CN1986852A - Method and device for preparing pure nickel and pare cobalt from ore - Google Patents

Abstract

The process of preparing pure metal Ni and Co with metal ore containing oxides of Ni, Co and Fe includes the following steps: 1. treating the ore with hydrogen at normal pressure and effective temperature in the presence of chlorine anion to prepare the first mixture of granular Ni and granular Co; 2. reaction of the first mixture and CO to prepare gaseous carbonyl nickel and the first residue with solid carbonyl nickel; 3. separating carbonyl nickel and thermal decomposing to obtain pure metal Ni; and 4. treating the first residue with gas mixture of NO and CO in effective amount to prepare nitrosyl tricarbonyl cobalt, separating nitrosyl tricarbonyl cobalt and thermal decomposing to obtain pure metal Co and regenerating the gas mixture, and removing regenerated gas mixture.

Description

The method and apparatus of preparation pure nickel and pure cobalt from ore

Technical field

The present invention relates to from the oxide compound that contains nickel, cobalt and iron ore, mineral, waste material, concentrate the apparatus and method for of preparation pure nickel and pure cobalt slag, metallurgical intermediate and the by product.

Background technology

Open on September 27th, 2004, and the Canadian Patent No.2461624 that licenses to Chemical Vapour MetalRefining Inc. has described a kind of method for preparing nickle carbonoxide from carbon monoxide and nickel source, described nickel source comprises elemental nickel, nickel compound or its mixture, condition for this nickel compound be not nickelous chloride itself or with the mixture of carbonic acid nickel minerals in, weight percent is above 50% nickelous chloride; Described method comprises: (a) using hydrogen treat nickel source under normal pressure and the efficient temperature at least, and when the precursor that has cl anion or original position to generate cl anion exists, preparation product nickel; (b) use carbon monoxide and product nickel reactant with the preparation nickle carbonoxide, and collect nickle carbonoxide.Described method provides the method for produced in high yields nickle carbonoxide under normal pressure, thereby this nickle carbonoxide can directly be used in follow-up deposition process and need not bunkerage.

U.S. Patent No. 6428601 B2 that licensed to Chemical Vapour Metal Refining Inc. on August 6th, 2002 described a kind of from contain cobalt metal component and nickeliferous and ferrous metal component mixture one of at least the method for the cobalt of preparation purifying, described method comprises: contain cobalt-carbonyl and be selected from metal carbonyl compounds one of at least nickle carbonoxide and the iron carbonyl from the preparation of metal component mixture; Nickle carbonoxide and/or iron carbonyl are separated with cobalt-carbonyl; With the nitrogen protoxide of significant quantity and carbon monoxide composite gas mixture process cobalt-carbonyl with preparation nitrosyl radical three cobalt-carbonyls; Decompose nitrosyl radical three cobalt-carbonyls behind the purifying obtaining the cobalt of purifying, and regeneration composite gas mixture is to recycle.Described method provides the high quality cobalt by adopting a kind of mode optional, continuous and the loop line.The method of optimizing comprises water and/or gas phase process step.

As everyone knows, metal is nickel and iron for example, can make from the metallic mixture of reductive by carbonylation method.Volatile nickle carbonoxide forms, is separated, separates also thermolysis to generate pure metal particles and CO (carbon monoxide converter) gas under high temperature and high pressure with iron carbonyl.Because carbonylation reaction has selectivity and other metals common and the nickel coexistence are easily separated, maybe can not form gaseous compound, and is high by the nickel metal purity of method for preparing.Owing to formed inseparable isotropic mixture, iron carbonyl can not be separated from nickle carbonoxide fully yet in contrast.

It is reported that the cobalt of normal and nickel and iron coexistence in metallic mixture such as ore and tailings under similar condition, especially when hydrogen and carbon monoxide are used to carbonyl compound formation together, also generates cobalt-carbonyl simultaneously.Because cobalt-carbonyl has than nickle carbonoxide and the much lower vapour pressure of iron carbonyl, it is trapped in the carbonylation reactor with the solid residue of carbonylation reaction usually, perhaps the volatilized carbonyl compound of part is taken out of, becomes solid residue after nickle carbonoxide and iron carbonyl are by fractionation.The further separation of cobalt generally included cobalt is dissolved in acid, again electrowinning.

Similarly, the carbonylation reaction by containing metal mixture in the basic solution can obtain the gasiform nickle carbonoxide and stay cobalt carbonyl compound and iron carbonyl compound in the solution.The further purification of cobalt is comprised acidifying to solution, follow by the extraction of organic solvent to cobalt.The cobalt that extracts is used the electroextraction purifying again.

Also have a few thing to attempt to utilize volatile cobalt-carbonyl precursor such as carbonyl hydrogenated cobalt to extract and obtain cobalt.For example, the paste mixture of cobalt, nickel and copper metal is handled under the pressure of 68 crust with the mixed gas of carbon monoxide-hydrogen, can be obtained the anionic mixture of nickle carbonoxide and cobalt-carbonyl.Volatile nickle carbonoxide outgases from solution and removes, and debris is filtered.The strong acid acidifying of the basic solution of carbonyl cobalt salt, volatile carbonyl hydrogenated cobalt (cobalthydrocarbonyl) is boiled and is removed from solution.Decompose the pure cobalt metal that carbonyl hydrogenated cobalt obtains containing 30ppm nickel, 0.4ppm iron and 0.1ppm copper subsequently.This process comprises several operation stepss, comprises to the filtration of solution with to the dilution and the acidifying of gained solution.

Other methods of separating cobalt-carbonyl from nickle carbonoxide comprise that adding ammonia is to generate { Co (NH ₃) ₆[Co (CO) ₄] ₂Precipitation, or from KOH ethanol liquid by to remove cobalt.

Known in alkaline aqueous solution, NO and Fe (CO) ₅Can prepare gasiform nitrosyl radical iron carbonyl Fe (NO) 95 ℃ of following reactions ₂(CO) ₂And, CoNO (CO) ₃Can be from ferruginous carbonyl compound component enrichment and distilling effectively, to obtain nonferrous CoNO (CO) ₃Gas obtains it decomposition pure cobalt metal (99.8%) subsequently.

Though H ₂The reductive agent that is used as metal oxide materials generating in the reaction of metal carbonyl with carbon monoxide subsequently, for example in the reaction of cobalt, has still generated inactive cobaltous sulfide.

Therefore, need a kind of improved method, when there being other metals, for example when nickel that originally exists with the corresponding metal oxide form and iron, described method can provide the appropriate form of cobalt metal, so that it reacts with carbon monoxide in conversion subsequently, effectively is converted into cobalt-carbonyl.

Summary of the invention

We have been surprised to find that when the oxide impurity of cl anion and nickel, iron and other metals exists, in the reduction reaction of cobalt oxide and hydrogen, can access a kind of mixture that comprises cobalt metal, although have other metals and nonmetallic substance in the ore, described mixture can generate the solid cobalt-carbonyl effectively with reaction of carbon monoxide.This discovery provides the method for preparing the pure metal cobalt by follow-up known process steps.

Therefore, one aspect of the present invention provides the method for preparing pure metallic nickel and cobalt from the ore of the oxide compound that contains nickel, cobalt and iron.Described method comprises:

(a) having cl anion or original position to generate in the presence of the precursor of cl anion, described ore is being used hydrogen treat under normal pressure and the significant temp at least, preparation contains first mixture of particle nickel and particulate cobalt;

(b) with described first mixture and reaction of carbon monoxide, with preparation gasiform nickle carbonoxide and first residue that contains the solid cobalt-carbonyl;

(c) described nickle carbonoxide is removed;

(d) with described nickle carbonoxide thermolysis to prepare described pure metallic nickel;

(e) with described first residue nitrogen protoxide of significant quantity and the composite gas mixture process of carbon monoxide, with preparation nitrosyl radical three cobalt-carbonyls;

(f) described nitrosyl radical three cobalt-carbonyls are decomposed preparing described pure metal cobalt, and regeneration composite gas mixture; With

(g) described regenerated composite gas mixture is removed.

Term in this specification sheets and claims " ore " comprises, but is not limited to heavy metal ore, mineral, metallic scrap, concentrated slag, metallurgical intermediate and by product.

Preferably, described chlorion is provided by a kind of compound that is selected from hydrogenchloride and metal chloride, and described metal chloride is preferably selected from the muriate of basic metal, alkaline-earth metal and transition metal, is more preferably nickelous chloride.Cl anion preferably from the gaseous mixture with described hydrogen blended gaseous hydrochloric acid mutually.Preferably, HCl that contains in the gaseous mixture and H ₂Mol ratio be approximately 1: 2.

Preferably, ore is at first handled under significant temp with hydrogen in first period, handles under described significant temp with described gaseous mixture in second period then again.

Described significant temp is preferably selected from 300 ℃-650 ℃, more preferably is selected from 350 ℃-550 ℃.

Embodiment

In order to understand the present invention better, only describe preferred embodiment for example now with reference to appended examples.

Embodiment

Embodiment 1

To contain the nickel oxide of nickel (54.5g) and cobalt (5.5g) and the original mixture of going back of cobalt oxide and put into carbonylation reactor.The reactor nitrogen purge is removed all oxygen, then this reactor H ₂S (1.5 crust) pressurization 15 minutes.Through H ₂After the S activation, carbon monoxide at 10 bar pressures and 85 ℃ of following reactors that import, was removed nickle carbonoxide through 5 hours from reactor.Subsequently, after most of nickel is removed, nitrogen protoxide NO was imported reactors 20 minutes in 85 ℃, and with CoNO (CO) ₃Form is removed the cobalt-carbonyl of generation.Reactor cleans with CO subsequently and used nitrogen purge in 20 minutes again.Contain 73.6% nickel and 21.5% cobalt in the reacted residue (4.5 gram).Nickel productive rate 94%, cobalt productive rate 82%.

Embodiment 2

In rotatable reactor, restrain NiCl with hydrogen reducing 90 in 450 ℃ ₂With 10 gram CoCl ₂Mixture.The original mixture of going back of gained nickel and cobalt is handled with carbon monoxide under 50 ℃ and normal pressure, and nickel promptly reacts the generation nickel carbonyl gas rapidly with carbon monoxide, described nickle carbonoxide from reactor, remove and in decomposition chamber in 175 ℃ of decomposition, CO recirculation.After all nickel is removed, NO is imported the CO air-flow to generate CoNO (CO) ₃, described CoNO (CO) ₃From reactor, move to second decomposition chamber.The nitrosyl radical cobalt-carbonyl is 150 ℃ of decomposition, and the gaseous mixture of gained is recycled.After most of cobalt was removed, this system was cleaned with nitrogen and nitrogen/oxygen mixed gas.Contain 64.3% nickel and 30.6% cobalt in the residue (2.6 gram).

Embodiment 3

In 450 ℃ of mixtures that restrain cobalt oxides down with the gaseous mixture reduction 90 gram nickel oxide and 10 of hydrogen/1%HCl.Identical condition among the extraction employing of nickel and the embodiment is extracted cobalt with NO subsequently again.Contain 63.8% nickel and 31.1% cobalt in the residue (2.8 gram).

Embodiment 4

The rock sample (100g) that will contain 2.2% nickel, 12% iron and 0.07% cobalt is heated to 750 ℃ with dry-off moisture in reactor.Temperature is reduced to 450 ℃ subsequently, uses H ₂The mixed gas cleaning reaction device of/1%HCl was also gone back original sample 4 hours.Reactor is chilled to 50 ℃, extracts nickel and part iron as carrier gas with the form of metal carbonyl with CO under normal pressure.Extract and obtained 6.1 gram products (32% nickel and 68% iron) in 5 hours.Nitrogen protoxide and carbon monoxide are introduced the form extraction Co of reactor with the nitrosyl radical cobalt-carbonyl together, obtain the cobalt of 60mg through extraction in 4 hours.

Though it is preferred embodiment more of the present invention that the disclosure is described and set forth, the present invention is not limited to these specific embodiments.On the contrary, the present invention includes the embodiment that all and an embodiment of describing and explaining and feature have identical function and mechanism.

Claims (9)

1. prepare the method for pure metallic nickel and cobalt from the ore of the oxide compound that contains nickel, cobalt and iron, described method comprises:

(a) having cl anion or original position to generate in the presence of the precursor of cl anion, described ore is being used hydrogen treat under normal pressure and the significant temp at least, preparation contains first mixture of particle nickel and particulate cobalt;

(b) with described first mixture and reaction of carbon monoxide, with preparation gasiform nickle carbonoxide and first residue that comprises the solid cobalt-carbonyl;

(c) described nickle carbonoxide is removed;

(d) with described nickle carbonoxide thermolysis to prepare described pure metallic nickel;

(e) with described first residue nitrogen protoxide of significant quantity and the composite gas mixture process of carbon monoxide, with preparation nitrosyl radical three cobalt-carbonyls;

(f) described nitrosyl radical three cobalt-carbonyls are decomposed preparing described pure metal cobalt, and regeneration composite gas mixture; With

(g) described regenerated composite gas mixture is removed.

2. the method for claim 1, wherein said chlorion is provided by a kind of compound that is selected from hydrogenchloride and metal chloride.

3. method as claimed in claim 2, wherein said metal chloride is selected from the muriate of basic metal, alkaline-earth metal and transition metal.

4. as claim 1 arbitrary described method to the claim 3, wherein said cl anion by in the gaseous mixture with described hydrogen mutually the blended gaseous hydrochloric acid provide.

5. as claim 1 arbitrary described method to the claim 4, wherein said ore was handled under described significant temp with hydrogen earlier in first period, handled under described significant temp with described gaseous mixture in second period then.

6. as claim 4 or the described method of claim 5, wherein said gaseous mixture comprises that mol ratio is about 1: 2 HCl and H ₂

7. as claim 1 arbitrary described method to the claim 6, wherein said cl anion is provided by nickelous chloride.

8. as claim 1 arbitrary described method to the claim 7, wherein said significant temp is selected from 300 ℃-650 ℃.

9. method as claimed in claim 8, wherein said significant temp are selected from 350 ℃-550 ℃.