• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The subject of this invention is a process for the recovery or recovery of acids from metal-containing solutions by spray roasting the solutions in a Sprühöstreaktor (2) and subsequent absorption and / or condensation of the resulting gases, wherein metal oxides are formed by the spray roasting. According to the invention, the metal oxides are reduced immediately after the spray roasting with the aid of a reducing agent (24) in a separate reduction furnace (20). The subject of this invention is also a device with which the method according to the invention is carried out.
    公开号:AT515414A4
    申请号:T255/2014
    申请日:2014-04-07
    公开日:2015-09-15
    发明作者:Jovan Dipl Ing Dr Techn Starcevic；Luis Dipl Ing Coronado
    申请人:Andritz Ag Maschf；
    IPC主号:
    专利说明:

    Process and apparatus for the recovery of acid from metal-containing solutions with oxide treatment
    The subject of this invention is a process for the recovery or recovery of acids from metal-containing solutions of these acids. By spray roasting the solutions and subsequent absorption and / or condensation of the gases formed on the one hand, the acids are regenerated and on the other hand formed metal oxides.
    The subject of this invention also forms an apparatus with which the method according to the invention is carried out.
    The metal-containing solutions of the acids are preferably HF, HNO 3, HCl, Fe, Cr, Mn, Ni compounds and mixtures of these compounds.
    For the recovery of acids, it is known that aqueous solutions of metal compounds are sprayed with the aid of nozzles in fine droplets into a heated reactor, a so-called spray roasting reactor. Due to the heat development, the liquid first evaporates (evaporation phase) and then the metal compounds begin to decompose (oxidation phase). The drops fall in free fall to the reactor bottom and are roasted within a few seconds, i. pyrolytically separated into a metal oxide and an acid moiety. The decomposition takes place at temperatures between 450 ° C - 900 ° C, preferably at 550 ° C-700 ° C instead. The acid moieties are removed at the reactor head and the oxide is removed via an opening in the reactor bottom. The acid moieties are then absorbed or condensed.
    Such acid regeneration methods are known from AT395312B. Also for the HCl decomposition, analogous processes are known, for example, from AT264248B. Here, the metal-containing solution of hydrochloric acid to be regenerated is evaporated countercurrently by the exhaust gas and then decomposed in the reactor.
    The spray roasting reactor can also be subdivided into two zones by means of internals, whereby in the upper zone an evaporation takes place at low temperature and in another directly adjacent zone a decomposition takes place at high temperature. Such a reactor is described in AT407757B.
    Because of the short residence time, there is always some residual acid content on the metal, e.g. Iron, bound, which often can not be sufficiently removed and remains as a disturbing impurity (acid residues) in the oxide. Sprühöstreaktoren are therefore also known in which in the reactor in a subsequent separated area further oxidation or post-roasting takes place. Thereby, a complete oxidation of the metal salts containing solutions can be achieved. Acid residues are thus largely removed from the oxide, resulting in a dry, acid-free metal oxide. Such a regeneration plant with Nachröstung is described in AT409373B.
    Especially in the old acid processing of spent stainless steel pickling baths with so-called PYROMARS plants (acid recovery plants) from Andritz, a powdered metal oxide is produced. The composition of the oxide corresponds to the composition of the scale of the pickled
    Stainless steel strips, it mainly contains iron (Fe), chromium (Cr), nickel (Ni), manganese (Mn) and optionally other metals.
    Mainly because of the relatively high nickel content of the metal oxides, the revenue that can be achieved by oxide utilization is a significant factor in the economics of the PYROMARS plants. Despite these relatively high market values, the oxide is more of a problem due to the lack of recovery technologies.
    In Europe, the resulting metal oxide is sent to industrial waste processing plants in Sweden or France. At POSCO in Korea and China (ZPSS), the oxide is reused in-house by mixing it with other waste, compressing it, and then adding it to steelmaking. However, there are other examples where operators of acid regeneration plants still do not have a satisfactory solution for the oxide utilization. In India or Malaysia, the oxide may not be exported for further processing due to export restrictions. From factories in China, the oxide is sold far below market value because there are no reasonable recycling options.
    The above-mentioned AT409373B also describes the possibility of reducing the post-roasting with reducing atmosphere such as e.g. H2, steam, methane or CO to operate. As a result, certain oxide modifications can be obtained in a favorable manner. However, post-roasting in a reducing atmosphere has the disadvantage that the oxidizing atmosphere in the top of the reactor has to be separated from the reducing atmosphere in the bottom. This is complex and usually only inadequately possible. In addition, high temperatures of 1300-1700 ° C can not be achieved in this lower reactor area, but these are necessary for the complete reduction of all metal oxides, especially chromium.
    This AT409373B roasting in a reducing atmosphere is therefore primarily suitable for the preparation of certain oxide modifications, but not for a substantially complete reduction of the oxide to metals.
    Although processes for the reduction of iron oxide to iron are known, but complex in terms of equipment and energy-intensive.
    The invention is therefore based on the object to provide a method and an apparatus with which the metal oxide obtained in the acid recovery can be processed more efficiently.
    This object is achieved by a process for the recovery or recovery of acids from metal-containing solutions of these acids, in which the metal oxides are reduced immediately after the spray roasting with the aid of a reducing agent in a separate reduction furnace.
    As a result, the resulting metal oxides can be converted by the reduction to metals directly on site into a higher quality product. There is no additional staff required for oxide reduction.
    Preferably, the metal oxides formed are fed directly after the spray roasting in the hot or hot state, the reduction furnace.
    Therefore, the metal oxide does not have to be dried and preheated before reduction because it is still hot from the roasting process.
    The exhaust gases from the reduction furnace are advantageously fed to the spray roasting reactor. Preferably, they are introduced tangentially into the spray roasting reactor. The reduction furnace does not need its own exhaust gas purification, as these exhaust gases are cleaned directly by the gas purification system of the acid recovery system. In addition, the hot exhaust gases of the reduction furnace can be used to heat the Sprühöstreaktors, thereby reducing the gas consumption of Sprühröstreaktors.
    The hot exhaust gases of the reduction furnace are preferably introduced into the spray roasting reactor in such a way that the flow conditions required for spray roasting are maintained and even improved by the tangential introduction since this induces a swirl in the flow.
    It makes sense if coal dust is used as the reducing agent for the reduction, but also the use of other reducing agents such as coke, hydrogen, methane or carbon monoxide is conceivable.
    It is also conceivable that aluminum powder is used as the reducing agent. This thermite reaction is very exothermic. Here, apart from the ignition energy, no further energy supply would be required for the reduction reaction.
    It is advantageous if the reduction furnace is heated by a plasma torch, thereby very high temperatures and good reduction conditions can be set, whereby even high-purity products that consist essentially of metals can be produced.
    It is also conceivable that the reduction furnace is a shaft furnace or that the reduction is carried out with the aid of a circulating fluidized bed.
    The invention also provides a corresponding device for carrying out the method according to the invention, with an oxide discharge for applying the metal oxide formed in Sprühröstreaktor. The Sprühöstreaktor is indirectly or directly connected via a line for the metal oxides with the reduction furnace, where the metal oxides are reduced to metals.
    Advantageously, the exhaust pipe of the reduction furnace is connected to the Sprühöstreaktor so that the Sprühöstreaktor is at least partially heated by the exhaust gases of the reduction furnace.
    1 shows a possible embodiment of the device according to the invention is shown. The acid regeneration plant 1 consists of a spray roasting reactor 2, into which a stripper 3, for example from a mixed acid pickling plant, is sprayed via nozzles 8. By means of a burner 4, e.g. Gas and combustion air are supplied, the Abbeize is heated and decomposed. At the burner level, temperatures range from 750 ° C to over 1000 ° C. From the top of the Sprühöst reactor 2, the hot exhaust gases to a
    Dust separator 9 passed, in which the remaining solids are deposited. Subsequently, the exhaust gases reach an absorption system 10 and a condensation system 11. In the subsequent exhaust gas purification 13, among other things, nitrogen oxides are removed. Such plant components for acid recovery are well known to those skilled in the art and are therefore not described in detail here.
    The regenerated acid is removed via the line 12 and can be supplied to the pickling process again.
    Below the roasting zone 5 is a Nachröstzone 6. The two zones 5 and 6 are separated by a rotating Krählwerk 7. By Krählwerk the metal oxide particles are transported to the reactor center, where they fall through a hole in the Nachröstzone 6.
    The heating of Nachröstzone 6 via a gas burner 14. At the bottom of Nachrösters 6 another Krählwerk 15 is arranged, which transports the oxide from the center of Nachröstbereiches to the edge to Oxidaustrag 16.
    The metal oxides pass through the conduit 17 into the reduction furnace 20. The metal oxides are still hot from the previous roasting process and need not be preheated and not dried.
    The reduction furnace 20 is heated here by a plasma torch 21 to which gas 22 and electrical energy 23 are supplied. In the plasma torch 21, electrical energy is converted into heat and transferred to the gas 22, which is in the plasma state. With the help of
    Plasma torch 21, temperatures of over 3000 ° C can be achieved.
    The reduction furnace 20, in addition to the oxides, a reducing agent 24 is supplied, this may for example be coal dust, methane, hydrogen, carbon monoxide or a synthesis gas, and the supply of aluminum powder is conceivable.
    Optionally, the reduction furnace 20 may be supplied with another additive via the conduit 25, e.g. a slag maker to obtain a purer metal.
    In the reduction furnace 20, the metal oxide is reduced by the reducing agent 24 and converted into the pure metal form. In the case of a mixed acid regeneration, the high-purity product 27 consists essentially of iron (Fe),
    Chromium (Cr), nickel (Ni) and manganese (Mn). It can therefore easily be resold or fed to a smelting furnace during steelmaking.
    The hot exhaust gases (about 1200 ° C) from the reduction furnace 20 are fed via the exhaust pipe 26 to the Sprühöstreaktor 2. The exhaust gases have a temperature of about 1200 ° C. As a result, the reduction furnace 20, on the one hand, does not need its own extraction or exhaust gas purification. On the other hand, the hot exhaust gases are used in the Sprühöstreaktor 2 for roasting, thereby reducing the gas consumption of the Sprühöst reactor 2 over conventional reactors.
    The embodiment shown in the drawing represents only a preferred embodiment of the invention. The invention also includes other embodiments in which, for example, the Sprühöstreaktor has only one zone.
    权利要求:
    Claims (10)
    [1]
    1. A process for the recovery or recovery of acids from metal-containing solutions by spray roasting the solutions in a Sprühöstreaktor (2) and subsequent absorption and / or condensation of the gases formed, wherein metal oxides are formed by the spray roasting, characterized in that the metal oxides be reduced immediately after the Sprühösten using a reducing agent (24) in a separate reduction furnace (20).
    [2]
    2. The method according to claim 1, characterized in that the metal oxides formed are fed directly after the Sprühösten still warm or hot state, the reduction furnace (20).
    [3]
    3. The method according to claim 1 or 2, characterized in that the exhaust gases from the reduction furnace (20) are supplied to the Sprühöstreaktor (2).
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the reducing agent (24) is used for the reduction of metal oxides coal dust.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the reduction furnace (20) by a plasma torch (21) is heated.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that the exhaust gases from the Sprühöstreaktor (2) and the exhaust gases from the reduction furnace (20) are brought together and cleaned together.
    [7]
    7. The method according to claim 6, characterized in that the Sprühöstreaktor (2) is at least partially heated by the hot exhaust gases from the reduction furnace (20).
    [8]
    8. A device for recovering or recovering acids from metal-containing solutions by spray roasting the solutions in a Sprühöstreaktor (2) with an oxide (16) for applying the Sprühöstreaktor (2) formed metal oxides, characterized in that the Sprühröstreaktor (2) indirectly or directly via a line (17) for the metal oxides with a reduction furnace (20) is connected, wherein the metal oxides in the reduction furnace (20) by the addition of a reducing agent (24) reducible and so into the metal mold (27) can be transferred.
    [9]
    9. Apparatus according to claim 8, characterized in that an exhaust pipe (26) of the reduction furnace (20) with the Sprühöstreaktor (2) is connected, so that the Sprühröstreaktor (2) by the exhaust gases of the reduction furnace (20) is at least partially heated.
    [10]
    10. Device according to one of claims 8 or 9, characterized in that the reduction furnace (20) by a plasma torch (21) is heated.
    类似技术:
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    同族专利:
    公开号 | 公开日
    AT515414B1|2015-09-15|
    WO2015155017A1|2015-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE2251385A1|1971-10-20|1973-04-26|Cationic Corp|PROCESS FOR THE RECOVERY OF ACID AND METAL FROM CONSUMED PICKLING SOLUTIONS|
    AT395312B|1987-06-16|1992-11-25|Andritz Ag Maschf|METHOD FOR RECOVERY OR RECOVERY OF ACID FROM METAL SOLUTIONS OF THIS ACID|
    AT409373B|1997-08-06|2002-07-25|Andritz Ag Maschf|METHOD AND DEVICE FOR WINNING OR RECOVERY OF ACIDS FROM SOLUTIONS|
    AT407757B|1999-03-22|2001-06-25|Andritz Patentverwaltung|METHOD FOR RECOVERY OF ACIDS FROM METAL SOLUTIONS OF THESE ACIDS|
    US3053626A|1959-05-08|1962-09-11|Chempro Inc|Decomposition of heavy metal sulfate solutions with the recovery of sulfur dioxide and the heavy metal oxide|
    NL132526C|1965-04-17|
    CN102091788B|2010-11-23|2013-07-17|北京科技大学|Method for industrially producing iron-based dispersion-strengthened material|AT522593B1|2019-09-24|2020-12-15|Sustec Gmbh|Recovery of acids and metals from dry salt compounds|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA255/2014A|AT515414B1|2014-04-07|2014-04-07|Process and apparatus for the regeneration of hydrochloric acid from metal-containing solutions with oxide treatment|ATA255/2014A| AT515414B1|2014-04-07|2014-04-07|Process and apparatus for the regeneration of hydrochloric acid from metal-containing solutions with oxide treatment|
    PCT/EP2015/056511| WO2015155017A1|2014-04-07|2015-03-26|Method and device for recovering acid from metal-containing solutions by means of oxide processing|
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