Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/22—Glass ; Devitrified glass
  • C04B14/24—Glass ; Devitrified glass porous, e.g. foamed glass
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/28—Treatment of water, waste water, or sewage by sorption
  • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
  • C03C1/002—Use of waste materials, e.g. slags
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
  • C03C11/007—Foam glass, e.g. obtained by incorporating a blowing agent and heating
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C12/00—Powdered glass; Bead compositions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
  • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
  • C02F2101/103—Arsenic compounds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
  • C02F2101/20—Heavy metals or heavy metal compounds
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2214/00—Nature of the non-vitreous component
  • C03C2214/08—Metals
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
  • Y10T428/2996—Glass particles or spheres

Definitions

• the invention relates to a granulate and a bulk material with or from such a granulate.
• the granulate is produced by sintering ground glass to a sintered body and then breaking the body into fragments.
• the invention also relates to a bulk material with broken foam glass fragments, in the glass starting material (e.g. waste glass) of pollutants, in particular antimony and / or arsenic, could be fixed.
• the glass starting material e.g. waste glass
• pollutants in particular antimony and / or arsenic
• the invention particularly relates to a bulk material for water purification.
• the bulk material for water purification contains a granulate from fragments of a sintered body sintered from ground metallurgical glass, in particular a broken granulate of a foam glass, or the bulk material consists entirely of such a granulate.
• sintered body is understood to mean a body that has been baked together from fragments of cottage glass by heating. In this body, the original parts remain essentially stationary during sintering. After the sintering, the fragments are connected to one another at least by bridges. Cavities remain between the sintered fragments of the smelting glass which, depending on the design of the sintering, are coherent, partially coherent or closed-pore.
• Foam glass is understood as a special form of such a sintered body.
• Foam glass beads are known from JP-A-6 048441. These are made by encasing a flammable core material.
• the coating consists alternately of a layer of a glass powder / foaming agent mixture and a layer of metal powder, in particular iron powder.
• a binder is required to form the jacket.
• the layering comprises at least one metal layer inside a layer of glass powder.
• the core material is burned by heat and the glass is foamed. This creates hollow spheres with a foam glass jacket in which a metal layer is embedded.
• a foam glass is known, which is made from natural, glassy minerals such as obsidian, pearlite, lava stone, shiratsu, etc.
• a metal carbonate for example calcium carbonate or magnesium carbonate, a nitrate such as potassium nitrate, and carbon, SiC and so on is added to this mineral.
• the natural glassy mineral in a certain grain size is mixed with the foaming agent and with sodium hydroxide, iron powder and water, dried at 200 degrees and foamed by heating ,
• a sound insulating material which consists of a foamed material, e.g. Foam, foamed water glass or a foam body made of volcanic glass or foam glass.
• This foam body contains a metal in powder form or as fibers. The following are described as metals: lead, zinc, tin, iron, aluminum, copper.
• DE-A-2334101 discloses a glass product and a method and a mixture for producing the glass product.
• container glass with lids, closures and labels is shredded and sintered in a mold, the glass particles not melting and the product therefore having a characteristic colored appearance.
• the glass particles can be pressed during the sintering or the particle mixture can be foamed. The glass particles grow together into a mass, but remain identifiable.
• a treatment agent is required for sintering, which preferably consists of pulverized, heat-treated excrement. This produces a high quality product from waste products using an inexpensive process.
• This glass product contains a metal part from the metal parts ground together with the glass.
• This metal content comprises 0.1 to 3 percent by weight of iron, but also tin (0.1 to 2%), aluminum (0.1 to 2%), and other metals (0.1 to 2%).
• cellulose derivatives and other organic substances are contained in the glass powder, because the hollow glasses used are ground uncleaned and unsorted.
• Foam glass production generally takes place in the following steps:
• Foam glass which is made from a powder mixture containing glass powder and a foaming agent that forms gas in the presence of heat in powder form, is closed-pore.
• a foam glass is known for example from EP-A-0 292 424 (Misag AG).
• EP-A-0 292 424 Misag AG.
• foam glass lumps are achieved by foaming a melting powder layer and breaking the foam glass layer thus formed.
• the foam glass layer breaks spontaneously when it cools down.
• the grain size that forms spontaneously corresponds approximately to the layer thickness.
• Such pieces of foam glass have a bulk density of about 250 kg / m3, and heavier and lighter foam glass can also be produced.
• Lumps of foam glass with closed pores float in the water. Since foam glass is closed-pore and waterproof, the pores are not filled with water, so that the buoyancy in the course that time doesn't let up.
• the foam glass has a high compressive strength of 6 N / mm2 on average. The compressive strength can also be selected between approx. 1 N / mm2 and approx. 10 N / mm2.
• the pore size, the pore density and the wall thickness of the pores can be regulated with the composition of the powder mixture. For example, the finer the foaming agent is pulverized, the smaller the pore size.
• Such a foam glass is used in the construction industry as a perimeter insulation, as a seeping layer, as a light-weight fill on underground with a low load-bearing capacity, and as a light aggregate for a very powerful lightweight concrete according to EP-Al 183 218 (Misapor AG).
• pollutants can be added to the foam glass.
• the semi-metals antimony and arsenic used in glazes and optical glasses also occur repeatedly in separately collected glass from households, although only in very small quantities.
• the process of foam glass production converts the pollutant antimony or arsenic contained in the raw glass or the glass structure so that the pollutant can be washed out of the foam glass upon contact with water.
• the possibilities of using such non-inert foam glass as a building material in environmentally sensitive applications, e.g. in hydraulic engineering are severely restricted.
• a bulk material made of broken foam glass lumps is, however, of first class suitability for example for slope drainage, route construction on marshy, poorly bearing ground, perimeter insulation, concrete production, especially for concrete walls with earth connection. The bulk material must therefore be suitable for contact with water.
• Group 1 Processes in which powdered iron is stirred into the waste water. Such processes are described in JP-A-01307497 for phosphorus removal, in US-A-5,575,919 for arsenic fixation by iron and sulfur powder, and in US-A-5,906,749 for copper removal from acidic waste water. A disadvantage of these processes is that sedimentation is then required, in which the resulting polluted iron sludge must be separated.
• Group 2 Processes in which iron powder is presented as a bed, through which the wastewater flows. Such methods are described in JP-A-08257570 for the removal of heavy metals and organochlorine compounds, and as a practically preferred embodiment with a mixture of iron filings and sand in US-A-6,387,276. There is an optimization conflict with these processes.
• the iron should be as fine-grained as possible in order to offer a high specific surface, on the other hand, the iron powder must be coarse-grained enough so that the layer remains sufficiently easily percolated. It is also disadvantageous that the finer pores of the fill "grow” due to rust formation. In processes that work with inert additives for "diluting" the iron bed, separation phenomena must be expected when filling and operating the reactors.
• Group 3 Processes in which the iron powder is moved. Such a method is described in US-A-5133873 (fluidized fluidized bed). Another method in which the iron granules are moved by vibration or by stirring is described in WO0110786. The formation of sinter-like agglomerations of the particles due to rust can be avoided by these processes, but the process engineering is complex. In any case (as in group 1) sedimentation of the sludge discharged from the fluidized bed must then take place.
• Group 4 Processes in which very fine-grained iron is anchored to a carrier material. US Pat. No. 6,242,663 discloses wastewater treatment with ultra-fine-grained iron particles (diameter 5-50 nm) which are anchored on silica gel.
• EP-A-0 436 124 discloses a filter body with fine-grained iron particles which are anchored on a mineral carrier material.
• the carrier material contains a binder (e.g. cement) and is foamed to provide a large specific surface.
• the structure is essentially open-pore.
• the disadvantage of this filter material is that the binder is generally strongly alkaline, which precludes use in the drinking water sector.
• Another problem is the fact that the mechanical strength of the granules is low, at least when there is a high proportion of pores.
• filter bodies with mineral binders are not long-term stable, since these binders are not completely water-insoluble. Acids in particular attack practically all known mineral binders.
• Methods are known from DE-A-195 31 801 and from DE-A-197 34 791 with which an open-pore expanded glass granulate can be produced.
• the process has in common that a powder mixture mainly containing glass powder is wetted and granulated into granules with a grain size of 0.8 to 4 or 1 to 4 m. The granulate is then sintered.
• pore formers can be used as pore formers.
• meltable wax beads For example, meltable wax beads, washable salts or gas-forming blowing agents.
• This open-pored body consists of expanded glass granules (for example granules according to DE-A-195 31 801 or DE-A-197 34 791), zeolite or ceramic, it being claimed that the catalytically active substances (for example iron ) are embedded in the granulate material or applied to the pore surface.
• the catalytically active substances for example iron
• the description gives no indication of how the substances can be stored in the base material differently than by applying them to the pore wall as described.
• the granules should be environmentally friendly, inexpensive to manufacture and can be produced from waste products.
• the granulate should be able to be produced in a quality with high compressive strength.
• the granules from fragments of a sintered body sintered from ground glass with a large number of inclusions of at least one active substance on the broken surfaces of the granules can be produced by conventional methods and in an extremely pressure-resistant quality.
• the active substance is embedded as a grain in the sintered body. Thanks to the active substance, which can interact with them if they come into contact with pollutants suspended or dissolved, especially in water the product is not only environmentally friendly, but can even be used to clean the environment.
• the main active substances are: iron powder, but also other metals, and / or other substances commonly used in wastewater treatment, such as activated carbon and zeolites.
• Metallic iron is an active substance for binding heavy metals. But other pollutants that are dissolved in the water can also be separated or destroyed by contact with the iron.
• the following reaction mechanisms are used: Destruction of pollutants through reduction (e.g. chlorinated hydrocarbons, nitrate and chromate), electrochemical separation of
• Pollutants due to cementation e.g. copper, mercury
• chemical precipitation e.g. phosphorus
• adsorption on Fe oxides or Fe hydroxides e.g. zinc and cadmium
• some pollutants e.g. arsenic, antimony
• several of these mechanisms interact.
• activated carbon is also a well-known active substance for binding a large variety of pollutants and is also able to bind microbes.
• the granulate is also characterized by its production.
• the granular active substance and the glass fragments are advantageously mixed homogeneously and the mixture is sintered as a layer, which sintered layer is then broken. This makes production very simple.
• the product manufactured in this way has excellent properties with regard to pressure resistance, angle of repose, flow through a bed, compressibility of a bed from the granulate, effectiveness in binding pollutants in waste water, etc.
• the granulate preferably has cavities in the sintered body. These allow the sintered body or the granulate to flow through and / or have a low specific weight. In this cavity, penetrating water can come into contact with grains of the active substance present there.
• the sintered body is advantageously foamed for many applications. However, it was found that, for example, an unfoamed sintered body is as efficient as a foamed one for wastewater treatment. Based on the surprisingly positive test results, it is assumed that the non-foamed sintered body is permeable to water, so that more active substance is involved in the wastewater treatment than only the portion visible on the surface of the granulate.
• the foam glass fragments consist predominantly of the contents of conventional foam glasses, namely glass and foaming agents, but have a content of metallic iron.
• the Iron particles exist as a variety of inclusions on the surface of the broken cells. This metallic iron is embedded in the foam glass matrix in the form of preferably homogeneously distributed, finest inclusions.
• the iron content in particular also allows a foaming agent to be used which has a reducing effect when foaming.
• a foaming agent increases the washability of the pollutants.
• the product is characterized by great environmental friendliness. This not only fixes the antimony, it also effectively binds other pollutants that occur in the waste glass, such as arsenic and chromate.
• the product can therefore be used in environmentally sensitive applications, e.g. in the field of hydraulic engineering.
• a broken piece of cellular glass made from smelted glass therefore has a large number of inclusions of metallic iron on the surfaces of these cells. This prevents that antimony or arsenic fixed in the glass, which surprisingly attains increased mobility due to the formation of foam glass, can be washed out of the foam glass.
• the inclusions are advantageously fine-grained and homogeneously distributed. It is assumed that the more homogeneous the distribution of iron, the better the pollutants are fixed.
• the iron inclusions enable the glass raw material of the foam glass to be obtained from waste glass, since the pollutants occurring in the waste glass are fixed by the iron. This means that foam glass made from recycled waste glass can be used for environmentally sensitive applications. This permits the advantageous use of the waste glass accumulating in huge quantities.
• foam glass can also be produced from a foamed glass melt, preference is given to a foam glass which is produced from a powder mixture by baking the powder mixture.
• the powder mixture contains glass powder, a foaming agent that forms gas under the influence of heat and fine-grained, metallic iron powder.
• the admixture of metallic iron powder is technically simple to implement in a foam glass produced in this way.
• the metallic iron in the foam glass is advantageously predominantly in a grain size between 1 micrometer and 2000 micrometers, preferably between 10 micrometers and 200 micrometers.
• the grain size of the iron remains unchanged despite the foaming process.
• metallic iron in this grain size is therefore added to a powder mixture to be foamed by heating.
• a mean grain size of the iron between 20 and 1000 micrometers, advantageously between 20 and 500 micrometers, in particular between 40 and 400 or 50 and 200 micrometers, is particularly preferred.
• Fine-grained iron powder is more expensive than coarse-grained iron powder, but has a significantly better effect when fixing pollutants in the foam glass.
• a preferred embodiment of the method therefore provides for coarse-grained iron powder to be ground together with the raw glass, thereby producing the finest iron dust, which is also dispersed very homogeneously in the glass powder.
• Fine-grained spray dust for example, can also be used as the iron powder.
• the iron contained in waste glass, eg bottle cap, which has been sorted out and added to waste iron, can advantageously be directly recycled in powdered form in the foam glass.
• a content of fine-grained, metallic iron in the foam glass is advantageously between 0.5 and 8 percent by weight, preferably between 1 and 4 percent by weight. In these areas, the addition of foaming agent is adaptable and the product has only slightly different application-related properties, such as pressure resistance, closed porosity, cell size, cell density, density, insulation value, etc.
• the narrower range has proven to be particularly suitable for sufficiently eliminating the ability to wash out the pollutants without impairing the other properties of the foam glass.
• the foam glass body therefore expediently has, like conventional quality foam glass, a density of between 200 and 800 kg / m 3, preferably between 300 and 500 kg / m3.
• a desired cell density is between 300,000 to 2,000,000 cells per cm3, and preferably over 600,000 pores per cm.3.
• the cells are also advantageously sealed off from one another.
• the desired compressive strength is certainly above 1 N / mm2, preferably above 4 N / mm2, particularly preferably above 6 N / mm2. Compressive strengths above 6 N / mm2 allow the foam glass to be used in a load-bearing area.
• the glass powder and the foaming agent are expediently present in a weight ratio between 85:15 and 98: 2.
• the foam glass contains fragments with broken cells.
• the use of such foam glass lumps is wide-ranging, in particular as inorganic or organically bound building material or as bulk material, for example in road construction, drainage, perimeter insulation or in slope stabilization.
• the broken foam glass granulate suitably has a grain size between dust and 64 mm. Loose or bound fillings from a foam glass of a single or a few grain sizes are useful for permeable volumes.
• the grain size should be selected according to the application.
• the granulate has a preferably balanced sieve curve with different grain sizes between dust and 64 mm for concrete or other bound bodies. Not all grain sizes are required. Supplementation with other additives is possible, the sieve curve of all additives advantageously giving a fuller curve.
• the invention also relates to a powder mixture for the production of environmentally compatible foam glass, which powder mixture according to the invention also has metallic iron powder in addition to the main constituent of glass powder from metallized glass, in particular waste glass powder, and a foaming agent which forms gas under the influence of heat.
• This powder mixture is essentially free of sodium hydroxide.
• the powder mixture advantageously has a metallic iron content of between 0.5 and 8 percent by weight, preferably between 1 and 4 percent by weight.
• the glass powder and the foaming agent are expediently in a weight ratio between 85:15 and 98: 2.
• the invention also relates to a process for the production of foam glass, in which glass powder from smelted glass, in particular waste glass, and a fine-grained foaming agent which forms gas under the influence of heat are homogeneously mixed with one another.
• the resulting powder mixture is applied - as in conventional foam glass production - in one layer to a base and this layer is heated in an oven.
• the baked and foamed glass is then cooled and broken into foam glass fragments.
• the method differs from conventional methods in that iron powder is additionally homogeneously mixed with the glass powder and the foaming agent in the production of the powder mixture. This allows foam glass production in particular under reducing or strongly reducing conditions.
• the addition of water is avoided.
• the powder mixture is therefore preferably mixed dry and not wetted onto the base and foamed as a loose fill.
• the breaking of the foam glass takes place in a first step due to stress cracks in the cooling foam glass.
• the resulting Foam glass fragments are easy to stack, transport and can sometimes be used in unchanged form. However, they can also be mechanically broken further, then sieved, for example, and individual grain sizes mixed together again in a certain mixing ratio.
• the advantage of the bulk material according to the invention is that its use in environmentally sensitive areas is harmless. This safety is given even if the glass starting material used is waste glass, or for other reasons contains more than 1 mg / kg or even more than 5 mg / kg antimony and / or arsenic. This has the advantage that the raw material does not need to be checked for pollutant content. No detection and sorting out of waste glass containing pollutants is required.
• the invention also relates to the use of the bulk material according to the invention as an additive for producing an inorganically or organically bound building material or as a loose bulk material.
• These uses are also in an environmentally sensitive area, especially in contact with groundwater, surface water or drinking water, e.g. possible in hydraulic engineering, civil engineering or building construction.
• Another object is to provide a bulk material for water purification which, among other things, can be used instead of sand in sand filters in sewage treatment plants.
• the bulk material for water purification should filter out solids in the water and pollutants dissolved in the water, e.g. Phosphates and heavy metals can bind.
• the bulk material for water purification is supposed to be large-scale industrial at an economical price and preferably partly. can be made from recycled waste.
• a bulk material for water purification which consists of a broken granulate of a sintered body made of ground glass, in particular a broken granulate of a foam glass, or has such a granulate.
• These granules are characterized by an active substance present in the broken surface and embedded as a grain in the glass matrix.
• the active substance is such a substance that is selected, especially the pollutants contained in the water interact. This interaction is generally an adsorption or a chemical reaction.
• the granules are produced by breaking a foamed or unfoamed sintered body. By breaking, the active substance grains embedded in the glass matrix reach the broken surface. In the case of unfoamed sintered bodies, it is assumed on the basis of the astonishing results that active substance present in the interior of the granulate also has an influence on the cleaning action of the granulate.
• This granulate can be produced in a wide variety of ways. By choosing the type and number of active substances, the grain size, the pore size and the specific weight (especially with foam glass), there is a wide range of possible uses.
• the primary active substances are: iron powder, but also other metals, and / or other substances commonly used in wastewater treatment, such as activated carbon and zeolites.
• the proportion of metallic iron is advantageously between 2 and 4% granules for building purposes.
• the iron content is advantageously between 4 and 20%, particularly preferably between 6 and 10%.
• Iron contents of up to 50% are conceivable.
• no improvement in the cleaning effect was found when the iron content was raised above 8%.
• it cannot be excluded that the iron content has a significant influence on the long-term effect of the granulate.
• activated carbon is also a well-known active substance for binding a large variety of pollutants and is also able to bind microbes.
• Selected zeolites are particularly suitable for use as an active substance, which is embedded in the sintered glass body. These zeolites are only activated by the high temperatures required for sintering. When sintering the glass or foaming the foam glass, these are therefore activated at the same time. Slightly soluble alkaline earth fluorides can advantageously be added to the glass flour, which convert to the desired easily soluble alkali fluorides during sintering.
• Aluminum powder and / or magnesium powder can also be present in the glass matrix. These metals form local electrochemical elements, thanks to which the iron dissolves with the formation of rust.
• closed-pore foam glass is also an ideal carrier for active substances. Contrary to expectations, closed-pore foam glass forms an ideal starting product for the production of bulk goods for water purification.
• the foam glass granulate is produced by breaking a foam glass layer or broken foam glass chunks of the open-pore or closed-pore foam glass. The grain can therefore be refined by breaking it as desired.
• the active substance is evenly distributed in these broken granules.
• the specific weight of the granulate can be set by controlling the production process.
• Closed-pore foam glass can be manufactured on a large industrial scale with very fine pore walls and yet with high compressive strength in a consistent quality. The surfaces of such broken granules consist of the concave pore surfaces of the broken pores.
• the effective surface of such granules is therefore very large. Active substances embedded in the walls or the pore surfaces are protected from abrasion in these concave depressions.
• the exchange between the effective granulate surface and the water to be cleaned is very large compared to the spherical one before, with the same filter volume and the same grain size Sintering granulated granules.
• the effective surfaces of the granules are large and easily accessible for water.
• a closed-pore foam glass is advantageously produced by heating a dry powder mixture which contains at least glass powder, the granular active substance and a foaming agent which forms gas under the action of heat.
• the active substance is therefore stored as a grain in the pore wall.
• the active substance is thus integrated into the glass matrix and mechanically held in the granulate.
• Recycled glass waste can be used as glass powder.
• the pore spaces cannot overgrow even if deposits are formed on and around the active grain.
• the foaming agent advantageously foams under reducing conditions.
• the e.g. Reducing conditions provided by SiC favor the integration of activated carbon in the glass matrix.
• Closed-pore foam glass usually has a main volume of relatively large pores, which are also called macropores.
• the walls between these macropores are also interspersed with smaller pores, which are also called micropores.
• the foam glass granulate of the bulk material advantageously has a largest pore size of the foam glass, which corresponds at least to the grain size of the foam glass granulate. This has the effect that practically all macropores are broken open, and thus the largest possible surface area of the granulate can be effective.
• a preferred grain size of the granules is between 1 and 6 mm, advantageously between 2 and 5 mm, particularly preferably between 3 and 4 mm.
• the granules obtained by such extensive breakage have a surface made up of partial areas of the pore surfaces of a number (for example 4 to 8) of macropores.
• a number for example 4 to 8
• the granules with protruding wall pieces reach into the concave depressions of an adjacent granule. This causes a good micro-swirling of water flowing through the pack. The water is therefore in intensive exchange with the very large surfaces of the broken pores.
• the foam glass granulate for the bulk material can advantageously have a water-soluble additive in the form of grains embedded in the foam glass.
• a water-soluble additive are formed, for example, by a halogen compound, an oxide, hydroxide, sulfate, carbonate or a phosphate of sodium, potassium, calcium, magnesium or iron.
• a water-soluble grain allows the granules to be broken down into a grain size which has a larger diameter than the diameter of the macropores, without the effectiveness of the pore surfaces of the unbroken pores being thereby robbed.
• the water-soluble additives dissolve during the use of the bulk material. As a result, additional pore surfaces of macropores and micropores gradually become effective. Therefore, with such a bulk material for water purification, there are always new, unused active substances.
• the additives can have a positive effect on the wastewater, e.g. by pH buffering, by continuous release of flocculants or oxidizing agents, nutrients and the like.
• Such a foam glass is expediently produced from a mixture containing at least glass powder, the granular active substance, a foaming agent which forms a gas under the action of heat and a granular water-soluble salt. This mixture is also spread out on a base as a powder layer without the addition of liquid and foamed by heating.
• Water-soluble salt is understood to mean in particular the sparingly soluble salts, which are referred to in English as “semi-soluble”. Such water-soluble salts are particularly suitable: gypsum, lime and / or pH-modifying substances such as magnesium oxide. Magnesium oxide has the advantages being environmentally friendly, buffering aqueous solutions at a pH of approx. 10.5 and thereby fixing practically all heavy metals as hydroxides.
• alkali fluoride can also be baked into the glass matrix and the foam glass granulate can then be treated with water. Together with water, the fluorides form hydrofluoric acid, which eats away the glass. For environmental reasons, such a treatment cannot, of course, be carried out by using it in the water to be cleaned.
• Hardly soluble alkaline earth fluorides can advantageously be added during the production of foam glass, which convert to the desired easily soluble alkali fluorides during the firing process.
• Aluminum powder and / or magnesium powder may also be present in the glass matrix. These metals form local electrochemical elements, thanks to which the iron dissolves with the formation of rust.
• the specific weight of the bulk material filled with water is advantageously set to 1000 + 200 kg / m 3. This results in a floating or almost floating bulk material for water purification. This can easily be backwashed.
• the weight of the foam glass or the buoyancy of the foam glass granulate can be adjusted by the pore volume of the non-broken pores. These are primarily the micropores in the pore walls of the macropores. On the other hand, the weight can be adjusted by the proportion of active substances. It has been shown, for example, that with an appropriate addition of foaming agent 80% of the foam glass granules with an iron content of up to 2% and float on the water, while with an iron content of 8% the granules sink to 80% in the water.
• the specific weight of the bulk material filled with water can be advantageous at around 1000 kg / m3 before the dissolution of the water-soluble salts and at over 1000 kg / m. 3 can be set after dissolving the water-soluble salts. This causes an automatic separation of the used bulk goods from the fresher due to gravity or the level of suspension of the granulate in the water to be cleaned.
• an iron content of 3 to 6 percent by weight of the dry weight in the granulate is appropriate.
• the granules can be influenced magnetically. This can be used to use a magnet to separate fine parts of the foam glass from a suspension with other contaminants. This advantage can also be used if the iron contained in the foam glass is not used to treat water pollutants.
• Sintered glass granules or foam glass granules doped with iron are also suitable for removing the finest paramagnetic particles from aqueous suspensions. Areas of application for this are, for example, in the processing of iron ores, but also in the wastewater sector (steelworks, etc.), and in the separation of the finest sludge containing iron oxide. Such sludges occur when iron powder has been dispersed in the waste water for the purpose of adsorbing pollutants. In order to subsequently remove this sludge (advantageously without flocculant or complex mechanical filtration) from the waste water stream, magnetic separation in a filter bed with the bulk material according to the invention doped with iron is appropriate.
• the magnetizable bed In order to bring the magnetic field as "close” to the suspension as possible, the magnetizable bed, through which the suspension flows, is arranged between magnetic poles. The paramagnetic particles present in the suspension are then magnetically bound to the iron particles present in the granulate (eg steel chips). The magnetic field is periodically switched off and the material deposited on the magnetized iron particles) embedded in the glass matrix is rinsed out. In order to form high magnetic field gradients, "pointed" surfaces or edges on the iron parts of the bed are preferred. In a preferred embodiment of the invention, the deposit consists of magnetizable, but rust-free iron filings (eg 0.5-5mm) in the granulate.
• the Bulk material according to the invention in addition to being magnetizable, has the advantages of very good percolation properties and a large active surface.
• the bulk material for water purification according to the invention can also be dispersed as a fine-grained powder in the waste water stream and, if it contains iron, can then be removed from it by means of magnets.
• the bulk material for water purification according to the invention can be used for wastewater purification in a multi-stage sewage treatment plant, in particular in the last stage. In modern systems, this stage consists of a sand filter that is periodically backwashed or continuously regenerated in a circuit.
• the bulk material according to the invention for water purification replaces this purely mechanical filter medium as an active filter medium. Thanks to its iron content, it binds phosphate residues and heavy metals that are still present.
• the large surface area, the high mechanical strength and the low specific weight make the bulk material (foam glass or non-foamed sintered glass) extremely suitable for use in such a filter stage.
• Part of the bulk material for water purification can be continuously drawn off and replaced with fresh or regenerated bulk material. The removed bulk material is regenerated chemically or preferably thermally.
• the bulk material according to the invention for water purification can also be used in drinking water treatment in order to bind pollutants such as arsenic, antimony, mercury, selenium, chromate, phosphate, nitrate, organochlorine compounds (such as CHC, pesticides).
• pollutants such as arsenic, antimony, mercury, selenium, chromate, phosphate, nitrate, organochlorine compounds (such as CHC, pesticides).
• Some endocrine pollutants and organic complexing agents are bound or destroyed with such a filter thanks to the presence of Fe °.
• the bulk material for water purification can also be used for rainwater treatment.
• One example is the treatment of rainwater that runs down from metal-covered roofs. Copper, lead, tin, zinc, in particular, can be separated from this before it seeps away or is fed to a sewer system.
• Fe ° can also be used to bind or destroy endocrine pollutants, regardless of the incorporation of iron into a carrier material.
• FIG. 2 shows an enlargement of a section through a closed-pore foam glass with an iron particle embedded therein.
• Fig. 3 shows a table with the course of the pollutant concentration in a
• Fig. 4 shows a schematic representation of two granules with inner surfaces of broken macropores on their surface. 5 shows schematically a section of a grinding surface of a non-foamed granulate according to the invention, sintered from glass powder and active grains. Fig. 6 diagram of the development of copper concentration in a solution, with
• FIG. 1 shows a diagram whose y-axis contains values for the substance concentration in an acidic eluate according to the Swiss Technical Ordinance on Pollutants in MUHgrams of pollutant per liter of eluate. Percentages of the weight fraction of metallic iron in a sample are given on the x-axis.
• the diagram shows the measured values of four samples: The measured values of a zero sample, that is a foam glass without iron addition, a first sample with an iron percentage by weight (1%), a second one with two percent by weight (2%) iron, and a third with three percent by weight (3%) iron content.
• the measured values for arsenic are 0.081 mg / L for the zero sample, 0.032 mg / L for the first sample, 0.005 mg / L for the second and 0.008 mg / L for the third.
• the material limit value for arsenic (0.01 mg / 1) can therefore be maintained by adding 2 to 3 percent by weight of iron powder to the powder mixture to produce a foam glass body.
• a mixture of 98% waste glass powder and 2% foaming agent from the production of a foam glass healing is used as raw material for four samples.
• the starting material of the applicant's foam glass production is used.
• the waste glass powder of the sample contains 10 mg / kg antimony and 11 mg / kg arsenic, which are fixed in the glass.
• 1%, 2% and 3% technical grade iron powder is mixed into a 200g sample of this mixture (i.e. 2g, 4g and 6g).
• the metallic iron powder has an average grain size of less than 100 microns.
• the three samples from powder mixtures according to the invention are foamed in a muffle furnace and, after cooling, result in foam glass bodies according to the invention. These foam glass bodies are granulated to 2 to 6 mm grain size.
• the foam glass body 21 shown in Figure 2 is made of a foam glass 11, which was obtained by heating a powder mixture to about 700 to 900 degrees. At these temperatures, the mineral foaming agent forms gas, which remains trapped in the now liquefied glass in the form of bubbles 13, 15.
• the size of the bubbles corresponds to the gas tightness that was developed at the same location, whereby for thicker layers, due to the pressure conditions, bubbles located below are on average somewhat smaller than bubbles located higher up.
• the foamed glass hardens Cool off, with the bubbles remaining as hermetically sealed pores in a pressure-resistant foam body.
• the iron particles 17 abut the interior in both of the macropores shown. Water flowing along the pore surface 19 of the macropore comes into contact with the iron. Pollutants present in the water are bound or destroyed during this contact. Some possible mechanisms of action are described above.
• FIG. 3 shows the results of two test series for removing copper or zinc from highly dilute aqueous solutions.
• a foam glass is presented, which is doped with 4% iron powder. 20g of this foam glass are granulated to 6 mm grain size and shaken "overhead" with 160 ml heavy metal solutions. The heavy metal solutions each contain 10 mg / L copper and 10 mg / 1 zinc. Periodically, samples are taken from the solution and analyzed for the heavy metal content.
• FIG. 3 clearly shows how the heavy metal contents in the solutions decrease very rapidly within a short time. After less than an hour of treatment, the cleaned solutions are already of drinking water quality.
• the foam glass granulate 21 shown schematically in FIG. 4 is broken smaller than the diameter of an average macropore.
• a water-soluble grain 27 is also shown in one grain. With the grain shown there is no need to open a pore that has not yet broken open. Nevertheless, a water-soluble grain is enclosed in the glass matrix of the wall.
• the water-soluble grain is magnesium oxide and has a water-cleaning effect. Inclusions from activated carbon or from water-soluble salts look similar, which can be added to the powder mixture of glass powder and foaming agent to delay the stressing of closed pores.
• the representation according to FIG. 5 is based in part on the assumption that when the glass flour is sintered without blowing agent, the glass particles do not fuse to form a void-free mass. It is assumed that there are air pockets between the softened or liquid glass particles, which are retained even after the sintered body 21 'has solidified. The air pockets shown are certainly too large. The size and number of air inclusions can be influenced depending on the sintering temperature and the grain size of the broken glass. For sintered glass, a larger grain is advantageously used for the starting product than for foam glass. It can be seen from FIG. 5 that the unblown sintered body 21 'is homogeneously interspersed with grains of an active substance 17 and possibly with cavities 15'.
• the cavities 15 in the foam glass body 21 are not spherical and significantly smaller. It is assumed that the cavities form a labyrinth through which water can flow or which is easily penetrated by pollutants or active substances. In any case, the test results with unfoamed sintered bodies according to the invention are surprisingly so good that it is assumed that A much larger area of the active substance iron is effective in the purification of waste water than only that which is visible on the surface of the granulate.
• FIGS. 6 and 7 show the results from experimental examples for water decontamination.
• the results from a test with inflated granules according to the invention are compared with the results from a second test with only sintered granules according to the invention.
• Ground glass from Misapor (grain size ⁇ 0.2 mm) is used as the starting material for the production of the foamed granulate.
• the ground glass from Misapor is mixed with 2% SiC and 8% iron powder (manufacturer: RochoU) in a ball mill and then foamed in a clay pot in a muffle furnace.
• crushed waste glass (grain size 0.355-0.5 mm) is used in the jaw crusher.
• the glass crushed in the jaw crusher is also mixed manually with 8% of the same iron powder (manufacturer: RochoU) and 21 ml of demineralized water and then sintered in a clay pot in a muffle furnace.
• Grain sizes of the starting products, proportions of foaming agent, metallic iron and water in the mixture, test quantities, grain size of the granulate and the temperature and the residence time of the two sinterings can be found in the following table.
• the copper solution used has the following properties: Cu (NO 3 ) 2 in HNO 3 with a concentration of 1000 mg / 1 Cu (Merck standard solution) diluted with demineralized water to a concentration of 10 mg / 1 Cu. This results in a pH value of -2.5 for the copper solution.
• the pH value of the solution taken is measured.
• the solution is then acidified with 1 ml of 1 molar HNO 3 solution and left to stand for 10 min. The solution is shaken occasionally during these 10 minutes. Now the solution is filtered (feed paper: Schleicher & Schüll) and schHessHch analyzed in the atomic absorption analysis spectrometer.
• the copper concentrations shown in FIG. 6 are measured in the samples taken after 5, 10, 20 and 40 minutes. Surprisingly, it can be determined that the foamed and sintered glass cut almost equally well. There are only small differences in the kinetics.
• closed-pore or open-pore foam glass and unfoamed sintered glass are used according to the invention as carrier material for an active substance enclosed therein, e.g. Iron dust, iron filings, activated carbon or magnesium oxide are used and broken down into granules.
• the granulate made of closed-pore foam glass is pressure-resistant, light and has a large, quickly effective surface made of concave pore surfaces of broken pores. The pore size and the specific weight of the granulate can be adjusted during production.
• a granulate made of non-foamed sintered glass has a high compressive strength and a higher specific weight. Despite its smaller macroscopically visible surface, it is just as effective as a foam glass granulate.
• the granulate can be produced industrially and economically from recycled glass waste.
• the granulate can be used as bulk material for water purification.
• the areas of application are, for example, drinking water treatment from groundwater, contaminated.
• the granulate can be regenerated chemically and thermally.
• the regenerated product can be blown into new foam glass or sintered into unexpanded sintered glass and then used as building material such as concrete aggregate or perimeter insulation, or again as bulk material for water purification.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Ceramic Engineering (AREA)
• Environmental & Geological Engineering (AREA)
• Water Supply & Treatment (AREA)
• Hydrology & Water Resources (AREA)
• Structural Engineering (AREA)
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• Inorganic Chemistry (AREA)
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• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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• Treatment Of Water By Oxidation Or Reduction (AREA)
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• Removal Of Specific Substances (AREA)

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• 2004
  • 2004-06-21 US US10/561,525 patent/US20070104949A1/en not_active Abandoned
  • 2004-06-21 JP JP2006515625A patent/JP2007506535A/ja active Pending
  • 2004-06-21 BR BRPI0411416-7A patent/BRPI0411416A/pt not_active Application Discontinuation
  • 2004-06-21 WO PCT/CH2004/000377 patent/WO2004113245A1/de active Application Filing
  • 2004-06-21 EP EP04737073A patent/EP1651580A1/de not_active Withdrawn
  • 2004-06-21 CA CA002529871A patent/CA2529871A1/en not_active Abandoned
• 2006
  • 2006-01-19 NO NO20060284A patent/NO20060284L/no not_active Application Discontinuation

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