• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a mortar or concrete material comprising cement, water, fine aggregate and coarse aggregate, where the fine aggregate is partially substituted by metallic mineral extraction (REMM) residues not subjected to heat treatment, with a pH less than 7, with a particle size less than 4 mm, and partially stabilized with limestone material comprising at least 60% calcite with a particle size less than 63 μm. The present invention also relates to the process of preparing said material and its use in the preparation of building materials. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2737525A1
    申请号:ES201830690
    申请日:2018-07-11
    公开日:2020-01-14
    发明作者:Sánchez María José Martínez；Sirvent Carmen Pérez；Serrano Fernando Meseguer
    申请人:Universidad de Murcia；
    IPC主号:
    专利说明:

    [0001] MATERIAL OF MORTAR OR CONCRETE WITH RESIDUES OF EXTRACTION OF METAL MINERALS AND PROCEDURE OF OBTAINING THE SAME
    [0002] TECHNICAL SECTOR
    [0003]
    [0004] The present invention falls within the field of the reuse of residues or wastes derived from mining operations, and their treatment for the manufacture of mortars or non-structural concrete.
    [0005]
    [0006] BACKGROUND OF THE INVENTION AND STATE OF THE TECHNIQUE
    [0007]
    [0008] The powerful development experienced by countries worldwide during the twentieth century and this one that we started, has generated a strong competition for natural resources that has made current land use unsustainable, decreasing its availability and long-term viability and turning it, to today, in a non-renewable natural resource.
    [0009]
    [0010] On the one hand, metal mining developed over the centuries, has left a great ecological liability in the form of large masses of waste accumulated in debris, dams of floating mud or rafts and even in marine areas.
    [0011]
    [0012] The metallic mining waste that presents dangerous substances in concentrations that can derive in ecotoxicity, comes from the exploitation of this type of minerals, classified according to the European List of Waste with the code 01 01 01, and its benefit or concentrate, procedure that is performed by a non-thermal physical-chemical treatment. Depending on the content of metals and, mainly, sulfur in the form of sulfides, the effect on the environment and living things can become critical.
    [0013]
    [0014] On the other hand, the limestone filler residues from the numerous aggregate classification plants constitute an inert waste that causes a strong environmental impact, since its current use is not sufficiently developed.
    [0015]
    [0016] From the EU it is intended to alleviate these tensions through its sustainable development policies, replacing a linear economy based on producing, consuming and throwing away, by a circular economy in which the “theoretically disposable” materials are continually reincorporated into the productive process, in the development of new products or raw materials.
    [0017] The homogeneous mixture of water, aggregates and cement in certain proportions, gives rise to two types of materials commonly known as mortars or concretes, depending on the granulometry of the aggregates used. Among all its properties, the most important is that this mixture, when in contact with water, reacts and becomes an easily moldable paste that quickly hardens like artificial stone reaching a great resistance, which has made this material into primordial constructive element from the beginning of the Roman Empire to the current date.
    [0018]
    [0019] Over time, its characteristics have evolved in parallel to the development of societies, improving, among other aspects, the tests that are carried out to ensure their quality and the additives used in their preparation.
    [0020]
    [0021] Currently, studies on concrete focus on achieving and, if possible, combining two main objectives: the recovery of waste as a method to mitigate the overexploitation of natural resources and / or the improvement of some of its properties, either by addition or by total or partial replacement as one of its essential components.
    [0022]
    [0023] There are studies that analyze the possibility of using PET waste as a partial substitute for aggregates in the manufacture of cement mortars, such as that reflected by [MAGARIÑOS OE, et. al., “ Study of mortars containing plastic flakes from post-industrial waste .” Building Materials, 1998, Vol. 48 (250)]. In this work, after studying different replacement percentages and analyzing the characteristics for each one of them, various economic, social and ecological benefits are deducted for which these wastes should be used as such.
    [0024]
    [0025] Other researchers focus their efforts on studying the partial replacement of some of the basic elements that make up the concrete with another material or residue, such as changing certain amounts of cement for volcanic slags and whose results are satisfactory under certain premises. [AL-SWAIDANI AM, " Production of more durable and sustainable concrete using volcanic slag as a cement substitute ." Building Materials. 2017, Vol. 67 (326)]
    [0026]
    [0027] There are also those who suggest adding residues directly to the original mixture, such as the work prepared by [LOPEZ-ZALDIVAR O., et. al., “ Cement mortars improved with the addition of carbonated fly ash from waste incineration .” Building Materials. 2015, Vol. 65 (319)], in which the production of cement mortars is proposed to the added to them, not as a substitute but as an element more, carbonated fly ash, which causes an increase in resistance with respect to the reference values of 25%.
    [0028]
    [0029] In addition to these, there are several studies on how to improve the properties of mortar / concrete by adding waste to this mixture. However, all of them are carried out with smelting slag or fly ash, residues that have necessarily undergone a thermal treatment in some of the stages prior to their generation, and therefore, little or nothing have to do with those used in this invention, direct discharge waste obtained by physical-chemical treatment, with high potential acidity and high content of soluble heavy metals and / or transition metals and, whose sole purpose at the present date, is a hazardous landfill, being even classified in the European Waste List with different codes: 10 and 01 01 01, respectively.
    [0030]
    [0031] The reintroduction of this waste into the production chain, would be in accordance with Law 22/2011, would comply with the 2020 European Strategy and avoid one of the immense problems arising from this type of farms.
    [0032]
    [0033] There is therefore a need to provide a mortar or concrete material, which gives rise to denser materials, with a good compressive strength after 28 days and that allows the retention of elements by any transfer route and, therefore, that they are optimal for use as a byproduct in the field of construction.
    [0034]
    [0035] BRIEF DESCRIPTION OF THE INVENTION
    [0036]
    [0037] The present invention solves the problems described in the state of the art since, it provides a process for the preparation of a mortar or concrete material from metal mineral extraction residues that gives rise to a material with good compressive strength properties. to 28 days since it exceeds 15 MPa.
    [0038]
    [0039] Thus, in a first aspect, the present invention relates to a non-structural mortar or concrete material (hereinafter, mortar or concrete material of the present invention), comprising cement, water, fine aggregate and coarse aggregate , where the fine aggregate is partially substituted by metallic mineral extraction (REMM) residues, not subjected to heat treatment, with a pH below 7, with a particle size of less than 4 mm (natural size or by crushing), and which are partially stabilized with limestone material comprising at least 60% calcite with a particle size of less than 63 pm.
    [0040] For the purposes of this invention, the following definitions will apply:
    [0041]
    [0042] 01. «LER»: European waste list.
    [0043] 02. «REMM»: waste classified in the European Waste List with code 01 01 01 “Waste of Extraction of Metallic Minerals”, in particular, all those derived from the operations of exploitation and concentration of minerals from mines of Pirita-Blenda- Galena (PBGs) with potential acidity generating minerals. Likewise, waste from the exploitation of other metal sulphides, oxides and carbonates that constitute ores of metals of economic interest such as iron, lead, copper, mercury, cadmium, zinc, nickel, silver, gold ...
    [0044] 03. «EHE-08»: 2008 structural concrete instruction.
    [0045] 04. "Valorisation" means any operation whose main result is that the waste serves a useful purpose by replacing other materials, which would otherwise have been used to fulfill a particular function, or that the waste be prepared to fulfill that function in the installation or the economy in general.
    [0046] 05. 'dangerous substance' means a substance classified as dangerous because it meets the criteria set out in Annex I, parts 2 to 5, of Regulation (EC) No 1272/2008.
    [0047] 06. "heavy metal" means any compound of antimony, arsenic, cadmium, chromium (VI), copper, lead, mercury, nickel, selenium, tellurium, thallium and tin, as well as these substances in their metallic forms, provided they are classified as dangerous
    [0048] 07. "transition metals": scandium, vanadium, manganese, cobalt, copper, yttrium, niobium, hafnium, tungsten, titanium, chromium, iron, nickel, zinc, zirconium, molybdenum and tantalum, as well as these substances in their metallic forms , provided they are classified as dangerous substances.
    [0049] 08. "stabilization": a process that changes the danger of the constituents of the waste and transforms it from dangerous to non-dangerous.
    [0050] 09. «solidification»: a process that only changes the physical state of the residue through additives without changing its chemical properties.
    [0051] 10. "partially stabilized waste" means waste that contains, after the stabilization process, hazardous constituents that have not been completely transformed into non-hazardous constituents and that can pass into the environment in the short, medium or long term.
    [0052] In a more particular embodiment, the mortar or concrete material of the present invention comprises:
    [0053]
    [0054] - at least 150 kg / m3 of cement,
    [0055] - fine aggregate, substituted by at least 20% by weight, of the total fine aggregate by REMM and limestone filler,
    [0056] - 0-70% by weight coarse aggregate,
    [0057] - at least 90 kg / m3 of water,
    [0058]
    [0059] In another more particular embodiment, the mortar material of the present invention comprises:
    [0060]
    [0061] - at least 150 kg / m3 of cement,
    [0062] - fine aggregate, substituted by at least 20% by weight of the total fine aggregate by REMM and limestone filler,
    [0063] - at least 90 kg / m3 of water,
    [0064]
    [0065] In another more particular embodiment, the concrete material of the present invention comprises:
    [0066]
    [0067] - at least 150 kg / m3 of cement,
    [0068] - fine aggregate, substituted by at least 20% by weight of the total fine aggregate by REMM and limestone filler,
    [0069] - 0-70% by weight of coarse aggregate, preferably between 40 - 70% by weight of coarse aggregate
    [0070] - at least 90 kg / m3 of water,
    [0071]
    [0072] In the present invention, cement refers to those cements specified in Table A.18.2, of Schedule 18 of EHE-08, preferably refers to sulfate resistant cements (SR cements).
    [0073]
    [0074] In another aspect, the present invention relates to a process for the preparation of mortar or concrete material of the present invention, (hereinafter, process of the present invention) from non-subject REMM metal mineral extraction residues by heat treatment and with a particle size of less than 4 mm (natural size or by crushing), as described above, which comprises the following steps:
    [0075] a) partial stabilization of REMM with limestone materials comprising at least 60% calcite and a particle size of less than 63 gm, until a pH between 7-10 is reached,
    [0076] b) homogenization of the mixture obtained in a) with water to saturation point,
    [0077] c) addition of cement, water and aggregates,
    [0078]
    [0079] d) homogenization of the mixture obtained in step c,
    [0080]
    [0081] In another more particular embodiment, the aggregate of step c) of the process of the present invention is selected from fine aggregate with a particle diameter less than 4 mm, coarse aggregate with a particle diameter greater than 4 mm and mixtures thereof.
    [0082]
    [0083] In another aspect, the present invention relates to the use of the non-structural mortar or concrete material of the present invention for the preparation of building materials.
    [0084]
    [0085] In the present invention, by construction materials it refers to materials for the preparation of coatings, sidewalks, curbs, bollards, planters, rigolas, sanitation pipes, concrete fillings, mass concrete walls, submerged blocks, port breakwaters, safety barriers on highways and highways, among others.
    [0086]
    [0087] DETAILED DESCRIPTION OF THE INVENTION
    [0088]
    [0089] The execution procedure of the present invention was carried out as described below:
    [0090]
    [0091] Once the previous study of characterization and risk analysis of the contaminated site containing the REMMs was carried out, a number of representative samples were taken, depending on the volume of waste and in the opinion of the expert and taken to the laboratory.
    [0092]
    [0093] With the residues in the laboratory, these were chemically and mineralogically characterized and, at the same time, a granulometric analysis was performed, crushing all those particles retained in the UNE-EN 933-2 sieve with a 4 mm aperture to an appropriate size.
    [0094]
    [0095] The partial stabilization phase involves the use of a limestone material that contains more than 60% calcite and the particle size is less than 63 microns, which allowed the pH of the REMMs to be stabilized to a neutral or slightly basic value. , immobilizing soluble metals or preventing them from precipitating in insoluble forms.
    [0096]
    [0097] For this, the acid generation potential of the wastes was determined, as described in the UNE-EN 15875 standard.
    [0098]
    [0099] This procedure was performed with the mixture about to saturate in water to force the reaction and to prevent the REMM from attacking some other component afterwards. and / or that they take part of the water destined to react with the cement due to hygroscopic phenomena or structural changes during the different crystallization phases.
    [0100]
    [0101] If for some reason it is not possible to execute this phase satisfactorily, the waste will be discarded and conveniently managed.
    [0102]
    [0103] Next, the dosage of cement, water, coarse aggregate (if a concrete is to be manufactured), REMM partially stabilized and fine aggregate (if the replacement of this is not complete) was chosen. The proportion of each of these components, with respect to cement, was a personal choice, except for the limestone material that, as mentioned above, will be a function of the REMM acid generation potential, and will depend, to a greater or lesser extent. measure, of the final characteristics of the desired product.
    [0104]
    [0105] As cited in Annex 18 of EHE-08, the only restriction for non-structural concrete is that the cement dosage and the minimum strength should be 150 kg / m3 and 15 N / mm2, respectively.
    [0106]
    [0107] The mixing procedure of the different components can be carried out using any method that ensures the homogeneity of the product. The addition of the REMMs will be carried out after partial stabilization, thus avoiding their reaction with any other component of the mixture.
    [0108]
    [0109] After the manufacturing process, the product was subjected to mechanical tests, determining its resistance to compression according to the UNE-EN 12390-3 standard for concrete or its resistance to bending and compression for mortars according to the UNE-EN 196-1 standard, to physical / chemical tests such as density, pH, conductivity, etc ... and a study of stabilization of soluble metals, analyzing the curing waters, in order to corroborate the perfect stabilization and encapsulation of the residues.
    [0110]
    [0111] If the results obtained during the previous stage are satisfactory, the stabilized / solidified product can have various industrial applications, mainly in the field of construction, otherwise it will be discarded and the process must be started again from stabilization.
    [0112]
    [0113] The product obtained has multiple applications in the construction sector, such as: coatings, sidewalks, curbs, bollards, planters, rígolas, sanitation pipes, filling concrete, mass concrete walls, port breakwaters, safety barriers in motorways and highways, sewage pipes, prefabricated slabs not rm a das. among other.
    [0114] The promotion and development of these materials implies great environmental, economic and social benefits, such as the protection of ecosystems and regeneration of highly degraded spaces, greater availability of raw materials by drastically reducing the exploitation of natural resources, reducing CO emissions. 2 to the atmosphere, creation of new markets, promote less dependence on the import of raw materials, etc ...
    [0115]
    [0116] EMBODIMENT OF THE INVENTION
    [0117]
    [0118] Example 1: manufacturing process of six cylindrical concrete specimens measuring 30 x 15 cm, with 50% substitution of fine aggregate with an equivalent mass of REMM plus limestone filler.
    [0119]
    [0120] The specimens were classified into two groups according to their manufacturing procedure:
    [0121]
    [0122] • Group A: Normal manufacturing procedure. Test tubes in which the mass of "REMM Filler Limestone" is added dry.
    [0123] • Group B: Modified manufacturing procedure according to the method of the proposed invention. Test tubes in which the mass of "REMM Filler Limestone" is added to the point of saturation in water.
    [0124]
    [0125] GROUP A and B:
    [0126]
    [0127] The origin of the waste used for both group A and group B was "La Bahía de Portman", one of the most polluted areas in the Iberian Peninsula. In it, the presence of a total of 60 million tons of hazardous waste is estimated as described above, the result of the intense mining activity carried out by the Roberto Laundry during much of the twentieth century.
    [0128]
    [0129] The sample was crusted and larger than 4 mm, so it was necessary to crush it to a size smaller than 4 mm. The chemical, mineralogical and granulometric characterization carried out in the laboratory, in the selected samples, yield the following particular values:
    [0130]
    [0131]
    [0132]
    [0133]
    [0134] REMM COMPOUNDS MOLECULAR FORMULA NATROJAROSITA PERCENTAGE NaFe3 (3 +) (SO4) 2 (OH) 6 60% SIDERITA FeCO3 15% PLASTER CaSO4.2H2O 4% MAGNETITA Fe2 + (Fe3 +) 2O4 5% PIRITA FeS2 10% QUARTER 3 - 3% - 3% 3 %
    [0135]
    [0136] TOTAL SOLUBLE REMM ELEMENTS LEAD 3,304 mg / kg 15 mg / kg CINC 3,205 mg / kg 306 mg / kg CADMIUM 56 mg / kg 3.8 mg / kg COPPER 160 mg / kg 82 mg / kg ARSENICO 632 mg / kg 4.1 mg / kg IRON 38% 25% SULFUR 15.01% <LD Based on the mineralogy of the waste and, following the steps described in the UNE-EN 15875 standard, it was determined that, in order to partially stabilize it, it was necessary to mix it with a mass of limestone material equivalent to 30% of the total mass of the residue.
    [0137]
    [0138] The limestone material used to carry out this procedure was a filler from the aggregate classification plants, since it is abundantly found, is economical and has high carbonate contents and whose characteristics are as follows:
    [0139]
    [0140]
    [0141]
    [0142]
    [0143] MEDIUM SIZE OF PARTICLE 55 mm
    [0144] USDA TEXTURAL CLASS franc
    [0145] BET SPECIFIC SURFACE 9 m2 / g
    [0146] RELATIVE DENSITY 2.3 g / cm3
    [0147] pH 8.3
    [0148]
    [0149]
    [0150]
    [0151] CALCITA CaCO3 84%
    [0152] DOLOMITA CaMg (CO3) 2 6%
    [0153] PHILOSILICATES illita 3%
    [0154] QUARTZ SiO2 7%
    [0155]
    [0156]
    [0157]
    [0158]
    [0159]
    [0160]
    [0161]
    [0162]
    [0163]
    [0164] GROUP A:
    [0165] Mixing the residue with the limestone filler was done dry, stirring both doughs for 5 to 10 min, to ensure homogeneity.
    [0166] B GROUP:
    [0167] The mixture of the residue with the limestone filler was done wet, bringing both masses almost to saturation in water, for which the necessary amount of it was added directly from the urban network and constantly stirred, between 5 and 10 min , to ensure its homogeneity.
    [0168] GROUP A and B:
    [0169] Once the REMMs were partially stabilized, they proceeded to manufacture the concrete which, in the end, meant the complete stabilization of them.
    [0170] For this, and based again on mineralogy, I 32.5 N / SR UNE 80303-1 cement was used, which corresponds to a sulfate-resistant Portland cement with a normal resistance of 32.5 MPa.
    [0171] The chosen dosage has been determined to prepare a concrete in ordinary mass, with a compressive strength at 28 days of 20 MPa and consists of:
    [0172]
    [0173] • 250 kg / m3 of cement.
    [0174] • 480 kg / m3 of fine aggregate with 50% replacement:
    [0175]
    [0176] or 240 kg / m3 of conventional fine aggregate.
    [0177]
    [0178] or 240 kg / m3 of homogenous mixture and to saturation point in water of REMM and limestone filler.
    [0179] • 1,600 kg / m3 of coarse aggregate.
    [0180] • 175 kg / m3 of water.
    [0181]
    [0182] The use of a rotating drum system to carry out the mixing of all these components ensures the homogeneity of the product. The mass to be taken from each of the materials will depend on its density and the volume of product to be manufactured.
    [0183]
    [0184] GROUP A:
    [0185]
    [0186] By adding partially stabilized and unsaturated residues in water, it was appreciated how they swell when they capture the dosing water that should react with the cement.
    [0187]
    [0188] As the mixing time progressed, instead of forming as expected, a homogeneous cemented mass of dense / semi-fluid appearance, solid cemented aggregates with spherical shape were formed which made it very difficult, if not almost impossible, to fill the molds of the test tubes homogeneously.
    [0189]
    [0190] For this reason, it was necessary to add between 50 and 100% of extra water compared to that initially proposed to achieve a minimally workable paste and, despite this, the final aspect was not that of a concrete in use.
    [0191]
    [0192] After 24 to 48 hours after the molds were filled, the demoulding was carried out.
    [0193]
    [0194] The appearance was of a solid state material that presented, at a glance, structural problems, since interstitial gaps were seen on the surface of the specimens.
    [0195]
    [0196] Once the demoulding phase was executed, the specimens were introduced in individual containers and completely covered with water, remaining in these conditions for at least 28 days.
    [0197]
    [0198] B GROUP:
    [0199]
    [0200] By adding partially stabilized waste and almost to saturation in water, it was appreciated how a homogeneous mass of dense / semi-fluid appearance was formed, which made it possible to easily fill the molds of the specimens.
    [0201]
    [0202] After 24 to 48 hours after the molds were filled, the demoulding phase was carried out.
    [0203]
    [0204] The appearance of the specimens with the procedure proposed by this invention was of a solid and structurally compact material.
    [0205] Once the demoulding phase was executed, the specimens were introduced in individual containers and completely covered with water, remaining in these conditions for at least 28 days.
    [0206]
    [0207] GROUP A and B:
    [0208]
    [0209] Each day, or if it is considered appropriate to establish another longer time interval, a sample of these waters was taken and chemical parameters such as pH, electrical conductivity and soluble metal content were analyzed, among others.
    [0210]
    [0211] After 28 days of curing, the specimens were extracted and subjected to compression resistance tests.
    [0212]
    [0213] The results detailed below represent the average value of the experiments carried out in the laboratory for each group during the investigation period prior to the writing of this invention.
    [0214]
    [0215]
    [0216]
    [0217] Curing water pH (---) 6.95 10.10 11.97
    [0218] C. Electric curing water (mS / cm) 2.09 13.63 12.02
    [0219] Soluble metals curing water (ppm) <LD <LD <LD
    [0220] Resistance Compression test pieces (MPa) 3.8 17.5
    [0221] Test tube density (kg / m3) X 2,244
    [0222] Suspended particles (%) 0 14 0
    [0223]
    [0224] GROUP A:
    [0225]
    [0226] Specimens manufactured according to the normal procedure:
    [0227]
    [0228] • retained soluble contaminants, but did not retain all particulates. • They did not reach the minimum compressive strength required by EHE-08 in order to be used as non-structural concrete.
    [0229]
    [0230] As a consequence, they have no application in the field of construction.
    [0231] B GROUP:
    [0232]
    [0233] Specimens manufactured according to the modified procedure proposed by this invention:
    [0234]
    [0235] • retained soluble and particulate contaminants, preventing dispersion into the environment.
    [0236] • Clearly exceeded the minimum compressive strength required by the EHE-08 to be used as non-structural concrete.
    [0237]
    [0238] As a consequence, they can be used in various applications as non-structural concrete in the field of construction.
    权利要求:
    Claims (5)
    [1]
    1. Mortar or concrete material comprising cement, water, fine aggregate and coarse aggregate, characterized in that the fine aggregate is partially substituted by metallic mineral extraction (REMM) residues not subjected to heat treatment, with a pH below 7 , with a particle size of less than 4 mm, and partially stabilized with limestone material comprising at least 60% calcite with a particle size of less than 63 pm.
    [2]
    2. Mortar or concrete material according to claim 1, comprising:
    - at least 150 kg / m3 of cement,
    - fine aggregate, substituted by at least 20% by weight of the total fine aggregate by REMM, - 0-70% by weight of coarse aggregate,
    - at least 90 kg / m3 of water,
    [3]
    3. Procedure for the preparation of mortar or concrete material from REMM metal mineral extraction residues not subjected to heat treatment and with a particle size of less than 4 mm according to any of claims 1-2, comprising the following steps :
    a) partial stabilization of REMM with limestone materials comprising at least 60% calcite and a particle size of less than 63 pm, until a pH of 7-10 is reached,
    b) homogenization of the mixture obtained in a) with water to saturation point,
    c) addition of cement, water and aggregates,
    d) homogenization of the mixture obtained in step c),
    [4]
    4. Use of a mortar or concrete material according to any of claims 1-2 for the preparation of building materials.
    [5]
    5. Use of a mortar or concrete material according to claim 4, wherein the building materials are for cladding, sidewalks, curbs, bollards, planters, rígolas, sanitation pipes, filling concrete, mass concrete walls, submerged blocks , port breakwaters, highway and highway safety barriers, sewage pipes, prefabricated slabs.
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    同族专利:
    公开号 | 公开日
    ES2737525B2|2020-05-28|
    EP3822239A1|2021-05-19|
    US20210276918A1|2021-09-09|
    WO2020012050A1|2020-01-16|
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    申请号 | 申请日 | 专利标题
    ES201830690A|ES2737525B2|2018-07-11|2018-07-11|MORTAR OR CONCRETE MATERIAL WITH WASTE OF METAL MINERAL EXTRACTION AND PROCEDURE FOR OBTAINING THE SAME|ES201830690A| ES2737525B2|2018-07-11|2018-07-11|MORTAR OR CONCRETE MATERIAL WITH WASTE OF METAL MINERAL EXTRACTION AND PROCEDURE FOR OBTAINING THE SAME|
    US17/259,204| US20210276918A1|2018-07-11|2019-07-09|Mortar or concrete material containing metallic mineral extraction residues and method for producing same|
    PCT/ES2019/070478| WO2020012050A1|2018-07-11|2019-07-09|Mortar or concrete material containing metallic mineral extraction residues and method for producing same|
    EP19834466.5A| EP3822239A1|2018-07-11|2019-07-09|Mortar or concrete material containing metallic mineral extraction residues and method for producing same|
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