EP2547435A1 - Réacteur et procédé de purification d'une solution de traitement - Google Patents

Réacteur et procédé de purification d'une solution de traitement

Info

Publication number
EP2547435A1
EP2547435A1 EP11755745A EP11755745A EP2547435A1 EP 2547435 A1 EP2547435 A1 EP 2547435A1 EP 11755745 A EP11755745 A EP 11755745A EP 11755745 A EP11755745 A EP 11755745A EP 2547435 A1 EP2547435 A1 EP 2547435A1
Authority
EP
European Patent Office
Prior art keywords
reactor
solution
fluidized bed
mixing member
solid matter
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Withdrawn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
EP11755745A
Other languages
German (de)
English (en)
Inventor
Jussi Vaarno
Mikko Ruonala
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.)
Outotec Oyj
Original Assignee
Outotec Oyj
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 Outotec Oyj filed Critical Outotec Oyj
Publication of EP2547435A1 publication Critical patent/EP2547435A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/382—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it with a rotatable device only
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/86—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis co-operating with deflectors or baffles fixed to the receptacle
    • B01F27/861—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis co-operating with deflectors or baffles fixed to the receptacle the baffles being of cylindrical shape, e.g. a mixing chamber surrounding the stirrer, the baffle being displaced axially to form an interior mixing chamber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
    • B01F27/91—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with propellers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the equipment and method defined in the independent claims 1 and 1 1 for purifying a process solution.
  • agitation reactors are cylindrical and they have standard diameters. Typically, they are provided with flow resistances, which are attached to the walls of the reactor and the purpose of which is to eliminate the central turbulence, which is considered harmful and which absorbs gas from the surface. Solid-solution processes normally require mixing, wherein both strong turbulences and sufficient circulation occur. One important process is, e.g., the removal of cadmium by cementation. Cadmium is one of the harmful substances in the electrolytic processing of zinc.
  • the feeding into the agitation reactor mostly takes place by feeding both the solid matter and the solution into the reaction space from above.
  • both the solid matter and the solution escape approximately at the slurry density of the reaction space.
  • the outlet of the slurry flow can preferably be mounted on the reactor wall to mainly take place as an overflow.
  • the solution rises from a fluidization part through a conical extension into a clarification part, from where there is a discharge outlet of the solution on the wall of the clarification part.
  • the process disclosed comprises the cementation of cadmium solution and zinc powder.
  • cadmium powder is formed, which due to its porosity is lighter and, at the same time, also finer.
  • One object is to prevent the exit of solid particles, which are formed as reaction products, out of the reactor along with the solution.
  • a difficulty in this case is also the adherence of hook-like particles to each other, e.g., agglomeration.
  • the agglomerates grow so large that the motion in the fluidized bed weakens and, finally, stops completely. Therefore, a flocculation solution that prevents the agglomeration of particles is fed into the fluidization space.
  • a mixing member that crushes the agglomerates is placed in the lower part and, correspondingly, fairly small flow resistances that receive the impact forces and prevent turbulences are placed on the walls.
  • the solution flows as directly as possible along the shortest route towards the exhaust unit, whereby the flow field is rendered the form of a reducing curved cone. This, again, means that the speed of the solution flow that carries possible particles increases and the particles have no chance of detaching from the flow.
  • the object of the present invention is to eliminate the disadvantages occurring in the prior art described above.
  • a novel, more effective method and equipment for purifying solid matter from the process solution by means of the fluidized bed are thus presented.
  • the separation of solid matter is enhanced by circulating the solution in the fluidized bed and the flexibility required by the process changes is increased by controlling the amount of solution to be circulated in the fluidized bed.
  • the invention relates to a reactor for purifying solid matter from the process solution in the fluidized bed, whereby the reactor comprises a means of feeding and removing the process solution, the reactor being formed from at least three parts, the lowermost of which is an essentially cylindrical reaction part for forming the fluidized bed; a conically upwards-widening calming part is attached to the upper part of the reaction part and a cylindrical clarification part is connected to the upper part of this, its diameter being the same as the upper part of the calming part, whereby a mixing member is placed in the reactor to circulate at least part of the process solution back to the fluidized bed and to control the amount of circulating solution in the fluidized bed.
  • the solution according to the invention the removal of solid matter is enhanced by gaining a better purification result by circulating the solution in the fluidized bed.
  • the solution according to the invention can respond to the changes without causing breaks in the process.
  • the mixing member is placed in the centre of the reactor to produce an axial flow in the solution in the reactor. Consequently, the most advantageous flow conditions are reached in the reactor.
  • the mixing member comprises a pipe element, the lower par of which extends below the fluidized bed. Consequently, the flow can be directed to flow through the fluidized bed.
  • the mixing member is a tunnel propeller.
  • the lower part of the reaction part of the reactor has a rounded shape. In that case, the flow that is fed from the pipe element of the mixing member into the lower part can most preferably and evenly be directed to the fluidized bed.
  • the feeder pipe of the process solution is placed above the mixing member, whereby the solution to be purified can be guided directly to the pipe element through the mixing member.
  • the upper part of the reactor comprises an overflow tank for removing the clarified solution from the reactor.
  • the reactor comprises a means, such as a pump arrangement, for transferring the solid matter out of the fluidized bed.
  • the amount of solution circulating in the fluidized bed is larger than the amount of solution fed into the reactor, enhancing the purification of the solution that is fed.
  • the solid matter that is removed from the solution to be purified is cadmium.
  • the invention also relates to the method of purifying solid matter from the process solution in the fluidized bed in the reactor, into which the process solution is fed to form the fluidized bed in the essentially cylindrical reaction part that is the lowermost part in the reactor, from which bed the flow further moves to the calming part that widens conically upwards into the upper part of the reactor part and, further, to the cylindrical clarification part that is connected to the upper part of the same, the diameter of the clarification part being the same as the upper part of the calming part, whereby at least part of the solution that is fed into the reactor is circulated to the fluidized bed more than once, and that the amount of circulating solution is controlled in the fluidized bed by means of the mixing member placed in the reactor.
  • the mixing member produces an axial flow in the process solution in the reactor, extending the flow below the fluidized bed. According to the invention, at least part of the solution that permeates the fluidized bed moves back to the pipe element that is connected to the mixing member, from where the solution circulates back to the fluidized bed.
  • solid matter is removed from the fluidized bed at desired intervals without stopping the process and emptying the reactor.
  • the amount of solution flowing in the fluidized bed is adjusted by the rotation speed of the mixing member. In that case, the rotation speed of the mixing member is decreased, when the amount of solution that is fed increases, whereas the rotation speed of the mixing member is increased when the amount of solution that is fed decreases.
  • the energy needed to fluidize the particles in the fluidized bed is produced by the mixing member.
  • the operation of the fluidized bed can be adjusted, whereby any variations in the process flow and particle size do not cause problems to the process.
  • the changes caused by the variation in capacity can preferably be implemented without having to stop the process.
  • the density of the fluidized bed and the solid matter content of the overflow can always be reactor-specifically optimized to suit the process status, respectively.
  • the dimensioning of a new reactor model can be made for a wide feeding range and, in practice; the capacity of the system can be controlled by the number of reactors.
  • the mixing member that circulates the solution produces the energy needed for the fluidization.
  • Fig. 1 a shows a vertical section of the reactor according to the invention
  • Fig. 1 b shows the reactor according to the invention as viewed in the direction A.
  • Fig. 1 a shows the reactor 1 according to the invention, wherein a liquid process solution 2 and solid matter are treated, so that the powdery solid matter forms a fluidized bed 3 with the liquid and, at the same time, reacts with the process solution 2 to be purified, which is fed into the reactor.
  • the flow fluidizes the solid matter that reacts with the solution.
  • the cementation reaction in question is to remove cadmium from the zinc-bearing solution, where the aqueous solution, i.e., Cd-bearing solution of the substance to be cemented flows through the bed of zinc powder. Now, a reaction takes place, according to which zinc dissolves in the solution and cadmium is removed from the solution.
  • the fluidized bed 3 is formed.
  • a conically upwards-widening calming part 5 and, further, a cylindrical clarification part 6 rise up for raising upwards the solution 9 that is mainly free of solid matter to be further removed to the overflow tank 1 1 in the upper part 10 of the reactor and to be further treated.
  • cadmium can further be removed from the solution 16 that is to be removed.
  • the lower part 7 of the reaction part 4 of the reactor has a rounded shape, which furthers the flow of solution 8 back to the fluidized bed 3.
  • the energy needed for the fluidization of the fluidized bed is produced by a separate rotary mixing member 12, which is placed in the reactor.
  • the mixing member i.e., a propeller, preferably a tunnel propeller, is placed below the fluid level in the reactor and it is protected by blades to prevent the absorption of air into the propeller.
  • the mixing member 12 is attached, e.g., to the upper structures of the reactor 1 and it is controlled by a control unit 13 outside the reactor.
  • the mixing member can be controlled automatically according to the solid matter content of the feeding flow or the overflow.
  • the propeller produces an axial flow in the process solution 2 that is fed along the feeder pipe 15 above the same, enabling the circulation of the solution through the fluidized bed 3 more than once.
  • Circulation in the fluidized bed 3 further enhances the separation of solid matter.
  • the solution 2 that is fed into the reactor moves to the pipe element 14 of the mixing member, such as a circulating tube, and from there to below the fluidized bed, from where it further flows through the bed 3, whereby the chemical component to be purified reacts with the solid matter of the bed.
  • the cross-sectional area of the reactor increases and when the flow velocity decreases, the particles floating in the bed are separated from the solution. Thereafter, part of the solution exits as an overflow and part moves back to the pipe element by means of the tunnel propeller to further flow through the fluidized bed.
  • the properties of the fluidized bed are controlled by the rotation speed of the pumping mixing member, and conforming to the changes in capacity takes place by adjusting the same. If the amount of solution fed into the reactor is increased, the rotation speed of the pumping mixing member is correspondingly decelerated; therefore, the fluidized bed remains stable. Correspondingly, the procedure is reversed, when the amount to be fed decreases.
  • the solid matter used for purification is removed upstream from the fluidized bed by means of a piping and pump arrangement 18, which is separate with respect to the flowing solution.
  • the removal of solid matter 17 is implemented by a suitable pump, such as an airlift pump, into the upper part 10 of the reactor and from there to be further treated.
  • the invention is illustrated by means of the following example.
  • a present well-known reactor for removing cadmium is compared with the reactor according to the invention.
  • Table 1 shows measurement results in both cases mentioned above.
  • 440 m 3 /h of process solution to be purified were fed into the reactor, whereby the flow velocity that floats the solid matter particles in the fluidized bed is 0.039 m/s.
  • the diameter of the fluidized bed can be increased to 3600 millimetres, the diameter of the present reactor remaining at 2000 millimetres.
  • the solution to be purified is subjected to axial flow under the effect of the rotational power of the propeller placed in the reactor, whereby under the effect of the flow, the solution is pushed into the pipe element of the propeller, i.e., the circulating tube, at a velocity of 1 .2 m/s.
  • the diameter of the pipe element of the propeller by which an advantageous stability of the fluidized bed is achieved, is 550 millimetres in the solution according to the invention.
  • the rate of flow required in conventional fluidization is always determined according to the amount of solution to be fed, but according to the example that applies the invention, the rate of flow can be increased to as much as 1023 cubic metres an hour.
  • the solution can be circulated according to changing conditions by adjusting the amount of circulating flow in the fluidized bed by a separate tunnel propeller.
  • the amount of circulating flow needed for the fluidization is controlled by the rotation speed of the tunnel propeller.
  • the control range of the circulating flow is 1000-1500 m 3 /h, whereby the flow rate of the solution fed into the reactor can be adjusted within a range of 0-900 m 3 /h.
  • the same reactor can thus conform to the changes in the process conditions.
  • the volume of the fluidized bed in the reactor can be increased to 15 m 3 .
  • only one reactor is needed in the solution according to the invention compared with a case, where conventionally a series of many reactors is used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Combustion & Propulsion (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Abstract

L'invention concerne un procédé et un réacteur permettant de purifier une substance solide à partir d'une solution de traitement (2) dans le lit fluidisé dans le réacteur, la solution de traitement étant fournie pour former le lit fluidisé (4) dans la partie de réaction sensiblement cylindrique (3) qui est la partie la plus basse dans le réacteur, à partir duquel lit le flux se déplace en outre vers la partie de stabilisation (5) qui s'étend coniquement vers le haut depuis la partie supérieure de la partie formant réacteur et, en outre, vers la partie de clarification cylindrique (6) qui est raccordée à la partie supérieure de ce dernier, le diamètre de la partie de clarification étant identique à celui de la partie supérieure de la partie de stabilisation, moyennant quoi au moins une partie de la solution (2) qui est fournie dans le réacteur (1) est acheminée vers le lit fluidisé (3) plusieurs fois, et la quantité de solution en circulation est contrôlée dans le lit fluidisé au moyen de l'élément de mélange (12) placé dans le réacteur.
EP11755745A 2010-03-18 2011-03-10 Réacteur et procédé de purification d'une solution de traitement Withdrawn EP2547435A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20100120A FI122098B (fi) 2010-03-18 2010-03-18 Reaktori ja menetelmä prosessiliuoksen puhdistamiseksi
PCT/FI2011/050208 WO2011113997A1 (fr) 2010-03-18 2011-03-10 Réacteur et procédé de purification d'une solution de traitement

Publications (1)

Publication Number Publication Date
EP2547435A1 true EP2547435A1 (fr) 2013-01-23

Family

ID=42074298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11755745A Withdrawn EP2547435A1 (fr) 2010-03-18 2011-03-10 Réacteur et procédé de purification d'une solution de traitement

Country Status (11)

Country Link
EP (1) EP2547435A1 (fr)
CN (1) CN102781566B (fr)
AU (1) AU2011228953A1 (fr)
BR (1) BR112012023477A2 (fr)
CA (1) CA2789235A1 (fr)
CL (1) CL2012002499A1 (fr)
EA (1) EA201290924A1 (fr)
FI (1) FI122098B (fr)
PE (1) PE20130757A1 (fr)
WO (1) WO2011113997A1 (fr)
ZA (1) ZA201206260B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10183293B2 (en) 2014-07-01 2019-01-22 Thinxxs Microtechnology Ag Reagent reservoir for fluids

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI126361B (en) * 2014-06-30 2016-10-31 Outotec Finland Oy Reactor for mixing liquids, gases and solids
FR3042986B1 (fr) * 2015-11-04 2017-12-15 Commissariat Energie Atomique Dispositif de melange de poudres par fluide cryogenique et generation de vibrations

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3994721A (en) * 1972-06-30 1976-11-30 Societa Mineraria E Metallurgica Di Pertusola Purifying a zinc-bearing solution by cementation
FI50715C (fi) * 1973-02-26 1976-06-10 Outokumpu Oy Tapa ja laite erottaa veteen liuenneita aineita toisistaan sementointi aineella.
AUPN034694A0 (en) * 1994-12-30 1995-01-27 Comalco Aluminium Limited Improved draft tube agitator
FI119379B (fi) * 2007-03-16 2008-10-31 Outotec Oyj Tapa tehostaa selkeytystä sekoitusreaktorissa ja sekoitusreaktori

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011113997A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10183293B2 (en) 2014-07-01 2019-01-22 Thinxxs Microtechnology Ag Reagent reservoir for fluids

Also Published As

Publication number Publication date
WO2011113997A1 (fr) 2011-09-22
BR112012023477A2 (pt) 2016-05-24
CA2789235A1 (fr) 2011-09-22
EA201290924A1 (ru) 2013-04-30
FI122098B (fi) 2011-08-31
FI20100120A0 (fi) 2010-03-18
CL2012002499A1 (es) 2013-02-08
ZA201206260B (en) 2013-04-24
CN102781566A (zh) 2012-11-14
CN102781566B (zh) 2014-09-24
PE20130757A1 (es) 2013-06-28
AU2011228953A1 (en) 2012-08-16

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