CN101204680A - Method for separating solid - Google Patents
Method for separating solid Download PDFInfo
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- CN101204680A CN101204680A CNA200710160303XA CN200710160303A CN101204680A CN 101204680 A CN101204680 A CN 101204680A CN A200710160303X A CNA200710160303X A CN A200710160303XA CN 200710160303 A CN200710160303 A CN 200710160303A CN 101204680 A CN101204680 A CN 101204680A
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- suspension
- flotation
- solid phase
- crystallisation
- solid
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/14—Flotation machines
- B03D1/1481—Flotation machines with a plurality of parallel plates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for separating two solid phases with different positions from the solution which contains at least one dissolvent and two dissolved solid phases, and the invention is characterized in that the method comprises the following procedures: a crystallization procedure a), wherein the suspending liquid of the crystal containing at least two solid phases in the dissolvent is obtained, a floatation procedure b), which is executed at the state that the separating gas flowing over the suspending liquid from the lower side to the upper side exists, wherein the solid phase is separated thereby that at least one in the two solid phases is taken as solid phase containing gas and is collected to the top of the suspending liquid and at least the other one solid phase is collected at the lower part of the suspending liquid, and at least one separation procedure c), wherein the solid phase containing gas is separated from the upper side of the suspending liquid and/or the solid phase is separated from the lower part of the suspending liquid respectively.
Description
Technical field
The present invention relates to from liquid phase, separate the method for two kinds of different solid phases of forming by crystallization and flotation.
Background technology
Separating from the mixture of substances of being made up of at least two kinds of solid matters or reclaim solid matter by crystallization is a kind of method commonly used.Unless it has been rendered as solution, otherwise the mixture of two kinds of solid phases to be dissolved in solvent or the solvent mixture.When separating, may there be system or eutectic system or both combinations that forms solid solution according to the kind difference of material.Under the situation of eutectic system, can be solid phase is separated from one another by crystallization.Under the situation of the ternary mixture that constitutes by two kinds of solids and solvent (mixture),, can crystallize out for a kind of solid phase of the situation of eutectic system or another kind of solid phase according to the position difference in phasor.Only in the just crystallization (no solid solution) simultaneously together of two kinds of solid phases of eutectic point.Eutectic point is temperature-dependent.Therefore usually can separate described two kinds of materials by crystallization.Only need at least two crystallisation steps to come separate substance and randomly concentrate by the Crystallization Separation eutectic mixture.This is very complicated in operation, and is accompanied by high energy.On the contrary, if crystallization can form the wherein simultaneous mixture of crystal of two kinds of solid phases, then only need a crystallisation step, but described crystal must be separated from one another in some way.
If the density of two kinds of solid phases is with different by the density of the saturated solvent of used solid phase, then they can be separated from one another during less than density of liquid phase in a kind of density of density another kind of solid phase greater than density of liquid phase of solid phase.In this case, the solid that proportion is lighter will swim on the liquid, and another kind of solid will deposit out as sediment.If the proportion of two kinds of solids all greater than liquid, then can pass the separation that liquid is realized solid by making gas sometimes from bottom to top.The deposition of solid that contains gas is on liquid, and another kind of solid deposits out as sediment.These method (flotation; Ullmanns Enzyklop die der technischen Chemie, Band 1, the 666-678 page or leaf, Verlag Urban ﹠amp; Schwarzberg, M ü nschen, Berlin 1951) and being used to for example ore dressing, wherein desired containing metal compound is separated from most of impurity of low-metal content.For example can use the liquid that does not dissolve described solid usually in the coal washing in ore dressing and other industrial separation of being undertaken, and described liquid comprises and can realize usefulness gas and the liquid washing agent to the different wetting of two kinds of solids by flotation.These methods can not provide pure material, and can only produce the enrichment of expectation component.
Because higher complexity and particularly high energy consumption, already known processes can not satisfactoryly maybe can not provide pure material, therefore the objective of the invention is to develop a kind of method that does not have one or more described defective.
Unexpected now the discovery, can be by following means that described component is separated from one another from the solution that comprises at least two kinds of other components, promptly make two kinds of components crystallize out together as solid phase separated from one another, and under the situation that has the air-flow that passes liquid from bottom to top to exist, formed suspension is separated into and floats over containing gas solid phase and gathering or being deposited in the solid phase of separation container bottom on the liquid, and solvent phase (mother liquor) by flotation.
Summary of the invention
Therefore the present invention relates to a kind of method of from the solution that contains at least a solvent and the solid phase of two kinds of dissolvings, separating two kinds of different solid phases of forming, it is characterized in that comprising: crystallisation step a) wherein obtains the suspension of crystal in described solvent of described at least two kinds of solid phases; Flotation step b), it carries out under the situation that the divided gas flow existence of flowing through described suspension is from bottom to top arranged, thereby at least a conduct in the separated two kinds of solid phases of wherein said solid phase contains the top that the solid phase of gas accumulates in suspension, and another kind of at least solid phase accumulates in the bottom of suspension; With at least one separating step c), wherein said contain the gas solid phase from suspension top and/or described solid phase separate respectively from the suspension bottom.
Washing agent or other additive can be do not added when the advantage of the inventive method is to carry out flotation, thereby extra Master Cost can not be produced and the solid phase that will separate can not polluted by other material.Owing in crystallization and flotation, used identical liquid or identical liquid system, so saved the arrangement step that is used to separate different liquids.In addition, the release additive also makes can reclaim mother liquor wholly or in part, thereby the output of the solid phase that will separate is improved.In addition, the inventive method is also advantageous in that the energy consumption that it is relatively low.Owing to only have a crystallisation step under the perfect condition in the method for the invention, so flushing process is less generally, the workload of putting used cleaning solution thus in order is also less.
Method of separating two kinds of different solid phases of forming from the solution that contains at least a solvent and the solid phase of two kinds of dissolvings of the present invention is characterised in that and comprises: crystallisation step a) wherein obtains the suspension of crystal in described solvent of described at least two kinds of solid phases; Flotation step b), it carries out under the situation that the divided gas flow existence of flowing through described suspension is from bottom to top arranged, wherein thereby at least a conduct in the separated described solid phase of solid phase contains gas solid polycondensation collection on the top of suspension, and another kind of at least solid phase accumulates in the bottom of suspension; With at least one separating step c), wherein said contain the gas solid phase by from suspension top and/or described solid phase separated respectively from the suspension bottom.
The prerequisite of the inventive method is not that all solid phases all form solid solution each other when being crystallization.For the situation of the solution that contains two kinds of dissolving solid phase A and B, in fact when crystallization, must almost only form the crystal and B crystal mutually of A phase.For three kinds of situations of dissolving the solution of solid phase A, B and C, has a crystallization separately mutually at least.Conditions of similarity is applicable to and contains the substance system that surpasses three kinds of solids.
Thereby another prerequisite of the inventive method is the solid phase that will separate to be had different affinitys to described flowing gas and not only can form proportion and be lighter than containing the gas solid phase but also can obtaining to overweight at least a solid phase of liquid of liquid.Usually, two kinds of solid phases separating need not to contain its density of gas all greater than described solvent or solution.
Method of the present invention can be used for the crystalline solid of separate dissolved in same solvent or solvent mixture.
Crystallisation step a)
Crystallisation step a) the middle crystallization of carrying out can carry out continuously or in batches, preferably carries out continuously.At crystallisation step a), can carry out any known method for crystallising.At crystallisation step a), preferably carry out evaporative crystallization or crystallisation by cooling.During evaporative crystallization, crystallization is that the evaporation isothermal ground along with a part of solvent carries out.During crystallisation by cooling, crystallization realizes by cooling solution.Crystallisation step a) in preferably in conjunction with cooling off and evaporative crystallization.This can be for example by cooling off and evaporate simultaneously a part of solvent, for example carries out crystallization and realize (for example vacuum crystallization) by applying vacuum.By in conjunction with cooling off and evaporative crystallization, can quicken the output that crystallization also can quantitatively improve crystal.
In the method for the invention, crystallisation step a) and particularly crystallization itself preferably at-40 ℃-300 ℃, preferably 0-150 ℃ and particularly preferably carry out under 10-100 ℃ the temperature.
Crystallisation step a) or crystallization can in crystallizer, cooler pan crystallizer (Gouda company) or the scraper-type crystallizer (Armstrong company) of for example simple stirred vessel of known all crystallizers of one of ordinary skill in the art, ventilation duct crystallizer, FC crystallizer, band thermopnore or fluid bed, carry out.
The solution that offers the crystallisation step of the present invention solid phase that comprises at least a solvent and dissolving a) can randomly have on a small quantity, and preferably less than 0.5 quality %, more preferably 0.0001-0.1 quality %'s is suspended in solid in the solution.Described solid preferably has described at least a at least two kinds of solid phases of being dissolved in the solution, preferred especially two kinds.Described in solution a small amount of solid that exists can serve as seed crystal and promote crystallization during crystallisation step a), particularly quicken crystal growth.
Be used for crystallisation step of the present invention solution a) and preferably have the solution that one or more polar liquid is made solvent.These polar liquids can be for example ether, ester, alcohol, preferably methyl alcohol, ethanol or isopropyl alcohol, ketone, preferably acetone or isophorone, acid amides, dimethyl formamide for example, nitrile, for example acetonitrile, or water.As possible, preferably use water as the solvent in the inventive method.Can use and contain two or various ingredients, as long as two in the particularly above-mentioned polar liquid or multiple, or the mixture of being made up of them is as solvent is these components complete miscibility each other.According to the difference of the solid phase that will separate, can use different solvents.One of ordinary skill in the art are easy to determine suitable solvent by simple preliminary test.If it is inorganic salts that the solid phase of separating has a kind of, then preferably make water or aqueous solvent or water and another kind of polar solvent, for example methyl alcohol or ethanol.
The mass ratio of solvent is preferably 10-99% in being supplied to the solution of crystallisation step, more preferably 30-90% and particularly preferably 50-75%.Preferably, there is above-mentioned small amount of solid in the selective solvent ratio that accounts for solution so that the described solid phase that is dissolved in the solution can be made at least by the amount of dissolving fully or dissolving in the solution.
Be supplied to the solution of the crystallisation step of the present invention solid phase that comprises at least a solvent and dissolving a) for example directly to discharge the liquid acquisition as the product of reaction.But, also can be dissolved in to prepare in the solvent and be used for crystallisation step solution a) by solid mixture with at least two kinds of solid phases.
The ratio that is dissolved in the solid phase in the solution can change in wide range.If only be dissolved with two kinds of solid phases at the solution that is used for crystallisation step, then the mass ratio of described two-phase is preferably 1: 100-100: 1, particularly preferably 1: 10-10: 1 and more particularly preferably 1: 5-5: 1.
If for example the product mixture of a chemical reaction (metathesis reaction as shown below) is used as the solution of crystallisation step of the present invention in a),
EF+GH→EH+FG
Then the ratio of two kinds of material EH and FG pre-determines basically by stoichiometric proportion.The mother liquor (the therefrom solution of fractional crystallization solid phase) that recovery has other accessory constituent that has randomly concentrated may cause departing from this ratio.In addition, in this mixture, also generally there is a spot of parent material (EF and/or GH).
According to selected solvent and selected process conditions for example pressure, temperature, time of staying or the like, before crystallization, to pre-determine contact angle Θ,, i.e. the trend of Shu Ru bubble adhesion to the formed crystal.
Formed angle when bubble contacts with solid phase, promptly so-called contact angle has been described the wetability of bubble at the surface of solids, and this wettability is influenced by interfacial tension.According to the difference of material system, contact angle may present 0-180 ° value.Can consider following scope for forming gas-solid aggregation:
0°<Θ<90°
Along with reducing of contact angle, the bubble that liquid centers on is pushed open from the more and more hydrophilic surface of solids.Gas-body aggregation can only form under certain condition.
90°<Θ<180°
Bubble more and more accumulates in the surface of solids.Adhesion strength improves along with the increase of contact angle.The surface is a hydrophobicity.
This makes can guarantee that bubble can accumulate on the solid particle of the projecting liquid of proportion.The averag density of air-liquid aggregation can become thus and be lower than mother liquor on every side, thereby can realize the target flotation.
Therefore following formula must be applicable to flotation:
M=quality wherein, ρ=proportion, m=quality, the mass fraction of w=component in gas/solid mixture.
Therefore have a critical contact angle, critical thus contact angle begins, and the bubble of minimum can be assembled, and makes the proportion of gas-solid aggregation less than mother liquor.Therefore, 90 ° transition region, fully may in addition the material system of contact angle Θ<90 ° in crystal also can form enough light gas-solid aggregation.
The difference of the contact angle of the solid that separates is preferably at least 25 °, preferably at least 30 °, preferably 30 °-100 ° and particularly preferably 50 °-75 °.
The mode of carrying out the crystallization of crystallisation step in a) is preferably to make at flotation step b) in should show as the median particle diameter d of that part of crystal that contains the gas solid phase
50Be 0.01mm-25mm, preferably 0.05-15mm and particularly preferably 0.1-5mm.The crystal size or the crystal size distribution of expectation can on purpose be set up by selective freezing temperature, seed crystal, average crystallite time (time of staying) and solvent for use for every kind of solid system that will separate, and can determine by simple preliminary test.Median particle diameter d
50Can for example use the LasenTec probe (to assemble light beam reflection measurement (FBRM) by known method with the measurement of corresponding distribution of particles; Measuring instrument: from the Lasentec of the Mettler-Toledo company of Giessen) carries out.At for example paper of Paul Barrett " Selecting In-Process Particle-Size Analyzers ", Chemical EngineeringProgress, in August, 2003, the 99th volume, has the description of pair measuring method at the 8th phase in the 26-32 page or leaf.
Carrying out crystallisation step is 1-40 quality %, preferably 3-20 quality % and the suspension of 5-10 quality % particularly preferably preferably to obtain a kind of solids content a).
Flotation step b)
At flotation step b), preferably in flotation unit, be separated at least a second solid phase that contains the gas solid phase and accumulate in the suspension bottom or be precipitated out that accumulates in suspension top by means of divided gas flow from the crystallisation step suspension that comprises at least two kinds of solid phases a).
At flotation step b), preferably use solids content to be 1-40 quality %, preferably 3-20 quality % and the suspension of 5-10 quality % particularly preferably.The suspension that obtains in a) at crystallisation step preferably is directly used in flotation step b).But, can be 1-40 quality % above adding certain amount of solvent, wash solution or starting soln in the suspension of desired value to obtain solids content also to solids content, preferably 3-20 quality % and the particularly preferably suspension of 5-10 quality %.
Under flotation conditions, all the components of suspension is inert gasses as far as possible or admixture of gas all can be used as flotation step b of the present invention) in divided gas flow.The preferred divided gas flow that uses is following gas, admixture of gas or their mixture: air, nitrogen, inert gas, hydrogen, carbon monoxide, carbon dioxide, forming gas, methane.Air or nitrogen are preferred divided gas flows, and nitrogen is extremely particularly preferred divided gas flow.
In the method for the invention, divided gas flow is preferably at flotation step b) thus in to make the volume ratio (Nl/l) of the suspension in the input flotation vessel in the divided gas flow of input and the unit at one time with the input of certain amount be 0.01-100Nl/l, 0.1-10Nl/l 0.2-2Nl/l particularly preferably also preferably.
Method of the present invention is preferably so that at flotation step b) in introduce the divided gas flow in the suspension the average bubble size be that the mode of 0.1 μ m-10mm is implemented preferably 1 μ m-5mm and particularly preferably 10 μ m-1mm.The bubble size can be determined by the range estimation photo.The average bubble size should be preferably than the median particle diameter d that is present in the particle in the suspension that will inflate
50Little 2 times, preferably little 5 times also particularly preferably little 10 times.The bubble size can be established by the pore size of selection device of introducing air-flow in flotation unit with by volume flow rate.Preferably, divided gas flow via the device that is fit to for example sintering metal or via be positioned at below the flotation unit 1/3rd, preferred below ten/in the lump particularly preferably the nozzle of flotation unit bottom introduce.
In the method for the invention, flotation step b) or flotation preferably at-40-300 ℃, preferably 0-150 ℃ and particularly preferably carry out under 10-100 ℃ the temperature.Flotation step b) or flotation preferably with the temperature of crystallisation step or with the corresponding temperature of discharge temperature from crystallisation step suspension a) under carry out.Like this, can avoid the dissolving again or the uncontrolled post crystallization of crystal, this post crystallization may be at the surface of flotation step equipment therefor crust.
Flotation step b) can under superpressure, normal pressure or low pressure, carry out.Flotation is preferably implemented down at normal pressure (measuring in the gas phase on liquid).
Preferably carry out the flotation step b of the inventive method) thus make flotation step b) in the mean residence time of the solid that will separate be 5 seconds-10 hours, preferably 60 seconds-5 hours also particularly preferably 600 seconds-1 hour.
Flotation step b) flotation in can be carried out in batches or continuously, preferably carries out continuously.For flotation, can use all known commercial plants (flotation unit) that are suitable for carrying out flotation, for example dissolved air floatation device, electric flotation unit, foam floating flotating device, flotation column, stirring flotation unit, centrifugal force field flotation unit, flotation cyclone separator or classification centrifuge with interior and/or outer inflation.In the method for the invention, preferably use has the outer and randomly interior Pneumatic flotation column of inflating.
Be preferred for flotation step b) flotation column preferably constitute by stainless steel tube.Be used to connect feed line and clean the joint of running pipeline (Klarlaufleitung) and the top that cleaning device is preferably mounted in described stainless steel tube.At lower area, described pipe preferably is tapered and forms a cone that has deliverying unit in the bottom.Installed within described pipe that a top has the perforate awl and the bottom has the gradually inflow container of thin awl.The supply of suspension can be for example one or more perforate in zone realizes tangentially between the awl by entering in described inflow container up and down.
Described raw material can use common aerating device for example to inflate reactor (having the pneumatic element (sintering metal) available from Mott company) or venturi type inflator (available from Timmer company) is inflated.
On the inflow container, the thin slice that is used for steady air flow can be installed.Under the inflow container, can there be one or more further inflation unit.
The layout of thin slice can have different choice.Preferably, thin slice with horizontal plane be that the angle (with reference to Fig. 4) of α is provided with, select this angle enough little to prevent that particle from directly further rising, also to select enough the thin slice so that the particle in precipitating can not slip away downwards greatly.The α angle be preferably more than or equal to 20 ° to being less than or equal to 80 °, be preferably more than or equal 60 ° to being less than or equal to 75 °.
The preferred length of thin slice can be by median particle diameter d and thin slice calculating apart from s each other.Preferably, the 10-200 that should be median particle diameter d apart from s doubly, preferably doubly (proportionality coefficient F) (s=d*F) for 50-150.The preferred length l that calculates thin slice thus is l=s/cos α (with reference to Fig. 4).
Separating step c)
At separating step c), separate on the described top that contains the suspension that the gas solid phase obtained from flotation step and/or (preferably with) described solid phase is separated with described suspension respectively by the bottom from described suspension.According to the characteristic difference of the solid phase that will separate, the distribution of solid phase may be different after flotation step.In the containing gas and may for example swim on the suspension surface, assemble from the teeth outwards or accumulate in suspension top mutually of suspension top enrichment, this top preferably account for the suspension total height less than 10%, preferably less than 5% and particularly preferably less than 1%.Preferably, the particle that contains the gas phase swims on the suspension surface.The non-gas that contains that accumulates in the suspension bottom may be deposited on the suspension bottom mutually or accumulate in the suspension bottom, this bottom preferably account for the suspension total height less than 10%, preferably less than 5% and particularly preferably less than 1%.Preferably, the non-particle deposition of gas phase that contains is in the suspension bottom.
Flotation step b) the top solid phase that obtains in can be at separating step c) with adhering to that solution (mother liquor) shifts out or the mixture of conduct and solution (mother liquor) shifts out.Crystal can for example filter press or filtering centrifuge separate with most of mother liquor by means of known industrial solids/liquid separation unit.By using solvent wash, can use when preparing starting soln used identical solvent to remove remaining impurity easily.The steam condensate liquid that obtains in evaporative crystallization can preferably be used as cleaning solution.Can preferably use the another kind of for example more volatile solvent that is not used for crystallization to wash in addition, so that the mode that washing can displacement washing is carried out and can be realized shorter drying time in drying.
The solid phase of bottom of assembling or being deposited on the suspension bottom, assembling or being deposited on described container when using flotation vessel is by machinery output from suspension/container, suitablely discharges or pumps as suspension (solid phase/mother liquor).These crystal equally separate, wash by the Separation of Solid and Liquid that is fit to as mentioned above and randomly carry out drying.
Two kinds of mother liquors and two kinds of cleaning solutions of being obtained in two crystal-like separation can randomly be recycled in the technology after concentrating.These solution can be used for preparing starting soln or can directly import crystallisation step a) or flotation step b).
For separating by-products can be discharged a part of mother liquor and/or cleaning solution.Thereby the discharge of accessory substance is preferably by partly discharging mother liquor, particularly preferably making and have the mother liquor of high less important concentration of component and be discharged from and realize by discharging the mother liquor concentrated in advance.
Two kinds of separated solids can be used as easily mobile crystal or be used as solution afterwards in being dissolved in solvent after drying.Dry can for example fluidized-bed layer seasoning or oar formula drying realize by known method.
In the method for the invention, method step a), b) and c) can carry out respectively or simultaneously in the space and/or on the time.Especially, crystallisation step a) and flotation step b) can carry out respectively or simultaneously in the space and/or on the time.But, crystallisation step a) and flotation step b) to carry out in same container may be favourable.Like this, particularly can reduce the complexity of device.In this preferred embodiment, can for example in flotation column, interior pipe (being described inflow container) be designed to double jacket.When this inflow container is cooled, can be at the inner suspension that produces of flotation unit.Also can evaporate a part of solvent, for example in a vacuum, formed evaporation bubble can further improve flotation effect.If crystal deposition is flowing on the chamber wall in crystallization process, the crystal that then maybe advantageously is deposited on the wall for example is removed by slow rotation of blade.
Flotation step b) and separating step c) and randomly crystallisation step a) also can be in a device, particularly carry out in the container.The benefit of this embodiment of the inventive method is only to need to use a container.In addition, also avoided with suspension when a container is transferred to another container because obstruction or thermal losses that deposition of solid caused.
Under above-mentioned prerequisite, method of the present invention can be used for for example following the separation:
-mixture or the solution of two kinds of solid A and B is separated into two kinds of independent component A and B,
-the solution that will comprise three kinds of solid A, B and C is separated into A and BC mixture, or is separated into B and AC mixture, or is separated into C and AB mixture,
-the solution that will comprise four kinds of solid A, B, C and D is separated into a kind of pure component respectively and comprises the part of other three kinds of components or be separated into the mixture of two two components respectively.Also can separate similarly and comprise the system that surpasses four kinds of components.
Especially, method of the present invention can be used for separate reacted mixture.For example, can be used for:
-separating inorganic salts from carboxylate
-separating inorganic salts from sulfonate
-separating inorganic salts from phosphonate
The inorganic salts that-separation is different
The organic salt that-separation is different
-separating organic acid from organic salt
-separating organic acid from inorganic salts.
In addition, method of the present invention can be used for (removing accessory constituent) for example following material of purifying: methionine, threonine, dodecanedioic acid, boric acid, citric acid, benzoic acid, salicylic acid, maleic acid, acrylic acid, methacrylic acid, tartaric acid, glucose or sucrose.
The utmost point particularly preferably, method of the present invention can be used for separating SMAS (MAS) and sodium chloride (NaCl) from the aqueous solution.
A preferred embodiment of the inventive method is as follows, and wherein SMAS and sodium chloride are used as at least two kinds of solid phases.
Obtain pure solid SMAS and solid sodium chloride in order water, to react in the aqueous solution that obtains from for example methallyl chloride and sodium sulfite, preferably carry out method of the present invention in the following manner: a) at crystallisation step, sodium chloride (NaCl) and SMAS (MAS) by from temperature for also evaporating a part of water simultaneously by solution being cooled to preferably 10-30 ℃ the saturated or almost saturated hot solution of about 80-100 ℃ MAS and NaCl, for example under the pressure of 20-40 millibar, crystallize out.Thus obtained suspension preferably has the water of 65-70 quality %, the NaCl of 19-21 quality % and the MAS of 10-15 quality %.The NaCl that crystallizes out is median particle diameter d preferably
50(centre chord length) is determined as 200-750 μ m according to FBRM, and preferably be 25 ℃ of absorption during nitrogen contact angle less than 45 °, preferably less than 40 °.The MAS that crystallizes out is median particle diameter d preferably
50Be 250-750 μ m, and preferably be 25 ℃ of absorption during nitrogen contact angle be preferably more than 75 ° greater than 70 °.Greatest differences between two contact angles makes can be by flotation, use the air or the nitrogen of room temperature easily, realizes the fabulous separation of two types of crystal.MAS is floating solid.MAS preferably machinery removes, washes and be dry.The suspension that NaCl can be used as NaCl and mother liquor removes, and from then on can leach NaCl in the suspension, and washing is also randomly dry.
1,2,3 and 4 couple of the present invention illustrates with reference to the accompanying drawings, but does not have any intention that limit the invention to these embodiments.
Description of drawings
Fig. 1 has shown the block diagram that can carry out the equipment of the inventive method.
Fig. 2 has shown the block diagram that can carry out the alternate device of the inventive method.
Fig. 3 has shown the flotation column that is used for embodiment 1.
Fig. 4 diagram has shown the size that is used to calculate flake alignment.
The specific embodiment
Fig. 1 has shown the block diagram that can carry out the equipment of the inventive method.Fore flow (1) and mother liquor claim circular flow (10) again, and cleaning solution (14) and (19) are transfused in the crystallizer (2) together, and crystallisation step a) carries out in described crystallizer (2).Therein, solvent for example the part of evaporation water (3) can be removed.Formed suspension (4) for flotation is transfused to flotation vessel (5), and wherein said suspension (4) is made up of the solvent solid phase different with at least two kinds.Feed the gas (6) as divided gas flow in flotation vessel (5), for example air, and gas (6) is most of in container (5) upper end overflows as discharging air-flow (7).This air-flow can be recycled in the container as a part that flows (6) when needed once more.If gas (7) is not recycled in the technology, the then suitable solvent carried secretly therefrom isolated is (for example by condensation or adsorption/absorption; Device does not show in block diagram).With the solid phase (8) that floats in the flotation vessel (5) on the solution, MAS for example, machinery remove also and leach in device (12) (for example filter or filtering centrifuge), and with the part (13) of stream (3) or randomly wash with the another kind of cleaning solvent that is fit to.The solid that is present in stream (18), for example MAS stream can directly be used, or is dried in a unshowned device and/or transforms.Second solid phase (9) with the precipitated form acquisition, for example sodium chloride flows, separated by machinery equally and leach in (16) (for example filter or filtering centrifuge) at device, and with the part (17) of steam or randomly wash with the another kind of cleaning solvent that is fit to.The solid (15) that is present in stream (15), for example NaCl stream can directly be used, or is dried in a unshowned device and/or transforms.The mother liquor of removing from container (5) (10) randomly is recycled to crystallizer (2) after isolating a shunting that is used to discharge accessory constituent (11).By mother liquor and cleaning solution, for example from the mother liquor of MAS washing with from filtrate (14) and (19) that the cleaning solution of NaCl washing constitutes, directly be recycled in the crystallizer (2) or be used to prepare starting soln (1).
Fig. 2 has shown the block diagram that can carry out the alternate device of the inventive method.In the method variant, crystallisation step and flotation step are implemented in same device (3 ') simultaneously.Parent material solution (1 ') is with returning stream (15 '), and randomly with the mother liquor stream (7 ') from device (3 '), is transfused to device (3 ').In addition, make divided gas flow (2 ') access to plant (3 ').Overflow in the upper end of separation container by the gaseous flow (4 ') that divided gas flow and solvent constitute.From then on can for example reclaim most of solvent in Fig. 2 in the stream by condensation (device feature does not show).This condensate liquid can be used for replacing stream (10 ') to make cleaning solution separately or as the mixture with one or more solvent.Perhaps, this condensate liquid can be used for preparing starting soln (1 ').After having separated most of solvent, divided gas flow can be recycled in the separation container.When air or nitrogen are used as divided gas flow and water and are used as solvent, do not need/suit convection current (4 ') to put in order.Device swims in solid phase on the mother liquor and partial mother liquid in (3 ') and is used as stream (5 ') and removes.In solid-liquid separator (8 ') by filtering and using solvent (10a ') washing from then on to isolate solid phase (11 ') in the stream subsequently.Obtain the mixture of mother liquor and solvent as filtrate (12 ').Mother liquor that is obtained and cleaning solution can randomly be collected respectively and use.Taken out the suspension (6 ') that constitutes by another kind of solid and mother liquor from the bottom of device (3 ').In solid-liquid separator (9 ') by filtering and using solvent (10b ') washing from described suspension flow, to isolate solid phase (13 ') subsequently.The mother liquor that has obtained as filtrate (14 ') and the mixture of solvent.Mother liquor that is obtained and cleaning solution can randomly be collected respectively and use.Described two kinds of filtrates provide stream (15 '), and it randomly directly is recycled in the device (3 ') afterwards or is used to prepare starting soln (1 ') concentrating and/or discharge shunting (16 ').In the method, can randomly a part of mother liquor be circulated by pipeline (7 ').
Fig. 3 has shown the flotation column that is used for embodiment 1.The suspension SU that has fed bubble is by in the charging input flotation column.This suspension enters and flows into funnel E.Whereby, can on purpose form slipstream in flotation unit inside.This stream can be compared with the stream of cyclone hydraulic separators inside.
Above flowing into funnel E thin sheet of metal sheet L is arranged, can rise to the flotation column top by its solid F2 that floats, and for example be removed by removal device at this.Flowing under the funnel, the solid F1 in the precipitation accumulates in the flotation column bottom, and described flotation column bottom is preferably conical and can for example remove solid F1 by unshowned conveying worm by it, and discharges from flotation column.The inlet of flow export is preferably located in and flows under the funnel E, and flow export itself is arranged on the inflow funnel, preferably on the thin sheet of metal sheet.The mother liquor (liquid F) that leaves flotation column from the flotation column bottom must upwards flow to flow export via described inlet, make like this its can not with residue flotation column contents mixed.This layout has guaranteed that the least possible solid discharges flotation column with mother liquor.Arrow among the figure is represented the possible direction of motion of solid (F1 and F2), liquid (F) and suspension (SU).
Fig. 4 illustrates the size that is used to calculate flake alignment.Wherein, l
MinThe minimum length of expression thin slice, s represents the distance between the thin slice, α represents the angle of thin slice and horizontal plane.
Used following test method in the present invention:
1. measurement of contact angle
Contact angle is measured by optical method.For this reason, with suitably big particle (>0.5mm) be clipped in the fixator.The described fixator of solid particle that comprises is immersed corresponding the measurement in the liquid.Apply bubble by means of nozzle to solid particle then.Utilize optical unit that the bubble that adheres to is taken pictures.Measure photo by diagram and determine contact angle.
2. median particle diameter d
50With corresponding particle diameter Determination of distribution
The median particle diameter d of crystal
50With corresponding particle diameter Determination of distribution is to use the LasenTec probe to carry out according to FBRM method (focused beam reflection measurement method), and wherein the Lasentec device is available from Mettler-Toledo company, Giessen.
Following examples are used for explaining in more detail the present invention, do not limit the protection domain that is provided by patent claims and specification.
Embodiment 1: embodiment
In a pilot-plant that comprises flotation column as shown in Figure 3, carry out separating of sodium chloride and SMAS.It is that 193.11mm, angle are 75 ° thin slice that flotation column has length l, and this thin slice 500mm at interval is provided with.Be computational length, the assumed median particle diameter is that 500 μ m and the coefficient (F) that is used to measure distance s are 100.
The synthetic starting soln that begins to have eutectic composition under 80 ℃ reactor outlet temperature is introduced in the container.Described synthetic starting soln comprises the water of 63.2 quality %, the MAS of 20 quality % and the NaCl of 16.6 quality %.From then on container, mother liquor with one from Pneumatic flotation column (as shown in Figure 3) return stream input the 5l double jacket container of diameter 200mm, high 400mm is housed and be equipped with diameter 80mm tangential transport agitator (200rpm) (rev/min) agitated crystallizer in.Within crystallizer, starting soln is cooled to 30 ℃ temperature.In addition, 20 millibars vacuum and evaporation water have thus also been applied.Return under the input of stream at 2kg/h starting soln and 1.6kg/h, can set up the distillate stream of 0.36kg/h water.
By means of relax delivery pump (the Mohno screw pump, from Netzsch company, model: MohnoNM15) will be transported in the Pneumatic flotation column from the suspension of agitated crystallizer.Directly in the porch of Pneumatic flotation column, the air that will have the regulation bubble form of 100-1000 μ m particle diameter distribution is that the inflation element of the porous sintered metal form of 5-50 μ m is introduced in the suspension via the aperture, and described bubble adhesion is to the MAS particle.
Enter pneumatic floating wash post after, air-MAS aggregation swims in the top of device selectively.The NaCl crystal settling that does not adhere to air comes out.In all cases, sediment is all taken a sample with floating thing and utilize laboratory suction filter from adhere to mother liquor, to separate and use demineralized water to wash with the ratio of 1: 1 pair of wet solid.For measuring moisture remnants, that sample is dry in common dry balance (from Mettler-Toledo company, the halogen moisture analyzer of Giessen).
Carry out twice circulation ( sample 1 and 2).As shown in table 1 below for the result that floating thing and sediment obtained in circulation.
Table 1: the result of circulation 1 and 2
Floating thing | Sediment | |||
Specimen coding | Dry [quality %] | MAS content [quality %] in the dry | Dry [quality %] | MAS content [quality %] in the dry |
1 | 75.1 | 99.8 | 87.7 | 9.1 |
2 | 70.0 | 99.8 | 74.5 | 9.7 |
Although washing with water is not the best, still obtained highly purified SMAS.
Embodiment 2: the calculating embodiment of commercial run
For by commercial run of the present invention, in embodiment 1, set and the basis of the mass flow that obtains on the calculated mass flow velocity, and utilize the Excel spreadsheet program of Microsoft to calculate its chemical composition by the material data of used material.Result calculated is shown in following table 2a-2e.The name of stream is identical with block diagram shown in Figure 1.When data are represented with % and specially do not pointed out in addition, in table, be meant quality % all the time.
Table 2a: the materials flow 1 and 3 of calculating
Unit | Feed stream (equipment) | Evaporation water (crystallizer) | ||||
Overall flow rate | kg/h | 16.5 | 8.1 | |||
Phase | Liquid | Gu | Liquid | Gu | ||
Indivedual flow velocitys | kg/h | 16.5 | 0 | 8.1 | 0 | |
Water | kg/h | 9.2 | 8.1 | |||
Water | % | 56 | 100 | |||
MAS | kg/h | 5.3 | ||||
MAS | % | 32 | ||||
Sodium chloride | kg/h | 1.9 | ||||
| % | 12 | ||||
The stream numbering | 1 | 3 |
Table 2b: the materials flow 4 and 10 of calculating
Unit | Flow to the stream of flotation | Circular flow | ||||
Overall flow rate | kg/h | 64.5 | 55.7 | |||
Phase | Liquid | Gu | Liquid | Gu | ||
Indivedual flow velocitys | kg/h | 57.9 | 6.6 | 55.7 | 0 | |
Water | kg/h | 38.9 | 36.8 | |||
Water | % | 67 | 66 | |||
MAS | kg/h | 8.4 | 5 | 8.4 | ||
| % | 14 | 76 | 15 | ||
Sodium chloride | kg/h | 10.6 | 1.6 | 10.6 | ||
| % | 18 | 24 | 19 | ||
The stream numbering | 4 | 10 |
Table 2c: the materials flow 8 and 13 of calculating
Unit | MAS stream from flotation to washing | Washings (MAS washing) | |||
Overall flow rate | kg/h | 6.7 | 5 | ||
Phase | Liquid | Gu | Liquid | Gu | |
Indivedual flow velocitys | kg/h | 1.7 | 5 | 5 | 0 |
Water | kg/h | 1.1 | 5 | ||
Water | % | 64.7 | 100 | ||
MAS | kg/h | 0.3 | 5 | ||
MAS | % | 17.6 | 100 | ||
Sodium chloride | kg/h | 0.3 | |||
Sodium chloride | % | 17.6 | |||
The stream numbering | 8 | 13 |
Table 2d: the materials flow 18 and 14 of calculating
Unit | MAS product stream | Mother liquor from the MAS washing | ||||
Overall flow rate | kg/h | 6.7 | 5 | |||
Phase | Liquid | Gu | Liquid | Gu | ||
Indivedual flow velocitys | kg/h | 1.7 | 5 | 5 | 0 | |
Water | kg/h | 1.6 | 4.5 | |||
Water | % | 97 | 90 | |||
MAS | kg/h | 0 | 5 | 0.2 | ||
| % | 2 | 100 | 4 | ||
Sodium chloride | kg/h | 0 | 0.3 | |||
| % | 2 | 6 | |||
The stream numbering | 18 | 14 |
Table 2e: the materials flow 9 and 17 of calculating
Unit | " sodium chloride stream " from flotation to washing | Washings (NaCl washing) | ||||
Overall flow rate | kg/h | 2.1 | 1.6 | |||
Phase | Liquid | Gu | Liquid | Gu | ||
Indivedual flow velocitys | kg/h | 0.5 | 1.6 | 1.6 | 0 | |
Water | kg/h | 0.4 | 1.6 | |||
Water | % | 66 | 100 | |||
MAS | kg/h | 0.1 | ||||
| % | 15 | ||||
Sodium chloride | kg/h | 0.1 | 1.6 | |||
| % | 19 | 100 | |||
The stream numbering | 9 | 17 |
Table 2f: the materials flow 15 and 19 of calculating
NaCl product stream | From the NaCl washing, before concentrating | |||||
Overall flow rate | kg/h | 2.1 | 1.6 | |||
Phase | Liquid | Gu | Liquid | Gu | ||
Indivedual flow velocitys | kg/h | 0.5 | 1.6 | 1.6 | 0 | |
Water | kg/h | 0.5 | 1.4 | |||
Water | % | 97 | 90 | |||
MAS | kg/h | 0 | 0.1 | |||
| % | 2 | 5 | |||
Sodium chloride | kg/h | 0 | 1.6 | 0.1 | ||
| % | 2 | 100 | 6 | ||
The stream numbering | 15 | 19 |
Table 2g: the materials flow 11,6 and 7 of calculating
Discharge currents | The divided gas flow air | Emergent gas | ||||||
Overall flow rate | kg/h | 1.6 | kg/h | 0.1 | 0.1015 | |||
Phase | Liquid | Gu | Gas | Gas | ||||
Indivedual flow velocitys | kg/h | 1.6 | kg/h | 0.1000 | 0.1015 | |||
Water | kg/h | 1.0 | Oxygen | kg/h | 0.0210 | 0.0210 | ||
Water | % | 66 | Oxygen | % | 21.0 | 20.7 | ||
MAS | kg/h | 0.2 | Nitrogen | kg/h | 0.0780 | 0.078 | ||
| % | 15 | Nitrogen | % | 78.0 | 76.8 | ||
Sodium chloride | kg/h | 0.3 | Water | kg/h | 0.0000 | 0.0015 | ||
| % | 19 | Water | % | 0.0 | 1.5 | ||
Air | kg/h | Residue | kg/h | 0.0010 | 0.0010 | |||
Air | % | Residue | % | 1.0 | 1.0 | |||
The stream numbering | 11 | 6 | 7 |
Claims (25)
1. separates the method for the solid phases of described two kinds of different compositions the solution of a solid phase of forming from the difference that contains at least a solvent and two kinds of dissolvings, it is characterized in that comprising:
Crystallisation step a) wherein obtains the suspension of crystal in described solvent of described at least two kinds of solid phases,
Flotation step b), it carries out under the situation that the divided gas flow existence of flowing through described suspension is from bottom to top arranged, thereby the solid phase that wherein said solid phase is separated to make at least a conduct in the described solid phase contain gas accumulates in the top of suspension, and another kind of at least solid phase accumulate in suspension the bottom and
At least one separating step c), the wherein said solid phase that contains gas by from suspension top and/or described solid phase separated respectively from the suspension bottom.
2. the method for claim 1 is characterised in that at crystallisation step and carries out crystallisation by cooling or evaporative crystallization in a).
3. the method for claim 1, be characterised in that crystallisation step a) in conjunction with carrying out crystallisation by cooling and evaporative crystallization.
4. at least one method among the claim 1-3 is characterised in that crystallisation step is to carry out a) under-40 ℃-300 ℃ temperature.
5. the method for claim 4 is characterised in that described crystallisation step is to carry out a) under 10 ℃-100 ℃ temperature.
6. at least one method among the claim 1-5 is characterised in that crystallisation step a) is undertaken by crystallisation by cooling, evaporative crystallization or vacuum crystallization so that should be at flotation step b) in show as that part of crystal of the solid phase that contains gas median particle diameter be 0.01mm-25mm.
7. at least one method among the claim 1-6 is characterised in that at flotation step b) in use the suspension of solids content as 1-40 quality %.
8. the method for claim 7 is characterised in that at flotation step b) in use the suspension of solids content as 5-15 quality %.
9. claim 7 or 8 method are characterised in that carrying out crystallisation step is 1-40 quality % to obtain solids content a), the suspension of preferred 5-10 quality %.
10. claim 7 or 8 method are characterised in that surpassing the solvent that adds q.s in the suspension of desired value to solids content is 1-40 quality % to obtain solids content, the suspension of preferred 5-15 quality %.
11. at least one method among the claim 1-10 is characterised in that flotation step b) under-40-300 ℃ temperature, carry out.
12. the method for claim 11 is characterised in that flotation step b) under 10-100 ℃ temperature, carry out.
13. the method for claim 12 is characterised in that flotation step b) with crystallisation step a) temperature or with the corresponding temperature of discharge temperature from crystallisation step suspension a) under carry out.
14. at least one method among the claim 1-13 is characterised in that and implements flotation step b) so that material at flotation step b) in mean residence time be 5 seconds-10 hours.
15. the method for claim 14 is characterised in that the mean residence time of material in flotation vessel is 600 seconds-1 hour
16. at least one method among the claim 1-15 is characterised in that at flotation step b) in introduce the divided gas flow of suspension the average bubble size be 0.1 μ m-10mm.
17. the method for claim 16 is characterised in that at flotation step b) in introduce the divided gas flow of suspension the average bubble size be 10 μ m-1mm.
18. at least one method among the claim 1-17 is characterised in that divided gas flow is at flotation step b) in so that the volume ratio (Nl/l) of the divided gas flow of input and the suspension of input flotation vessel is the input of the amount of 0.01-100Nl/l.
19. the method for claim 18 is characterised in that divided gas flow is at flotation step b) in so that the volume ratio (Nl/l) of the divided gas flow of input and the suspension of input flotation vessel is the input of the amount of 0.1-2Nl/l.
20. at least one method among the claim 1-19, be characterised in that crystallisation step a) and flotation step b) carry out respectively in the space and/or on the time.
21. at least one method among the claim 1-19, be characterised in that crystallisation step a) and flotation step b) in same container, carry out.
22. at least one method among the claim 1-21 is characterised in that flotation step b) and separating step c) and randomly crystallisation step a) in a device, carry out.
23. at least one method among the claim 1-21 is characterised in that SMAS and sodium chloride are used as at least two kinds of solid phases.
24. at least one method among the claim 1-22 is characterised in that water is used as solvent.
25. at least one method among the claim 1-22 is characterised in that the solid mixture that will be made up of at least two kinds of solid phases is dissolved in the solvent to prepare a) middle solutions employed of crystallisation step.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102006060117.3 | 2006-12-20 | ||
DE102006060117A DE102006060117A1 (en) | 2006-12-20 | 2006-12-20 | Separation of two different solid phases from a solution uses crystallizing and flotation with a gas flow |
Publications (1)
Publication Number | Publication Date |
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CN101204680A true CN101204680A (en) | 2008-06-25 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNA200710160303XA Pending CN101204680A (en) | 2006-12-20 | 2007-12-19 | Method for separating solid |
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CN (1) | CN101204680A (en) |
DE (1) | DE102006060117A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104475425A (en) * | 2014-11-24 | 2015-04-01 | 湖南华曙高科技有限责任公司 | Recycling method for selective laser sintering indirectly-molded residual and waste materials |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5690484B2 (en) * | 2009-12-11 | 2015-03-25 | 日揮株式会社 | Crystallization method and crystallizer |
EP3955264A1 (en) * | 2020-08-13 | 2022-02-16 | EnBW Energie Baden-Württemberg AG | System and method for separating boric acid crystals from a boric acid-water mixture |
-
2006
- 2006-12-20 DE DE102006060117A patent/DE102006060117A1/en not_active Withdrawn
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2007
- 2007-12-19 CN CNA200710160303XA patent/CN101204680A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104475425A (en) * | 2014-11-24 | 2015-04-01 | 湖南华曙高科技有限责任公司 | Recycling method for selective laser sintering indirectly-molded residual and waste materials |
Also Published As
Publication number | Publication date |
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DE102006060117A1 (en) | 2008-06-26 |
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Open date: 20080625 |