• 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 hydrochloric acid from metal-containing solutions of hydrochloric acid by pyrohydrolytic treatment and subsequent absorption or condensation of the resulting gaseous hydrogen chloride to form hydrochloric acid. According to the invention, a first substream of the metal-containing solution of the hydrochloric acid is subjected to the pyrohydrolytic treatment, and a second substream of the metal-containing solution is fed to the absorption column. The subject of this invention is also an apparatus for carrying out the method according to the invention.
    公开号:AT514420A4
    申请号:T748/2013
    申请日:2013-09-26
    公开日:2015-01-15
    发明作者:Frank Dr Bärhold
    申请人:Andritz Ag Maschf；
    IPC主号:
    专利说明:

    Process and apparatus for the regeneration of hydrochloric acid
    The subject of this invention is a process for the recovery or recovery of hydrochloric acid from metal-containing solutions of hydrochloric acid by pyrohydrolytic treatment of the solution and subsequent absorption or condensation of the resulting gaseous hydrogen chloride to form hydrochloric acid. The subject of this invention is also an apparatus for carrying out the method according to the invention.
    Metal-containing hydrochloric acid is obtained, for example, in the metal industry when pickling carbon steel. These solutions contain free hydrochloric acid and chloride-dissolved metals, such as iron. The hydrochloric acid with about 18% HCl and as little as possible iron is added to the last pickling section and is passed in countercurrent to the strip. From the first pickling section, the spent pickling solution is stripped off at about 120 g / 1 Fe and regenerated.
    Several methods have already been developed by which the hydrochloric acid can be recovered from the spent pickling solution.
    AT395312B describes a process in which the acid is recovered by spray roasting the metal-containing solution and then absorbing and / or condensing the resulting gases in an aqueous absorption solution. The metal oxides formed during pyrohydrolysis are removed at the bottom of the spray roaster.
    EP 0775760 describes a similar process for the recovery of acid by pyrohydrolytic treatment, wherein the Abbeize is subjected to pre-evaporation before the pyrohydrolysis.
    The structure of these systems is known to those skilled in the art or from ÄT395312B and EP 0775760 and is therefore not described in detail.
    Depending on the size of the system, the energy requirement for HCl regeneration in a conventional system is approx. 650 -700 kcal per liter of pickling applied. The fuel used is usually a gaseous fuel.
    A drawback of the present HCl regeneration process by spray roasting is that the preconcentration of the scrubber (Venturi cycle) does not reach the maximum possible metal concentration, thus unnecessarily much water is evaporated, which requires a very high energy requirement for the acid regeneration.
    The invention is therefore based on the object to reduce the energy requirements for the acid regeneration over conventional SprühöstSystemen.
    This object is achieved by a process for the recovery or recovery of hydrochloric acid from metal-containing solutions of hydrochloric acid according to claim 1.
    According to the invention, the metal-containing solution is divided into a first and a second partial stream. The first partial stream of the metal-containing solution of hydrochloric acid is subjected to the pyrohydrolytic treatment. However, the second partial stream of the metal-containing solution of hydrochloric acid is not subjected to the pyrohydrolytic treatment, but fed to the absorption column. This will increase the metal content throughout the system pickle / regeneration.
    It is no longer the entire metal-containing solution of hydrochloric acid of the pyrohydrolytic treatment .zugeführt, but only a partial flow. As is apparent from the embodiment, the content of free acid is not changed, so that the pickling effect is not deteriorated.
    By the invention, the potential savings in fuel at about 25%, in addition, the power consumption is reduced, since the exhaust gas volume is equally lower.
    Preferably, the metal-containing solution of the hydrochloric acid is subjected to evaporation before the pyrohydrolysis, thereby the solution is concentrated.
    The gases coming from the pyrohydrolytic treatment can be cooled by direct contact with the metal-containing solution of hydrochloric acid. As a result, the metal-containing solution is concentrated. During the concentration, approximately the maximum possible iron concentration can be achieved, so less water must be evaporated.
    In a specific embodiment, the first partial stream of the concentrated metal-containing solution of hydrochloric acid is subjected to the pyrohydrolytic treatment and the second partial stream of the concentrated metal-containing solution of hydrochloric acid is fed directly to the absorption column or it can also be previously mixed with rinse water.
    In this embodiment of the invention, the regenerated acid contains an increased level of trivalent iron, which is known to improve pickling.
    It is favorable if the process according to the invention is used for the regeneration of hydrochloric acid from an iron-containing solution. It is useful if after the absorption column, a regenerated hydrochloric acid having an iron content of more than 10 g / 1 iron, preferably more than 40 g / 1 iron, is obtained.
    In the pickling, the hydrochloric acid is thus not enriched as usual from approximately 0 g / 1 Fe to 120 g / 1 Fe, but from e.g. 40 g / 1 Fe to 160 g / 1 Fe or from 50 g / 1 Fe to 170 g / 1 Fe.
    The process according to the invention can be used either for the regeneration of the hydrochloric acid from a pickling process or else from a leaching process.
    The invention also provides a corresponding apparatus for recovering or recovering hydrochloric acid from metal-containing solutions, comprising a feed line for the solution, a pyrohydrolysis reactor and at least one absorption column, in which the preferably cooled exhaust gas is introduced.
    According to the invention, the feed line for the metal-containing solution to the pyrohydrolysis reactor has a branch, so that only part of the metal-containing solution of hydrochloric acid can be fed to the pyrohydrolysis reactor and another partial stream of the metal-containing solution of hydrochloric acid can be fed to the absorption column.
    The feed line for the second partial stream can either open directly into the absorption column or else into the feed line for rinsing water.
    In the following an embodiment of the invention will be described with reference to drawings. Show it:
    Figure 1 is a schematic of the mass flows in a conventional pickling plant with acid recovery.
    Fig. 2 is a schematic of the mass flows in a pickling plant with acid recovery according to the invention;
    FIG. 1 shows a scheme for a pickling plant 1 with an acid recovery plant 2 (ARP) according to the prior art. In this pickling plant with a throughput of 2 million tonnes of low alloy steel per year with a pickling loss of 0.4% (as Fe) 1200 kg / h iron dissolved. Regenerated hydrochloric acid with a free HCl content of 194.6 g / l is pumped from the ARP (Acid Recovery Plant) 2 to the pickling plant 1.
    In the pickling plant 1, the hydrochloric acid reacts essentially according to the following reaction
    and is thus consumed or converted to ferric chloride.
    At an iron content of about 121 g / l and a free acid content of 47 g / 1, the pickling solution is consumed and the acid recovery system (ARP) 2 is supplied. The required capacity of the ARP is 10 m3 / h, the fuel gas requirement is 27896 MJ / h. The absorption column in the acid recovery plant 2 are supplied with 11.11 ml of water per hour for absorption or condensation of the gases coming from the roasting reactor. In addition, 1200 kg of iron are discharged from the roasting reactor as Fe 2 C> 3.
    Similarly, an exhaust flow with 10.99 tonnes of steam per hour leaves the ARP.
    Figure 2 shows a scheme for a pickling plant 1 with an acid recovery system 2 according to the invention.
    Regenerated acid with a free HCl content of 194.6 g / l is also pumped from the acid recovery plant 2 (ARP) to the pickling plant 1. By adding a portion 6 of the spent pickling solution along with rinse water to the absorption column, the regenerated acid has an iron content of 39.9 g / l. In pickling plant 1, the same amount of iron as in FIG. 1 is dissolved and the hydrochloric acid is consumed.
    At a free acid content of about 47 g / 1, the pickling solution is consumed and is supplied via the feed line 3 of the acid recovery system 2 (ARP). In this case, however, the iron content is 161 g / 1.
    The supply line 3 to the ARP has a branch 4, a partial stream 5 of the spent pickling solution is thereby fed to the pyrohydrolysis reactor (spray roaster) and another partial stream 6 of the spent pickling solution is fed to the rinsing water of the absorption column.
    The pyrohydrolysis is so compared to Figure 1, only a smaller amount of spent pickling solution supplied in order to deposit the same amount of iron (1200 kg / h Fe). In this case, only 7.52 m 3 / h are fed to the pyrohydrolysis step of the ARP and the remaining 2.48 m 3 / h together with the water of the absorption column. The fuel gas requirement is therefore only at 21319 MJ / h.
    The saving of fuel gas is thus 23.6%.
    In addition, electrical energy, especially for the exhaust fan, saved because the process gas volume decreases by the same proportion. About the exhaust now leave only 8.2 tons of steam per hour, the ARP.
    Since in both embodiments, both the regenerated and the spent acid each have the same content of free HCl, the inventive method has no negative effect on the staining effect.
    In a further variant of the invention, the spent acid is first concentrated in a chiller for the hot exhaust gases, e.g. in a Venturi cycle. The concentrated metal-containing solution (concentrate) is then divided into a first and a second partial flow. The first part-stream is fed to the pyrohydrolysis reactor and the second part-stream of the concentrated pickling is fed to the absorber or to the rinsing water conducted to the absorber.
    Table 1 summarizes the results of some calculations:
    Table 1:
    The comparison in Table 1 shows that the energy saving potential is greater when the stripping agent is applied to the absorber and not its concentrate. The metal content in the regenerated acid is controlled by the amount of metal-containing solution that is mixed into the rinse water for the absorber application. The rinse water consumption decreases accordingly.
    With an HCl regeneration for 5.3 m3 / h Abbeize (for approx. 1 million tons of pickling power / year), a saving of> approx. 200 k € / year.
    In a new plant, the investment costs are also lower.
    In existing systems, the invention can be used to a significant increase in performance.
    权利要求:
    Claims (10)
    [1]
    1. A process for the recovery or recovery of hydrochloric acid from metal-containing solutions of hydrochloric acid by pyrohydrolytic treatment of the solution and subsequent absorption and / or condensation of the resulting gaseous hydrogen chloride to form hydrochloric acid, HaHnrnh characterized in that a first partial stream of the metal-containing solution of hydrochloric acid the pyrohydrolytic treatment is subjected and wherein a second partial stream of the metal-containing solution of hydrochloric acid is not subjected to the pyrohydrolytic treatment, but is fed to an absorption column.
    [2]
    2. The method according to claim 1, characterized in that the metal-containing solution of hydrochloric acid is subjected to evaporation prior to the pyrohydrolytic treatment.
    [3]
    3. The method according to claim 1 or 2, characterized in that coming from the pyrohydrolytic treatment gases are cooled by direct contact with the metal-containing solution of hydrochloric acid, wherein the metal-containing solution is concentrated, and wherein thereafter the first substream of the concentrated metal-containing solution of hydrochloric acid the pyrohydrolytic treatment is subjected and the second partial stream of the concentrated metal-containing solution of hydrochloric acid of the absorption column is supplied.
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the second substream of the metal-containing solution of hydrochloric acid is mixed with rinse water before it is fed to the absorption column.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the hydrochloric acid is obtained from a ferrous solution.
    [6]
    6. The method according to claim 5, characterized in that after the absorption column, a regenerated hydrochloric acid having an iron content of more than 10 g / 1 iron, preferably more than 40 g / 1 iron, is obtained.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the metal-containing solution of the hydrochloric acid comes from a pickling process and the regenerated metal-containing hydrochloric acid is fed back to the pickling process.
    [8]
    8. The method according to any one of claims 1 to 6, characterized in that the metal-containing solution of the hydrochloric acid originates from a leaching process and the regenerated metal-containing hydrochloric acid is fed back to the leaching process.
    [9]
    9. A device for recovering or recovering hydrochloric acid from metal-containing solutions, comprising a feed line (3) for the metal-containing solution to an acid recovery plant (2), wherein the acid recovery plant (2) a pyrohydrolysis reactor for pyrohydrolytic treatment of metal-containing solutions and at least one Absorption column for the absorption and / or condensation of the gases coming from the pyrohydrolysis reactor, characterized in that the feed line (3) or a feed line to the pyrohydrolysis reactor has a branch (4), so that only a partial flow {5) of the metal-containing Solution of the hydrochloric acid can be fed to the pyrohydrolysis reactor and wherein another partial stream (6) of the metal-containing solution of hydrochloric acid of the absorption column can be fed.
    [10]
    10. The device according to claim 9, characterized in that in an exhaust pipe between the pyrohydrolysis reactor and the absorption column, a cooling unit is arranged, in which the supply line (3) opens, so that the hot exhaust gases from the pyrohydrolysis reactor for cooling with the metal-containing Solution can be brought into contact, wherein the metal-containing solution can be supplied to the pyrohydrolysis reactor only after the cooling unit and wherein the branch (4) for the two partial streams (5) and (6) is arranged only after the cooling unit.
    类似技术:
    公开号 | 公开日 | 专利标题
    AT395312B|1992-11-25|METHOD FOR RECOVERY OR RECOVERY OF ACID FROM METAL SOLUTIONS OF THIS ACID
    AT508774B1|2011-04-15|METHOD OF GAINING BZW. RECOVERY OF SALPETIC ACID AND FLUIC ACID FROM SOLUTIONS OF STAINLESS STEEL INSERTS
    AT403698B|1998-04-27|METHOD FOR RECOVERY OR RECOVERY OF ACIDS FROM METAL SOLUTIONS OF THESE ACIDS
    AT514420B1|2015-01-15|Process and apparatus for the regeneration of hydrochloric acid
    AT412001B|2004-08-26|METHOD FOR RECOVERY OR RECOVERY OF ACIDS
    EP0964830B1|2003-07-02|Method for producing hyperazeotropic hydrochloric acid from metal chloride solutions
    DE3022180A1|1981-12-24|METHOD FOR WASHING H | 2 | S FROM COOKING GAS
    DD257595A5|1988-06-22|METHOD AND APPARATUS FOR RELIEVING SMOKE GASES
    DE1567575C3|1975-07-24|Process for the production of chlorine
    AT408764B|2002-03-25|Process for obtaining or recovering hydrochloric acid from solutions which contain metal chlorides, in particular used pickling acid
    DE3308849C2|1987-07-30|
    AT406168B|2000-03-27|METHOD FOR RECOVERY OR Recovery of hydrofluoric acid and nitric acid
    DE600904C|1934-08-03|Process for the production of a mixed fertilizer containing calcium phosphate and nitrogen
    DE1446367A1|1969-03-20|Process for the immediate recovery of low hydrates of iron | sulphate and regeneration of sulfuric acid from emaciated | pickling baths
    AT300730B|1972-08-10|Process for the recycling of hydrochloric acid
    DE878940C|1953-06-08|Process for drying the gases containing sulfur dioxide formed by the cleavage of diluted waste sulfuric acids and to be processed on highly concentrated sulfuric acid
    AT205311B|1959-09-25|Process for the continuous regeneration of hydrochloric and sulfuric acid pickling liquors
    DE663968C|1938-08-17|Process for the revitalization of cupro salt solutions which were used to remove carbon monoxide from hydrogen-containing gases
    DE536428C|1931-10-23|Process for removing ammonia and hydrogen sulfide from gases
    DE1667445C3|1978-05-18|Process for scrubbing sulfur dioxide from exhaust gases
    DE1072859B|1960-01-07|Method of stripping copper
    DE973884C|1960-07-07|Process for the continuous regeneration of pickling liquors
    DE866751C|1953-02-12|Process for pickling iron and steel with recovery of the pickling agent
    CH545129A|1973-12-15|Silicon fluoride absorption
    DE1954761B2|1975-02-20|Process for the production of ammonium perrhenate
    同族专利:
    公开号 | 公开日
    WO2015043721A1|2015-04-02|
    AT514420B1|2015-01-15|
    US20160244330A1|2016-08-25|
    US10494259B2|2019-12-03|
    CN205653510U|2016-10-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    AT395312B|1987-06-16|1992-11-25|Andritz Ag Maschf|METHOD FOR RECOVERY OR RECOVERY OF ACID FROM METAL SOLUTIONS OF THIS ACID|
    AT403698B|1995-11-27|1998-04-27|Andritz Patentverwaltung|METHOD FOR RECOVERY OR RECOVERY OF ACIDS FROM METAL SOLUTIONS OF THESE ACIDS|
    AT407756B|1999-03-22|2001-06-25|Andritz Patentverwaltung|METHOD FOR RECOVERY OF ACIDS FROM METAL SOLUTIONS OF THESE ACIDS, PREFERABLY HC1 AND FE COMPOUNDS|
    US20020039554A1|1999-03-22|2002-04-04|Albert Lebl|Process for regeneration of acids from spent acids|
    AT407758B|1999-04-07|2001-06-25|Andritz Patentverwaltung|Process for obtaining or recovering acids|
    WO2002038819A2|2000-11-08|2002-05-16|Hatch Associates Ltd.|Process for regeneration of spent acid halide leach solutions|
    NL132526C|1965-04-17|
    US3529931A|1968-07-12|1970-09-22|Nat Lead Co|Regenerating hci from iron chloride solutions|
    BR9205481A|1991-11-22|1994-04-26|Tech Resources Pty Ltd|Process and apparatus for forming an aqueous chloride bleach|CN111266063B|2020-01-23|2021-11-02|马克斯环保设备有限公司|Heating system for acid regeneration|
    CN111349798B|2020-03-17|2021-08-27|中国科学院过程工程研究所|Neodymium iron boron waste recycling system and method|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA748/2013A|AT514420B1|2013-09-26|2013-09-26|Process and apparatus for the regeneration of hydrochloric acid|ATA748/2013A| AT514420B1|2013-09-26|2013-09-26|Process and apparatus for the regeneration of hydrochloric acid|
    PCT/EP2014/002489| WO2015043721A1|2013-09-26|2014-09-15|Method and device for regenerating hydrochloric acid|
    CN201490001076.XU| CN205653510U|2013-09-26|2014-09-15|Be used for palingenetic equipment of hydrochloric acid|
    US15/024,755| US10494259B2|2013-09-26|2014-09-15|Method and device for regeneration of hydrochloric acid|
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