JPS5919972B2 - Recirculation of metal carbonates to the reduction circuit in the Cyprion process - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dissolving metal content in manganese nodules.

Methods are known for recovering copper, nickel, cobalt and molybdenum from manganese nodule raw material by means of aqueous ammonia leach solutions containing cuprous ions.

The method [that is "Cuprion"]
Copper, nickel,
To allow metals such as cobalt and molybdenum to dissolve.

The ground manganese nodules are contacted with an ammoniacal leaching solution containing cuprous ions in the reaction vessel to reduce manganese oxides in the nodules.

In order to remove these carryover metals from the residue, the nodule residue is washed with an ammoniacal ammonium carbonate solution.

The reducing solution is recycled to the reaction vessel where the manganese nodules are added.

A reducing gas, such as carbon monoxide, is passed through the reaction vessel to retain a sufficient amount of cuprous ions.

However, the above method requires a large reactor, or a large number of smaller reactors to process small production quantities of metal.

According to the present invention, it has been found that the capacity of the reactor required for the reduction circuit is influenced by the copper content of the reducing liquid.

The required reactor size may be reduced if the amount of dissolved copper in the cuprous ion reducing solution is increased.

Recirculating mixed metal salts of carbonate into the reduction circuit is a practical method for increasing the copper content of the cuprous ion reducing solution during the reduction circuit.

The dissolved copper content of the reducing solution in the reduction circuit is 1 og/1
If a quantity of 1.3 is maintained, the reactor size required for the above-mentioned known process can easily be reduced to 1.

Of course, the higher the copper content in the reducing liquid, the smaller the size of the reduction reactor can be made.

It is an object of the present invention to provide an improved method for dissolving the metal content in manganese nodules.

Another object of the present invention is to provide the Cuprion Process 1 with a relatively high amount of cuprous ions in each step of the process.

The object of the present invention is to provide a multi-step process for continuous reduction of manganese nodules.

Another object of the present invention ("by the Cuprion process", in which the grouped copper content of the reducing solution in the reduction circuit is about 1.0 g/13 or more).

The object of the present invention is to provide a multi-step process for continuous extraction of metals from manganese nodules.

Yet another object of the present invention is to provide a practical method for increasing the copper content of the reducing solution in the Cuprion process.

Yet another object of the present invention is to provide an improved cuprion process that includes a step of recycling the basic metal carbonate feed to the reduction circuit.

The method of the invention comprises ([) in a reaction vessel containing cuprous ions such that the cuprous ions reduce manganese nodules in the manganese-containing iron to enable the metal content to dissolve. The metal content is recovered from the manganese-containing ore by charging the ore into the reactor vessel, and the cuprous ions are continuously regenerated by reducing gas. An improved method involves recycling recovered metal to the reaction vessel to increase the dissolved copper content.

Firstly, the method of the present invention will be described in its broadest general context by the following more detailed description.

The present invention is directed to the recovery of metals from deep sea manganese nodules.

For purposes of this patent specification and claims, complex ores found in the deep seabeds of oceans and lakes containing manganese, iron, copper, Ni'fl, Mo+Jbdenum, cobalt and other metals are used. , deep-sea manganese nodules, manganese nodules, or nodules.

Seabed mineral deposits are composed of nodules lying freely on the surface of soft seabed-produced materials, grains in seabed-processed materials, crust on hard rocky outcrops on the seafloor, calcareous rock piles, and alternative light in animal remains. (repl acem en t f i I)
as I-il-1n, and in other minor forms,
be discovered.

Samples of this mineral were collected by drag dredging, a method used by oceanographers for many years.
dging) or deep sea water dressing, a method used in commercial operations to mine these deposits.

Regarding the deep sea nodule collector. U.S. Patent No. 3480
No. 326 and No. 3504943.

The properties and chemical content of deep-sea nodules vary greatly depending on the region from which they are obtained.

Elsevier Publishing, Elsevier Marine Library, Joan El Melo, 1 Mineral Sources of the Sea, 1965, 127-
On page 241, various aspects of manganese nodules are discussed.

For detailed chemical analysis of nodules from the Atlantic Ocean, see 196
6, New York, Reinhold Publishing, Earl.
Edited by W Fairbridge, “Encyclopedia of Oceanography” 4
pages 49-450, and U.S. Patent No. 3169
It is described in No. 856.

For the purpose of the present invention, composite ores containing approximately the following metal content range on a dry basis are used:

Metal content analysis range Copper 0.8-1.8% Nickel 1.0-2.0% Cobalt 0.1-0.5% Molyfden
0.03-0.1% manganese10.
0-40.0% Iron 4.0-25.0% The remainder of the ore is oxygen as oxides, oxygen as clay minerals with smaller amounts of quartz, apatite, biotite, sodium and potassium feldspar and Consists of irrigation water.

Of the many components that make up manganese nodules, the emphasis is on economics, with copper and nickel being the most important metals in most seabed ores.

In the cuprion method, manganese deep-sea nodules, which are raw materials, are mixed with cuprous ions (cu) in an ammoniacal ammonium carbonate aqueous solution.
”).

The copper ions reduce the manganese in the nodule, allowing metals such as copper, nickel, cobalt and molybdenum to dissolve, while leaving undesirable metals such as iron in the solid residue.

In the reduction process. Manganese dioxide in deep sea nodules is reduced to manganese carbonate by cuprous ions according to the following reaction.

MnO2+2Cu(NI(3) closed 4NH3+CO2+
H20→Mn COs + 2Cu (NHs) 2
++20H-(1) The cupric ion shown in formula (1) is reduced back to the cuprous state by carbon monoxide according to the following reaction.

2Cu(NH3)4''+10Co+20H--+2o.

(NH3)・+4NH3+. . 2+H2o(2) The cuprous ion is used up in reaction (1) and regenerated in reaction 2).

The net overall reaction for the reduction step is the sum of equations (1) and (2), ie, equation (3).

MnO2+Co-+MnCO3 (3) In order to provide an effective reactor system for the cuprion process, it is necessary to balance the rates of reactions (1) and (2).

Regeneration from cupric ions In order to retain optically active cuprous ions during all stages of the Cuprion process, there is a need for a catalyst that can be used to reduce cupric ions to cuprous ions. Since the amount is controlled by the substantial amount of cuprous ions,
The cuprous ion concentration must be kept at a fairly high value.

actually. If the amount of cuprous ions is less than about 29,773 (at atmospheric pressure and temperature less than about 40° C.), effective regeneration of cuprous ions is not commercially possible.

One way to keep cuprous ion concentrations fairly high at all stages of the process is to inject nodule feedstock at multiple points.

This multi-point injection method facilitates the regeneration of cuprous ions by reducing the possibility that the nodules will use up the supply of cuprous ions in any reactor by reacting with it.

In accordance with the present invention, it has been found that the efficiency of the Cuprion process is increased if the reducing solution solution in the reduction circuit is maintained at a copper content of about 10 g/11 or more.

With respect to the phrase "soluble copper" as used throughout this specification, it is intended to indicate that it is copper in the co-ionic state, ie, of the cuprous or cupric type.

According to the invention, the amount of soluble copper in the reductant in the reduction circuit is reduced by the amount of soluble copper in the reductant (pregnant) that is otherwise sent to the LIX extraction.
ant I 1 quar) aside.

Stripping the liquid to obtain a metal carbonate starch containing basic copper carbonate as well as nickel, cobalt and molybdenum, and in sufficient quantities to retain the desired amount of soluble copper in the reduction circuit. and is increased by recycling the precipitate into the reduction circuit.

Without this metal carbonate recirculation. The amount of soluble copper in the reducing solution is only 4-6 g/It.

By recycling the basic metal carbonate, the amount of soluble copper in the reducing solution can be increased by any desired amount up to the solubility limit.

From this point of view, the recycled solids are not pure oxides, but rather mixed oxide carbonate-hydroxide starches with one composition difference.

It goes into solution as a metal amine carbonate salt.

The method of the invention will be more clearly explained by the following example in conjunction with FIG.

First, however, let us note that the following description relates to the operations carried out in the test factory.

However, the results obtained from the test plants allow those skilled in the art to design commercial equipment for processing large quantities of nodules.

The pilot plant was designed to have a nodule processing capacity of 0.451-77 days with a 3.5% solids or slurry residence time in the reduction section for up to 3 hours.

The processes carried out in the test factory can be classified into the following sectors:

1. Mineral beneficiation 2. Reduction-leaching 3. Oxidation and cleaning-leaching 4. BMC recirculation 5. LIX separation of metals 6. Electrowinning Nodules used in the beneficiation pilot plant process are present after they are mined from the deep seabed. Place it in a 2081 (55 gallon) drum while still dry.

Air dry the nodules to facilitate processing at the test plant.

After it dries and before entering the first crushing circuit, the "cone and quarter"
ter)” method.

The first ore crushing circuit processes raw material nodules at 2.5 crrL (11 nc
h) Consists of a Jacobsen Full Nelson crusher to achieve a particle size that passes through the sieves.

Thereafter, the ore is further passed through a Stedman section cage mill to reduce the particle size to pass a 6 mesh screen (-6 mesh).

The nodule is then conveyed on a belt feeder to drums for storage or further processing.

The second milling circuit is the final stage of beneficiation before the nodule enters the reduction stage.

The circuit was illuminated by a drum of cage-milled ore placed at the head of a hydraulic scale feeder.

Consists of a hopper.

The scale feeder is used to meter the nodule at a constant speed to the open rod mill for final grinding.

The rod mill produces nodules from -6 mesh particle size.

Make the particle size about -60 mesh.

When the nodules enter the rod mill, they are moistened with synthetic seawater so that the nodules have a humidity within about 40%.

This moisture content corresponds to the moisture present in the nodule when collected from the seabed.

From this point of view, in commercial operations where nodules are processed immediately after being mined from the seabed.

It should be noted that the steps of drying or moistening the nodules are unnecessary.

However, for pilot plant operations, it has been found convenient to air dry the nodules and then moisten the nodules so that they have the same moisture content as freshly mined nodules.

It has been found advantageous to add recycled reductant to the rod mill.

In commercial methods, to provide a fluid to facilitate attrition and to reduce dust problems without introducing more water into the circuit causing undesirable dilution.
Recycled reducing fluid is advantageous for maintaining a suitable copper concentration in the reducing circuit, as well as providing a fluid that is effective during the milling process itself.

Details of the recirculating fluid circuit are detailed below.

The reduction-leaching section of the reduction-leaching test plant is the section where the nodules are chemically reacted to render the metal of interest soluble in a strong ammoniacal ammonium carbonate solution.

This is achieved by reducing and converting the MnO2 in the nodule to MnCO3.

After leaving the rod mill, the nodules are passed through a conduit into a vibrator (not shown).

The purpose of the vibrator is to remove any floating objects (tramp mate).
real) should also be removed.

The vibrator used is a Sweco vibrating screen.

The material that enters and exits the vibrator] is actually a liquid slurry.

The vibrator is connected to a regulating water tank (not shown).

The purpose of the conditioning water tank is to act as a storage unit so that the process equipment should not be shut down in case of adverse effects on some parts of the separator.

After leaving the adjustment tank, the slurry is sent to the reduction circuit by the supply pump.
I'm pumping it up.

The reduction circuit includes six reactors connected in series.

These reactors are 22M (60 gallon) capacity reactors, with 1591 (42 gallon) capacity used in actual processing.

Each reactor is constructed of 316 stainless steel and is equipped with an agitator, pressure gauge, level gauge and gas sp
arging) device.

Reduction and leaching in these reactors are carried out at temperatures between 40 and 70°C.
temperature in the range of , pH 9 in the range of 10.0 to 10.8 and a pressure of about 1 atmosphere.

Gas sparging occurs from the bottom of the reactor where a reducing gas containing 95% carbon monoxide and 5% hydrogen is introduced.
Directed under the stirrer.

These mixtures are used because they resemble reducing gas mixtures that are available in commercial quantities.

of course. Hydrogen is not necessary for that purpose.

In fact, the only gas needed for the process is carbon monoxide.

The exhaust gas leaving the reactor is first passed through a condenser which removes some of the water in the gas before going to an exhaust gas rotameter which gives an indication of the amount of gas leaving the reactor.

The exhaust gas is passed through an ammonia scrubber and released into the atmosphere.

The reactor itself has one gravity overflow (overfl) so that there is a cascade system from the first to the sixth reactor.
ow).

One important embodiment of a multipoint injection scheme provides the same amount of feedstock to each of the first four reactors.

In other words, the rally pumped from the 1 ore processing circuit
25% of the total goes to each of the first four reactors.

However, it should be noted that there are many possible ways to achieve multipoint injection.

That is, the nodule slurry can be injected into three, four, or more reactors; the amount of slurry entering any particular reactor need not be equal to the amount entering another.

However, it has been found to be advantageous to avoid at least the last injection into the reactor.

That is, each part of the nodule should pass through two successive stages, so there should be no nodule injection into the last stage.

It should be noted that this pilot factory process does not have nodule injection in the last two stages.

Each reactor contains a mechanical impeller to achieve mechanical agitation that disperses the gas and suspends the solids.

It was established that the reaction rate of cuprous ion regeneration is influenced by the gas-liquid mass transfer rate of carbon monoxide.

The speed is determined by the method used to disperse the gas.
be influenced by this.

It is mainly influenced by the surface area of the gas-liquid interface.

While the nodules are being fed to the first four reactors, a carbon monoxide (J) sparge is applied to the bottom of each reactor as needed.
rge).

The slurry in these reactors is approximately 3.5% solids;
The average residence time in the system is 20 minutes per stage.

The slurry overflowing the last reactor is flocculated to promote settling before entering the clarifier.

Purifiers are used to separate liquids from solids.

° The reduction-leaching circuit also includes a gas metering mechanism.

As mentioned above, the reducing gas is 95% carbon monoxide and 5% hydrogen.

1% methane tracer in reducing gas
) was found to be advantageous.

Methane is in material equilibrium
) was used to help establish the

The reducing gas is supplied through a pressure reducing valve and a gas toque riser (total
-i ze r g is fed from a portapull cylinder.

Gas is metered separately in each of the six reactors as necessary to keep the cuprous ions within the various side legs.

Gases were also investigated by gas chromatography.

STARTUP The process of the present invention is used as a continuous process in which the nodules are successively processed to provide a variety of desired metals.

To achieve continuous steady state 4, the reaction vessel must be loaded with starting material.

Therefore, in each of the six reactors, approximately 1009711
of total ammonia and about 15 g of total carbon dioxide.

After exposing the ammonia-ammonium carbonate solution to the reactor, metallic copper is added and partially oxidized.

The metal is added as copper powder and oxidized to convert some of the copper to cuprous ions.

Along with cuprous ions, hydroxyl ions are also produced.

A sufficient amount of metallic copper is added so that copper dissolves in 10 gil.

The next step in the start-up procedure is to check the cuprous ion concentration.

The mixture from each reactor is then analyzed to ensure that the cuprous ion concentration is acceptable at approximately 7 gills.

If more cuprous ions are needed, this can be achieved by passing reducing gas to the bottom of the reactor.

The first three reactors consist of finger pumps that pump solution into a jacket containing a pH electrode.

It has a pH loop. Next, measure the pH using the indicator on the control board.

pH is a valuable control measure and can be used to indicate whether carbon dioxide, ammonia or cuprous ions have exceeded certain limits.

After loading the reaction vessel for startup as described above,
Add manganese nodules to the first four reactors.

The overall feed rate to the four reactors was approximately 13.5 mm of nodule.
6ky (301bs) 7 o'clock.

When the nodules are fed into the reactor, carbon monoxide is approximately 1.9
It is sparged through the bottom of one reactor at a linear velocity of 8 standard m°/h.

In this regard, it should be noted that the amount of carbon monoxide fed to each stage reactor is controlled by the cuprous ion concentration of the contents of any particular reactor.

This is determined by periodically analyzing the contents of the reactor.

During startup, this is done every 30 minutes and continues once an hour while the process is in the steady state phase.

About 45M (120 gallons) of reduced slurry is added to the purifier at 7 o'clock.

The solids exit from the bottom of the purifier in the form of a slurry with a solids content of about 40%.

The overflow from the purifier is a clear liquid that constitutes the recycled reductant.

However, after exiting the purifier, the recirculated recycle liquid enters a conditioning water tank that is in communication with an ammonia replenishment system.

Gaseous ammonia and carbon dioxide gas are also purged into the ammonia replenishment system to maintain the liquid ammonia and carbon dioxide levels.

At steady state, the amounts are about 1oo, 9/l ammonia and about 25 gill CO2 content.

After leaving the dosing device, the liquid is pumped by a metering pump through a heat exchanger to the first reactor and attrition mill.

Heat exchanger 11 removes the heat generated during the process.

Oxidation and Cleaning - Leaching In the oxidation and cleaning - leaching circuit 11, the purifier underflow is combined with the second stage cleaning fluid and the resulting rally carries cuprous ions in the purifier underflow for subsequent processing. is easily oxidized in air to convert into cupric ions.

The oxidized slurry 11 is then pumped into a countercurrent decantation mechanism (CCD) consisting of seven stages of a countercurrent cleaning device.

The washing-leaching stage is carried out batchwise in 9 tanks.

It should be noted that nine stages are used in the test factory to mimic a countercurrent cleaning mechanism.

Although this arrangement is not truly countercurrent, it can be shown that a seven reactor countercurrent arrangement is advantageous.

Two special devices used in the test factory are required, one device being filled or the other being empty.

The cleaning-leaching mechanism uses the drain cleaning method (di splac).
Metal solubilization is completed when the e-ment wash process is performed.

i o o g7i ammonia and i o o g7g
Fresh cleaning fluid is added to the seventh stage of the system as a solution containing carbon dioxide gas.

To effect countercurrent cleaning, liquid is transferred from one tank of the sedimentation or rally to another suitable tank in the system every 12 hours.

What is the carbon dioxide concentration? In a fertilizing fluid containing approximately 65 g/11 CO2, the entire cleaning mechanism and even the outlet are different.

This reduction in C02 concentration is due to the fact that the lary entering the oxidation and washing-leaching circuit has a liquid phase containing only 25 g/lj of CO2.

The fertilizing liquor containing the metals to be recovered is decanted from the first washing step into a conditioning tank.

Fresh metal-free ammonia solution is added to the final solids washing step.

The metal content in solution ranges from about 0 in fresh cleaning solution to 6-8 g/! in fertilizing solution! 1 of copper and 5 to 1 og/11 of nickel.

Of course, other metals are also present in the fertilizing fluid, but nickel and cobalt are the main metals of interest.

After the washing-leaching step, the fertile metal-containing liquid is pumped for further processing as described below.

The second stage wash liquor is recycled to the oxidation reactor.

The tailings, which are nothing but reduced nodules with all non-ferrous metals washed away, and manganese converted to manganese carbonate are placed in a conditioning tank.

From the conditioning water tank they are then pumped to a steam stripping unit where the ammonia and 002 are released.

The tailings are then drummed.

Ammonia and 002 obtained in the steam stripper can be recycled.

BMC Recycle A small stream 10 of basic metal carbonate (BMC) is recycled to the first stage 11 as necessary to maintain an acceptable amount of total copper in the system.

This basic metal carbonate stream compensates for undissolved copper leaving the reduction loop in the purifier underflow.

To provide the basic metal carbonate stream 10, a portion of the fertilizing fluid 12 (wash effluent) from the oxidation and wash-leaching circuit is subjected to removal of ammonia and carbon dioxide gas to precipitate the basic metal carbonate. For this purpose, steam stripping is carried out in batches.

Precipitate or basic metal carbonate with approximately 609/13 NH
3 and 609/11 in an aqueous solution containing CO2.

This BMC feed ore is pumped into the first stage of the reduction circuit.

The amount of BMC feed added to the reduction circuit varies depending on the amount of soluble copper present in the reduction reactor and the copper concentration desired in the reduction circuit.

It has been found to be advantageous to keep the soluble copper content of the reduction circuit at an amount of 10 g or more.

Therefore, the amount of soluble copper in the reduction circuit is consumed, so B
MC feed is prepared and recycled to the reduction circuit.

Of course, the basic metal content of the BMC feed is controlled by the basic metal content of the treated nodules.

The basic metal carbonate stream 10 contains primarily solubilized copper and nickel, however small amounts of molybdenum and cobalt are also present.

It is clear that what controls the amount of BMC recirculated ore fed into the reduction circuit (1) is the amount of metallic copper in the BMC ore feed.

For more details on BMC feeding. The section titled ``Specific Specifics of BMC Recirculation'' is discussed below.

LIX Separated Fertilizer (1) Contains various metals including copper, nickel, cobalt and molybdenum.

11 in the LIX separation circuit, from each other and from the fertilizing fluid,
The purpose is to separate copper, nickel, cobalt and molybdenum.

First, the copper and nickel are co-extracted with an organic extractant in one mixer/settler series.

The organic extractant is I, 1X-64N in kerosene matrix.

LIX-64N is an extractant sold by General Mills Chemical Company.

Copper- and nickel-free liquid (raffinate) is
It is sent to a storage tank before it is steam stripped.

An organic extractant containing copper and nickel is added to NH4HCO3.
Washing with solution and subsequently with ammonium sulfate solution removes ammonia entrained during the extraction.

This washing operation ("mixer" is carried out in a separate system of settling tanks).

The organic extractant is then stripped with a weak H2SO4 solution (pH about 3) to preferentially remove the nickel.

Then strip the copper, it is stronger (16
1/A') is achieved using a H2so4 solution.

The copper- and nickel-free organic extractant is recycled through the metal extraction circuit of the LIX process.

The raffinate, which contains only cobalt, molybdenum 2 and some trace impurities not extracted into the organic phase, is sent to a conditioning tank for further processing to recover cobalt and molybdenum.

In the cobalt and molybdenum recovery circuit, ammonia and C02 are stripped from the raffinate.

Ammonia and CO2 are condensed and returned to the process for recycling.

Next, water lime is added to the raffinate in the steam stripper.

The resulting slurry is stirred and then allowed to settle.

The solution, which no longer contains cobalt and molybdenum, is recycled to the process as fresh wash solution.

To bring the solution to the specified concentration, add ammonia and 00
Add 2.

Electrowinning Metal recovery is accomplished by electrowinning copper and nickel from the solutions prepared in the LIX apparatus described above.

This process is carried out in separate units, batchwise for copper recovery and continuous for nickel recovery.

Transfer the metal-containing liquid once a day.

Specific Specifications for BMC Recirculation A comparison of the process of the present invention with the known process described above will now be considered by combining Figures 2 and 3.

The known process is schematically illustrated in FIG.

In the known process, the nodules 20 are treated in reaction vessels 21, 22, 23, as shown in FIG.

The treated nodules then flow into the clarifier at 24.

Fertilizing fluid comes out of the purifier at 26.

A portion of the fertilizing liquid is recycled at 28 to the reactor 21.

The portion of the flow of fertilizing liquid 32 that is not recycled to reactor 21 is sent to an extraction circuit.

The reduced mineral mud water 34 is sent to the cleaning circuit. In the process of the present invention, as schematically shown in FIG.
The steam or dripping water is directed towards it.

In this regard, it should be noted that the BMC recirculation rate will vary depending on the copper concentration desired in the recycling circuit.

BMC steam) Sending wash effluent (fertilizing fluid) of about 1 to IJ tube (1), reducing the copper concentration in the reduction reactor to about 2.5
increases by a factor of 4,3 to i og7g.

The basic carbonate process starch formed in steam stripping section 37 is filtered at 38, dissolved in water containing NH3 and CO2 and sent in stream 28 to the reduction circuit.

Stream 28 is recycled directly to the reduction circuit and fertilizer stream 32
is sent to LIX extraction.

The remaining portion of the wash effluent 40] is distributed.

BMC recirculation increases the copper content and total metal content of the reductant in vessel 21.

The highest limit of copper concentration that can be achieved with this method (1, controlled by the solubility limit of the metal amine carbonate salt, which is 40-60
It is between g/11.

Next, an example of steam slipping occurring in the container 37 will be shown.

A total of 5,111,135 gallons of wash effluent containing 4-89/13 copper and 5-10 g/13 nickel was batch steam stripped.

The temperature during stripping is initially 82-102℃ (1
80°F to 216°F).

The precipitate was black in color, and the precipitate analysis showed 13.9
%Cu, 17.7%Ni, 5.95%CO3.

This indicates that there is a large amount of cupric oxide in the block.

The precipitate could be filtered. The remaining liquid was analyzed for 0.0959/13 Cu and 0.154 g/II Ni, indicating adequate removal of copper and nickel.

The precipitate is 100g, #NH3 and 45jj/II C
Dissolved in an aqueous solution containing O2.

Completely dissolved in this solution within 15 minutes at ambient temperature (25° C.).

Solubility of 99.8% Cu and 99.4% Ni was obtained.

A comparison between the process of the present invention and the known process is shown in Table 11 A21 below.
It was shown to.

In this regard, it should be noted that the process of the present invention can be accomplished without multipoint injection of nodules.

Indeed, what is clear from the foregoing with respect to Figures 2 and 3 points towards a continuous method with single point injection of nodules.

By following the teachings of the present invention, the amount of copper in a reaction vessel can be increased in an effective manner.

The specific examples in this specification are provided to facilitate understanding of the present invention, and the present invention is limited only by the scope of the claims.

Preferred embodiments of the present invention are as follows.

(1) Charge the ore into the reaction vessel of the reduction circuit, recover a portion of the dissolved metal after the dissolved metal passes through the reduction circuit, and reduce the soluble copper content of the reaction vessel to at least 10g/! An improved method as claimed in the claims, characterized in that the recovered metal is recycled to the optical reduction circuit in order to retain the amount of metal.

(2) at a speed of light to maintain the amount of soluble steel in the reducing solution of the reduction circuit within the range from 109/l to the solubility limit;
An improved method of claim or (1) above, wherein the precipitate is formed and recycled.

(3) The improved method described in (1) or (2) above, in which the 1% carbonate mixed metal salt method forms a resin.

(4) A fertile metal-containing liquid is directed into the extraction circuit, a portion of the fertilizing liquid is diverted from the extraction circuit to the rubble, and a portion of the fertilized liquid is diverted from the extraction circuit to the side to obtain a metal carbonate process material containing basic carbonates. Dripping of the solution is carried out and the precipitate is recycled to the reduction circuit in an amount sufficient to retain the desired amount of copper in the reduction circuit. ) to (3).

(5) The improved method described in (4) above, wherein the diverted fertilizing liquid is stripped with steam.

(6) Recirculating the precipitate to the reaction vessel as a stream of basic metal carbonate.

Claims and the improvement method described in any one of (1) to (5) above.

(7) a circuit for washing and leaching the reduced nodules with an aqueous solution containing ammonia and carbon dioxide; a portion of the fertile metal-containing liquid from the circuit in which the reduced nodules are washed and leached; is steam stripped to remove ammonia and carbon dioxide and precipitate the basic metal carbonate, and the precipitated basic metal carbonate is recycled to the reduction circuit. 1)～
Improved method according to any one of (6) (8) Dissolving the precipitated basic metal carbonate in an aqueous solution containing ammonia and carbon dioxide.

The improvement method described in (7) above.

[Brief explanation of drawings]

Figure 1 is a flow sheet showing the process of the present invention;
The figure is a schematic diagram of a known process, and FIG. 3 is a schematic diagram corresponding to FIG. 2 showing the process of the present invention. 10...Flow of basic metal carbonate, 12...
...Fertilizing fluid, 20...Baby boom, 21.22,2
3...Reaction vessel, 32... Fertilizing liquid flow, 31... Container, 40... Washing effluent, 42... Carbonate Strip liquid.

Claims (1)

[Scope of Claims] 1. In a reaction vessel containing cuprous ions, the cuprous ions reduce manganese nodules in the manganese-containing ore in order to enable the metal content to dissolve. In a method in which the metal content is recovered from the manganese-containing ore by charging the ore into a manganese-containing ore, and the cuprous ions are continuously regenerated by reducing gas, the dissolved metal content is recovered,
The method is characterized in that the metal content recovered in the reaction vessel is recycled to increase the dissolved copper content of the reaction vessel. Improvement method.