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Publication numberUS2868677 A
Publication typeGrant
Publication dateJan 13, 1959
Filing dateJul 30, 1956
Priority dateJul 30, 1956
Publication numberUS 2868677 A, US 2868677A, US-A-2868677, US2868677 A, US2868677A
InventorsErnst W Kopke
Original AssigneeUltra Sucro Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Clarification and demineralization process for b-molasses and similar materials containing concentrated impurities
US 2868677 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Jan. 13, 1959 E. w. KOPKE 2,863,677


o o 0 Q o o o o 99 O o o h': Vac. Pun V004 P0" 'C'.' Vac. Pan

A-Mo/asses Contaminated "5 'Mo/asses IN V EN TOR.

Ems) I V. Kop/re-v BY his affomeys MAJ.

Jan. 13, 1959 E. w. KOPKE 2,868,677



R ECYCLE DEMINERALIZED EXCLUDED LIQUOR LIQUOR LIQUOR INVENTOR. Ernst W Kop/re BY his 'affomeys 1i ted States Patent 2,868,677 Patented- Jan. 13-, 1 959 Ernst W. Kopke, New York, N. Y.,. assignorto Ultra- Sucro Company, New York; N. Y., a partnership Application July 30, 1956, Serial No. 600,778 11 Claims. (Cl.127-46) This invention relates to processes of manufacturing sugar and more especially to the. clarification and demineralization of sugar solutions so. as to. overcome restrictions existing in sugarfactories, especially but not exclusively in raw sugar factories. They also exist in beet sugar manufactureto extents and degrees whichdiffer due to the diiference in the amounts and kinds of impurities in beets as compared with cane.

The restrictions lower considerably the yield of'sugar from the raw material.

Also, these restrictions have resulted in molasses which contain bacterial and other impurities that restrict the use ofmolasses.

Moreover, the impurities themselves'while undesirable in the sugar and molasses have longbeen known to be useful; but their usefulness has been limited because of the inability to effectively separate them from. the molasses.

Reverting to the matter of increasing sugar yields, various mineral salts which are present always in considerable amounts in sugar liquors (generally referred to as ash forming material) exert a restrictive effect. on finalstage crystallization of sugar from the solutiom That gains in sugar yields are attainable through the removal of mineral salts has been abundantly provedinoperations of various sorts in both beet and cane sugar production. However, demineralization, as usually practiced, has been costly, chiefly because of the need for regenerants such as caustic soda and acid when the. removal of mineral salts is accomplished by means of ion exchange. Therefore, commercial adaptations have not proceeded as rapidly as the'attainable, and proved, gains in'sugar yield would appear to warrant. The'mode of incorporating demineralization according, to my present process involves distinct economies as well as functionaladvantages, particularly in: the final stages of crystalliza-- tion, and results in substantial economic benefits.

One objectiveof my process" is toipjrovide for clarificationand demineralization ofsugar' bearing solutionsatuav processing stage where the maximum gain in increased yield ofsugar, purer molasses and separation of the impurities from the molasses is accomplished at minimunr cost in equipment and in operation.

Another objective is to incorporatca clarification and demineralization process in raw cane sugar factories in the molasses and sugar with separate collection thereof, and increasing the capacity of existing final stage equipment such as vacuum pans, crystallizers and centrifugals.

Other objects and advantages will become apparent as the invention isdescribed in connection with the drawings.

In the drawings:

Fig. 1 is a flow diagram of a raw' cane sugar manufacturing process in which is incorporated a clarification and a demineralization stage according to the present process.

Fig. 2 is a detailed flow diagram of the clarification stage.

Fig. 3 is a fragmentary sectional view of a centrifugal separator bowl.

Fig. 4 is a detailed flow diagram of the demineralization stage.

Accomplishment ofthe above-mentioned objectives by: my invention involves, primarily:

(1) Clarification and demineralization of B mo lasses or any other molasses or syrup just before itisto be subjected to-final vacuum pan boiling and crystalliza-- tion.

-(2) Employment of anion exclusion facility which utilizes a single resin. bed to remove mineral salts and other non-sugars while retaining within the resin bed, the sucrose solute which is thenremoved bywater rinse, avoiding therebythe use of costly regenerants.

(3 Employment of a step or series of steps which in-- sures and' safeguards the production of raw sugar from cane in areas where adherence to the. raw sugar standard-- of production is commercially desirable.

Thousands ofcycles of successful and-- economical de mineralization of clarified molasses inaccordance with-my invention have proved" the dependability, high efiicieney and economy ofthe principle of removing. the mineral salts by ion exclusion. Major economies. in equipment and operation, whichare unattainablewhen using ,ion-ex-- change, are provided; and purer.molassesandsugar,aswell as a separation of the impurities as a separate byproduct are attained, by use of a special resin which retains by adsorption within the resin the-low ion sucrose solute while the highly ionized? solutes of themineral salts and 'other'non sugar's are excluded.

Atypical cycle ofmy ionexclusion stage embodies;

(i)" The passing of a batch'ofmolasses throughan ion exclusion resin bed which is adsorbent of the sucrose solute soas to retain within the special porous resin struc 'ture of the bed, the sucrose solute while the high ion salts in solution, and other non-sugar materials, pass. through; I

(ii) Upon" and follo'win'gthemolasses, introducing water which removes the sucrose solute from the. adsorbent' bed'asthewater passes through the bed;

.(iii) Recycling theinitial-portion of the efiiuent which issues just after the water and sucrose solute begin to show in the efilue'nt, in order to extract the impurities which'inthat portionare' higher proportionately than-in thesuccee'ding'portion;

(ii/)1 Fractionating theefiluent to collectthe-high purity portionthe're'of' separately from the mineral salt soluteand non-sugar containing liquor, so'that .thehigh purity portion can subsequently be separately boiled and crystallized.

Although the procedurein dilferent sugar factories dif- 6r to continuous clarifiers 16 from which the clarified juice is drawn off. The sludge is delivered to a vacuum filter 18 in which the remaining juice is mostly drawn off and the mud cake sweetened off by application of a spray of water which lowers the sucrose content.

The clarified juice is generally of l415 Brix. it is delivered to a supply tank 20 (with the sweetened water from the vacuum filter, if desired) and then to a multiple elfect evaporator 22 in which it is subjected to a series of stages of boiling, each being at an increasing stage of vacuum. The finally concentrated liquor (termed syrup) at about 60 to 70 Brix is held in supply tank 23. Subsequent concentration of this syrup involves the development of crystals in single effect cells 24 (vacuum pans) in which exact control can be maintained under vacuum of 26.5 to 27.5 inches of mercury.

The mixture of crystals and mother liquor from the vacuum pan 24 is optionally delivered to crystallizers 26 for further crystallization. In centrifugals 28 the crystals are separated from the mother liquor of the resulting massecuite. The expelled liquid or A molasses is then delivered to the B vacuum pan 30 for further concentration, alone or with syrup from the supply tanks 23. The resulting mixture is treated in the crystallizers 26; and the sugar crystals are separated from the B molasses in the centrifugal 28.

Clarification of the juiceafter heating and liming-is not, as a rule, highly efficient in the removal of insoluble material. Certain impurities that are insoluble at this stage, including colloids and other substance of specific gravity closely approximating that of the surrounding liquid, pass through into the clarified liquid. As the juice becomes concentrated in its boiling in the evaporator into syrup, the unremoved insoluble impurities become more concentrated and they exert an effect adverse to crystal development and curing of the sugars. This add especially to the difficulty of final-stage crystallization and limits the practical end point of sugar recovery.

Moreover, during the process of concentration by boiling in both the evaporator and in the vacuum pans (the latter reducing the water content of the massecuite to approximately five percent) there is usually a considerable additional precipitation of non-sugars and various forms of impurities.

As a result of these two sorts of impurities (precipitates and insolubles) in the latter stage liquors, i. e., in the A" and B molasses (and because of the concentration of these impurities, especially in the B molasses) the usual procedure of boiling the B molasses in the vacuum pan involves excessive contamination and a relatively high degree of viscosity. Such contamination and viscosity retards the boiling process and it also actually terminates crystal formation in the pan sooner than that which would be attainable in the absence of these impurities.

The steps preceding boiling the molasses in both the A and B stages are not so seriously affected by the insoluble and precipitated impurities because, first, they are not in such concentrated form and, second, the purities of the liquors and massecuites are much higher at this stage and can be handled and adequately cured in the centrifugal without trouble. Therefore, there is no special benefit, in the production of raw sugar, in removing either the insoluble impurities or the soluble mineral salts prior to the B molasses.

Besides the insoluble and precipitated impurities above referred to, a third kind of impurity, namely, mineral salts which are still in solution, exert a particularly serious retardment on the final stage of crystallization.

For the purpose of removing the soluble mineral salts and certain other non-sugars, I employ an ion exclusion process after having clarified the molasses, as will now be described.

Referring to Fig. 2, the molasses is introduced into a mixing tank 40 through pipe line 41 by operating valve 42. In this tank, the molasses is diluted to approximate carry-over of insoluble material.

1y 40-50 Brix. Either milk of lime (CaO) or suitably fired magnesium oxide (MgO) is introduced through pipe line 43 by operating valve 44 so as to raise the pH to between 8.5-9.5 approximately. The most advantageous amount of alkalinity varies with the quality and characteristics of the liquor and the impurities to be dealt with. Phosphoric acid is then added through pipe 45 by operating valve 46 to the extent of establishing a pH of 6.76.9. The temperature is raised by heating with steam coils 4-7 while the material is vigorously stirred by stirrers 48. The prepared liquor is dropped into receiving tank Where it is further stirred and where a flocculating aid is added, such as an organic polyelectrolyte, for example, having the characteristics of adding to precipitated fiocs and entraining the more finely suspended materials such as colloids. The temperature is maintained or adjusted to F. in the tank which serves as supply tank for the clarifier or, in the embodiment illustrated, centrifugal separators.

In clarifying molasses solutions, excellent results are obtained by the use of a solid bowl centrifugal separator 50 having a cylindrical bowl with an imperforate side wall 51 and annular inturned flange 52, 53 at its top and bottom edges. At the bottom of the bowl there is an annular hood 54 having its outer edge inclined downwardly and close to the inner wall of the bowl. This hood is secured to the base of the bowl by a perforated annular plate 55. The hood and perforated plate serve to uniformly distribute the incoming liquor and accelerate it to the approximate peripheral speed directly adjacent to the inner surface of the bowl. In order to insure maintaining of high centrifugal force throughout the flow, an annular baflle plate 56 is secured close to the upper head. This plate 56 extends so that its outer edge is located at approximately half of the depth of the material under treatment while the inner edge extends an inch nearer the axis than the surface of the liquor under treatment. The bowl, hood 54, plate 55 and baffle 56 are all rigidly aflixed to an axle or drive shaft 57 and are bal anced to rotate without vibration.

The solid separator bowl is rotated to produce a force about 2,000 times gravity or more and is preferably driven by an electric motor 58 through a fluid coupling 58c; but other driving means may be employed and other methods of clutching or coupling may be used.

The solid separator bowl is operated at full speed and flow rate until the liquor outflow shows evidence of At that time inflow of liquor is shut off and water is introduced to remove the remaining liquor. As the machine is stopped the sludge is removed, preferably by a discharge plow similar to those used on sugar curing centrifugals. The clarified liquor discharges over the top flange 52 and passes down into the gutter 50g from whence it flows into a receiving tank (not shown) while the sludge is dropped into a conveyor 59.

Since the sludges delivered into the scroll conveyor 59 contain a considerable amount of sucrose, they are delivered to the vacuum filter 18 (Fig. 1) where, in carrying over the surface of the drum the sludge is sweetened otf thorugh the application of a spray, or several sprays, which wash out the sucrose bearing liquor.

The clarified molasses is delivered to a supply tank 60 wherein its temperature is adjusted to about 180 F. by a thermostat 62 controlling the flow of steam in a line 64 connected with the tank.

The clarified molasses from the supply tank 60 of approximately 40 Brix and at a temperature of approximately 180 F. or higher is delivered through a pipe 66, upon opening a control valve 68 therein, to a column 70 containing a resin bed 72.

During passage of the molasses through the resin bed, the low polar sucrose solute is adsorbed and/or retained by the resin while the more highly ionized weight in solution-is, 2.2,:eq uivalents, fi zrliter.

solutes, i. e., of. the. relatively. high pol'ar, position such as mineral salts. and: certain. non-sugars,- are, excluded by the resins and pass on. with the, efiiuent?through. the pipe.74.upon openingofvalves76 therein When it: appears that the. adsorbingcapacitywf the bearing the low. ion sucrose liquor. This relatively nominal amount of intermediate. mixed. fractions; is recycled so. as. to; avoid sucrose. loss,, by opening; valvew82 in pipe line 84* returning; toytanlc 60.. When: the efiiuent appears clear enough the recycling valve782; is. closediand the valve. 86 in pipe 8.8 is; opened-. to; separately collect the demineralized liquor.

While severali types of: resin can' be: employcch. satisfactory results; have been obtained: in;- thezuse; of: a" high porosity, sulfonated polystyrene resim. ,crosselinked. at aboutd; and of 56-100. mesh. T-heslowr cross-linkage (indicating highporosity and adsorbing; capacity: of, resin matrix) is structurally selective;bywcontrol.of the amount ofdivinylbenzene"addedrpriorrto; sulfonation; 1

One example; of a resin. that; has beent. found suitable, but without limitation of:the1inventiom thereto; isi sulfonated styrene divinylbenzene copolymerizate, which has 1.8 sulfonic groups pen benzene ring: The equivalent In conformity, with the requirementsof this inventiomand the adsorption of. low polar sucrose solute, it, is essential .that resin porosity is provided adequate to accommodate. the molecular structure of sucrose. Otherresins having said properties may be us'edi The amount ofrmolassestreated in each cycle is gauged according. to, the. adsorbing. capacity: of the resin.- bed. With constant flow rate and predetermined amountxof water rinse for removalof the. sucrose. solute: fromrthe resin bed, the cycles are accurately; timedand areaautotmatically controlled. Retaining resins stabilit -;-.-and functional effectiveness is accomplished by periodic-rinse of the resin with a salt (NaCl) solution from asupply tank 90 through pipe line 92 opening a valve 94 therein, while valves 68 and 79 are closed. The salt rinse is run-off through a separate outlet pipe 96. Since no ion exchange takes place in the sense that applies to ion exchange processes, no regenerants are required.-

Upon completion of the demineralization treatment, the density of the finally treated liquor is somewhat low for direct introduction into a vacuum pan for the final boiling and development of crystals. Therefore, arsmall multiple effect evaporator 97 is provided into which the clarified and demineralized liquor is delivered from the exclusion unit. This concentrates the liquor to a suitable density of about 80 Brix.

The clarified, demineralized, reconcentrated liquor is delivered to the vacuum pan supply tanks'98 which supply the C vacuum pan 99. Development of the crystals proceedsunder these conditions rapidly and to a greater extent than is possible when the insoluble impurities and mineral salts are present as in usual practice.

Among the principal advantages of the ion exclusion method of removing mineral salts and certain other nonsugars, from sugar solutions, as compared to ion exchange are:

(a) More rapid, and greater frequency of, cycles and, therefore. less equipment and lower cost. 1

(b) Simpler and easier control.

(1c), Elimination. of backwash: prior to regeneration, as required for ion exchange.

(d) Greatly reduced dilution and, therefore, less evaporation required.

(a) Avoidance of' low pH: phases of cycles:and:associated susceptibilitytosucrose inversion;

(f) Elimination of requirement for cooling. Preferred temperature during-the. ion exclusioncycle. is at. least 1805-1851" FL -g) No regenerants; required.

From the foregoing it will be understood that. because the sucrose solute is adsorbed while: the impurities are excluded? by" the resin in: the: demineralization stage, I have'found it IIIOESt; practical and advantageous'to' apply the demineralization stage. at that place or' to those liquids in the manufacture of sugar wherethe percentage of'impuritiesperunitof volume is relatively high and the percentageof sugar content is relatively low. In cane sugar practice. that pointiswreached-with the B molasses. Similarly, aflination liquorsa containa relatively high percentage. of impurities. butzhave: higher sugar content than B? molasses. An. equivalent point is reached in the final molasses inbeetsugar practice, despite-the fact that final molasses from beetscommonly has higher purity, i. e., contains more sugar than cane B molasses. The. greater sugar content; in" final molassesfrom beets is. due largely to the diificulty in handling impurities from beets. which are different innature fromcane impurities.

To. all: of; these, and'in fact toany-material, solution or liquor where' substantially equivalent limits andcon- ,ditions. of purity; and impurities exist, my invention is applicable: to greatadvantage.

To further indicate the: value and importance of treating B'm0lasses,.a contrast with known ion-exchange processes may be drawn. In ion exchangers, the impurities arebroken downand drawn into the type of: resintheres employed: The sugar? remains and passes on. Hence; a: liquor containing a. low percentage of" impurities: can more" readily. be treated, although other difficulties: may arise: due. to theamuclr larger volume which must be: handled and less' favorable" temperature conditions: and: pH values, especially in treating juices;

Although: my process" is especia'lly'aimed to. increase the yield-of1raw sugarifrom cane because thatis the basis. forsmoreyprofitablei operations by reduction of unit cost, other; important: results flow from the invention; The: resulting-molasses isspurerand canbe used in the food industry" where; molasses heretofore has notbeen satisfactory because of the still-retained impurities. Also, certain bacterial impurities are no longer present, providing a more sterile molasses and enabling the molasses to be stored longer Without spoiling. Further reduction in bacterial impurities can be accomplished by treating the clarified and demineralized molasses with ultra-violet light and using sterile Water.

In addition, the impurities separated out in the excluded" liquor are useful with food for cattle and poultry Where heretofore the whole molasses at higher cost had to be used or further costly processing was necessary to extract the desired substances, vitamins and minerals.

Other indirect benefits of this process are evidenced by the completely clean final crystallizer sugars, sometimes designated C or D sugars. Ordinarily these sugars are highly contaminated and are far too low in grade and purity to be sold directly commercially. The

Another result is that crystallization, especially in the final stage, proceeds much more rapidly and further than is otherwise the case.

Again the final molasses instead of being the usual highly contaminated blackstrap is, on the contrary, a-

clean food-grade product, high in vitamins and suitable as a food component.

Many modifications within the scope of the invention will occur to those skilled in the art. Therefore, the invention is not limited to the precise form of the embodiment disclosed.

What is claimed is:

1. The process of clarifying and demineralizing B molasses, afiination liquors and like sugar bearing solutions which contain a similarly comparatively high percentage of impurities from previous crystallization, comprising removing precipitated and insoluble impurities to clarify the solution, subsequently passing the clarified solution through a bed of low cross-linked high porosity highly ionized resin having the property of adsorbing sugar and by ion-exclusion excluding impurities, collecting the excluded-impurity-containing eifiuent, rinsing out the sugar by passing water through said resin bed, and collecting the sugar-bearing rinse separately for subsequent extraction of sugar, and maintaining the temperature during the ion-exclusion stage and rising up to at least 180 F.

2. The process as claimed in claim 1 in which the solution is diluted to about 40 to 50 Brix approximately, prior to clarification.

3. The process as claimed in claim 2 in which the clarification comprises adding basic and acidic reagents giving a resultant clarified solution having a pH of about 6.76.9 approximately, adding a fiocculating medium and removing the precipitated and insoluble materials.

4. The process as claimed in claim 3 in which the bed comprises a high porosity, highly ionized, sulfonated styrene divinylbenzene copolymerizate resin.

5. The process as claimed in claim 1 in which the clarification comprises adding basic and acidic reagents giving a resultant clarified solution having a pH of about 6.76.9 approximately, adding a flo-cculating medium and removing the precipitated and insoluble materials.

. 6. The process as claimed in claim 5 including collecting an initial small fraction of the sugar-bearing rinse, and recycling said small fraction through said resin bed, and collecting the remainder of the sugar-bearing rinse separately for subsequent extraction of sugar.

7. The process as'claimed in claim 6 in which the bed comprises a"'high porosity, highly ionized, sulfonated styrene divinylbenzene copolymerizate resin.

8. The process as'claimedin claim 1 in which the clarification comprises adding basic and acidic reagents giving a resultant clarified solution having a pH of about 6.7-6.9 approximately, adding a flocculating medium and removingthe precipitated and insoluble materials, said resin bed containing a high porosity, highly ionized, sulfonated styrene divinylbenzene copolymerizate resin.

9. The process of producing purified molasses from impure materials such as B molasses, affination liquors and like sugar bearing solutions which contain a similarly comparatively high percentage of impurities from previous crystallization, comprising removing precipitated and insoluble impurities to clarify said impure material, passing the said clarified impure material through a bed of low cross-linked, high porosity, highly ionized resin having the property of adsorbing sugar and by ion-exclusion excluding impurities, collecting the excluded-impuritycontaining efiluent, rinsing out the sugar from the resin by passing water through said resin bed and collecting the sugar bearing rinse separately, and maintaining the temperature during the ion exclusion stage and rinsing up to at least F.

10. The process as claimed in claim 9 in which the bed comprises a high porosity, highly ionized, sulfonated styrene divinylbenzene copolymerizate resin.

11. The process as claimed in claim 9 including subjecting the purified molasses to ultra-violet light to sterilize said purified molasses.

References Cited in the file of this patent UNITED STATES PATENTS 1,956,260 Wadsworth et al Apr. 24, 1934 2,388,194 Vallez Oct. 30, 1945 2,391,649 Shat'or Dec. 25, 1945 2,684,331 Bauman July 20, 1954 OTHER REFERENCES

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2971868 *May 2, 1958Feb 14, 1961Rohm & HaasIon exchange process
US3044904 *Feb 15, 1960Jul 17, 1962Central Aguirre Sugar CompanySeparation of dextrose and levulose
US3044905 *Feb 15, 1960Jul 17, 1962Dow Chemical CoSeparation of fructose from glucose using cation exchange resin salts
US3044906 *Feb 15, 1960Jul 17, 1962Dow Chemical CoSeparation of fructose from glucose using a cation exchange resin salt
US3481783 *Aug 24, 1967Dec 2, 1969Braunschweigische Masch BauMolasses purification
US3884714 *Jul 9, 1973May 20, 1975Pfeiffer & LangenProcess for making sugar from molasses by ion removal
US3975205 *Nov 27, 1974Aug 17, 1976Suddeutsche Zucker-AktiengesellschaftProcess for working up molasses
US4046590 *Sep 8, 1976Sep 6, 1977California And Hawaiian Sugar CompanyProcess for the production of a colorless sugar syrup from cane molasses
US4101338 *Apr 27, 1976Jul 18, 1978Sucrest CorporationProcess for recovering useful products from carbohydrate-containing materials
US4359430 *Feb 24, 1981Nov 16, 1982Suomen Sokeri OsakeyhtioBetaine recovery process
US5795398 *Jun 7, 1995Aug 18, 1998Cultor Ltd.Fractionation method of sucrose-containing solutions
US6093326 *Sep 9, 1997Jul 25, 2000Danisco Finland OyMethod for the fractionation of molasses
US6187204Aug 13, 1999Feb 13, 2001Danisco Finland OyMethod for the fractionation of molasses
US6214125 *Jun 1, 1998Apr 10, 2001Danisco Finland OyFractionation method for sucrose-containing solutions
US6224776Feb 10, 1999May 1, 2001Cultor CorporationMethod for fractionating a solution
US6482268 *Dec 22, 2000Nov 19, 2002Danisco Finland OyFractionation method for sucrose-containing solutions
US6572775Feb 27, 2001Jun 3, 2003Cultor CorporationMethod for fractionating a solution
US6649066Dec 13, 2000Nov 18, 2003Danisco Finland OyMethod for the fractionation of molasses
US6663780Jan 31, 2002Dec 16, 2003Danisco Finland OyMethod for the fractionation of molasses
US6685781Oct 11, 2002Feb 3, 2004Danisco Sweeteners OyFractionation method for sucrose-containing solutions
US6875349Mar 11, 2003Apr 5, 2005Cultor CorporationMethod for fractionating a solution
US6896811May 9, 2002May 24, 2005Danisco Sweeteners OyChromatographic separation method
US7229558Jan 11, 2005Jun 12, 2007Danisco Sweeteners OyChromatographic separation method
US20030006191 *May 9, 2002Jan 9, 2003Danisco Sweeteners OyChromatographic separation method
US20030173299 *Mar 11, 2003Sep 18, 2003Heikki HeikkilaMethod for fractionating a solution
U.S. Classification127/46.3
International ClassificationC13B35/06
Cooperative ClassificationC13B35/06
European ClassificationC13B35/06