CN1045476C - Chloride assisted hydrometallurgical copper extraction - Google Patents

Abstract

The present invention relates to a method for extracting copper from a sulphide copper ore or a concentrated object. The method comprises the following steps that the ore or the concentrated object is pressurized and oxidized in the presence of oxygen and an acidic chloride solution to obtain generated pressurization oxidation filtrate and an insoluble basic copper sulphate salt, and the pressurization oxidation is carried out in the presence of a bisulphate ion source or a sulphate ion source, such as sulfuric acid; the amount of the added sulphate ion source at least is the value that the amount of sulphate generated in situ in the pressurization oxidation is subtracted from the stoichiometric amount of sulphate ions required by the generated basic copper sulphate salt. In the specific example, the pressurization oxidation is carried out according to the preset ratio of H to Cu so that the pressurization oxidation filtrate contains the main copper part in the ore or the concentrated object, and simultaneously, the basic copper salt contains the minor copper part in the concentrated object. The present invention also provides a method of selecting H and Cu according to the ore or the concentrated object, wherein the proportion of the selected H to Cu can ascend with the descending of the level of the ore or the concentrated object. In the other example, the basic copper salt is dissolved in the following normal pressure leaching step. A dense copper solution which is suitable for the electrolysis and the smelting is obtained by the solvent extraction. The present invention also provides a method of extracting zinc and nickel from the ore.

Description

The auxiliary hydrometallurgical copper extraction of muriate

FIELD OF THE INVENTION

The present invention relates in the presence of chlorion hydrometallurgical process to copper sulfide ore or enriched material.Also relate to the processing that copper removal also contains the mixed ore of zinc or nickel outward.

The background of invention

Copper sulfide ore is (as chalcopyrite (CuFeS ₂)) hydrometallurgical process be debatable because from these ores effectively the necessary severe condition of the pressure oxidation of lixiviate copper cause the sulfide in the ore to be oxidized to vitriol, need the expensive neutral acid of carrying out in a large number thereby produce.Attempted to make the enriched material of sulfide can lixiviate under gentle relatively condition already, sulfide only be oxidized to elemental sulfur but not until becoming vitriol under this condition.These methods are included in the preceding pre-treatment enriched material of pressure oxidation, make the enriched material of sulfide easier of lixiviate; And as United States Patent (USP) 4,039,406 described in the presence of chlorion the lixiviate enriched material.In the method, as United States Patent (USP) 4,338,168 describedly are transformed into solid-state Basic Chrome Sulphate with the copper number in the enriched material, from Basic Chrome Sulphate copper number are restored subsequently.4,039, in the described method of 406 patents, the sulfide of a large amount of (20-30%) in ore or the enriched material still is oxidized to vitriol, and causing needs more substantial oxygen and produce sulfuric acid in the process of pressurization lixiviate.This is unfavorable especially for the higher low level enriched material of S/Cu ratio.

The invention provides a kind of hydrometallurgical extraction method of copper, the sulfide oxidation that present method has reduced in ore or the enriched material becomes the amount of vitriol, and can handle high-level and low-level copper mine stone or enriched material.

The general introduction of invention

The invention provides a kind of from copper sulfide ore or enriched material the method for extracting copper, be included under the existence of oxygen and acid chloride solution ore or enriched material are carried out pressure oxidation, with the pressure oxidation filtrate of acquisition generation and the step of insoluble Basic Chrome Sulphate salt, it is characterized in that pressure oxidation is to carry out in the presence of bisulfate ion or source of sulfate ions, described ion source is selected from sulfuric acid and the metal sulfate of hydrolysis in acidic solution; And the bisulfate ion that is added or the amount of source of sulfate ions are to generate the sulfate radical of the required stoichiometry of Basic Chrome Sulphate salt or the amount that hydrogen sulfate ion deducts the sulfate radical of ground, pressure oxidation Central Plains generation at least.

According to specific examples of the present invention, present method also comprises the step that the filtrate of pressure oxidation is recycled to the pressure oxidation section; The Basic Chrome Sulphate that is made by pressure oxidation with the lixiviate of hydrosulphate solution in the lixiviate second time with the dissolving alkali type nantokite, generates in the solution and contains the lixiviate mother liquor of copper sulfate and form solid residue; From solid residue, separate the lixiviate mother liquor; The lixiviate mother liquor is adopted the solution extraction method, to generate dense copper solutions and raffinate; Raffinate is recycled to the step of lixiviate for the second time.In this example, can under 115-175 ℃ temperature, carry out pressure oxidation.Pressure oxidation also can be about among 445kPa (50psig)-1825kPa (250psig) at oxygen partial pressure to be carried out.Copper concentration in pressure oxidation filtrate is about in the scope of 10-25g/ liter.

Pressure oxidation better is at predetermined H ⁺Carry out in/Cu the mol ratio, wherein H ⁺Represent the hydrogen ion in the acid chloride solution, Cu represents the copper in ore or the enriched material, so that make copper concentration in the final pressure oxidation filtrate that pressure oxidation forms equal to be recycled to the copper concentration of the pressure oxidation filtrate of pressure oxidation substantially.

Chlorine in being recycled to the pressure oxidation filtrate of pressure oxidation section should be maintained at about the 8-20g/ liter than substrate concentration, better is about the 11-14g/ liter, preferably about 12g/ liter.

In specification sheets, relate to muriatic use.But, obviously can use bromide to replace muriate if necessary.

Lixiviate for the second time is preferably in the pH value and is about among the 1.3-2.2 and carries out.Have found that this dissolving that will make copper reaches maximum, and make the dissolving of iron reach minimum.More particularly, lixiviate for the second time should be carried out in the pH of about 1.6-1.9 scope.

Lixiviate for the second time can be at about 20-70 ℃, is preferably under about 35-45 ℃ the temperature to carry out.

With regard to the lixiviate second time, find the residence time less than 1 hour, for example suited in 15-20 minute.

Raffinate can be split into first part that comprises about 2/3 raffinate and the second section that comprises about 1/3 raffinate, first part can be recycled to the section of lixiviate for the second time, can carry out the secondary solvent extraction to second section and form secondary lixiviant and secondary raffinate.This secondary lixiviant can be used as the solvent extraction that extraction agent is used for vat liquor.This method also can be included in and be about 1.5-3 at pH before the secondary solvent extraction second section is carried out neutralization first time, and is about 9-10 at pH the secondary raffinate is carried out the secondary neutralization, the step of also therefrom removing the dissolved metal with antacid content.

In another example of the present invention, pressure oxidation is at predetermined H ⁺Carry out in/Cu the mol ratio, wherein H ⁺The hydrogen ion of representative in acid chloride solution, Cu represents the copper in ore or the enriched material, make pressure oxidation filtrate contain the first part's copper in ore or the enriched material, contain the second section copper in ore or the enriched material in the alkali type nantokite, this example also comprises the steps: to separate pressure oxidation filtrate and alkali type nantokite; In lixiviate second time step,,, form second copper solutions and solid residue with the dissolving mantoquita with hydrosulphate solution lixiviate alkali type nantokite; And the pressure oxidation filtrate and second copper solutions carried out solvent extraction, be formed for the dense copper solutions that cupric electrolysis is smelted.

This method also can comprise the steps: before solvent extraction copper, second copper solutions and pressure oxidation filtrate are carried out the solvent extraction of zinc with the organic zinc extraction agent, forming the extraction agent of first and second zinc loads respectively, and form the first and second zinc raffinates respectively; With the organic copper extraction agent the first zinc raffinate is carried out solvent extraction, form the extraction agent and the first bronze medal raffinate of first bronze medal load; Extraction agent with first bronze medal load carries out solvent extraction to the second zinc raffinate, forms the extraction agent and the second bronze medal raffinate of second bronze medal load; Back extraction zinc from the extraction agent of first and second zinc loads is formed for the dense zinc solution of electrolysis for production.Before the second zinc raffinate is carried out solvent extraction, the second zinc raffinate is carried out the neutralization of a step or multistep, to form neutral solution respectively and to form the calcium sulfate resistates respectively; Behind each neutralization procedure, respectively neutral solution is separated from the calcium sulfate resistates, formed final neutralization solution; Final neutralization solution is further carried out the zinc solvent extraction, form final zinc raffinate; Extraction agent with first bronze medal load carries out solvent extraction to this final zinc raffinate.

Beyond the dezincification, the extraction agent of second zinc load a spot of copper of also may having loaded, this method also can comprise the step of handling the extraction agent of second zinc load with zinc sulfate solution with reflux type, so that with a little copper of loading in the zinc displacement extraction agent, form untainted substantially zinc solution and be used for electrolysis for production, a plurality of successive sections are used in described processing.

Can use the extraction agent of first zinc load that pressure oxidation filtrate is carried out the zinc solvent extraction, form the extraction agent of second zinc load, and comprise the extraction agent of back extraction zinc formation zinc back extraction from the extraction agent of second zinc load; And the extraction agent of reusing the zinc back extraction carries out the zinc solvent extraction of second copper solutions.

This method also can comprise uses the organic nickel extraction agent that first and second raffinates of copper solvent extraction are carried out the nickel solvent extraction, forms the extraction agent of first and second nickel load respectively and forms the first and second nickel raffinates respectively; And, be formed for the dense nickel solution step of electrolysis for production by back extraction nickel in the extraction agent of first and second nickel load.

In addition, the present invention also provide a kind of from copper sulfide ore or enriched material the method for extracting copper, be included in the step of lixiviate for the first time with acid chloride solution lixiviate ore or enriched material, form first copper solutions and insoluble alkali type nantokite; Separate first copper solutions and alkali type nantokite; In lixiviate second time step,,, form second copper solutions and solid residue with the dissolving mantoquita with hydrosulphate solution lixiviate alkali type nantokite; With organic extractant first and second copper solutionss are carried out solvent extraction, form dense copper solutions and be used for therefrom electrolysis for production copper.

According to another aspect of the present invention, can select predetermined H according to the rank of ore or enriched material ⁺The ratio of/Cu, selected ratio value rises with ore or other decline of enriched material level.The rank of ore or enriched material in the scope of 28-22 weight % copper, H ⁺The mol ratio of/Cu is about 0.7-1.0.

Another example of the present invention provides a kind of method of extracting copper, and bisulfate ion wherein or sulfate ion comprise sulphuric acid soln or the copper-bath that adds from outside.

The present invention also may extend to and uses the inventive method manufactured copper, zinc and nickel.

From the description of the better example of following the present invention, can be more clearly visible objects and advantages of the present invention.

The accompanying drawing summary

Fig. 1 is the schema of the hydrometallurgical copper extraction method of an example of the present invention, and it is suitable for handling high level copper mine stone or enriched material.

Fig. 2 is the schema of the hydrometallurgical copper extraction method of another example of the present invention, and it is suitable for handling medium to low-level copper mine stone or enriched material.

Fig. 3 is the schema of the hydrometallurgical copper extraction method of another example of the present invention, and it goes back extracting zinc except extracting copper.

Fig. 4 is the schema of the hydrometallurgical copper extraction method of another example of the present invention, and it goes back extraction of nickel except extracting copper.

The detailed description of better example

The inventive method has enough adaptability to process the copper concentrate of copper rank by low (containing according to appointment 15% bronze medal or lower) paramount (containing approximately 35% or higher).

Put it briefly, this method comprises the pressure oxidation section, normal pressure lixiviate section, one or more solvent extractions and electrolysis for production section. The concentrate of different stage need to carry out different processing in the pressure oxidation section, needs different modes of operation. These modes are called as respectively mode A and mode B. In the mode A that is applicable to high-level Copper Ores or concentrate lixiviate, at not lixiviate of pressure oxidation copper. In the mode B that is applicable to medium and the lixiviate of low level Copper Ores, at pressure oxidation lixiviate copper.

The below will describe this dual mode successively.

Mode A

Fig. 1 is the flow chart of mode A. The method is included in the pressure oxidation section 12 of carrying out in pressure oxidation container or the autoclave, normal pressure lixiviate section 14, first and secondary solvent extraction section 16 and 18 and electrolysis for production section 20.

In pressure oxidation section 12, all Copper Ores all change into basic copper sulfate CuSO₄·2Cu(OH) ₂ This processing is to implement with oxygen in the presence of acidic chloride solution. With oxygen and HCl and H₂SO ₄Import together in the autoclave to reach this purpose. Temperature in the autoclave is about 130-150 ℃, and pressure is about 800-1500kpa (100-200psig). This is the gross pressure that comprises oxygen pressure and steam pressure. About 0.5-2.5 of the time of staying hour and usually in autoclave, carry out in a continuous manner this reaction. But if necessary, this reaction also can mode in batches be carried out.

Solids content in autoclave is maintained at about 12-25% (being that 150-300g/ rises solid), and this is to be determined by thermal balance and viscosity limits.

With the slurry that makes in the autoclave by one group of one or more flash tank 22 discharging so that with earth pressure release to atmospheric pressure, cool the temperature to 90-100 ℃. The liquid of slurry partly is called as the product solution of pressure oxidation section 12, and represents with label 21.

Filter the slurry from flash tank 22 shown in 24, the filter cake of washing formation is in order to eliminate as far as possible entrained mother liquor up hill and dale.

To be recycled to pressure oxidation section 12 by the pressure oxidation filtrate that filter 24 obtains, but a small amount of about 5% minute flow liquid (bleed) (shown in 26) will be arranged. Minute flow liquid 26 is that the concentration by the ore that may dissolve in pressure oxidation section 12 or the soluble metal in the concentrate determines. Divide flow liquid 26 to remove the metal that is present in the copper concentrate with the form of solid residue in 28 usefulness lime treatments, such as zinc and magnesium, to reduce these metals gathering in the pressure oxidation circulation. Pressure oxidation circulation is 24 to be back to the circulation of pressure oxidation section 12 to shunting section (bleed) 26 by pressure oxidation section 12 to flash tank 22 to filter again. It is by label 23 expressions.

Shown in 27, front to dividing a flow liquid 26 to carry out solvent extraction at minute flow liquid processing section 28. Solvent extraction 27 is to implement with suitable organic extract liquid, in order to remove copper from minute flow liquid 26. This solvent extraction is relevant with solvent extractions 16 and 18, again relates in the description with these two extraction sections below.

Before pressure oxidation 12, at first shown in 30, copper concentrate is ground so that with particle diameter be down to make about 97% particle particle diameter less than 325 orders, be equivalent to 15 microns of P80 (80% by). Grinding steps 30 is to carry out in the solution of minute flow liquid processing section 28 in circulation. Therefore, the slurry to minute flow liquid processing section 28 shown in 32 carries out liquid/solid phase separation, and solution is recycled to ground section 30, and casts out zinc/magnesium shunting residue shown in 17.

The solution that is recycled to ground section 30 is that pH is about 10 alkaline chloride mother liquor. Use this mother liquor can make the water addition in the pressure oxidation circulation 23 reduce to minimum, this is important for maintenance thermal balance, for keep chloride solution as much as possible in pressure oxidation circulation 23.

As mentioned above, at pressure oxidation 12 not lixiviate copper but it is changed into insoluble alkali type nantokite. The feed liquid that adds in the pressure oxidation section 12 is the lixiviate mother liquor that is come by filter 24 recirculation, represents with label 25. Although in feed liquid 25, have copper, there is not copper to be leached again, namely being in operation makes copper concentration in the feed liquid 25 that adds to pressure oxidation section 12 be equal to copper concentration in the product solution 21 that is obtained by pressure oxidation section 12. This is called as Δ [Cu²⁺]=0。

The feed liquid 25 that adds to pressure oxidation section 12 contains that the 15g/ that has an appointment rises Cu and 12g/ rises Cl and about 30-55g/ rises sulfuric acid. Acid is to replenish H₂SO ₄The form of (common 93%) adds. The product solution 21 that is made by pressure oxidation section 12 contains also that the 15g/ that has an appointment rises Cu and 11-12g/ rises Cl, but its pH is 3. In product solution 21, substantially do not contain acid, because acid all is consumed and changes into alkali type nantokite in pressure oxidation section 12.

As mentioned above, the liquid material 25 that adds to pressure oxidation section 12 is to be made of the part recycled filtrate that is added with sulfuric acid. The effect immediately that adds acid in the filtrate is the acidity that adds to for the filtrate of the autoclave of pressure oxidation 12, but have found that wonderful most important effect is to add acid, more particularly add sulfate ion and can in fact suppress in the pressure oxidation section 12 oxidation from the element sulphur of concentrate.

If do not add acid, such as United States Patent (USP) 4,039,406 described methods are such, and the sulphur of oxidation accounts for the 25-30% of concentrate Raw sulphur usually. But if add acid, discovery is oxidized to the sulphur of sulfate radical and is down to 5-10%. This improvement is the beneficial effect of essence for the hydrometallurgical extraction method. Sulphur is oxidized to sulfate radical can form extra cost in several ways, as react needed extra oxygen, in and the sour required additional agents that forms of oxidation and since sulphur be oxidized to sulfuric acid be strong heat release and heat extraction equipment that must use. In fact this limited the production capacity of carrying out the autoclave of pressure oxidation 12.

It is believed that in pressure oxidation section 12 can following change chemical reaction process by adding acid:

Do not add acid:

(1)

Add acid:

(2)

In two reactions, copper all with the form precipitation of alkali type nantokite, is found mainly to contain alkali formula blue vitriol in the precipitation.

By first reaction as seen, sulfate radical in the Basic Chrome Sulphate is to be formed by the raw material sulphur oxidation in the enriched material, and by second reaction as seen, sulfate radical is from the sulfate ion in the acid of adding in the autoclave, thereby eliminated the needs that sulphur is oxidized to sulfate radical.Therefore, in second reaction, pure consumption sulfate ion forms alkali type nantokite.Experiment find to suppress the about 25-75g/ liter of the needed vitriolic amount of oxidation of sulphur, depends on solid percentage ratio in the type of enriched material and the enriched material.

In the test work of reality, the amount of oxidation of sulphur is more than the amount shown in two reactions.First reaction has 1/6 or 16.7% sulphur oxidized, and experiment finds that the amount of oxidation is about 25-30%.With regard to adding acid, the sulphur of test card express contract 2-16% is oxidized to sulfate radical, but not as illustrated be zero oxidation, if second reaction is only reaction.Therefore, these reaction equations are not reflected at what happens in the pressurization lixiviate section 12 exactly, and have only provided a kind of approximate overview.

In pressure oxidation circulation 23, should preserve muriate as far as possible, but have the 3-10% muriate to stay in the solid product and loss approximately by strainer 24 usually at every turn.Therefore, must add HCl or other chloride source and replenish muriate, make that chloride content is the 12g/ liter in the feed liquid 25.On strainer 24, wash the solid that makes by pressure oxidation section 12 up hill and dale and the muriate loss can be reduced to minimum.The consumption of washing water is subjected to keeping the restriction of isorrheic requirement in pressure oxidation circulation 23.Only damage by water consumption is in the steam 29 and the filter cake behind the strainer 24 of flash distillation step 22 in the circulation 23.Therefore, need to use from minute recirculation solution of flow liquid processing section 28 so that in grinding steps 30, make the enriched material slurryization, and will reduce to minimum by the fresh water input amount that enriched material is brought in the pressure oxidation section 12 thus.

Have found that it is favourable keeping at least 15g/ to rise Cu, can reduce muriate with solid-state basic copper chloride CuCl in the product solution 21 that pressure oxidation section 12 makes ₂3Cu (OH) ₂The loss of form, if the copper that does not have capacity in the solution will form basic copper chloride to form Basic Chrome Sulphate:

(3)

The acid that can add capacity in pressure oxidation 12 in autoclave so that solution keeps minimum enough copper of limiting the quantity of, satisfies making Cl become CuCl ₂The stoichiometry requirement, reduce above-mentioned reaction with this.With regard to 12g/ in the solution rose muriate, stoichiometric Cu amount was:

Therefore, 15g/ rises Cu and prevents the minimum amount of a large amount of muriates with the safety of alkali type nantokite form loss.

On the other hand, the copper concentration in the product solution 21 that pressure oxidation section 12 makes should be low as far as possible, generates CuS to reduce the reaction of elemental sulfur and copper sulfate solution.This reaction can take place in pressure oxidation 12 or in the slurry of discharging from autoclave but before filtration step 24:

(4)

This reaction is nonconforming especially, because CuS is insoluble under the diluted acid condition of normal pressure lixiviate section 14.Therefore can not reclaim copper, cause copper to be lost in the resistates of formation.

In order to reduce the formation of cupric sulfide, need make the copper concentration in the product solution 21 low as far as possible, promptly for some enriched material, should be lower than the 30g/ liter.The formation tendency of CuS is obviously relevant with the enriched material type that is subject to processing, and is medium to the high-level easier formation of enriched material CuS.Therefore, although there is not the problem of copper concentration in low-level enriched material in product solution 21, it can not bear high level enriched material.

As now known to, preferably high level enriched material (promptly being higher than 35% bronze medal) is handled, make in the product solution 21 of generation copper concentration low as far as possible, promptly be lower than 25g/ and rise Cu.

15g/ rises Cu owing to need to keep in the solution at least in pressure oxidation circulation 23, therefore has the copper concentration range that best 15-25g/ rises Cu for high-level enriched material.With regard to other enriched material of middle grade, the upper limit can be extended significantly, and for the low level ore, the concentration of copper is not main.

Copper concentration in pressure oxidation filtrate 29 can be controlled by the acid that adds required amount in the feed liquid 25 that is circulated to pressure oxidation section 12 simply.When adding more acid, increased the concentration of copper owing to the dissolving Basic Chrome Sulphate:

(5)

Adding 1g/ rises acid can make copper concentration increase about 1g/ liter.The actual concentrations of required acid is whether the calibrating of the product solution 12 that makes to the feed liquid 25 of pressure oxidation section 12 with by pressure oxidation section 12 by comparison loop by rule of thumb satisfies Δ [Cu ²⁺]=0 and being determined.But the liquor capacity of circulation 23 is determined by thermal equilibrium.

Add to that the solid weight percentage can at random change in the copper concentrate slurry of pressure oxidation section 12.The enriched material solid weight that adds to pressure oxidation section 12 is by the decision of the amount of the copper that will reclaim.The weight of solution is mainly determined by the thermal equilibrium of pressure oxidation section 12.

The service temperature that requires in pressure oxidation section 12 is about 150 ℃, and this heat mainly should be supplied with by the reaction heat of sulfide ore in the autoclave and high pressure oxygen.For high-level enriched material (enriched material of handling as the mode A that soon narrated), this means low relatively S/Cu than and therefore in autoclave the copper that is subject to processing per ton produce less heat.The heat that discharges is not because the oxidation of copper mostly, but owing to the oxidation of other two kinds of principal element iron and sulphur in the enriched material produces.If the rank of enriched material is high, then S/Cu and Fe/Cu are lower, thereby have reduced the generation of heat.

For the starting temperature from for example 50-80 ℃ (temperature commonly used of pressure oxidation filtrate 29, this filtrate is through filter 24 back recirculation) reaches service temperature, must control the amount of the water that needs heating, because this is main heat rejection in pressure oxidation section 12.Slurry in autoclave is infeasible with indirect mode cooling or heating, for example uses heating coil or cooling worm, forms fouling because can go up at all surface (especially at heat exchanger).Cause very poor heat transfer characteristic.It also is infeasible carrying out direct heating for isorrheic consideration by injection steam or water.Therefore, need and add the balance that thermal equilibrium between the thermal capacity of material (being the feed liquid 25 and the enriched material slurry of recirculation) keeps heat by the heat that provides by reaction heat.Here controllable primary variables is the volume of feed liquid 25.This is a distinguishing characteristics between mode A and the mode B.In the mode B that will describe, the liberated heat of being represented by the heat of copper product per ton is very big.Therefore, can in the feed liquid 25 that is circulated to pressure oxidation section 12, use bigger liquor capacity.

In case fixed liquor capacity, just can determine the acidity of solution, because the total amount of acid is by keeping Δ [Cu ²⁺This requirement of]=0 is determined.Usually, with regard to high-level enriched material, the acid that needs about 35-55g/ to rise.

Have found that it is favourable adding a small amount of suitable tensio-active agent, tensio-active agent can change liquid elemental sulphur (S in pressure oxidation 12 ⁰) physics and chemical property.Adding a small amount of (being the 0.1-3g/ liter) tensio-active agent such as Sulfite lignin and quebracho micromicro in pressure oxidation feed liquid 25 reduces the viscosity of liquid sulfur in the autoclave and changes its chemical property.

Adding tensio-active agent, can to reduce the reason of oxidation of sulphur also not really clear, but be favourable to this method.It is believed that it is owing to reduced viscosity, thereby reduced the tendency that liquid sulfur and solid pause in autoclave, cause the residence time of these materials to reduce, therefore reduced thio-oxidizing tendency takes place.

If also find to add tensio-active agent, can make the reaction of copper mine stone more complete, this obviously is because more low viscous sulphur can " moistening " unreacted sulfide ore, thereby makes the reaction that requires carry out fully.

The reason that adds copper concentration in the sulfuric acid may command pressure oxidation filtrate 29 in pressure oxidation feed liquid 25 has been described in reaction (5).The total reaction of the pressure oxidation of the chalcopyrite ores that adding sulfuric acid carries out is shown not by top reaction (2).

Can write out and use CuSO ₄Replace H ₂SO ₄Similar reaction as source of sulfate ions:

(6)

It should be noted that with react (2) in 1 mol sulfuric acid compare, reaction (6) needs the vitriol of 3/2 mol sulfuric acid copper form.If therefore use CuSO ₄Replace sulfuric acid as source of sulfate ions, need to use the CuSO of 1.5 times of mole numbers ₄Consider these factors, the inventor has introduced this notion of excess of sulfur acid group equivalent (ExcessSulphate Equivalent), is used for calculating adding how much acid could obtain the copper concentration that require and still consider to react (6) to pressure oxidation feed liquid 25.

With regard to reaction (6), can calculate required " preferably " acid amount of constant copper concentration in the pressure oxidation filtrate 29.This notion of excess of sulfur acid group equivalent is useful.

Excess of sulfur acid group equivalent equals available sulfate radical in the pressure oxidation feed liquid 25 that is used for pressure oxidation 12 formation Basic Chrome Sulphates.The available sulfate radical is for CuSO ₄And CuCl ₂The benchmark that is limited (Base Level) is excessive.

CuSO ₄And CuCl ₂Benchmark should be enough to make and contain the muriate that 12g/ rises in the muriatic solution and become CuCl ₂Form, having 4.3g/ to rise Cu in addition approximately is CuSO ₄Form.Rise muriate corresponding to 12g/, CuCl in the solution ₂Concentration be that 134.5/71 * 12=22.7g/ rises CuCl ₂, this CuCl ₂Comprised the copper of 10.7g/ liter in solution.Therefore in addition 4.3g/ rises copper and means the CuCl that is combined to that is total up to the 15g/ liter in benchmark ₂And CuSO ₄Copper.

Therefore, the available sulfate radical is CuSO ₄Whole sulfate radicals of form deduct benchmark.For example, if the total concn of copper is the 28g/ liter in pressure oxidation filtrate 29, then the available sulfate radical is that 28-15=13g/ rises Cu, and 13 * 98/63.5=20g/ rises H ₂SO ₄, as from CuSO ₄The available sulfate radical.

Excess of sulfur acid group equivalent (ESE) is to derive from CuSO ₄Sulfate radical divided by 1.5 calculate:

ESE=(can derive from CuSO ₄The sulfate radical of form)/1.5

Therefore, be that the 28g/ liter maybe can derive from CuSO in the copper total concn ₄Sulfate radical be in the example that rises of 20g/, from CuSO ₄ESE be the 20/1.5=13.3g/ liter.

At last, free acid equivalent rises H for for example 52g/ in the pressure oxidation feed liquid 25 if require ₂SO ₄, then the amount of required acid is 52 to deduct ESE (13.3g/ liter) or 38.7g/ rises H ₂SO ₄This is to be circulated to the amount that must add in the feed liquid 25 of pressure oxidation section 12, so that keep constant copper concentration in pressure oxidation filtrate 29, promptly 15g/ rises the benchmark of Cu.

Can write out and use Fe ₂(SO ₄) ₃And ZnSO ₄Replace H ₂SO ₄Other reaction as source of sulfate ions.At ZnSO ₄Situation under, suppose that zinc is hydrolyzed into basic zinc sulfate ZnSO ₄3Zn (OH) ₂(this is the subsalt that zinc is similar to Basic Chrome Sulphate).These react available reaction (7) and (8) expression.

(7)

(8)

The solid that is made by pressure oxidation section 12 is handled at 14 pairs of these solids of normal pressure lixiviate section under the about 1.5-2.0 situation of pH value with the acid raffinate that elementary lixiviate section 16 forms, to dissolve Basic Chrome Sulphate through behind the strainer 24.Lixiviate step 14 is carried out under about 40 ℃ of temperature, about 15-60 of the residence time minute.Percent solids is about 5-15% or about 50-170g/ liter usually, although can operate beyond this scope.

In normal pressure lixiviate step 14, alkali type nantokite almost completely dissolves, and has a spot of iron that is present in the enriched material to enter solution.

In general, contain the 10-20g/ that has an appointment in the lixiviate mother liquor 33 that liquid/solid phase separating step 34 produces and rise Cu (different), and 0.1-1.0g/ rises Fe and about 0.1-1.0g/ rises muriate with the difference of the percent solids that adds to lixiviate section 14.Most this iron and muriate are from the raffinate 37 that adds but not from the solid of pressure oxidation, promptly they are recirculation.The about 0.1-0.2g/ of general each circulation dissolving rises iron and muriate.

Have found that the extraction of copper is about 95-98% by the initial material that adds to pressurization lixiviate section 12.Discovery is extracted to iron in the solution approximately less than 1%.

The slurry 31 that is formed by normal pressure lixiviate section 14 is not impossible filter but be difficult to filter but be easy to sedimentation.In view of need the solid of lixiviate thoroughly being washed, strain (CCD) cycles of washing (label is the solid-liquid section of being separated 34 among Fig. 1) so slurry 31 pumps are inclined to adverse current.In CCD circulation 34, solid is added to the middle simultaneously reverse entry that adds of one group of thickening tank (thickeners).Wash solid in this way, remove the solution of deentrainment.Need 3-5 thickening tank (not shown) to make the mother liquor of carrying secretly in the final residual thing reduce to Cu approximately less than 100ppm with the wash ratio (water is than solid) of about 5-7.

By the dense mud of the effusive thickening tank of last thickening tank is to contain 50% solid final residual logistics 35 approximately.Can handle this resistates and reclaim precious metal, as Jin Heyin, or as tailings.Can use known method, reclaim precious metal as cyanide process.The main component of residual stream 35 is ferric oxide and elementary sulfur, if the market condition permission can use flotation process that it is reclaimed.

By the effusive thickening tank spillage of first thickening tank is the product solution 33 that adds to primary solvent extraction section 16 as shown in the figure.This solution contains the 12g/ that has an appointment and rises that Cu, 1g/ rise Cl and 0.5g/ rises Fe.

Best copper concentration is determined by solvent extractions 16 extracts the copper of maximum from solution 33 ability.Because the raffinate that the solvent extractions 16 of about 1/3 part forms will be neutralized at last, it is important therefore reducing to copper content minimum in this raffinate.

Because dense copper solutions can cause raffinate to have higher acid concentration, thereby can reduce extraction efficiency, extracts so be preferably in rare copper solutions.But from the viewpoint of cost of investment, dense solution is because volume is little and more cheap.From certain viewpoint, increase the size that concentration can not reduce solvent extraction unit, because (ⅰ) have maximum organism carrier band amount,, make water volume and organic phase volume keep equating by the water circulation (ⅱ) for the blended purpose.Therefore, the cumulative volume of the organic extractant and the aqueous solution is only determined by the volume of organic extractant.Maximum organic carrier band amount, thereby that is the volume of organic phase, be that concentration and the characteristic by selected concrete organic solvent determined.For special solvent, as LIX available from HenkelCorporation ^TMReagent, the maximum carrier band amount of each round-robin is about 12g/ and rises Cu when 40% volumetric concentration in thinner.Therefore, product solution 33 also should contain the 12g/ that has an appointment and rises Cu.

In primary solvent extraction section 16, copper is extracted from the product solution 33 that is formed by CCD thickening tank spillage in two steps, form and to contain the 20g/ that has an appointment and rises the raffinate 37 that free acid and about 0.3-1g/ rise Cu.Most of this raffinate 37 is recirculated to normal pressure lixiviate section 14, is superfluous but according to the demand of 14 pairs of acid of normal pressure lixiviate section 25-30% is arranged approximately, must neutralize.This superfluous liquid 121 is shunted away and is neutralized shown in 36.

Neutralization is carried out in two steps, farthest to reclaim copper and to prevent the neutral resistates because copper content and the environmental problem that may cause, promptly the copper that does not reclaim in the raffinate 37 can in and the time precipitation, and dissolving again in afterbay for example subsequently.

The neutral the first step is to carry out among the 2-3 at pH shown in 38, uses and compares more economical Wingdale as reaction reagent with lime.Neutralized reaction product is filtered the water washing of the solid that obtains from external water source 45 40.Shown in 41, abandon the solid of mainly forming by calcium sulfate and ironic hydroxide.Therefore, in and the second section of raffinate, form the step of the resistates that comprises calcium sulfate and metal oxide.

Filtrate 39 is delivered to secondary solvent extraction section 18 to reclaim remaining copper number.Secondary solvent extraction 18 have benefited from first in and 38, and make secondary raffinate 43 have very low copper concentration, be about 0.03-0.06g/ usually and rise Cu.

Shown in the dotted line among Fig. 1, secondary solvent extraction section 18 is used identical organic extractant with first solvent extraction circuit 16.This organic extractant is also relevant with the solvent extraction 27 of the branch flow liquid 26 of pressure oxidation filtrate.Be recirculated to secondary solvent extraction section 18 and lead to first extraction section 16 subsequently by the organic extractant of back extraction from washing water 122 washings of external water source 45 and 44 in 42 usefulness.The organism 125 that back extraction obtains is told a part and is led to solvent extractions 27.The raffinate that before entering washing section 42 solvent extractions 27 is formed adds in the organism 123 of the load that solvent extractions 16 forms.The washing water 47 that washing section 42 is formed lead to pressure oxidation strainer 24, as the washing water that add strainer 24.The washings that forms adds in the pressure oxidation filtrate 29, thereby reclaims contained copper and muriate composition from solvent-extracted washing water (47).

In secondary solvent extraction section 46, neutralize once more from the raffinate 43 of secondary solvent extraction section 18, be to carry out in 10 and filter to remove all dissolved heavy metals this time, be formed on the solution 51 that is used to wash final lixiviate resistates 35 in the CCD circulation 34 as washing water 48 at pH.Shown in 53, abandon the solid residue that fillter section 48 produces.

44, load and be to use through the organic back extraction of washing and implement from the spent acid of electrolysis for production section 20 or electrolytic solution 55, to obtain bright sulfur acid copper solutions or rich copper electrolyte 57, subsequently this solution is led to electrolysis for production section 20 and use usual manner to carry out electrolysis for production.

This shows that all solution stream in the method do not produce waste liquid in the method all by recirculation like this.Only abandon the solid resistates in the method.

Mode B

Fig. 2 is the schema of mode B, use with prior figures 1 example in identical label indicate in present method and corresponding section of previous examples or step.For example, pressure oxidation section 12 is also represented with 12, normal pressure lixiviate section is also represented with 14, the electrolysis for production section is also represented with 20, flash tank represents with 22 that also pressure oxidation filtrate represents with 24 that also the shunting of pressure oxidation filtrate 29 is handled and represented with label 28, ground section represents that with label 30 the CCD cycles of washing is represented with label 34.

In the method, pressure oxidation section 12 is used for the most copper oxidation that the enriched material that adds is contained and lixiviate to solution.To solution, the 10-15% that only has an appointment is retained in the resistates with the form of Basic Chrome Sulphate the copper that 85-90% usually arranged approximately by lixiviate.

The condition of pressure oxidation 12 is identical with condition among the mode A in autoclave, but percent solids (being the 150-225g/ liter) is lower.

In the method, Δ [Cu ²⁺] be generally 30-40g/ and rise Cu, promptly bigger from copper concentration in the product solution 21 of pressure oxidation section 12.Add to feed liquid 25 in the pressure oxidation section 12 and contain usually that 10-15g/ rises Cu and 12g/ rises Cl, and about 20-30g/ rises sulfuric acid.

In the method, different with the situation of Fig. 1 example, not to the sulfuric acid of pressure oxidation section 12 addings from external source.In the method, acid obtains from the recirculation of present method, i.e. recirculation by pressure oxidation filtrate 29 obtains.The product solution 21 that is obtained by pressure oxidation section 12 contains approximately when the about 2-2.5 of pH that 40-50g/ rises Cu and 11-12g/ rises Cl.

Must be controlled at the amount of the copper of pressure oxidation section 12 lixiviates to the product mother liquor 21, so that obtain the distribution of copper in mother liquor (85-90%) and resistates (10-15%) that require.This distribution causes containing in the lixiviate resistates a small amount of but the Basic Chrome Sulphate solid of significant quantity.PH can indicate the existence of Basic Chrome Sulphate easily, because it is a kind of buffer reagent.When having very high concentration of copper sulfate in the solution, the pH scope is that 2-2.5 shows that promptly Basic Chrome Sulphate is arranged.PH is lower than 2, and nearly all Basic Chrome Sulphate will dissolve, and is higher than 2.5, then can form too many Basic Chrome Sulphate, makes can not have enough copper in the solution 21.

The main method of control is to control the amount of acid in the raw material mother liquor 25 that adds in the pressure oxidation section 12.Can use the sour level of degree of neutralization control of the solvent extraction raffinate of pressure oxidation filtrate 29 raffinates that describe below successively.Usually, must in and the acid of about 25-50%, depend on the amount of needed acid.

The acid that produces in pressure oxidation 12 is different and depend on employed condition with the difference of enriched material.If enriched material produces a large amount of acid in pressure oxidation 12, then feed liquid 25 needs acid seldom can obtain desired result.The amount that enters the minimum copper the mother liquor 21 from the enriched material that adds is about 10%.Be lower than 10%, pH reduces to low the concentration of iron fast rise that is enough to make in the pressure oxidation filtrate 29.In general, iron is about 10-50ppm, if but pH less than 2 and Basic Chrome Sulphate from resistates, disappear, then iron can increase to about 1g/ liter soon.This be do not wish to see because there are several impurity elements (as As and Sb) only when molten iron is separated, could from solution, remove.Therefore, not having iron in the solution is the good assurance of low impurity content in the pressure oxidation filtrate 29.Iron itself also is impurity, must avoid it as far as possible in electrolysis for production circulation 20.

But another factor can make the content maximum of copper in the solution.If it is lower to be surprised to find the concentration of copper already, in fact some enriched material can lixiviate get more thorough.It is believed that this or because formed secondary CuS as mentioned above, or since some relate to due to other phenomenon of oxidation characteristic of main mine material, the difference of chalcopyrite in the high density copper solutions.Have found that the elementary sulfur that produces can apply or in fact seal unreacted chalcopyrite particle in the reaction process of pressure oxidation 12, hinder the contact of reaction reagent, thereby cause the copper recovery of difference.This phenomenon can with copper level in the solution increase and obviously aggravation.Can be as mentioned above by using tensio-active agent to overcome or alleviating this phenomenon.This problem is for some enriched material, and particularly high-level enriched material is more serious than other enriched material.Therefore, for these enriched materials, need limit copper concentration (promptly greater than about 95%) in pressure oxidation filtrate all sidedly.For reaching this purpose, needing the copper (promptly in the resistates that pressure oxidation 12 forms but not in the pressure oxidation filtrate) of remarkable ratio is Basic Chrome Sulphate.Usually, if necessary, the copper of 20-40% can be various solids so that make copper concentration low as to be enough to obtain high copper recovery.

High level enriched material has the problem of copper concentration in low copper recovery and the solution.Therefore, along with must having more a high proportion of copper, other rising of level becomes various solids.The test of using three kinds of different enriched materials to carry out has illustrated this relation: enriched material # %Cu H ⁺/ Cu Cu distribution %

Mol ratio mother liquor part resistates part total yield

1 41 0.55 0 100 97.3

2 28 0.70 63 37 95.7

3 22 0.96 85 15 94.7

H ⁺/ Cu mol ratio is meant the H in the acid of adding ⁺Than the Cu in the enriched material that adds.H in the acid that adds ⁺Be meant the hydrogen ion that all disassociations of acid (even should acid not exclusively disassociation under the condition of place) are produced.H shown in the table ⁺It is the optimum value that can obtain the experiment acquisition of best result.

With regard to high-level enriched material #1, selected method is mode A, and wherein all copper all becomes solid Basic Chrome Sulphate and Δ [Cu ⁺]=0.This H ⁺/ Cu is than being the Δ [Cu for obtaining requiring that experiment obtains ⁺The necessary value of]=0 result.

With regard to medium rank enriched material #2, select mode B for use, but have the copper of significant quantity to become the solid Basic Chrome Sulphate.This is by making H ⁺/ Cu ratio remains on enough low, makes it is not that whole copper all are dissolved in the mother liquor.

With regard to low level enriched material #3, still select mode B for use, but pass through H in this case ⁺/ Cu makes minimum copper enter resistates than being adjusted to enough height.

(concentration is that rare 3-10g/ rises H from solvent extraction section 16 with circulation ₂SO ₄) raffinate 37 at the resistates of lixiviate section 14 lixiviates from pressure oxidation section 12.Because many copper have entered pressure oxidation filtrate 29 in pressure oxidation 12, and a spot of pressure oxidation resistates is only arranged, therefore copper concentration is very rare in the lixiviate mother liquor 31 that normal pressure lixiviate section 14 forms.Thereby produce rare raffinate 37 in solvent extractions 16.Normal pressure lixiviate mother liquor 31 contains usually that 3-7g/ rises Cu and 0.2-0.5g/ rises Fe.

As mode A, the slurry that normal pressure lixiviate section 14 forms is difficult to filter.Gu but in CCD equipment 34, use one group of thickening tank can obtain good liquid/separation and washing earlier.As 46 indications, washing water 51 are by being provided from solvent extraction section 16, the raffinate that is neutralized.This is similar to mode A.Lower and the smaller volume of metal content that only main difference is solution 33.

The solution 33 that normal pressure lixiviate section 14 is produced adopts solvent extraction 16.Copper-containing solution 29 from pressure oxidation section 12 is adopted solvent extraction 50.Therefore two kinds of solvent extractions operations, promptly 16 and 50, handle different mother liquor stream 33 and 29 respectively.The organic extractant that is used for the solvent extraction operation in solvent extraction 16 and 50 is general (common), and this is a feature of the inventive method.

As shown in Figure 2, will at first import in the solvent extraction circuit 16 from the back extraction organism 125 of conventional back extraction operation 44, it has the rarest copper concentration in aqueous stream 33, therefore requires the organic extraction agent content low as far as possible so that load effectively.

To deliver to solvent extractions 50 from the organism 126 of the load of solvent extraction section 16 subsequently, and locate it at this and contact with the mother liquor 29 of copper concentration more.Solvent extraction 50 not necessarily will obtain high extraction ratio, because the raffinate 63 that this extraction section forms is recycled to pressure oxidation section 12 as shown in the figure.On the other hand, the raffinate 37 that is formed by solvent extractions 16 only has part recirculation, and part is neutralized so that remove excessive acid from circulation 46.Therefore, it is important obtaining high copper recovery in solvent extractions 16.

Raffinate 37 as mode A 36 by being shunted out, about 1/3 121 flow to 120 of neutralizing zone 46,2/3 and be recycled to normal pressure lixiviate section 14.Be to make copper content quite low (promptly being lower than 100ppm) from the raffinate 37 of solvent extractions 16 before neutralizing zone 46, to need not employed secondary solvent extraction section among the mode A with the important difference of mode A.This is because lower copper concentration and liquor capacity makes that the efficient of solvent extraction 16 is higher.

Shown in 42, wash the organism 65 of operating 16 and 50 loads that produce by two step solvent extractions of serial connection in two steps with reflux type with dilute acid solution 122.This mainly is the aqueous solution that removes deentrainment from the organism 65 of load, particularly reduces muriatic content at organism before 44 carry out back extraction.The amount of washing water is about the 1-3% of organism volume.The final washing mother liquor 47 that generates is recirculated to pressure oxidation section 12.

Use from the waste electrolyte 55 of electrolysis for production section 20 at the organism 69 of 44 back extractions, be formed for pure copper solutions or rich copper electrolyte 57 that usual manner carries out electrolysis for production through washing.

Raffinate 63 is split into by the H that requires 70 ⁺Two portions 72,74,72 parts that/Cu mol ratio is determined are recirculated to pressure oxidation section 12.Be neutralized to pH with Wingdale be 2 to 74 parts and filter 78 76.Shown in 80, solid residue is washed and abandons.Filtrate 82 with 72 part recirculation, is formed the feed liquid 25 that adds to pressure oxidation section 12.Therefore, the second section neutralization with raffinate forms calcium sulfate resistates and neutralization solution, separates this resistates and neutralization solution is recycled to the pressure oxidation section.

Therefore, present method new feature is to use general organism extracting copper from two kinds of different aqueous materials mother liquors.Thereby for reduction fund and running cost in the solvent extraction circuit provide significant saving measure.Simultaneously, it allows to use a large amount of water in normal pressure lixiviate CCD circulation, thereby can carry out good washing to final resistates, and can also reclaim copper from so rare mother liquor.

Have found that thio-oxidizing degree depends on the type (as the rank of the enriched material of handling and mineralogy) of enriched material and the condition of pressure oxidation 12 to a great extent in pressure oxidation 12.Some enriched material has very high sulphur oxidisability (sulphur that is about in the enriched material is oxidized to sulfate radical), and is obvious especially to containing less than this effect of low level enriched material of about 28 weight %Cu.The inventor finds that this species diversity is unconspicuous to copper itself, and is tangible for the copper in the enriched material/sulphur ratio.Because copper mine stone is usually by chalcopyrite and other ore, particularly pyrite FeS ₂Or pyrrhotite FeS composition, so major impurity is iron and sulphur in the copper concentrate.

When using the low level enriched material, mode B solves excessive thio-oxidizing problem in the pressure oxidation 12 by the formation that intentional dissolving 90% bronze medal also farthest reduces Basic Chrome Sulphate.The reaction of chalcopyrite is:

(6)

Therefore, contain a large amount of copper sulfate and cupric chloride by the filtrate 29 that pressure oxidation section 12 generates, these mantoquitas are processed into the pure copper-bath towards electrolysis for production section 20 in solvent extractions 50.

Fig. 3 has shown the Wet-process metallurgy method of going back extracting zinc except copper.Use the label identical to show in present method and corresponding section of previous examples or step with previous examples.

As the situation of previous examples, enriched material also grinds in ground section 30.

The pressure oxidation of zinc-copper mixing enriched material is to use similar in appearance to the method for oxidation of the enriched material that only contains copper as shown in Figure 2 to carry out.

The oxidation of zinc is same as copper or easier than copper, and zinc is easier to enter lixiviate mother liquor 29 but not the pressure oxidation resistates.This is to become basic zinc sulfate because compare the not too easy hydrolysis (promptly under higher pH) of zinc with copper.

That is found during image height rank copper concentration is such, and the recovery of copper or zinc is not hindered by high solvency action trend obviously.Therefore, most copper and zinc are entered in the pressure oxidation filtrate 29, promptly as mode B.The oxidation of sulphur is low, makes that the amount of the acid of generation is low in pressure oxidation 12.So in order to obtain high H ⁺In fact/Cu ratio needs recirculation through all acid of the least possible neutral from solvent extractions 12.The acid that adds can be to contain about 10g/ to rise that Cu, 5g/ rise Zn and 12g/ rises the H of the height of Cl to the 75g/ liter ₂SO ₄

Zinc and copper that pressure oxidation filtrate 29 is contained quite big concentration depend on the material concentrate composition.With regard to the enriched material that contains 20%Cu and 5%Zn, pressure oxidation filtrate 29 can contain the 50g/ that has an appointment and rise Cu, 15g/ and rise Zn and 12/ liter of Cl.

As shown in the figure, the pressure oxidation raffinate is used for carrying out lixiviate from the raffinate 37 of solvent extraction section 16 14 in an identical manner, forms the Cu-Zn mixing solutions as the solvent extraction circuit feed liquid.Elder generation extracting zinc, extracting copper subsequently.

As among the mode B to the copper concentrate, have two kinds of current will carry out solvent extraction and handle.Pressure oxidation filtrate 29 is contained high Cu and Zn metal, and the content of two kinds of elements is all very low in the normal pressure vat liquor 33.

The new installation that is used for solvent extraction circuit as top example is continued on for the solvent extraction of zinc, and rare mother liquor is contacted with organic extractant, and dense mother liquor is contacted with it.In this case, have two circulations, one is used for zinc, and another is used for copper.

Can first extracting copper, extracting zinc subsequently depends on the selection of organic extractant and to the avidity of two kinds of elements.The inventor finds to use DEHPA (diethylhexyl phosphoric acid) can obtain satisfied result as first extraction agent (its to the selectivity of zinc greater than the selectivity to copper).Therefore, carried out two step DEHPA extractions 100 and 102, the first step extraction 100 is to from the dense mother liquor 29 of pressure oxidation section 12 to rare mother liquor 33, the second step extraction 102, so that reclaim zinc and copper is stayed in the solution.

When the acid concentration that exists is high, the obstruction of the extracted character that the DEHPA extracting zinc is differed from.In practice, this means pH be about 1.4 or about 7-10g/ rise H ₂SO ₄, in fact extraction has stopped.For addressing this problem, having added at pH is the solvent extraction that the middle neutralizing zone 104 of 2 neutral is used for zinc.Therefore the solvent extraction of zinc divides two steps, i.e. the step 102 and second step 103, and the centre is a neutralization procedure 104.Before the acid concentration that forms in by raffinate stopped, step 102,103 only can extract 5-7g/ separately and rise Zn.By neutralization procedure 104 in the middle of using, total zinc extraction can increase to 10g/ liter or more.Will be from the raffinate 97 of first extraction section 102 at the inexpensive Wingdale (CaCO of 104 usefulness ₃) be neutralized to pH and be about 2-2.5,98 the calcium sulphate solid that form are leached and abandon.Subsequently filtrate 99 is added to second solvent extractions 103.The feed liquid that adds to second extraction section often contains that 10g/ rises Zn and 50g/ rises Cu, and pH is 2-2.5.After the extraction, second raffinate often contains 5g/ and rises Zn, 50g/ and rise Cu and 8g/ and rise acid.

With regard to solvent extraction circuit 16, zinc concentration is very low, makes it not constitute problem.

Zinc content best in pressure oxidation filtrate 29 depends on the extracting power of zinc solvent extraction circuit to zinc to a great extent.Because existing extraction agent (as DEHPA) is very weak to the extracting power of zinc, therefore, before acid accumulation stopped reaction in owing to raffinate, about 5-7g/ of a maximum that can be extracted of existence rose the value of Zn.Further extraction need neutralize to acid.Neutralization procedure can extract the more Zn of volume in the middle of using, but this centre neutralization procedure has been removed sulfate radical from circulation, the oxidation that this sulfate radical must be by sulphur or circulate to pressure oxidation that the fresh acid of adding replenishes in 23.

Neutralization procedure is expected to compatiblely with the balance of sulfate radical in the middle of one, therefore, preferably keeps Δ [Zn ²⁺] (zinc concentration in the pressure oxidation filtrate 29 deducts the zinc concentration in the recirculation raffinate 72) be about the 10g/ liter.Like this, if be recycled to the pressure oxidation section, contain 5g/ from the sour feed liquid of the raffinate 72 of solvent extractions and rise Zn, then the filtrate 29 that generates of pressure oxidation can contain the 15g/ that has an appointment and rises Zn.This restriction of comparing Δ [Zn] with the method that is used for Cu has shown the characteristics that are used for the Zn method.The solvent-extracted extracting power of bigger Cu means that the acidity that rises with the about 7-10g/ of zinc compares, and the acidity in higher raffinate (rises H up to 75g/ ₂SO ₄) can obtain down good Cu extraction.Therefore can rise extracting Cu the materials flow of Cu from 50g/.

After the extraction, to the faulty optionally result of zinc, the organism 106 of loading from Zn (DEHPA) round-robin contains number of C u, and is mingled with dense Cu mother liquor simply as the DEHPA extraction agent.Usually, the Zn/Cu ratio is about 150-300 in from the organism 106 of the solvent-extracted load of Zn: 1.As not removing Cu, then all Cu can be with Zn by back extraction in solvent back extraction step 114, and by back extraction to adding in the rich zinc electrolyte 120 of zinc electrolysis for production section 118.The zinc electrolysis for production needs very pure rich zinc electrolyte, if make the Zn negative electrode of satisfied (pure) under rational current efficiency.Zn/Cu must be about 100,000: 1 in rich zinc electrolyte.Therefore, before electrolysis for production must from the load organism 106 or from rich zinc electrolyte, remove nearly all Cu.The organism 106 of purification load is quite easy.

In order to remove these copper, (as the 3-10 step, being generally for 5 steps) washs or treatment step 106 to need several steps.Washing is carried out with zinc sulfate weakly acidic water solution.Mode with serial connection is arranged washing section, and promptly the treated organism of drawing from first washing section enters second washing section, and so by other all sections, discharges from last washing section until organism.Because some zinc are washed out with copper, therefore the amount of the washing water that add need be reduced to minimumly, and several washing sections are arranged in reflux type to replace original washing section.

The washing mother liquor 110 that generates is recycled in the normal pressure lixiviate circulation to reclaim copper and zinc value.

After the washing, be prepared for the organic streams 112 that the waste electrolyte 116 from zinc electrolysis for production loop 118 extracts from DEHPA in stripping section 114 back extractions.Thereby make the rich zinc electrolyte 120 that is used for electrolysis for production zinc under the high current efficiency.

After back extraction step 114, to extraction solvent further in stripping section 131 back extractions so that before extraction agent is recycled to solvent extractions 100, remove de-iron.Back extraction step 131 is to use HCl supply solution 133 to implement, and it is imported into the pressure oxidation section.

Respectively at solvent extractions 16 and 50 selective copper extraction agents (as LIX ^TM) raffinate 122 and 124 from the extraction of DEHPA zinc is extracted.

The design of circulation 16 and 50 is used general organism similar in appearance to the design of mode A, is used for solvent extractions 16 earlier, uses this organism in solvent extractions 50 subsequently.Wash and back extraction at the organism of 42 and 44 pairs of loads respectively as before subsequently.

Owing to neutralize in the zinc circulation in front, therefore find in solvent extraction 50 circulations very low to the neutral demand.

As before will be from LIX ^TMThe raffinate of extraction is recycled to pressure oxidation section 12 and normal pressure lixiviate section 14 respectively.

Fig. 4 has shown the hydrometallurgical extraction method that also reclaims nickel except copper.

Use the label identical with corresponding section of representative and previous examples or step in the method with previous examples.

With regard to nickel-copper concentrate, present method is very similar to the method for extracting zinc, but all available solvent extraction agents to the selectivity of nickel all less than selectivity to copper.Therefore, nickel solvent extraction circuit 130 and 132 all places corresponding copper solvent extraction circulation 16 and 50 back respectively.

Being recycled to before the solvent extractions 130 and will washing at washing section 137, subsequently in 139 back extractions from the nickel extraction agent 135 of the load of solvent extraction section 132.Back extraction step 139 is to use smelts from nickel electrowinning that 140 waste electrolyte realized.

In addition, because the extractibility of nickel is very poor, shown in 134 and 136, need for example to neutralize on the spot respectively with ammonia.Ammonia must reclaim from corresponding raffinate and recirculation by for example lime boil step 128.

To be described further the inventive method by embodiment below.Embodiment 1-7 has illustrated the pressure oxidation 12 of present method.Embodiment 8 and 9 has illustrated normal pressure lixiviate step 14.The solvent extraction of embodiment 10 and 11 explanation present method.

Embodiment 1

(test #258)

Under following condition, the copper concentrate from the Highland Valley Copper Mine of British Columbia is carried out pressure oxidation and normal pressure lixiviate: pressure oxidation normal pressure extraction temperature: 150 ℃ of temperature: 40 ℃ of residence time: 60 fens clock times: 60 minutes pressure: 1500kpa (200psig) pH:1.5-1.7 pressure oxidation enriched material weight: 225g % (37.9Cu in batches, 21.4Fe, 28.3S) feed liquid: 1100ml g/ liter (26.1Cu, 12.4Cl, 24.8H ₂SO ₄0ppmFe) filtrate: 985ml g/ liter (30.1Cu, 12.2Cl, 3.4pH, 10ppmFe) normal pressure lixiviate: feed liquid: 3000ml g/ liter (1.9Cu, 0.8Cl, 0.91Fe) filtrate: 3915ml g/ liter (20.0Cu, 0.9Cl, 0.88Fe, 1.9pH) resistates: 154g % (1.27Cu, 29.5Fe)

The results are shown in table 1

Table 1

Cu% distributes		Δ[Cu 2+]	The %Cu extraction	H +/ Cu mol ratio	The oxidation of % sulphur
						Filtrate	Resistates
0％	100％							0.9	97.7％	0.41	9.1％

In these embodiments, all Δ [Cu ²⁺] value all converts and be back to the volume of (back-calculated) constant feed liquid and pressure oxidation filtrate.In the normal pressure extracting solution, add acid as required to obtain as the described final pH of condition.Copper percentile shown in the table 1 is meant the percentile of pressure oxidation.

This shows that except feed liquid, pressure oxidation filtrate contains extra copper hardly.All copper from the enriched material that adds all exist with the form of Basic Chrome Sulphate.9.1% sulphur generation oxidation is only arranged, and the total yield of copper is 97.3% after the normal pressure lixiviate.The oxidation of sulphur is calculated with the sulfate radical balance method.

Embodiment 2 and 3

(test #263 and #265)

(but the acid in the pressure oxidation feed liquid of embodiment 2 is 0, the acid in embodiment 3 is the 35g/ liter) carries out two tests again under the condition identical with the foregoing description 1.Result at table 2 couple embodiment 1-3 compares.The test of embodiment 1-3 is carried out in autoclave in the batch-wise mode.

Table 2

Embodiment	Acid in the feed liquid (g/ liter)	Δ[Cu 2+]	The extraction of %Cu	The oxidation of % sulphur
					2	0	-14.7	97.1％	13.8％
1	25	0.9	97.7％	9.1％
					3	35	9.9	97.4％	7.9％

This shows that the acidity in the pressure oxidation feed liquid (feed) influences the oxidation of sulphur.By the acid in the pressure oxidation feed liquid is increased to the 35g/ liter by 0, the oxidation of sulphur can be reduced to 8% by 14%.The acidity of pressure oxidation feed liquid also influences the variation of copper concentration between feed liquid and filtrate.It is to keep the balance of copper stabilized metal in the pressure oxidation process needed that about 25g/ rises acid.If the concentration of acid is higher than the 25g/ liter in feed liquid, copper can gather in filtrate.

Embodiment 4

(test #198)

Use the enriched material among the embodiment of front, condition is carried out the test of successive pressure oxidation test replacement batch-wise below using in autoclave:

Pressure oxidation

Temperature: 150 ℃

The residence time: 149 minutes

Pressure: 1500kpa (200psig)

Layout (compartments) number: 4

Solid drying speed: 4.0kg/hr@69% solid

Acid feed rate: 12.4 liters/hr

Solution charge temperature: 85 ℃

Enriched material: Highland Valley Copper

Normal pressure lixiviate (on sample):

Temperature: 40 ℃

pH: 1.5-1.7

Pressure oxidation product slurry sample is filtered, under the normal pressure extracting condition, filter cake is carried out lixiviate to measure the total yield of copper in batches.Pressure oxidation enriched material weight: 49kg% (39.5Cu, 16.85Fe, 24.9S) feed liquid: 139 liters of g/ liters (13.1Cu, 11.7Cl, 53.7H ₂SO ₄, 286ppmFe) product solution (estimation volume): 125 liters of g/ liters (17.5Cu, 3.1pH, 10ppmFe) normal pressure lixiviate resistatess: 34kg % (1.3Cu)

The results are shown in table 3

Table 3

Cu% distributes		Δ[Cu 2+]	The %Cu extraction	H +/ Cu mol ratio
					Filtrate	Resistates
	1％	99％	2.6	97.6％	0.50

This shows that very most of copper from enriched material all exists with the form of alkali type nantokite; Only have an appointment and 1% be present in the filtrate.Δ [Cu ²⁺] value is little, total percentage extraction of copper is 97.3% after the normal pressure lixiviate.By the sulfate radical balance between material and the product stream calculate sulfur oxidation rate be 6.6%, proved and in feed liquid, used high concentration sulphate can farthest reduce the oxidation of sulphur.

Embodiment 5

(test #206)

Carry out another test similar, still in autoclave, carry out in a continuous manner to embodiment 4.Contain the copper of higher concentration and less acid this moment in the feed liquid:

Pressure oxidation

Temperature: 150 ℃

The residence time: 149 minutes

Pressure: 1500kpa (200psig)

Volume: 34 liters

Layout (compartments) number: 4

Solid drying speed: 4.0kg/hr@69% solid

Acid feed rate: 12.4 liters/hr

Solution charge temperature: 72 ℃

Enriched material: Highland Valley Copper

The normal pressure lixiviate:

Temperature: 40 ℃ of pH:1.5-1.7 pressure oxidation enriched material weight: 47kg % (40.1 Cu, 15.6Fe, 24.9S) feed liquid: 143 liters of g/ liters (34.1Cu, 12.1Cl, 33.6H ₂SO ₄,

16ppmFe) 129 liters of g/ liter (12.4Cu of product solution (estimation volume), 3.2pH, 4ppmFe) normal pressure lixiviate resistates estimated weight: 33kg % (1.47Cu) table 4

Cu% distributes		Δ[Cu 2+]	The %Cu extraction	H +/ Cu mol ratio	The oxidation of % sulphur
						Filtrate	Resistates
-18.5％	118.5％							-23	97.4％	0.35	4.2％

How the present embodiment proof can to 33.6g/ rise H by add the concentration that copper can reduce acid in the feed liquid in feed liquid ₂SO ₄, be different from the 53.7g/ liter among the embodiment of front.

Following test is to use the low level enriched material, carries out with mode B, is used to illustrate this example of the present invention.In this example, require the most copper lixiviate in the enriched material to solution.

Embodiment 6

(test #352)

Test by following condition with batch mode: pressure oxidation normal pressure extraction temperature: 150 ℃ of temperature: 40 ℃ of residence time: 60 fens clock times: 60 minutes pressure: 1500kpa (200psig) pH:1.5-1.7 pressure oxidation enriched material weight: 225g % (22.8Cu, 25.3Fe, 28.9S) feed liquid: 1100ml g/ liter (13.6Cu, 11.7Cl, 34.0H ₂SO ₄, 0ppmFe) product solution (estimation volume): 1035ml g/ liter (53.5Cu, 10.9Cl, 2.9pH, 32ppmFe) normal pressure lixiviate filtrate: 1420ml g/ liter (3.4Cu, 0.7Cl, 1.7pH, 2.3H ₂SO ₄, 0.62Fe) resistates estimated weight: 184g % (1.43Cu, 27.6Fe)

The results are shown in table 5

Table 5

Cu% distributes		Δ[Cu 2+]	The %Cu extraction	H +/ Cu mol ratio	The oxidation of % sulphur
						Filtrate	Resistates
79％	21％							35.0	95％	0.95	13.5％

The major portion of copper is in filtrate in this case, and the oxidation ratio of sulphur is 13.5%, and extraction obtains 95.0%Cu.Because high H ⁺/ Cu ratio has and represents in the report that 79%Cu enters in the filtrate.

Embodiment 7

(test #88)

In autoclave, carry out another test by following condition with identical low level enriched material in a continuous manner:

Pressure oxidation

Temperature: 150 ℃

The residence time: 53 minutes

Pressure: 1500kpa (200psig)

Layout (compartments) number: 5

Solid drying speed: 7.2kg/hr@68% solid

Acid feed rate: 32.8 liters/hr

Solution charge temperature: 45 ℃

Enriched material: Island Copper

The normal pressure lixiviate

Temperature: 40 ℃

pH: 1.5-1.7

Pressure oxidation

Enriched material weight: 55kg % (22.5Cu, 25.4Fe, 29.1S)

Feed liquid: 250 liters of g/ liters (9.4Cu, 13.2Cl, 35.0H ₂SO ₄)

Product solution (estimation volume): 225 liters of g/ liters (50.8Cu, 2.8pH)

The normal pressure lixiviate

Resistates (estimated weight): 47kg % (1.4Cu)

The results are shown in table 6

Table 6

Cu% distributes		Δ[Cu 2+]	The %Cu extraction	H +/ Cu mol ratio	The oxidation of % sulphur
						Filtrate	Resistates
73％	27％							36.3	94.6％	0.83	16.5％

Be again because high H ⁺/ Cu ratio has the major portion of report expression copper to enter in the pressure oxidation filtrate.

Embodiment 8 and 9

The present embodiment explanation is used for normal pressure lixiviate of carrying out in a continuous manner and the countercurrent washing operation of mode A and mode B.The operational condition of two embodiment is as follows:

Operational condition
			Parameter	The normal pressure lixiviate	Countercurrent washing
Temperature	40-45℃	32-25℃
			Final pH	1.7	3.5
Number of reactors	3	5 posts of 5 mixing tanks
			The cumulative volume of 3 reactors	69 liters	Do not have (n/a)
The residence time	45-60 minute	Do not have

The example of the mode A (Fig. 1) of embodiment 8 explanation present method, wherein copper is completely contained in the pressure oxidation filter cake substantially, and the example of embodiment 9 explanation mode B (Fig. 2) wherein only has the small portion copper-clad to be contained in the filter cake.The result lists in table 7 and the table 8 respectively.The full-process extracting rate of copper is 97.5% among the embodiment 8, is 94.6% in embodiment 9.

Table 7

Mode A embodiment-materials flow composition and volume/weight
							Materials flow	Volume (liter) or weight (kg)	The % solid	[Cu] g/ liter	[free acid] g/ liter	[Cl] g/ liter	[Fe] g/ liter
Elementary raffinate 120	1225 liters	0.0	0.5	26	1.1	0.3
							Waste electrolyte divides the flow liquid extraction	5.8 rise	0.0	35.2	204	--	--
The part filter cake	155Kg (wetting)	81	23％	Do not have	Do not have	Do not have
							Normal pressure lixiviate spillage 31	1390 liters	4	18	pH1.64	1.2	0.3
Flocculation agent	70 liters	1.0g/ rise	Do not have	Do not have	Do not have	Do not have
							Condensing agent	36 liters	1.0g/ rise	Do not have	Do not have	Do not have	Do not have
Add to the washing water of CCW51	800 liters	0.0	--	pH3.6	1.0	--
							CCW#5 under logistics 35	228kg	41	1.7% 0.17g/ liter	Filtrate pH3.1	1.1	0.05
Tap water PLS dilution	360 liters	0.0	--	pH5	--	--
							Carry out the filtrate of solvent extraction 33	2370 liters	Elimination	11	pH1.9	1.1	0.3

Table 8

Mode B embodiment-materials flow composition and volume/weight
							Materials flow	Volume (liter) or weight (kg)	The % solid	[Cu] g/ liter	H 2SO 4The g/ liter	[Cl] g/ liter	[Fe] g/ liter
Elementary raffinate 120	300 liters	0.0	0.0	11	1.0	0.3
							Waste electrolyte divides the flow liquid extraction	10.2 rise	0.0	30	180	12ppm	0.1
The part filter cake	154Kg (wetting)	75	3.9％	Do not have	Do not have	Do not have
							Normal pressure lixiviate spillage 31	440 liters	27	7.5	1.3	1.3	Do not have
Flocculation agent	51 liters	1.0g/ rise	Do not have	Do not have	Do not have	Do not have
							Condensing agent	41 liters	1.0g/ rise	Do not have	Do not have	Do not have	Do not have
Add to the washing water of CCW51	628 liters	0.0	0.1	pH3.0	0.9	0.03
							CCW#5 in logistics 35	216kg	39	1.3% 0.12g/ liter	Filtrate pH2.9	0.9	0.03
Tap water PLS dilution	0 liter	0.0	--	--	--	--
							Carry out the filtrate of solvent extraction 33	980 liters	Do not have	4.1	1.2	0.8	0.4

Embodiment 10 and 11

The solvent extractions of present embodiment explanation present method.In embodiment 10, present method is according to Fig. 1 example, and embodiment 11 is according to Fig. 2 example.In both cases, operating parameters is as follows:

The mixing tank residence time: 3-6 minute

Temperature: 40-45 ℃

The organic extractant of copper: 40% (v/v) LIX@70:30 (v/v) 860n:84N

Organic thinner: 60% (v/v) ORFOM SX-11

The results are shown in table 9 and table 10.The label that is equal to different materials flows is shown in Fig. 1 and Fig. 2 respectively.

Table 9

Materials flow	Volume (basic Huaihe River (basis): 24 hours) rises	[Cu] g/ liter	H 2SO 4The g/ liter	[C1] ppm	Copper loss in final raffinate is lost
						Product solution 33	3168	11.5	1.5	1050
Raffinate 120 (to normal pressure lixiviate section)	2112	0.5	18	1050
						Raffinate 121 (to neutralizing zone)	1056	0.5	18	1050
Filtrate 39	1056	0.5	pH2	1050
						Secondary raffinate 43	1056	0.05	1.7	1050
Solution 51	1056	0.004	pH9	1050	0.1％
						Washing water
122	43	0	pH1.3	0
						Washed product 47	43	0.45	6.2	220
The extraction agent 123 of first stage load	3168	17
						The extraction agent 124 of secondary load	3168	6.35
Back extraction extraction agent 125	3168	6.2
						Waste electrolyte 55	3168	41	200	20
Rich copper electrolyte 57	3168	30	184	20

In embodiment 11, about 2/3 back extraction extraction agent bypass is to solvent extractions 16 and be introduced directly in solvent extractions 50 the first step of (having 2 steps).Only have 1/3 back extraction extraction agent to be added to solvent extractions 16, produce the extraction agent of stage load just, this extraction agent is imported into second step of solvent extractions 50, makes the extraction agent 65 that is merged into load from the materials flow of solvent extractions 16 and 50.

Table 10

Materials flow	Volume (benchmark: 24 hours) rises	[Cu] g/ liter	H 2SO 4The g/ liter	[Cl] **G/ rises ppm	The copper extraction
						Product solution 33	1152	4.1	pH1.9	**0.89
Raffinate 120 (to normal pressure lixiviate section)	768	0.08	9.3	--
						Raffinate 121 (to neutralizing zone)	384	0.08	9.3	--
Solution 51	384	0	pH9	-	0.7％
						Pressure oxidation filtrate 29	778	49.9	pH3.2	**11.36
Raffinate 63	778	12.9	56.5	-	0.1％
						Filtrate 82	Do not have	12.9	pH2	--
Washing water 122	43	0	pH1.3	0
						Washed product 47	43	8.7	21.5	4.9
The extraction agent 126 of load	1152	10.3
						The extraction agent 65 of load	3168	18.2
Back extraction extraction agent 125	3168	6.07
						Waste electrolyte 55	3168	28.5	184	21
Rich copper electrolyte 57	3168	40.8	167	23

Although only to the present invention preferably example describe in detail, the present invention is not limited.In appended claim scope, can carry out various variations to it.

Claims (51)

1. the method for an extracting copper from copper sulfide ore or enriched material comprises the steps:

In the presence of oxygen and acid chloride solution, ore or enriched material are carried out pressure oxidation, pressure oxidation filtrate and insoluble Basic Chrome Sulphate salt to obtain to generate is characterized in that pressure oxidation is to carry out in the presence of bisulfate ion or source of sulfate ions.Described ion source is selected from the sulfuric acid and the metal sulfate of hydrolysis in acidic solution; And the bisulfate ion that is added or the amount of source of sulfate ions are to generate the sulfate radical of the required stoichiometry of Basic Chrome Sulphate salt or the amount that hydrogen sulfate ion deducts the sulfate radical of ground, pressure oxidation Central Plains generation at least.

2. the method for claim 1 also comprises the following steps:

The filtrate of pressure oxidation is recycled to the pressure oxidation section;

The Basic Chrome Sulphate that is made by pressure oxidation with the lixiviate of sour sulfur acid group solution in the lixiviate second time with the dissolving alkali type nantokite, generates in the solution and contains the lixiviate mother liquor of copper sulfate and form solid residue;

From solid residue, separate the lixiviate mother liquor; The lixiviate mother liquor is adopted the solution extraction method, to generate dense copper solutions and raffinate;

Raffinate is recycled to the step of lixiviate for the second time.

3. method as claimed in claim 2 is characterized in that pressure oxidation is at predetermined H ⁺Carry out in/Cu the mol ratio, wherein H ⁺The hydrogen ion of representative in acid chloride solution, Cu represents the copper in ore or the enriched material, makes copper concentration in the final pressure oxidation filtrate that is produced by pressure oxidation equal to be recycled to the copper concentration in the pressure oxidation filtrate of pressure oxidation substantially.

4. method as claimed in claim 3, the chloride concentration that it is characterized in that being recycled in the pressure oxidation filtrate of pressure oxidation section remains on the 8-20g/ liter.

5. method as claimed in claim 4, the chloride concentration that it is characterized in that being recycled in the pressure oxidation filtrate of pressure oxidation section remains on the 11-14g/ liter.

6. method as claimed in claim 5, the chloride concentration that it is characterized in that being recycled in the pressure oxidation filtrate of pressure oxidation section remains on the 12g/ liter.

7. as any one described method among the claim 2-6, it is characterized in that pressure oxidation is at predetermined H ⁺Carry out in/Cu the mol ratio, the H+ representative hydrogen ion in acid chloride solution wherein, Cu represent the copper in ore or the enriched material, makes copper concentration in the final pressure oxidation filtrate that is made by pressure oxidation in the scope of 10-25g/ liter.

8. method as claimed in claim 2 is characterized in that lixiviate for the second time is to carry out in the pH of 1.3-2.2 scope.

9. method as claimed in claim 8 is characterized in that lixiviate for the second time is to carry out in the pH of 1.6-1.9 scope.

10. method as claimed in claim 2 is characterized in that lixiviate for the second time is to carry out in 20-70 ℃ temperature range.

11. method as claimed in claim 10 is characterized in that lixiviate for the second time is to carry out in 35-45 ℃ temperature range.

12. method as claimed in claim 2 is characterized in that also comprising dense copper solutions is carried out electrolysis for production, therefrom reclaims the step of copper.

13. method as claimed in claim 12, it is characterized in that being used for solvent extraction method from the lixiviate mother liquor of the lixiviate second time comprises this lixiviate mother liquor is mixed the extraction agent that forms load with organic extractant, wash this load extraction agent with water, with the extraction agent that the sulphuric acid soln back extraction should be loaded, be formed for the dense copper solutions of electrolysis for production.

14. method as claimed in claim 13, it is characterized in that sulfuric acid comprise recirculation from electrolysis for production exhaust or waste electrolyte.

15. method as claimed in claim 2, it is characterized in that raffinate is split into first part that comprises 2/3 raffinate and the second section that comprises 1/3 raffinate, wherein first part is recycled to the section of lixiviate for the second time, second section is carried out the secondary solvent extraction, to remove copper, form secondary lixiviant and secondary raffinate.

16. method as claimed in claim 15 is characterized in that this secondary lixiviant is used as organic extractant and is used for solvent extraction from the lixiviate mother liquor of lixiviate second time section.

17. method as claimed in claim 15, also being included in the secondary solvent extraction preceding is that 1.5-3 carries out the neutralization first time to second section at pH, with antacid content, and to be 9-10 at pH carry out the secondary neutralization to the secondary raffinate, with antacid content and therefrom remove the dissolved metal.

18. method as claimed in claim 17, it is characterized in that from lixiviate second time section separating lixiviate mother liquor and solid residue be to use the adverse current to incline the method for straining carries out, and the secondary raffinate after neutralization for the second time is recycled, and the washing water that incline in the method for straining as adverse current are used to wash solid residue.

19. the method for claim 1 is characterized in that pressure oxidation is to carry out under 115-175 ℃ temperature.

20. the method for claim 1 is characterized in that pressure oxidation is is to carry out in the boosting of 445kpa-1825kpa at oxygen partial pressure.

21. the method for claim 1, it is characterized in that in the pressure oxidation process, forming liquid elemental sulphur, and be included in the pressure oxidation process and in the pressure oxidation section, add the step of tensio-active agent with the viscosity that farthest reduces liquid elemental sulphur.

22. the method for claim 1 is characterized in that pressure oxidation filtrate is recycled to the pressure oxidation section as bisulfate ion or source of sulfate ions.

23. method as claimed in claim 22, also comprise filtrate is recycled to the pressure oxidation section before, pressure oxidation filtrate is carried out solvent extraction therefrom to remove the step of dissolved copper.

24. the method for claim 1 is characterized in that bisulfate ion or source of sulfate ions comprise sulphuric acid soln or the copper-bath that is added by external source.

25. the method for claim 1 is characterized in that pressure oxidation is the H at 0.7-1.0 ⁺Carry out in/Cu the mol ratio, wherein H ⁺The hydrogen ion of representative in acid chloride solution, Cu represents the copper in ore or the enriched material, make pressure oxidation filtrate contain the first part's copper in ore or the enriched material, contain the second section copper in ore or the enriched material in the alkali type nantokite, and comprise the steps:

Separate pressure oxidation filtrate and alkali type nantokite;

In lixiviate second time step,,, form second copper solutions and solid residue with the dissolving mantoquita with hydrosulphate solution lixiviate alkali type nantokite;

And the pressure oxidation filtrate and second copper solutions carried out solvent extraction, be formed for the dense copper solutions that cupric electrolysis is smelted.

26. method as claimed in claim 25 is characterized in that solvent extraction comprises the steps:

With organic extractant second copper solutions is carried out solvent extraction, to form the extraction agent and first raffinate of first load;

Extraction agent with first load carries out solvent extraction to pressure oxidation filtrate, forms the extraction agent and second raffinate of second load; And

Back extraction copper from the extraction agent of second load forms extraction agent and the dense copper solutions that is used for electrolysis for production through back extraction.

27. method as claimed in claim 26 is characterized in that before back extraction copper from the extraction agent of second load, the extraction agent that washes this second load with water is therefrom to remove muriate.

28. method as claimed in claim 27 is characterized in that the water recirculation behind the extraction agent of washing second load, to wash the insoluble alkali type nantokite that produces in ore or enriched material pressure oxidation process.

29., it is characterized in that the method for straining carries out from being to use separating of second copper solutions of the lixiviate second time and solid residue the adverse current to incline as any one described method among the claim 25-28.

30. method as claimed in claim 26 is characterized in that the extraction agent recirculation through back extraction is used for the solvent extraction of second copper solutions, to produce the extraction agent and first raffinate of first load.

31. method as claimed in claim 26 also comprises the step that second raffinate is recycled to the pressure oxidation section as acid chloride solution.

32. method as claimed in claim 31 is characterized in that before the second raffinate recirculation second raffinate being split into first part and second section, and with first part's recirculation of raffinate, the relative quantity of first part and second section is by H ⁺The mol ratio decision of/Cu.

33. method as claimed in claim 32 also comprises the neutralization of the second section of raffinate, forms calcium sulfate resistates and neutralization solution, separates this resistates and neutralization solution is recycled to the step of pressure oxidation section.

34. method as claimed in claim 26 also comprises first raffinate is recycled to the step that the second lixiviate section is carried out lixiviate as sour sulfur acid group solution.

35. method as claimed in claim 34 is characterized in that before the first raffinate recirculation the less important part that first raffinate is split into the major portion that comprises 2/3 raffinate and comprises 1/3 raffinate, and with the step of first part's recirculation of this raffinate.

36. method as claimed in claim 35 also comprises the second section of this raffinate that neutralizes, and forms the step that comprises calcium sulfate and metal hydroxides.

37. as claim 26 or 36 described methods, comprise that also separation is by in the second section of first raffinate and the resistates that produces, and with the neutralization solution that forms as incline washing water recirculation in the method for straining of adverse current, the step of the solid residue that produces with washing lixiviate for the second time.

38. method as claimed in claim 25, also comprise to pressure oxidation filtrate and second copper solutions carry out solvent extraction in case from solution the step of extracting zinc.

39. method as claimed in claim 25, also comprise to pressure oxidation filtrate and second copper solutions carry out solvent extraction in case from solution the step of extraction of nickel.

40. method as claimed in claim 25 is characterized in that selecting predetermined H according to the rank of ore or enriched material ⁺/ Cu mol ratio; This ratio value descends with ore or enriched material rank and raises.

41. method as claimed in claim 40, the rank that it is characterized in that ore or enriched material is in the scope of 28-22 weight % copper.

42. method as claimed in claim 5 is characterized in that copper removal also contains zinc outward in ore and the enriched material, and comprises the steps:

Before solvent extraction copper, with the organic zinc extraction agent second copper solutions and pressure oxidation filtrate are carried out the solvent extraction of zinc, forming the extraction agent of first and second zinc loads respectively, and form the first and second zinc raffinates respectively;

With the organic copper extraction agent the first zinc raffinate is carried out solvent extraction, form the extraction agent and the first bronze medal raffinate of first bronze medal load;

Extraction agent with first bronze medal load carries out solvent extraction to the second zinc raffinate, forms the extraction agent and the second cupric raffinate of second bronze medal load; And

Back extraction zinc from the extraction agent of first and second zinc loads is formed for the dense zinc solution of electrolysis for production.

43. method as claimed in claim 42 is characterized in that before the second zinc raffinate is carried out solvent extraction, and the second zinc raffinate is carried out the neutralization of a step or multistep, to form neutral solution respectively and to form the calcium sulfate resistates respectively; Behind each neutralization procedure, respectively neutral solution is separated from the calcium sulfate resistates, formed final neutralization solution; Final neutralization solution is further carried out the zinc solvent extraction, form final zinc raffinate;

Extraction agent with first bronze medal load carries out solvent extraction to this final zinc raffinate.

44. method as claimed in claim 42 is characterized in that with the extraction agent of first zinc load pressure oxidation filtrate being carried out the zinc solvent extraction, forms the extraction agent of second zinc load, and comprises the steps:

Back extraction zinc forms the extraction agent of zinc back extraction from the extraction agent of second zinc load; And

The extraction agent of recirculation zinc back extraction carries out the zinc solvent extraction of second copper solutions.

45. as claim 42 or 43 described methods, beyond it is characterized in that dezincifying, the extraction agent of second zinc load a spot of copper of also having loaded, described method also can comprise the step of handling second zinc load extraction agent with zinc sulfate solution with reflux type, so that replace a little copper that extraction agent is loaded with zinc, form untainted substantially zinc solution and be used for electrolysis for production, a plurality of successive sections are used in described processing.

46. method as claimed in claim 6 is characterized in that copper removal also contains nickel outward in ore or the enriched material, and comprises the steps:

Use the organic nickel extraction agent that first and second raffinates of copper solvent extraction are carried out the nickel solvent extraction, form the extraction agent of first and second nickel load respectively and form the first and second nickel raffinates respectively; And

Back extraction nickel from the extraction agent of first and second nickel loads is formed for the dense nickel solution of electrolysis for production.

47. method as claimed in claim 46 is characterized in that with the extraction agent of first nickel load second raffinate of copper solvent extraction being carried out the nickel solvent extraction, forms the extraction agent of second nickel load, and comprises the steps:

Back extraction nickel from the extraction agent of second nickel load, the extraction agent of formation nickel back extraction; And

The extraction agent of recirculation nickel back extraction carries out the nickel solvent extraction to first raffinate of copper solvent extraction.

48. the method for extracting copper comprises the steps: from copper sulfide ore or enriched material

In lixiviate first time step, in the presence of oxygen, use acid chloride solution lixiviate ore or enriched material, form first copper solutions and insoluble alkali type nantokite;

Separate first copper solutions and alkali type nantokite;

In lixiviate second time step,,, form second copper solutions and solid residue with the dissolving mantoquita with hydrosulphate solution lixiviate alkali type nantokite; And

With organic extractant first and second copper solutionss are carried out solvent extraction, form dense copper solutions, supply the therefrom usefulness of electrolysis for production copper.

49. method as claimed in claim 48 is characterized in that described solvent extraction comprises the steps:

With organic extractant second copper solutions is carried out solvent extraction, to form the extraction agent solution and first raffinate of first load;

Extraction agent solution with first load carries out solvent extraction to first copper solutions, forms the extraction agent solution and second raffinate of second load; And

Back extraction copper from the extraction agent of second load forms extraction agent and the dense copper solutions that is used for electrolysis for production through back extraction.

50. method as claimed in claim 49 is characterized in that the extraction agent recirculation through back extraction is carried out solvent extraction to second copper solutions, forms the extraction agent solvent and first raffinate of first load.

51., comprise that also second raffinate is recycled to the section of lixiviate for the first time as acid chloride solution carries out lixiviate as claim 49 or 50 described methods.

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