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    • 专利摘要:
    Hereby a slag is disclosed which, based on the dry matter and expressed as the total of the metal present as the elemental metal and the presence of the metal in an oxidised state, comprises: a) at least 7% by weight and at most 49% by weight % iron, Fe, b) at least% by weight and at most 44% by weight of silica, SiO2, and c) at least 2.0% by weight and at most% by weight of calcium oxide, CaO, characterized in that the slag comprises on the same basis : d) a maximum of 1.00% by weight of zinc, Zn, and e) a maximum of 0.3% by weight of lead, Pb. An improved object comprising the slag, a process for the production of the slag, and a number of uses of the slag are also disclosed, wherein the slag up to at most 1.50% by weight of zinc and to at least 1.0% by weight of CaO may include.
    公开号:BE1024028B1
    申请号:E2016/5223
    申请日:2016-03-30
    公开日:2017-11-06
    发明作者:Mathias Chintinne；Charles Geenen；Dirk Goris
    申请人:Metallo Belgium；Metallo Chimique；
    IPC主号:
    专利说明:

    IMPROVED SNAIL FROM THE PRODUCTION OF NON-
    FERROMETALS
    Field of application of the invention
    The present invention relates to the production of non-ferrous metals, such as copper, based on primary sources, i.e. fresh ore, based on secondary base material, also referred to as recyclable materials, or based on combinations thereof. Recyclable materials can be, for example, by-products, waste materials and materials with an expired usage cycle. More in particular, the invention relates to an improved slag, as a by-product of such production of non-ferrous metals.
    BACKGROUND OF THE INVENTION
    The available basic materials for the production of non-ferrous metals generally contain a multitude of metals. Due to the strict purity requirements that non-ferrous metals must meet in high volumes for most applications, the various metals in the production process must be separated from each other. The processes for the production of non-ferrous metals generally comprise at least one and usually a plurality of pyrometallurgical process steps in which metals and metal oxides are both in a molten, liquid state, and in which the metal oxides can be separated from the molten metal phase by gravity as a separate liquid slag phase. The slag phase is usually withdrawn from the process as a separate stream, and this separation can lead to the production of a slag as the by-product of metal production.
    The non-ferrous metals can be produced on the basis of fresh ore as a starting material, also called primary sources, or on the basis of recycled materials, also called secondary basic materials, or on the basis of a combination thereof.
    Over the years, the recovery of non-ferrous metals based on secondary basic material has become an activity of paramount importance. The recycling of non-ferrous metals after use has become a crucial factor in the industry, due to the continued high demand for such metals and the decreasing availability of high-quality fresh metal ores. Also the processing of secondary base materials usually involves the use of pyrometallurgical process steps, such as melting furnaces, which generate slag as a by-product.
    Snail mainly contains metal oxides that are liquid at high temperatures. In melting furnaces for non-ferrous metals, for example melting furnaces for copper, lead or zinc, the metal oxides are in the liquid state and have a lower density than the liquid molten metals. The metal oxides can then be separated from the metals by gravity. The slag is usually cooled and crushed / sorted by size, and can be used in the production of concrete, as a substitute for stones and gravel, as an aggregate in road construction, and if they are finely ground, they are also interesting due to their exceptional hardness for use as blasting sand or blasting grit.
    Some substances that can be found in the known slag products from the prior art are considered to be harmful to the environment. Especially lead, and to a certain extent also zinc, are important examples of such undesirable substances. Zinc and lead are both metals that can escape from the slag through leaching; the presence of significant concentrations thereof excludes many uses of the slag product, especially in economically attractive applications, and can make the dumping of these slag on waste sites much more complex and difficult, since they are usually considered "hazardous waste". Whether their use is accepted in certain applications is often determined by testing the leaching behavior of the snails. Elements such as Pb and Zn are prone to leaching and can lead to a certain snail failing such an acceptance test.
    Moreover, the Pb content of a product or composition can limit its use, since lead has caused concern because of a possible toxic effect on reproduction. In some jurisdictions, the classification limits for the relevant CLP regulations (classification, labels, packaging) are currently under discussion, with the aim of establishing a specific classification limit (SCL) for Pb and Pb-containing products. Possibly the limit would be set very low, even as low as 0.03% by weight Pb. The commercially available slags that originate from the production of non-ferrous metals have a Pb content that is generally considerably higher than the already much higher content of 0.3% by weight. Where this CLP regulation will come into effect, the slags from non-ferrous metal production will have to meet additional labeling requirements, making the commercialization and acceptance of these slags difficult or even impossible for many of the current applications. and may also increase the burden of certain forms of waste disposal, such as landfill. In this context, it should be noted that certain end uses, such as the use of slag as blasting sand, mean that the waste by-product of the blasting operation, including the slag, must usually be dumped as landfill waste. The lead content of the slag can therefore be a serious obstacle to the use of the slag in some of the current valuable end applications, such as sandblasting.
    In S. Monosi et al, 'Non Ferrous Battle as Cementitious Material and Fine Aggregate for Concrete', presented during the 3rd CANMET / ACI International Symposium on Sustainable Development of Cement and Concrete, 2001, a snail was reported that 4.77 weight% Zn and 2.03% Pb, and which was tested as a constituent for concrete, to replace Portland cement and / or natural sand. The slag also contained 14.65% by weight of SiC> 2. Leaching tests showed that zinc and lead were released, but at values that remained below the 1998 Italian legal standard.
    However, the inventors have found that the presence of zinc in the slag, at the levels used in the work of Monosi, significantly slows the curing of concrete and other structural compositions, such as cement forms. This effect on the curing speed is an impediment to the use of slag containing substantial amounts of Zn as cementitious material and / or as aggregate in concrete or cement forms.
    Therefore, there is still a need for a slag resulting from the production of non-ferrous metals that represents a lower risk of leaching metals, in particular a slag with a lead content and / or a zinc content low enough to prevent any cause. give cause for concern about leaching, such that the snail can be acceptable for use in economically attractive end applications, and can be upgraded through that use.
    In addition, there is still a need for a slag that results from the production of non-ferrous metals and has a Pb content of less than 0.03% by weight, which would therefore have the advantage of being exempt from additional label requirements under the possible impending CLP regulation in certain jurisdictions.
    Furthermore, there is still a need for a slag that results from the production of non-ferrous metals and that does not entail the disadvantage of slowing the cure speed of concrete or cement containing this slag as a cementitious material or aggregate.
    U.S. Pat. No. 4,571,260 discloses a process for recovering the metal values of materials containing tin and / or zinc, in particular of materials comprising lead, by heating and melting the starting materials in a Kaldo converter. , together with coke as a reducing agent and a large amount of limestone and iron oxide as a flow agent, in a sequential sequence of a batch process that begins with an oxidation step. In at least one subsequent reduction step, zinc and, if present, tin can be smoked and recovered from the furnace exhaust gas. The large amount of flow agents is needed to give the slag a viscous consistency at the chosen reduction temperatures, such that the coke can be kept in suspension in the slag with intensive shaking or stirring, in particular in the later part of the reduction period . The 8 tons of slag that remained as a residue in the only example of US 4,571,260 contained 1.5% Pb and 1.0% Zn. This slag still contains amounts of zinc and lead that can give rise to concerns about the leaching of metal. The final slag in US 4,571,260 was dumped as waste.
    Patent WO 2014/046593 A1 discloses an improved method for recovering vaporizable metals and / or metal compounds from molten slag, using a submerged jet called high energy plasma gas. The advantage is that high volatilization rates can be achieved far below the previously required average slag temperatures. This entails the advantage of a reduced energy requirement, a reduced need for slag formers or fluxes, and thereby also a reduced final amount of slag, and a reduced wear of refractory materials. In the examples, mixtures of 1000 kg of dust from an electric arc furnace (EAF), 100 kg of coke and 100 kg of sand are treated to produce slag containing only 1.3% by weight of ZnO, which corresponds to 1.04% by weight Zn, and up to 26.0 weight% SiO 2. The slag produced in WO 2014/046593 A1 still contains enough zinc to cause concern about the leaching of metal. In WO 2014/046593 A1 there is also no mention of possible beneficial effects of the snails in question when they are used in certain end applications.
    Patent WO 2013/156676 A1 discloses a method for processing slag from the non-ferrous metallurgy, for converting it into a pulverized material suitable for applications other than dumping. The process includes a reduction step in which iron in the slag must be reduced to a sufficient extent for the metal phase to contain enough iron to make the metal phase magnetic. The method involves sufficient mixing to keep the metal droplets in the molten slag and to prevent the droplets from settling on the bottom of the furnace. The method further comprises evaporating zinc, lead, arsenic and cadmium from the mixture. The generated slag-metal mixture that remains in the reduction furnace is drained and cooled. The cooled mixture is crushed and ground to a grain size of 20 µm - 15 µm. Metals and any sulphides are separated from the slag, for example by magnetic separation. By way of example, the processing of slag containing 4% Zn or 2.4% Zn is described. The slag used as a starting material is treated with silicon carbide (Examples 1 and 2) or with carbon (Example 3) as a reducing agent. In Example 3, nitrogen was bubbled through the mixture after the reduction. The resulting metal alloy and slag mixtures contained high levels of Fe, less than 1.00 weight% Zn, to only 0.08 weight% Pb, and either at least 45 weight% SiO 2 or at most 1.3 weight% CaO. Metal inclusions were found in the slag that contained both copper and iron. The slag-metal mixtures of Examples 1 and 3 were crushed and subjected to magnetic separation to separate the metals out. Only in Example 3 was the composition of the final remaining non-magnetic slag recorded, and this composition was surprisingly similar to the composition recorded for the mixture of metal alloy and slag before the metal phase was separated out. The final slag is rich in SiO 2 and contains no more than 1.4% CaO. It is proposed in WO 2013/156676 to use the remaining slag in road construction, in applications as filling soil, or as a component for concrete and cement. In WO 2013/156676 no mention is made of a potential active function of the slag described in the construction industry and / or for inorganic polymers.
    There is still a need for upgrading the slag as a by-product from the production of non-ferrous metals produced as a by-product in the processing of primary and secondary base materials, using an easy and simple process, to a quality that is acceptable with regard to possible leaching of metal, and which is in addition capable of making an active, technical and therefore economically interesting contribution in the form of a further use of the slag without the disadvantages described above.
    The present invention has for its object to eliminate the above problem from at least alleviate, and / or to provide improvements in general.
    Summary of the invention
    According to the invention, a slag is provided, a process for producing the slag, and applications of the slag as defined in any of the appended claims.
    In one embodiment, the invention provides a slag, as a by-product from the production of non-ferrous metals, which on a dry product basis comprises the presence of a metal expressed as the total of the elemental metal present and the presence of the metal in an oxidized state, preferably as an oxide form of the metal, by itself and / or in combination with other metals: a) at least 7% by weight and at most 49% by weight of iron, Fe, b) at most 1, 30% by weight of copper, Cu, c) at least 24% by weight and at most 44% by weight of silica, SiO2, and d) at least 2.0% by weight and at most 20% by weight of calcium oxide, CaO, the slag on the same basis comprises: e) at most 1.00% by weight of zinc, Zn, and optionally at least 0.10% by weight of Zn, f) at least 0.40% by weight and at most 2.5% by weight of magnesium oxide, MgO, g) at least 4.0% by weight and at most 12% by weight aluminum oxide, Al2 O2 and g) 0.100% by weight of lead, Pb, and optionally at least 0% by weight of Pb.
    In one embodiment, the present invention provides an object which comprises as a binder and / or as an aggregate the slag of the present invention, wherein the slag comprises at most 1.50% by weight of zinc, Zn.
    The inventors have determined that the slag of the present invention is able to act as a binder in a geopolymer system. The inventors have further established that the slag according to the present invention can also form a very suitable aggregate for use in such a geopolymer system, and that its use as an aggregate furthermore ensures extremely good properties of the products produced with such a geopolymer system .
    In another embodiment, the invention provides a process for the production of a second slag according to the present invention, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, the process comprising the comprises the following steps: • providing a first slag containing at least one metal selected from zinc, lead and combinations thereof, • placing the first slag in a volatilizer or “fumer”, • the volatilizing olf “fumen” of at least one metal selected from zinc, lead and combinations thereof, from the first slag, using at least one plasma burner, to obtain a second slag, and • removing the second slag from the volatilizer or "fumer" .
    The inventors have found that the slag according to the present invention can be produced without problems with the process according to the present invention, and in particular that the process is capable of achieving the desired low levels of Pb and Zn in a single, trouble-free manner. relatively simple process step. The inventors believe that this process entails considerable advantages compared to processes known in the art, such as the process from WO 2013/156676 A1 which comprises a first reduction step in an electric oven, followed by a finely ground the material and a magnetic separation of the metal particles from the remaining slag. The inventors have further determined that the process of the present invention does not require the large amounts of flux material required for other methods known in the art, these materials leading to weakening and possibly even suppressing the technical contribution that the slag can otherwise when using it as a binder in the construction industry.
    The inventors have further established that the slag according to the present invention has a sufficiently low content of zinc and / or lead so that the slag does not represent any concerns regarding the leaching of metal, and can therefore be considered acceptable in more economically interesting end applications.
    The inventors have further established that with the process of the present invention a slag can be produced with a very low Pb content, which can therefore make it possible to avoid the additional labeling requirements that could be imposed by the CLP regulations that certain jurisdictions. As a result, the slag can also remain acceptable without problems for use in many of the current applications where conventional slag may run the risk of becoming unacceptable or undesirable. Moreover, in the event that a surplus of the slag is available that exceeds the commercial demand for it, the costs and cost of dumping such a surplus of the slag according to the present invention remain limited.
    The inventors have further established that the slag of the present invention, particularly when the process of the present invention is used, contains a particularly low content of zinc. The inventors have found that when the slag according to the present invention is used in concrete and / or cement, the curing speed of the composition is no longer considerably reduced, as is the case with slag with a higher Zn content. The process is preferably monitored and / or controlled electronically, more preferably by a computer program.
    In yet another embodiment, the invention provides for various uses of the slag according to the present invention, as stated in a number of usage claims.
    The inventors have found that the slag of the present invention, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, can be used as an active binder in the building industry. The slag can be used to partially replace portland cement. Such an activity may be referred to as "puzzolanic action," which is defined as a measure of the rate of reaction by the time or reaction rate between a puzzolan and Ca 2+ or Ca (OH) 2 in the presence of water. The speed of the puzzolane reaction depends on the intrinsic characteristics of the puzzolane, such as the specific surface, the chemical composition and the active phase content. Physical surface adsorption is not considered to be part of the puzzolan operation because irreversible molecular bonds are not formed during that process. The inventors have found, for example, that when slag is added according to the present invention, in an amount of about 30% as a substitute for portland cement, 30% less of the portland cement can be used, while from this mixture a concrete product can be produced with a compressive strength that is only 6% lower than the compressive strength of the same product produced with 100% cement. Without wishing to commit to this theory, the inventors believe that this capacity is conferred by the low presence of zinc, below the level at which it can act as a poison or as a contaminant that disrupts the action of the snail. The inventors have found that a similar slag containing about 8% by weight of zinc was unable to exhibit this effect.
    In yet another embodiment, the invention therefore provides for use of the slag according to the present invention as a component selected from the list consisting of a filler, a binder, and combinations thereof, in the building industry.
    The inventors have found that the slag according to the present invention, particularly when ground, when this second slag was used to partially replace portland cement as the binder in a composition, delivered significantly better performance than the equivalent derived from the first slag whose slag according to the present invention was derived by using the process of the present invention, and which contained about 8% by weight of zinc, Zn, and in the range of 0.3 - 0.5% by weight of lead, Pb. The inventors believe that this difference in performance may be due to the lower zinc content, based on the observation that zinc delays the action of conventional cement. The inventors have found that this difference in performance is already considerable in the case of the slag comprising at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO.
    The inventors have determined that the slag of the present invention can also be used to produce a number of other technical effects.
    In one embodiment, the slag according to the present invention, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, can be used in an end application selected from applying a wear layer and / or or cladding for roofing tiles or roofing slates, as a component of sand or grit, as a foamed component of tiles, as a black colorant, preferably in building products, more preferably in black tiles, as black hard chunks, preferably for decorative purposes, and as ballast high density, preferably for underwater applications, more preferably for hydraulic applications, and for combinations thereof.
    In yet another embodiment, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, the invention provides an effect selected from the reduction of the baking temperature of a brick or a brick. clay brick, for sound insulation, for X-ray shielding, and combinations thereof.
    The inventors have determined that the slag has a high material density, in the range of 2.9 - 4.0 tons / m3. Moreover, it was found that the snail is non-porous. Consequently, the slag can have the effect of good sound insulation. The inventors have further established that in particular the high material density makes the slag suitable and extremely interesting for X-ray shielding.
    The inventors have established that the snail has a very dark black color. Although the black color is quite common for phayalitic snails, the inventors have found that this color is extremely stable in the snail of the present invention, particularly in comparison with many alternative colorants. Thanks to the low zinc content and the low lead content, the slag according to the present invention can therefore be used as a suitable colorant for producing black building products, such as black floor tiles, which are currently particularly popular, and for which iron oxide, FeO, is currently used. which, however, is a rarer and fairly expensive base material.
    Detailed description
    The present invention will be described with reference to specific embodiments; however, the invention is not limited thereto, but is only determined by the claims.
    Furthermore, the terms first, second, third, and the like, in the description and claims, are used to distinguish between similar elements, and not necessarily to describe a sequential or chronological order. The terms are interchangeable under appropriate circumstances, and the embodiments of the invention may function in sequences other than described or illustrated herein.
    Furthermore, the terms upper, lower, top, bottom, and the like are used in the description and the claims for descriptive purposes, and not necessarily to describe relative positions. The terms thus used are interchangeable under appropriate circumstances, and the embodiments of the invention described herein may function in other orientations than described or illustrated herein.
    The term "comprising", used in the claims, should not be interpreted as being limited to the means listed thereafter; it does not exclude other elements or steps. The term is to be interpreted in the sense that it specifies the presence of said properties, numbers, steps or components as indicated, but does not exclude the presence or addition of one or more other properties, numbers, steps or components, or groups thereof from. The scope of the expression "a device comprising means A and B" should therefore not be limited to devices that consist solely of components A and B. It means that for the present invention, the only relevant components of the device A and B to be. Accordingly, the terms "comprising" and "including" include the more restrictive terms "essentially consisting of" and "consisting of."
    In this document, unless otherwise indicated, quantities of metals and oxides are expressed according to the usual practice in pyrometallurgy. The presence of each metal is generally expressed as its total presence, regardless of whether the metal is present in the elemental form (oxidation state = 0) or in any chemically bonded form, which is typically an oxidized form (oxidation form). state> 0). For the metals that can be relatively easily reduced to their elemental form, and that can occur as molten metal in the pyrometallurgical process, it is quite common to express their presence in terms of their elemental metal form, even when the composition of a slag is specified in which the majority of such metals may in fact be present in an oxidized form. Therefore, for the composition of a slag such as the slag of the present invention, the Fe, Zn, Pb, Cu, Sb, Bi content is reported as elemental metals. Less noble metals are more difficult to reduce under non-ferrous pyrometallurgical conditions and are mainly in an oxidised form. These metals are usually expressed in terms of their most common oxide form. Therefore, for the composition of slag, the content of Si, Ca, Al, Na is generally expressed as S102, CaO, Al2O3, Na2 O, respectively.
    The Kaldo process, which is used in U.S. Pat. No. 4,571,260 and in WO 2013/156676 A1, is a conventional pyrometallurgical process in which a top blown rotary converter (TBRC - Kaldo) oven or Kaldo converter), in which molten metal as the heavier phase and a molten slag phase as the lighter phase can occur together. The heat is supplied in this process with the help of an oxygen-fuel flame and later by the introduction of coke or another suitable reducing agent into the already melted liquids. The plasma process of the present invention uses a plasma burner to volatilize some of the metals from the slag. The process according to the present invention is more efficient because the very high temperature plasma stream, with temperatures far above 1500 ° C and easily reaching at least 3000 ° C and even 5000 ° C, is capable of causing local temperatures that are much higher higher than the average temperature in the melt, and more flexible compared to conventional burner systems because it makes it possible to control the oxygen potential virtually independently of the amount of heat generated.
    In one embodiment, the slag of the present invention comprises at least 8% by weight of Fe, preferably at least 10% by weight, more preferably at least 15% by weight, even more preferably at least 20% by weight, even more preferably at least 25% by weight %, preferably at least 30% by weight, more preferably at least 35% by weight, even more preferably at least 37% by weight. In another embodiment, the slag according to the present invention comprises at most 48% by weight of Fe, preferably at most 47% by weight, more preferably at most 45% by weight, even more preferably at most 43% by weight, even more preferably at most 41% by weight. The Fe content in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885.
    In one embodiment, the slag of the present invention comprises at least 24 weight%, more preferably at least 25 weight%, even more preferably at least 26 weight%, even more preferably at least 27 weight%, preferably at least 28 weight%, more preferably at least 29%, even more preferably at least 30.0 weight%. In another embodiment, the slag of the present invention comprises at most 42 weight% SiO 2, preferably at most 40 weight%, more preferably at most 37 weight%, even more preferably at most 33 weight%, even more preferably at most 32% by weight. The SiO 2 content in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 12677. The SiO 2 content can also be determined indirectly, first by the silicon content, Si, to be determined using the method in accordance with DIN EN ISO 11885, and then converting this result to the SiO 2 oxide.
    In one embodiment, the slag of the present invention comprises at least 1.0 weight% CaO, preferably at least 1.2 weight%, more preferably at least 1.4 weight%, even more preferably at least 1.75 weight% , even more preferably at least 2.0% by weight, preferably at least 2.25% by weight, more preferably at least 2.50% by weight, even more preferably at least 3.00% by weight. In another embodiment, the slag of the present invention comprises at most 18 weight% CaO, preferably at most 15 weight%, more preferably at most 12 weight%, even more preferably at most 10 weight%, even more preferably at most 8.0% by weight. The CaO content in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885.
    In one embodiment, the slag of the present invention comprises at most 1.50% by weight of Zn, preferably at most 1.40% by weight, more preferably at most 1.30% by weight, even more preferably at most 1.20% by weight %, even more preferably not more than 1.10% by weight, preferably not more than 1.00% by weight, more preferably not more than 0.90% by weight, even more preferably not more than 0.80% by weight, even even more preferably at most 0.70% by weight. The content of Zn in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.10% by weight of Zn.
    In one embodiment, the slag of the present invention comprises at most 0.100% by weight, preferably at most 0.050% by weight, more preferably at most 0.040% by weight, even more preferably at most 0.030% by weight, even more preferably at most at most 0.026% by weight. The content of Pb in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.005% by weight of Pb.
    In one embodiment the slag according to the present invention comprises at most 1.30% by weight of copper, Cu, preferably at most 1.10% by weight, more preferably at most 1.00% by weight, even more preferably at most 0, 90% by weight, even more preferably at most 0.80% by weight, preferably at most 0.75% by weight, more preferably at most 0.70% by weight, even more preferably at most 0.60% by weight, even more preferably at most 0.40% by weight. The content of Cu in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.05% by weight of Cu.
    In one embodiment, the slag of the present invention comprises at most 2.5% by weight of magnesium oxide, MgO, preferably at most 2.00% by weight, more preferably at most 1.50% by weight, even more preferably at most 1, 3% by weight, even more preferably at most 1.20% by weight, preferably at most 1.10% by weight, more preferably at most 1.00% by weight. The MgO content in a slag from non-ferrous metal production can be determined by converting the analytical result for magnesium, Mg, to MgO. The magnesium content for such a slag is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.40% by weight of MgO, preferably at least 0.50% by weight. %, more preferably at least 0.60% by weight, even more preferably at least 0.70% by weight, even more preferably at least 0.75% by weight.
    The method described in DIN EN ISO 11885 uses atomic emission spectroscopy with inductively coupled plasma (ICP-AES), also known as optical emission spectroscopy with inductively coupled plasma (ICP-OES).
    In one embodiment the slag according to the present invention comprises at most 2.0% by weight of sulfur, S, preferably at most 2.00% by weight, more preferably at most 1.50% by weight, even more preferably at most 1, 25% by weight, even more preferably at most 1.00% by weight, preferably at most 0.50% by weight, more preferably at most 0.40% by weight, even more preferably at most 0.30% by weight, even more preferably, at most 0.20% by weight. The content of S in a slag from non-ferrous metal production is preferably determined by largely following the method described in ISO 15350. In another embodiment, the slag comprises at least 0.05% by weight of S.
    In one embodiment, the slag of the present invention further comprises at least 9% by weight and at most 63% by weight of iron oxide, expressed as FeO. This content is again expressed on the same basis as in claim 1, i.e. based on the dry matter. The FeO content can easily be obtained by converting the elemental Fe content to FeO. In this context, the Fe content is expressed as the total of the elemental metal present and the presence of the metal in an oxidized state. In one embodiment, the slag of the present invention comprises at least 10 weight% FeO, preferably at least 12 weight%, more preferably at least 15 weight%, even more preferably at least 20 weight%, even more preferably at least 30 % by weight, preferably at least 40% by weight, more preferably at least 45% by weight, even more preferably at least 50% by weight. In another embodiment, the slag of the present invention comprises at most 60% by weight of FeO, preferably at most 58% by weight, more preferably at most 56% by weight, even more preferably at most 54% by weight, even more preferably at most 53% by weight.
    In one embodiment, the slag according to the present invention comprises at most 5.0% by weight of sodium oxide, Na 2 O, preferably at most 4.50% by weight, more preferably at most 4.00% by weight, even more preferably at most 3, 75% by weight, even more preferably at most 3.50% by weight, preferably at most 3.25% by weight, more preferably at most 3.10% by weight, even more preferably at most 3.00% by weight, even more preferably at most 2.90% by weight. The Na20 content in a slag from non-ferrous metal production can be determined by converting the analytical result for sodium, Na, to Na20. The sodium content of such a slag is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 1.00% by weight of Na 2 O.
    In one embodiment, the slag of the present invention further comprises, on the same basis, at least 4.0% by weight and at most 12% by weight alumina, Al 2 O 3. Preferably the slag comprises at least 5.0% by weight, even more preferably at least 6.0% by weight, preferably at least 7.0% by weight, more preferably at least 7.5% by weight, even more preferably at least least 8.0% by weight. In another embodiment, the slag of the present invention comprises at most 11.5 weight% or Al 2 O 3, preferably at most 11.0 weight%, more preferably at most 11.0 weight%, even more preferably at most 10, 5% by weight, even more preferably at most 10.0% by weight. The content of Al 2 O 3 in a slag from non-ferrous metal production is preferably determined in accordance with the method described in DIN EN ISO 11885 for determining the aluminum content, in American English: aluminum, and the converting the result to the aluminum oxide Al203.
    In one embodiment, the slag of the present invention comprises at most 1.50% by weight of zinc oxide, ZnO, preferably at most 1.40% by weight, more preferably at most 1.30% by weight, even more preferably at most 1, 20% by weight, even more preferably at most 1.10% by weight, preferably at most 1.05% by weight, more preferably at most 1.00% by weight, even more preferably at most 0.95% by weight, even more preferably at most 0.90% by weight. The level of ZnO in a slag from non-ferrous metal production can be determined by converting the analytical result for zinc, Zn, into ZnO. The zinc content of such a slag is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.25% by weight of ZnO.
    In one embodiment, the slag of the present invention comprises at most 0.323% by weight of lead oxide, PbO, preferably at most 0.300% by weight, more preferably at most 0.250% by weight, even more preferably at most 0.200% by weight, with even more preferably at most 0.100% by weight, preferably at most 0.050% by weight, more preferably at most 0.030% by weight, even more preferably at most 0.028% by weight, even more preferably at most 0.020% by weight. The content of PbO in a slag from non-ferrous metal production can be determined by converting the analytical result for lead, Pb, to PbO. The lead content of such a slag is preferably determined in accordance with the method described in DIN EN ISO 11885. In another embodiment, the slag comprises at least 0.005% by weight of PbO.
    In an embodiment of the slag according to the present invention, the iron present in the slag is mainly present in the phalamic structure Fe 2 SiO 4, also known as iron chrysolite.
    In an embodiment of the slag according to the present invention, the slag has an amorphous substance content of at least 30% by weight, as determined by quantitative X-ray diffraction analysis (XRD analysis) using Topas Academy Software V5 and Al203 as internal standard, preferably at least 50% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight, even more preferably at least 85% by weight, content of amorphous substance. A higher content of amorphous substance in the slag brings with it the advantage that the slag exhibits a better grindability. This property is particularly interesting when small particles are desired, such as when the slag is intended for use as a binder. In another embodiment, the slag is at least substantially crystalline, such as, for example, at least 30% crystalline, preferably at least 50%, more preferably at least 70%. A high crystalline content entails the advantage of high hardness and high strength, and also of a very dark black color, which is particularly desirable in other end applications such as, for example, as rough stone blocks and for other decorative purposes.
    In one embodiment, the slag of the present invention is in the form of a granulate with an average particle diameter (d50, calculated on a weight basis and available by sieving) of at least 0.5 mm and at most 5.0 mm, preferably at least 0 , 7 mm, more preferably at least 0.9 mm, and optionally at most 3.0 mm, preferably at most 2.0 mm. The fineness of the ground slag can also be expressed by means of the "Blaine value", a value that is often used to indicate the fineness of the "gravel" (the specific surface area) of cement. The fineness of gravel is determined by measuring the air permeability [cm2 / g] in accordance with DIN 1164 part 4. The Blaine value of the slag in an embodiment according to the invention should be in the range of 1800 - 6000, and is preferably at least 2000, more preferably at least 2200, even more preferably at least 2500, even more preferably at least 3000. In one embodiment, the Blaine value of the slag is at most 5500, preferably at most 5000, more preferably at most 4500, and even more preferably at most 4000. These Blaine values are particularly advantageous when the slag is used as a binder.
    In one embodiment, the slag according to the present invention is in the form of a powder with an average particle diameter (d50), determined by wet sieving and therefore an average calculated by weight, of at least 10 µm and at most 500 µm, preferably at least 20 µm, more preferably at least 30 µm, and optionally at most 200 µm, preferably at most 100 µm, more preferably at most 50 µm. This entails particular advantages when the snail is intended to be used as a binder.
    In an embodiment of the slag according to the present invention, at least 90% by weight of the particles (d90) have a diameter of at most 200 µm, determined by wet sieving, preferably of at most 150 µm, more preferably of at most 100 p.m. This entails the advantage that the amount of larger particles is greatly limited, such that the slag is very easy to handle and leads to a smooth porridge when the slag is used as a binder.
    In one embodiment, the slag according to the present invention is in the form of lumps with an average particle diameter (d50, calculated on a weight basis) of at least 4 mm and at most 200 mm. In a specific embodiment, the slag has an average particle diameter in the range of 4-20 mm. This form of the slag is very suitable for other applications, such as for example aggregate. In another specific embodiment, the slag has an average particle diameter in the range of 50 - 200 mm. This shape of the snail can for instance be suitable for use in the form of decorative elements, such as, for example, rough stone blocks.
    In an embodiment of the object according to the present invention, the object further comprises an aggregate, the aggregate preferably comprising sand and / or the slag according to the present invention, which comprises at most 1.50% by weight of zinc, Zn. The applicants have established that the slag is also extremely suitable as an aggregate in the construction industry, alone or in combination with other aggregates such as sand. The slag can lead to improvements in terms of strength and can also improve the aesthetics of the end product.
    In an embodiment of the object of the present invention, the slag comprises at least 1.0% CaO and the slag is present as a binder, the object further comprising an activator. Applicants have determined that the slag of the present invention can act as an active binder capable of reacting with a suitable activator and thereby exhibiting strong binding properties for aggregates. The slag can therefore be used as a substitute for portland cement, or as the only binder in an object, in the latter case being considered as a "geopolymer" which can, for example, impart fire and heat-resistant properties to coatings, adhesives, composites, etc. .
    Geopolymers are generally amorphous materials with framework structures with repeating units, which in this case include Fe and Si atoms that are linked by shared oxygen atoms. The applications for geopolymers are very varied, and many of them are dictated by the fire and heat resistance of the materials.
    In an embodiment comprising an activator, the activator is selected from the group consisting of sodium hydroxide, NaOH, potassium hydroxide, KOH, sodium silicate, Na 2 SiO 3, potassium silicate, K 2 SiO 3, and combinations thereof, the activator preferably being NaOH.
    In one embodiment, the object according to the present invention is a building element, preferably an element selected from the frame consisting of a tile, a paving stone, a block, a concrete block, and combinations thereof.
    The object according to the present invention can optionally be baked, which can entail the advantage of a color change, the end result being, for example, a reddish color. A curing step can also be used, at a temperature lower than baking, but for example at a temperature in the range of 120 - 250 ° C, which in addition to the aesthetic aspects can also contribute to the mechanical properties of the object.
    In one embodiment, the object of the present invention has a foam structure. This entails the advantage that the conductivity for heat and sound is lowered, such that the object can exhibit heat and / or sound insulation properties, and can achieve wider acceptability in applications where these properties are desired or required.
    In one embodiment of the process of the present invention, the first slag is introduced into the volatilizer as a liquid. This entails the advantage that the feed material does not have to be melted in the volatilizer or "fumer", such that the amount of heat to be supplied to the volatilizer is limited. It is extremely advantageous to combine the process according to the present invention with other pyrometallurgical processes at the same location, which can produce the first slag in liquid form and which can be supplied as such in the volatilization device according to the present invention without problems.
    In an embodiment of the process according to the present invention, the first slag is heated in the volatilizer, preferably by means of the plasma burner.
    In one embodiment of the process of the present invention, at least a portion of the first slag is melted using the plasma burner in the volatilizer. This entails the advantage that also fixed first slag can be processed in the process according to the present invention.
    In one embodiment of the process according to the present invention, during plasma fuming, the plasma burner is immersed in the molten slag present in the fumigator. This entails the advantages of a strong stirring of the molten slag by the flow of hot plasma fluid, of intensive contact of the slag with the high temperature plasma fluid, and of a highly effective volatilization of the metals that are susceptible to are smoked, such as zinc and lead.
    In an embodiment of the process of the present invention, an oxide selected from CaO, Al 2 O 3, and combinations thereof, is added to the slag in the volatilizer, preferably at a temperature of at least 1000 ° C, preferably at least 1050 ° C, more preferably about 1150 ° C. This entails the advantage that the final composition of the second slag can be further optimized and stabilized after volatilization, and that it makes the slag more suitable for specific end applications by also influencing its mineralogy. Applicants have found that high temperature addition, as indicated, and in the molten state, is more effective in achieving the desired effects.
    In an embodiment of the process of the present invention, the second slag is cooled to the solid state, the second slag preferably being removed from the volatilizer as a liquid. The advantage is that the volatilization device can be released for further processing of slag while the second slag cools. The slag can be cooled and / or made solid by bringing the slag into contact with a cooling medium, such as, for example, air, possibly ambient air.
    In one embodiment of the process of the present invention, cooling of the slag is performed by contacting the liquid second slag with water. Applicants have found that water cooling is very effective and can be carried out in various ways, resulting in relatively well-controlled cooling speeds.
    In an embodiment of the process of the present invention, the second slag is cooled at a speed of at least 40 degrees Celsius per second, preferably at least 50 degrees Celsius per second, more preferably at least 60 degrees Celsius per second. Applicants have determined with the higher cooling rate, as indicated, that a higher amorphous substance content can be obtained from the slag, which is interesting for certain end uses, such as, for example, when the slag is intended for use as a binder.
    In an embodiment of the process according to the present invention, the process further comprises the step of grinding the solid second slag, preferably grinding the slag into powder.
    In an embodiment of the process according to the present invention, the second slag is cooled at a speed of at most 30 degrees Celsius per second, preferably less than 30 degrees Celsius per second, more preferably at most 20 degrees Celsius per second. Applicants have found that at the lower cooling rate, as indicated, a lower amorphous substance content can be obtained from the slag, and therefore a higher crystalline content, which is interesting for certain end uses, such as, for example, when the slag is intended for use as aggregate or for decorative purposes.
    In an embodiment of the present invention, the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, and the slag is used as a binder for aggregates, preferably as an active binder, preferably as a binder with puzzolan effect. Applicants have found that the slag can act as a binder to replace cement, such as, for example, when cement is partially replaced by it, such as, for example, portland cement, but also as a binder for producing geopolymer compositions.
    In an embodiment of the present invention wherein the slag is used as a binder for aggregates, the slag is used as a substitute for portland cement, preferably as a partial replacement for portland cement.
    In an embodiment of the present invention wherein the slag is used as a binder for aggregates, the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, and the slag is used as a binder in an inorganic polymer composition , preferably in combination with a base, more preferably as the main binder in an inorganic polymer composition, even more preferably as the only binder in an inorganic polymer composition.
    In one embodiment of the present invention, the use further comprises the step of foaming the inorganic polymer composition. The result is a foamed composition, which may be desirable for its insulating properties with respect to heat and / or sound.
    In an embodiment that includes foaming, the slag can be used to improve heat and / or sound insulation.
    In an embodiment of any of the uses according to the present invention, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, the slag is used in combination with an additional oxide or a precursor thereof selected from calcium oxide, CaO, alumina, Al 2 O 3, calcium hydroxide, Ca (OH) 2, calcium carbonate, CaCO 3, calcium sulfate, CaSO 4, wherein the slag and its additional oxide or precursor are preferably mixed together before the use.
    Applicants have found that the additional oxide or its precursor can be added as a blast furnace slag, as a suitable non-ferrous slag, as gypsum-containing residues, thus comprising CaSO4 .2H2O, as compositions containing quicklime, such as suitable filter dust, calcium oxide (Ca (OH) 2), or as limestone (CaCO 3). The applicants have further established that the additional oxide or its precursor can be added to the liquid molten slag before it has solidified. The advantage of this addition to the liquid is that the additional oxide or its precursor can be thoroughly mixed with the slag of the present invention.
    The technique of treating materials with plasma is well known in the art. In WO 2011/136727 A1 a method is disclosed for treating with plasma a waste material that is flowing at room temperature, such as for example liquids and slurries, and in particular evaporator concentrate from nuclear power plants. The purpose of the treatment is to minimize the volume of waste treated in this way. An oxidizing gas is supplied in a plasma generator, and the highly heated plasma gas with high enthalpy is then mixed with the waste material in a mixing zone. The starting material comprises approximately 15% organic and inorganic material and approximately 25% salts. During the treatment, the water is volatilized, the organic components are completely dissolved and partly burned, the inorganic materials are melted and oxidized. After the mixing zone, a separation device is provided in which liquid inorganic materials are separated from the gas stream. The resulting glass matrix / slag product comprises metals and oxides, and is preferably bound in a leach-resistant silicate slag, and suitable slag-forming materials, such as, for example, crushed glass, sand / quartz, etc., can be added to the mixing zone or to the flowable waste in order to promote the formation of leach-resistant glass matrix / slag product. The glass / slag product can then be transported to the final storage without further treatment.
    Also in WO 2014/046593, which has already been discussed above, the use of a plasma burner to produce a hot gas with a temperature higher than 3000 ° C, or even higher than 4000 ° C, for the treatment of slag is described. . GB 2448556 and GB 2445420 disclose a piasmene process for the glazing of nuclear waste. EXAMPLE 1: Production of slag by plasma volatilization
    Pilot tests were carried out on a 3-tonne scale, which showed that the second slag can be produced from the first slag using a submerged plasma system.
    The tests were conducted in the installations of Scanarc Plasma Technologies. The reactor was energized by a plasma burner with a capacity of 1 MW submerged under the surface of the liquid slag. The volatilization of the slag was carried out by injecting natural gas through the burner and / or coke through a feed hole at the top of the reactor. The slag composition was checked at regular intervals by taking a sample through a sample hole. The slag composition evolved over time as seen in Table 1, the data being expressed in% by weight relative to the total slag composition.
    Table 1
    The final slag was analyzed in more detail and further showed the concentrations shown in Table 2.
    Table 2
    The final slag was rapidly cooled by granulation in cold water, resulting in an amorphous substance content of 72% by weight, determined by XRD. A portion of the same slag was slowly cooled by pouring them over a metal plate, resulting in an amorphous substance content of 44% by weight, determined by XRD. The XRD technique used was quantitative X-ray diffraction analysis using Topas Academy Software V5 and with Al 2 O 3 as internal standard.
    The Zn content of the slag clearly decreased during plasma treatment. The Pb content also decreased further during treatment. After about 200 minutes, a Zn content of less than 1% and a Pb content of less than 0.03% by weight were achieved. EXAMPLE 2: Production of tiles based on the slag
    A compressed inorganic polymer sample was produced using fast-cooled slag from Example 1 as a binder, and using slow-cooled slag from Example 1 as an aggregate. For the binder, a portion of the slag was crushed, and the resulting slag powder had a particle size distribution with 90% by weight of the particles having a particle diameter in the range of 50 to 70 µm. The slag was milled in a centrifugal mill (Retsch ZM100) with a screen opening of 80 µm. The particle size distribution (PSD) was measured by wet laser scattering analysis (Malvern Mastersizer S) and found to have a d90 <70 µm. As an aggregate, another part of the slag was milled, and from the result a mixture was produced by sieving and re-mixing with a particle size distribution that was very similar to that of standard sand or Norm Sand according to industry standard EN 196-1. To obtain a particle size of slag aggregate that was comparable to CEN standard sand (EN 196-1), the slow-cooled slag was gradually ground in a disk mill (Retsch® DM 200). The crushed particles were then divided into fractions of 0.08 mm - 0.16 mm, 0.16 mm - 0.5 mm, 0.5 mm - 1 mm, 1 mm - 1.6 mm and 1.6 mm - 2 mm. This was done by means of a column of sieves (of the Retsch® type) with the above-mentioned mesh sizes on a vibrating sieve shaker (Retsch® AS 200 basic). Batches of slag aggregate with desired amounts of individual fractions were produced by mixing the resulting fractions in the percentages prescribed in EN 196-1. Furthermore, an activating solution was used which was produced by mixing, in a ratio of 50/50 (w / w), commercial water glass (Na 2 SiO 3) obtained from abcr GmbH, Karlsruhe (DE), as sodium silicate, water glass, 39 - 40% silicates in water, with a solution of 6N (6 mol / liter) NaOH in water. The following mixing ratios were used: • Activating solution / binder: 0.48 / 1.0 • Aggregate / binder: 4.7 / 1.0
    To produce the inorganic polymer sample, the binder was first added slowly and with stirring to the activating solution, and the result was mixed for an additional 30 seconds. The aggregate was then added slowly for about 1 minute while the mixing was maintained. The mixing was then continued to arrive at a total duration of 3 minutes. An automatic mixer (Dispermat AE) was used at a constant mixing speed of 600 rpm.
    The resulting dry mixture was compressed using a hydraulic laboratory press (MIGNON SSN / EA) at a pressing force of ~ 75 MPa for about 15 seconds in a mold of 50 * 50 * 27 mm3 (length χ width χ height). The dimensions of the final product were 50 χ 50 χ 22 mm3 (length χ width χ height). The tiles compressed in this way were first cured for 24 hours at a temperature of 180 ° C in an autoclave under a high pressure of approximately 10 bar excess pressure, followed by a period of 27 days in a controlled air environment at a temperature of 20 ° C and a relative humidity of 90%. EXAMPLE 3: Tile performance testing
    The tiles from Example 2 gave the following results when testing performance.
    The compressive strength was measured in the direction of the largest dimension of the sample, by means of a pressure test machine of the Schenck-RM100 model (press speed 1 mm / min). Four samples were tested. The compressive strength at 28 days was found to be 102.4 ± 4.4 MPa. It also appeared that this compressive strength was already achieved after the 1st curing day. The compressive strength remained the same after the additional curing period of 27 days.
    For comparison, a similar tile was produced using standard sand obtained from Normensand GmbH, Germany, as the aggregate. The replacement of slag aggregate with standard sand was carried out on the basis of the same volume in order to maintain the same dimensions. The tile, based on standard sand, achieved a compressive strength of only 35 ± 1 MPa.
    The water absorption of the slag-based tiles was measured according to IS0 10545-3: 1995, and was found to be approximately 4.8% by weight. After the complete curing period of 28 days, no efflorescence could be observed by visual inspection of the tiles.
    Now that this invention has been fully described, it will be appreciated by those skilled in the art that the invention can be implemented in a wide range of parameters within what is claimed, without departing from the scope of the invention as defined by the claims.
    权利要求:
    Claims (33)
    [1]
    Conclusions
    A slag comprising, based on the dry matter, and wherein the presence of a metal is expressed as the total of the metal present as the elemental metal and the presence of the metal in an oxidised state, a) at least 7% by weight and at most 49% by weight of iron, Fe, b) at most 1.30% by weight of copper, Cu, c) at least 24% by weight and at most 44% by weight of silicon dioxide, S1O2, and d) at least 2.0% by weight and at most 20% by weight of calcium oxide, CaO, characterized in that the slag comprises on the same basis: e) at least 0.10% by weight and at most 1.00% by weight of zinc, Zn, f) at least 0.40% by weight % and at most 2.5% by weight of magnesium oxide, MgO, g) at least 4.0% by weight and at most 12% by weight of aluminum oxide, Al2O3, and h) at most 0.100% by weight of lead, Pb.
    [2]
    The slag according to claim 1, further comprising, on the same basis, at most 5% by weight of sodium oxide, Na 2 O.
    [3]
    The slag according to any of the preceding claims, further comprising, on the same basis, at most 11.5 weight% alumina, Al 2 O 3.
    [4]
    The slag according to any of the preceding claims, with an amorphous substance content of at least 30% by weight.
    [5]
    An object comprising as aggregate the slag according to any of the preceding claims, comprising at most 1.50% by weight of zinc, Zn.
    [6]
    An object comprising as binder the slag of any one of claims 1-4, which comprises at most 1.50% by weight of zinc, Zn.
    [7]
    The object of the preceding claim wherein the slag comprises at least 1.0% CaO and wherein the slag is present as a binder, the object further comprising an activator.
    [8]
    A process for the production of a second slag according to any one of claims 1-4, wherein the second slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, the the process comprises the steps of: providing a first slag containing at least one metal selected from zinc, lead, and combinations thereof, placing the first slag in a volatilizer, volatilizing an amount of at least one metal, selected from zinc, lead, and combinations thereof, from the first slag, using at least one plasma burner, to obtain a second slag, and removing the second slag from the volatilizer.
    [9]
    The process according to claim 8, wherein during the volatilization the plasma burner is immersed in the molten slag present in the volatilizer.
    [10]
    The process according to any of claims 8-9, wherein the second slag is cooled to become a solid.
    [11]
    The process according to any of claims 8-10, wherein the process is monitored and / or controlled at least partially electronically, and preferably by a computer program.
    [12]
    The process according to any of claims 8 to 11, wherein the second slag is incorporated into an article as a binder and / or as an aggregate.
    [13]
    The process according to the preceding claim wherein the slag is present as a binder, the article further comprising an activator.
    [14]
    The process according to the preceding claim, wherein the activator is selected from the group consisting of sodium hydroxide, NaOH, potassium hydroxide, KOH, sodium silicate, Na 2 SiO 3, potassium silicate, K 2 SiO 3, and combinations thereof, the activator being preferably NaOH.
    [15]
    The process according to any of claims 11 to 14, wherein the object is a structural element, preferably an object selected from the list of a tile, a floor tile, a block, a concrete block, and combinations thereof.
    [16]
    The process of any one of claims 11 to 15, wherein the article has a foamed structure.
    [17]
    Use of the slag according to any of claims 1 to 4 as an ingredient selected from the list consisting of a filler, a binder, and combinations thereof, in the building industry.
    [18]
    The use according to the preceding claim, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, and wherein the slag is used as a binder for aggregates.
    [19]
    The use according to any of claims 17 to 18, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, as a binder in an inorganic polymer composition.
    [20]
    Use of the slag according to any of claims 1-4, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, in a final application selected from application of a wear layer and / or cladding for roofing tiles or roofing slates, as a component of sand or blasting grit, as a foamed component of tiles, as a black colorant, preferably in building products, more preferably in black tiles, as black hard chunks, preferably for decorative as high-density ballast, preferably for underwater applications, more preferably for hydraulic applications, and for combinations thereof.
    [21]
    The use of the slag according to any of claims 1-4, wherein the slag comprises at most 1.50% by weight of zinc, Zn, and at least 1.0% by weight of CaO, for an effect selected from the reduction of the baking temperature of a brick or clay brick, for sound insulation, for protection against X-rays, and combinations thereof. Item V
    [22]
    1. Reference is made for the following documents: D1 PIATAK NM ET AL: "Mineralogy and the release of traces from battle from the Hegeler Zinc smelter, Illinois (USA)", APPLIED GEOCHEMISTRY, PERGAMON, AMSTERDAM, NL, part 25, No. 2, February 1, 2010 (2010-02-01), pages 302-320, XP026870399, ISSN: 0883-2927 [found on 2009-12-11] D2 MALDONADO B ET AL: "Early copper melt at Itziparatzico, Mexico "JOURNAL OF ARCHAEOLOGICAL SCIENCE, ACADEMIC PRESS, NEW YORK, NY, US, Vol. 36, No. 9, September 1, 2009 (2009-09-01), pages 1998-2006, XP026268579, ISSN: 0305-4403, DOI: 10.1016 / J.JAS.2009.05.019 [found on 2009-05-27] D3 CHIARANTINI L ET AL: "Copper production at Baratti (Populonia, Southern Tuscany) in the early Etruscan period (9th-8th centuries BC)", JOURNAL OF ARCHAEOLOGICAL SCIENCE, ACADEMIC PRESS, NEW YORK, NY, US, Vol. 36, No. 7, July 1, 2009 (2009-07-01), pages 1626-1636, XP026096749, ISSN: 0305-4403, DOI: 10,101 6 / J.JAS.2009.03.026 [found on 2009-03-31] D4 HU HUIPING ET AL: "The recovery of Zn and Pb and the manufacture of lightweight bricks from zinc melt stroke and clay", JOURNAL OF HAZARDOUS MATERIALS, part 271, February 19, 2014 (2014-02-19), pages 220-227, XP028841324, ISSN: 0304-3894, DOI: 10.101 6 / J.JHAZMAT.2014.01.035 D5 K. VERSCHEURE ET AL: "Continuous Fuming or Zinc-Bearing Residues: Part II. The Submerged-Plasma Zinc Fuming Process ", METALLURGICAL AND MATERIALS TRANSACTIONS B, part 38B, February 2007 (2007-02), pages 21-33, XP002745351, D6 PETKOVIC, D., DOKIC, J., MINIC, D:" PROCENA ENERGETSKE EFIKASNOSTI PROCESA FUMOVANJA SLJAKE SAHTNOG TOPLJENJA NA OSNOVU MATERIJALNOG I TOPLOTNOG BILANSA ", IMK-14, part XVI, no. 37, April 2010 (2010-04), pages 43-45,
    [23]
    2. Document D1 refers to the analysis of the Hegeler Zinc Smelter. Referring to table 6 of said document, several strokes having the composition falling within the composition as claimed in claim 1 are disclosed, compare following samples 1 / 1.5; 11 / 9a, 9c, 9d ,, 10 and 11. The subject matter of claims 1 and 5 is not novel about D1. 2.1 Furthermore, having a composition complying with the one of claim 1 is known from D2 (see table 2, eg samples c2b, da or z1 a) and D3 (cf. table 2, samples 1 -4c, 2-1 a) . Thus, the subject matter of claim 1 is anticipated by any of D2 or D3.
    [24]
    3. The use of stroke from a smelter, such as e, g, known from D1, as a filler or binder in the construction industry is well known in the art, compare e.g. D4 (see abstract). Thus, the subject-matter of claim 11 lacks inventiveness in view of the combination of D1 and D4.
    [25]
    4. The additional features disclosed in dependent claims 2-4, 6, 7 and 12-15 are either known from the prior art cited above (see passages indicated) or considered as a resuit or routine work conducted by a skilled metallurgist without need of any inventive activity. Item VII
    [26]
    1. The relevant background art disclosed in D5 and D6] is not mentioned in the description, nor are these documents identified therein. Item VIII
    [27]
    1. The subject matter for which protection is sought is not clear. In particular: 1.1 The subject matter of claims 5-7 refers to an object including the battle according to any of the preceding claims. This stroke should be presented as a binder and / or an aggregate. However, during the production of the object it has to be expected that the stroke reacts with the other component (s) of the object. Therefore it is highly disputable if and in what manner the original form of the battle and its composition can be detected from the final product. For that reasons, said claims refer to an undefined object. 1.2 According to claim 1, the contents of CaO and Zn are limited to at least 2.0% wt and at most 1.00% wt, respectively. However, reading the claims 8-15, all of them being dependent on claim 1, the content of CaO is at least 1.0% wt and the content of Zn is at most 1.5% wt. Thus, there is an inconsistency between claims 1-4 on one side and said claims on the other. Item V
    [28]
    1. Reference is made to the following documents: D1 PIATAK NM ET AL: "Mineralogy and the release of trace elements from the Hegeler Zinc smelter, Illinois (USA)", APPLIED GEOCHEMISTRY, PERGAMON, AMSTERDAM, NL, part 25, No. 2, February 1, 2010 (2010-02-01), pages 302-320, XP026870399, ISSN: 0883-2927 [found on 2009-12-11] D2 MALDONADO B ET AL: "Early copper melt at Itziparatzico, Mexico "JOURNAL OF ARCHAEOLOGICAL SCIENCE, ACADEMIC PRESS, NEW YORK, NY, US, Vol. 36, No. 9, September 1, 2009 (2009-09-01), pages 1998-2006, XP026268579, ISSN: 0305-4403, DOI: 10.1016 / J.JAS.2009.05.019 [found on 2009-05-27] D3 CHIARANTINI L ET AL: "Copper production at Baratti (Populonia, Southern Tuscany) in the early Etruscan period (9th-8th centuries BC)", JOURNAL OF ARCHAEOLOGICAL SCIENCE, ACADEMIC PRESS, NEW YORK, NY, US, Vol. 36, No. 7, July 1, 2009 (2009-07-01), pages 1626-1636, XP026096749, ISSN: 0305-4403, DOI: 10.1016 / J .JAS.2009.03.026 [found on 2009-03-31] D4 HU HUIPING ET AL: "The recovery of Zn and Pb and the manufacture of lightweight bricks from zinc melt stroke and clay", JOURNAL OF HAZARDOUS MATERIALS, part 271, February 19, 2014 (2014-02-19), pages 220-227, XP028841324, ISSN: 0304-3894, DOI: 10.1016 / J.JHAZMAT.2014.01.035 D5 K. VERSCHEURE ET AL: "Continuous Fuming or Zinc-Bearing Residues: Part II. The Submerged-Plasma Zinc Fuming Process ", METALLURGICAL AND MATERIALS TRANSACTIONS B, part 38B, February 2007 (2007-02), pages 21-33, XP002745351, D6 PETKOVIC, D., DOKIC, J., MINIC, D:" PROCENA ENERGETSKE EFIKASNOSTI PROCESA FUMOVANJA SLJAKE SAHTNOG TOPLJENJA NA OSNOVU MATERIJALNOG I TOPLOTNOG BILANSA ", IMK-14, part XVI, no. 37, April 2010 (2010-04), pages 43-45,
    [29]
    2. Document D1 refers to the analysis of slag from the Hegeler Zinc Smelter. With reference to Table 6 of said document, different slags are disclosed with the composition falling within the composition of claim 1, cf. the following samples I / 1.5; 11 / 9a, 9c, 9d, 10 and 11. The subject matter of claims 1 and 5 is therefore not new compared to D1. 2.1 Furthermore, a slag with a composition that meets that according to claim 1 is known from D2 (see Table 2, for example samples c2b, c1a or z1a) and D3 (cf. table 2, samples 1-4c, 2-1a). Therefore, the subject matter of claim 1 is anticipated by D2 or D3.
    [30]
    3. The use of slag from Zn smelter, for example as known from D1, as a filler or binder in the building industry is known in the prior art, cf. for example D4 (see extract). Therefore, the subject matter of claim 11 does not include inventiveness given the combination of D1 and D4.
    [31]
    4. The additional measures disclosed in the dependent claims 2-4, 6, 7 and 12-15 are either known from the prior art as quoted above (see the indicated passages) or are considered to be a result of routine work performed by a skilled metalworker without inventive step. Item VII
    [32]
    1. The known state of the art disclosed in D5 and D6 is not mentioned in the description, nor is mention made of these documents. Item VIII
    [33]
    1. The matter for which protection is sought is unclear. In particular: 1.1 The subject matter of claims 5-7 refers to an object comprising the snail of any one of the preceding claims. This slag must be present as a binder and / or an aggregate. However, during production of the object, it can be expected that the slag reacts with the other component (s) of the object. It is therefore highly debatable whether and how the original form of the slag and its composition can be detected in the final product. For these reasons, an undefined object is referred to in the stated claims. 1.2 According to claim 1, the calcium oxide and zinc contents are limited to at least 2.0% by weight and at most 1.00% by weight. Reading claims 8-15, all of which are dependent on claim 1, the calcium oxide content is at least 1.0 weight percent and the zinc content is at most 1.5 weight percent. Therefore, there is an inconsistency between on the one hand claims 1-4 and on the other hand the said claims.
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    同族专利:
    公开号 | 公开日
    CN107849637A|2018-03-27|
    WO2016156394A1|2016-10-06|
    JP2022008582A|2022-01-13|
    ES2877505T3|2021-11-17|
    US20180057911A1|2018-03-01|
    CA2981243A1|2016-10-06|
    RU2020112963A|2021-10-06|
    CN113149474A|2021-07-23|
    PL3277852T3|2021-10-18|
    RS62000B1|2021-07-30|
    MX2017012477A|2018-06-18|
    PT3277852T|2021-06-21|
    CN107849637B|2021-05-18|
    JP2018519428A|2018-07-19|
    RU2017135543A3|2019-07-17|
    BE1024028A1|2017-10-31|
    KR20180015118A|2018-02-12|
    RU2719977C2|2020-04-23|
    EP3277852A1|2018-02-07|
    RU2017135543A|2019-04-08|
    EP3277852B1|2021-04-07|
    US20210222269A1|2021-07-22|
    US10982301B2|2021-04-20|
    EP3865598A1|2021-08-18|
    CL2017002444A1|2018-03-23|
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    法律状态:
    2018-02-05| FG| Patent granted|Effective date: 20171106 |
    优先权:
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    EP15248015.8|2015-04-03|
    EP15248015|2015-04-03|
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