EP3452636A1 - Procédé de régénération d'acide résiduaire à petite échelle - Google Patents

Procédé de régénération d'acide résiduaire à petite échelle

Info

Publication number
EP3452636A1
EP3452636A1 EP17720825.3A EP17720825A EP3452636A1 EP 3452636 A1 EP3452636 A1 EP 3452636A1 EP 17720825 A EP17720825 A EP 17720825A EP 3452636 A1 EP3452636 A1 EP 3452636A1
Authority
EP
European Patent Office
Prior art keywords
chloride solution
metal chloride
reactor vessel
equal
waste metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17720825.3A
Other languages
German (de)
English (en)
Inventor
David Konlechner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
John Cockerill UVK GmbH
Original Assignee
CMI UVK GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CMI UVK GmbH filed Critical CMI UVK GmbH
Publication of EP3452636A1 publication Critical patent/EP3452636A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide [Fe2O3]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors

Definitions

  • the present invention relates to a method for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel.
  • the present invention relates to a system for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel of the system.
  • pickling treatments with hydrochloric acid are widely used to remove rust and accretion (scales) adhering to the surface of products or processed goods.
  • metals to be coated require pre-treatment to remove rust or scale, impurities and contaminants.
  • the pickling process generates a considerable quantity of waste liquid (or waste pickling liquor) containing the dissolved metal salts of Iron, Chromium, Copper, Nickel and Zinc as well as residual free acid. Leaching of iron containing ores is often realized by means of hydrochloric acid. Also semiconductor lead frames are often subjected to etching treatments with hydrochloric acid.
  • the hydrochloric acid concentration is usually controlled to remain in the range of 12 - 18% by weight.
  • free hydrochloric acid is converted to iron salts and other metallic salts, thus gradually reducing the washing or etching capacity. Therefore, usually, free hydrochloric acid is added, thus generating large amounts of waste liquid containing iron chloride and optionally free hydrochloric acid.
  • This waste iron chloride solution comprises ferrous chloride, ferric chloride or combinations thereof and optionally reaction products of other treated metals with hydrochloric acid, like chlorides of zinc, nickel, copper, etc., and such liquids have been disposed of as industrial waste. In recent years, the costs of disposal or treatment of such industrial waste have risen sharply, and hydrochloric acid itself is relatively expensive.
  • waste metal chloride solution typically of the order of several cubic meters of waste metal chloride solution per hour
  • waste pickling installations typically of the order of several cubic meters of waste metal chloride solution per hour
  • waste pickling liquor waste pickling liquor
  • waste treatment of the waste metal chloride solution is typically performed by executing lime treatment of the waste metal chloride solution (or waste pickling liquor), and by using fresh hydrochloric acid (typically also involving transporting the waste metal chloride solution (or waste pickling liquor) away and performing the lime treatment by a waste treatment supplier company.
  • metal oxide typically iron oxide
  • the object of the present invention is achieved by a method for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel, the waste metal chloride solution comprising at least one oxidizable component, the method comprising the following steps:
  • the waste metal chloride solution is fed to the reactor vessel, and - while the reactor vessel being operated in a first mode of operation - an oxidation step is performed within the reactor vessel at an oxidation temperature exceeding 90°C and at an oxidation pressure exceeding 0,3 MPa, wherein at least a part of the waste metal chloride solution is oxidized during the oxidation step, wherein an at least partly oxidized metal chloride solution is obtained from the waste metal chloride solution, wherein the oxidized part of the at least partly oxidized metal chloride solution corresponds to at least a part of the at least one oxidizable component of the waste metal chloride solution prior to the oxidation step,
  • the at least partly oxidized metal chloride solution is at least partly hydrolyzed during a hydrolyzes step - performed within the reactor vessel while the reactor vessel is operated in a second mode of operation - at a hydrolyzes temperature exceeding 120 °C and at an appropriate hydrolyses pressure, wherein during the hydrolyzes step hydrochloric acid (HCI) and solid ferric oxide Fe 2 0 3 are obtained.
  • HCI hydrochloric acid
  • Fe 2 0 3 solid ferric oxide
  • a small hydrochloric acid regeneration plant is proposed, using a batch process, in order to regenerate the hydrochloric acid by the decomposition of FeCI 3 in liquid phase.
  • the proposed method and system has a wide flexibility and is able to also handle small amounts of waste metal chloride solution (or waste pickling liquor) in an economically competitive manner.
  • the method and system of the present invention provides the possibility to regenerate hydrochloric acid also to small or medium-sized installations or companies (especially for disposal demands of waste metal chloride solution (or waste pickling liquor) of, say, less than 1000 liters or 1500 liters per hour, especially in the range from 100 liters per hour to 1000 liters per hour (or in the range of 100 liters per hour to 1500 liters per hour) of waste metal chloride solution (or waste pickling liquor)), thereby providing the possibility to be independent from sourcing of hydrochloric acid as well as disposal of waste metal chloride solution (or waste pickling liquor). It is especially advantageous according to the present invention that common acid resistant construction materials and dimensions can be used, thus lowering the investment costs, e.g.
  • the inventive method and system is able to be realized as a standalone unit, able to send data to the process control installations of the process generating the waste metal chloride solution (or waste pickling liquor) to be treated. Additionally, the inventive system is able to be realized as an ISO container solution, i.e. it can be brought to the intended site in a pre-assembled manner, with only connections to be performed in the course of the installation process. Additionally, conducting the process according to the present invention, is able to be fully automated such that only a minimum manpower for operation and maintenance of the process is required, such as - depending on the automation level - between 15% and 50% of an operator is (permanently) required to run the process.
  • the method and the system according to the present invention not only reduces investment costs for the installation of the system but also reduces the requirements as to space: For example, a system for a feed flow of 500 liters per hour of waste metal chloride solution (or waste pickling liquor) can be installed in two 20' ISO Containers.
  • the reactor vessel is not continuously used for the same reaction step (but alternatingly for the oxidation step, as well as for the hydrolyses step), its volume or size needs - while being adapted to the flow volume of waste metal chloride solution to be treated - to be relatively larger (as compared to a reactor vessel, designed to treat the same amount of waste metal chloride solution volume, being used continuously for one and the same reaction step), thus providing the possibility to use the reactor vessel (both for conducting the oxidation step and the hydrolyses step) is an economically competitive manner.
  • the costs for the reactors at required standard sizes are in the same range, and it makes no big difference if it is one size bigger ore smaller.
  • the present invention provides a solution for the need to have (pickling) acid (especially hydrochloric acid) available for upstream processes, especially pickling processes, and at the same time having a concept for the disposal of waste metal chloride solution (or waste pickling liquor).
  • waste metal chloride solution especially waste pickling liquor
  • the amount of produced metal chloride solution (or waste pickling liquor) is too small to install a pyro metallurgical regeneration system according to conventional methods as an economically competitive operation of such regeneration systems using conventional methods typically requires volumes of waste metal chloride solution (or waste pickling liquor) per time unit of at least 2 cubic meters per hour.
  • the waste metal chloride solution comprises at least one oxidizable component (typically ferrous oxide).
  • the at least one oxidizable component is, at least partly, oxidized.
  • the waste metal chloride solution is transformed in an at least partly oxidized metal chloride solution.
  • non-soluble components are obtained, notably iron oxide, which are separated, typically during a filtering operation.
  • the first mode of operation of the reactor vessel is conducted batch wise for a certain time and the reaction product of the oxidation step is stored in a first storage element. Subsequent to operating the reactor vessel several times (batches) according to the first mode of operation, the reactor vessel is operated in the second mode of operation for some time, during which the hydrolyzes step is performed.
  • the at least partly oxidized metal chloride solution, stored in the first storage element is processed in order to recover the hydrochloric acid, especially until the first storage element is emptied or at least emptied to a considerable level of typically more than 50%, preferably more than 70%, and most preferably more than 90% of its volume. Thereafter (i.e.
  • the reactor vessel is again operated in the first mode of operation, i.e. for oxidizing several times (fresh) waste metal chloride solution, and the use of the reactor vessel is repeated in view of a batch processing (or semi-continuous process with storage of treated solutions in separate bins or containers between single processing steps) with regard to the waste metal chloride solution.
  • waste metal chloride solution is fed (in the first step) to the reactor vessel, and the oxidation step is performed within the reactor vessel at an oxidation temperature exceeding 90°C and at an oxidation pressure exceeding 0,3 MPa.
  • the oxidation step at least a part of the waste metal chloride solution is oxidized (thereby, an at least partly oxidized metal chloride solution is obtained from the waste metal chloride solution).
  • the oxidized part of the at least partly oxidized metal chloride solution corresponds to at least a part of the at least one oxidizable component of the waste metal chloride solution prior to the oxidation step.
  • the oxidation step is initiated by means of feeding pressurized oxygen into the reactor vessel.
  • the chemical reaction of the oxidation step provides further energy, the content of the reactor vessel is inherently heated, i.e. the temperature increased.
  • the chemical process within the reactor vessel during the oxidation step is controlled by the supply in oxygen to the reactor vessel; i.e. the oxidation process is terminated in case that additionally suppled oxygen is not absorbed or reacted by the content of the reactor vessel.
  • typically non-soluble (solid) iron oxide is produced (Fe 2 0 3 ).
  • the residual at least partly oxidized metal chloride solution (mostly FeCI 3 -solution) is pumped to the first storage element.
  • the at least partly oxidized metal chloride solution, obtained during previously conducting the first step is fed to a first storage element, and additional waste metal chloride solution is fed to the reactor vessel batch wise,
  • the first step is performed (with respect to the additional waste metal chloride solution) and thereby additional at least partly oxidized metal chloride solution obtained from the additional waste metal chloride solution,
  • the at least partly oxidized metal chloride solution - especially additionally, also the additional at least partly oxidized metal chloride solution - is fed, from the first storage element, to the reactor vessel.
  • the at least partly oxidized metal chloride solution (stored in the first storage element) is fed (from the first storage element) to the reactor vessel - typically this feeding operation comprising feeding the reactor vessel with the (initial) at least partly oxidized metal chloride solution, and additionally preferably also with the additional at least partly oxidized metal chloride solution, and/or the further additional at least partly oxidized metal chloride solution, thereby (completely, or almost completely) emptying the first storage element.
  • the (initial) waste metal chloride solution preferably at least approximately corresponds (chemically) to the additional waste metal chloride solution, and/or to the further additional waste metal chloride solution, the different terms (“initial waste metal chloride solution”, “additional waste metal chloride solution”, and “further additional waste metal chloride solution”) regarding the waste metal chloride solution are primarily used to refer to different points in time that the corresponding volumes are fed to the reactor vessel.
  • the corresponding volumes of waste metal chloride solution are typically (continuously) generated by one and the same upstream process such as a pickling process or the like (or by (at least roughly) one and the same combination of upstream processes such as different pickling processes and/or galvanizing processes, etc.), and, hence, only marginally vary with respect to the respective content of free (hydrochloride) acid, water, and metal chlorides or other constituents.
  • the corresponding volumes of waste metal chloride solution i.e.
  • the initial waste metal chloride solution, the additional waste metal chloride solution, etc. are generated - at different points in time - by different upstream processes (such as different pickling processes, galvanizing processes, etc.), and, hence, comprise more important variations with respect to the respective content of free (hydrochloride) acid, water, and metal chlorides or other residual elements.
  • the at least partly oxidized metal chloride solution is obtained from the waste metal chloride solution.
  • the at least partly oxidized metal chloride solution corresponds (chemically) to the additional at least partly oxidized metal chloride solution, and/or to the further additional at least partly oxidized metal chloride solution, the different terms (“initial at least partly oxidized metal chloride solution”, “additional at least partly oxidized metal chloride solution”, and “further additional at least partly oxidized metal chloride solution”) regarding the at least partly oxidized metal chloride solution are primarily used to refer to different points in time that the corresponding volumes are generated in the reactor vessel and/or fed to the first storage element.
  • the waste metal chloride solution comprises at least one oxidizable component (typically ferrous oxide) which is oxidized during the oxidation step, thereby yielding non-soluble components, notably iron oxide, which are separated as part of the oxidation step (i.e. during operating the reactor vessel in the first mode of operation), typically during a filtering operation.
  • oxidizable component typically ferrous oxide
  • non-soluble components notably iron oxide
  • typically a given volume of waste metal chloride solution yields a smaller volume of corresponding at least partly oxidized metal chloride solution.
  • the first storage element has a first storage capacity
  • the reactor vessel in the first mode of operation such that (with an empty or almost empty first storage element) at least a volume of the waste metal chloride solution corresponding to the predetermined multiple of the capacity of the reactor vessel can be (successively) fed to the reactor vessel, the oxidation step performed, and the corresponding at least partly oxidized metal chloride solution fed to the first storage element (effectively resulting in (at least virtually) filling and emptying the reactor vessel a number of times corresponding, at least roughly, to the predetermined multiple, prior to requiring to switch the operation of the reactor vessel to the second mode of operation.
  • the reactor vessel is at least partly emptied, preferably at least 50% emptied, more preferably at least 70% empties, most preferably at least 90% emptied.
  • the waste metal chloride solution comprises, as the at least one oxidizable component, ferrous chloride (Iron(ll) chloride), wherein the waste metal chloride solution preferably comprises between 14 weight % to 28 weight %, preferably approximately 22 weight % of ferrous chloride (Iron(ll) chloride).
  • the inventive method and system can be used efficiently in order to treat waste metal chloride solution of a plurality of different industrial processes such as various pickling processes, galvanizing processes or the like.
  • the waste metal chloride solution prior to conducting the first step, is subjected to a pre- concentration step yielding concentrated waste metal chloride solution, wherein the concentrated waste metal chloride solution comprises, as the at least one oxidizable component, ferrous chloride (Iron(ll) chloride), wherein the concentrated waste metal chloride solution preferably comprises between 22 weight % to 45 weight %, preferably approximately 40 weight % of ferrous chloride (Iron(ll) chloride).
  • the at least partly oxidized metal chloride solution comprises, as at least part of its oxidized part, ferric chloride (Iron(lll) chloride), wherein the at least partly oxidized metal chloride solution preferably comprises between 12 weight % to 25 weight %, preferably approximately 20 weight %, of ferric chloride (Iron(lll) chloride).
  • the inventive method and system can be used efficiently in order to recover at least part of the metal (especially iron) (in the form of non-soluble metal oxide (especially iron oxide)) from the total metal content (especially total iron content) that is present in the waste metal chloride solution.
  • the values of the at least partly oxidized metal chloride solution comprising between 12 weight % to 25 weight %, preferably approximately 20 weight %, of ferric chloride (Iron(lll) chloride) are applicable in case that a constant chlorine amount and no special evaporation procedure is applied.
  • the waste metal chloride solution comprises, besides the at least one oxidizable component, free hydrochloric acid.
  • the inventive method and system can be used efficiently in order to recover used hydrochloric acid from waste liquids, especially pickling liquors, of different industrial processes such as various pickling processes, galvanizing processes or the like.
  • the oxidation temperature applied during the first step (oxidation step) is equal or superior to 1 10°C and equal or inferior to 250°C, preferably equal or superior to 130°C and equal or inferior to 200°C, more preferably equal or superior to 140°C and equal or inferior to 170°C, most preferably equal or superior to 145°C and equal or inferior to 155°C, and/or
  • the hydrolyzes temperature applied during the second step is equal or superior to 130°C and equal or inferior to 300°C, preferably equal or superior to 150°C and equal or inferior to 230°C, more preferably equal or superior to 160°C and equal or inferior to 180°C, most preferably equal or superior to 165°C and equal or inferior to 175°C.
  • the oxidation pressure applied during the first step (oxidation step) is equal or superior to 0,3 MPa and equal or inferior to 1 ,2 MPa, preferably equal or superior to 0,6 MPa and equal or inferior to 1 ,0 MPa, more preferably equal or superior to 0,7 MPa and equal or inferior to 0,9 MPa, most preferably equal or superior to 0,75 MPa and equal or inferior to 0,85 MPa and/or
  • the hydrolyses pressure applied during the second step is equal or superior to 0,05 MPa and equal or inferior to 1 ,2 MPa, preferably equal or superior to 0,08 MPa and equal or inferior to 0,8 MPa, more preferably equal or superior to 0,09 MPa and equal or inferior to 0,5 MPa, most preferably equal or superior to 0,95 MPa and equal or inferior to 0,2 MPa.
  • a concentration and heating step occurs during the hydrolyses step, until the boiling point of the solution within the reactor vessel is reached. Afterwards, the solution is progressively boiled down. However, in order to maintain the optimal hydrolyses conditions within the reactor vessel, it is preferred to progressively add at least partly oxidized metal chloride solution from the first storage element.
  • hydrochloric acid (or vapor thereof) and iron oxide (Fe 2 0 3 ) are generated, and thereby the at least partly oxidized metal chloride solution is used until the first storage element is emptied.
  • the content of the reactor vessel at this moment is fed to the first storage element, hence the reactor vessel emptied, in order to be ready for the oxidation step to be performed with a new load of waste metal chloride solution.
  • the present invention also relates to a system for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel of the system, the waste metal chloride solution comprising at least one oxidizable component, the system comprising at least the reactor vessel, wherein the system is configured such that the reactor vessel is operable in a first mode of operation and in a second mode of operation and such that:
  • the waste metal chloride solution is fed batch wise to the reactor vessel, and - while the reactor vessel being operated in the first mode of operation - an oxidation step is performed within the reactor vessel at an oxidation temperature exceeding 90°C and at an oxidation pressure exceeding 0,3 MPa, wherein at least a part of the waste metal chloride solution is oxidized during the oxidation step, wherein an at least partly oxidized metal chloride solution is obtained from the waste metal chloride solution, wherein the oxidized part of the at least partly oxidized metal chloride solution corresponds to at least a part of the at least one oxidizable component of the waste metal chloride solution prior to the oxidation step, — the at least partly oxidized metal chloride solution is at least partly hydrolyzed during a hydrolyzes step - performed within the reactor vessel while the reactor vessel is operated in a second mode of operation - at a hydrolyzes temperature exceeding 120 °C and at an appropriate hydrolyses pressure, wherein during the hydrolyzes step hydrochloric
  • the present invention it is thereby advantageously possible to provide a system (or a treatment station) that requires comparatively low installation costs as well as reduced maintenance costs. According to the present invention, it is advantageously possible to combine the advantages of spray pickling and dip pickling and to minimize the risk of over-pickling. It is furthermore advantageous that the spent acid of such a system is of a quality such that it can be treated in regeneration plants without additional investment considering in particular the FeCI 3 concentration in such spent acid.
  • the system additionally comprises a first storage element, wherein the system is configured such that, while the reactor vessel is - especially repeatedly - operated in the first mode of operation, the at least partly oxidized metal chloride solution (30), obtained during previously conducting the first step, is fed to a first storage element (210), and additional waste metal chloride solution is fed to the reactor vessel batch wise,
  • the system is configured such that subsequent to operating the reactor vessel in the first mode of operation and prior to operating the reactor vessel in the second mode of operation, the at least partly oxidized metal chloride solution - especially additionally, also the additional at least partly oxidized metal chloride solution - is fed, from the first storage element, to the reactor vessel.
  • the system additionally comprises a second storage element, wherein the system is configured such that - during the hydrolyzes step - additional waste metal chloride solution (from upstream process) is fed to and stored in the second storage element.
  • the first storage element has a first storage capacity
  • the reactor vessel has a second storage capacity, wherein the ratio of the first and second storage capacity is greater than 2:1 , preferably greater than 3:1 , more preferably greater than 5:1 , and most preferably greater than 10:1.
  • the present invention it is thereby advantageously possible to avoid that changes in the mode of operation of the reactor vessel need to occur too often:
  • the first storage capacity corresponds to roughly 5 times the second storage capacity
  • the more the first storage capacity is increased (relative to the effective volume of the reactor vessel regarding the first mode of operation), the less frequent a change in the mode of operation of the reactor vessel needs to be applied.
  • the effective volume of the reactor vessel, and hence its size is able to be scaled according to the needs of the upstream processes.
  • the system is configured to treat a quantity of waste metal chloride solution corresponding to equal to or superior to 10 l/hour and equal to or inferior to 5000 l/hour, preferably corresponding to equal to or superior to 30 l/hour and equal to or inferior to 3000 l/hour, more preferably corresponding to equal to or superior to 60 l/hour and equal to or inferior to 2000 l/hour, most preferably corresponding to equal to or superior to 100 l/hour and equal to or inferior to 1500 l/hour.
  • Figure 1 schematically illustrates a system according to the present invention for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel of the system, wherein the system comprises the reactor vessel, a first storage element as well as a second storage element.
  • FIG. 1 schematically illustrates a system 100 according to the present invention for processing waste metal chloride solution using batch processing involving different modes of operation of a reactor vessel 200 of the system 100, wherein the system 100 comprises the reactor vessel 200, a first storage element 210 as well as a second storage element 220.
  • the system 100 comprises - besides the reactor vessel 200, the first storage element 210, and the second storage element 220 - a first ball valve 121 (preferably an automatic ball valve), a second ball valve 122 (preferably an automatic ball valve), a feeding pump 123, a filter element 124, a circulation pump 125, a filter pump 126, a cooling element 127 (or cooler), a pressure valve 128, a condenser 129, and a regenerated acid storage tank 130 (third storage element 130) having an outlet 131 connected to the upstream process requiring fresh (or regenerated acid).
  • the reactor vessel 200 comprises an oxygen inlet 132
  • the filter (or filter element 124 comprises an oxide outlet 133.
  • the system 100 also comprises a heating module that is able to provide additional heating for the contents of the reactor vessel 200.
  • the heating module comprises an additional pump 134 and a heating element 135:
  • the content of the reactor vessel 200 is pumped, at least partly, by the additional pump 134 to the heating element 135, is heated in the heating element 135, and is afterwards re-introduced in the reactor vessel 200 (arrow designated by encircled reference sign 7).
  • the heating module does not necessarily be provided or installed as part of the system 100.
  • the oxidation step is performed with the heating module switched on during an initial phase of the oxidation step (covering, e.g. 10% to 70% of the total time required for performing the oxidation step), and during the residual time of the oxidation step (after the initial phase), the heating module is switched off (as the reaction itself is producing sufficient heat).
  • the first storage element 210 is a FeCI 3 storage tank, used to store the at least partly oxidized metal chloride solution 30.
  • the second storage element 220 is a waste acid storage tank, i.e. a buffer tank to store waste metal chloride solution 10 during time intervals of the reactor vessel 200 being used in the second mode of operation.
  • Waste metal chloride solution 10 (as produced by an upstream process, not shown in Figure 1 ) is fed to or buffered in the second storage element 220 (arrow designated by encircled reference sign 1 ).
  • the reactor vessel 200 is operated in the first mode of operation (being more or less empty).
  • the (initial or initial portion of) waste metal chloride solution 10 is fed (trough the feeding pump 123) from the second storage element 220 to the reactor vessel 200 (arrow designated by encircled reference sign 2).
  • oxygen is added to the waste metal chloride solution 10 (through oxygen inlet 132) in order to perform the oxidation step with regard to the (initial) waste metal chloride solution 10.
  • non-soluble parts generated in the liquid within the reactor vessel 200
  • filter element 124 involving the filter pump 126 and the cooling element 127
  • the resulting at least partly oxidized metal chloride solution 30 is fed to the first storage element 210 (arrow designated by encircled reference sign 3), thereby emptying the reactor vessel 200.
  • the first or initial batch of waste metal chloride solution has thus been processed regarding the oxidation step.
  • the process is continued by feeding an additional waste metal chloride solution 10' from the second storage element 220 to the reactor vessel 200 (arrow designated by encircled reference sign 2), and performing the oxidation step in an analogous manner, thereby obtaining additional at least partly oxidized metal chloride solution 30' (as well as non-soluble parts being removed by means of the oxide outlet 133), the additional at least partly oxidized metal chloride solution 30' being likewise fed to the first storage element 210 (arrow designated by encircled reference sign 1 ).
  • the process might be further continued by feeding (once or more often) further additional waste metal chloride solution, and obtaining further additional at least partly oxidized metal chloride solution until the first storage element 210 is filled with at least partly oxidized metal chloride solution 30.
  • the reactor vessel 200 is operated in the second mode of operation, performing the hydrolyses step: the at least partly oxidized metal chloride solution 30 (either fed from the first storage element 210 (arrow designated by encircled reference sign 4) or the residual at least partly oxidized metal chloride solution of the last batch of performing the first step (arrow designated by encircled reference sign 5)) is at least partly hydrolyzed during the hydrolyses step.
  • the reactor vessel 200 is operated in the second mode of operation, at a hydrolyzes temperature exceeding 120 °C and at an appropriate hydrolyses pressure.
  • hydrochloric acid (HCI) is generated (and fed through pressure valve 128 and condenser 129 (arrow designated by encircled reference sign 6) to the regenerated acid storage tank 130 (third storage element 130); from there, the regenerated acid is recycled through outlet 131 towards the upstream process generating the waste metal chloride solution 10) and solid ferric oxide Fe 2 0 3 areobtained (and removed through outlet 133).
  • HCI hydrochloric acid
  • waste metal chloride solution 10 having a relatively low concentration of typically between 14 weight % and 28 weight % of the at least one oxidizable component.
  • a concentrated waste metal chloride solution 20 (having a higher concentration of an at least one oxidizable component) is treated in the reactor vessel 200 according to the same method.
  • the upstream processes do not provide a concentrated waste metal chloride solution 20 (having such higher concentration of the at least one oxidizable component), hence, the waste metal chloride solution 10 being generated by the upstream processes is subjected to a pre-concentration step yielding the concentrated waste metal chloride solution 20.
  • this pre-concentration step is not shown in Figure 1 .
  • the concentrated waste metal chloride solution 20 comprises, as the at least one oxidizable component, ferrous chloride (Iron(ll) chloride), in a concentration of preferably between 22 weight % to 45 weight %.
  • the regeneration of the hydrochloric acid is executed in a batch wise manner in two steps, comprising the oxidation step and the hydrolyses step.
  • the waste metal chloride solution or waste pickling liquor
  • FeCI 3 i.e. the at least partly oxidized metal chloride solution 30
  • This process step is repeated and the at least partly oxidized metal chloride solution 30 (FeCI 3 ) is stored in a buffer tank (first storage element 210).
  • the operation mode is switched and the FeCI 3 is decomposed by heating the solution up to a certain temperature (hydrolyses temperature).
  • HCI hydrochloric acid
  • iron oxide iron oxide
  • the same vessel i.e. the reactor vessel 200
  • CAPEX condensed and can be used again, the iron oxide is separated as byproduct.
  • This approach advantageously reduces space requirements, CAPEX (capital expenditure), and allows to serve a market segment which has currently no access to total waste metal chloride solution (or waste pickling liquor) regeneration systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Processing Of Solid Wastes (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un procédé de traitement d'une solution de chlorure de métal résiduaire par traitement par lots, la solution de chlorure de métal résiduaire comprenant au moins un constituant oxydable, le procédé comprenant les étapes suivantes : - dans une première étape, la solution de chlorure de métal résiduaire est acheminée vers une cuve de réacteur, et une étape d'oxydation est effectuée dans la cuve de réacteur à une température d'oxydation dépassant 90 °C et à une pression d'oxydation dépassant 0,3 MPa, au moins une partie de la solution de chlorure de métal résiduaire étant oxydée pendant l'étape d'oxydation, une solution de chlorure de métal au moins partiellement oxydée étant obtenue à partir de la solution de chlorure de métal résiduaire, la partie oxydée de la solution de chlorure de métal au moins partiellement oxydée correspondant à au moins une partie dudit constituant oxydable de la solution de chlorure de métal résiduaire avant l'étape d'oxydation, - dans une seconde étape, après la première étape, la solution de chlorure de métal au moins partiellement oxydée est au moins partiellement hydrolysée pendant une étape d'hydrolyse réalisée dans la cuve de réacteur à une température d'hydrolyse dépassant 120 °C et à une pression d'hydrolyse appropriée, de l'acide chlorhydrique étant obtenu pendant l'étape d'hydrolyse.
EP17720825.3A 2016-05-04 2017-05-04 Procédé de régénération d'acide résiduaire à petite échelle Withdrawn EP3452636A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16168382 2016-05-04
PCT/EP2017/060698 WO2017191279A1 (fr) 2016-05-04 2017-05-04 Procédé de régénération d'acide résiduaire à petite échelle

Publications (1)

Publication Number Publication Date
EP3452636A1 true EP3452636A1 (fr) 2019-03-13

Family

ID=56112814

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17720825.3A Withdrawn EP3452636A1 (fr) 2016-05-04 2017-05-04 Procédé de régénération d'acide résiduaire à petite échelle

Country Status (4)

Country Link
EP (1) EP3452636A1 (fr)
CN (1) CN109477227A (fr)
EA (1) EA038738B1 (fr)
WO (1) WO2017191279A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111330651B (zh) * 2018-12-19 2022-11-04 中国石油天然气集团有限公司 废离子液体催化剂处理方法及装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3682592A (en) 1970-07-20 1972-08-08 Pori Inc Treatment of waste hci pickle liquor
CA2728504C (fr) * 2008-06-19 2017-08-29 Nobuyoshi Takahashi Procede de traitement permettant de recuperer de l'oxyde de fer et de l'acide hydrochlorique
EP2536858A1 (fr) * 2010-02-18 2012-12-26 Neomet Technologies Inc. Procédé pour la récupération de métaux et d'acide chlorhydrique

Also Published As

Publication number Publication date
WO2017191279A1 (fr) 2017-11-09
CN109477227A (zh) 2019-03-15
EA201800588A1 (ru) 2019-04-30
EA038738B1 (ru) 2021-10-13

Similar Documents

Publication Publication Date Title
RU2495827C2 (ru) Способ регенерации оксида железа и хлористоводородной кислоты
CN105132932B (zh) 一种镀锌件返洗废酸液的回收处理方法
CN102161548A (zh) 电镀废水的回用处理方法及其设备
CN205381955U (zh) 废盐酸再生装置
EP0362978B1 (fr) Procédé pour le traitement de déchets caustiques contenant des cyanures et des métaux
EP3452636A1 (fr) Procédé de régénération d'acide résiduaire à petite échelle
CN106241758A (zh) 用于酸性废液的回收装置及工艺
US20030026746A1 (en) Regenerating spent pickling liquor
EP0655518B1 (fr) Système pour la recirculation de la matière de traitement dans les procédés de traitement et friction de surface
CN105110540B (zh) 一种镀锌酸洗废盐酸的回收处理方法
RU2305720C2 (ru) Способ удаления оксида железа с поверхности титановых компонентов
CN112813443A (zh) 酸洗液除铁再生设备和方法
CN1974853A (zh) 钢铁工业酸洗废弃盐酸循环利用并回收纳米铁粉及一氧化碳的方法
CN107651793A (zh) 一种盐酸酸洗废水处理系统
Randazzo et al. Metals recovery from waste pickling solutions by reactive precipitation
CN206109122U (zh) 一种盐酸酸洗废水处理系统
CN108483411A (zh) 一种除去硫酸废液中双氧水的处理装置及其处理方法
CA2437096C (fr) Systeme et methode de production de chlorure ferrique a partir de quantites reduites d'acide chlorhydrique a des fins de traitement de l'eau
CN108780669B (zh) 用于处理来自金属表面的净化的废水的方法、废水处理装置和废水处理装置的用途
US20040202595A1 (en) Treatment for waste pickling solutions containing iron and method of ferric oxide formation
CN110407175A (zh) 酸洗废液处理系统及回收设备
CN216458885U (zh) 废润滑油中金属的连续化脱除系统
CN108793095A (zh) 溶液除杂方法和溶液除杂系统
CN220867517U (zh) 三氯化铁蚀刻液连续在线再生利用装置
CN217025656U (zh) 废酸液回收处理装置

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20181204

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20201201