Device and method of producing compounds by precipitation

FIELD: process engineering.

SUBSTANCE: invention relates to device and method of producing compounds by precipitation of solid substances. Proposed device comprises reactor provided with inclined settler. Proposed method comprises mixing initial substances in reactor, precipitation of compounds in reaction zone, partial separation of mother leach from precipitated product in inclined settler, separation of product suspension, its filtration and drying. Invention covers also mixed powder of nickel-cobalt hydroxide with WET-surface of less than 20 m2/g and impact density exceeding 2.4 g/cm3.

EFFECT: suspension with concentration exceeding stoichiometric one.

29 cl, 13 dwg, 5 ex

 

This invention relates to a device and method of producing compounds in the deposition of the solution to precipitate solids, and physical and chemical properties of the resultant particles of solids are easily selected and can be set independently from each other and thus can be derived products with adjustable properties with high spatial-temporal output.

Many technically important solid-state compounds produced by deposition from solutions, and, as solvents are water, organic solvents and/or mixtures thereof. This may occur, for example, during rapid cooling, the unexpected decrease in the solubility of the compounds to be deposited in the contact of another solvent in which the compound less soluble, or as a result of chemical reactions in which the compound is poorly soluble in the solvent, generally first appears. The solid phase, newly formed by deposition in the homogeneous formation of nuclei of crystallization, consists of a large number of small primary crystals, which after sintering to form secondary particles or join those already present secondary particles.

The properties of the primary and secondary particles have, as a rule, clearly defined requirements in order to achieve necessary for the application properties. The properties of the primary crystals and formed from them agglomerates of course depend on the process parameters. The number of parameters relating to the process, depending on the circumstances may be relatively large. To physical and chemical process parameters include, for example, temperature, concentration of solutions of the starting substances, the concentration of excess precipitating reagent in the mother liquor, the concentration of catalyst, pH, ionic strength, and other important, more related to the technical installation options for the implementation of the method include the residence time, concentration of solids, mechanical energy transfer, the geometry of the reactor, the mixing mode with agitators of different types or pumps. The fundamental specifications of the method is naturally periodic or continuous nature of the work. Continuous deposition processes provide the opportunity for even received the product. It is clear that for the parameters of the process, there are certain areas in which they can be installed. So the original substances in the solutions of the original substances have maximum solubility, which may not be exceeded. This implies the maximum possible concentrate the walkie-talkie solid product in suspension product. However, this concentration can also be limited by the solubility of the neutral salt, if formed during the deposition process in the mother liquor. On the other hand, it may be necessary to work with the concentrations of neutral salts that are less than natural concentrations caused by the concentration of the original substance. Often there is such a problem that the setting of the process parameters that affect the properties of the primary particles are not optimal or even counterproductive for the required properties of the secondary particles. The art lies in selecting such process parameters that result in a reasonable compromise between the properties of primary and secondary particles.

Thus, there are a number of additional conditions, which hamper a precise definition of characteristics of the product. In addition, some product features, such as specific surface area, porosity, shock density, bulk density, distribution of particle size, fluidity, the size of the crystals etc. are not achievable, although this occur in the absence of restrictions is often possible. For example, some of the metal oxides is observed that the specific surface under these conditions the reaction is strictly monotonically decreases with increasing content of solids, however, it is impossible mouth is o be catching extrapolated solids content for the desired specific surface area, because this content should exceed naturally resulting solids content.

As the example used in modern batteries high performance with multiple charging as components or initial substance pure or mixed hydroxides of transition metals, which are usually obtained when the deposition processes. So, for example, Nickel hydroxide doped with cobalt and zinc is the active component of the positive electrode in a Nickel-metal-hydride, respectively, Nickel-cadmium batteries (Z.Kristallogr., 220 (2005), 306-315). In the case of the known Nickel-metal hydride batteries, for example, are now using the electrode obtained foam technologies that make use of the positive active material in the form of spheroidal particles.

The spheroidal particles are also used increasingly important repeatedly rechargeable lithium-ion/polymer batteries. For a long time, mainly based on economic considerations, worldwide efforts are being made to replace partially or completely the expensive cobalt, which is still contained in the lithium-ion/polymer battery (LiCoO2). For this purpose intensively studied among other compounds of metals of Ni, Mn and Al, such is AK, for example, Li(Ni,Co,Mn)O2or Li(Ni,Co,Al)O2. The first stage here is to obtain the corresponding spherical hydroxide prior to substances that are synthesized by coprecipitation, if necessary, finally covered with a layer, then through heat treatment with the addition of the lithium component to turn in the final oxide product.

Depending on the battery type, manufacturer, and application of the battery is currently used in various compositions of materials, but before the actual manufacturer of spherical hydroxides task is to manufacture a large number of products with very different characteristics, which moreover find very close limits of tolerance among themselves with respect to chemical and preferably physical properties. Obviously, this problem can be solved is to generally be economically feasible to produce, not with a large number of facilities for obtaining and using one easily changeable, adjustable for each of the characteristics (conditions), but very stable and definitely working installation and technology. As a rule, in the specs accurately indicate all significant chemical and naturally preferably all physical properties, such as, for example, the distribution of particle sizes, tight drums is here, specific surface area and microcrystalline structure (crystal size). All these properties of a substance depend on a number of parameters (such as, for example, the concentration of the original substance, neutral salts and solids, the residence time in the reactor, the temperature, the introduction of energy etc), and these naturally affect not necessarily in the same sense on the desired properties of the product. Therefore, the possibility of implementing certain combinations of properties, for example, hydroxide starting substances is possible in only one, universal adjustable mounting system is a very big challenge - and it provided the necessary economic efficiency.

However because of physical reasons, it is impossible to simultaneously maximize the porosity and shock density ductile material, since the requirements for these two values contradict each other. However, there are some dependencies between the individual properties of the product, which can move within certain limits. The art is to find the different combinations of parameters installation and implementation with almost one technology installation at least partially independent of the job physical product characteristics source hydroxide substances, important for the manufacture of batteries.

In JP Hei 4-68249 described continuous recip is of spherical hydroxides of Nickel. In a heated reactor with a stirrer and a flow continuously submit a solution of Nickel salt, alkali and add aqueous ammonia. After 10-30 hours stationary state is achieved in the reactor system, then it is possible to continuously output from the reactor product with consistent quality. The average residence time in the reactor is from 0.5 to 5 hours. When implementing this method, the concentration of solids in suspension and the concentration of the neutral salt in the mother liquor forcibly connected through stoichiometry precipitation reaction. In addition, temperature-dependent boundary solubility of the formed neutral salts determines the maximum attainable concentration of solids in suspension. Achieve the concentration of solids in suspension, which is independent of the concentration of neutral salts or very high, for example, many times, of course it is impossible by the method according to JP Hei 4-68249.

In EP 0658514 B1 published information about the continuous precipitation of metal hydroxides decomposition of linecomplete in the presence of alkalis in the reactor with the injected jet. In this reactor initial matter, unlike a reactor with a stirrer, the output stream from the nozzle, mixed with the reaction medium. Described in JP Hei 4-68249 restrictions on raising conc is the source of matter in suspension also act in the way that described in EP 0658514 B1.

In the US 2003/0054252 A1 described active materials for lithium-ion batteries, as well as receive them. For the deposition of substances predecessors recommended for use with periodic work, which is the outer circulation transparent uterine liquor pumped from the upper region of the reactor and the input side of the tube deposition, through which he bottom rushes back into the reactor. As a result of such flow direction up created obstacles that are too small particles was achieved through the tube deposition vessel receiver for the finished product. In this vessel-the receiver can settle only those particles that have reached a certain minimum size. A method of obtaining a substance precursor in the deposition, described in US 2003/0054252 A1, does not allow independent from one another installation process parameters. Direct intervention in the development of the distribution of particle sizes in the defined ejection fraction of fine particles in the slurry is impossible to implement this method.

In this regard, the objective of the invention is to create a device and a method, with which the intervals of values of certain parameters (for example, the concentration of the starting substances, the content of solid substances of the suspension, the salt concentration in the mother liquor) be set independently from one another and thereby result in the expansion of existing and creation of new degrees of freedom to maximize the flexibility of the method of obtaining solids by deposition from solutions. The objective of the invention is to create a device and method that enable a controlled interference with the distribution of particles during the deposition process. Another objective of this invention to provide devices and methods that allow you to repeatedly increase the concentration of solids compared to the maximum achievable according to the prior art.

These tasks are solved by using the structure of the device includes a reactor with an integrated sloped sump, hereafter referred to as "integrated reactor-clarifier (ISRO=IRKS)presented on Fig.1-3, and use the ISRO as a Central unit in connection with other devices (e.g., filters, tanks, pumps etc) during the process in which after deposition of compounds with formation of a suspension of the product, consisting of product and mother liquor, through the inclined clarifier suck uterine liquor and particles of the product so that it is possible controlled vozdeystviyna distribution of particles sizes and multiple increase in the concentration of solid particles.

The subject of this invention is, therefore, integrated reactor-clarifier (ISRO). The reactor can be an installation of cylindrical shape, see figure 4 and 5 (6), or parallelepipedal form, see figure 1-3 (1), flat, wavy or conically made bottom. In the bottom of the reactor may be provided with an opening through which, if necessary, the slurry may be pumped out by a pump and again pumped into the reactor, see figure 4 and 5 (14). To obtain a homogeneous product deposition is important that the initial products were well mixed when entering the reactor. This type of reactor can also be operated as a reactor with a stirrer, see Fig.1-3. In this case usually use disk stirrers, agitators with inclined blades, INTERMIG-mixer or other mixer, specially adapted to these problems mixing. Selection, installation and sizing of suitable mixers are described, for example, in the book ZIokarnik, Ruehrtechnik, Theorie und Praxis, Which, 1999. The device of the reactor with stirrer has a decisive impact on the particle size, distribution of particle size and particle behavior in the deposition reactor.

The processes of deposition in units of ISRO according to this invention, depending on the product can be carried out both at room temperature and at no more the coy or higher temperature. The temperature during the deposition process on the units of ISRO according to the invention in this regard may be from -20°C. to 100°C. Preferably, the processes of deposition is carried out at a temperature of from 20 to 90°C, more preferably at a temperature of from 30 to 70°C. Particularly good results are obtained, for example, when the precursor chemicals for the manufacture of batteries, such as oxides Nickel hydroxides of Nickel, mixed Ni,Co-oxides, respectively, mixed Ni,Co-hydroxides get at a temperature in the range from 30 to 70°C. the process Temperature is set and adjusted, if necessary, by using a heat exchanger, respectively, cooling, see figure 10 and 11 (4). In the case when working with external circulation, the heat exchanger can be installed on it, see Fig (3).

The inclined clarifier may reside anywhere in the reactor, for example, can be installed over the top of the reactor, see figure 3 (4) and 4 (7). To reduce the height of the building, the inclined clarifier can preferably be installed at the bottom of the reactor, see figure 1 and figure 2 (4), and 5 (7). Install the ISRO is used for the deposition of chemical compounds from solutions. In an inclined settler uterine liquor together with a defined fraction of small particles of solid matter is separated from the suspension product. This turbid liquid, the content is relevant to several g/l solids in most cases, return to the reactor and again combined with a suspension of the product. In the collecting part of this turbid liquid of a suspension of the product gets the share of the smaller particles and the distribution of particle sizes is shifted to higher D50-values. Another task inclined clarifier is to get a pre supernatant, containing only a small amount of solids, of which the simplest way the result of the filter can be separated transparent uterine liquor.

In order to increase the separation capacity of the inclined clarifier, you can embed one or more of the plates, see figure 1 (3), 3 (3), 4 (8) 5 (8), in which solid particles, after they as a result of sedimentation has reached the surface of the plates, glide back down in homogeneous mixed suspension. Plates are mounted in an inclined settler plane surface of its bottom. Plates are flat plates that can be made from plastic, glass, wood, metal or ceramics. Plate thickness depending on material and product can be up to 10 cm, Preferably applied to the plate of a thickness of from 0.5 to 5 cm, more preferably from 0.5 to 1.5, see Plate rigidly embedded in the inclined clarifier. They can also be removable, see Fig.6 (21) and Fig.7 (26). In this case, they slide under the Shi system is, installed on the inner sides inclined clarifier, see Fig.7 (25), or embedded in the inner side of the grooves, see Fig.6 (22). The bus system can be made with the possibility of height adjustment, resulting in inclined clarifier becomes greater flexibility in terms of choice of the distance between the plates. The inclined clarifier may have a cylindrical shape with a circular cross section and parallelepipedal shape with rectangular cross-section, see Fig.6 (20) and Fig.7 (24)so that the inclined clarifier functioned without clogging in the reverse slippage of particles, the angle of the inclined clarifier with respect to the horizontal is between 20 and 85°, preferably from 40 to 70°, more preferably from 50 to 60°. The inclined clarifier may also be movably attached to the reactor. With such design, the angle can be varied during the process.

In a preferred embodiment of the invention the inclined clarifier at the entrance inside the reactor has a stove, see figure 2 (5) and 5 (9), which is plane-parallel to the plane of the inlet inclined clarifier. This plate prevents clogged inclined settler in the input area of highly concentrated suspension.

For a better understanding of the mechanism of functioning of the installation of the ISRO according to this invention the following is detailed product description product the e explanation based Fig. Solid particles (30) down an inclined settler Fig a certain speed, depending on their shapes and sizes. If to take into account, for example, Stokowski friction, the deposition rate caused by the effective force of gravity is proportional in the case of spherical particles the square of the diameter of the particles. This speed is superimposed upward component of velocity laminar flow of fluid in an inclined settler. All the particles of a liquid, in which the contribution of the deposition rate is less than or equal directed upward component of flow velocity of the liquid will not be able to go down to the surface of the plate (31) or on the surface of the inclined bottom of the tank and then are carried along with the flowing fluid from the inclined clarifier.

In the case when the contribution of the deposition rate of particles larger than the upward component of the velocity of fluid flow is the movement of particles down a constant speed of descent. Whether such a particle passed through the flow or none of the inclined clarifier varies at a constant rate of fluid flow from the vertical distance of the particle from the plate at the entrance to the inclined clarifier, and the length and angle of inclination of the inclined clarifier. It is easy to understand that there is a critical particle radius of rorelative to which the tale is th all particles with r more rocompletely trapped in an inclined settler. Straight line (32) on Fig shows the trajectory of the particle with the boundary radius rabout. The trajectories of all particles, the radius of which is greater find a smaller angle with respect to horizontal and securely so they fall on a plate or bottom plate. This means that they are delayed. Selection conditions in an inclined settler, in particular, the velocity of fluid flow, it is possible, therefore, to set the upper limit of the diameter of the particles to small particles, which leave the inclined clarifier overflow through the top.

While flowing the fluid from the inclined clarifier through the receiver of the stream flows back into the reactor with a stirrer, a total system nothing changes. If using a pump to make the selection of part of the liquid is clouded by small particles of solid matter from the receiver thread, a certain proportion of fine particles is withdrawn from circulation and thereby, it is possible to influence the distribution of particle sizes. This creates new opportunities variations of the processes of deposition, which results in the particle sizes and the distribution of particle size can be affected independently of the other installation options.

In the described selection part of the muddy stream of concentration of the solids in which the receiver input stream typically ranges from 0.5 to 5% concentration of solids in the reactor, naturally also increases the concentration of solids in the slurry reactor, because together with purposeful selection of the number of small particles is drawn disproportionately to the number of the mother lye. Generally, it is desirable and undesirable only when the concentration of solids in the reactor should be maintained at a low level, and the regulation of other threads substances are not able to withstand high concentrations of particulate matter. Depending on the number and specifications of this proportion of fine particles in conclusion, may again be admixed to the suspension product. The determining factor is the separation in the system of the reactor-clarifier.

In this case, it is recommended uterine liquor take away from the receiver flow through the filter element, see figure 10 (16), and the remainder directly to pump back into the reactor in order to increase the concentration of turbid fluid. When making the same amount of small grains sucked less than the mother lye. As small grains in this case denote such particles whose dimensions do not exceed 30% D50value distribution of particle sizes. It may be the preferred selection from the receiver thread in the system only uterine liquor through the filter element. Topozone, first, multiple increases in stoichiometric solids content in the reactor and, secondly, to break the link between the concentration of neutral salts, if necessary, resulting from the precipitation reaction, and the concentration of solids. Concentration ratio solids and salts in the reactor can result in the possibility of selection of the mother lye, for example, to increase not only due to the increase in the concentration of solids at a constant salt concentration, but also due to the fact that at a constant concentration of solids in the reactor serves the solvent not containing salt, and simultaneously through the filter element from the system select an equivalent amount of the mother lye.

The achievement of additional degrees of freedom while increasing flexibility, ISRO according to this invention are explained in more detail below on the example of both parameters of salt concentration and content of solids to the total reaction AX+BY=>AUsolid+Isolution. OH and BY means of the original substance in solutions of initial substances and I mean dissolved in the mother liquor salt. AY means insoluble solid substance precipitated product.

Figure 9 schematically shows the expansion of existing and creation of new degrees of freedom d is I the above reaction. In the diagram mean:

(40) - technical border

(44) - chemical boundary

(41, 43) - border economy.

Figure 9 bold segment (1-2) shows the interval, which according to the prior art corresponds to the variations of both parameters of the process, namely: the concentration of the neutral salt in the mother liquor and the concentration of solids in suspension. On top of this straight line is limited by the solubility of salt I, the bottom is limited by the border of the economy for the minimum content of solids. Thus, due to the stoichiometry of the reaction according to the prior art, there is a one-dimensional space, limiting both. By setting the ISRO according to this invention and the method according to the invention, this one-dimensional region is extended to two-dimensional region (42), given that the maximum concentration of solids increases many times and at the same time can be significantly reduced salt concentration and can be composed of many combinations of the now extended ranges, the concentration of solids and the concentration of neutral salts. Acquired as a result of this flexibility of the process is obvious. Vertical movement on the chart up corresponds to the selection of the mother lye and leads to the corresponding surface is increased by the concentration of solids. Horizontal movement on the chart to the left corresponds to the introduction of additional solvent with simultaneous selection of an appropriate number of the mother lye.

Installing the ISRO according to this invention can be operated in both open and closed. A closed system is, for example, ink-jet reactor, shown in figure 4 and figure 5 (6) and Fig (1). In the case of this reactor inclined clarifier can be installed in the upper part of the reactor, see figure 4 (7), and in the lower part of the reactor, see figure 5 (7). The original substance is in this case introduced into the reaction zone of the reactor through one or more nozzles, and in the reaction zone of the original substances are subjected to intensive mixing, respectively homogenization, see Fig (2) and figure 4 and figure 5 (11). The installation of the ISRO according to this invention can be used for deposition, which is conducted periodically. However, preferably it is used for deposition processes carried out continuously.

Further, the invention relates to a method for producing compounds in the deposition, in which the individual process parameters (for example, the concentration of the starting substances, the content of solids in suspension, the concentration of salt in the mother liquor) during deposition can be installed independently of one another, and t is thus becomes possible controlled interference distribution of particles during the deposition process and as a result creating products with desired particle sizes with certain physical properties, especially economically and with a very high space-time yield. In connection with this object of the invention is a method of obtaining compounds by precipitation, consisting of the following stages:

- cooking at least a first and a second solution of the original substances,

connection along at least a first and a second solution of the original substances in the reactor 1 according to the claim,

- create a homogeneous mixed reaction zone in the reactor,

- deposition of compounds in the reaction zone with the creation of a suspension of the product consisting of insoluble product and mother liquor,

- partial separation of the uterine liquor from the precipitated product in an inclined settler,

- obtain a suspension of the product of the deposition, the concentration of which is higher than the stoichiometric concentration,

- selection of suspension of the product from the reactor, filtration, washing and drying the product deposition.

In the method according to this invention, the solutions of the original substance is injected into the reactor using a system of pumps. In the case when referring to the installation of the ISRO according to this invention with a reactor with a stirrer, the starting materials are mixed using a mixer. In the case, to the Yes setting the ISRO made in the form of jet reactor, mixing of the starting compounds is carried out by the jet coming out of the nozzle, see Fig (2). For good mixing can be input in the reactor, the air or inert gas. To achieve a more uniform quality of the product you want the original products were homogeneous mixed in the reaction zone of the reactor. During mixing, respectively, homogenizing starting compounds, the reaction begins deposition in which is formed the product and mother liquor. A suspension of the product enriched in the lower part of the reactor to the desired concentration. To achieve directional enrichment suspension of the product in the method according to this invention the mother liquor is partially sucked off through the inclined clarifier, see figure 10 (5). Preferably a partial selection of the mother lye is carried out with a pump in place of the overflow inclined clarifier. The solids content in iridescent fluid is up to 50%, preferably 30%, more preferably up to 15% and even more preferably up to 5% of its content in the suspension product. An important role in the development of the distribution of particles during the deposition process plays the maximum size of particles in the overflow. Particles in the overflow are referred to as fine grains. The maximum size of particles in the overflow may faced the ü up to 50%, preferably to 40%, more preferably up to 30% of the D50value distribution of particle sizes.

In the method according to this invention may be achieved by the concentration of the suspension containing the product of deposition, significantly exceeding the stoichiometric possible concentration of product deposition. This concentration may be 20 times the stoichiometric value. To achieve a particularly high concentration of the product in suspension required the selection of a larger number of the mother lye. It is possible to take even up to 95% of the mother lye. The number of selected parts of the fallopian alkali depends on the chosen process parameters, such as concentration of the original substance, the salt concentration of the mother lye, as well as the concentration of solids in suspension.

The method according to this invention is schematically presented in figure 10 and for a better understanding explained below.

In a reactor with a stirrer (1), equipped with a stirrer (2) with adjustable speed, heat exchanger (3), if necessary, a pump (4) and a sloped sump (5), which contains the adjustable height plate (25), plane-parallel its input hole, continuously using dosing pumps (6) - (8) to introduce the solutions of the starting substances, if necessary, the solutions of catalysts and solvents in Homo the military mixed reaction zone of the integrated system of the reactor-clarifier (ISRO) according to this invention. The resulting slurry product with a pump (10) is drawn through the regulation of filling or flows via the free overflow (11). When receiving large particles may be appropriate for inclusion in the action of the circulation pump (4), to avoid the danger of sedimentation.

The pump (12) depending on the height of the inclined clarifier (5) if necessary, in smoothscale performance, delivers a portion of this fluid with a very low concentration of small grains in the receiver (13), equipped with a mixer (14), and then the fluid free flow (15) may flow back into the reactor (1). Depending on the volumetric flow and the dimensions of the inclined clarifier there is a limit of separation of particle sizes, so that only particles smaller than this limit, served in the circulation receiver (13). Up until the entire flow of turbid fluid pumped by the pump (12) flows through the free flow of (15) back, of course, that in the reactor (1) nothing changes. Changes occur only when the fallopian liquor or solid particles are removed from the system. The following describes the selection of the mother lye.

Through the filter element (16), for example through the filter hose, used for filtering the cross flow pump (17) sucks away from the receiver (13) transparent uterine liquor and delivers the th second circulation receiver (18). This receiver pump (21) delivers continuously or at certain time intervals samples of the solution is preferably automatic analysis of the mother lye. Continuous monitoring, for example, through the measurement and control of pH-values using a probe (20) can be implemented directly in the containing transparent uterine liquor circulation receiver (18). Installing the ISRO according to this invention can thus be controlled in a simple way the composition of the mother lye during deposition, which is of course very difficult in the case of suspensions with high solids content. In that case, when the circulation of the receiver (18) select the pump (22) the mother liquor from the system, the concentration of solids in the reactor (1) can be set regardless of the concentration of the starting materials. Thus, there is also a gap dependence between the concentration of solids in suspension and the concentration of salts in the mother liquor produced during many precipitation reactions as side products.

The natural concentration of solids can be repeatedly increased and achievable spatial-temporal outputs of the conventional methods are not possible or only with great difficulty realizable. Direct selection uterine liquor during the filtration cross flow, to the / establishment, which include, for example, in the circuit between the pump (4) and the reactor (1), is not practiced due to the fact that as a result of high concentrations of solids may eventually lead to blockage, which is very likely.

In that case, when precipitated BaSO4from a solution of BA(OH)2and sulfuric acid as by-product water is formed and tearing dependencies between the parameters is reduced to such process parameters as the concentration of VA and N2SO4in the solutions of the starting substances and the concentration of BaSO4in suspension product. During the precipitation of Nickel hydroxide, for example, the interaction of a solution of Nickel sulfate and sodium lye produces sodium sulfate as a by-product. The solids content in the suspension and the concentration of salt in this case can be set independently from each other. The increase in the content of solids described above. In the case when it is necessary to set the concentration of salt regardless of the initial concentrations of the substances, you can use the pump (9) to supply water to the system, and using a pump (22) to remove the appropriate amount of the mother lye, so that, for example, the desired concentration of solids will be stored.

A significant feature of the method according to this invention, as well as installation with integrated reactor otstojnika the ISRO is also that, selecting the part of the muddy stream of the system by a pump (23), from the reaction system display a certain proportion of small grains and thus directly influence the development of the distribution of particle sizes in the product. In addition, the above has already indicated that circulating receiver (13) has an upper limit of the grain size for the particles of a solid substance, which is determined by the dimensions of the inclined clarifier (5) and the volume of the circulation pump (12). The agitator (14) provides a homogeneous distribution of fine particles in the liquid. This creates an opportunity for a well-defined sampling fraction of fine grains of the overall system and thus from the reactor (1). Typically, the fraction of small grains is only a few percent of the total mass, but their share decisively affect the course of the distribution of grain sizes in the solid substance produced in the reactor. Direct intervention in the mechanism of growth of particles during deposition reaction in the case of conventional methods according to the prior art cannot and is implemented here for the first time. The resulting opportunities are multifaceted. This is not only a controlled shift of the D50the size distribution of particles, but also creates the possibility to set the width of the distribution. The process appears, thus, resulting in the emergence of this new degree of freedom the best POS of the activity management in particular, can be obtained spherical particles with a higher average grain size, compared to those that were previously possible under the reaction conditions.

The method according to the invention, schematically represented at 11, differs from the above described method, presented in figure 10, the fact that there is integrated reactor-clarifier with a sloped tank that is installed on the reactor top. On Fig presents the method according to this invention, in which the deposition reaction is conducted in a closed setting the ISRO (1), done as a jet reactor.

Using the installation of the ISRO and method according to this invention, it is possible to obtain various chemical compounds, physical properties such as grain size distribution grain size, bulk density, shock density, particle shape, etc. can act purposefully, so that in the end you receive the products with the desired properties. Such compounds are, for example, carbonates or basic carbonates of cobalt, Nickel or zinc, to which may be added various alloying elements. The method according to the invention is also suitable for the production of oxides of zinc, copper oxide or silver oxide. Next install the ISRO and method according to the SNO present invention are well suited to obtain oxides of tantalum, oxides of niobium, tantalate and niobate, titanium dioxide, zirconium dioxide and hafnium dioxide, and oxides can be doped with metals with a different degree of valence, such as rare earth metals such as yttrium, ytterbium, or scandium. Dimolybdate ammonium, heptamolybdate ammonium dimolybdate, heptamolybdate, paroolifraasi, paraformat ammonium, spheroidal tungsten acid and molybdenum acid can be preferably obtained by the process according to this invention.

The oxides of rare earth metals can also be obtained. Installing the ISRO and the method can be preferably used to obtain spinels, perovskites and connections solids with a rutile structure. It is difficult soluble gelidity and sulfides can also be obtained by the method according to this invention with a high space-time yield and with high shock densities. Installing the ISRO and method according to this invention is particularly well suited for obtaining covered with a layer of products in which a uniform coating layer of a different kind can be carried out in highly concentrated suspensions.

Especially preferably can be obtained in this way compounds that are used as substances precursor for use in the electrochemical cell and/or as a material for the electrodes in the manufacture of fuel cells. A substance that is produced by deposition according to this invention include the hydroxides of Nickel, oxyhydroxide Nickel, which can be doped by one or more divalent or trivalent metals such as Co, Zn, Mn, Al and/or trivalent rare earth metals or possibly a covering layer in the form of hydroxides of cobalt, or, for example, hydroxides of aluminum basic components such as, for example, Nickel hydroxide. Phosphates litigate with well-defined properties can also be obtained from the ISRO-way. Particularly preferably produced by the method according to the invention mixed hydroxides of Nickel-cobalt General formula NiXCo1-x(OH)2which are preferably used as substances predecessors in electrochemical cells or as an electrode material in the manufacture of fuel elements.

The subject of this invention in this regard are powdered and mixed hydroxides of Ni,Co General formula NiXCo1-x(OH)2where 0<x<1, which have a WET surface (BET means a specific surface area determined according to the method of brunauer, Emmett and teller (Brunauer, Emmet, Teller)measured according to ASTM D of 3,663, less than 20 m2/g and shock density, measured In accordance with ASTM b 527, more than 2.4 g/cm3.

P is edocfile mixed hydroxides of Ni,Co have a BET surface of less than 15 m 2/g and shock more density of 2.45 g/cm3more preferably WET-the surface is less than 15 m2/g and shock density of more than 2.5 g/cm3even more preferably WET-the surface is less than 15 m2/g and shock more density of 2.55 g/cm3.

Powder mixed hydroxides of Ni,Co according to this invention differ in that they have D50-the value indicated on the instrument MasterSizer In accordance with ASTM b 822, equal to from 3 to 30 μm, more preferably from 10 to 20 microns.

Mixed hydroxides Mi,according to this invention can be obtained as in spheroidal form, and in the form of regular particles. Preferred mixed hydroxides of Ni,Co according to this invention are distinguished especially spheroidal particle shape, form factor which has a value of more than 0.7, more preferably higher than 0.9. The form factor of the particles can be determined according to the method described in US 5476530, columns 7 and 8 and figure. This method allows to determine the form factor of the particles, which is a measure of the sphericity of the particles. The form can also be identified by SEM-images (scanning electron microscope) materials. The form factor is determined from the evaluation of the coverage of the particles and the sectional area of the particles and definitions for each of these values likely diameter. These diameters are determined by the formula

U=U/π dA=(4A/π)1/2

The form factor of the particles f is determined from the coverage of the particles U and the sectional area of the particles And the formula

In the case of an ideal spherical particle diameters of dAand dUboth were the same size and the result is a form factor equal to unity.

On Fig is given as an example SEM image obtained by scanning electron microscope, a mixed hydroxide of Ni,Co, obtained in example 1.

Application installation the ISRO and method according to this invention thus greatly increase the flexibility of the apparatus and method in comparison with classical deposition in conventional reactor system and the resulting benefits can be used for various types of connections. These advantages of the present invention can be summarized as follows:

a) made the separation is important for the deposition process parameters, such as concentration of the original substances, the concentration of solids and the concentration of the neutral salt, and thereby acquired a new degree of freedom, which decisively improve the ability of tasks to product the required properties;

b) as a result of removing the dependency of time of solids in the reactor and the time spent mother liquor in the reactor increases about transtorno-time yield and with it the performance of production;

c) found an entirely new degree of freedom in the selection of system specific amount of fines that can deliberately affect the distribution of particle sizes and therefore have an impact on the properties of the resulting product in the sense of acquisition given the optimum properties required for the application.

The invention is explained in more detail hereinafter by examples.

The physical parameters of the products shown in the examples is determined as follows:

the crystal sizes calculated from the half width of the 101-x-reflex;

- specific WET-the surface is determined according to ASTM D of 3,663;

- D50the value is determined from the distribution of particle sizes measured on the instrument MasterSizer;

- shock density determined In accordance with ASTM b 527;

- the form factor is determined by the method described in US 5476530.

Examples

Example 1

In the device the ISRO presented on figure 10, the load 200 l water uterine liquor containing 2 g/l NaOH, 13 g/l NH3, 130 g/l Na2SO4. Then include the circulation pump (4) with a volume flow of 5 m2/h and pump (2) with a volume flow rate of 90 l/h Pump (12) takes the mother liquor from the inclined clarifier (5) in the circulation receiver (13), from which he through the free flow of (15) is returned in the device is the ISRO. Once the liquid begins to exit outage (15)includes a pump (17), which takes the uterine liquor through the filter element (18) in the circulation receiver (18), from which he through the free flow of (19) is poured back into circulation receiver (13). The volumetric flow of the pump (17) is 90 l/h After switching on the mixer (14) with a speed of 300 rpm (=rpm) and the mixer (2) at a rate of 544 rpm and after using heat exchanger (3) in the entire system will be established temperature 48°C, include dosing pumps for solutions of the starting materials. The pump (6) with a volume flow rate of 25 l/h submits a solution of sulphate of metal, which contains 101,9 g/l of Nickel and 18.1 g/l cobalt. Pump (7) with a volume flow rate of 5.6 l/h doses soda lye (NaOH) with a concentration of 750 g/HP Pump (8) delivers a 3.1 l/h 25% ammonia solution, and the pump (9) takes the 21,8 l/h of demineralized water into the reactor. Finally connect the pump (21) and (22), which produce a selection of uterine liquor from the system. The pump (22) takes the 46,9 l/h in the purification of wastewater, which also remove ammonia. The pump (21) takes 1 l/h fallopian liquor in an automatic analyzer, which is three times per hour determine the content of ammonia and excess sodium lye. The pump (10) through the adjustment of the filling out of the reactor the resulting suspension of the product with the content of the solid substance 600 g/l to sequentially connected to the filter Suction, at which carry out the filtration and washing. After 100 hours the reactor reaches steady state. The product formed in the next 24 hours, after washing in 400 l of water are placed in a drying Cabinet at a temperature of 80°C. and dried until reaching a constant weight. Get 115 kg mixed hydroxide Ni.Co (Ni,Co)(OH)2with the following product features:

crystal size: 110 Å (angstroms),

the specific BET-surface: 6.3 m2/g

D50value: of 11.2 μm,

shock density: 2,46 g/cm3.

From REM-picture on Fig visible special sphericity of the obtained mixed hydroxide of Ni,Co, form factor which is 0.8.

Example 2

In the device the ISRO presented on figure 10, the load 200 l water uterine liquor containing 2 g/l NaOH, 13 g/l NH3, 130 g/l Na2SO4. Then include the circulation pump (4) with a volume flow of 5 m2/h and pump (2) with a volume flow rate of 90 l/h Pump (12) takes the mother liquor from the inclined clarifier (5) in the circulation receiver (13), from which it through the free flow of (15) is returned in the unit of ISRO. Once the liquid begins to exit outage (15) includes a pump (17), which takes the uterine liquor through the filter element (16) in the circulation receiver (18), which through the free flow of (19) is poured about atno in circulation receiver (13). The volumetric flow of the pump (17) is 90 l/h After switching on the mixer (14) with a speed of 300 rpm and the agitator (2) at a rate of 544 rpm and after using heat exchanger (3) in the entire system will be established temperature 48°C, include dosing pumps for solutions of the starting materials. The pump (6) with a volume flow rate of 25 l/h submits a solution of sulphate of metal, which contains 101,9 g/l of Nickel and 18.1 g/l cobalt. Pump (7) with a volume flow rate of 5.6 l/h doses soda lye (NaOH) with a concentration of 750 g/HP Pump (8) delivers a 3.1 l/h 25% ammonia solution, and the pump (9) takes the 21,8 l/h of demineralized water into the reactor. Finally connect the pump (21) and (22), which produce a selection of uterine liquor from the system. The pump (22) takes 15,4 l/h in the purification of wastewater, which also remove ammonia. The pump (21) takes 1 l/h fallopian liquor in an automatic analyzer, which is three times per hour determine the content of ammonia and excess sodium lye. Pump (23) remove 32 l/h cloudy solution with a solids content of 1.5 g/l of the device the ISRO (circulation receiver (13)). The pump (10) through the adjustment of the filling out of the reactor the resulting suspension product with a solids content of 600 g/l to sequentially connected to the filter Suction, which carry out the filtration and washing. After 100 hours the slave is you're the reactor reaches steady state. The product formed in the next 24 hours, after washing in 400 l of water are placed in a drying Cabinet at a temperature of 80°C. and dried until reaching a constant weight. Get 115 kg of a mixed hydroxide of Ni,Co (Ni,Co)(OH)2with the following product features:

crystal size: 108 Å,

the specific BET-surface: 6.1 m2/g

D50-value: 15,2 μm,

shock density: of 2.54 g/cm3,

form factor: 0,9.

Example 3

In the device of the ISRO, presented on 11, load 200 l water uterine liquor containing 5 g/l NaOH, 10 g/l NH3, 172 g/l Na2SO4. Then include the circulation pump (4) with a volume flow of 5 m2/h and pump (2) with a volume flow rate of 90 l/h Pump (12) takes the mother liquor from the inclined clarifier (5) in the circulation receiver (13), from which it through the free flow of (15) is returned in the unit of ISRO. Once the liquid begins to exit outage (15) includes a pump (17), which takes the uterine liquor through the filter element (16) in the circulation receiver (18), which through the free flow of (19) is poured back into circulation receiver (13). The pumping speed of the pump (17) is 90 l/h After switching on the mixer (14) with a speed of 300 rpm and the agitator (2) with a speed of 480 rpm and after using heat exchanger (3) in the entire system will be those who temperature 45°C, include dosing pumps for solutions of the starting materials. The pump (6) with a volume flow rate of 20.4 l/h submits a solution of sulphate of metal, which contains 109,6 g/l of Nickel and 2,84 g/l cobalt, and EUR 7.57 g/l of zinc. Pump (7) with volumetric flow to 4.62 l/h doses soda lye (NaOH) with a concentration of 750 g/HP Pump (8) gives a rate of 1.51 l/h 25% ammonia solution, and the pump (9) takes the 8,29 l/h of demineralized water into the reactor. Finally connect the pump (21) and (22), which produce a selection of uterine liquor from the system. The pump (22) takes 3 l/h in the purification of wastewater, which also remove ammonia. The pump (21) takes 1 l/h fallopian liquor in an automatic analyzer, which is three times per hour determine the content of ammonia and excess sodium lye. Pump (23) remove 20,5 l/h cloudy solution with a solids content of 2.0 g/l of the device the ISRO (circulation receiver (13)). The pump (10) through the adjustment of the filling out of the reactor the resulting suspension product with a solids content of 360 g/l to sequentially connected to the filter Suction, which carry out the filtration and washing. After 90 hours the reactor reaches steady state. The product formed in the next 24 hours, after washing in 400 l of water are placed in a drying Cabinet at a temperature of 80°C and dried before reaching the post of the permanent weight. Get 93 kg of a mixed hydroxide of Ni,Co,Zn (Ni,Co,Zn)(OH)2with the following product features:

crystal size: 67 Å,

the specific BET-surface: 10.1 m2/g

D50-value: 15,1 μm,

shock density: 2,40 g/cm3,

form factor: 0.75 in.

The example for comparison 1

In the device the ISRO presented on figure 10, the load 200 l water uterine liquor containing 2 g/l NaOH, 13 g/l NH3, 130 g/l Na2SO4. Then include the circulation pump (4) with a volume flow of 5 m3/h and pump (2) with a volume flow rate of 90 l/h Pump (12) takes the mother liquor from the inclined clarifier (5) in the circulation receiver (13), from which it through the free flow of (15) is returned in the unit of ISRO. Once the liquid begins to exit outage (15)includes a pump (17), which takes the uterine liquor through the filter element (16) in the circulation receiver (18), from which he through the free flow of (19) is poured back into circulation receiver (13). The volumetric flow of the pump (17) is 90 l/h After switching on the mixer (14) with a speed of 300 rpm and the agitator (2) at a rate of 544 rpm and after using heat exchanger (3) in the entire system will be established temperature 48°C, include dosing pumps for solutions of the starting materials. The pump (6) with volumetric flow 4,01 l/h gives a solution of the sulphate of the metal, of which the first contains 101,9 g/l of Nickel and 18.1 g/l cobalt. Pump (7) with a volume flow rate of 0.89 l/h takes the soda lye (NaOH) with a concentration of 750 g/HP Pump (8) takes 0,50 l/h 25% ammonia solution, and the pump (9) takes the 3,49 l/h of demineralized water into the reactor. Finally connect the pump (21), which selects from 1 l/h the mother lye and submit to the automatic analyzer, which is three times per hour determine the content of ammonia and excess sodium lye. The pump (10) through the adjustment of the filling out of the reactor the resulting suspension product with a solids content of 96 g/l to sequentially connected to the filter Suction, which carry out the filtration and washing. After 100 hours the reactor reaches steady state. The product formed in the next 24 hours, after washing in 400 l of water, placed in a drying Cabinet at a temperature of 80°C. and dried until reaching a constant weight. Get 115 kg of a mixed hydroxide of Ni,Co (Ni,Co)(OH)2with the following product features:

crystal size: 106 Å,

the specific BET-surface: 13.1 m2/g

D50value TGV: 21,3 μm,

shock density: 2,23 g/cm3.

The example for comparison 2

In the device the ISRO presented on figure 10, the load 200 l water uterine liquor containing 5 g/l NaOH, 10 g/l NH3, 172 g/l Na2SO4. Then include circulation the first pump (4) with a volume flow of 5 m 3/h and pump (2) with a volume flow rate of 90 l/h Pump (12) takes the mother liquor from the inclined clarifier (5) in the circulation receiver (13), from which it through the free flow of (15) is returned in the unit of ISRO. Once the liquid begins to exit outage (15) includes a pump (17), which takes the uterine liquor through the filter element (16) in the circulation receiver (18), from which he through the free flow of (19) is poured back into circulation receiver (13). The volumetric flow of the pump (17) is 90 l/h After switching on the mixer (14) with a speed of 300 rpm and the agitator (2) with a speed of 480 rpm and after using heat exchanger (3) in the entire system will be established temperature 45°C, include dosing pumps for solutions of the starting materials. The pump (6) with volumetric flow 6,69 l/h submits a solution of sulphate of metal, which contains 109,6 g/l Nickel, 2,84 g/l cobalt and EUR 7.57 g/l of zinc. Pump (7) with a volume flow rate of 1.52 l/h takes the soda lye (NaOH) with a concentration of 750 g/HP Pump (8) gives a rate of 1.51 l/h 25% ammonia solution, and the pump (9) takes the 8,29 l/h of demineralized water into the reactor. Finally connect the pump (21), which selects from 1 l/h the mother lye and submit to the automatic analyzer, which is three times per hour determine the content of ammonia and excess sodium lye. The pump (10) through adjustment of filling the position is it from the reactor the resulting suspension product with a solids content 120 g/l for downstream filter Suction, at which carry out the filtration and washing. After 90 hours the reactor reaches steady state. The product formed in the next 24 hours, after washing in 150 l of water are placed in a drying Cabinet at a temperature of 80°C. and dried until reaching a constant weight. Get 30.5 kg of a mixed hydroxide of Ni,Co,Zn (Ni,Co,Zn)(OH)2with the following product features:

crystal size: 63 Å,

the specific BET-surface: 12.0 m2/g

D50-value: 11,9 μm,

shock density: 2,21 g/cm3.

1. Device for producing compounds by precipitation in the reactor, wherein the reactor is equipped with a sloped sump.

2. The device according to claim 1, characterized in that the angle of inclination of the inclined clarifier is from 20 to 85°.

3. The device according to claim 1 or 2, characterized in that the angle of inclination of the inclined clarifier is from 40 to 70°.

4. The device according to claim 1 or 2, characterized in that the inclined clarifier contains the plate(s)set(s) plane-parallel to its bottom.

5. The device according to claim 4, characterized in that the inclined clarifier contains at least one plate.

6. The device according to claim 1 or 2, characterized in that the inclined clarifier is inside the side on each side of the system is the adjustable height of the tire, consisting of at least one pair of tires.

7. Device is about according to claim 1 or 2, characterized in that the inclined clarifier is inside the side on each side of the at least one groove for mounting plates.

8. The device according to claim 6, characterized in that the plate(s) slide(are) on the tires.

9. The device according to claim 7, characterized in that the plate(s) slide(are) along the slots.

10. The device according to claim 4, characterized in that the plates have a thickness of at least 0.5 cm

11. The device according to claim 1 or 2, characterized in that the inclined clarifier is at the entrance of the plate, which is located inside the reactor and a set of plane-parallel surfaces of the inlet inclined clarifier.

12. The method of obtaining compounds by precipitation, consisting of the following stages:
preparing at least one first and one second solutions of the starting substances,
connecting together at least one first and one second solutions of the starting substances in the reactor according to claim 1,
the creation of a homogeneous mixed reaction zone in the reactor,
the precipitation of the compounds in the reaction zone with the creation of a suspension of the product consisting of insoluble product and mother liquor,
partial separation of the uterine liquor from the precipitated product in an inclined settler,
obtaining a suspension of the product of the deposition, the concentration of which is higher than the stoichiometric concentration,
selection of suspension of the product from d is Chora,
filtering and drying the product deposition.

13. The method according to item 12, characterized in that a partial selection of the mother lye perform direct selection inclined overflow sump.

14. The method according to item 13, wherein the content of solids in the overflow inclined clarifier is from 0 to 50% of its content in the suspension product.

15. The method according to item 13, wherein the content of solids in the overflow inclined clarifier is from 0 to 30% of its content in the suspension product.

16. The method according to item 13, wherein the content of solids in the overflow inclined clarifier is from 0 to 15% of its content in the suspension product.

17. The method according to one of p-16, characterized in that the maximum particle size in the overflow inclined clarifier is 30% of D50value distribution of particle sizes.

18. The method according to item 12, characterized in that the concentration of deposited product in suspension exceed the stoichiometric amount.

19. The method according to item 12 or 13, characterized in that up to 90% of the mother lye is separated in parts.

20. Powder mixed hydroxide of Ni,Co General formula NixCo1-x(OH)2where 0<x<1, characterized in that it has a BET-surface, measured according to ASTM D of 3,663, less than 20 m2/g and shock density improvement is d, measured In accordance with ASTM b 527, more than 2.4 g/cm3.

21. Powder mixed hydroxide of Ni,Co according to claim 20, characterized in that it has a WET surface, measured according to ASTM D of 3,663, less than 15 m2/g and shock density, measured In accordance with ASTM b 527, more of 2.45 g/cm3.

22. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that it has a WET surface, measured according to ASTM D of 3,663, less than 15 m2/g and shock density, measured In accordance with ASTM b 527, more than 2.5 g/cm3.

23. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that it has a WET surface, measured according to ASTM D of 3,663, less than 15 m2/g and shock density, measured In accordance with ASTM b 527, more than 2.55 g/cm3.

24. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that it has the D50-the value indicated on the instrument MasterSizer In accordance with ASTM b 822, equal to from 3 to 30 microns.

25. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that it has the D50-the value indicated on the instrument MasterSizer In accordance with ASTM b 822, equal to from 10 to 20 microns.

26. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that the powder particles have a spheroidal shape.

27. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that the powder particles have a Fort is a factor of more than 0.7.

28. Powder mixed hydroxide of Ni,Co according to claim 20 or 21, characterized in that the powder particles have the form factor over 0.9.

29. The use of powder mixed hydroxide of Ni,Co, one of PP-28 for the manufacture of electrochemical cells or electrode in the manufacture of fuel cells.



 

Same patents:

FIELD: electrical engineering.

SUBSTANCE: proposed material comprises mixed lithium and transition metal oxide represented by the following formula containing surplus lithium and nickel with mean oxidation degree exceeding 2+ to display improved rate characteristics at high charge/discharge rates: Li1+aNi'bNi"cMndCoeO2 (I), where a, b, c, d and e are determined by equation 1.1 ≤(1+a)/(b+c+d+e)<1.3; mean oxidation degree of each said transition metal element id represented as follows: Ni'>2+, Ni"=3+, Mn=4+ and Co=3+; 0≤e≤0,1; 0.2<b+c≤0.55, 0.2<d≤0.55 and l(b+c)-d|≤0.1.

EFFECT: stable crystalline structure and perfect dynamic characteristics of rate at high charge/discharge rates.

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The invention relates to the field of non-ferrous metallurgy and can be used in the battery industry

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The invention relates to chemistry and can be used in the electrical industry, as well as in the production of enamels, glass, and for synthesis of other compounds Nickel

The invention relates to the field of chemical technology, particularly to a material based on Nickel hydroxide used in electrochemical elements

The invention relates to electrochemistry, in particular, compositions of hydrate of oxide of Nickel used in the production of chemical current sources

The invention relates to the production of nanostructured materials by chemical means
The invention relates to ferrous metallurgy and can be used to produce spherical hydrate of oxide of Nickel used in the battery industry
The invention relates to the field of production of Nickel compounds, hydroxides, and can be used in the manufacture of alkaline batteries

The invention relates to the field of hydrometallurgy of non-ferrous metals and can be used to produce spherical hydrate of oxide of Nickel, used in the manufacture of batteries
The invention relates to the field of producing compounds of Nickel, in particular to technology hydroxide Nickel (II) used for current sources, for example, in the composition of the active mass of the positive electrodes of alkaline batteries

The invention relates to the hydroxides of cobalt, which can be used in the synthesis of industrial catalysts and high-tech materials
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