used as the manufacture of cement raw material; Process water recycles, and outwards discharging is not so the present invention can help environmental protection to the environment influence that works the mischief.
4, the present invention is strong to the adaptability of raw material, applicable to various nickeliferous oxidation materials (contain once, secondary resource), nickel resources is fully utilized and protects, and good popularization value is arranged.
5, technology of the present invention is simple and direct, is convenient to mass-producing and implements, and is directly used in large industrialized production.
Description of drawings: Fig. 1 is technical process of the present invention.
Embodiment embodiment 1: adopt the 1st batch of laterite, composition sees Table 5.
Table 5 Yuanjiang River laterite chemical component table
Prepare burden by the direct melting ratio of components of table 2 raw material, make flux with lime, quartz, fluorite, coke powder is made reductive agent, melting in the 20KVA single-phase arc funace.
Add furnace charge: raw ore 10Kg, lime 1.5Kg, quartzy 2.5Kg, coke powder 0.5Kg (ratio of components: mineral aggregate: lime: quartz: coke powder=100: 15: 25: 5), fusion process electric current: 300A; Voltage: 50V; Smelting temperature: 1450 ~ 1500 ℃; Smelting time: 55min.
Melting obtains alloy 0.93Kg, alloy nickeliferous 8.04%; Obtain slag 8.35Kg, slag nickeliferous 0.06%; Metallic nickel direct yield in the alloy: 93.1%; The metallic nickel rate of loss is 6.24% in the slag; The total yield of nickel is 99.34% in Rhometal and the slag.
Used electric arc furnace power is the 20KVA single-phase electricfurnace; Burner hearth specification: φ 250 * 350mm; Graphite Electrodes specification: 50 * 50 * 600mm; Specified commutating voltage: 20KW, induction voltage regulator model: TSTA-100/0.5,
Operating process control condition: electric current: 200 ~ 400A; Voltage: 30 ~ 60V; Smelting temperature: 1450 ~ 1600 ℃; Smelting time: 40 ~ 60min; Process produces smoke content:＜0.5%, and after reclaiming, dust collecting system returns batching;
Embodiment 2: adopt II to criticize laterite, composition sees Table 6
Table 6 Yuanjiang River laterite chemical component table
Prepare burden by table 3 raw materials pretreatment (drying) back melting ratio of components, make flux with lime, quartz sand, fluorite, coke powder is made reductive agent.With mineral aggregate 10Kg, lime 1.0Kg, quartzy 2.0Kg, coke powder 0.5Kg (ratio of components: mineral aggregate: lime: quartz: coke powder=100: 10: 20: 5) mix after, in retort furnace under 300 ℃ through the 4h drying and dehydrating, add melting in the 20KVA single-phase arc funace then; Fusion process electric current: 200A; Voltage: 50V; Smelting temperature: 1450 ~ 1480 ℃; Smelting time: 50min.
Melting obtains alloy 1.25Kg, alloy nickeliferous 7.20%; Obtain slag 8.12Kg, slag nickeliferous 0.04%; Metallic nickel direct yield in the alloy: 93.75%; The metallic nickel rate of loss is 3.38% in the slag; The total yield of nickel is 97.13% in Rhometal and the slag.
Embodiment 3: adopt III to criticize laterite, at 1100 ℃ of roasting 5h, raw ore and sintered material composition see Table 7 to add 1.6Kg coke powder (ratio in 8% adds) among the raw ore 20Kg.
Table 7 Yuanjiang River laterite chemical component table
Prepare burden by table 4 raw materials pretreatment (sintering) back melting ratio of components, get sintered material 10Kg, add lime 0.5Kg, quartzy 1.0Kg, coke powder 0.5Kg (ratio of components: mineral aggregate: lime: quartz: coke powder=100: 5: 10: 5); Add melting in the 20KVA single-phase arc funace then; Fusion process electric current: 350A; Voltage: 40V; Smelting temperature: 1450 ~ 1520 ℃; Smelting time: 45min.
Melting obtains alloy 1.52Kg, alloy nickeliferous 9.35%; Obtain slag 8.8Kg, slag nickeliferous 0.033%; Metallic nickel direct yield in the alloy: 96.03%; The metallic nickel rate of loss is 1.96% in the slag; The total yield of nickel is 97.99% in Rhometal and the slag.
Claims (3)
1, a kind of method of extracting Rhometal from laterite comprises: laterite drying and dehydrating, sintering prereduction, electrosmelting obtain operations such as thick Rhometal, refining Rhometal, it is characterized in that comprising following steps:
(1) moisture laterite recited above is heated to 300 ℃ in process furnace, time 2 ~ 4h makes moisture content in the ore＜7%;
(2) dried material is allocated into 5 ~ 8% coke powder and in the sintering cellar for storing things, carried out sintering, 800 ~ 1200 ℃ of temperature, furnace charge sintering time in sintering oven is 4 ~ 6h;
(3) will be by gained sintered material and flux (lime, quartz) and reductive agent (coke powder) by following mixed: sintered material: lime: quartz: nut coke=100: 3 ~ 8: 8 ~ 15: 3 ~ 8, wherein the lime composition is: CaO＞85%, P＜0.02%, S＜0.2%, granularity 50～80mm; Quartzy composition is: SiO
2＞98%, P
2O
5＜0.02%, granularity 5～60mm; The coke powder composition is: C＞82%, S＜0.6%, P＜0.02～0.06, from powdery ~ 20mm;
(4) furnace charge that sinters is added the melting of electric arc furnace submerged arc.
2. the method for from laterite, extracting Rhometal according to claim 1, the power that it is characterized in that described electric arc furnace is the 20KVA single-phase electricfurnace; Burner hearth specification: φ 250 * 350mm; Graphite Electrodes specification: 50 * 50 * 600mm; Electric current: 200 ~ 400A; Voltage: 30 ~ 60V; Smelting temperature: 1450 ~ 1600 ℃; Smelting time: 40 ~ 60min.
3, a kind of thick Rhometal refining is smart Rhometal method is as follows:
1. in the cast steel bag, add lime (or yellow soda ash) desulfurization, service temperature: 1550 ~ 1600 ℃;
2. Si, P, C are taken off in oxygen blast in converter or converting furnace, service temperature: 1650 ℃; Alloy is cast 15Kg or 22.5Kg/ piece, and the blowing slag returns electrosmelting and reclaims nickel.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565837B (en) * | 2009-06-03 | 2011-01-19 | 北京矿冶研究总院 | Method for producing electrolytic nickel by laterite nickel-cobalt enrichment |
| CN101463403B (en) * | 2009-01-16 | 2012-04-18 | 洮南市金升冶金产品有限公司 | Nickel iron smelting technique by laterite nickel ore |
| CN110527783A (en) * | 2019-10-14 | 2019-12-03 | 江苏江南铁合金有限公司 | A kind of technique improving the nickel recovery rate in ferronickel production |
| CN111518976A (en) * | 2020-06-12 | 2020-08-11 | 山东煜龙环保科技股份有限公司 | Method for producing ferro-silico-aluminum alloy by using low-grade iron ore powder |
| CN112708714A (en) * | 2020-12-18 | 2021-04-27 | 邢台德勤工矿工程有限公司 | Ferronickel refining process |
| CN113025832A (en) * | 2021-03-02 | 2021-06-25 | 重庆大学 | Nickel extraction and CO mineralization from laterite-nickel ore2Method (2) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102226233B (en) * | 2011-05-27 | 2012-11-21 | 广西盛隆冶金有限公司 | Method and system for pretreating lateritic nickel ore |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5749939A (en) * | 1996-12-04 | 1998-05-12 | Armco Inc. | Melting of NI laterite in making NI alloyed iron or steel |
| CN1300352C (en) * | 2005-09-16 | 2007-02-14 | 刘沈杰 | Nickel-iron smelting process from nickel oxide ore containing crystal water through blast furnace |
| CN1970807A (en) * | 2006-12-05 | 2007-05-30 | 上海成富经济发展有限公司 | Process for electrosmelting ferronickel |
-
2007
- 2007-07-09 CN CNB2007100660196A patent/CN100478477C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463403B (en) * | 2009-01-16 | 2012-04-18 | 洮南市金升冶金产品有限公司 | Nickel iron smelting technique by laterite nickel ore |
| CN101565837B (en) * | 2009-06-03 | 2011-01-19 | 北京矿冶研究总院 | Method for producing electrolytic nickel by laterite nickel-cobalt enrichment |
| CN110527783A (en) * | 2019-10-14 | 2019-12-03 | 江苏江南铁合金有限公司 | A kind of technique improving the nickel recovery rate in ferronickel production |
| CN110527783B (en) * | 2019-10-14 | 2021-05-28 | 江苏江南铁合金有限公司 | Process for improving nickel yield in nickel iron production |
| CN111518976A (en) * | 2020-06-12 | 2020-08-11 | 山东煜龙环保科技股份有限公司 | Method for producing ferro-silico-aluminum alloy by using low-grade iron ore powder |
| 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 |
| CN113025832A (en) * | 2021-03-02 | 2021-06-25 | 重庆大学 | Nickel extraction and CO mineralization from laterite-nickel ore2Method (2) |
| CN113025832B (en) * | 2021-03-02 | 2022-07-15 | 重庆大学 | Nickel extraction and CO mineralization from laterite-nickel ore2Method (2) |
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|---|---|
| CN100478477C (en) | 2009-04-15 |
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