DE2363568A1 - METAL PRODUCTION METHOD - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ BV Den. Hague, Netherlands

"Process for the extraction of metals"

Priority: December 22nd, 1972, the Netherlands, no.7217491

The invention relates to a method for obtaining one or more. Hetallkoiaponenten of metals of the group IB, HB, HIß, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements (Perlodic Table of the Elements according to the Handbook of Chemistry and Physics * The Chemical Rubber Company, 52nd edition), in which a liquid medium containing one or more compounds and / or complexes of one or more of the aforementioned metals is brought into contact with a reducing gas and at least one metal component is precipitated in the process.

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In order to separate metals from their ores or from waste materials, the ores or waste materials are sorted according to many processes treated in such a way that compounds, such as salts, of the concerned Metal can be obtained in aqueous solution. In the vast majority of cases, a solution of connections is made by get two or more metals in water. In order to separate and obtain the metals in ■ aqueous solution, extraction processes can be used in which the Metals from the aqueous phase into a liquid organic medium

■ -dium be transferred. The mixtures obtained can also thereby obtained v / earth that the ores or waste materials on such

■ ■ are treated in such a way that the metals are directly, e.g. by means of organic. Acids ^ are absorbed in an organic medium.

According to Dutch patent application 7QO9544, materials from groups IB, TIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements can be separated from one another by separating two or more of the metals in the form of compounds and / or complexes upstream in an organic ^Msdium: are prepared by reacting with a reducing gas, a Matall- 'component of the metals contained in the organic Mediura is selectively precipitated.

Under "metal components" v / ground in the present description The metals are also understood in the form in which they are obtained from organic solutions or suspensions of metal compounds be precipitated by reduction. The metal components are

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are optionally mainly made of pure metal, but in some cases can also consist of oxides or hydrides of the respective Metals consist or contain these metal compounds.

pie presence of so-called inoculum material in the liquid organic medium before the start of the reduction process to initiate the Formation of the metal components often leads to advantages. Finely divided metal powder is particularly suitable for this purpose.

- - how

finely divided carbons / colloidal graphite / and finely divided carbon to which a certain amount of palladium oxide is applied. The use of inoculum enables the reaction temperatures and pressures used to be reduced, the reaction time to be shortened, and leads to a more complete precipitation. In addition, the ^: Use of inoculum leads to a higher selectivity in the precipitation of various metal coraponants.

The continuous operation of the aforementioned method of extraction one or more metal components leads to considerable difficulties. Provided the inoculum in one of particles If the existing fixed bed is used, the agglomeration of the particles leads to an ever decreasing contact between the liquid organic medium and the inoculum. The agglomerated particles and the precipitated metal adhere also on the inside of the reactor walls and are difficult to remove from the reactor walls. It was also

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observed that the process according to German Offenlegungsschrift 1 583 902 "is carried out in a reactor in which the inoculum is kept in suspension by stirring as the liquid organic medium, eu deposits of metal on the inner walls of the reactor 'leads to the stirrer ¹ ' which are 'difficult to remove again' - a continuous process must therefore be terminated after a relatively short period of time. The aforementioned difficulty is also described in the US patents 2 '734 821 and 2 740 708.

It was a jetst Verfahr® "additionally Gk found in which this considerably lesser extent © aufto

of 'metal components srar in

Accordingly, the invention relates to a process for obtaining one or more metal compounds from groups IB, IIB, _V HIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements , in which a liquid, one or more compounds and / or a complex © © Ines' © is the organic medium containing several of the aforementioned metals with a r @ dusier © nd. Gas is contacted and at least a metal component is precipitated that is characterized by this; that the -omq aniseHe 'medium maci / or the reducing gas voia "ous © n t & aeh above with eiaer for äi © Erg @ uguag of a · Fli © ßb @ tteg öusr @ ieh @ Näea G © ~ -

passed through a bed with pieces of vaccine material

Müäima with

through a non-fluidized solid of inoculum particles directed, the fluidization of the Betty "" reaches, j when particles appear in bed for the first time that are no longer

are constrained by other particles in their movements. · becomes d <« Flow rate of the organic medium urad / od «r -d« <? reducing Gases increased further, "this will soon lead you <3a:? U that

first time
all particles to / no longer "through other *» particles in their »

Movements' being hindered. According to the invention, the "s" l "i-2 + - Said flow velocity represents the velocity required to maintain a fluidized bed through the from below fluid flowing above is required as a minimum. At this required minimum flow rate, the fixed bed has ceased to exist as such, and it can be assumed - -that the porosity of the bed, i.e. the ratio of the total space between the particles to the total volume of the bed is 1; The minimum speed required can easily be determined experimentally.

The surprising effect of the present invention is that practically all of the _{fc) metal coraponent (s} ) obtained is (are) precipitated on the particles of the inoculum and that the individual particles of the inoculum nevertheless remain separate from one another. This leads to the fact that the process according to the invention is carried out continuously over long uninterrupted periods of time with continuous feeding of fresh seed material particles "to the fluidized bed and with continuous removal of the liquid organic medium in which the seed material and the

(is) precipitated (η) metal component (η) suspended from the

Fluidized bed can be carried out.

It is possible to fluidize the bed by applying to achieve a sufficiently large feed rate of the reducing gas. However, for this purpose it is common such a high gas feed rate is required that relatively large amounts of unreacted reducing Gas must be withdrawn from the fluidized bed. This Problem does not arise · when the fluidization of the bed is achieved 'that the liquid organic medium with sufficiently high speed is passed through the bed from bottom to top.

The minimum velocity of the liquid required to fluidize the bed is usually so large that after a single passage * of the organic medium through the Fluidized bed "only" a part of the corresponding metal component ^ n) has been precipitated. Accordingly, it is recommended / one only slightly and preferably by a maximum of 10 percent above the minimum speed required for fluidization lying flow rate of the liquid organic medium from bottom to top "to be applied through the inoculum bed. Contains" the liquid organic medium, after being passed through the fluidized bed once, still reducible metal compounds and / or -complex, it may partially return to the bottom of the Fluidized bed are introduced. In this way, the return

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guiding the liquid with continuous feeding of fresh liquid organic medium, one or more Compounds and / or complexes of one or more of the aforementioned Contains metals, and with continuous withdrawal of one Sidestream of used liquid medium which practically no longer contains any metal compounds and / or complexes can be obtained. The aforesaid adding and removing of fresh particles or precipitated metal components can of course be carried out at the same time. The liquid organic Medium can completely after flowing through the bed or partially again for the extraction of aqueous solutions from either ores or scrap. of the metals in question will.

The particle size of the inoculum is not critical. However, since the particles are all the more active, the smaller their particle size is, it is preferred to use particles with a maximum particle size of less than 1 mm and in particular less than 0.2. For example, particles with a maximum size of 0.2 to O, O5 or-von-O ^f , Ol up to 0.001 mm can be used «. A powder of the metal to be precipitated during the reduction is preferably used as the seed material. Particularly good results are obtained when copper is obtained as a metal component from a liquid medium containing copper compounds and / or complexes, in particular when "copper powder and / or a copper-plated metal powder" like a copper-plated nickel powder as

UZ, ·:}

Inoculation material to be used-.

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The organic part of the compounds and / or complexes of the metals present in the liquid organic medium can be derived from all substances which are able to keep the metal in solution or suspension in the liquid organic medium. Particularly suitable compounds are those which can be used to extract the metal from aqueous solutions of compounds (for example salts) of the metals in question. Such substances can be amines, amine salts / sulfonates, trialkylsulfonium salts, organic phosphates, phosphonates, "phosphites, alkylphosphoric acids and, in particular, carboxylic acids," such as the naphthenic acids, aliphatic ^ -hydroxyo kimes, such as 5,8 * diethyl-7-hydroxy-docedan-6 -oxime, and aromatic 2-hydroxyphenoximes such as 2-hydroxy-5-dodecylbenzophenoxime ₍ can be used.

The substances from which the ■ compounds and / or complexes of the metals to be separated are preferably derived are secondary and especially tertiary carboxylic acids or mixtures of carboxylic acids, which mainly consist of tertiary carboxylic acids, the metal salts of which are soluble in organic solvents. . Sub-tertiary carboxylic acid wird- a - acid-understood in the gebunden'ist the carboxylic acid tragende'Kohlenstoffatom directly to 4 carbon atoms * From this acid class (■ ^z: .B, Pivaiinsäure containing) ..- are preferably the Ά-lkancarbon-

atoms acids "having at least 6-und'insbesondere mit'9 * '* to 11 carbon Tertiary _e used it können'jedoch'auch / alkanecarboxylic acids

with a lower 'or * a-larger- (e.g.' from 15 to 19) Carbon & number will be used «. ■. - ·.,.

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Basic elements of various alkanecarboxylic acids (especially of alkanecarboxylic acids with 9 to 11 carbon atoms) are used with good results. These tertiary alkanecarboxylic acids -can be produced in a simple manner, -by -an olefin (or a mixture of olefins) in the presence of an acidic Catalyst (e.g. hydrogen fluoride or sulfuric acid or mixtures of boron trifluoride and phosphoric acid) with carbon monoxide and water converts. The acids formed do not contain any primary acids and secondary acids in general-in-one Amount not exceeding 15 percent by weight; = It is not necessary separating these secondary acids from the tertiary acids to be used according to the invention; da-the secondary acids neither the extraction of the metal from the aqueous solution nor the formation of a metal component 'when contacting' the liquid hinder organic medium with a reducing gas.

Are the compounds and / or complexes of the metal to be separated 'Organic liquids, they can be called as such liquid organic medium in the process according to the invention If they are not liquids, a liquid organic compound or mixture is required of liquid organic compounds' (also as diluents to use * the compounds and / or complexes of the to be separated for the production of a liquid organic medium Metals can be used as a suspension in such a diluent are present, but are preferably dissolved in the diluent.

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- OK

In the process according to the invention, in the reaction inert organic compounds can be used as diluents. The diluent preferably contains the liquid organic compounds that act as extractants suitable for the aqueous solutions of compounds (e.g. salts) of the metals to be separated »If the metals e.g. separated off in the form of salts of the aforementioned tertiary carboxylic acids are to be, these tertiary carboxylic acids can be particularly useful as diluents / solvents for the aforementioned salts can be used. Such solutions can be obtained in a simple manner by using aqueous solutions of compounds (e.g. salts) of the metals in question with an excess of tertiary carboxylic acids, based on the to extracting metals, extracted, or by dissolving the waste metals or waste metal compounds such as the oxide in an excess of these acids.

The diluent can advantageously be inert aliphatic compounds such as chlorinated aliphatic hydrocarbons (e.g. 1,2-dichloroethane) and alcohols with long chains contain. The diluent preferably contains saturated aliphatic hydrocarbons as aliphatic compounds substances (cyclic and non-cyclic hydrocarbons) of these Compound class. In particular, mixtures of saturated aliphatic hydrocarbons with a boiling point are used used between 150 and 25O ° C (kerosene).

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Are "the metals to be extracted from an aqueous one, these If metals are separated, e.g. as a salt-containing solution, the use of liquid organic media with an excessively high solubility in water can be avoided. Are the liquid organic, the compounds and / or complexes of the metals containing media by treating ores or scrap materials (e.g. battery plates) obtained with the organic, e.g., carboxylic acid-containing material, there are no strict requirements required with regard to the solubility of the liquid organic medium in water.

Carbon monoxide and sulfur dioxide are suitable as reducing gases. However, preference is given to using hydrogen, which is readily available and easy to handle. Hydrogen has the great advantage that the substance that is used to form the compounds and / or complexes of the metals in liquid organic

frequently

Shem medium is used in the hydrogenation. / recovered again will. For example, if a metal salt of a carboxylic acid is hydrogenated in a liquid organic medium, the Precipitation of the metal component also releases the relevant carboxylic acid. This can again lead to the formation of metal salts turn back.

It is not possible for the separation of all of the aforementioned metal groups suitable reaction conditions with regard to the temperature to be used, the pressure to be used and the one to be used Response time. Choosing these from each other

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independent parameters depend not only on the type and the amount of the Mota3Ie to be separated and the compounds and / or complexes of these metals in the liquid organic medium, but also on the desired degree of separation. For example, if two metals are present in the liquid organic medium, it may be desirable to carry out the reduction in such a way that a certain amount of a metal component of one fecal is obtained which is practically free of the other metal, but it can also be desirable to provide a two metals containing metal component and a residual solution, which is substantially free of one of the metals in question - to win. In each case, it can be advantageous, by means of separate experiments, to determine the best reaction conditions to achieve a specific goal with regard to the separation of the metals in question before- J bi &

100 bar abs. and preferably from 5 to 70 bar “abs. f _e

When extracting a copper component, special Expediently, temperatures of 175 to 25O ° C are used. Such temperatures and pressures are used that the desired separation of the metals is within an acceptable range Period of time (from e.g. 0.25 to 4 hours) is carried out. If a very short period of time is chosen for the reduction, then may vary slightly from. this time to be signified Advice effects on the completeness of the separation of the relevant Metals lead, while very long reduction times t-n are economically disadvantageous,

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It can be seen that that

Process according to the invention for separating metals can be carried out in stages. In an initial stage, a metal component is practically completely precipitated from the liquid organic medium by treatment with a reducing gas. After this metal component has been separated off, the remaining liquid is treated in a second stage with the same or a different reducing gas and a second metal component is thereby practically completely separated off. This step-by-step process v / ix ~ d carried out until the liquid organic medium contains practically only one metal component. The best possible reaction temperatures t reaction back and reaction times to be used in each stage can be determined by separate experiments.

It is advantageous to separate the suspension of inoculum and precipitated metal component in the liquid organic medium withdrawn from the fluidized bed into a liquid and a solid substance as soon as possible after being sieved from the bed, since the compounds and / or complexes of the originally im In the liquid organic medium present metals released organic substances naicjan to dissolve the MeLaI! components again. This applies. eg especially when salts of (ZoB. tertiary) carboxylic acids have been used. The metal components can be separated from the organic medium by means of suitable processes, for example by filtering off.

If the recovered metal component contains two metals, so

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can do this either by conventional methods or by Separated return to a method according to the invention will. In the latter case, of course, a fresh / unin-

gang materialgeruisch
/ of the metals to be separated in the form of compounds

and / or complexes of ores and / or scrap metals 2u.gespe.ist. '' - '

example

A solution containing the copper salts of a mixture of tertiary alkanecarboxylic acids with 10 carbon atoms per molecule and these alkanecarboxylic acids as such in a concentration of 0.09 to 1 mol per liter in a kerosene fraction with a low aromatic content with a boiling range at atmospheric pressure of 210 to 230 C. from untp.n upwards, through a vertically arranged stainless steel reactor tube with an inner diameter of 1 cia and a volume of 30 cm "passed" The Re & ktorrohr is equipped with a horizontal sieve that?> the underside of a bed of metal particles with a The total volume is 11.7 cm. The metal particles consist of copper-plated nickel and have a particle size of less than 0.149 mm. Hydrogen is fed in immediately above the sieve at a rate of 3 Nl / hour. A pressure is applied in the reactor tube abs of 1.5 bar. maintain \ the off from the top of the reactor tube kerosene solution is to cIcjl separation of the hydrogen cooled to temperatures of 80 to 90 ° C · and then after heating to a temperature before; 225 ° C introduced back into the bottom of the reactor tube. The ■

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Copy.

The rate at which the kerosene solution is passed through the bed, the time required for the solution to be circulated once and the number of passes through the reactor (number of passes of the volume of the kerosene solution of 11.7 ml through the bed) are determined according to the in the fourth listed in the table. The table also shows the copper yields achieved.

Tabel

attempt
No. Flow velocity
. digkeifc the
Kerosene solution
cw / spk. Attempt
duration,
Hours. Count of
Passes Copper-
yield,
Prop; ent 1 0 _f 09 1.5 22.5 60-70 2 0.7 1 40 30-40

In experiment no. 1, which is not according to the invention, the flow rate becomes intentionally kept so low that the day bed is not fluidized. After completing this, there is no attempt considerable part of the bed made of relatively large '

'agglomerated metal particles, some of which are on the inside stick to the wall of the reactor tube and difficult to remove r.ind.

In experiment no. 2 according to the invention, a flow rate is used used, which is just used to fluidize the bed.

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COPY *

BATH ORIGINAL

enough. After the end of the experiment, the particles of copper-plated nickel powder are still separate and the The inside of the reactor wall is practically free of copper deposits. The bed volume has increased to 12.5 cm. The relatively low yield of 30 to 40 percent can be increased by increasing the hydrogen pressure.

Claims

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Claims (4)

Claims 1. Process for the production of one or more metal components of metals of groups IB, UB ₁ IIIB, IVB , VB, VIB, VIIB and VIII of the Periodic Table of the Elements, in which a liquid, one or more compounds and / or complexes of one or more the organic medium containing the aforementioned metals is contacted with a reducing gas and at least one metal component is precipitated in the process, characterized in that the organic medium and / or the reducing gas from bottom to top with one a flow rate that is sufficient for the creation of a fluidized bed is passed (v / ground) through a bed of inoculum particles. 2. The method according to claim 1, characterized in that the fluidization of the bed is carried out by the liquid organic medium with a sufficiently high flow rate runs through the bed from the bottom up. 3. The method according to claim 2, characterized in that the liquid organic medium with a flow rate * is passed through the bed, which exceeds the minimum value required for fluidization by a maximum of 10 percent. 4. The method according to claim 1, characterized in that the inoculum in ^ particles with a largest particle diameter 40 9826/0874 less than 1 mm is used. 5 »Method according to claim 1 to 4, characterized in that that a finely divided metal powder is used as the inoculum. 6. The method according to claim 5, characterized in that copper powder and / or copper-plated metal powder is used as the seed material (are). 7 .. The method according to claim 1 to 6, characterized in that that copper compounds and / or complexes are used as metal compounds and / or complexes. 8. The method according to claim 7, characterized in that
the process is carried out at temperatures from 175 to 250 ° C. 9. The method according to claim 1 to 8 , characterized in that salts of tertiary alkanecarboxylic acids are used as metal compounds and / or complexes. 10. The method according to claim 9, characterized in that
tertiary carboxylic acids with 9 to 11 carbon atoms per molecule can be used. . 409826/0874 11. The method according to claim 1 to 10, characterized in that that hydrogen is used as the reducing gas. 12. The method according to claim 1 to 11, characterized in that that a liquid organic medium is used which contains a compound or compounds which are used as extraction agents for the extraction of aqueous solutions of the relevant Metal compounds suitable (suitable). 13. The method according to claim 12, characterized in that a medium is used as the liquid organic medium which contains a tertiary alkanecarboxylic acid. 14. The method according to claim 1 to 13, characterized in that that a medium is used as the liquid organic medium, the one or more saturated aliphatic hydrocarbons (e) contains. 15. The method according to claim 14, characterized in that a medium is used as the liquid organic medium, which is a mixture of saturated aliphatic hydrocarbons with a boiling point at atmospheric pressure of 150 to Contains 25O ° C. 4 0 9 8 2 6 / 087A *