CN100383259C - Method for recovering nickel and cobalt from nickel oxide ore and nickel silicide ore - Google Patents

Abstract

The present invention relates to a method for recovering nickel-to-cobalt from nickel oxide ore and nickel silicate ore, which comprises the following procedures: the nickel oxide ore and the nickel silicate ore which are in crude ore are milled until-200 meshes are in the proportion of 80 to 90 wt%; powdered coke with the weight of 5 to 15% of that of the crude ore, a chlorinating agent with the weight of 10 to 30% of that of the crude ore and an auxiliary agent with the weight of 0.1 to 1.0% of that of the crude ore are added to prepare pellets with the particle diameter of 5 to 15MM; then, materials are processed by adopting the technology of chloridization segregation calcination-magnetic separation; the temperature of a high temperature zone of a segregation rotary kiln is controlled to be 1000 to 1300DEG C, the temperature of the kiln tail is controlled to be from 400 to 600DEG C, the rotation rate of the rotary kiln is controlled to be from 0.75 to 2 revolution per minute, and the time is controlled to be 1 to 2 hours; after segregated and calcined, the product which enters a magnetic separator with the magnetic field strength of 1500 to 3000 gauss is separated. Finally, nickel-to-cobalt mixed concentrate can be obtained, the nickel grade is from 5 to 15%, the recovery ratio of the nickel is from 80 to 85%, the cobalt grade is from 0.3 to 1.7%, and the recovery ratio of the cobalt is from 70 to 80%.

Description

From nickel oxide ore silicic acid nickel minerals, reclaim the method for nickel cobalt

One, technical field:

Invention relates to a kind of method that reclaims nickel, cobalt from nickel oxide, silicic acid nickel minerals.Belong to the Mineral Processing Engineering field.

Two, background technology

Because the excellent properties of nickel metal makes nickel become national defense industry and the indispensable raw material of civilian industry, has extremely important status and effect in national economy.Known in the world nickel ore deposit has three types: i.e. cu-ni sulphide ore bed, nickel oxide mineral deposit and weathering crust silicic acid nickel ore deposit.The nickel oxide mineral deposit be nickeliferous peridotites in the torrid zone or the subtropical zone form the argillaceous ore of forming by hydrous oxides such as iron, aluminium, silicon that loosens through large-scale secular weathering leaching is rotten.Because the oxidation of iron, ore takes on a red color, so be called as laterite.Laterite and silicic acid nickel ore deposit account for 3/4ths of present world saving, but the nickel master metal will be formed by the nickel sulfide ore smelting at present, accounts for 60%.Major cause is to extract nickel from nickel sulfide ore, can use simple, economic mechanical beneficiation method, and the selecting and smelting technology of nickel oxide ore, silicic acid nickel minerals does not reach a standard as yet, can't utilize difficulty big with conventional beneficiation method sorting nickel oxide ore, especially silicic acid nickel minerals.The second largest nickel minerals Yuanjiang River nickel minerals of China belongs to the silicic acid nickel minerals, has reconnoitred clearly that reserves are about 540,000 tons, and the Soviet Union helps us to build existing so far nearly 60 years history from the fifties, but fails well exploitation so far.

Under the powerful situation of the current nickel market requirement, the world nickel manufacturer and the investor have an optimistic view of one after another in the production of some nickel oxide ore resource-rich country development and increase nickel and satisfy the demand in nickel market.For example the Cuba of nickel oxide ore reserves maximum was carrying out the work of inviting outside investment in pyrogenic attack Saprolite ore deposit in recent years always, to increase the yearly capacity of 3～50,000 t nickel.Some newly-built and extension projects are carried out several big nickel production commercial cities there to increase by the yearly capacity of 8～120,000 t in the national New Caledonia of nickel oxide ore resource quality best (nickeliferous product are the highest), the world.Philippines, Indonesia also have some the nickel manufacturers and the investor to seek development there.By the end of the year 2003, China's nickel resources retained reserve (metal) under existing mining technique condition, can supply the just lower of exploitation less than 7,000,000 t.And China's nickel minerals concentrates on a few provinces and regions again based on lean ore.Survey data according to ground and show, the Gansu Jinchuan Mining Area is the maximum copper nickel sulfide mineral bed in the whole nation, accounts for 70% of national retained reserve; Next is Xinjiang, and nickel metal reserves are about 860,000 t; Occupying tertiary is the golden gentle Yuanjiang River in Yunnan, and the nickel minerals reserves are less than 700,000 t, and the Yuanjiang River nickel minerals is the silicic acid nickel minerals, selects the smelting difficulty big.The mountain range that simmers tea in Shaanxi occupies the 4th, nickel gold mine reserves about 200,000 t, but based on lean ore, grade at the rich ore more than 1% less than 40,000 t.In addition, molybdenum nickel minerals, clean mountain of ancient India copper nickel sulfide mineral near the boat in Sichuan crust nickel minerals (people adopt, unauthorized and excessive mining), the zunyi, guizhou, backlands district, osmanthus, Guangxi also finds the nickel minerals point, but the prospecting degree is very low, is difficult to calculated reserves.Along with investigation and prospecting is carried out in a deep going way, might find that reserves are big, quality nickel oxide ore resource preferably.

The base conditioning method that known nickel oxide ore, silicic acid nickel minerals adopt has following four kinds: the ferronickel melting, make that sulphur melting, reduction roasting-ammonia leaching go out, high pressure sulfuric acid leaches.

Adopt the factory of ferronickel melting to mainly contain many Ni Anbo smeltery, New Caledonia, the Colombia plug Rome Tuo Sha factory of French nickel company, the smeltery, eight families of SUMITOMO CHEMICAL company.The nickel massfraction is 20～30% in the product of output, and nickel recovery is 90～95%, and cobalt can not reclaim.This technology is at first with ore reduction to 50～150mm, send dry kiln to be dried to not only non-caked but also not too efflorescence of ore then, send calcination rotary kiln again, under 700 ℃ of temperature, and dry, preheating and calcining, output calcining; After calcining adds electric furnace, add the volatile coal of 10～30mm again, through 1000 ℃ retailoring, the thick Rhometal of output; Thick Rhometal is again through blowing output finished product Rhometal.

It is in 1500～1600 ℃ of fusion process producing the ferronickel melting technology that nickel is made sulphur melting production technique, adds sulphur, and output is hanged down nickel sulphur, produces nickelic sulphur by bessemerizing again.There is many Ni Anbo smeltery, New Caledonia, the Indonesian Sulawesi Henry David Thoreau A Ke smeltery of French nickel company in the main factory that produces nickelic sulphur.The general nickel massfraction of nickelic sulphur product is 79%, and the sulphur massfraction is 19.5%.Whole process nickel recovery about 70%.

Reducing roasting ammonia extract technology is with the laterite drying, grinds, reducing roasting under 600～700 ℃ of temperature make nickel, cobalt and part iron be reduced into alloy, and then 4 stage countercurrent ammonia soaks, utilize nickel and cobalt can form the characteristic of title complex, make valuable metals such as nickel, cobalt enter leach liquor with ammonia.Leach liquor is through sulfide precipitation, mother liquor of precipitation of ammonium deironing again, ammonia still process, and output alkali formula single nickel salt, alkali formula single nickel salt changes into nickel oxide through calcining again, also can be through original production nickel powder also.Up to the present, adopt the Ya Bulu refinery of the Australian QNI of only having of this art breading laterite company and the Ni Jialuo smeltery of Cuba in the world.The nickel massfraction reaches 90% in the general nickel block of producing, and the rate of recovery of whole process nickel reaches 75～80%.Compare with the pyrometallurgical smelting flow process, cobalt can be partially recycled, the rate of recovery about 40～50%.

The high pressure acid leaching process is at 250～270 ℃, under the high-temperature and high-pressure conditions of 4～5MPa, with dilute sulphuric acid valuable metals such as nickel, cobalt are dissolved with iron, aluminium mineral, in subsequent reaction, control certain conditions such as pH value, impurity element hydrolysis such as iron, aluminium and silicon are entered in the slag, and nickel, cobalt selectivity are advanced people's solution.Leach liquor neutralizes, precipitates the high-quality nickel cobalt of output sulfide with the hydrogen sulfide reduction.Nickel cobalt sulfide is by the supporting output the finished product of traditional refinery practice.Pressurized acid leaching smeltery the earliest is the Mao A smeltery of Cuba, its design year milling of ores 2,000,000 t, product is a nickel cobalt sulfide, nickel cobalt output is respectively 2.27 ten thousand t and 2000t, nickel, the cobalt rate of recovery reach 90%～95% and 80%～90% respectively, are higher than ammonia and soak flow process and firing method process.The metal recovery rate height of pressurized acid leaching, but the factory of the employing pressurized acid leaching technology of going into operation does not in recent years reach the ideal effect of expection.

Three, summary of the invention

The purpose of this invention is to provide a kind of method that from nickel oxide ore, silicic acid nickel minerals, reclaims valuable minerals such as nickel, cobalt.At nickel oxide ore, silicic acid nickel minerals characteristic, adopt chlorination segregation roasting-magnetic separation process that material is handled, can get the nickel grade is 5～15%, the rate of recovery is 80～85%; The cobalt grade is 0.3～1.7%, and the rate of recovery is 70～80% nickel cobalt collective concentrate.

Invention is achieved through the following technical solutions:

1. raw ore is handled: raw ore nickel oxide ore or silicic acid nickel minerals are broken be milled to-200 orders and account for 80～90wt%, add the coke powder (guaranteeing the weakly reducing atmosphere in next step segregation calcination process stove) of raw ore weight 5～15%, 10～30% chlorizating agent, 0.1～1.0% auxiliary agent, make particle diameter 5～15mm pelletizing, carry out drying then, be dried to and contain moisture＜5～10wt%, described chlorizating agent comprises sodium-chlor (NaCl) or calcium chloride (CaCl ₂) in a kind of, described auxiliary agent comprises cupric chloride (CuCl), ammonia chloride (NH ₄Cl), in P551, MOP, the dimethyl thiocarbamate copper one or more, guarantee weakly reducing atmosphere in next step segregation calcination process stove with adjusting the coke powder proportioning;

2. segregation calcination process: dry back pelletizing enters the segregation rotary kiln and carries out roasting, in order to make furnace charge reach the desired temperature of segregation, adopt the mode of combusting coal fines that required heat is provided, and carry out with reverse-flow roasting mode (material add Inbound and fuel add Inbound opposite), control segregation rotary kiln high temperature zone temperature is 1000～1300 ℃, kiln end temperature is 400～600 ℃, 0.75～2 rev/min of rotary kiln rotating speed, material was residing time in furnace 1～2 hour, can get the segregation product that the permivar disperse distributes, shrend after the segregation product is come out of the stove;

3. magnetic separation is handled: the broken ore grinding of the segregation product after the shrend is that 1500～3000 Gausses' magnetic separator sorts to entering magneticstrength after-200 orders account for 75～95wt%, when raw ore nickel grade is 0.8～2%, the cobalt grade is 0.08～0.15% o'clock, can get the nickel grade after segregation roasting-magnetic separation is 5～15%, and the rate of recovery is 80～85%; The cobalt grade is 0.3～1.7%, and the rate of recovery is 70～80% nickel cobalt collective concentrate;

4. vent gas treatment

Segregation calcination process rotary kiln exhaust gas is carried out flue dust collecting and tail gas acid mist purifying treatment, return briquetting behind the flue dust collecting, tail gas is qualified discharge after the acid mist purifying treatment.

5. compare advantage and the positively effect that the present invention has with known technology

(1) flow process of the present invention is simple, and investment cycle is short, instant effect.

(2) the present invention compares with known technology, has more comprehensively reclaimed valuable metals such as nickel, cobalt, has favorable economic benefit.

(3) the present invention notes the protection of environment when reclaiming valuable metal, has accomplished emission-free discharging substantially.

Four, description of drawings

Fig. 1 is a process flow sheet of the present invention.

Five, embodiment

Embodiment 1: Yuanjiang River silicic acid nickel minerals, the nickeliferous grade 1.2% of raw ore, cobalt grade 0.08～0.1%.Crushing raw ore to-3mm-0mm, is milled to-200 orders with Raymond mill again and accounts for 80～90wt%, add granularity and be-coke powder 12.5wt%, the chlorizating agent CaCl of 3mm-0mm ₂25wt%, auxiliary agent MOP 0.5wt% mixing group ball, make the pelletizing of particle diameter 8-15mm, airing is to moisture＜8% in air, adding high temperature zone temperature is 1000～1200 ℃, kiln end temperature is the roasting of emanating in 400～500 ℃ the segregation rotary kiln, 1.2 rev/mins of rotary kiln rotating speeds, roasting time 1-1.2 hour, roasting fuel is fine coal, and the roasting mode is reverse-flow roasting, and roasting product is discharged into shrend in the pond, the shrend product is pulled ore grinding after fragmentation out, grinding fineness accounts for 75～78wt% for-200 orders, and with magneticstrength H=2800 ± 50 Gausses' magnetic separator sorting, magnetic product is nickel cobalt collective concentrate, collective concentrate nickel grade 11.5%, the rate of recovery 84.5%, cobalt grade 0.56%, the rate of recovery 78.5%.

Embodiment 2: Philippines's red soil nickel ore, sample ore is taken from Philippines, nickeliferous grade 1.28% in the raw ore, cobalt grade 0.041%.Crushing raw ore is arrived-3mm-0mm, be milled to-200 orders with Raymond mill again and account for 80～90wt%, add granularity and be-the coke powder 10wt% of 3mm-0mm, chlorizating agent (NaCl) 30wt%, auxiliary agent (dimethyl thiocarbamate copper) 0.6wt% mixing group ball, grade 5-10mm, airing is to moisture＜3～5% in air, add high temperature zone temperature and be 1000～1200 ℃ of kiln end temperatures and be the roasting of emanating in 400～500 ℃ the segregation rotary kiln, 1 rev/min of rotary kiln rotating speed, roasting time 1.5-2 hour, roasting fuel is fine coal, the roasting mode is reverse-flow roasting, roasting product is discharged into shrend in the pond, and the shrend product is pulled ore grinding after fragmentation out, and grinding fineness accounts for 90wt% for-200 orders, magnetic separator sorting with magneticstrength H=2000 ± 50 Gausses, magnetic product is nickel cobalt collective concentrate, and collective concentrate nickel grade is 6.44%, and the rate of recovery is 82.03%, the cobalt grade is 0.19%, and the rate of recovery is 71.14%.

Embodiment 3: Hanyuan cobalt nickel minerals, the nickeliferous grade 0.14% of raw ore, cobalt grade 0.25%.Crushing raw ore to-3mm-0mm, is milled to-200 orders with Raymond mill again and accounts for 80～90wt%, add granularity and be-coke powder 5wt%, the chlorizating agent (CaCl of 3mm-0mm ₂) 23wt%, auxiliary agent (CuCl: NH ₄Cl=1: 1) 1wt% mixing group ball, grade 8-15mm, airing is to moisture＜3～5% in air, add high temperature zone temperature and be 1000～1300 ℃ of kiln end temperatures and be the roasting of emanating in 500～600 ℃ the segregation rotary kiln, 2 rev/mins of rotary kiln rotating speeds, roasting time 1-1.5 hour, roasting fuel is fine coal, the roasting mode is reverse-flow roasting, roasting product is discharged into shrend in the pond, and the shrend product is pulled ore grinding after fragmentation out, and grinding fineness accounts for 95wt% for-200 orders, magnetic separator sorting with magneticstrength H=1800 ± 50 Gausses, magnetic product is nickel cobalt collective concentrate I, concentrate nickel grade 2.12%, the rate of recovery 66.62%, cobalt grade 3.5%, the rate of recovery 66.03%; Scan with magneticstrength H=3000 Gauss's magnetic separator again, obtain magnetic product nickel cobalt collective concentrate II, concentrate nickel grade 0.72%, the rate of recovery 4.67%, cobalt grade 1.12%, the rate of recovery 4.07%, cobalt total yield 70.1%, nickel total yield 71.29%.

Claims (2)

1. method that from nickel oxide ore silicic acid nickel minerals, reclaims the nickel cobalt, raw ore nickel oxide ore or silicic acid nickel minerals are broken mill, the coke powder that adds raw ore weight 5～15%, 10～30% chlorizating agent and 0.1～1.0% auxiliary agent briquetting, dry, dry back pelletizing enters the segregation rotary kiln and carries out roasting, control segregation rotary kiln high temperature zone temperature is 1000～1300 ℃, kiln end temperature is 400～600 ℃, 0.75～2 rev/min of rotary kiln rotating speed, roasting time 1～2 hour gets permivar segregation product, enters magnetic separator and sort after the segregation product after the shrend carries out broken ore grinding, get nickel cobalt collective concentrate, it is characterized in that:

1). described auxiliary agent comprises one or more in cupric chloride, ammonia chloride, P551, MOP, the dimethyl thiocarbamate copper;

2). the broken abrasive particle degree of described raw ore accounts for 80～90wt% for-200 orders, makes particle diameter 5～15mm pelletizing, is dried to contain moisture＜8wt%;

3). the broken abrasive particle degree of described segregation product after shrend accounts for 75～95wt% for-200 orders;

4). the magneticstrength of control magnetic separator is 1500～3000 Gausses.

2. a kind of method that from nickel oxide ore silicic acid nickel minerals, reclaims the nickel cobalt according to claim 1, it is characterized in that: the nickeliferous grade 0.14% of raw ore, cobalt grade 0.25%, with crushing raw ore below 3mm, be milled to-200 orders with Raymond mill again and account for 80～90wt%, add granularity and be-coke powder 5wt%, chlorizating agent 23wt% and CuCl: the NH of 3mm ₄Cl=1: 1 auxiliary agent 1wt% mixing, make group's ball of grade 8-15mm, airing is to moisture＜5% in air, adding high temperature zone temperature is 1000～1300 ℃, kiln end temperature is the roasting of emanating in 500～600 ℃ the segregation rotary kiln, 2 rev/mins of rotary kiln rotating speeds, roasting time 1-1.5 hour, the roasting mode is reverse-flow roasting, roasting product is discharged into shrend in the pond, the shrend product is pulled ore grinding after fragmentation out, grinding fineness accounts for 95wt% for-200 orders, with magneticstrength H=1800 ± 50 Gausses' magnetic separator sorting, gets the nickel cobalt collective concentrate I of nickel grade 2.12% and cobalt grade 3.5%, scan with magneticstrength H=3000 Gauss's magnetic separator again, obtain the nickel cobalt collective concentrate II of nickel grade 0.72% and cobalt grade 1.12%.