Method for manufacturing manganese sulphate component, apparatus for manufacturing manganese and zinc sulphate components, sulphate component combination and uses

Abstract

The object of the invention is a method, to manufacture a manganese sulphate component from the black mass material (11) of used alkalin batteries (11'). The method comprises a first acid dissolution (201) carried out on the black mass material in the presence of water (12) and sulphuric acid (13) to dissolve zinc (20), potassium (30) and chlorine (35) from the black mass material into a zinc sulphate component (16); a first filtration (202) to separate the zinc sulphate component from a manganese component (15) remaining from the first acid dissolution; a second, acid dissolution (301) carried out on the manganese component in the presence of purified, water ( 12'), sulphuric acid and at least one reducing agent (14) to form a suspension (41) from the manganese component; a second filtration (302) to remove an insoluble solid, matter (26), such as, for example, graphite (27), carbon black (28) and plastic (29), from the suspension to form a process solution (17); a sulphide precipitation (105, 303) and at least one subsequent separation step (106, 304) to remove zinc (46) and copper (21) from the process solution formed, after which the manganese sulphate component (24) formed is suitable for use as a fertiliser (24.1) or as a fertiliser component in agriculture, or as an industrial raw material ( 24.2). In addition, the object of the invention is also an apparatus for manufacturing manganese and zinc sulphate components, a sulphate component combination and uses.

Description

[0001] METHOD FOR MANUFACTURING MANGANESE SULPHATE COMPONENT, APPA- RATUS FOR MANUFACTURING MANGANESE AND ZINC SULPHATE COMPONENTS, SULPHATE COMPONENT COMBINATION AND USES The invention relates to a method for manufacturing a manganese sulphate component from black mass material of used alkaline batteries via an acid treatment. Furthermore, the invention also relates to a corresponding manufacturing apparatus, a sul- phate component combination and uses of the sulphate compo- nents.

[0002] The applicant's international patent application, publication number W02019 / 150005 , relates to the acid dissolution of the black mass from alkaline batteries and, in addition, the puri- fication of the resulting manganese- and z inc-cont aming dis- solution product for use as a fertiliser. More specifically. the use of the dissolution product as a trace element in plant cultivation is discussed. Here, the zinc and manganese con- tained in the black mass are dissolved in the presence of water, citric acid and sulphuric acid. The end product is a raanganese- and zinc-containing sulphate solution product. However, its industrial application possibilities are very limited. In prac- tice, it is only suitable for the above-mentioned use as a fertiliser in agriculture.

[0003] The purpose of this invention is to provide a method for di- versifying the products derived from the black mass material obtained from alkaline batteries. More specifically, the pur- pose of the invention is tof manufacture a manganese sulphate component, which is a manganese sulphate solution suitable for use as an agricultural fertiliser and / or as a manganese-con- taining raw material for industrial applications. The charac- teristic features of the method according to the invention are presented in Claim 1. Additionally, the purpose of the invention is to provide a corresponding apparatus. The characteristic features of the apparatus according to the invention are pre- sented in Claim 26. In the invention, the black mass material from alkaline bat- teries is dissolved in several steps using chemical methods. In this case, the method yields different end products. More specifically, the zinc and manganese of the black mass material of used alkaline batteries are separated from each other in the invention into sulphate components in aqueous solution forms.

[0004] Additionally, metals and metal compounds can be removed using chemical methods from the manganese sulphate separated accord- ing to the method from the black mass material. The end product of this method is an aqueous solution form of the manganese sulphate component. It is suitable for use as a fertiliser in agriculture, or as an industrial raw material.

[0005] In addition to separating and producing the manganese sulphate component in an aqueous solution form, the method according to the invention can be used to separate and produce other end products as well from the black mass material. One such product is a zinc sulphate solution. According to one embodiment, it can be utilised in the zinc industry as a raw material for the zinc production process. According to another embodiment, the zinc sulphate solution formed can also be utilised as a ferti- liser component in agriculture. The zinc sulphate solution can be used alone and / or as a sub-component with other raw material components. An example of the latter is precisely the manganese sulphate component manufactured, for example, by the method according to the invention.

[0006] More specifically, according to one embodiment the method ac- cording to the invention includes at least two water-based acid treatment steps in the form of acid dissolution. The first acid dissolution is performed on the black mass material in the absence of a reducing agent. The second acid dissolution is performed in the presence of at least one reducing agent on the manganese component that has been separated from the black mass material as a result of the first acid dissolution. In the acid treatments of the method according to the invention, no actual precipitate formation occurs. Therefore, the separation of sub- stances in the acid treatments is based on the different solu- bility properties of the substances originally present in the black mass material.

[0007] After the acid treatments and the subsequent separation of the insoluble solid matter fractions, the process solution formed in the method, formed from the manganese component, can undergo sulphide precipitation according to one embodiment. This is achieved by using at least one sulphide source. Sulphide pre- cipitation forms a metal sulphide precipitate. It is separated from the process solution. The sulphide precipitate can also be utilised as an industrial raw material. The manganese sul- phate component formed after this precipitate separation is suitable for use as a fertiliser in agricultural applications. It is also suitable as an industrial raw material. Still other end products obtained by this method include, for example, carbonaceous material in its various forms.

[0008] In addition to its several end products, the invention offers a number of different advantages in terms of their quality. For example, the manganese sulphate used by the battery industry has very low limit values for magnesium and calcium. One example of this is a value of less than 50 ppm, i.e. , roughly < 25 mg / L, when the Mn solution is 150 g / L. Magnesium and calcium are usually present in ores. Both of these have to be removed from the virgin material when producing manganese sulphate. This is achieved by using highly complex and polluting processes. Owing to the invention is enabled very pure manga- nese sulphate to be produced from the black mass material of alkaline batteries, which has a low magnesium and calcium con- tent. In this case, the separate removal step for these sub- stances, which is characteristic of virgin material, is prac- tically unnecessary.

[0009] The chemicals and reagents used in the preferred embodiments of the method according to the invention have been selected in a manner optimised for further processing of the end products.

[0010] In this case, the method uses chemicals whose components are already present in the refining and waste treatment processes employed by industry. Consequently, there is no need for a separate removal process in industry. One example of the first process is the use of sodium sulphide as a reagent for sulphide p r e c i p i t a t i o n .

[0011] Furthermore, in the method according to the invention, the energy and chemical consumption is also significantly lower than, for example, in the production of pure manganese sulphate from virgin manganese ore. Other additional advantages achieved by the invention are apparent from the description and the characteristic features are apparent from the appended claims. The invention, which is not limited to the embodiments presented below, is described in more detail with reference to the ac- companying drawings, in which

[0012] Figure 1 shows as a rough block diagram sub-steps of the method according to the invention.

[0013] Figure 2 shows as a rough flow diagram an example of the method according to the invention for the first acid treatment, Figure shows as a rough flow diagram an example of the method according to the invention for the second acid treatment and subsequent steps,

[0014] Figure 4 shows as a schematic diagram an example of the apparatus according to the invention,

[0015] Figure 5 shows as a flow diagram an example of a more detailed embodiment of the invention,

[0016] Figure 6 shows as a flow diagram one embodiment of the sub-steps involved in separating the sulphide precipitate from the process solution ob- tained by the method according to the inven- tion,

[0017] Figure 7 shows as a flow diagram one embodiment of the sub-steps involved in forming a zinc- and manganese-cont aining fertiliser solution product from the end products obtained by the method according to the invention,

[0018] Figure 8 shows as a flow diagram one embodiment of adjusting the pH level and manganese content of the suspension in the final step of the second acid dissolution,

[0019] Figure 9 shows an embodiment of a washing process per- formed on the black mass material before the first acid dissolution, and Figure 10 shows an embodiment of a black mass material washing apparatus for the washing process shown in Figure 9.

[0020] Firstly, relating to the method according to the invention, some exemplary pre-treatment steps are explained, which are carried out before the method according to the invention it- self. The main purpose of the pre-treatment steps is to prepare and separate the black mass material contained in the used alkaline batteries received. The chemical treatment method according to the invention is applied to this black mass mate- rial. A person skilled in the art will understand that the pre- treatment steps presented here as examples are not necessarily an essential part of the treatment method according to the invention, at least not in the sense that performing one or more of them, for example, in the same geographical location as the treatment method according to the invention itself is performed, would be in any way essential to the invention. The pre-t reatment steps presented as examples do not, for example, include sub-steps involving chemical treatment, as the treat- ment method according to the invention itself does. In this case, they can be outsourced if necessary, for example. The pre-t reatment could then be performed by a subcontractor in their respective places, for example.

[0021] According to an exemplary embodiment, the pre-treatment process may begin with crushing of alkaline batteries to produce the black mass material. Crushing may be carried out, for example, with a hammer crusher or a shear crusher. However, using a hammer crusher here is advantageous as it leaves sizes of the plastic separators in the alkaline batteries larger. Tn this case, the plastic separators are not torn apart much by the hammers, unlike with the blades of a shear crusher, for example. Thus, using a hammer crusher makes it easier to separate the plastic during the screening step. Additionally, not as much fine plastic shreds are carried along with the mass to the subsequent acid treatment step of the black mass.

[0022] According to one embodiment, crushing of batteries is followed by the separation of metal pieces from the black mass. According to one embodiment, this can be divided into two sub-steps: magnetic and non-magnetic separation of metals. The steel shells of alkaline batteries are first separated by magnetic separation. After this, the material is fed onto a conveyor. According to one embodiment, the non-magnetic metal fractions can be thrown away from the conveyor by means of an eddy current separator. These fractions include, for example, brass pins and other possible non-ferrous pieces. The separated metals can be sent for recycling.

[0023] After the eddy current separation, the mass can be screened to a suitable particle size. This can be achieved, for example, with a vibrating screen. An example of this is a particle size of < 1.7 mm, but other sizes are equally possible. The undersize fraction from the screen is ready raw material for chemical treatment according to the method of the invention. It can be fed directly into a dissolution reactor 31 (Figure 4) . It can also be stored in a separate feed silo for treatment according to the method. The oversize fraction from the screen can, in turn, be returned to crushing, such as, for example, the afore- mentioned hammer crushing. Crushing is carried out to reduce the large mass granules in the oversize fraction. The crushed oversize fraction is re-screened. The plastic shred fraction remaining as an oversize fraction from this screen is recovered and can be sent for energy use, for example. The crushed un- dersize is, in turn, fed onto the conveyer of the eddy current treatment system and then, again through subsequent screening, used as raw material for chemical treatment according to the

[0024] According to one embodiment, for example as an alternative to eddy current separation, after magnetic separation the material can be further crushed with a roller crusher, which is a more powerful method compared to the coarser crushing achieved by a hammer crusher, before screening. By crushing the black mass with a roller crusher to a very fine, almost dust-like particle size, it may be possible to avoid the aforementioned eddy cur- rent separation. The crushed black mass is then screened with a finer mesh screen. In this case, non-magnetic metal fragments and plastics remain on the screen. The undersize fraction from the screen is raw material ready for chemical treatment accord- ing to the method of the invention.

[0025] Figure 1 shows as a rough block diagram an example of an in- dustrial method according to the invention for manufacturing a manganese sulphate component from the black mass material de- rived from used alkaline batteries by acid treatment. Unlike laboratory-scale operations, this industrial method refers to an operation in which it is possible to process tons of starting raw material into an end product on a daily basis.

[0026] The method includes as its main steps at least one acid treat - merit step 101, 103 and at least one filtration step 102, 104.

[0027] Additionally, the method may include a possible sulphide pre- cipitation step 105 followed by precipitate separation 106. The method is characterised in that, in addition to the manganese sulphate component formed at the end of said main steps 101 to 106 of the method, other products suitable for use as industrial raw materials are obtained from one or more of the main steps of the method. Thus, the method can be employed to diversify the range of end products made from the black mass material and their applications. In addition to these aspects, the end prod- ucts are chemically simpler. This improves their usability in subsequent processes.

[0028] In the method, the acid treatment of the black mass material is performed as step 101. The purpose of this is to form, more specifically, to separate the manganese component from the black mass material through acid dissolution. The separated manganese component is then additionally treated according to the method by means of a second acid treatment 103 and subse- quent sub-steps 104 to 106 to obtain a pure MnSO4solution as one of the end products of the method. According to one embod- iment of the method, a precipitate is formed to the process solution formed in the method from the manganese component by precipitation in at least one sub-step 105 of the method. This precipitate is separated from the process solution in at least one subsequent sub-step 106. Any other metals and metal com- pounds originally present in the black mass material, and thus also in the manganese component separated therefrom, are re- moved in the precipitate.

[0029] Figure 2 shows an example of the sub-steps of the method ac- cording to the invention as a flow diagram of its initial stage. The steps of Figure 2 correspond here to steps 101 and 102 in the block diagram of Figure 1. Reference is also made to the apparatus diagram shown in Figure 4. More specifically, the method includes forming a manganese component 15 from the black mass material 11. This is achieved by treating the black mass material 11 in at least one acid treatment step 101. This at least one acid treatment step 101 is acid dissolution 201. Here, the formation of manganese component 15 can now be un- derstood more specifically as its separation from the black mass material 11, and even more specifically, as its separation from the first suspension 25 formed from the black mass material 11 .

[0030] As mentioned above, the overall treatment method according to the invention includes two acid treatment steps 101, 103 car- ried out as acid dissolutions 201, 301, the latter of which is explained below with reference to Figure 3. Of these, the first acid dissolution 2.01 is carried out on the black mass material 11 in the presence of water 12 and sulphuric acid 13. The first acid dissolution 201 is carried out to separate metallic zinc 20 from the black mass material 11. It involves dissolution of metallic zinc 20 from the black mass material 11 and a liquid- solid separation. The metallic zinc dissolved from the black mass material 11 is mainly separated from the solid manganese component 15 remaining from the first acid dissolution 201. At this stage in the first acid dissolution 201, the insoluble manganese component 15 is present throughout the entire solu- tion volume. Thus, it is suspension 25 formed by the sulphate solution 16 and the manganese component 15. The manganese com- ponent 15 is separated from the suspension 25 as filtration step 202 that follows the acid dissolution 201.

[0031] Tn the first acid dissolution 201, the black mass material 11 is fed into the dissolution reactor 31 by mixing it with a suitably calculated amount of water. As an example, the amount of water 12 used here can be approximately twice the weight ratio of water relative to the black mass material 11 to be dissolved. However, the less water 12 used, the stronger the zinc sulphate solution 16 obtained from the first acid disso- lution 201, which in turn reduces transportation costs and storage capacity requirements for the zinc sulphate solution 16. The amount of water can be adjusted, for example, to suit the customer's requirements for the fertiliser product, how- ever, within the limits of the solubility of zinc and manganese.

[0032] After adding water 12, sulphuric acid 13 is added into the reactor 31. The sulphuric acid 13 is initially fed into the reactor 31 cautiously. Thus, according to one embodiment, the first acid dissolution 201 includes optimising the feed rate of the sulphuric acid 13. This is carried out at least at the beginning of the acid dissolution 201. In this optimisation, the course of the reaction between the alkaline potassium hy- droxide and the sulphuric acid 13 in the forming suspension 25 is more specifically optimised. This reaction produces potas- sium sulphate and water. The water 12 forms an aqueous matrix for the zinc sulphate 16 formed during the acid dissolution 201 of the black mass mate- rial 11. In this aqueous matrix, the metallic zinc 20 present in the black mass material 11 dissolves into the sulphuric acid 13, simultaneously forming gaseous hydrogen. This causes the suspension 25 to foam. Thus, according to one embodiment, the first acid dissolution 201 may also include optimisation of the sulphuric acid 13 feed to control hydrogen formation. Also this optimisation can be performed at least at the beginning of the acid dissolution 201. Here, more specifically, hydrogen for- mation in the suspension 25 is optimised by slowing it down. During dissolution 201, the sulphuric acid 13 reacts with the metallic zinc, which is in solid form in the black mass material 11, and also with the zinc oxide, in this case, it converts the released zinc 20 in the aqueous solution into zinc sulphate (ZnSO4) 16.

[0033] The water 12 of the first acid dissolution 201 can be, for example, tap water. In addition to tap water, the water used can also be washing water 43' of the manganese component 15, which will be separated from the suspension 25 (Figure 4) fur- ther on. This water is generated from the rinsing step of the manganese component 15. This washing water 43' contains zinc, calcium and magnesium still remaining in the manganese compo- nent 15 after its separation step, more generally, residues of the zinc solution. These are recovered by recycling the washing water 43' and thus also removed from the formed manganese com- ponent 15. This washing water 43' can be recycled to the next dissolution batch of the black mass 11 as its base solution.

[0034] Additionally, according to another embodiment, washing water 48 ' of the solid matter fraction 26 to be separated from the second suspension 41 further on can also be used as the water for the first acid dissolution 201 (Figure 4) . This water is generated from the filtration step 302 of the second suspension 41. During this step, the carbon- and plastic-containing solid matter 26 is separated from the second suspension 41 to form the process solution 17. In this case, the solid matter fraction 26 remaining in the filtration means 42 is further washed with said washing water 48. After washing, the washing water 48' contains manganese remaining in the solid matter fraction 26. It is recovered by recycling the washing water 48 ' . Also this washing water 48 ' can be recycled to the next dissolution batch of the first acid dissolution 201 as its base solution.

[0035] In connection with the above-mentioned optimisation of the feed rate of the sulphuric acid 13, according to one embodiment, at the beginning of the first acid dissolution 201, 5 to 10% of the total amount of sulphuric acid 13 may be fed at a lower volumetric flow rate compared to the feed of the remaining amount of sulphuric acid 13, for example to reduce foaming of the suspension 25. According to one embodiment, the feed rate of the sulphuric acid 13 at the beginning of the dissolution may then be, for example, 5 to 50%, more specifically 5 to 40% and even more specifically 10 to 30% of the maximum feed rate of the sulphuric acid 13 used in the dissolution.

[0036] According to one embodiment, the first acid dissolution 201 also includes foam decomposition. It can be achieved, for ex- ample, with one or more defoamers. Foam decomposition is per- formed at least in the initial stage of the first acid disso- lution 201. Foam decomposition is performed so that the foam decomposes quickly from the suspension 25, preventing it from taking up space in the reactor 31. Thus, it enables a larger batch size and faster process operation. The defoamer can ad- vantageously be biodegradable. In this case, the sulphate com- ponents 16, 24, which are formed as end products, are better suited to be used as a fertiliser, as they do not contain any non-biodegradable additive that ends up in the field with the fertiliser. An example of such non-biodegradable component is silicone oil, which is commonly used for antifoaming. An al- ternative or additional method for foam decomposition can be a mechanical arrangement, such as, for example, a whip 39.

[0037] Once the initial foaming phase has settled, the remaining sul- phuric acid 13 is fed into the reactor 31. This can be done as quickly as the cooling equipment 37.1 and the pump of the reactor 31 allow. According to one embodiment, the first acid dissolution 201 can also include optimising the temperature to 30 to 50 °C. The heat energy removed by the cooling equipment 37.1, 37.2 of the apparatus 10 can also be utilised in the process. One way to do this is to use it to neat the washing water 43 of the precipitates that will be formed later. In this case, no separate heating is required. Heating the washing water 43 is not necessary for the implementation of the inven- tion. However, using warm water has the advantage that it more easily binds zinc sulphate residues in the manganese component 15 during the subsequent washing step for the manganese compo- nent 15. Otherwise, the method according to the invention can be carried out at room temperature (no heating is required) . Additionally, the method according to the invention can be carried out at normal pressure (no pressurisation or special pressure-resistant reactors are required) .

[0038] The end result of the first acid dissolution 201 is the afore- mentioned suspension 25. This can be separated to liquid and solid fractions. In the embodiment shown, filtration of the suspension 25 formed in the first acid dissolution 201 is per- formed as step 202 after the first acid dissolution 201. The solid fraction present in the suspension 25, and which is to be separated therefrom, is formed by the manganese component 15 that is insoluble in the first acid dissolution 201. It practically comprises manganese dioxide 15fand graphite 27, carbon black 28 and plastic shreds 29 mixed in with it, col- lectively known as the solid matter fraction 26. According to one embodiment, filtration 202 of the suspension 25, i.e., the separation of the manganese component 15 and the zinc sulphate solution 16, can be carried out, for example, using suitable filtration means 32. An example of the filtra- tion means 32 can be, for example, a frame filter 32 ' . During filtration 202, the amount of soluble metallic zinc 20, potas- sium 30 and chlorine 35 is reduced from the manganese component 15 remaining after the first acid dissolution 201, i.e. , the manganese component 15 separated from the black mass material 11. These elements have now dissolved from the black mass ma-- serial 11 during the first acid dissolution 201 and form the liquid fraction of the suspension 25, i.e. , the zinc sulphate solution 16, which is to be separated from the suspension 25. In addition, the liquid fraction contains manganese 45 dis- solved in the suspension 25 in the first acid dissolution 201, which is also in the form of sulphate. This manganese 45 orig- inates from manganese compounds dissolved from the black mass material 11, which are also present in it, in addition to the manganese dioxide 15’ , which did not dissolve in the first acid dissolution 201. These manganese compounds, which dissolve di- rectly in sulphuric acid 13 without the use of hydrogen peroxide 14 ' , more generally, a reducing agent 14, are formed in the black mass material 11 as a result of various electrochemical reactions during the use of alkaline batteries 11" . The manganese component 15 originates from the formation step

[0039] 201 of the suspension 25, i.e. , dissolution of the black mass material 11 in the presence of water 12 and sulphuric acid 13. In this way, two functions are achieved in the same process step 201 : dissolution of the black mass material 11 into a potassium- and chlorine-containing zinc sulphate solution 16 and, in addition, formation of the manganese component 15, which is to be further processed and separated from the sus- pension 25, into the suspension 25 formed during dissolution 201. The amount of the manganese component 15 (expressed as dry matter) can be 40 to 60% of the original amount of dry black mass 11.

[0040] The zinc sulphate solution 16 contains at least metallic zinc 20, potassium 30 and chlorine 35 originating from the black mass material 11. The zinc 20 and potassium 30 are present in the zinc sulphate solution as corresponding sulphates (ZnSCA and K2SO4) . Chlorine 35, in turn, is present in the zinc sulphate solution 16 as chloride (C1-) . An example of this may be zinc chloride. These substances, which are removed with the zinc sulphate solution 16, are formed into sulphates and chlorides at the latest during this dissolution step 201, if they are not already such in the black mass material 11. The manganese com- ponent 15 is present at this stage throughout the solution volume. Thus, it is the aforementioned suspension 25, more specifically the first suspension.

[0041] According to one of the first embodiments, the filtered, acidic zinc- and manganese-containing sulphate solution 16 (with an approximately concentration of 100 g / L of Zn, and 60 g / L of Mn) can even be used as such, for example, as a raw material 16.2 for the zinc industry. There, the sulphate solution 16 can be used by mixing it in a suitable ratio with a raw solution made from virgin materials used in the zinc industry process. Mixing is possible because the manganese, potassium and chlorine res- idues contained in the zinc- and manganese-containing sulphate solution 16 remain relatively lower than the concentrations normally found in the raw solution. According to one embodi- ment, the potassium content of the zinc sulphate solution 16 can be, for example, 5 to 25 g / L, more specifically 10 to 25 g / L and even more specifically 15 to 25 g / L. The chlorine content may correspondingly be, for example, 0.01 to 5 g / L, more specifically 0.5 to 4 g / L and even more specifically 1 to

[0042] 3 g / L.

[0043] Thus, according to one of the first embodiments, the area of application of the solution 16 can be, in addition to agricul- tural use, in the zinc industry without the need of water washing of the alkaline battery mass to remove potassium 30 and chlorine 35 originating from the black mass material 11 before performing the first acid treatment step 101. In other words, water washing of the black mass material 11 is not a necessary sub-step from the point of view of the invention and the ap- plication of the solution 16. In this case, the first acid treatment step 101 can be performed even without separate water washing of the black mass material 11, and thus also without separate need to treat the potassium- and chlorine-containing solution formed by this water washing. When combining the zinc sulphate solution 16 formed in the first acid dissolution with the raw solution of the zinc process, the amounts of the po- tassium, chlorine and manganese in the zinc sulphate solution 16 remain relatively below the limit values of the standard solution used in the zinc process. Instead of forming a separate (waste) fraction, all components can then be processed in the same location, i.e., in zinc industry processes.

[0044] According to another embodiment, the black mass 11 can also be pre-treated by a washing process 101 ' before the first acid dissolution 101 (Figure 1) . This washing process 101 ' can re- duce the amount of potassium and chlorine components in the black mass material 11 before the formation of the zinc sulphate solution 16 by the first acid dissolution 101, 201 from the black mass material 11. One of the particular advantages of the washing process 101 ' is that it can reduce the amount of chlo- rine 35' contained in the zinc sulphate solution 16 formed, especially in the first acid dissolution 101. In this case, the zinc sulphate solution 16 is obtained in a more favourable form in terms of its chlorine content for use in the zinc industry.

[0045] This particular advantage is related to the possible subsequent use of the zinc sulphate solution 16 for manganese precipita- tion using ozone. The smaller amount of chlorine 35' in the zinc sulphate solution 16 prevents the catalytic decomposition of ozone in the zinc industry. Another additional advantage is related to the fact that using the zinc sulphate solution 16 directly in the form of an aqueous solution in the zinc industry saves energy. Especially potassium solutions are often crys- tallised to dryness, which consumes a huge amount of energy. In this case, this is not necessary, as any potassium in the solution 16 will remain in the structure of the solid jarosite formed in the zinc industry process. Tn this case, it will then be removed from the solution by spontaneously precipitating into solid matter.

[0046] Figure 9 shows an embodiment of this washing process 500 ' for the black mass 11. Figure 10, in turn, shows an example of a possible washing apparatus with a washing water circulation 49. According to an embodiment, the washing process 500 ' of the black mass material 11 can be carried out after the material 11 has passed through screening 54, following crushing and possible eddy current separation steps. After screening 54, the material 11 can be directed into slurry container 55 containing washing water 51. Washing takes place in batches 11.1, 11.2. As step 901, a batch 11.1 of the black mass material 11 is washed in the container 55 with the washing water 51. In the container 55, the washing water 51 and the black mass material 11 can be mixed to transfer the potassium 30fand chlorine 35' contained in the material 11 to the aqueous phase, i.e. , to the washing water 51. According to one embodiment, the amount of washing water 51 per mass batch 11.1 can be, for example, 0.8 to 2 times the amount (weight %) of the mass batch 11.1.

[0047] After washing 901, the slurry 56 formed during mixing is trans- ferred from the container 55 to a separation device 57. As step 902, the washing water 51 ' that has undergone washing step 901 is separated from the washed black mass material 11 by the separation device 57. According to one embodiment, the separa- tion device 57 may be, for example, a roll filter 57 ' . In addition, in the roll filter 57 ' as much of the washing water 51 ' as possible can be sucked out of the material 11. Suction can be performed, for example, at least at the beginning of the filtration .

[0048] According to one embodiment, the washed and filtered material 11 can be further rinsed as step 903 after filtration 902 of the material 11. Rinsing 903 can be performed while the material 11 is still in the same separation device 57, now in the roll filter 57 ' , where the washing water 51 ' was separated from the material 11. In this case, rinsing takes place through the material 11. Clean water 52 is used to rinse the material 11. In addition, rinsing the material 11 for the mass batches 11.1, 11.2 is performed with a substantially smaller liquid volume than the volume of the washing water 51 used to wash the mate- rial 11 in step 901.

[0049] As step 904, the rinsing water 53 of the mass batches 11.1,

[0050] 11.2 is separated from the black mass material 11. According to one embodiment, the washing water 51 ' used for washing the material 11 and the used rinsing water 53 from rinsing step 903 can be combined as step 905. This combination of the washing water 51 ' and the used rinsing water 53 form the washing water 51 for the subsequent mass batches 11.2, ll.n. Thus, it is used as the washing water 51 in washing step 901 of the subsequent material batches 11.2, ll.n. In other words, the washing pro- cess 101 ' , 500 ' then takes place with a closed washing water circulation 49. The washed and rinsed black mass material 11* can, in turn, be transferred from the filter 5 / ’ into the dissolution reactor 31.

[0051] As a result of step 905, i.e., combining the washing and rinsing waters 51 ' , 53, the potassium-containing water 51 ' originating from washing of the previous mass batch 11.1 is used as part of the washing water 51 used in washings of the subsequent mass batches 11.2, ll.n. In this case, the potassium 30 ' and chlorine 35' released from the following mass batches 11.2, ll.n are transferred to this washing water 51. Thus, it becomes concea- trated with respect to both of the aforementioned components 30 ' , 35' . One example of possible further uses 59 of the con- centrated washing solution 60, which is now mainly a potassium hydroxide solution, is neutralisation of acidic waters in the mining industry. Another example of use can be soil improvement in agriculture, for example by adjusting the pH. In this case, the solution 60 may be oxidised and / or treated with UV light prior to use to make it more suitable for said application.

[0052] When the washed mass batches 11.1, 11.2 are always filtered and in addition also rinsed with the clean water 52, the washing water 51 circulating in the washing process 101 ' , 500 ' gradu- ally becomes concentrated. This is because the amount of the clean water 52 used for rinsing the material 11 is substantially less than the amount of the washing water 51 itself in washing step 901 of the material 11. According to one embodiment, the amount of the clean rinsing water 52 used for rinsing the mass batch 11.1 may be, for example, 5 to 25% (by weight) of the amount of the washing water 51 used for washing the mass batch 11.1. Thus, in each washing cycle, this amount of the clean water 52 is introduced into the closed washing water circula- tion 49.

[0053] The recycling and combining cycles of the used washing water 51 ' with the used rinsing water 53 are continued, for example, until the available washing water 51 storage capacity 58 is filled. As the material 11 is rinsed and the rinsing water 53 is combined with the washing water 51 ' that has undergone wash- ing step 901, the total amount 50 of available washing water 51 in the washing process 101 ' , 500 ' increases in a controlled manner throughout. In this case, the washing water 51 can be concentrated, for example, to the extent that the liquid vol- umes allow (step 906) . During the pilot phase tests, as a result of the washing and rinsing cycles and the combining of the corresponding liquids 51 ’ , 53, the wash water 51 has been con- centrated, for example, to concentrations of K of about 80 g / L and Cl of about 10 g / L. In this case, there have been approxi- mately five washing and combining cycles. When the available storage capacity 58 of the washing water 51 has been filled, step 907 is performed to make room for a new batch of washing water. This is done by transferring the previous batch of wash- ing water, i.e., the concentrated washing solution 50, for further use 59. The base water for the new batch of washing water can be, for example, tap water.

[0054] According to one embodiment, when the material 11 is subjected to the aforementioned washing process 101’ , 500 ' as a pre- treatment, compensation can be made for the amount of water required for dissolving the material 11 fed to the dissolution reactor 31 in the first acid dissolution 201, 501. In other words, the moisture contained in the material 11 itself after the washing process 500 ' is then taken into account. That is, it is a matter of taking into account the water that enters the reactor 31 with the material 11. This maintains the correct liquid balance of the first acid dissolution 201, 501.

[0055] As regards the utilisation in the zinc industry of the zinc sulphate solution 16 manufactured by the method according to the invention, it has the additional advantage that it can be utilised in the zinc industry directly in the form of an aqueous solution. In the zinc industry, the zinc sulphate solution 16 is known to be used to precipitate metallic zinc by electrolysis using an electric current.

[0056] Figure 3 shows an example of the method according to the in- vention as a rough flow diagram for the latter half of the method, i.e. , the second acid treatment 103 and also the sub- sequent, partly optional sub-steps 104 to 106 of the method, which results in formation of the manganese sulphate component 24 as the end product.

[0057] Treatment of the solid manganese component 15 obtained as a result of the first acid treatment 101 is continued by forming a process solution 17 from the manganese component 15. This is initiated by subjecting the manganese component 15 to a second acid treatment step 103. This is again acid dissolution 301, as shown in Figure 3, in this case now a second acid dissolu- tion. More specifically, in the second acid dissolution 301, the solid manganese component 15 remaining from the first acid dissolution 201, is dissolved. Dissolution is first carried out to form a second suspension 41, and to form a process solution 17 to be further filtered from the second suspension 41. As step 301 of the method, the manganese component 15 is dis- solved in a second acid dissolution in the presence of purified water 12 ' , sulphuric acid 13 and at least one reducing agent 14 to form a second suspension 41, which is further separated by filtration to form a process solution 17. The acid dissolution 301 takes place again in a reactor, this time in a second dissolution reactor 40. Thus, this can be referred to as reducing acid treatment and reducing acid dissolution. The purified water 12 ' forms an aqueous matrix for the sulphate formed during the acid dissolution 301 of the manganese compo- nent 15, into which dissolution takes place. During dissolu- tion, sulphuric acid 13 and at least one reducing agent 14 react with the solid manganese dioxide 15' present in the man- ganese component 15. In this case, they break down the structure of manganese dioxide (MnO2) 15fand convert the manganese re- leased from it into an aqueous solution, i.e. , now a second suspension 41, as manganese sulphate (MnSO4)) . The second acid dissolution 301 is started by feeding the man- ganese component 15 into a dissolution reactor 40 initially filled with the purified water 12. ' . According to one embodi- ment, the amount of the water 12 ' may be, for example, approx- imately 0.3 to 1.5 times, more specifically 0.5 to 1.5 times, and even more specifically 0.5 to 1.2 times the amount of the wet manganese component 15. Correspondingly, the moisture con- tent of the manganese component 15 may be, for example, 30 to 55%, more specifically 30 to 50%. The water is now therefore the purified water 12' . The purified water 12 ' contains as little calcium and magnesium as possible, which are very typi- cally found naturally in tap water. In this case, tap water is often referred to as "hard water" . By using the purified water 121in dissolution, the calcium and magnesium concentrations of the end product, i.e. , the manganese sulphate component 24, can be minimised. Otherwise, these would be detrimental to the end product, i.e. , the manganese sulphate component 24.

[0058] At this stage, according to one embodiment, a possible manga- nese content analysis can also be performed for the acid-soluble manganese component 15. One way to do this is to take a sample from the mass solution (a suspension of the purified water 12'and manganese component 15) in the reactor 40, which is then suction filtered and washed with water. The sample thus treated is then dissolved in a suitable acid mixture to produce a liquid. The resulting liquid from the dissolution is then ana- lysed. However, such an analysis does not need to be performed every time. If the manganese content of the manganese component 15 stabilises across production batches, the dosing of chemi- cals can be done according to some routine dosing.

[0059] Next, the calculated amount of sulphuric acid 13 is added to the reactor 40. The amount of sulphuric acid 13 is based on either the measured or assumed manganese content of the manga- nese component 15.

[0060] The formula for the second acid dissolution 301 is:

[0061] MnO2 + H2SO4 + H2O2 — > MnSO« + 2 H2O + O2 (1)

[0062] It shows that at least one mole of acid and one mole of peroxide are required for one mole of manganese. Once the precise amount of manganese itself has been determined, for example by the analysis presented above, it is possible to calculate how much manganese was contained in the manganese component 15 fed into the reactor 40, and consequently, how much chemicals its (op- timal) dissolution will require. However, the chemical amounts may also deviate from these calculations due to the consumption of chemicals in so-called side reactions. Nevertheless, the calculations provide a preliminary indication of the required addlitions. sulphuric acid 13 is a preferred dissolution chem- ical for use in the process according to the invention. f or example because in the battery industry, which is one exemplary application for the end product 24.2 obtained by the method according to the invention, battery materials, including man- ganese, are produced by precipitating metals as solid hydrox- ides out of a sulphate solution. This leaves behind a sodium sulphate solution. By using sulphuric acid 13 for dissolution, manganese sulphate is specifically formed in ready-to-use so- lution form, from which manganese is subsequently precipitated as hydroxide. Well-known industrial processes involve dissolv- ing solid manganese sulphate in water. The manganese sulphate is then powdery and dusts during pouring into water, creating occupational safety risks (for example, manganism) . In the case, however, the product according to the invention is al- ready in liquid form. Thus, this eliminates the dangerous dusty work step characteristic of the known method.

[0063] Next, at least one reducing agent 14 is fed into the reactor 40 to decompose the manganese dioxide 15' contained within the manganese component 15 and to form a second suspension 41 there- from. The reducing agent 14 may be hydrogen peroxide 14 ' , for example. In the example of chemical concentrations shown below, the amount of hydrogen peroxide 14 ' may be approximately equal to that of sulphuric acid 13. The sulphuric acid 13 and hydrogen peroxide 14' must be of sufficient strength to make the amount of water in the end product relatively small. Excessive water would result in a manganese sulphate solution 24 ' that is too dilute. The strength of the sulphuric acid solution may be, for example, 80 to 95% (a specific example: 93%) . The strength of the hydrogen peroxide 14 ' may be, for example, 40 to 70%, more specifically 40 to 60%, more preferably 45 to 55%. A specific example of the strength of hydrogen peroxide 14 ' can be 50%. According to one embodiment, hydrogen peroxide 14' and sul- phuric acid 13 can be used in slightly excessive amounts, as some of the hydrogen peroxide 14 / can be consumed in so-called side reactions. In this case, all of the manganese dioxide 15' is guaranteed to dissolve.

[0064] Cooling 3'7.2 is also used in the reactor 40. This prevents the spontaneous decomposition of hydrogen peroxide 14 ' in the re- actor 40. If the reactor 40 is too warm, the consumption of hydrogen peroxide 14' would increase. In addition, a biode- gradable defoamer can be used here, if necessary, to suppress surface level rise in the reactor 40.

[0065] The reducing agent 14 used in dissolution can be one or more selected from the following: peroxide 14*, citric acid, one or more sugars. Of these examples, peroxide 14*, such as, for example, hydrogen peroxide 14 ' , is however the most advanta- geous in that it is more effective compared to the other re- ducing agents 14 mentioned as examples. In addition, only water remains in the process as a residue from peroxide 14*, and no organic carbon residues, for example. Nor is carbon dioxide formed, as would be the case when using citric acid, for exam- ine pH of the second suspension 41 is close to zero at the start of the second acid dissolution 301. Towards the end of dissolution 301, the pH of the suspension 41 is raised to a suitable level, for example, approximately to pH 1.5 to 2.5.

[0066] The flow diagram in Figure 8 shows this step in a little more detail as one possible embodiment. The pH is now also raised by means of hydrogen peroxide 14' , which is added in small doses as step 801. The hydrogen peroxide 14' acts here to raise the pH if the manganese component 15 containing insoluble man- ganese dioxide 15’’ is still present in the suspension 41. In this case, the hydrogen peroxide 14 ' consumes the free sulphuric acid 13 present in the suspension 41, while simultaneously forming manganese sulphate in the suspension 41 through a reaction between these two and manganese dioxide 15' , as was also case in dissolution. If, on the other hand, all the man- ganese dioxide 15’ of the manganese component 15 has already dissolved, the addition of hydrogen peroxide 14 ’ no longer raises the pH value of the suspension 41, but only dilutes it.

[0067] This is determined as steps 802, 803 and 805 by filtering a sample of the suspension 41 (802) , determining the pH of the sample (803) and determining the change in pH (805) . If it is found in step 805 that the pH of the suspension 41 no longer raises with the addition of hydrogen peroxide, then as step 806 manganese component 15 is added to the suspension 41. Addition- ally, if necessary, hydrogen peroxide 141is added to the sus- pension 41, as mentioned above as step 801, to raise the pH to the desired level, which is examined again as step 804. In other words, according to one embodiment, the method may in- clude optimising (adjusting) the pH value and manganese content of the second suspension 41 by adjusting the amounts of hydrogen peroxide 14 ' and manganese dioxide 15' in the second suspension

[0068] Use of peroxide 14* for pH adjustment is advantageous here because, for example, in the subsequent filtration 304 follow- ing sulphide precipitation 303 of the process solution 17 formed from the suspension 41, use of peroxide 14* as a pH adjuster guarantees the functionality of the filtration means 33, com- pared to, for example, sodium hydroxide, which would be a log- ical choice as a pH adjuster due to its affordability and availability. During the pilot phase tests of the method, the applicant has observed that sodium hydroxide causes problems in the form of clogging of the filter 33. In the process ac- cording to the invention, it forms a very fine precipitate that clogs the filter 33. This problem does not exist when hydrogen peroxide 14 / is used. An additional advantage of hydrogen per- oxide 14 ’ is that no excess components remain in the residual precipitate, unlike when sodium hydroxide is used, for example, which leaves a hydroxide precipitate.

[0069] According to an embodiment, the pH of the second suspension 41 is raised before separation of the solid matter 26. This is a preferred sequence of operations because when using the manga- nese component 15 to raise the pH of the suspension 41, any hydroxides formed during neutralisation remain in the larger (coarser) mass. In this case, they are more easily filtered out in step 505.

[0070] Also, the reactor 40 of the second acid dissolution 301 is arranged with cooling 37.2 for the duration of the dissolution process, since the process is strongly exothermic. In addition, cooling the reactor 40 to the temperature of 40 degrees or preferably even below reduces the significant gas formation caused by the hydrogen peroxide 14 ' . A cooler suspension 41 foams less, enabling faster dissolution. In addition, cooling 37.2 makes it is easier to see into the reactor 40 as mist does not form as easily. The reactor 40 may also have a breaking "whip" 39 or similar device fitted to the upper part of the mixer shaft 38 arranged to the reactor 40 to keep the foam layer rising under control. A further option for implementing anti-foaming in this acid dissolution, as in the previous one, may be the use of ultrasound (not shown) .

[0071] The second suspension 41 formed from the manganese component 15, i.e., manganese dioxide 15' , by the second acid treatment 301 is filtered as step 302 after the second acid treatment step 301. Filtration is carried out in order to separate the solid matter 26 remaining from dissolution from the second suspension 41. This solid matter 26 includes, for example, graphite 27, carbon black 28 and plastic shreds 29. The liquid fraction remaining after filtration 302 forms, in turn, the process solution 17 to be further processed. According to one embodiment, filtration 302 of the suspension 41, i.e. , separa- tion of the process solution 17 and the solid matter 26, can be carried out, for example, with a suitable filtration means 42. An example of such filtration means 42 may be again, for example, a frame filter 42 ’ .

[0072] As a result of filtration step 302 following the second acid dissolution step 301, the solid matter 2.6 remaining in the filtration means 42 can again be washed with the water 48.

[0073] Ordinary tap water can also be used for this step. The washing water 48 ' is then available as a base solution for the first acid dissolution 201. Once the process solution 17 has been completed, i.e. , after separation 302 of the insoluble solid matter fraction 26 fil- tered from the second suspension 41, metals and / or metal com- pounds are precipitated as step 303 from the process solution 17 containing manganese in sulphate form. This precipitation takes place using at least one sulphide source 19. In this case, this procedure can be called sulphide precipitation. For this purpose, the process solution 17 formed in filtration 302 is transferred to the sulphide precipitation reactor 34, which belongs to the apparatus 10. In the reactor 34, sulphide pre- cipitation takes place by adding at least one sulphide-contain- ing substance 19 as a reagent to the process solution 17 in order to precipitate metals and / or metal compounds from the process solution 17 as sulphide precipitation. During sulphide precipitation 303, the zinc and copper concentrations of the process solution 17 are affected by removing them using at least one sulphide source 19 added to the process solution 17.

[0074] Some examples of the sulphide sources 19 may be one or more of the following: (gaseous) hydrogen sulphide (H2S) , sodium sulphide (Na2S) 19' (dissolved in water) and / or possibly solid manganese sulphide (MnS) . Further processing of the sulphide precipitate 23 formed may be carried out by the zinc industry. The sulphide sources 19 are then preferably selected so that the further processing of the sulphide precipitate 23 formed does not require special, non-convent ional methods for treating metals originating from the chemicals used in sulphide precip- it at ion . In sulphide precipitation 303, the pH of the process solution 17 increases so that it is approximately pH 6 in the final solution. The zinc 46 and copper 21 still present in the process solution 17 precipitate in sulphide precipitation 303 as solid metal sulphides 22. Then they settle to the bottom of the process solution 17. These are present in the process solution

[0075] 17 before sulphide precipitation 303 takes place as the corre- sponding sulphates, i.e. , as zinc sulphate and copper sulphate. The toxic gaseous hydrogen sulphide formed during sulphide ad- dition is treated to be harmless using a suitable gas scrubbing

[0076] Preferably, the sulphide source 19 is sodium sulphide 19' . It has been found that sodium sulphide 19' is an easy chemical in this context due to its solubility and also due to its feeda- bility into the reactor 34. In step 303, the sulphide anion reacts with the soluble metal cations in the process solution 17. Then they form solid metal sulphides. These can then be separated from the sulphide-precipitated process solution 18 as a precipitate 23. Sodium sulphide 19' can be added to the process solution 17 as an aqueous solution.

[0077] Sodium sulphide 19' is a particularly preferred chemical tor use as a sulphide source 19 in this context, as the sodium it contains is also present in processing of the manganese sulphate solution 24 ' into the industrial end product . When the manga- nese sulphate solution 24 ' is subsequently precipitated into a battery chemical, this precipitation is hydroxide precipita- tion. Most often, the chemical used for this is sodium hydrox- ide. In this case, the sodium in the sodium hydroxide itself will in any case enter the manganese sulphate solution in the battery chemical process, and will remain in this solution. Therefore, the sodium originally contained in the manganese sulphate solution 24' manufactured by the method according to the invention, which originates from sulphide precipitation carried out in the method, is not a problem in practice, as it will enter anyway from the sodium hydroxide used in the manga- nese sulphate solution of the battery chemical process. The method also includes at least one separation step 304 fol- lowing sulphide precipitation 303 to reduce, preferably remove, zinc 46 and copper 2.1 from the sulphide-precipit ated process solution 18 as solid metal sulphides 22. During this separation step, the precipitate 23 containing the metal sulphides 22 is separated from the sulphide-precipitated process solution 18. Zinc 46 is present here mainly as zinc sulphide, but copper 21 is also present as a precipitated metal sulphide 22.

[0078] The manganese sulphate component 24 separated from the sulphide precipitate 23 as an aqueous solution 24 ' can be further diluted with water, for example to improve its frost resistance and / or to adjust the pH. The latter can be done, for example, with s u 1 p h u r i c a c i d . After sulphide precipitation 304, the finished manganese sul- phate component 24 formed from the sulphide-precipitated pro- cess solution 18 by filtration 305 is an aqueous solution 24 ’ . It is suitable for use as a fertiliser 24.1 or fertiliser component in agriculture, and / or as an industrial raw material 24.2. As an industrial raw material 24.2, the manganese sul- phate component 24 can be used in the battery industry, for example. The solution is suitable for this purpose if it com- plies with the concentration limits set for impurities. These are determined by analysing the solution. The analysis moni- tors, for example, the zinc, copper, magnesium and calcium concentrations in the solution. Manganese sulphate component 24, manufactured according to the invention, contains magnesium and calcium in a concentration of less than 25 mg / L. In this case, the manganese sulphate component 24 is, in terms of said substances, suitable as such as, for example, a raw material used in the battery industry. In other words, it is suitable for this without removing said substances from the manganese sulphate component 24.

[0079] The manganese content of the manganese sulphate component 24 may be 150 to 200 g / L, for example. The pH of the finished aqueous solution 24' for further processing / use may be in the value range of pH 3 to 6. The value depends on whether or not sulphide precipitation has been performed on the solution 24' .

[0080] Without sulphide precipitation, the pH of the aqueous solution is in the range of pH 3 to 4. In this case, it is at least suitable for agricultural use. In addition to agricultural use, the pH of the aqueous solution 24' , which is also suitable as an industrial raw material 24.2, and therefore sulphide pre- cipitated, may in turn be in the range of pH 5 to 6, because sulphide precipitation raises the pH value of the solution 24' . In this case, as an industrial raw material 24.2, for example the chemical consumption in hydroxide precipitation of the so- lution 24' is lower. Regarding the quantitative yields of the method, approximately three times as much zinc sulphate solu- tion 16 is formed as manganese sulphate solution 24 ’ .

[0081] Further processing of the graphite-containing solid matter 26 formed during the second acid dissolution 301 and separated from the second suspension 41 as step 302 can be carried out, for example, by separating any plastic shreds 29 from a mixture of graphite 27 and carbon black 28, After this, the graphite 27 is purified using peroxide dissolution, for example. The separated and purified graphite can then be used as a raw material in the battery and primary cell industry.

[0082] Figure 5 shows an example of an industrial -scale method accord- ing to the invention as a flow diagram, and Figure 4 shows a corresponding apparatus diagram that is slightly more detailed than the application example presented earlier. However, a per- son skilled in the art will understand that the more detailed implementation shown in the figures and in this application is only one specific application example of the method and also of the apparatus assembly according to the invention. The var- ious sub-assemblies of the method presented and their imple- mentation methods achieve different, even mutually independent, inventive advantages. Therefore, not all of the sub-assemblies and steps shown in Figure 5, for example, or their more detailed sub-steps shown in Figures 6 to 8, are absolutely necessary for implementing the concept according to the invention or achiev- ing the advantages. In Figure 5, with regard to the first acid dissolution 501 and the subsequent filtration 502 of the first suspension 25, i.e. , the separation, i.e. , formation, of the manganese component 15 therein, reference is made to Figure 2 and steps 201 and 202 therein .

[0083] As step 503, according to one embodiment, the manganese compo- nent 15 may be washed with water 43 prior to the second acid treatment step 504. Washing is performed to reduce the amounts of soluble zinc and calcium residues from the manganese component 15. According to one embodiment, the washing water 43 is at least partially purified water from which calcium and magnesium have been removed. This minimises the amounts of calcium and in addition also magnesium, which are typically present in tap water, in the remaining manganese component 15. Some possible examples for preparing the washing water 43, as well as the purified water 12 ' used in the second acid disso- lution, include ion exchange technology and reverse osmosis. According to one embodiment, the washing water 43 obtained from the filtered precipitate can be treated by reverse osmosis. In this case, the purified water flowing through the reverse os- mosis can be used for the next washing. The concentrated metal- containing solution remaining on the other side of the membrane can be returned in its concentrated form to the zinc solution 16 used for agricultural purposes, for example. In agricultural use, the components separated from the washing water are not harmful, but their presence there is even beneficial. Washing of the manganese component 15 can be carried out in a frame filter 32. ' , which is an example of the filtration means 32. A feed and recovery of the washing water 43 has been ar- ranged in connection with the filtration means 32. As previ- ously stated, the washing water 43' resulting from washing of the manganese component 15 can be utilised by using it in steps 501 in the dissolution process 501 of the black mass 11 as a base solution, instead of / in addition to the clean water 12.

[0084] In the presented embodiment, the filtration means 32 is a frame filter 32 ' . Washing of the manganese component 15 is carried out after the filter chambers of the frame filter 32 ' have been filled, i.e. , before the filter 32 ' is emptied. In this case, the washing water 43 flows through the precipitate cakes and rinses away the zinc and calcium mixed within the manganese component 15. The washing water 43' is collected in a washing water container downstream of the filter 32 ' . From there, it can then be returned as raw material for the next zinc disso- lution process 501. Once washing step of the manganese compo- nent 15 has been completed, the chambers of the filter 32 ' are opened and the precipitate cakes are dropped out of the filter 32 ' . This process is repeated until the entire mass solution batch, i.e. , the first suspension 25, has been filtered. In addition to the purified water 43, ordinary tap water can be used to wash the manganese component 15. Also this washing water can be directed to be the base solution of the first acid dissolution 501. One way to do washing is to initially perform one or more washings on the precipitate batch with ordinary tap water as a pre-rinse, followed by one or more final washings with purified water 43 as an additional rinse.

[0085] Regarding steps 504 to 506, i.e. , concerning dissolution of the moist, water-washed manganese component 15 remaining in the frame filter 32 ' , formation of the process solution 17 there- from and the possible subsequent sulphide; precipitation, ref- erence is made to Figure 3 and steps 301 to 303 therein, as well as the related explanation. It should also be noted in this context that the process solution 17, which mainly con- tains manganese sulphate, would in itself be suitable (with a pH adjusted to suit plants) as a fertiliser for agricultural use. Therefore, it does not necessarily require sulphide pre- cipitation and the subsequent separation of the sulphide pre- cipitate, which in the embodiment presented for the process solution 17 are carried out as some sub-steps of the method.

[0086] In this case, the method of manufacturing the manganese sul- phate component 24 from the black mass material 11 of used alkaline batteries 11 ' would only include the first acid dis- solution 201, which is carried out on the black mass material 11 in the presence of water 12 and sulphuric acid 13 to dissolve the metallic zinc 20 from the black mass material 11 into the zinc sulphate component 16; the first filtration 202 to sepa- rate the zinc sulphate component 16 formed in the first disso- lution from the manganese component 15 remaining from the first acid dissolution 201; the second acid dissolution 301, which is carried out on the manganese component 15 in the presence of purified water 12 ’ , sulphuric acid 13 and at least one reducing agent 14 to form the suspension 41 from the manganese component 15, and the second filtration 302 to remove the in- soluble solid matter fraction 26, such as, for example, graph- ite 27, carbon black 28 and plastic 29, from the suspension 41 to form the process solution 17. In other words, the method would then be carried out without steps 303 and 304 of Figure 3 and steps 506 and 507 of Figure 5.

[0087] For step 507, i . e . , separation of the sulphide precipitate 23 from the sulphide-precipitated process solution 18, reference is made to Figure 6. In one embodiment, according to the flow diagram shown in Figure 6, step 507, i.e., separation of the sulphide precipitate 23 from the sulphide-precipitated process solution 18, can be divided into several sub-steps 601 to 603. One possible combination of these is shown as an example below. According to one embodiment, separation of the precipitate 23 containing metal sulphides 22 from the sulphide-precipitated process solution 18 is initiated, for example, by settling as step 601. This process can also be referred to as clarification of the sulphide-precipitated process solution 18. In this case, settling / thickening of the sulphide-precipitated process solu- tion 18 is carried out under suitable conditions by gravity. Here, the fine-grained and heavy sulphide precipitate 23 set- tles at least to the lower part of the solution volume and, most preferably, to the bottom of the container. Settling is preferably carried out in a conical container / thickener . In this case, the precipitate 23 accumulates in the bottom cone of the container and is more easily separable from there as step 602.

[0088] Clarification is followed by step 603, which involves separa- tion of the clearer solution layer from the sett ling / thickening container at the upper part of the solution volume. According to one embodiment, for example, filtration can be used here with suitable filtration means 33. According to one embodiment, it can be, for example, a frame filter 33' . The sulphide pre- cipitate 23 separated from the sulphide-precipitated process solution 18 can be used, for example, as a raw material in the zinc industry, thus forming a product component in its own right.

[0089] According to one embodiment, if it is desired to produce zinc- and manganese-containing fertiliser solution 24.1 ' separately for agricultural use, the formed sulphate solutions 16, 24 ' can be combined at the appropriate ratio. An example of this is shown in Figure 7. For this purpose, according to one embodi- ment, the method includes, as step 701, combining the manganese sulphate component 24, 24.1 and the zinc sulphate solution 16.1 obtained from the filtration 202, 502 following the first acid treatment step 201, 501, to form a zinc-- and manganese-contain- ing fertiliser solution 24.1 ' for fertiliser use. The mixture solution formed can be diluted with water if the concentrations are too high. As a specific example of the concentrations, 60 g / L of Zn and 67 g / L of Mn, can be mentioned. Also in here, it is advantageous if the black mass material 11 is water-washed before the first dissolution process 201, 501 in order to reduce its potassium and chlorine content. In particular, with a lower amount of potassium in the solution 16, the end product is more stable in terms of its storability. In addition, this embodiment of the method also includes, as step 702, neutralisation of the fertiliser solution 24.1'with one or more neutralising chemicals 36. By this process, the pH value of the solution is adjusted to be suitable for plants.

[0090] In addition, neutralisation also removes iron from the solu- tion. In this case, neutralisation renders the solution suita- ble for use in aqueous form in agriculture as a spray applica- tion. Some examples of neutralising chemicals 36 are zinc oxide (ZnO) , manganese oxide (MnO) and / or sodium hydroxide (NaOH) .

[0091] Black mass can also be used for neutralisation at this stage. The pH value of the solution before neutralisation may be pH 0.5 to 2, more specifically 0.5 to 1.5. After neutralisation, the pH value is at least pH 2.5, preferably pH 3 to 4.5. In this case, iron 47 is also precipitated out and later removed in filtration 703 following neutralisation 702. The iron 47 here originates from the black mass 11. It is mixed with fine- grained steel dust left over from crushing the batteries. Iron 47 is in the solution in the form of sulphate. As a result of precipitation, iron 47 exists in the form of hydroxide, which can be filtered out of the solution.

[0092] Using the black mass 11, which contains manganese dioxide 15’ and hydrogen peroxide 14 ' to decompose it, for pH adjustment at this stage, is advantageous because the zinc and potassium contained in the black mass 11 also contribute to raising the pH of the solution. As containing zinc compounds soluble in sulphuric acid and potassium hydroxide, both of these neutral- ise the acid and raise the pH. In other words, in addition to the mere mutual reaction between manganese, acid and peroxide

[0093] 14*, other reactions occur here that raise the pH value of the fertiliser solution.

[0094] Finally, as step 703, the neutralised fertiliser solution 24.1 ' is filtered 703 in order to remove the iron 47 precipitated during neutralisation step 702. in addition, at the same time solid zinc and manganese hydroxides are removed. These are also formed when the pH increases.

[0095] According to an exemplary calculation, if there is, for exam- ple, 100 g of dry black mass 11, then it contains 8.01 g of graphite-containing residual precipitate. Of the residual pre- cipitate, 94% comprises substances other than zinc and manga- nese. In this case, the residual precipitate contains 7.53 g of a mixture of graphite 27 and plastic shreds 29. In other words, in this case, the black mass 11 contains 7.5% (by weight) of this mixture relative to the original amount of black mass 11.

[0096] In addition to the method described above, another object of the invention is an apparatus 10 for the production of manganese and zinc sulphate components 16, 24 by acid treatment 101, 103 from the zinc- and manganese-cont aining black mass material 11 of used alkaline batteries 11 ' . The apparatus 10 includes dis- solution means 31 ' , 40 ' for forming suspensions 25, 41 by acid treatments 101, 103. The acid treatments 101, 103 are now acid dissolutions 201, 301. In the presented embodiment, the first acid dissolution 201 is arranged to be carried out with the first dissolution means 31 ' . This now includes the dissolution reactor 31 with its accessories. The dissolution reactor 31 is now adapted to form the first suspension 25 from the black mass material 11 in the presence of water 12 and sulphuric acid 13. The second acid dissolution 301 is arranged to be carried out by the dissolution reactor 40 with its accessories, which forms part of the dissolution means 40 ' . This dissolution reactor 40 is now adapted to form the second suspension 41 from the man- ganese component 15 formed from the black mass material 11 in the first acid dissolution 201. This takes place in the dissolution reactor 40 in the presence of purified water 12 ’ , sulphuric acid 13 and at least one reducing agent 14. The dissolution reactor 40 for the second acid dissolution 301 may be a separate reactor unit or may be shared with the reactor 31 for the first acid dissolution 201.

[0097] Furthermore, the apparatus 10 includes the first and second separation means 32*, 42*. The first separation means 32* now comprise the filtration means 32, such as, for example, the frame filter 32 ' . The first separation means 32* now serve to separate the zinc sulphate component 16 from the manganese component 15 formed during separation in the first suspension 25. The second separation means 42* now comprise the filtration means 42, such as, for example, the frame filter 42 ' . The second separation means 42* now serve to separate the solid matter fraction 26, such as, for example, graphite 27, carbon black 28 and plastic 29, from the process solution 17 formed during separation in the second suspension 41. The separation means 32*, 42* can include, in addition to the filtration means 32, 42, also the storage, feeding and recovery of the washing waters

[0098] 43, 48 used in connection with the filtration means 32, 42. These are intended for washing the precipitates and further feeding them, for example, to the first acid dissolution 201, 501 as its base solution.

[0099] In addition, the apparatus 10 comprises possible precipitation means 34 ' for precipitating metals and / or metal compounds from the process solution 17 by using at least one sulphide source 19. The precipitation means 34'comprise the sulphide precipi- tation reactor 34 with its accessories. They comprise, for example, the feed and container for at least one sulphide source 19, as well as the thickener and settler container (not shown) .

[0100] Furthermore, the apparatus 10 may comprise possible third separation means 33* for separating from the process solution 17 the precipitate 23 containing metal sulphides 22. The third separation means 33* may comprise the filtration means 33, such as, for example, the frame filter 33' . The manganese sulphate component 24 treated and formed by the apparatus 10 in accord- ance with the method is suitable for use as a fertiliser 24.1 in agriculture, or as an industrial raw material 24.2. Addi- tionally, the zinc sulphate component 16 formed by the appa- ratus 10 is suitable for use as a raw material 16.2 in industry, especially in the zinc industry.

[0101] The apparatus 10 does not necessarily comprise, i.e. , it may be without, essential means for washing the black mass 11 with water before its acid treatment step 101, more specifically before its first acid dissolution 201. On the other hand, as stated above, according to another embodiment, water washing may also be possible. With regard to the apparatus for this, reference is made to the above description and Figure 10. As is clear from the above description of the method, the apparatus 10 can also be implemented, for example, without the precipitation means 34 ’ and associated separation means 33* for forming the sulphide precipitate 23 and removing it from the process solution 17. Even without these, the end product, i.e., the process solution 17, obtained from the second acid disso- lution 301 with its associated steps, is suitable for use as a fertiliser for agriculture as it is, with its pH adjusted to be suitable for plants. However, the more preferred embodiment of the apparatus 10 is that shown in the figures. In this case, with the same single apparatus assembly and also with the same method, it is possible, with very minor changes, to produce in the same process plant components 16.1, 24.1 or the end product for agricultural use, such as, for example, a fertiliser (for example without sulphide precipitation) , as well as components 16.2, 24.2 for industrial needs (production of manganese sul- phate 24 with sulphide precipitation) .

[0102] Another object of the invention is also a sulphate component combination, i.e. , sulphate components. The sulphate component combination, i.e. , sulphate components, is formed from the black mass material 11 of used alkaline batteries 11 ' by the acid treatment 101, 103. The acid treatment 101, 103 is at least one acid dissolution 201, 301. Of these, in the first acid dissolution 201, the black mass material 11 is dissolved 101, 201 in the presence of water 12 and sulphuric acid 13 to form the first suspension 25. The solid manganese component 15 is formed from the first suspension 25 by separating therefrom an agueous zinc sulphate component 16 containing at least zinc 20. This formed zinc sulphate component 16 in aqueous solution form subsequently forms one of the sulphate components of the combination, which is suitable for use as a fertiliser 16.1 or as a fertiliser component in agriculture or as a raw material 16.2 in industry, more specifically in the zinc industry.

[0103] In the second acid dissolution 301, the manganese component 15 is dissolved 103, 301 in the presence of purified water 12' , sulphuric acid 13 and at least one reducing agent 14 to form the second suspension 41. The process solution 17 containing manganese sulphate is formed from the second suspension 41 by separating the solid matter fraction 26 therefrom. This solid matter fraction 26 contains at least graphite 27, carbon black 28 and plastic 29. Metals and / or metal compounds are precipi- tated 105, 303 from the process solution 17 by using at least one sulphide source 19. These comprise one or more of the following: zinc 46, copper 21. The precipitate 23 containing metal sulphides 22 is separated 106, 304 from the process so- lution 17. The manganese sulphate component 24 formed thereaf- ter in the form of an aqueous solution constitutes one of the sulphate components of the combination, which is suitable for use as a fertiliser 24.1 in agriculture, or as an industrial raw material 24.2. Still other objects of the invention are uses of the sulphate components 16, 24 manufactured by the method. One of the first of these uses is the use of the zinc sulphate component 16.1, 16.2, which is obtained in the aqueous solution form using the method according to the invention, as shown in Figure 2. This zinc sulphate component 16.1, 16.2 is used in manufacturing of the end product selected from fertiliser and zinc.

[0104] Another of these uses is the use of the manganese sulphate component 24.1, 24.2, which is obtained in the aqueous solution form using the method according to the invention. This manga- nese sulphate component 24.1, 24.2 is used in manufacturing of the end product selected from fertiliser and battery chemical .

[0105] A person skilled in the art will understand that also the solid matter fraction 26 and its sub-components as well as the metal sulphide precipitate 23 and its sub-components, both of which are manufactured using the method according to the invention, can be used as raw material in processes in which the substances contained therein are, for example, separated into their own end products or are further processed into other products con- taining them.

[0106] Furthermore, the invention may include products containing the manganese sulphate component 24 and / or the zinc sulphate com- ponent 16, both of which have been obtained by the method according to the invention.

[0107] The process according to the invention does not produce any wastewater. The water circulation in the process is closed. All process washing waters and residues from previous solvent batches can be returned to the process or further processed into products. It should be understood that the above description and the accompanying drawings are intended only to illustrate the pre- sent invention. Therefore, the invention is not limited to the above embodiments, but many different variations and modifica- tions of the invention will be apparent to a person skilled in the art, which are possible within the scope of the inventive concept defined by the appended claims.

Claims

CLAIMS1. A method for manufacturing a manganese sulphate component from black mass material (11) of used alkaline batteries (11' ) , the method comprising:- a first acid dissolution (201) performed on the black mass material (11) in the presence of water (12) and sul- phuric acid (13) to dissolve zinc (20) , potassium (30) and chlorine (35) from the black mass material (11) into a zinc sulphate component (16) ,- a first filtration (202) to separate the zinc sulphate component (16) from a manganese component (15) remaining from the first acid dissolution (2.01) ,- a second acid dissolution (301) performed on the manga- nese component (15) in the presence of purified water(12' ) , sulphuric acid (13) and at least one reducing agent(14) to form a suspension (41) from the manganese component(15) ,- a second filtration (302) to remove an insoluble solid matter fraction (26) , such as, for example, graphite (27) , carbon black (28) and plastic (29) , from the suspension (41) to form a process solution (17) ,- a sulphide precipitation (105, 303) and at least one subsequent separation step (106, 304) to remove zinc (46) and copper (21) from the formed process solution (17) , after which the resulting manganese sulphate component (24) is suitable for use as a fertiliser (24.1) or as a fertiliser component in agriculture, or as an industrial raw material (24.2) .

2. The method according to Claim 1, characterised in that- in the sulphide precipitation (105) , metals and / or metal compounds, comprising one or more of the following: zinc (46) , copper (21) , are precipitated (303, 506) from theprocess solution (17) using at least one sulphide source (19) ,- a precipitate (23) containing metal sulphides (22) is separated (106, 304, 507) from a sulphide-precipitated process solution (18) .

3. The method according to Claim 1 or 2, characterised in that the first acid dissolution (201) comprises optimising a feed of sulphuric acid (13) , at least at the beginning of the acid dissolution (201)- to optimise a course of a reaction between an alkaline potassium hydroxide of the black mass material (11) and the sulphuric acid (13) in formation of potassium sulphate and water, and / or - to slow down formation of hydrogen when the metallic zinc (20) of the black mass material (11) dissolves in the sulphuric acid (13) .

4. The method according to any one of Claims 1 to 3, charac— terised in that at the beginning of the first acid dissolution(201) , 5 to 10% of the total amount of sulphuric acid (13) is fed at a lower volumetric flow rate compared to the feed of the remaining amount of sulphuric acid to reduce a foaming of the zinc sulphate solution (16) formed during the first acid dis- solution (201) ,5. The method according to any one of Claims 1 to 4, charac- terised in that the method comprises washing step (503) of the manganese component (15) prior to the second acid treatment step (103) with purified water (43) to reduce soluble zinc, magnesium and calcium residues from the manganese component(15) .The method according to any one of Claims 1 tocharacterised in that the method comprises- combining (701) the manganese sulphate component (24) and the zinc-containing sulphate solution (16.1) obtained from filtration (202) following the first acid treatment step (201) to form a zinc- and manganese-cont aining fer- tiliser solution (24.1') for fert rinser use,- neutralising (702) the fertiliser solution (24.1' ) with one or more neutralising chemicals (36) , filtering (703) the neutralised fertiliser solution (24.1 ' ) to remove precipitated iron (47) .

7. The method according to any one of Claims 1 to 6, charac- terised in that the method comprises a washing process (101 ' , 500 ’ ) of the black mass material (11) in a closed washing water circulation (49) prior to the first acid dissolution (101, 201, 501) to reduce an amount of potassium (30 ’ ) and chlorine (35’ ) in the black mass material (11) .

8. The method according to Claim 7, characterised in that the washing process (101'' , 500' ) of the black mass material (11) is carried out by increasing in a controlled manner a total amount (50) of a washing water (51) and concentrating the wash- ing water (51) by- washing (901) a batch (11.1) of the black mass material (11) with the washing water (51) ,- separating (902) the washing water (51' ) from the black mass material (11) ,- rinsing (903) the black mass material (11) with a smaller amount of clean water (52) compared to the amount of the washing water (51) used in the washing (901) ,- separating (904) a rinsing water (53) from the black mass material (11) ,- combining (905) the rinsing water (53) and the washing water (51' ) to form the washing water (51) to be used inwashing (901) of the next batch (11.2) .

9. The method according to Claim 7 or 8, characterised in that in the amount of water (12) introduced into the first acid dissolution (201, 501) , a moisture originating from the washing process (101', 500 ’ ) of the black mass material (11) is taken into account.

10. The method according to any one of Claims 7 to 9, charac— terised in that the washing process (101" , 500" ) is carried out on the black mass material (11) , the zinc sulphate solution (16) of which, formed in the first acid dissolution (201, 501) , further use is in industry, where manganese is precipitated from the zinc sulphate solution (16) with ozone.

11. The method according to any one of Claims 7 to 10, charac- terised in that an amount of clean rinsing water (52) used to rinse the mass batch (11.1, 11.1, 11. n) is 5 to 25% (by weight) of the amount of the washing water (51) to be concentrated used for washing the mass batch (11.1, 11.1, ll.n) .

12. The met" hod according to any one of Claims 1 to 6, charac- terised in that the first acid treatment step (101) is carried out without separate water washing of the black mass material13. The method according to any one of Claims 1 to 12, charac- terised in that the precipitate (23) containing metal sulphides (22) is separated (304) from the sulphide-precipitated process solution (18) by means of clarification (601) and subsequent filtration (603) .

14. The method according to any one of Claims to 13, charac- terised in that the sulphide source (19) is one or more selectedfrom the following: sodium sulphide (19' ) , hydrogen sulphide and / or manganese sulphide.15, The method according to any one of Claims 1 to 14, charac- terised. in that the sulphide source (19) is sodium sulphide(19') .

16. The method according to any one of Claims 1 to 15, charac- terised in that the reducing agent (14) is one or more selected from the following: peroxide (14*) , citric acid and / or one or more sugars .

17. The method according to any one of Claims 1 to 16, charac- terised in that the reducing agent (14) is peroxide (14*) , such as, for example, hydrogen peroxide (14 ' ) .18, The method according to any one of Claims 1 to 17, charac- terised in that the water (12) of the first acid dissolution (201) is one or more of the following, comprising: - tap water,- washing water (43' ) of the manganese component (15) separated from the first suspension (25) , and / or- washing water ( 48 ’ ) of the solid matter fraction (26) to be separated from the second suspension (41) .

19. The method according to any one of Claims 1 to 18, charac- terised in that the manganese component (15) formed during the first acid dissolution (201, 501) is manganese dioxide (15' ) . 20, The method according to any one of Claims 1 to 19, charac- terised in that a pH value and manganese content of the second suspension (41) and / or the process solution (17) are adjusted by an amount of peroxide (14*) , such as, for example, hydrogen peroxide (14 ' ) , and manganese dioxide (15' ) in the secondsuspension (41) and / or process solutution (17).

21. The method according to any one of Claims 1 to 20, charac- terised in that the method is carried out without the sulphide precipitation (105, 303) of the process solution (17) formed from the suspension (41) using at least one sulphide source (19) , and without the subsequent separation step (106, 304) of the precipitate (23) containing metal sulphides (22) from the process solution (17) , whereby the formed manganese sulphate component (24) is suitable for use at least as a fertiliser (24.1) in agriculture.

22. The method according to any one of Claims 1 to 21, charac- terised in that the manganese sulphate component (24) contains magnesium and calcium at a concentration of less than 25 mg / L, whereby the manganese sulphate component (24) is, with respect to these substances, suitable as such for use as a raw material in the battery industry without a need to remove these sub- stances .

23. The method according to any one of Claims 1 to 22, charac- terised in that the first acid dissolution (201, 501) comprises decomposing a foam with one or more defoamers at least in an initial step of the acid dissolution (201, 501) , the defoamer preferably being biodegradable.

24. The method according to any one of Claims 1 to 23, charac- terised in that the first acid dissolution (201, 501) comprises cooling to optimise a temperature to 30 to 50 °C.

25. The method according to any one of Claims 1 to 24, charac- terised in that the second acid dissolution (301, 504) comprises cooling to reduce the gas formation caused by the hydrogen peroxide ( 14') .

26. An apparatus for manufacturing manganese and zinc sulphate components from a black mass material (11) of used alkaline batteries (11* ) by acid treatment (101, 103) , the apparatus (10) comprising- dissolution means ( 31 ' , 40' ) to form suspensions (25, 41) by acid treatments (101, 103) , being acid dissolutions (201, 301) , first from the black mass material (11) in a presence of water (12) and sulphuric acid (13) , and then from a manganese component (15) formed from the black mass material (11) in a presence of purified water (12' ) and sulphuric acid (13) and at least one reducing agent (14) ,- first and second separation means (32*, 42*) to separate first said zinc sulphate component (16) from the manganese component (15) formed during a separation in a first sus- pension (25) , and then to separate a solid matter fraction (26) , such as, for example, graphite (27) , carbon black (28) and plastic (29) , from a process solution (17) formed during a separation in a second suspension (41) , - optional precipitation means (34 ' ) to precipitate metals and / or metal compounds from the process solution (17) us- ing at least one sulphide source (19) ,- optional third separation means (33*) to separate a precipitate (23) containing metal sulphides (22) from the process solution (17) , after which said manganese sulphate component (24) formed is suitable for use as a fertiliser(24.1) in agriculture, or as an industrial raw material(24.2) , while the zinc sulphate component (16) formed is suitable for use as a raw material (16.2) in industry, especially in a zinc industry.

27. The apparatus according to Claim 26, characterised in that the third separation means (33*) comprise a filtration means (33) , such as, for example, a frame filter (33' ) .

28. A sulphate component combination formed from a black mass material (11) of used alkaline batteries (11 ' ) by acid treat- ment (101, 103) , comprising at least two acid dissolutions (201, 301) , and wherein- the black mass material (11) is dissolved (101, 201) in a presence of water (12) and sulphuric acid (13) to form a first suspension (25) ,- a solid manganese component (15) is formed from the first suspension (25) by separating therefrom a solution-form zinc sulphate component (16) containing at least zinc (20) , potassium (30) and chlorine (35) , after which this formed aqueous solution form zinc sulphate component (16) is suitable for use as a fertiliser (16.1) in agriculture, or as a raw material (16.2) in industry, especially in a z i n c i n du s t r y ,- the manganese component (15) is dissolved (103, 301) in a presence of purified water ( 12 ' ) , sulphuric acid (13) and at least one reducing agent (14) to form a second suspension (41) ,- a manganese sulphate-containing process solution (17) is formed from the second suspension (41) by separating therefrom a solid matter fraction (26) containing at least graphite (27) , carbon black (28) and plastic (29) , - metals and / or metal compounds, comprising one or more of the following: zinc (46) , copper (21) , are precipitated (105, 303) from the process solution (17) using at least one sulphide source (19) ,- a precipitate (23) containing metal sulphides (22) is separated (106, 304) from the process solution (17) , after which a manganese sulphate component (24) formed in a form of aqueous solution is suitable for use as a fertiliser (24.1) in agriculture, or as an industrial raw material ( 24.2 ) .

29. Use of a manganese sulphate component, wherein the manga- nese sulphate component (24) in aqueous solution form is ob- tained by the method according to any one of Claims 1 to 25, as a component (24.1) in the manufacture of a fertiliser end product, or as an industrial raw material (24.2) .

30. Use of a zinc sulphate component, wherein the zinc sulphate component (16.1, 16.2) in aqueous solution form is obtained by the method according to any one of Claims 1 to 25, as a compo- nent (16.1, 16.2) in the manufacture of an end product selected from fertiliser and zinc.

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