Multicolumn sequential extraction of ionic metal derivative

FIELD: process engineering.

SUBSTANCE: invention may be used in hydrometallurgy. Proposed invention allows separating such metals as uranium, nickel, copper and cobalt present in liquid wastes of ore leaching. Solution containing metal ions is forced through stationary layer of resin, Particularly, through, at least, three zones. Note here that solution drive appliances are arranged between adjacent zones and between last and first zones. Proposed method comprises several sequences, each comprising, at least, one step selected from steps of adsorption, washing and desorption. Every next sequence is performed by shifting fronts into zones downstream of circuit with identical increment unless cyclic shift of inlet and discharge points.

EFFECT: optimised amounts of components, higher efficiency.

15 cl, 13 dwg, 2 ex

 

The present invention relates to a method multicolumn sequential separation and device for implementing this method. The invention is applicable, in particular, to highlight the derivatives of metals, such as derivatives of uranium, Nickel, copper, cobalt and other precious metals present in the liquid waste leaching in hydrometallurgical processes.

Currently, in the field of metallurgy is used several methods of extraction of metal components. In particular, when the ore has a low content of metal derived, using methods of leaching, which consist in removing soluble metal fractions by leaching with a suitable solubilizing solution. As the metal derivatives are dissolved in the form of ions, the final step is the separation of substances of interest from impurities or other contaminants.

Methods of separation are bringing into contact one or more liquid phases (called mobile) with the solid phase (called stationary). Ionic metal derivative, introduced in the liquid phase enters the interaction or cooperation of different nature with the stationary phase, as is the case in ion-exchange chromatography. Therefore you shall essenia in chromatographic device differs from the displacement of other products, contained in the processed raw materials. Based on this difference interactions can purify or enrich one faction ionic metal derivative.

Proposed methods for carrying out ion exchange in a continuous mode. In the document US-A-2815332 described system with a closed cycle, in which the resin is moving in a countercurrent liquid. This cycle contains four zones, isolated valves and intended respectively for saturation, washing, regeneration and washing. Resin moves in the zones and from one compartment to another in a countercurrent liquid phase under the action of hydraulic impulses.

Was developed for chromatography system, called SMB (Simulated Moving Bed - pseudopodial layer). Thus, in US-A-2985589 described continuous chromatographic method, SMB, in which the resin for chromatography stationary and spread across several departments, but its displacement is simulated displacement at regular intervals provisions of the input and output of fluids. In this case, the position of the input (power and eluent) and output (extract and raffinate) define four zones. In US-A-6375851 described system with six zones, adaptation to the process of ion exchange previously described in US-A-2985589. The system described in document US-A-6375851 based on SMB, except for the stage of regeneration, which is offset in front. Thus, I the water and the outputs of the liquids are moved, usually at the same time, synchronously and in accordance with a certain sequence.

In all systems was provided by a perfect continuity of the circulation of all the fluids. These systems lead to a very large number of columns, and the size of the columns is determined by the smallest regular sequence.

For methods used in hydrometallurgy, in particular methods of ion exchange, as is the case in WO 2007/087698, stages and regeneration steadily followed by the washing steps. In a periodic process, these stages are often implemented at the optimum flow rate relative to the kinetics of binding or desorption. Thus, modern methods do not allow for the separation process on a large scale that it would be economically advantageous because it requires too much pitch for columns and processed products. This disadvantage is all the more real that none of the methods used at the present time, does not allow the entire processing cycle, in particular the stage of regeneration of the resins in a continuous mode.

To this drawback is added that all the methods require the use of very large quantities of water, and it is in production regions, which are typically located in desert areas, as well as large quantities of the agent of regeneration, which in most cases is much Ki the pilot. In this case, the added problems of economic, ecological problems and problems of protection of natural resources.

The present invention relates to a method on an industrial scale, which optimizes the amount of the agent of regeneration, resin and water involved in the cycles of selection ionic metal derivative, present in the leaching solution method, which also allows you to achieve higher productivity in mining production plant. The method according to the invention is environmentally friendly, allows to obtain an increased yield of desired metal derivatives and is much more advantageous from the point of view of the economy than the methods corresponding to the prior art.

This is, in particular, the allocation method on the resin through sequential multicolumn selective retention, for marking metal ion derived from a leach solution containing the metal ion derived by conducting this solution through a fixed bed of resin selective to the metal, by the way, contains at least three zones, and means conducting fluid located between adjacent zones and between the last and the first area, and this method contains several posledovatelno is her and each sequence includes at least one step, selected from phase adsorption, washing step, stage desorption carried out simultaneously or not, and each following sequence is carried out by displacement of the fronts in areas down the circuit with essentially the same increment, prior to the periodic displacement of the points of introduction and discharge.

This method may contain a subsequence without the introduction of raw materials.

According to another aspect of the invention the method is characterized in that it contains several sequences, and each sequence includes at least one of the following stages:

(a) introducing a certain volume of wash solution to the input of the first zone and substantially simultaneously discharge the same volume of a liquid diluted with the specified ionic metal derivative at the point on the diagram below this zone;

(b) introducing a certain volume of the specified solution leaching of the raw material input to the second zone and substantially simultaneously discharge the same volume of liquid, enriched with impurity or impurities, relatively weaker held, at the point located at the diagram below this zone;

(c) introducing a certain volume of wash solution to the input of the third zone and essentially simultaneous abstraction of the same volume of a liquid diluted by the agent of regeneration, UB is not the point, located at the diagram below this zone;

(d) the optional introduction of a certain amount of resources to address contamination at the inlet of the fourth zone and substantially simultaneously discharge the same amount of diluted liquid, at the point located at the diagram below this zone;

(e) introducing a certain volume of eluent to the input of the fifth zone and substantially simultaneously discharge the same volume of liquid, enriched specified metal derivative at the point on the diagram below this zone;

moreover, the steps (a), (b), (c), (d) and (e) are performed simultaneously or not;

each of the following sequence is carried out by periodic displacement of the points of introduction and withdrawal down the scheme, essentially for the same increment of volume,

and including, in addition, phase

(f) displacement of the fronts in at least zones (b) and (e) to the periodic offset.

According to another variant of the invention, the method differs in that it contains several sequences, and each sequence includes the following steps:

(a) introducing a certain volume equalizing solution to the input of the first zone and substantially simultaneously discharge the same volume of liquid containing the first regeneration solution, and then equalizing the solution at the point n is held by the scheme below this zone;

(b) introducing a certain volume of leaching solution processed raw materials containing ionic metal derivative, to the input of the second zone and substantially simultaneously discharge the same volume of liquid containing the impurity or impurities, relatively weaker held, at the point located at the diagram below this zone;

(c) introducing a certain volume of wash solution to the input of the third zone and essentially simultaneous abstraction of the same volume of a liquid diluted by admixture or admixtures, held relatively weaker than ionic metal derivative, at the point located at the diagram below this zone;

(d) introducing a certain volume of solvent at the inlet of the fourth zone and substantially simultaneously discharge the same volume of liquid containing the metal ion is derived, at the point located at the diagram below this zone;

(e) introducing a certain volume of regenerant to the input of the fifth zone and substantially simultaneously discharge the same volume of liquid containing the most strongly retained impurities at the level of the point located at the diagram below this zone;

moreover, the steps (a), (b), (c), (d) and (e) may be conducted simultaneously or not;

each of the following sequence is carried out by periodic displacement of cockvore and bringing down the scheme, essentially with the same increment of volume,

and containing, in addition, phase

(f) displacement of the fronts at least in the zone (c) to the periodic offset.

According to another variant embodiment of the invention the method is characterized in that the steps (d) and (e) are carried out with the same fluid, in this case, these stages correspond to the stages consisting in:

(d) introducing a certain volume of the agent of regeneration to the input of the fourth zone and substantially simultaneously discharge the same volume of liquid, enriched specified ionic metal derivative at the point on the diagram below this zone;

and then the fourth and fifth zones are combined into a single fourth the area.

According to another variant embodiment of the invention the method is characterized in that the steps (a), (b), (c) and (d) are performed at least partially simultaneously.

According to another variant implementation of the method is characterized by the fact that the displacement of the fronts in different zones shifts fronts simultaneously.

According to another variant implementation of the method differs in that the displacement of the fronts contains the following steps:

(i) the establishment of a circuit between different zones, the first zone to the fifth zone; and

(ii) the implementation of the circulation in the specified path for the displacement of the fronts.

According to another version done by the means of the invention the displacement of the fronts contains the following steps:

(i) creating a first zone offset by hydrodynamic connecting the output of the first zone to the entrance of the second zone and hydrodynamic connecting the output of the second zone to the third zone, and shift down the circuit from entering the first zone to give the entrance to the first zone offset, and the offset up to the scheme from the third zone to give the output of the first zone offset; and

a second area offset by hydrodynamic connecting the output of the third zone to the entrance of a quarter zone, hydrodynamic connecting the output of the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone, and shift down the circuit from the input of the third zone to give the input of the second zone offset, and the offset up to the scheme from the first zone to give the output of the second zone offset; and

(ii) introducing a certain volume of wash solution to the input of the first zone offset and essentially simultaneous abstraction of the same volume of wash solution is collected at the outlet of the first zone offset

(iii) introducing a certain volume of wash solution to the input of the second zone offset and essentially simultaneous abstraction of the same volume of wash solution is collected at the outlet of the second zone offset.

According to another variant of the invention, the method differs in that asanee displacement fronts in different zones shifts the fronts asynchronously.

According to another variant embodiment of the invention the method is characterized by the fact that the displacement of the fronts contains the following steps:

(i) creating a first zone of the first offset by hydrodynamic connecting the output of the first zone to the entrance of the second zone and hydrodynamic connecting the output of the second zone to the third zone; and

creating a second zone of the first offset by hydrodynamic connecting the output of the third zone with the inlet of the fourth zone, hydrodynamic connecting the output of the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone; and

(ii) introduction of a certain volume of the specified solution to the input of the first zone offset and essentially simultaneous abstraction of the same volume of a liquid diluted by the agent of regeneration, from the outlet of the first zone of the first displacement;

(iii) introducing a certain volume of the agent of regeneration to the input of the second zone offset and essentially simultaneous abstraction of the same volume of a liquid diluted with the specified metal ion derived from the output of the second zone of the first displacement;

(iv) creating a first zone of a second displacement by means of hydrodynamic connecting the output of the first zone to the entrance of the second zone and hydrodynamic connecting the output of the second zone to the third zone, and shift down the circuit from the input of the first zone, to give an entrance to the first zone of the second offset, and the offset up to the scheme from the third zone to give the output of the first zone of the second offset; and

creating a second zone of a second displacement by means of hydrodynamic connecting the output of the third zone with the inlet of the fourth zone, hydrodynamic connecting the output of the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone, and shift down the circuit from the input of the third zone to give the input of the second zone offset, and the offset up to the scheme from the first zone to give the output of the second zone offset; and

(vi) introducing a certain volume of wash solution to the input of the first zone of the second offset and essentially simultaneous abstraction of the same volume of fluid, enriched with impurity or impurities, relatively weaker deducted from the first zone of the second offset

(vii) introducing a certain volume of wash solution to the input of the second zone of the second offset and essentially simultaneous abstraction of the same volume of liquid, enriched specified metal ion derived from the output of the second zone of the second offset.

According to another variant embodiment of the invention the method is characterized in that in step (f) carry out the displacement of the fronts in all areas to periodic offset.

According to the other variant of the invention, the method differs what periodic displacement input hold from one column to one column.

According to another variant embodiment of the invention the method is characterized by the fact that the periodic displacement of the input is carried out from two columns to two columns.

According to another variant embodiment of the invention the method is characterized by the fact that these areas contain at least one column, preferably at least two columns.

According to another variant embodiment of the invention the method is characterized by the fact that the increment of the volume, in accordance with which move above the point of introduction, and these points derive essentially corresponds to the fraction of the area of the absorbent material.

According to another variant embodiment of the invention the method is characterized by the fact that the increment of the volume, in accordance with which move above the point of introduction, and these points derive essentially corresponds to the volume of the column.

According to another variant of the invention, the column is equipped with a multi-way valves.

According to another variant embodiment of the invention the method is characterized by the fact that the periodic shift stages is synchronous.

According to another variant embodiment of the invention the method is characterized by the fact that the periodic shift stages is asynchronous.

Coz the ACLs another variant embodiment of the invention the method is characterized by the fact that that said liquid diluted with the specified metal ion derived, at least partly carried out at the step (b).

According to another variant embodiment of the invention the method is characterized by the fact that there is an extra area, and the fact that it contains, in addition, step (g) the introduction of all or part of the liquid, diluted specified ionic metal derivative obtained in step (a), at the level specified secondary zone, and the selection is essentially the same volume of wash solution at the point located at the diagram below this zone.

According to another variant embodiment of the invention the method is characterized in that the step (b) contains two podata (b1) and (b2), and the intermediate step of adjusting one parameter of the solution, in particular by changing the pH.

According to another variant embodiment of the invention the method is characterized by the fact that this liquid is diluted by the agent of regeneration obtained in step (c)at least a part is held on the stage (d)may, after it is executed.

According to another variant embodiment of the invention the method is characterized by the fact that the recovered wash solutions at least part held on the steps (a) and/or (c).

According to another variant implementation of the method according to the invention contains at least 3 columns and 4, the guide is Dinamicheskie line.

According to another variant of the invention, the method differs in that the chromatography is ion-exchange chromatography type, and ionic metal derivative is a salt selected from complexes of uranium, gold, copper, zinc, Nickel, cobalt and PGM (platinum group metal), preferably a salt of uranium, in particular sulfate uranium.

According to one preferred variant of the implementation phase of regeneration includes a step of purification of a strong base, such as potassium hydroxide or sodium, which is optional washing step with water, then the recovery phase resin acid, such as sulfuric acid.

According to another variant embodiment of the invention the method is characterized by the fact that the eluent is sulfuric acid.

Finally, the invention relates to a device for removing contaminants for implementing the method according to the invention.

The invention is illustrated in the drawings, where:

- Figure 1 schematically shows one variant of the method with SMB according to the prior art;

- figure 2 schematically shows the column in its environment in the installation according to the variant embodiment of the invention;

- figure 3 schematically shows a first variant implementation;

- figure 4 schematically shows a second variant implementation;

fee is ur 5 schematically shows a third variant of implementation;

- figure 6 schematically shows a fourth variant of implementation;

- figure 7 schematically shows a variant implementation of the method with SMB according to the prior art;

- figure 8 shows schematically the displacement of the fronts in accordance with the sequence of transitions according to a variant embodiment of the invention;

- figure 9 shows a diagram of the asynchronous shift the discharge line flushing according to another variant embodiment of the invention;

- figure 10 shows a diagram of the asynchronous shift of the supply line with a sequence of transitions according to another variant embodiment of the invention;

- figure 11 shows the method according to the invention with 6 hydrodynamic lines;

- figure 12 shows a different sequence in the method according to the invention, carried out with 5 liquids;

- figure 13 shows the method according to the invention.

The figures use the following symbols:

WWater
FDdiluted ionic metal derivative
Fleach solution containing the metal ion derived (downloadable solution or "submission", the content is Asa desired metal connection)
RAFThe raffinate
RDdiluted regeneration solution
Rthe agent of regeneration
EXTExtract
displEviction substances
AdsAdsorption
Preadspreadsorbed
Water displ.The displacement of water (rinsing)
WaterWater
H2SO4displ.The displacement of sulfuric acid (regeneration)
Sparepending
WashFlushing
Regeregeneration
Wash neutralneutral washing
Acidified wateracidified water
Wasteidcee drains
Step timethe duration of a sequence
Stepsequence

According to the present invention under ionic metal derivative is meant any type of ionized metal complexes, in particular but without limitation, the complexes formed by uranium and gold, and also complexes obtained in the extraction of copper, zinc, Nickel, cobalt, and PMG (platinum group metals). Preferably the metal derivative is a complex formed by uranium, even more preferably sulfate uranium. The counterion may be a sulfate, a carbonate or the other. In particular, in sulfuric acid solution, the uranium (IV) is mainly in the form of uranyl cations UO2+2and also in the form of sulfate complex UO2SO4UO2(SO4)2-2etc. To further the example of uranium will be used to illustrate ionic metal derivative, without limiting, however, the scope of the invention only a single product.

According to the present invention under leach solution is defined as any solution coming from the hydrometallurgical extraction process, containing in solution or suspension of metal produced in the water in their ionic form, such as previously defined. Leachate compositions depend, of course, from the geological nature of the ore used. For example, the solution leaching of uranium ore contains approximately 100-500, for example, about 350 ppm of uranium, silica at about 200-1000, for example, about 500 ppm, iron at about 500-20000, for example, about 1000 ppm, all these substances are present in most, as well as other compounds, such as vanadium. Solution leaching of copper ore contains from 1 to 5 g/l, for example, about 3 g/l of copper, from 3 to 10 g/l, for example, about 6 g/l of iron, from 100 to 1000 ppm, for example, about 400 ppm of silica and other impurities, such as aluminum or manganese.

In reality, the addition of vanadium to uranium or iron for copper, the most common impurities are impurities originating from the waste material, in particular silicates. These impurities can interfere with the technique for the extraction of the desired substance having a tendency to contact the resin and thereby limit its exchange capacity.

According to the invention the ionic metal derivative may be most strongly held stationary phase, but also the least strongly held stationary phase. As an example, let's specify that when the adsorption method according to the invention is used to separate substances such as uranium, the most heavily abstain the tsya stationary phase impurities, whereas the withholding is a metal ion derived.

According to the present invention the step of adsorption refers to the phase in which the injected raw material containing a metal ion derived, which you want to select, and then one or more of the products contained in raw materials, binds to the solid phase. This phase corresponds to the phase of loading.

According to the present invention the step of desorption refers to the phase in which the product or products that were bound on a solid medium pass into the liquid phase. Thus, the adsorption process, naturally contains at least one stage of adsorption and at least one stage of desorption.

According to the present invention under the washing step refers to the step between the step of adsorption and desorption, or Vice versa, and allows you to update the liquid phase contained in the column or columns. This stage may also be referred to as "stage wash".

The method according to the invention allows a better optimization of the boot sequence leach solution for processing and cleaning of selected products; this leads to a reduction of the used volumes and fewer by-products.

Furthermore, the method according to the invention offers one or more of the following advantages:

- Design of m is a mechanical designs, without moving parts, since the columns fixed. Columns are compact, and you can use multi-way valves on each column.

- Simplified maintenance, as it is possible to separate the column from the cycle without stopping the process for loading the resin or chromatographic media, General maintenance, etc. of maintenance Requirements similar to the requirements for periodic process, for which, as we know, they are low.

- Management process is easy because you only need to change the settings of the machine to process changes and adjustments zones of the process (no need to change any mechanical parts). In addition, you can use the flow meter in each column for each phase of the process.

- To easily increase capacity by simply adding columns to the available columns and changing the process parameters, to modify the zone.

These and other benefits if any, will be disclosed in the following description.

In figures 1, 3-6 description is given in relation to salt (sulfate) uranium, but it is understood that the method according to the invention is applicable to any metal ion derived and is applicable to any type of chromatography are well known to the specialist.

In any case, recall that ionic metal derivative tie in the ion exchange is regarded as the extract (X), as it is most exchange, and that impurities, at least the currency, referred to as the raffinate (R). These conditional rules will be applied to the other examples in this application, the term "strongly held" or "the least strongly held" is used when ion exchange is absent.

Ion exchange resins are classic, and wash solutions, and solutions for regeneration. In the present case and metal compounds in anionic form will be used by strong anion-exchange resin type I or type II (polymer of polystyrene and divinylbenzene containing Quaternary amino groups, such as Amberjet 4400 Cl™, Amberlite 920U Cl™, Dowex 21 K™) or weak anionic resin. In the case of the metal compounds in the cation form will be used by strong cation exchange resin (polymer of polystyrene and divinylbenzene containing sulfopropyl, such as Amberlite IR252™) or weak. In some cases, will apply selective resin (polymer of polystyrene and divinylbenzene containing special chelating group). These resins will have a view either gels or macrostock having a suitable particle size distribution (coefficient of heterogeneity close to 1.1; effective size of 0.3 to 1.6 mm).

From this point of view, the invention does not differ from ur is VNA techniques in the field of ion exchange. You can use anyone - or cation-exchange resin, strong or weak, depending on the specific case processing.

You can also use multiple systems consistently; in particular, it is possible to demineralization using the first system with a cationic resin, and then the second system with anionic resins.

The present invention is illustrated for example in the following description of three embodiments, conducted with reference to figures 3-5 of the attached drawings, while figure 1 describes an implementation option according to the prior art. Salt of uranium taken as a typical example of a metal ion derived which is representative of the substance treated in the process of ion-exchange chromatography.

According to figure 1 the apparatus comprises eight columns 1, 2, 3, 4, 5, 6, 7 and 8 filled with ion exchange resins. The operation of this unit type SMB, corresponding to the prior art, is illustrated below. It should be remembered that the displacement stages go from left to right, this corresponds in reality to shift columns right-to-left.

Step (a) includes the steps in which the introduction of a certain volume of water W to the input columns 1 and essentially simultaneous abstraction of the same volume of dilute metal salt from the exit of the column 2, and column 1 and 2 form the first zone. With the introduction of water in the city is the Achal stage, it should be remembered that due to the offset column 1 immediately before this was, in fact, column 2 (before offset). Column 2 immediately before the offset is filled with a dilute solution of uranium salt (which was not related to ion exchange). Front clean water then shifted lower and, therefore, column 1 goes from being diluted salt of uranium" (and it is understood that in this column there is a salt of uranium, subjected to ion exchange) in the state of "water" (salt of uranium, passed through ion exchange in this column). Column 2, which directly before this was column 3, moves from the state of "salt of uranium" (with the associated uranium, having passed through the ion exchange) in the state diluted salt of uranium" (with the associated uranium, having passed through the ion exchange), and at the bottom of column 2 extract cleanup solution leaching of ionic metal derivative, in diluted condition, first relatively concentrated, and then more and more diluted. Indeed, in this column is no longer available for exchange, and therefore, the diluted solution is simply washed away along the columns; we are talking about displacement solution of uranium. This recovered dilute solution is usually returned to the original tank with the solution that you want to clear, or immediately at the head of the column 3.

Step (b)includes the steps the purpose of which is the introduction of a certain volume specified leach solution at the inlet of the column 3 and essentially simultaneous abstraction of the same volume of liquid, enriched raffinate from the exit of the column 4. Column 3 is supplied leaching solution, but this column corresponds to column 4, located directly in front of her, that is the column in which the salt of uranium already partially passed through the ion exchange, and also containing a dilute salt of uranium, which has not been exchanged. Also column 4 corresponds to column 5, which is immediately behind it, i.e. the column with water. Column 4 is column predictable, as it gets the salt solution of uranium depleted in column 3. In column 3 is pumped by the solution of uranium salt, and the front of saturation moves forward in column 3, while the front leach solution, which is exchanged with the centers, moving in column 4 (column predictable). At the outlet of the column 4 of the collected raffinate, namely treated solution, which is not exchanged with the resin, passing from a very dilute solution to a more concentrated solution of the raffinate.

Step (c) includes steps, the purpose of which is the introduction of a certain volume of water at the inlet of the column 5 and essentially simultaneous abstraction of the same volume of a liquid diluted agent regenerat and, from the exit of the column 6. Column 5 is powered by water, while columns 6 goes dilute the agent of regeneration. Indeed, column 6 immediately before the offset was column 7, and therefore, immediately after the offset she gets what emerges from the column 5, that is, water with a small amount of the agent of regeneration. Thus, what emerges from the column 6 represents the diluted agent of regeneration.

Step (d) includes the steps aimed at the introduction of a certain amount of the agent of regeneration at the inlet of the column 7 and essentially simultaneous abstraction of the same volume of liquid, enriched in a metal salt, from the exit of the column 8. Column 7 is supplied with the agent of regeneration and is connected to the column 8. This column 8 represents the column 1 immediately before the shift, therefore, immediately after the offset in column 8 provides the agent of regeneration, resulting in front of the agent of regeneration is advancing in column 8, and then at the bottom of the column 8 extract extract is first diluted and then more and more concentrated, and when the recoverable amount begins to decrease, the stages of the shift.

Thus, at the end of the sequence N in the column head 1 have water and passed through ion exchange salt of uranium bound to the resin. In the head of the column 2 are passed through the ion exchange salt of uranium,water, and the remainder requiring cleaning solution of uranium salt. In the head of the column 3 are fully openevsys salt of uranium cleanup leaching solution. In the head of the column 4 are partially openevsys salt of uranium (not all centers exchanged), the raffinate (part requiring purification of leach solution, which was not connected) and the remainder requiring purification of leach solution. In the head of the column 5 have wash water and resin, ready to transmit. In the head of the column 6 are flush water, diluted agent of regeneration, and the centers regenerated. In the column head 7 are fully regenerated centers (ready to exchange with uranium salt) and the regeneration solution. In the head of the column 8 are partially regenerated centers, diluted regeneration solution and the extract (partial).

Thus, at the beginning of the next sequence of N+1 and according to the schema in which the columns are shifted to the left by shifting the points of input and output to the right, you have the following configuration. Water is held in column 2, in the head which is a salt of uranium exposed to exchange water, and the remainder requiring purification of leach solution. In the head of the column 3 are fully obmenivatsa salt of uranium and require cleaning leaching solution, and in this case column 3 takes what emerges from the column 2. In the head of the column 4 are part of the but obmenivatsa salt of uranium (not all centers were sharing), the raffinate (part requiring cleaning solution of uranium salt, which was not connected) and the remainder requiring purification of leach solution, and this column takes then require cleaning leaching solution. In the head of the column 5 is flush water and resin, ready to transmit, and it takes what emerges from columns 4 and depleted raffinate solution of uranium salt, which will be exchanged with ions in the column of predatorprey. In the head of the column 6 (column, which contains the regenerated centers and a dilute solution of the agent of regeneration), serves wash water. Column 7, which also contains the fully regenerated centers (ready to exchange with the salt of uranium)receives water from the column 6 and diluted regeneration solution, which is withdrawn from the bottom. In the head of the column 8 are partially regenerated centers and diluted regeneration solution, and it serves a solution of the agent of regeneration.

Thus, the threads that will go in the head of the column would be as follows. In the head of the column 2, which already contains the top partially openevsys salt of uranium enters the leaching solution. Thus, there is a gap of fronts and the gradient, which is not observed. In the head of the column 8 regeneration solution into the column partially regenerated diluted Agen the om regeneration, and so locally the result is a mixture of pure agent of regeneration with untreated agent of regeneration. The gradient is again not observed.

Thus, it is seen that the classical SMB system used in ion-exchange resins, even if she has the advantage of continuous operation, however, is not free from drawbacks, which are always visible at the level of regeneration.

Due to the phase displacement of the fronts in the areas to the periodic displacement, the invention allows to overcome this problem and not to touch gradients. The phase displacement of the fronts is usually in the same column. The following description refers to the three options for implementation. The displacement of the fronts produced by introducing a fluid selected in the columns, or the existing circulation of fluids in the closed loop, water injection (drilling fluid) or the introduction of raw materials and the agent of regeneration after the introduction of water.

In figures 3, 4 and 5 of the installation is identical in terms of columns, the only difference being the order of the columns and, possibly, the presence of intermediate tanks (not shown).

The installation includes columns(1, 2, 3, 4, 5, 6, 7 and 8), filled with the same quantity of resins suitable for the present invention, which is defined previously.

These columns are arranged in series, and each contains the input and output. Typically, as will become clear below, the AC is every input can accept an aqueous solution for processing, the regeneration solution, recovered water, acidified salt of uranium, sulfuric acid. Typically, as will become clear below, each output can provide a diluted salt of uranium, the raffinate, extract, recovered water, diluted sulfuric acid, a salt of uranium (extract). Each column, in addition, is connected with the previous and next column.

This principle is presented in figure 2. As shown in figure 2, the valves can be multi-way valves, in particular 6-way. These multi-way valves themselves known and managed classically electric motor. Preferably the valves are driven by turning on one step at a time in the operation mode. For certain modes, you can bring the valves into action, turning them into several sectors, for example, when it is desirable to separate one column to make this column a specific sequence.

According to the first variant implementation, shown in figure 3, after a sequence of N identified by sequence 1.1 in the figure, have the configuration described above in connection with the SMB system.

Then produce the displacement of the fronts during the sequence 1.2. This offset is obtained by closure of the columns in the cycle and the implementation of the circulation.

This displacement is carried out with the increment in one column, catching the Yaya fluid to circulate in the circuit. Displaced volume corresponds to the volume of one column.

Thus, at the beginning of the sequence N+1 given the following columns. So, in the head of the column 4 are partially obmenjatsja centers, as for the liquid, it represents what was in the head of the column 3 (these already obmenjatsja centers are no longer available for exchange), that is, requiring purification of leach solution (hence, the composition essentially identical to the composition of that column will get more). Column 8 contains then partially regenerated centers and the solution of the agent of regeneration (i.e., the composition essentially identical to that column will get more). Thus, the power of the column is performed with a constant gradient as the concentration in the head of these columns do not change. This is true also for the other columns. Column 6 has a top that was in the head of the column 5, namely water, and will also get water. Column 2 is at the top of what was in the head of the column 1, namely water, and will also get the water.

As for the second variant implementation, shown in figure 3, after a sequence of N identified by sequence 1.1 in the figure, have the configuration described above in connection with the SMB system.

Then the displacement of the fronts during the sequence 1.2. This offset is obtained by the circuit in the circuit of the two zones of displacement. The first zone displacement is the area that contains columns 2, 3, 4 and 5. The second zone displacement is the area that contains columns 6, 7, 8 and 1.

This offset is made with increments in one column by water injection in the head zone offset. Displaced volume corresponds to the volume of one column.

Thus, at the beginning of the sequence N+1 receive the same columns as in the first embodiment. The difference lies in the exclusion volume of the column of water. Indeed, between the two parts of the process of obtaining/regeneration buffer has water to avoid contamination of various substances. This water buffer in the first embodiment, simply shifted, whereas in the second embodiment, it is replaced. Thus, in the second embodiment, the bottom of columns 1 and 5 derive the volume of water in the same column, that is, the recovered water (Rec W). This recovered water is carried out in the intermediate pool, and it can be used to supply columns of the wash water. You can also use some of this water with fresh water for rinsing. The other sequences are the same as in the first embodiment.

In the first and second embodiments, the implementation of the displacement of the fronts is synchronous because all fronts move simultaneously with one increment of volume. Incoming fronts move with Chrono onto the fronts.

In the first and second embodiments, the implementation of a subsequence, without introducing a raw material corresponds to the subsequence 1.2 (or 2.2, depending on the sequence).

According to the third variant of implementation, shown in figure 5, after a sequence of N identified by sequence 1.1 in the figure, have the situation described above in connection with the SMB system.

Then make a first offset fronts during the sequence 1.2. This is the first offset is obtained by creating a circulation of two zones of the first offset. The first area of the first displacement is the area that contains columns 3, 4, 5 and 6. The second area of the first displacement is the area that contains columns 7, 8, 1 and 2. The solution of uranium salt is introduced into the column 3, which causes the first offset in the first zone. Then the head of the column 4 is requiring purification of leach solution. The contents of the column 6 is extracted at the bottom, it diluted the agent of regeneration. The agent of regeneration enter in column 7, which causes the first offset in the second zone. On top of the column 8 in this case is the solution of the agent of regeneration.

Then made a second displacement of the fronts in the sequence 1.3. This is the second displacement is obtained by creating a circulation of two zones of the second offset. The first area of the second offset is the area that contains columns 2, 3, and 5. The second area of the second offset is the area that contains columns 6, 7, 8 and 1. At this time, water is injected into the columns 2 and 6. This causes the second offset fronts. The composition of the head of the column 3 is at the top of column 4; this again leachate solution that you want to clear. From this point of view, the composition at the top of the column 4 has not changed during this second shift. In the same way at the level of the column 8 get the part with the head of the column 7, and it is the agent of regeneration. Also from this point of view, the composition of the head of the column 8 has not changed. What has changed in the course of this second bias is the compounds in columns 5 and 1, so as to receive the raffinate at the bottom of the column 5 and the extract at the bottom of the column 1. During this second shift restore "buffer" of water between the two parts of the process of obtaining/of regeneration, to avoid contamination of various substances.

In the third embodiment, the displacement of the fronts is asynchronous, since all incoming fronts do not move synchronously with the output of fronts. In this example, we first shift the incoming fronts, and then shift-facing fronts, but it can also occur in reverse order.

In the third embodiment, the subsequence without the introduction of raw materials corresponds to the subsequence 1.3 (or 2.3, depending on the sequence).

Number number is NN in the zone of displacement or in the zone, corresponding to the areas (a), (b), (c) and (d)are not necessarily constant. Change the number of columns in each zone can be advantageous to take advantage of each column. As an example, you can have the first set of columns in the state of elution (columns of displacement), which is constant, whereas the zone of receipt and regeneration have variable length, for example, two columns for receiving and one column for regeneration, then one column for receiving and two columns on regeneration. As another example, if we consider the set of columns of M, we can have the full sequence (the set of all sequences (a), (b), (c), (d) and offset) to M-1 or M-2 columns, or M-M columns. In this case, you can disable, for example, for maintenance, one, two or m columns with a layer of resin or all of the valves and lines tied to this column.

Indeed, the method according to the invention allows the selected phase on the selected column independently of the other columns, if necessary. Continuous processes according to the prior art it is impossible. For example, as mentioned, you can disable one column. You can also within a given sequence to change the power of the column. When the column gets the water, you can use recuperando the water, and then carry on this column with fresh water, which allows to optimize the water flow. You can also provide a column of alternating raw materials or changing regenerating solutions. In comparison with the methods according to the prior art, it is possible to play better rates of leaching and production. In particular, these methods according to the prior art provide a continuous dilution of supply of flush water. This leads, inter alia, to increase the rate of passage through the zone of adsorption (ion exchange). Thus, the optimum hydraulic conditions for each sequence step in the continuous process according to the prior art are not observed. The invention can best benefit from optimum hydraulic conditions, better managing each stage, since the duration of stages (a), (b), (c) and (d) are not necessarily equal. Thus, it is possible to optimize for each column.

The method can be optimized to obtain an optimized supply of liquid columns, adding to the liquid emerging from the columns to re-use them in the following columns.

You can also order all other columns were columns of displacement, in particular the additional column displacement at the level of step (b), and also to have an additional step of receiving the recovered water. This is t an implementation option, shown in figure 6, includes the use of 9 columns. Columns 1, 2, and 3 correspond to columns 1, 2, and 3 in figures 3, 4 and 5. Columns 4 and 5 correspond to column 4 in figures 3, 4, 5. Column 6 is new in comparison with the variants of the implement shown in figures 3, 4 and 5. Column 7 corresponds to columns 5 and 6 in figures 3, 4, 5. Columns 8 and 9 correspond to columns 7 and 8 in figures 3, 4 and 5. The mode of operation is identical to mode of embodiments of figures 3, 4 and 5. Here is also applied to the circuit in the circuit. Also set two zones of displacement is possible, according to the second variant of implementation, as follows: first zone offset contains columns 2-7, and the second zone offset contains columns 8, 9 and 1. You can also specify the zone of the first and second evictions in accordance with the third embodiment. The first and second zones of the first offset contain columns 3-7, on the one hand, and 8-2, on the other hand. The first and second zones of the second offset contain columns 2-7, on the one hand, and 8, 9 and 1, on the other hand. In the embodiment of figure 6 the flow coming from the column 3, at once supplies the column 4. In the embodiment of figures 6 (all, as in other variants of the implementation) can be customized pH of different fractions, which are held on the columns. For example, you can ensure that the pH of the fractions that were in contact with sa is Oh-filled column (3), was below 2 before its implementation to the next column. Changing the pH can also change the type of ionic metal derivative, preferably linked to the resin. You can also submit leaching solution into multiple columns in parallel.

The invention is applicable also to any type of chromatographic separation of any type of products. In particular, in the method according to the invention can be used 5 (or more) of the input fluids:

- Boot environment, or load: this fluid contains raw materials for processing and buffer composition, pH, salt content, which allows introducing this medium in the column to adsorb the desired molecules on the stationary phase. At the exit from the boot phase column contains a stationary phase in which the adsorbed metal ion derived, as for the liquid phase in the column, it consists of diluted boot environment (FD, Feed Diluted).

- Wash environment, salinity and pH of which is identical with the boot environment, but not containing raw materials for processing. This step updates the liquid phase of the column and allows you to remove from the raw material compounds that are not held stationary phase. In the case of uranium salt is used, for example, water or an aqueous acid solution.

The elution of the desired substance: liquid nature that change the nature of interactions between the target molecule and the stationary phase, allows you to decarbonate target molecules with the stationary phase, and the target molecules are collected then in the output fluid. For leaching of sulphate of uranium typical eluent, according to the invention is sulfuric acid, and when the uranium is in the form of carbonate uranium complex is washed or sodium chloride, or solutions of carbonates of ammonium or of sodium.

- Regeneration: after elution of impurities can be strongly adsorbed on the stationary phase, which may impair the stability or sanitary specifications. The inventors have seen that these impurities in the case of uranium mining and copper can be silica or iron. Can also be used in a liquid containing an acidic additives as sulfuric acid. In the case of uranium salt, described earlier stages of elution of the desired substance and regeneration are carried out simultaneously, and the agent of regeneration (sulfuric acid) is exchanged with the centers of the resin to release the salt of uranium.

- Introduction of the solvent corresponding to the flushing medium used after downloading, enables you to release the casing from the solvent or solvent regeneration before the upcoming load. Thus, the saved buffer between the load and the end of the regeneration; talk about the adjustment.

- Optional introduction cleaning the Reda will allow you to clean the resin from impurities, in particular silica, which is connected to the resin, competing with uranium, limiting thereby the kinetics of loading and elution. Typically in the case of the invention, the cleaning medium is used a base, preferably a strong, such as sodium hydroxide or potassium hydroxide.

The invention proposes a method, which allows 5 stages:

Stage a: called equalization, in which the equalizing solution is introduced into at least one column of the system to clear it from the regeneration of the solvent it contains. For area adjustment reserved liquid will first consist mainly of regeneration solution, and then mainly from equalizing solution.

Step b: called loading, in which is introduced a solution of raw materials for processing. Desired molecules then bind to the chromatographic medium, together with other impurities. At the outlet of this zone, below the insertion point, the exhaust fluid contains the least retained impurities.

Stage c: called flushing, which is used to wash the column, where it replaces the liquid phase, containing, in particular, impurities, not withheld wash solvent.

Stage d: called elution, in which the injected solution, modifying the desired interaction of the molecules with chromatographic n is Cetelem, that also allows you to wash the desired molecule. At the exit from the zone of elution of the given first liquid will contain a wash solution, and then the solution enriched ionic metal derivative.

Stage e: called regeneration, which enter recovery solution that allows you to separate impurities, is very strongly adsorbed on the media.

In the invention of the periodic displacement of the input points can be made from column to column; thus, it is possible to control each column (or area) independently. The invention allows for the operation of each column (or zone) independently; in particular, the offset of the I/leads can be synchronous, asynchronous, as well as the phase displacement of the fronts can be synchronous or asynchronous, and can be applied from column to column (from zone to zone). You can also use one column (or zone) to perform a single operation or several columns (or zones) for other operations; thus, it is possible to displace the point I/o and fronts one of the column for a given zone, and two or more columns for other specified area.

The figure 7 shows the method according to the preceding level, multi-synchronous, periodic, and without waiting using different fluid. Between each of these feeds, you can specify one area: for example, between the hearth is her raw material (Feed) and feed equalizing fluid is set to the loading area. Between wash solution (Wash) and raw materials (Feed) specified area washing, etc. These zones correspond to the first, second, third, fourth and fifth zones of the method according to the invention (in the case of metal salts and ion-exchange resin fourth and fifth zones can be combined, and eluent and the agent of regeneration are the same fluid). The figure 7 shows the periodic displacement. Here is found the same principle, which is illustrated in figure 1 (corresponding to the case of four liquids).

If we consider the column N 9, at the end of the cycle it is in the boot configuration. After the switch it is located just before the exit of the washing step. Therefore, what emerges from this column immediately after switching lines, yet also contains raw materials, it contains the crude ionic metal derivative, which is actually diluted and lost.

In the present invention, the load line, and each line supplying fluid can actually free to move relative to the other lines with the ability to have a subsequence of the displacement fronts. Indeed, each offset fronts can be made from line to line, synchronously or asynchronously, and so the line-by-line. Any valid combination, and it is understood that the displacement of the fronts includes Myung is our least offset front raw materials, preferably the offset front of the agent of regeneration. This offset fronts, at least at the level of a single column, which is under load, in systems according to the prior art is not possible.

You can also offset fronts with increment in one column, and increment more or less columns.

Asynchronous mode allows you to reduce the total number of columns, leading to the coexistence in the same column multiple zones within a specified period.

Figure 11 is an example of the method according to the invention with several hydrodynamic lines, here the number 8. In the case presented in the figure 11 shows the separation of impurities, such as defined previously. In one embodiment, columns 1 and 2 supply water as a washing solution and get the solution diluted ionic metal derivative. In column 3 of adsorption is served raw materials, while below the column of predatorprey supplied that goes from the column 3 (which can be combined with what comes out of the wash column 1, i.e. dilute solution of the raw material)and output columns of predatorprey obtained effluent (raffinate). Columns 5, 6 and 7 are used to remove one or more impurities, depending on the procedure, which thevisitor considered impurities. In the case of silica spend cleaning hydroxide, followed by regeneration of the resin with sulfuric acid. Each processing stage is followed by a washing step. Column 8 is washed with water, and effluent is added to sulfuric acid. This solution is the eluent, which is held on the columns 9 and 10, the output of which is the extract. This extract gives the ionic metal derivative, and the separated water can be returned to the process (here shown as a return for leaching in columns 1 and 2).

While the method described in figure 7 shows these stages in accordance with a periodic process, without sequence, in which the offset injection of various solutions is performed synchronously and not on the queue, figure 12 shows the way in which offsets are asynchronous and serial. Thus, figure 12 shows an example implementation of steps (a)-(e) according to the invention in a system with 6 columns, in which the period is divided into 5 subsequences corresponding to offset some of the discharge lines at different points in the sequence.

At the beginning of the first sequence is the following situation:

the discharge line equalizing solution is in column 1,

a - line injection of regeneration solution and eluent are in column 2. As Clare is the proof earlier, in the case of overlapping lines is the advantage of a lower line, in this case, the discharge line eluent.

the discharge line of the washing solution is in column 3,

the discharge line of the solution of the processed raw material is in column 4.

This configuration corresponds to the subsequence of 1.1, which lasts from t=0 to, for example, t=0,24*Δt.

At the end of subsequence 1.1 of their shift one column, for example a line of elution. Start subsequence 1.2, configuration is as follows:

the discharge line equalizing solution is in column 1,

the discharge line regenerant is in column 2,

the discharge line eluent combined with the injection of wash solution to the column 3. Dominated by the bottom line, in column 3 we wash solution,

the discharge line of the solution of the processed raw material is in column 4.

Subsequence 1.2 lasts, for example, from t=0,24*Δt to t=0,36*Δt.

At the end of subsequence 1.2 shift, such as line flushing. Start subsequence 3, the configuration is as follows:

the discharge line equalizing solution is in column 1,

the discharge line regenerant is in column 2,

the discharge line eluent is in column 3,

- line nagatani the wash solution is applied on the discharge line of solution processed raw materials in the column 4. The download is after washing, prevails input raw materials. Thus, in column 4 introduces the solution of the processed raw materials.

Subsequence 1.3 lasts, for example, from t=0,36*Δt to t=0,60*Δt.

At the end of subsequence 1.3 displace simultaneously egalitarian line and line regeneration. Start subsequence 1.4, the configuration is as follows:

the discharge line equalizing solution is in column 2,

the discharge line regenerant is superimposed on the discharge line of eluent in column 3. Prevails in the rear line, in this case, the input eluent.

the discharge line of the washing solution is applied on the discharge line of solution processed raw materials in the column 4. Download is below flush, therefore, prevails introduction of raw materials. Thus, in column 4 introduces the solution of the processed raw materials.

Subsequence 1.4 lasts, for example, from t=0,60*Δt to t=0,76*Δt.

At the end of subsequence 1.4 make the transition corresponding to the displacement of ionic metal derivative contained in the liquid phase of the column 4, column 5. For this stop to enter the solution of the processed raw material, thus, it is the transition from stage (b) loading, which corresponds to the displacement of the fronts of the concentrations of the liquid phase is not retained impurities and ionic meta is symbolic derivative, to step (c). Thus, the transition is stopping supply of the processed raw material, which corresponds to a displacement fronts caused by the step (c).

Start subsequence 1.5, the configuration is as follows:

the discharge line equalizing solution is in column 2,

the discharge line regenerant is superimposed on the discharge line of eluent in column 3. Prevails bottom line, in this case, the injection of eluent

the discharge line of the washing solution is in column 4.

Subsequence 1.5 lasts, for example, from t=0,76*Δt to t=Δt.

At the end of subsequence 1.5 the first period ends, the solution of the processed raw material is introduced into the column 1.5.

Then you can start subsequence 2.1 sequence 2; note that the subsequence 2.1 sequence 2 is similar to the subsequence 1.1 sequence 1 except that the line is shifted by one column.

Thus, it seems that asynchronous offset allows the sequence 1 column 2 stages of elution, regeneration and adjustment, in fact, this allows to reduce the number of columns in comparison with the method using the offset of the synchronous type.

It also appears that thanks to the invention the sequence re the ode, corresponding to the termination of discharge of solution processed raw material (step (b)), allows not to lose the metal ion is derived, is still contained in the column 4 at the end of the sequence 1.4.

You can also use multiple lines eluents, for example, for the treatment of solutions containing multiple ionic metal derivative, which desorbers or exchanged ions in different conditions. The first eluent would selectively removing the first metal ion is derived, and the second eluent would selectively removing the second metal ion is derived. One example of application includes removing milk proteins.

In the description of the present invention, the term "column" should be understood as meaning a physical column or a completely different part of the column, which can be identified as a section, when the physical column contains the entry point and excretion on several levels. Thus, the only physical column can be divided into several sections, or cells, and the invention can be applied to this configuration.

Thus, the invention is applicable to all desired products that can be identified by chromatography. For example, the invention allows to distinguish ionic metal derivative such as a salt of uranium, and stationary phase t is aetsa ion-exchange resin, and wash solution is water.

Examples

The following examples illustrate the invention, but not limit it.

Example 1. Ionic metal derivative

The method according to the invention is applicable to all types of metal derivatives, such as uranium salt, such as uranyl sulfate; Nickel, cobalt or copper, using a cationic resin, washed with acid, for example sulfuric acid. Thus, the invention provides a way of separating metal ion derived from a leach solution containing such a derivative and impurities, by conducting this solution through a fixed bed of ion exchange resin, and contains at least four successive zones, and means for conducting fluid between adjacent zones and between the last and first areas, and the said metal salt is selectively exchanged ions upon contact with the specified ion exchange resin, and at least one of the impurities is subjected to a relatively smaller exchange with this ion exchange resin than metal salt, and ion-exchange capacity of the ion exchange resin to recover under the action of the agent of regeneration,characterized in thatit contains several sequences, and each sequence contains the following steps:

(a) CC is engaged in a certain volume of water at the entrance to the first zone and substantially simultaneously discharge the same volume of liquid, diluted specified metal salt, at the point located at the diagram below this zone;

(b) introduction of a certain specified volume of aqueous solution at the inlet of the second zone and substantially simultaneously discharge the same volume of liquid, enriched in admixture or admixtures subjected to relatively smaller currency, at the point located at the diagram below this zone;

(c) introducing a certain volume of water at the inlet of the third zone and essentially simultaneous abstraction of the same volume of a liquid diluted with eluent, at the point located at the diagram below this zone;

(d) introducing a certain volume of solvent at the inlet of the fourth zone and substantially simultaneously discharge the same volume of liquid, enriched in a metal salt, at the point located at the diagram below this zone;

moreover, the steps (a), (b), (c) and (d) may be conducted simultaneously or not;

each of the following sequence is performed by periodic displacement of the points of entry and removal down the scheme, essentially with the same increment of volume,

and containing, in addition, phase

(e) displacement fronts in areas to periodic offset.

In the case of uranyl sulfate eluent is an acid solution. If we compare the method according to the invention with a continuous manner according to the prior art when the ass is authorized performance get uranyl salts, this method allows you to receive substantial benefits. The performance is the same material consumption is severely reduced, the flow of water below, the formation of liquid waste is reduced, and the number of columns is also reduced.

Example 2. Ionic metal derivative, uranyl sulfate.

To effect the release of uranium used the following method.

Boot environment (leaching solution containing uranium and its impurities), contains raw materials that are required to process. This environment allows ionic metal derivative to gain a foothold in the stationary phase. After the boot phase column contains a stationary phase in which the uranyl sulfate associated ionic forces.

The washing step updates the liquid phase of the column, so that the impurities contained in the liquid phase of the column is not washed out simultaneously with the metal salt in phase elution.

Wednesday elution of uranyl sulfate is a sulfuric acid concentration of 2M. Indeed, she was quite active eluent uranium IV because of the very high stability of anionic complexes of uranyl-sulfate.

The experiment presented according to the way multi-column sequential separation of uses in this example, 8 columns, according to the following sequences and subsequences, which are shown n the figure 13. For each numbered column sequence specified layer volumes (BV), transmission rate (BV/h)and duration.

Sequence 1

Subsequence 1.1: first 4 columns specify the loading area. Column 5 is in the regeneration zone. Columns 1 and 4, and 5 and 7 are connected in series. Column 8 is cleaning or pending.

Subsequence 1.2: In this subsequence column 5 is almost fully recovered and no longer contains uranyl sulfate, then he goes into the zone of leaching.

Subsequence 1.3: In this subsequence column 1 is almost saturated leach solution containing uranium, which must be extracted, in this case, he goes to wash.

Sequence 2

It is identical to the sequence 1, but shifted by one column.

For the described system, the test is performed with the download speed of 413 m3/h, leach solution contains 0.35 g/l of uranium and impurities characteristic of the raw material coming from the extraction process by leaching. The method used for the separation of this solution are listed below.

Average consumption: 413 m3/PM

The length of the subsequence 1: 3,43 PM

The length of the subsequence 2: 0,50 PM

Duration podpol the sequences of 3: 0,21 PM

Duration of sequence: 4,14 PM

The capacity of the resin: a 29.9 g/l

1. The method of separation of the resin by selective sequential multicolumn hold for separation of metal ion derived from a leach solution containing the metal ion derived by conducting this solution through a fixed bed of the resin, and the method includes at least three zones, this means conducting fluid is placed between adjacent zones and between the last and the first area, and the method contains multiple sequences, and each sequence contains at least one step selected from a stage of adsorption, washing step, stage desorption carried out simultaneously or not, and each following sequence is carried out by displacement of the fronts in the area down under the scheme, essentially, with the same increment, up to the periodic displacement of the points of entry and discharge.

2. The method according to claim 1, characterized in that it contains multiple sequences, each of which contains at least one of the following stages are carried out:
(a) introducing a predetermined volume of wash solution to the input of the first zone and essentially simultaneous abstraction of the same volume of a liquid diluted ionic metal derivative, at the level of precision and, located at the diagram below this zone;
(b) introducing a predetermined volume of solution leaching of the raw material input to the second zone and essentially simultaneous abstraction of the same volume of fluid, enriched with impurity or impurities, relatively weaker held, at the point located at the diagram below this zone;
(c) introducing a predetermined volume of wash solution to the input of the third zone and essentially simultaneous abstraction of the same volume of a liquid diluted by the agent of regeneration, at the point located at the diagram below this zone;
(d) the optional introduction of a specified amount of funds to eliminate pollution at the inlet of the fourth zone and essentially simultaneous abstraction of the same volume of diluted liquid at the point located at the diagram below this zone;
(e) introducing a predetermined volume of eluent to the input of the fifth zone and essentially simultaneous abstraction of the same volume of liquid, enriched specified metal derivative at the point on the diagram below this zone;
moreover, the steps (a), (b), (C), (d) and (e) are conducted simultaneously or not;
in this case, each following sequence is carried out by periodic displacement of the points of entry and removal down the scheme, essentially, with the same increment of volume,
and contains also the stage at which carry out:
(f) the offset is of the fronts in at least zones (b) and (e) to the periodic offset.

3. The method according to one of claims 1 or 2, characterized in that the steps (d) and (e) is carried out with the same liquid, and these stages correspond then to the step consisting in:
(d) introducing a predetermined volume of the agent of regeneration to the input of the fourth zone and essentially simultaneous abstraction of the same volume of liquid, enriched specified ionic metal derivative at the point on the diagram below this zone;
and the fourth and fifth zones are then combined into a single fourth the area.

4. The method according to claim 1, characterized in that steps (a), (b), (C) and (d) are performed at least in part simultaneously.

5. The method according to claim 1, characterized in that the displacement of the fronts in different zones shifts fronts simultaneously.

6. The method according to claim 5, characterized in that the displacement of the fronts contains the following stages are carried out:
(i) the establishment of a circuit between the different zones from the first zone to the fifth zone; and
(ii) the implementation of the circulation circuit for shifting fronts.

7. The method according to claim 5, characterized in that the displacement of the fronts contains the following stages are carried out:
(i) creating a first zone offset by hydrodynamic connecting the output of the first zone to the entrance of the second zone and hydrodynamic connecting the output of the second zone to the third zone, and shift down the circuit from entering the first zone to about the level of the inlet of the first zone offset, and offset up to the scheme from the third zone to ensure the release of the first zone offset; and
a second area offset by hydrodynamic connecting the output of the third zone with the inlet of the fourth zone, hydrodynamic connecting the output of the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone, and shift down the circuit from the input of the third zone to provide input of the second zone offset, and the offset up to the scheme from the first zone to ensure the input of the second zone offset; and
(ii) introducing a predetermined volume of wash solution to the input of the first zone offset and essentially simultaneous abstraction of the same volume of wash solution is collected at the outlet of the first zone offset
(iii) introducing a predetermined volume of wash solution to the input of the second zone offset and essentially simultaneous abstraction of the same volume of wash solution is selected at the output of the second zone offset.

8. The method according to claim 1, characterized in that the displacement of the fronts in different zones shifts the fronts asynchronously.

9. The method according to claim 8, characterized in that the displacement of the fronts contains the following stages are carried out:
(i) creating a first zone of the first offset by hydrodynamic connecting the output of the first zone to the entrance of the second zone and gidrodinamicheskogo is connecting the output of the second zone to the third zone; and
creating a second zone of the first offset by hydrodynamic connecting the output of the third zone with the inlet of the fourth zone by hydrodynamic connecting the output of the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone; and
(ii) the introduction of a specified amount of the specified solution to the input of the first zone offset and essentially simultaneous abstraction of the same volume of a liquid diluted by the agent of regeneration, from the outlet of the first zone of the first offset;
(iii) introducing a predetermined volume of the agent of regeneration to the input of the second zone offset and essentially simultaneous abstraction of the same volume of a liquid diluted with the specified metal ion derived from the output of the second zone of the first offset;
(iv) creating a first zone of a second displacement by means of hydrodynamic connecting the output of the first zone to the entrance of the second zone and hydrodynamic connecting the output of the second zone to the third zone, and shift down the circuit from entering the first zone to provide entrance to the first zone of the second offset, and the offset up to the scheme from the third zone to ensure the release of the first zone of the second offset; and
(v) creating a second zone of a second displacement by means of hydrodynamic connecting the output of the third zone with the inlet of the fourth zone, the hydrodynamic connection output is and the fourth zone to the entrance of the fifth zone and hydrodynamic connecting the output of the fifth zone to the input of the first zone, and shift down the circuit from the input of the third zone to provide input of the second zone offset, and the offset up to the scheme from the first zone to ensure output of the second zone offset; and
(vi) introducing a predetermined volume of wash solution to the input of the first zone of the second offset and essentially simultaneous abstraction of the same volume of fluid, enriched with impurity or impurities, relatively less strongly held, from the outlet of the first zone of the second offset,
(vii) introducing a predetermined volume of wash solution to the input of the second zone of the second offset and essentially simultaneous abstraction of the same volume of liquid, enriched specified metal ion derived from the output of the second zone of the second offset.

10. The method according to claim 1, characterized in that in step (f) provide for the displacement of the fronts in all areas to periodic offset.

11. The method according to claim 1, characterized in that the increment of the volume, in accordance with which move above the point of introduction, and these points are removed, essentially corresponds to the fraction of the area of the absorbent material, preferably essentially corresponds to the volume of the column.

12. The method according to claim 1, characterized in that the liquid, diluted ionic metal derivative, at least partially carried out in step (b).

13. The method according to claim 1, characterized in that it has the I additional area, moreover, it also contains step (g) the introduction of all or part of the liquid, diluted specified ionic metal derivative obtained in step (a), at the level specified secondary zone, and selection of, essentially, the same volume of wash solution at the point located at the diagram below this zone.

14. The method according to claim 1, characterized in that the chromatography is ion exchange chromatography, and ion metal derivative is a salt selected from complexes of uranium, gold, copper, zinc, Nickel, cobalt and PGM, preferably a salt of uranium and, in particular sulfate uranium.

15. The method according to claim 1, wherein the eluent is sulfuric acid.



 

Same patents:

FIELD: physics.

SUBSTANCE: device (1) for continuous countercurrent chromatography has several rotating chambers (2, A, B, C) placed around an axis of rotation (D), said chambers being configured to contain the liquid or mixture of liquids under investigation. Separate chambers are connected through liquid-conducting connections (3) such that two liquids flow in opposite directions. One of the liquids first passes through several chambers and then returns to the first chambers in the direction of flow. The mixture of liquids is also fed into chambers (A, B, C) from sides (22) of chambers (B, C, A) lying near the axis of rotation, after coming out of neighbouring chambers (A, B, C) opposite the direction of rotation from the side (21) which is far from the axis of rotation.

EFFECT: high efficiency of separation in continuous mode, and high efficiency of complete mixing and subsequent phase separation.

13 cl, 3 dwg

FIELD: metallurgy.

SUBSTANCE: method involves stages of (a) material interaction with acid leaching solution in presence at least of one iron compound and acidophilic microorganisms at least capable of oxidating ferrous iron, and (b) leaching. Leaching stage (b) is performed at control of molar ratio of dissolved ferric iron to dissolved molybdenum and it is assumed equal at least to 6:1, preferably at least to 7:1 and after leaching there performed is stage of (c) molybdenum extraction at least from one solid and liquid residue of the leaching process. Finally, molybdenum is extracted from leaching residue of leaching process. Final degree of Mo extraction from sulphide material containing molybdenum is 89%.

EFFECT: effective molybdenum extraction from sulphide material containing molybdenum.

24 cl, 21 dwg, 9 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: in invention claimed are devices and methods for continuous anti-current desorption of target materials. Device for substance desorption from ion-exchange resin which has sorbated on it admixtures and target materials, includes first and second chamber. Resin is supplied into first chamber, and is transported from first chamber to second chamber, and desorbing solution is supplied into second chamber, and is transported from second chamber into first chamber. Admixtures, which have less affinity with resin, than target material, can be desorbed from resin, and target material can be sorbed on resin from desorbing solution in first chamber. Flow of admixtures, which has high admixture concentration and relatively low concentration of target material, is released from first chamber through first outlet. Target material is desorbed from resin in second chamber, and enriched flow, which has low admixture concentration and relatively high concentration of target material, is released from low parts of first and/or second chamber through second outlet.

EFFECT: extension of arsenal of means for substance desorption from ion-exchanging resin.

41 cl, 6 dwg, 1 tbl, 5 ex

The invention relates to the field of metallurgy, namely the recovery of noble metals and platinum group metals from the poor and ultrametric industrial waste

The invention relates to a process for recovering molybdenum from aqueous solutions of tungstate and can be used in ferrous and nonferrous metallurgy, as well as treatment of industrial and domestic wastewater
The invention relates to a method for producing tungsten and/or molybdenum-containing solution from the alkaline solution of the opening of the respective raw materials

The invention relates to hydrometallurgy, in particular coal sorption technology for the recovery of precious metals from solutions and slurries

The invention relates to methods of regeneration of the anion exchange resin saturated with noble metals

FIELD: metallurgy.

SUBSTANCE: method includes uranium sorption by anion exchange resin, uranium de-sorption from saturated anion exchange resin by sulphuric acid and obtaining finished product from strippant. Note that uranium de-sorption from saturated anion exchange resin is done by sulphuric acid solution with concentration 70-100 g/l with the presence of 1-2 mole/l of ammonia sulphate.

EFFECT: decrease of sulphuric acid content in desorbing solution and rich eluate and reduction of sulphuric acid consumption, decrease of desorbing solution flow and anion exchange resin ratio at de-sorption, increase of uranium content in rich eluate at decrease of rich eluate volume and decrease of uranium residual content by 1-2 levels in anion exchange resin after de-sorption.

1 tbl, 3 ex, 2 dwg

FIELD: metallurgy.

SUBSTANCE: method of gold extraction from mercury-containing cyanic solutions consists in sorption by ion-exchange resin of AM-2B mark. Then mercury de-sorption is carried out from saturated ion-exchange resin at a temperature 40-50°C and for 6 hours and aurum de-sorption. Note that mercury de-sorption is done by solution containing sulfuric acid 30-50 g/l with the presence of hydrogen peroxide 5-10 g/l.

EFFECT: reduction of mercury content in saturated gold-containing ion-exchange resin till safe concentration or complete elimination of mercury penetration into finished products.

5 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: extraction method of rare-earth elements from solutions containing multiple excess iron (III) and aluminium, with pH=0.5÷2.5 involves sorption using macroporous sulfocationite as sorbent. At that, as sorbent there used is macroporous sulfocationite containing more than 12 to 20% of divinyl benzene.

EFFECT: effective extraction of amount of rare-earth elements from solutions.

4 tbl, 4 ex

FIELD: metallurgy.

SUBSTANCE: method for extracting metals from depulped ores involves crushing, ore depulping in leached solution and sorption of metal. Leaching is performed in ultrasound pulp cavitation mode. Metal sorption on ion-exchange resin is performed from pulp filtration solution in intensity field of alternating current in sorption activation mode of extracted metal and suppression of sorption of impurities. At that, polarity of electrodes is constantly changed to avoid deposition of metal on cathode. Leaching and sorption of metal is performed in a unit providing solution circulation till the specified completeness of leaching from ore and its complete sorption on ion-exchange resin is achieved.

EFFECT: improving metal extraction intensity.

2 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to ion exchange and can be used for sorption extraction of iron from salt solutions formed when processing aluminium-containing material using acid techniques. Extraction of iron to residual content of Fe2O3 in the purified solution of not more than 0.001% is carried out through sorption of iron with a cationite in H-form, containing aminodiacetic functional groups. The iron sorption and desorption steps are alternated without intermediate washing of the cationite. Iron is desorbed in counterflow conditions with nitric acid solution.

EFFECT: method enables elective extraction of iron, reduces acid consumption and prevents loss of aluminium in the process.

3 cl, 1 tbl, 6 ex

FIELD: hydrometallurgy.

SUBSTANCE: the invention relates to hydrometallurgy of precious metals and can be used to extract palladium from wasted catalysts, including catalysts of low-temperature oxidation of carbon oxide (II) based on γ-Al2O3, containing palladium chloride (II) and cupric bromide (II). The method includes acid leaching of palladium from wasted catalysts from the chloride solution. Furthermore, the acid leaching is carried out by 1 M solution of hydrochloric acid. The resulting solution is diluted with water to pH 1. The sorption of palladium is carried out from the diluted solution using chemically modified silica containing grafted groups of γ-aminopropyltriethoxysilane.

EFFECT: increased amount of extracted palladiumusing a cheap nitrogen-containing sorbent, the high speed of the process and the possibility to regenerate the sorbent.

4 tbl

FIELD: mining.

SUBSTANCE: invention refers to the area of the extraction of gold, palladium and platinum from hydrochloric solutions. The method comprises their anionite sorption and desorption. The sorption shall be performed with low-basic anionites. After sorption, desorption with a mixture of sodium sulfite salts mixture Na2SO3 and sodium nitrite NaNo2.

EFFECT: quantitative extraction of complex chlorides of gold, palladium and platinum from aqueous solution in a wide range of hydrogen chloride concentrations.

1 ex

FIELD: chemistry.

SUBSTANCE: method involves sorption of platinum (II, IV) and rhodium (III) through contact of the solution with a strongly basic anionite and then desorption from the anionite. Sorption is carried out from freshly prepared and held solutions on a Purolite A-500 anionite, containing a quaternary ammonium base as a functional group. Desorption from the anionite is carried out in two steps: at the first step - 24 hours after contact with 2M NH4SCN solution or 2M KNO3 solution to extract platinum. At the second step - after a further 24 hours with 2M HCl solution or 1M thiourea solution in 2M H2SO4 solution to extract rhodium.

EFFECT: simple and cheap method of separating platinum and rhodium, and possibility of realising the method not only in freshly prepared, but chloride solutions held for some time; the method is environmentally safe.

1 dwg, 3 tbl, 4 ex

FIELD: metallurgy.

SUBSTANCE: procedure consists in preparation of water pulp from raw material, in introduction of sulphuric acid and anionite into it for leaching and in extraction of vanadium from pulp by sorption. Upon sorption saturated anionite is withdrawn and washed; vanadium is de-sorbed from anionite and regenerated anionite is introduced to the stage of leaching and sorption. Also, water vanadium pulp is prepared from vanadium containing raw material. As such there is used oxidised slag or slime at pH 11.5-7.5. Sulphuric acid is introduced into prepared water pulp at S:L=1:2 to pH 4.5-4.0. Vanadium is extracted from pulp by counter-flow sorption at pH 4.5-1.8 with following saturated ionite washing at drainage. Value of pH in pulp is maintained at 4.5-4.0 at withdrawal of saturated anionite, while at introduction of regenerated anionite - 2.0-1.8.

EFFECT: raised extraction of vanadium, elimination of upset of sparingly soluble forms of vanadium at moment of leaching, facilitation of completeness of sorbent saturation and minimal concentration of impurities on it, reduced consumption of sulphuric acid, reduced number of operations in process flow sheet.

2 cl, 4 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: procedure consists in refining solution of ammonia paratangstate with sulphate of ammonia from molybdenum impurity. Further, refining is carried out with ion exchange on anionite AM-n and with thermal decomposition of ammonia paratangstate at temperature 600-800°C till production of tungsten trioxide. Tungsten trioxide is refined with zone sublimation at temperature 900-950°C in a continuous flow of oxygen. Further, trioxide of tungsten is heterogeneous reduced with hydrogen at temperature 700-750°C till production of powder of tungsten. Powder is compressed to tungsten rod which is subjected to electronic vacuum zone re-crystallisation till production of tungsten crystal. Tungsten crystals are melt in electron vacuum in a flat crystalliser with melt of flat ingot of tungsten on each side at total depth not less, than twice. A tungsten rod is treated with chlorine prior to zone re-crystallisation at rate of chlorine supply 100 ml/min and temperature 300°C during 1 hour.

EFFECT: raised purity of tungsten designed for thin film metallisation by magnetron target sputtering and improved electro-physical parametres of applied thin layers.

1 ex

FIELD: food industry.

SUBSTANCE: invention relates to a method for purification of defatted milk contaminated with copper, lead and zinc in a concentration from 0.13, 0.23 and 0.34 of MAC respectively. According to the method, one introduces into defatted milk with residual fat content equal to 0.10-0.20% a sorbent preliminarily hydrated with distilled water which sorbent may be represented by alumina oxide powder, broken rice or licorice roots extraction residue, the weight ratio of milk to the sorbents being 25:1. Then one proceeds with maintenance during 20-30 minutes at a temperature of 50-55°C and the sorbent removal by centrifugal method in a milk purifier separator.

EFFECT: invention allows to reduce concentration of copper, lead and zinc and bacterial population in milk and to produce a product of better quality.

1 tbl, 1 ex

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