• 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:
    In a process for working up iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts, the dusts and primary oxygen are introduced into a mixing chamber, the dusts are deagglomerated by the action of shear forces and mixed with the primary oxygen to obtain a dust-oxygen mixture, wherein the dust-oxygen mixture is discharged via an annular throttle gap from the mixing chamber into an expansion chamber having a reduced pressure compared to the mixing chamber, from which the dust oxygen mixture is ejected together with the latter into a combustion chamber by the impulse of a fuel, in particular fuel gas jet, in which the mixture is melted under supply of secondary oxygen and in the presence of elemental chlorine and optionally chloride carriers to melt droplets, the resulting iron chlorides are stripped off in gaseous form and those of iron oxides and possibly chromium oxides befoth agglomerated melt droplets and the melt is collected in a melt container.
    公开号:AT519251A4
    申请号:T588/2016
    申请日:2016-12-30
    公开日:2018-05-15
    发明作者:Edlinger Alfred
    申请人:Radmat Ag；
    IPC主号:
    专利说明:

    The invention relates to a process for working up iron oxide and phosphorus oxides and, if appropriate, chromium oxide-containing dusts, and to an apparatus for carrying out the process.
    In the chemical industry, in iron and non-ferrous metal production, in mining, in waste and sewage sludge incineration, in the production of biomass energy and the like, fine dust accumulates, whose recycling and landfill have not been satisfactorily resolved. Such fine dusts preferably have a particle size of less than 250 μm and can be composed of inorganic and organic compounds. They arise, e.g. also by drying various sludges and represent a high environmental impact.
    Inorganic constituents are, for example, CaO, MgO,
    SiO 2, Al 2 O 3, Cr 2 O 3, Fe x O, P 2 O 5, TiO 2, SO x, alkalis,
    Halides, sulfides, sulfites, sulfates, various oxygen-affinity metal species (sub-group elements, in particular Zn). Organic ingredients include, for example, ozokerites, earth waxes, fatty acids, hydrocarbons (aromatics, aliphates), dioxins, furans, PCBs, biphenyls, biocides, antibiotics, hormones, endocrines, drug residues and the like.
    Due to their composition, e.g. Sewage sludge can no longer be utilized agriculturally and should preferably be fed to a mono-combustion. However, the utilization of the resulting combustion residues is still not satisfactorily resolved, since these also have a high pollutant potential. In addition, the existing iron and steel form
    Phosphorus oxides insoluble compounds, which greatly reduce the plant availability of the phosphate content.
    In WO 03/070651 Al a device for melting dusts has already been proposed, in which the dusts are injected with a carrier gas into a combustion chamber, the dusts are introduced axially and the carrier gas tangentially into a cyclone and the cyclone via a in the essentially axially directed discharge opening is connected to a combustion chamber. Characterized in that the combustion chamber is preceded by a cyclone, which is effective as Dosierzyklon, it is possible to give the material by the tangential injection of carrier gas a correspondingly rotating movement, which leads to the dust entering the subsequent combustion chamber under a defined spin. In this case, coaxially to the Zyklonaustragsöffnung fuel and optionally further carrier gas can be injected into the combustion chamber. Such a coaxial feed of fuel makes it possible to mix the dusts injected under a swirl in a first area with the fuel gases, whereupon a rapid melting of the dusts is made possible with particularly rapid temperature transfer in the flame.
    However, the devices known from the prior art lead to problems in the dust supply, in particular in the burner mouth, since it is in the region of the transition from the cold region of the dust supply to the hot combustion chamber, i. This results in frequent overheating, fusing, sticking and sintering as well as caking and agglomeration (so-called "beard formation").
    The droplet discharge after the combustion chamber also leads to caking problems in the downstream exhaust gas treatment with corresponding material losses (for example CaO, P2O5 or p2). The hermetic efficiency is very low, since a large part of the heat is dissipated by the large volume of exhaust gas and is not used in the system.
    Furthermore, the slag melt has a comparatively low thermal conductivity. This leads to big problems in the tapping area, so that it often leads to blockages, which leads to great effort during operation.
    The treatment of sewage sludge or sewage sludge ash poses special problems. Sewage sludge can also contain environmental toxins, such as heavy metals, halogens, pesticides, herbicides, antibiotics, carcinogenic and mutagenic pollutants, chlorinated hydrocarbons, polychlorinated biphenyls, hormones and endocrines in addition to largely harmless natural products. Among the metals contained in sewage sludge are, in addition to the heavy metals copper, zinc and cadmium, various oxides of calcium, silicon and aluminum to call, in particular the presence of iron oxides makes it impossible to obtain pure phosphorus, since phosphorus combines with iron to form phosphorous iron and thus can not be recovered in the presence of iron. The content of various metals and heavy metals usually prevents the direct use of sewage sludge as a fertilizer, which is why sewage sludge and sewage sludge ash must be deposited in large quantities. The
    Phosphate availability, measured, for example, as "citrate solubility", is very low for plants because of the high iron oxide content, and the landfilling of sewage sludge means that the valuable materials contained, and in particular those that are not only of interest to the fertilizer industry, can not be used.
    In WO 2012/065798 Al has been proposed to treat sewage sludge with chloride carriers and then subjected to an oxidative thermal treatment. This procedure results in the metals contained in the oxidation step being converted into metal chlorides which are excessively volatile at the very high temperatures due to the chloride addition and can therefore be removed with the gas phase. The remaining fraction may subsequently be subjected to a reduction in which pure phosphorus can be obtained from the phosphorus oxides contained. A reprocessing of dusts is not described in WO 2012/065798 Al.
    The invention now aims to provide a method and a device with which or the iron oxide and phosphorus oxides and optionally chromium oxide dusts for the production of phosphorus can be worked up efficiently and economically, in particular the problems of bonding, the formation of Caking and Agglomerattaildung and the very high combustion chamber temperatures are to be avoided.
    To solve this problem, the invention provides in a process for working up iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts essentially that the dusts and primary oxygen are introduced into a mixing chamber, the dusts disagglomerated by the action of shear forces and mixed with the primary oxygen are to obtain a dust-oxygen mixture, the dust-oxygen mixture is discharged via an annular throttle gap from the mixing chamber into an opposite the mixing chamber reduced pressure expansion chamber, from which the dust-oxygen mixture by the pulse of a Fuel, in particular fuel gas jet is ejected together with this in a combustion chamber in which the mixture is melted under supply of secondary oxygen and in the presence of elemental chlorine and optionally chloride carriers to melt droplets, wherein the resulting iron chlorides and the g gf. Evolved chromium chloride is removed in gaseous form and agglomerated by iron oxides and possibly chromium oxides largely freed melt droplets and the melt is collected in a melt container.
    The dusts to be worked up are preferably pyrolyzed, pulverized sewage sludge or sewage sludge liquor originating from the combustion of sewage sludge. Sewage sludge ash is particularly preferred because it has a high content of up to 25 wt .-% phosphorus oxides.
    The slagging of sewage sludge or its ashes together with elemental chlorine or chloride carriers, e.g. Clz, CaCl2, HCl, KCl, NaCl leads to volatilization of Fe in the chloride form:
    In the case of the addition of chlorine gas (Cl2), the oxygen in the FeO is oxidized by the chlorine gas, forming FeCl2 / FeCl3 and free, oxidized oxygen (Oa), thereby reducing the chlorine to chloride anions:
    ("Reaction I")
    This reaction, referred to as "oxychlorination" thus means that O 2 'is "oxidized" by Cl 2 and the elemental chlorine is reduced to chloride anions (CI ").
    In this case, a metallization of the iron oxides to be prevented because they would otherwise not be accessible to the chloridation reaction. In order to prevent metallization of FeO, the procedure is such that an oxidizing atmosphere is maintained in the combustion chamber with respect to the oxidizing agent chlorine. Ensuring an oxidizing atmosphere means, in particular, that in addition to the C02 from the combustion still free oxygen (O2) is present in the combustion gas. However, even in the absence of free O 2, the oxychlorination still proceeds very rapidly at a CO partial pressure of up to 30% by volume (remainder CO 2). Apparently, the oxidized oxygen of Reaction I is rapidly degraded to CO 2 by CO, which has a positive effect on the above reaction equilibrium.
    With regard to the ratio of FeCl3 and FeCl2 formation, it has been found that the valence state of Fe is dependent on the O 2 -treatment pressure (in addition to the chlorine partial pressure) in the combustion chamber. At high O 2 partial pressure, predominantly FeCl 3 forms, which has a boiling point of 319 ° C. In the rather reducing range (no O2, but only CO2 / CO in the combustion chamber) predominantly FeCl2 forms, which has a boiling point of 1.026eC, wherein in the combustion chamber as mentioned a CO partial pressure of at most 30 vol .-% should be present. At a higher CO partial pressure undesirable compounds form. At a CO partial pressure of about 40 vol .-%, various undesirable chlorine-iron oxide phases begin to form with substoichiometric Wüstit share, which are no longer accessible to chlorination. At a CO partial pressure of about 60% by volume, metallic iron and elemental phosphorus begin to form and, as a consequence, the unwanted Fe3P (iron phosphorus).
    It was found that a higher oxygen partial pressure in the presence of free oxygen leads to the formation of FeCl3 predominantly instead of FeCl2. If there is no free oxygen, but mainly CO2, more FeCl2 is formed, which is less volatile than FeCl3.
    To obtain FeCl 2 / FeCl 3, i. for the oxychlorination, it is necessary that the fuel is anhydrous. Preferably, anhydrous CO is used as the fuel gas. Alternatively, coal dust can be used as fuel.
    The dusts introduced into the mixing chamber according to the invention have a particle size distribution which is characterized by a value d.sub.50 of <250 .mu.m.
    The dusts can be introduced as cold or / and as hot dusts in the mixing chamber.
    To carry out the method according to the invention, the invention provides a device comprising a mixing chamber with a feed opening for the task of dusts and with a discharge, wherein in the mixing chamber of a rotary drive rotatably driven, in particular rod-shaped mixing elements are arranged, opening into the mixing chamber nozzles for Incorporation of primary oxygen are provided and the discharge opening is formed by an annular throttle gap, further comprising an expansion chamber, which is arranged on the throttle gap, and a combustion chamber, which is arranged on the expansion chamber, wherein a coaxial with the annular throttle gap disposed in the Burner lance for introducing a fuel jet is provided expansion chamber or downstream of the expansion chamber, so that a dust-oxygen mixture by the impulse of the fuel jet together with this from d expansion chamber can be ejected into the combustion chamber, wherein in the combustion chamber nozzles for the supply of secondary oxygen, and further comprising a subsequent to a discharge opening of the combustion chamber melt container for collecting the resulting in the combustion chamber melt droplets and a trigger for removing the exhaust gases.
    In the context of the method and the device according to the invention thus come as essential components, the mixing chamber, the expansion chamber and the combustion chamber used.
    The mixing chamber serves to deagglomerate the dusts and mix them with the primary oxygen. For this purpose, shearing forces are generated in the mixing chamber, wherein this is preferably done by rotating, in particular rod-shaped mixing elements. In particular, it is provided that alternately rotating mixing elements and static mixing elements are arranged in the flow direction of the dusts. The static mixing elements act as static baffles and the rotating mixing elements act in the sense of turbulence of the dusts or the dust-oxygen mixture. The static mixing elements are preferably formed by rods which are mounted on the cylindrical housing of the mixing chamber and protrude from this radially into the interior of the mixing chamber. The rotating mixing elements are preferably likewise formed by rods, which are attached to a rotatably mounted about the cylinder axis of the housing rotor and protrude from this radially outward. The rotational speed of the rotor is preferably 30-200 min-1. The static and the rotating mixing elements overlap each other seen in the axial direction, so that between the static and the rotating mixing elements, a shearing action is generated and at the same time a turbulence takes place.
    The turbulence is further promoted by the fact that, as corresponds to a preferred embodiment, the nozzles for the introduction of the primary oxygen are arranged on the static mixing elements. The exit angle of the nozzles can be adjusted so that it comes to an optimal turbulence of the registered dust-like material.
    Preferably, there is a pressure gradient between the dust feed and the combustion chamber, which is a flow of the
    Dust-oxygen mixture causes toward the combustion chamber. For an evenly distributed over the cross section dust entry into the combustion chamber of the inventively provided annular throttle gap at the discharge of the mixing chamber of importance. Due to the throttling effect of the throttle gap, a very uniform dust distribution over the circumference of the throttle gap is achieved. Eventually entrained Staubagglomerat is disintegrated on the shear in this throttle range.
    In the expansion chamber immediately adjoining the discharge opening of the mixing chamber, a suction effect is produced which results at least in part from the fuel jet which is introduced in this region in order to introduce the dust-oxygen mixture into the combustion chamber. The injector effect of the fuel jet leads to an optimal premixing of the still cold oxygen-fuel-dust mixture.
    This results in the combustion chamber, a dense cold dust cloud in front of the burner mouth, whereby the intense heat radiation from the combustion chamber is greatly reduced to the burner system. The dense cloud of flue gas ignites due to their high inlet flow velocity only some distance away from the burner opening in the combustion chamber. The ignition speed of the flue cloud is, for example, 0.4 m / sec, the ignition speed is lower in comparison to the pure flame propagation speed, since the dense dust cloud delays it greatly. Only after falling below a critical dust density, depending on their flow velocity, ignites the
    Mixture in the hot combustion chamber very evenly. The described thermal protection of the burner mouth prevents caking or sintering of the supplied dust by the pre-stored in the combustion flue cloud.
    In the combustion chamber succeeds further turbulence by the supply of secondary oxygen. The supply of secondary oxygen may in this case preferably take place via an annular nozzle arranged coaxially with the fuel jet. The secondary oxygen jet in this case envelops the dust-oxygen-fuel mixture ejected into the combustion chamber and leads to uniform loading of the combustion chamber volume, where rapid, uniform combustion, heating and droplet formation of the material to be introduced occurs because of its large specific surface area. The heating, the melting and the thermochemical reactions are carried out here depending on the grain size and the particle size distribution of the dust preferably within 0.2 to 1.5 sec, with combustion gas temperatures of up to 1800 ° C are observed. The flow rate in the combustion chamber may preferably be 0.2-2.0 m / sec.
    The premixing of a cold gas-dust mixture still in the burner head area, as described above, and the secondary oxygen entry provide for a remote from the burner mouth ignition of the mixture and thus prevent the unwanted and dangerous caking / Ansintern the dust in the burner head area.
    By adjusting the combustion stoichiometry, defined as the ratio of the sum of fuel and
    Organic fraction in the dust to oxygen, an oxidizing atmosphere (lambda> 1) can be generated in the combustion chamber, so that the dust-oxygen-fuel mixture in the combustion chamber in the presence of elemental chlorine (CI2) and possibly chloride carriers in an oxidizing atmosphere to melt droplets can be melted. The resulting iron chlorides are removed with the exhaust gas. In order to agglomerate the droplet stream freed from iron oxides and, where appropriate, chromium oxides, it is passed into a melt container in which the melt is collected. In this case, the procedure is preferably such that the fuel / droplet mixture is guided from the combustion chamber through a highly turbulent agglomerating hot gas venturi into the region of the melt container. Its outlet mouth is directed to the melt contained in the melt container, wherein due to the impingement of the impact and the surface tension of the melt is a substantial droplet deposition from the gas phase.
    The resulting melt has, in contrast to molten metal only a very low thermal conductivity. Preferably, the melt is backed by a Sn / Cu / Ni alloy melt. This conducts the heat very well, protects the refractory structure of the melt container and collects sedimented metals from the melt. The alloy melt is preferably composed such that it forms a low-viscosity melt between 1050 ° C. and 1250 ° C. For example, this melt can be heated inductively in the low-frequency range, with turbulent stirring via the Lorentz force.
    The essentially iron-free mineral melt collected in the melt container is largely pollutant-free and can be used in a variety of ways.
    Preferably, the melt may be subjected to reduction to obtain elemental phosphorus. In particular, a carbothermal slag reduction can be carried out, in which highly pure elemental phosphorus ("white phosphorus", Pa) can be obtained in very high yield, since no phosphorus iron can be formed as undesirable by-product The reduction on an at least partially inductively heated column is known for example from WO 2006/079132 A1, this document also a corresponding device for carrying out a With an at least partially inductively heated coke column, extremely high temperatures can be achieved, whereby a reducing atmosphere can be set, since the carbon of the column does not react with combustion products and in particular e is not in thermal equilibrium with CO2. For the reduction of the melt to obtain elemental phosphorus (P2), it is advantageous if the melt has a CaO / SiO 2 ratio of 0.4-1.4. This can be achieved by adding lime carrier, e.g. CaCOs and / or CaO, or from CaCl2 to the melt or to the dusts to be worked up. Particularly advantageously, the setting of the CaO / SiO 2 ratio is achieved by adding a dust fraction which is obtained in the mechanical treatment of steel slag. In steelmaking e.g. With the LD method or the electric arc furnace, slags with a high CaO content are obtained. These are usually treated mechanically for the recovery of metallic iron, leaving a highly problematic dust fraction. This dust fraction can be added to the dusts to be worked up as an additive for adjusting the required basicity (CaO / SiO 2). Since the said dust fraction also contains phosphorus and chromium, this not only makes it possible to utilize the otherwise problematic dust to be dumped, but also to recover the phosphor contained by the oxychlorination according to the invention. As could be observed, under the described chlorination conditions, the chromium content of said dust fraction originating from the workup of the steelworks slags can be favorably removed, the chromium content being transported into the gas phase, namely by volatilization in the form of chromium oxychloride (CrO 2 Cl 2) and chromium chloride (CrCl 2 , CrCl3, CrCli), and an iron and chromium-free melt is obtained. The described utilization of the dust fraction is of particular interest for steelmaking from high phosphate iron ores, e.g. so-called "minette ores", which are no longer smelted due to the high proportion of P. Such steel slags have P20s values of up to 20% by weight, which were previously possible as "Thomas flour" or phosphorus fertilizers Utilization of the slag is not permitted today due to the high chromium content of the slag.
    Alternatively, the substantially iron-free melt can also be used to make a fertilizer.
    The water vapor granulation of the melt leads to a highly porous granulate, which has optimal plant availability due to the absence of iron. The phosphate plant availability, for example, is much larger than in the known Thomas flour, as has been shown, inter alia, in the citric acid test. In addition, the absolute chromate freedom of such alternative fertilizers is worth mentioning.
    Alternatively, pollutant-free phosphoric acid can be prepared from the melt. By acidification of the melt with sulfuric acid, high purity phosphoric acid is recovered. The calcium compounds arise as a practically insoluble gypsum, the silica precipitates colloidally.
    Alternatively, by granulating the melt in sulfuric acid, superphosphates can be prepared.
    In connection with the feature of the invention, according to which the dust-primary oxygen mixture is melted to melt droplets in the presence of elemental chlorine and possibly chloride carriers, it is in principle possible that the chloride carriers are already contained in the dusts to be processed, or that elemental Chlorine and optionally the chloride carrier is added during the process according to the invention. In the first case, the chloride may preferably be introduced as HCl with the dusts in the mixing chamber. For example, a sewage sludge ash to be processed can be pretreated with HCl. This saves the addition of CaCl 2 during the process of the invention. The pretreatment can be carried out, for example, by treating sewage sludge ash with gaseous HCl in a fluidized bed. The sewage sludge ash can also be processed with aqueous hydrochloric acid to a suspension; The disadvantage here, however, is that the product must be dried before further processing.
    In the second case, the addition of elemental chlorine and possibly chloride carriers can be carried out in different phases of the process. Preferably, the chloride can be introduced as gaseous HCl separately from the dusts in the Mischkaramer. But it is also possible that Cl2 gas is introduced into the mixing chamber and / or in the combustion chamber. The addition of elemental chlorine gas leads to a very rapid reaction to FeCl2 / FeCl3 and thus to the intended iron volatilization. The addition of Clj gas is preferably via the coaxial with the fuel jet arranged annular nozzle, i. with the secondary oxygen.
    Alternatively, as the chloride carrier CaCl 2 can be introduced into the mixing chamber and / or into the combustion chambers.
    With respect to the pressure ratios in the mixing chamber, the expansion chamber and the combustion chamber is preferably provided that the combustion chamber is kept under a pressure lying under the pressure of the expansion chamber. Furthermore, it is preferred if there is a pressure level below the expansion chamber in the combustion chamber. There is thus a falling pressure gradient from the mixing chamber via the expansion chamber to the combustion chamber, on the one hand the transport of the feedstock in the desired direction and on the other hand, the desired
    Mixing of the oxygen-fuel-dust mixture and the spacing of the flame from the burner mouth causes. The pressure gradient can preferably be achieved by arranging a Saugzuggebläses in the trigger.
    The expansion of the dust-primary-oxygen mixture taking place in the expansion chamber is promoted by the annular throttle gap, through which the dust-primary-oxygen mixture is discharged from the mixing chamber into the expansion chamber. Preferably, the throttle gap in this case surrounds the discharge opening of the mixing chamber annular. In order to produce an additional shearing action in the throttle gap, it is preferably provided that the throttle gap is delimited by two annular surfaces which have a relative rotational speed to one another. The speed gradient between an annular surface formed on a rotary ring and an annular surface formed on a rigid ring effectively disintegrates dust agglomerate entrained from the mixing chamber.
    The exhaust gas containing iron chlorides of the combustion chamber can be used in various ways. According to a preferred procedure, the exhaust gas of the combustion chamber containing the iron chlorides is cooled with addition of water and subjected to pyrohydrolysis, the iron chlorides being converted into magnetite (Fe 3 C> 4) and / or hematite (Fe 2 O 3) and HCl.
    Indirect, anhydrous cooling gives FeCl 2 and FeCl 3, which can be used, for example, in water treatment as a phosphate precipitant.
    An alternative use of the exhaust gas provides that the exhaust gas containing the iron chlorides and possibly melt droplets with the addition of iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts (as cold material) is cooled and the cooled dusts optionally together with the solidified melt droplets in the mixing chamber be introduced. This allows a secondary dust return to the burner system. In order to facilitate the return, the trigger preferably has a separator for separating solid particles from the exhaust stream.
    Preferably, the addition of iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts in the exhaust gas is also carried out with the addition of carbonate, hydroxide, oxidic and / or hydrous additives. The possibly entrained slag droplets freeze preferentially on the cold material. In particular, carbonaceous additives (eg limestone) are calcined under strongly endothermic conditions ("deacidified"), which leads to the desired strong reduction in temperature, but the cold material can preferably also contain hydrocarbons or carbon carriers, so that here too the strong endothermic heterogeneous and homogeneous water gas reaction resp Thus, the sensible heat of the exhaust gas is converted into chemical energy in the form of Ha and CO. This fuel thus formed can then be used outside the process of the invention as fuel gas and significantly improves the economics of the process.
    Preferably, the addition of iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts in the exhaust gas is also carried out with the addition of Cl 2 gas and optionally O 2, so that a kind of "pre-chlorination" of dusts takes place, in which the FeO contained in the added dusts again one In view of the addition of chlorine gas in the presence or addition of free O 2, especially FeCl 3, which has a boiling point of 319 ° C. and can be taken off in gaseous form with the cooled exhaust gases of the combustion chamber, is formed The solid constituents of the exhaust gas are separated off in the separating device and returned to the mixing chamber, in order to enrich the melt with Cu, Zn, Cd, alkali or hydrogen To avoid Hg chlorides is preferably a subset of especially 5-15 Wt .-% of the separated solid particles withdrawn before the task in the mixing chamber and thus excluded from the return to the mixing chamber.
    The gases remaining after the separator can be subjected to fractional condensation or cooling to obtain FeCl3 (boiling point 319 ° C) and FeCl2 (boiling point 1,026 ° C) separated from each other.
    As regards the arrangement of the nozzles for the supply of secondary oxygen into the combustion chamber, a preferred embodiment provides that the nozzles are arranged along a ring arranged coaxially with the burner lance and preferably at the inlet of the fuel jet into the combustion chamber. With regard to the design of the annular nozzle, it is preferred if the alignment of the nozzle axes of the individual nozzles alternately perpendicular, i. parallel to the fuel jet, and are arranged inclined inwards to the fuel jet. On a nozzle with a vertical nozzle axis thus follows a nozzle with an inclined nozzle axis, on this again a nozzle with a vertical nozzle axis, etc. The alternating secondary nozzle axes have a positive effect on the dust and heat distribution in the combustion chamber. In particular, the problematic dust sintering at the burner mouth ("beard formation") can be greatly reduced or prevented by backflow effects at the burner mouth Backflow conditions become particularly important if one wishes to agglomerate the droplets forming from the dust in a targeted manner into larger droplet units or to perform gas / melt reactions in the combustion chamber, which leads to a corresponding necessary increase in the average droplet residence time in the combustion chamber. The particles can be melted to be slagged in the subsequent melt sump.
    The invention will be explained in more detail with reference to embodiments shown schematically in the drawing. 2 shows a sectional view of the mixing chamber together with the expansion chamber and burner, and FIGS. 3 and 4 show a detailed view of an annular nozzle for use in the combustion chamber.
    Fig. 1 shows a mixing chamber 1, in which via a schematically indicated line 2 dusts can be introduced. The mixing chamber 1 has a cylindrical housing, on which a plurality of annular channels 3 are arranged, to which oxygen can be supplied via lines 4 and which are in communication with the nozzles 5 for primary oxygen discharging inside the mixing chamber 1. To the discharge opening 6 (Fig. 2) of the mixing chamber 1, an expansion chamber 7 adjoins, which in turn opens into the combustion chamber 8. At the mouth of the expansion chamber 7 in the combustion chamber 8, a burner opening is formed, via which a fuel, in particular fuel gas jet together with a dust-Primary oxygen mixture is ejected into the combustion chamber 8 f. The mixing chamber 1, the expansion chamber 7 and the combustion chamber 8 are arranged coaxially. An annular nozzle 9 is arranged coaxially to the burner mouth at the inlet of the fuel jet into the combustion chamber 8 and connected to a schematically indicated line 10 for the supply of secondary oxygen. The annular nozzle 9 comprises a plurality of nozzles 11 arranged along a coaxial with the burner mouth (FIG. 2).
    The combustion chamber 8 further has, at the transition into the melt container 14, a venturi nozzle 12 and a diffuser 13, via which the melt droplets and melt droplet agglomerates formed in the combustion chamber 8 are introduced into the melt container 14 and collected there as a melt bath 15. The melting bath 15 is located on a Sn / Cu / Ni alloy melt 16. The tapping of the melt 15 via a gas-tight tapping syphon 17. The deduction of originating from the combustion chamber 8 exhaust gases via the gas chamber 18 of the melt container 14 and the at this connected hood 19. The trigger 19 leads into a separator 20 for separating solid particles from the exhaust stream. The severed solid
    Particles can be returned via the line 2 in turn the mixing chamber 1. The gaseous fractions are optionally supplied to a further utilization via the line 21.
    The induced draft fan 22 provides the necessary negative pressure.
    In the hood 19 opens at the bottom of a line 23, via which the cooling of the exhaust gas serving substances can be introduced. Via this line 23, e.g. the Kaltgutaufgabe, i. the addition of iron oxide and phosphorus oxides and possibly chromium oxide-containing dusts, which are separated after passing through the trigger 18 via the separation device 20 and recycled via line 2. Alternatively, however, water can also be injected via line 23, with which the waste gas containing the iron chloride is cooled and subjected to pyrohydrolysis, the iron chlorides being converted into magnetite (Fe 3 C> 4) and / or hematite (F aO 3) and HCl, where Magnetite or hematite can be discharged via the separator 20. In this case, the Feststoffaustragsöffnung the separator 20 is not connected to the line 2.
    In the detail view according to FIG. 2, the mixing chamber 1, the expansion chamber 7 and the burner mouth are shown. It can be seen that in the interior of the mixing chamber 1 in the axial direction alternately static mixing elements 24 and rotating mixing elements 25 are arranged. The mixing elements 24, 25 are formed by bars, the static bars 24 are mounted on the housing and project radially inwardly and the rotating rods 25 are fixed to a rotating axial tube 26. At each level, a plurality of circumferentially distributed static bars 24 and rotating bars 25 are provided. On or in the static bars 24, the nozzles 5 are arranged. The rotatably mounted tube 26 is coupled to a rotary drive, not shown.
    Furthermore, a throttle gap 27 is provided in the mixing chamber 1, which is formed between a stationary ring 28 and a rotating ring 29 which is also secured to the rotating tube 26. The throttle gap 27 is arranged coaxially to the axis of the mixing chamber 1 or to its discharge opening 6. In the interior of the rotating tube 26, a fuel lance 30 is arranged adjustable in height, wherein the ejection nozzle of the fuel lance 30 opens below the throttle gap 27 in the expansion chamber 7 and emits a schematically indicated fuel jet 31.
    The annular nozzle 9 is at the mouth of the expansion chamber into the combustion chamber 8, i. arranged at the burner mouth and surrounds this annular. The nozzle openings of the annular nozzle 9 are denoted by 11 and are alternately parallel to the axis and inclined inwards or outwards.
    In Fig. 3 (vertical cross section) and 4 (horizontal cross section), the annular nozzle 9 is shown enlarged. It can be seen that the annular nozzle 9 has an annular nozzle chamber 32, which has a circular row of hole nozzles 11 formed in a nozzle plate 33. The annular nozzle chamber 32 is surrounded by a cross-sectionally U-shaped cooling water channel 35, which comprises a cooling water inlet 36 and a cooling water outlet 37. Furthermore, the ring nozzle can carry a refractory jacket 38.
    权利要求:
    Claims (21)
    [1]
    claims:
    A process for the treatment of iron oxide and phosphorus oxides and optionally chromium oxide-containing dusts, in which the dusts and primary oxygen are introduced into a Mischkaroroer, the dusts are deagglomerated by the action of shear forces and mixed with the primary oxygen to a dust-oxygen mixture to obtain the dust-oxygen mixture is discharged through an annular throttle gap from the mixing chamber into an opposite the mixing chamber having reduced pressure expansion chamber from which the. Dust-oxygen mixture by the pulse of a fuel, in particular fuel gas jet together with this in a combustion chamber is discharged, in which the mixture is melted under supply of secondary oxygen and in the presence of elemental chlorine and optionally chloride carriers to melt droplets, the resulting iron chlorides withdrawn in gaseous form and weitestg of iron oxides and possibly chromium oxides Immediately liberated melt droplets agglomerated and the melt is collected in a melt container.
    [2]
    2. The method according to claim 1, characterized in that the melt is subjected to a reduction for the extraction of elemental phosphorus.
    [3]
    3. The method according to claim 1 or 2, characterized in that the chloride is introduced as HCl with the dusts in the mixing chamber or separately introduced as gaseous HCl from the dusts in the mixing chamber.
    [4]
    4. The method of claim 1, 2 or 3, characterized in that Cl2 gas is introduced into the mixing chamber and / or in the combustion chamber.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that is introduced as the chloride carrier CaCl 2 in the mixing chamber and / or in the combustion chambers and / or in the melt container or is introduced premixed with the dusts to be worked up.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the supply of secondary oxygen via a coaxial with the fuel jet arranged, annular nozzle takes place.
    [7]
    7. The method according to any one of claims 4 to 6, characterized in that the addition of Clz gas via the annular nozzle, in particular as Cl2 / 02 mixture occurs.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the combustion chamber is held under a pressure lying under the pressure of the expansion chamber.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the exhaust gas containing the Eisenchloride the reaction chamber is cooled by addition of water reactive and subjected to pyrohydrolysis, wherein the iron chlorides to magnetite (FejO ^) and / or hematite (Fe203) and HCl are reacted.
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that anhydrous CO is used as fuel gas.
    [11]
    11. The method according to any one of claims 1 to 10, characterized in that the exhaust gas containing the iron chlorides and optionally melt droplets is cooled with the addition of iron oxide and phosphorus oxides and optionally chromium-containing dusts and the cooled dusts optionally together with the solidified melt droplets in the mixing chamber are introduced.
    [12]
    12. The method according to any one of claims 1 to 11, characterized in that the shear forces are applied in the mixing chamber by rotating, in particular rod-shaped mixing elements.
    [13]
    13. The method according to claim 12, characterized in that in the flow direction of the dusts alternately rotating mixing elements and static mixing elements are arranged, wherein the static mixing elements preferably have nozzles for expelling the primary oxygen.
    [14]
    14. The method according to any one of claims 1 to 13, characterized in that the annular throttle gap is bounded by two annular surfaces having a relative rotational speed to each other.
    [15]
    15. An apparatus for carrying out a method according to one of claims 1 to 14, comprising a mixing chamber with a feed opening for the task of dusts and with a discharge, wherein in the mixing chamber of a rotary drive rotatably driven, in particular rod-shaped mixing elements are arranged in the mixing chamber opening nozzles are provided for introducing primary oxygen and the discharge opening is formed by an annular throttle gap, further comprising an expansion chamber, which is arranged adjacent to the throttle gap, and a combustion chamber, which is arranged on the expansion chamber, wherein a coaxially arranged to the annular throttle gap , in the expansion chamber or downstream of the expansion chamber opening burner lance for introducing a fuel, in particular fuel gas jet is provided so that a dust-oxygen mixture by the impulse of the fuel jet together m it can be ejected from the expansion chamber into the combustion chamber, wherein in the combustion chamber nozzles for the supply of secondary oxygen, and further comprising an adjoining a discharge opening of the combustion chamber melt container for collecting the resulting in the combustion chamber melt droplets and a trigger for removing the exhaust gases ,
    [16]
    16. The apparatus according to claim 15, characterized in that in the flow direction of the dusts in the mixing chamber alternately rotating mixing elements and static mixing elements are arranged, wherein the static mixing elements preferably have the nozzles for expelling the secondary oxygen.
    [17]
    17. The apparatus of claim 15 or 16, characterized in that the nozzles for the supply of secondary oxygen optionally together with chlorine gas, arranged along a coaxial with the burner lance ring and preferably at the inlet of the fuel jet into the combustion chamber.
    [18]
    18. Device according to one of claims IS to 17, characterized in that the annular throttle gap is bounded by two annular surfaces, wherein at least one annular surface is drivable to rotate.
    [19]
    19. The method according to any one of claims 15 to 18, characterized in that in the trigger line for introducing iron oxide and phosphorus oxides and optionally chromium oxide-containing dusts or water opens.
    [20]
    20. The method according to any one of claims 15 to 19, characterized in that the trigger is provided with a Saugzuggebläse.
    [21]
    21. The method according to any one of claims 15 to 20, characterized in that the trigger has a separator for separating solid particles from the exhaust stream.
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    同族专利:
    公开号 | 公开日
    EP3562967B1|2021-11-24|
    WO2018122599A1|2018-07-05|
    EP3562967A1|2019-11-06|
    AT519251B1|2018-05-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2005094153A1|2004-04-01|2005-10-13|Patco Engineering Gmbh|Device and method for oxidizing, reducing, calcining, sintering, or melting dusts using a dosing cyclone with a fuel lance|
    EP1591546A1|2004-04-27|2005-11-02|Patco Engineering GmbH|Process of recovering metals and/or metal oxides from steelworks dusts|
    WO2007068025A2|2005-12-16|2007-06-21|Patco Engineering Gmbh|Method for reprocessing metallurgical dust or grinding dust, and apparatus for carrying out said method|
    BE1004481A6|1990-06-29|1992-12-01|Centre Rech Metallurgique|Method and device for the pyrometallurgical treatment of a pulverulentsubstance containing a compound of one or more metals|
    DE19510874A1|1995-03-24|1996-09-26|Gruenzweig & Hartmann|Method and device for melting silicate recycling raw materials|
    PL213915B1|2009-06-22|2013-05-31|Henryk Karcz|Method and installation for energy recycling from meat and bone meal|
    AT509593B1|2010-11-15|2011-10-15|Sgl Carbon Se|METHOD FOR REPROCESSING ORGANIC WASTE MATERIALS|
    DE102015206170A1|2015-04-07|2016-10-13|Sgl Carbon Se|Process for the treatment of dusts containing zinc for the production of a usable zinc product and for the production of an artificial iron ore|WO2021152386A1|2020-02-02|2021-08-05|Radmat Ag|Method for separating phosphorus and/or phosphorus compounds from phosphorus carriers and/or phosphate carriers containing iron |
    法律状态:
    2020-09-15| PC| Change of the owner|Owner name: ALFRED EDLINGER, AT Effective date: 20200721 |
    优先权:
    申请号 | 申请日 | 专利标题
    ATA588/2016A|AT519251B1|2016-12-30|2016-12-30|Process for the reprocessing of iron oxide and phosphorus oxides containing dusts|ATA588/2016A| AT519251B1|2016-12-30|2016-12-30|Process for the reprocessing of iron oxide and phosphorus oxides containing dusts|
    EP17849828.3A| EP3562967B1|2016-12-30|2017-12-29|Method and device for treating dusts|
    PCT/IB2017/001607| WO2018122599A1|2016-12-30|2017-12-29|Method and device for treating dusts|
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