EP0613953B1 - Fruktose und Dextrose enthaltender flüssiger Süssstoff - Google Patents

Fruktose und Dextrose enthaltender flüssiger Süssstoff Download PDF

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Publication number
EP0613953B1
EP0613953B1 EP93301559A EP93301559A EP0613953B1 EP 0613953 B1 EP0613953 B1 EP 0613953B1 EP 93301559 A EP93301559 A EP 93301559A EP 93301559 A EP93301559 A EP 93301559A EP 0613953 B1 EP0613953 B1 EP 0613953B1
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EP
European Patent Office
Prior art keywords
fructose
solution
dextrose
stream
crystallization
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.)
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EP93301559A
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English (en)
French (fr)
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EP0613953A1 (de
Inventor
Francis M. Mallee
Lawrence R. Schwab
Larry W. Peckous
Donald W Lillard
Robert V. Schanefelt
Daniel K Tang
Gary A Day
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Primary Products Ingredients Americas LLC
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Tate and Lyle Ingredients Americas LLC
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Priority claimed from US07/747,764 external-priority patent/US5350456A/en
Priority claimed from US07/747,773 external-priority patent/US5230742A/en
Priority to US07/747,773 priority Critical patent/US5230742A/en
Priority to US07/747,775 priority patent/US5234503A/en
Priority to US07/747,764 priority patent/US5350456A/en
Priority claimed from US07/747,775 external-priority patent/US5234503A/en
Priority to AT93301559T priority patent/ATE176503T1/de
Priority to DE69321456T priority patent/DE69321456T2/de
Priority to ES93301559T priority patent/ES2126627T3/es
Priority to DE69323414T priority patent/DE69323414T2/de
Priority to AT93301560T priority patent/ATE171982T1/de
Priority to ES93301560T priority patent/ES2124283T3/es
Application filed by Tate and Lyle Ingredients Americas LLC filed Critical Tate and Lyle Ingredients Americas LLC
Priority to EP93301560A priority patent/EP0613954B1/de
Priority to EP93301559A priority patent/EP0613953B1/de
Priority to AU33991/93A priority patent/AU662391B2/en
Priority to CA002091706A priority patent/CA2091706A1/en
Priority to ZA931871A priority patent/ZA931871B/xx
Priority to JP07412893A priority patent/JP3399576B2/ja
Priority to HU9301156A priority patent/HUT67470A/hu
Priority to BR9301098A priority patent/BR9301098A/pt
Publication of EP0613953A1 publication Critical patent/EP0613953A1/de
Publication of EP0613953B1 publication Critical patent/EP0613953B1/de
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Priority to GR990400653T priority patent/GR3029569T3/el
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/10—Crystallisation
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K11/00—Fructose
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar

Definitions

  • This invention relates to a process for the preparation of a fructose and dextrose containing liquid sweetener and of crystalline fructose. More particularly, it relates to a process wherein the fructose is obtained by the isomerization of dextrose and a process for the concurrent production of anhydrous crystalline fructose and a syrup consisting essentially of fructose and dextrose.
  • the process involves crystallizing fructose by cooling a solution of fructose such that differing levels of supersaturation are produced during different periods of crystal growth. Moreover the process may be employed to produce a purified and concentrated fructose syrup.
  • Fructose is a monosaccharide highly valued as a nutritive sweetener.
  • the vast majority of fructose sold in the USA is derived from corn starch with the principal form of the product being High Fructose Corn Syrup (HFCS).
  • HFCS High Fructose Corn Syrup
  • the commercially available and used syrups contain from 42% to 90% by weight fructose on a dry solids basis (dsb) with the remainder predominately being dextrose.
  • the HFCS commonly used as a sucrose replacement in soft drinks typically comprises 55% fructose, 41% dextrose, and 4% higher saccharides (all percentages dsb).
  • the solids content of such a syrup is usually about 77% by weight.
  • HFCS HFCS
  • the principal source of raw material in the United States is corn starch obtained by the wet milling process. However, starches of comparable purity from other sources can be employed.
  • a starch slurry is gelatinized by cooking at high temperature.
  • the gelatinized starch is then liquefied and dextrinized by thermostable alpha-amylase in a continuous two-stage reaction.
  • the product of this reaction is a soluble dextrin hydrolysate with a dextrose equivalent (DE) of 6-15, suitable for the subsequent saccharification step.
  • DE dextrose equivalent
  • the pH and temperature of the 10-15 DE hydrolysate is adjusted for the saccharification step.
  • the hydrolysate is further hydrolyzed to dextrose by the enzymatic action of glucoamylase.
  • saccharification can be carried out as a batch reaction, a continuous saccharification is practised in most modern plants.
  • glucoamylase is added to a 10-15 DE hydrolysate following pH and temperature adjustment.
  • the carbohydrate composition of typical high-dextrose saccharification liquor is: 94-96% dextrose, 2-3% maltose; 0.3-0.5% maltotriose; and 1-2% higher saccharides (all percentages dsb).
  • the product will typically be 25 to 37% dry substance.
  • This high-dextrose hydrolysate is then refined to produce dextrose feedstock for the isomerization reaction.
  • Immobilized isomerase enzyme columns are used continuously over a period of several months. During this period very large volumes of dextrose feedstock pass through the columns. Extremely low levels of impurities such as ash, metal ions, and/or protein in the feedstock can accumulate and lead to decreased productivity of the enzyme. For these reasons dextrose feedstock is refined to a color of 0.1 (CRA x 100) and a conductivity of 5-10 micromhos.
  • Carbon-treated, filtered, and deionized, high-dextrose liquor is evaporated to the proper solids level for isomerization.
  • the feedstock is chemically treated by the addition of magnesium ions, which not only activate the immobilized isomerase, but also competitively inhibit the action of any residual calcium ions, which are potent inhibitors of isomerase.
  • the isomerization reaction which converts some of the dextrose to fructose, is commonly carried out on a stream comprising 94-96% (dsb) dextrose and 4-6% (dsb) higher saccharides, at 40-50% dry substance.
  • the stream has a pH of 7.5-8.2 at 25°C and will be subjected to the action of the isomerase enzyme for 1/2 to 4 hours at 55-65°C.
  • the operating pH is usually a compromise between the pH of maximum activity (typically around pH 8) and the pH of maximum stability (typically pH 7.0-7.5). This is complicated by the fact that the dextrose feedstock is not pH stable at temperatures around 60°C. Some decomposition occurs producing acidic by-products which results in a pH drop across the isocolumn during operation.
  • the typical manufacturing process employs secondary refining or polishing of the 42% HFCS product. Some additional color is picked up during the chemical treatment and isomerization when the feedstock is held at a higher pH and temperature for a period of time. The product also contains some additional ash from the chemicals added for isomerization. This color and ash are removed by secondary carbon and ion exchange systems. The refined 42% HFCS is then typically evaporated to 71% solids for shipment.
  • U.S. Patent No. 1,979,781 discloses mixing a raw sugar syrup (i.e., one not mixed with glucose syrup or with invert sugar syrup) at 60° Brix (60% dry solids) with 1 to 2% by weight activated carbon and heating to 134°C for a short period of time.
  • U.S. Patent No. 2,763,580 broadly discloses treatment of sugar liquors (e.g., cane, beet or corn sugars) having solids contents of between 10 and 60%, especially 20 to 56%, by weight at 51.7 to 93.3 ° C (125 to 200°F) with activated carbon.
  • the patent discloses that partial treatment can be carried out at one concentration or condition, after which the treatment can be completed at a higher concentration (obtained by evaporation) or other condition.
  • U.S. Patent No. 3,684,574 discloses carbon-treatment of a syrup containing about 20% (dsb) fructose at a dry solids as low as 20% dry solids and subsequent concentration of the syrup.
  • U.S. Patent No. 4,395,292 discloses feeding a carbon-treated mixture of fructose and dextrose having from 10 to 70% dry solids, preferably 40%, to a fractionating column and concentrating the fructose containing extracts.
  • US-A-4395292 discloses that extracts containing over 90% fructose can be obtained and has one example (Example No. 7) wherein a 40% dry solids feed was fractionated to produce a fraction having 100% (dsb) fructose at 9% dry solids.
  • the HFCS product from the isomerization reaction typically contains 42% fructose, 52% unconverted dextrose, and about 6% oligosaccharides. For reasons previously discussed, this product represents the practical maximum level of fructose attainable by isomerization. In order to obtain products with higher levels of fructose, it is necessary to selectively concentrate the fructose. Many common separation techniques are not applicable for this purpose, since they do not readily discriminate between two isomers of essentially the same molecular size. However, fructose preferentially forms a complex with different cations, such as calcium. This difference has been exploited to develop commercial separation processes.
  • Chromatographic fractionation using organic resins is the basis for the second commercial separation process (see , K. Venkatasubramanian, "Integration of Large Scale Production and Purification of Biomolecules," Enzyme Engineering , 6:37-43, 1982).
  • an aqueous solution of dextrose and fructose e.g., 42% HFCS
  • fructose is retained by the resin to a greater degree than dextrose.
  • Deionized and deoxygenated water is used as the eluent.
  • VEFCS Very Enriched Fructose Corn Syrup
  • the dextrose-rich raffinate stream is recycled to the dextrose feed of the isocolumn system for further conversion to 42% HFCS.
  • a raffinate stream containing dextrose and fructose and having a fructose level higher than that of the feed stream can be recycled through a fractionator to maintain a high solids level and to reduce water usage.
  • a raffinate stream rich in oligosaccharides can be recycled to the saccharification system.
  • Procedures available for achieving these goals include recycling techniques, higher equalization of the resin phase with proper redistribution in a packed column, and the addition of multiple entry and exit points in the column. These approaches can be used to increase the purity and the yield.
  • crystalline fructose may be prepared by adding absolute alcohol to the syrup obtained from the acid hydrolysis of inuline (Bates et al., Natl. Bur. Std. Circ. C440,399, 1942).
  • inuline Bates et al., Natl. Bur. Std. Circ. C440,399, 1942.
  • the preparation of fructose from dextrose is described in U.S. Patent 2,354,664 and U.S. Patent 2,729,587 describes its preparation from sucrose by enzymatic conversion.
  • Fructose forms orthorhombic, bisphenoidal prisms from alcohol which decompose at about 103-105°C.
  • Hemihydrate and dihydrate crystalline forms are also known, but it is preferable to avoid the formation of these species inasmuch as they are substantially more hygroscopic than the anhydrous form and have melting points close to ambient temperature. These properties make these crystalline forms of fructose very difficult to handle.
  • Solvent Crystalline Fructose is prepared by a process wherein an organic solvent, such as denatured ethyl alcohol, is mixed with a high-fructose stream (95% dsb). This stream crystallizes as it is cooled to form pure crystalline fructose. The product is centrifuged to separate it from the mother liquor, desolventized, and dried.
  • an organic solvent such as denatured ethyl alcohol
  • U.S. Patent 4,199,374 describes a process for producing SCF. Fructose is crystallized from a solution of VEFCS in ethanol. The solution is seeded with fine crystals of fructose or glucose. The crystals are harvested by filtration, centrifugation or other suitable means. These crystals are then washed with alcohol and dried under vacuum. The moisture content of the alcohol and syrup must be carefully controlled in this process in order to obtain free-flowing fine crystals of fructose.
  • DFS dried fructose sweetener
  • a high fructose stream derived from fractionation is dried in a rotary dryer, then sized in a classifier containing screens and grinders.
  • U.S. Patent 4,517,021 describes the preparation of such a granular, semi-crystalline, solid fructose which comprises less than about 2% water by weight. The patent discloses that about 60 weight percent of the product is crystalline fructose, and less than 35 weight percent is amorphous fructose.
  • a drum dryer is used, with air having an initial temperature of 50-80°C. A portion of the solid fructose product may be recycled as the crystallization initiator.
  • An aqueous process can also be used to produce crystalline fructose.
  • An aqueous crystalline fructose process typically starts with a high fructose feed stream which is cooled to crystallize the fructose from solution. A number of references describe such a process.
  • anhydrous fructose is obtained from an aqueous solution of fructose (min. 95% ds).
  • the pH of the solution must be between 3.5 and 8.0.
  • the fructose solution is concentrated under vacuum until the water content is between 2 and 5%.
  • the solution is cooled to 60-85°C, seeded with crystalline fructose, and stirred vigorously while the temperature is maintained at 60-85°C.
  • the patentee states that a crystalline mass results which, after slow cooling, can be crumbled or ground and subsequently dried to produce a non-sticking, free-flowing, finely-crystalline powder.
  • the process is said to avoid the formation of the glass phase product which ordinarily results when fructose solutions of this type are concentrated in a vacuum and allowed to cool in the usual manner.
  • fructose is crystallized from an aqueous fructose/glucose solution of 90% ds and containing 90-99% (dsb) fructose.
  • the solution is saturated (58-65°C).
  • the fructose is crystallized from the solution by adding fructose crystals of homogeneous size. The formation of new crystals is minimized by keeping the distances of the seed crystals from each other suitably short and maintaining the degree of supersaturation between 1.1 and 1.2.
  • the volume of the solution is increased, either continuously or stepwise, as the crystallization proceeds.
  • the optimum pH of the fructose solution is said to be 5.0.
  • the crystals so obtained reportedly have an average crystal size between 200-600 microns. Centrifugation is used to separate the crystals from the solution.
  • U.S. Patent 3,928,062 discloses that anhydrous fructose crystals are obtained by seeding a solution containing 83-95.5% (dry basis) total sugar comprising 88-99% fructose. Crystallization may be accomplished by simply cooling the solution under atmospheric pressure or by evaporating water under reduced pressure. Formation of the hemihydrate and dihydrate are avoided by carrying out the crystallization within a certain range of fructose concentrations and temperatures. This range lies within the supersaturation area below the point at which the hemihdyrate begins to crystallize out. It is said that the mother liquor may be used repeatedly for the crystallization of further crops in the same manner as the first crop without any additional treatment. The addition of seed crystals may be achieved using a form of massecuite which was previously prepared by suspending the crystals in the fructose solution.
  • crystalline fructose is produced by seeding a fructose syrup (88-96% dsb) with 2-15 weight percent fructose seed crystals and permitting the seeded syrup to stand at about 10 to 32.2 ° C (about 50 to 90°F) at a relative humidity below 70%. Crystallization is said to require 2 to 72 hours.
  • the crystalline product produced by the process is in the form of large pellets.
  • U.S. Patent 4,164,429 describes a process and apparatus for producing crystallization seeds. A series of centrifugal separations are employed to select seed crystals from the seeded solution which fall within a predetermined size range.
  • the invention broadly relates to the integrated production of a plurality of sweeteners which contain fructose and in particular the production of a liquid phase fructose containing sweetener and crystalline fructose.
  • this invention relates to a process for producing crystalline fructose and a liquid-phase sweetener comprising fructose and dextrose, said process comprising crystallising fructose from a fructose containing aqueous solution, and adding dextrose to the mother liquor, the fructose depleted solution, or to a solution derived therefrom.
  • this process comprises:
  • the fructose crystallization step can be performed in a plurality of passes if desired, but it is preferred that it be done in a single pass.
  • molasses This molasses is generally so impure that it has value only as an animal feed supplement or fermentation media.
  • U.S. Patent No. 3,928,062 teaches that the mother liquor from fructose crystallization can be used repeatedly for crystallization of further crops of fructose crystals.
  • This process does, however, entail a sacrifice of gains made in fractionation in that the whole point of fractionation is to remove dextrose to prepare a crystallizer feed and thus the addition of dextrose to the mother liquor sacrifices part of the enrichment achieved through fractionation.
  • the process involves splitting a dextrose and fructose containing feed stream into a first and a second stream, fractionating the first stream to produce a high fructose stream from which fructose is crystallized and removed leaving a mother liquor which is added, at least in part, to the second stream to produce a liquid sweetener. Since the mother liquor still has a high fructose content, the sweetener will have a relatively higher fructose:dextrose ratio than the initial feed stream.
  • the initial fructose and dextrose containing feed stream can be produced from a dextrose containing aqueous feed stream by partially isomerizing the dextrose to fructose.
  • crystalline fructose and a stream comprising dextrose and fructose from a feed stream comprising dextrose by:
  • this invention relates to a process for producing crystalline fructose and a liquid-phase sweetener comprising fructose which comprises:
  • the mother liquor remaining after crystallization is a saturated solution of fructose.
  • the prior art e.g. U.S. Patent 3,928,062 teaches that the mother liquor can be used repeatedly for the crystallization of further crops of crystals.
  • the saturated mother liquor must be heated and concentrated to obtain a suitable supersaturated solution of fructose and thus enable crystallization in the mother liquor. It has been found that rather than enabling the crystallization of further crops, one should inhibit further crystallization so that the mother liquor can be used to produce a liquid-phase sweetener.
  • the mother liquor is a saturated solution of fructose.
  • This aspect of the invention is related to the other aspects of this invention discussed above, in that further crystallization is avoided.
  • this aspect does not necessarily require the sacrifice of fractionation gains because inhibiting further crystallization does not necessarily require addition of dextrose, i.e. simple dilution of the mother liquor with water will serve to inhibit crystallization without diluting the fructose purity of the mother liquor on a dry solids basis.
  • this invention relates to a process for producing multiple fructose sweeteners, at least one of said sweeteners comprising dextrose and fructose, which process comprises:
  • “Fructose sweeteners” in this context includes any sweetener containing fructose without regard to whether the fructose is in solution, dispersed, amorphous or crystalline.
  • the higher-fructose extract can be used to produce a syrup containing fructose, crystalline fructose, or a semi-crystalline fructose wherein at least a portion of the fructose is in an amorphous solid phase.
  • the fractionation of an isomerized dextrose syrup, i.e., one containing both fructose and dextrose, to produce a fructose sweetener is commonly conducted by taking off a dextrose raffinate and a fructose extract, and recycling the remaining fractionation output.
  • U.S. Patent No. 4,395,292 states that such an operating condition is preferred.
  • a fructose extract having a higher concentration than a single extract can be obtained without increasing the aggregate degree of resolution of the isomerized feed and all of the problems associated therewith (e.g., reduced fractionation capacity, greater evaporation load from increased elution water, and/or deleterious pressure drop due to higher elution water flow rates needed to increase resolution).
  • the utility of the lower-fructose extract is of a narrower scope than the utility of the higher-fructose extract (i.e., it would be difficult to use the lower fructose extract to produce crystalline fructose), but the fructose therein can be used to upgrade the fructose content of corn syrups containing even less fructose, e.g. by admixture with an isomerized corn syrup (e.g., 42% fructose corn syrup) to produce a higher-fructose corn syrup (e.g., a 55% fructose corn syrup).
  • an isomerized corn syrup e.g., 42% fructose corn syrup
  • this invention relates to a process for producing crystalline fructose and a liquid-phase sweetener comprising dextrose and fructose which comprises:
  • This embodiment is particularly advantageous because the fructose concentration (dsb) commonly required to feasibly crystallize fructose from an aqueous solution is so high that fractionation of a dextrose/fructose feed stream from an isomerization process to produce a single extract may be impractical.
  • the degree of resolution needed to produce a single extract having a sufficiently high fructose purity to be useful as a crystallizer feed will often so reduce the fractionation capacity and/or increase other difficulties associated with fractionation that such resolution is impractical.
  • a possible drawback of taking both higher-fructose and lower-fructose extracts and separately using them to produce a crystalline sweetener and a liquid-phase sweetener, respectively, is that the amount of fructose in the lower-fructose extract that is available for upgrading the fructose content of an isomerized corn syrup is less than that available in a single fructose extract taken with the same aggregate degree of resolution. Thus, the total amount of fructose (dsb) available as a liquid-phase sweetener is reduced. This drawback is ameliorated by the availability of the mother liquor from the crystallization of part of the fructose of higher-fructose extract.
  • mother liquor containing fructose, a lower-fructose extract and an isomerized corn syrup are mixed to prepare a liquid-phase sweetener (e.g., a 55% fructose corn syrup).
  • a liquid-phase sweetener e.g., a 55% fructose corn syrup
  • this invention relates to a process for producing crystalline fructose from a solution comprised of fructose comprising:
  • FIG. 5 of the accompanying drawings shows typical cooling curves used in prior art crystallization processes.
  • Curve A is a natural cooling curve and curve B is a controlled curve designed to achieve a constant level of supersaturation.
  • Figure 4 shows a variable saturation cooling curve according to this invention. A comparison of the two figures shows the stark differences between the conventional curves and the curve of this invention.
  • the use of a cooling rate in an intermediate cooling period that is slower than the rates of cooling in the initial and final rates allows one to minimize both spontaneous nucleation in the solution and heat-induced degradation of the fructose in the solution, especially during the initial cooling period.
  • the reduction in nucleation results in a crystalline product having a more nearly uniform particle size distribution and the reduction in heat damage increases the yield of fructose crystals and mother liquor and reduces the level of degradation product impurities in the mother liquor, thus improving its utility as a source of fructose for a liquid-phase sweetener.
  • the purification step conveniently involves contacting the solution with activated carbon, preferably at elevated temperature, e.g. at above 60 ° C, preferably about 71 ° C.
  • the purified fructose solution may then be concentrated by solvent evaporation to bring the overall concentration up to a desired level.
  • a fructose concentration above 71% dsb, preferably above 90% dsb and a dry solids content of less than 50%, for example less than 40%, especially less than 35%, e.g. 1 to 25% or 15 to 30%, and raises the concentration in terms of dry solids content, e.g. to above 40%.
  • this invention relates to a process for preparing a concentrated solution of fructose comprising:
  • fructose syrups having a high concentration (dsb) of fructose should have a relatively low solids concentration when in the presence of activated carbon to reduce the formation of by-products (e.g., difructose) which can reduce the availability of fructose in the syrup, inhibit crystallization of fructose from the syrup, and/or affect the organoleptic properties of the syrup or a sweetener prepared therefrom.
  • Tables II and III show the effect of solids concentration on difructose formation in a high fructose (95+% dsb) syrup over time in contact with activated carbon.
  • this invention also relates to a process for producing crystalline fructose comprising:
  • the sequence of contacting and then evaporating the high-fructose stream ensures that the contacting is performed at comparatively low solids because high-fructose extracts are typically at low solids upon elution from a fractionation column.
  • this invention relates to a process for producing crystalline fructose comprising:
  • the mother liquor resulting from the crystallization of fructose will be mixed with an aqueous liquid (e.g., tap water, sweet water, saccharide syrups such as 42% fructose corn syrups, and the like) to reduce the solids content prior to treatment with activated carbon and then evaporation to higher solids.
  • an aqueous liquid e.g., tap water, sweet water, saccharide syrups such as 42% fructose corn syrups, and the like
  • the resulting higher solids solution can be used in a variety of ways, e.g., as a crystallizer feed, a high fructose corn syrup sweetener or production stream therefor, all of which benefit from the advantages discussed above which result from reducing the solids concentration of the mother liquor before treatment with activated carbon and subsequent evaporation.
  • An important feature of the present invention is the synergy which obtains when anhydrous crystalline fructose (ACF) is produced in conjunction with EFCS (enriched fructose corn syrup).
  • ACF hydrous crystalline fructose
  • EFCS enriched fructose corn syrup
  • the yield of fructose crystals from a fructose massecuite is typically on the order of 40-55%, e.g. 45%. Longer crystallization times may increase the yield, but only at the expense of process throughput.
  • a significant advantage is had by integrating fructose crystallization with a process which not only provides the fructose feed for the ACF crystallization process but also can accept without penalty the non-crystallized fructose from the ACF process.
  • the noncrystallized portion is recycled through the crystallization process.
  • undesirable by-products such as difructose, 5-(hydroxymethyl)-2-furfural (HMF) and higher saccharides tend to build up in the recycle stream since crystallization is essentially selective for fructose.
  • HMF 5-(hydroxymethyl)-2-furfural
  • the recycle stream eventually becomes so contaminated with by-products that it must be purged from the system with the concomitant loss of a substantial quantity of fructose.
  • the present invention solves the problem of by-product built up by incorporating the solution phase material which remains after the crystallization of fructose (the mother liquor) into a process which produces high-fructose, liquid-phase sweetener(s). In this fashion unwanted by-products are not concentrated in that portion of the integrated process which produces ACF, but rather are continuously removed from that system.
  • This integration obviates the need for fructose-containing purge streams thereby conserving fructose in more economically valued products.
  • EFCS 55% HFCS
  • fractionation is required to make syrups having a fructose content higher than approximately 48%.
  • dsb 95% fructose
  • Fractionation techniques are known which will provide a 95+% fructose stream from a feed comprising about 42% (dsb) fructose (the typical output from dextrose isomerization). Thus, it is possible to obtain an ACF feed stream from an EFCS process with little or no modification.
  • the fractionation system is of the simulated moving bed chromatographic type, as is well-known in the art.
  • starch is first converted to dextrose using the conventional enzyme-based process described hereinabove.
  • the isomerization step employs an enzyme to convert dextrose to fructose.
  • the enzyme is fixed to a carrier and is stationary in a column (isocolumn) until it is replaced when it is exhausted.
  • One advantage of the present invention is that it permits the efficient utilization of increased quantities of isomerase in the isocolumns. Owing to seasonal fluctuations in the demand for EFCS (55% fructose), a producer who invests in additional isomerase to meet peak demand must pay for that increased level of isomerization capacity throughout the year even when his EFCS production is at a relatively low level.
  • a producer can efficiently utilize the increased level of isomerization by channeling more of the high-fructose stream from the fractionation train to EFCS production when demand for that product is high and employing a greater portion of that stream in ACF production when demand for EFCS is lower. In this way an investment in increased isomerization capability can be effectively utilized throughout the year.
  • Fractionation occurs in a train, or group of vessels containing resin which operate in sequence to separate fructose from dextrose in the syrup feed stream.
  • the feed stream and elution water stream are fed into the train and one or more high-fructose product streams, a high-dextrose raffinate stream, and/or one or more high-oligosaccharide raffinate streams are removed.
  • the high-dextrose stream is recycled to isomerization for conversion to fructose while the high-fructose stream(s) goes into the ACF portion of the process or is blended to make EFCS.
  • Fractionation capacity is measured by the feed flow rate, percent fructose in the product stream, and recovery of fructose in the stream. For a given dsb, fructose content, the higher the fractionation capacity, the lower the fructose conversion that is needed in isomerization. Therefore, to lower the isomerase ingredient cost, fractionation is preferably continuously operated at its maximum capacity.
  • the fractionation product must be greater than about 90% (dsb) fructose and preferably greater than 95% (dsb) fructose. Since this is higher than the 90% (dsb) fructose normally isolated in an EFCS process, special operating conditions for conventional fractionation systems have to be used that may result in decreased fractionation capacity. These are: 1) slowing the syrup feed rate without changing the elution water ratio to enhance resolution and/or, 2) increasing the elution water ratio to enhance resolution. These operating conditions have the disadvantage of either decreasing product throughput and/or adding water which must subsequently be removed, entailing at least the expenditure of additional energy. There is, however, a preferred alternative.
  • the 95+% (dsb) fructose stream which is preferred as the feed for the crystalline fructose portion of the disclosed process may be obtained by taking an appropriately narrow cut from the product stream of the fractionation system of a conventional process for the production EFCS.
  • One such fractionation system which is particularly preferred is described in United States patent No. 5122275 (Rasche). The teachings of this disclosure are expressly incorporated herein.
  • a preferred way of operating the above-referenced chromatographic separation apparatus when employed in the fractionation system of the present invention is to increase the eluant-to-feed ratio from about 1.7 to about 2.0.
  • the syrup feed is preferably about 60% dry substance by weight and is maintained at a temperature of about 60°C (140°F).
  • the raffinate stream from the fractionation system may be apportioned in a manner similar to that used to divide the extract stream. In this way a stream relatively rich in oligosaccharides may be isolated for recycle to the saccharification system, sent to a separate, dedicated saccharification system, or purged from the system.
  • Oligosaccharides are undesirable in the extract stream since at least a portion of that stream is used as feed to the fructose crystallization portion of the process and the crystallization of fructose is preferably accomplished from a solution containing a minimum of other species. Likewise, oligosaccharides are undesirable in the liquid-phase sweetener produced by the process of the present invention, hence only a limited quantity of such oligosaccharides can be removed from the system via the liquid-phase product.
  • An additional advantage is had by recycling an oligosaccharide-rich stream from the fractionation system to the saccharification system.
  • Such a stream will typically be relatively low in dry substance content, most commonly about 10% d.s.--i.e., it is about 90% water by weight.
  • the starch slurry resulting from the liquefaction/dextrinization portion of the process must typically be diluted prior to saccharification.
  • the water in the oligosaccharide stream can substitute for at least a portion of the water used as a diluent for the starch slurry thereby conserving water and decreasing the evaporation capacity required for the system as a whole.
  • the high-fructose extract from fractionation is blended with the product of isomerization (typically 42-48% (dsb) fructose) to obtain the desired fructose content in the final product (55% (dsb) for EFCS).
  • mother liquor from the centrifugation step of the crystallization process containing about 88-92% (dsb) fructose, preferably 90-92% (dsb) fructose, at approximately 83% d.s. is additionally available for blending.
  • dsb fructose
  • dsb preferably 90-92% fructose
  • the pH of the aqueous fructose solution from which fructose crystals are to be obtained is preferably between about pH 3.7 and about pH 4.3, teachings to the contrary ( see , e.g., U.S. Patent 3,883,365) notwithstanding.
  • Proper control of the pH of the fructose feed to the crystallizer is necessary to minimize the formation of difructose anhydrides.
  • the presence of difructose anhydrides in the crystallizer has been found to result in lower crystallizer yields and adversely affects the size distribution of the fructose crystals that are formed. It is believed that the rate of formation of anhydrides is at a minimum in the pH range 3.7 to 4.3. Higher anhydride formation rates obtain both above and below this range. It is further believed that the formation of color formers is favored at higher pH levels.
  • Crystalline fructose was added to a sample of VEFCS (90% fructose, dsb) to produce a syrup comprising approximately 95% (dsb) fructose.
  • the syrup was subsequently subjected to treatment with granular activated carbon as described in the section of this disclosure entitled "Carbon Treatment”. Thus, this syrup was treated in the same way as feed to the crystallizer.
  • Mono-anhydrides are calculated from the difference in the fructose assay before and after hydrolysis of the sample.
  • Fructose solubility is calculated from the fructose assay (before hydrolysis) and the solids content of the sample.
  • the pH 4 sample exhibited less color formation, exhibited a decrease in total acetaldehyde content, and had a solubility not significantly different from the pH 5.5 sample.
  • a pH 4 feed syrup for an ACF process therefore has advantages over a pH 5.5 feed with regard to product yield and mother liquor quality as a result of its lower color content. Lower pH apparently minimizes color and difructose formation and has negligible effect on solubility.
  • pH adjustment is conveniently accomplished subsequent to fractionation and prior to carbon treatment.
  • the viscosity of the fructose solution is relatively low at this point in the process and thus is is relatively easy to obtain thorough mixing of the solution with the acid or base used for pH adjustment.
  • acids and bases suitable for this purpose are known in the art. Especially preferred are hydrochloric acid (HCl) to lower pH and anhydrous sodium carbonate (Na 2 CO 3 , "soda ash”) to raise pH.
  • the 95+% (dsb) fructose feed stream for the crystallization process is preferably carbon treated prior to concentration by evaporation.
  • One purpose of carbon treatment is to remove impurities that may inhibit crystallization.
  • Another purpose is to remove impurities such as color bodies, HMF, furfural, and acetaldehyde which adversely affect the quality of the mother liquor and consequently impair its use as a component of a liquid-phase sweetener.
  • Carbon treatment is preferably accomplished with granular carbon, at a dosage of about 1-3% dry substance, or powdered carbon, typically at a lower dosage than granular carbon.
  • the temperature of the syrup is preferably about 71 ° C (160 ° F) and the syrup is typically 15 to 30, preferably about 20 to about 25, percent by weight dry substance.
  • Carbon treatment is most advantageously performed immediately following fractionation and before evaporation. Carbon treating at low solids concentration has been found to keep fructose loss to difructose below 0.5%. If carbon treatment is accomplished after evaporation, fructose losses greater than 2.5% can be expected.
  • the syrup temperature should preferably be approximately 71 ° C (160 ° F) (as compared to 60 ° C (140 ° F)) to prevent microbial growth in the carbon adsorber and also to lower the syrup viscosity to obtain better diffusion into the carbon particles.
  • the amount of difructose formed in aqueous solutions of at least 95% (dsb) fructose at varying dry solids was measured.
  • the aqueous solutions were mixed in a flask with 2.7% granular carbon (dry solids of granular carbon by weight of the dry solids of the aqueous solutions) and agitated at 71 ° C (160 ° F) for 24 hours. Samples were taken at 0, 6, 14 and 24 hours for measurement of the difructose contained therein. The results are shown below: Difructose (% dsb) at: Time (hrs) Dry Solids: 25% ds 50% ds 0 0.25 0.47 6 0.32 0.85 14 0.38 1.62 24 0.78 1.94
  • the following four trials were designed to simulate the operation of a commercial scale carbon-treating tower in a plug flow manner; i.e., to allow measurement of difructose formation in a dynamic flow system as compared with the static system of an agitated flask.
  • a possible explanation may be that the formation of difructose is catalyzed and/or co-catalyzed by material being removed from the aqueous solution by the carbon and thus the buildup of this material on the carbon causes an increasing rate of conversion of fructose to difructose over the time of use of the carbon.
  • a carbon check filter may be used on the syrup leaving the carbon column to remove any carbon fines in the stream. Efficient filtering is important because any insoluble material that passes into the crystallizer will be centrifuged into the crystalline fructose and directly affect product quality.
  • the carbon treatment enhances the quality of that material as well. Since EFCS is normally carbon-treated near the end of the process (i.e., after blending), the mother liquor from the centrifuge has been refined by two carbon treatments by the time it reaches the final product.
  • the driving force for the crystallization is super-saturation obtained by cooling high-fructose syrup to a point below its saturation temperature.
  • the saturation curve for fructose (concentration vs. saturation temperature) is very steep.
  • a fructose feed syrup requires approximately 25-30.6C ° (45-55F ° ), e.g. 26.1C ° (47F ° ), of cooling.
  • the evaporators are preferably designed and operated to concentrate the solution with minimum heat damage to the syrup.
  • One preferred way of effecting evaporation entails a two-step process.
  • the feed syrup is first concentrated in a 6-pass tube-type falling film evaporator having multiple effects and mechanical recompression.
  • the 95+% (dsb) fructose stream from the carbon treatment step is supplied to the evaporator at about 20 to about 25 percent by weight dry substance, at a temperature of about 87.8 ° C (190 ° F), and at a pH of about 3.7 to about 4.3.
  • the output of this step is a syrup having about 55 to about 65 percent by weight dry substance.
  • the output from the first step is fed to a plate-type, rising film, single effect evaporator operated at about 23 to about 24 in Hg vacuum.
  • the output of the second step is a syrup at about 73.9 ° C to about 79.4 ° C (about 165 to about 175 ° F) having about 88 to about 90 percent by weight dry substance.
  • the evaporator is operated at about 26 in Hg vacuum such that the product temperature is about 60 ° C to about 65.6 ° C (about 140 to about 150 ° F), thereby minimizing the loss of fructose.
  • the main criterion in crystallizer feed evaporator design and operation is to concentrate the solution which minimum heat damage to the syrup.
  • the most troublesome heat damage to crystallizer feed syrup is conversion of fructose to difructose which reduces yield in the crystallizer.
  • the formation of difructose is favored by high temperature, high concentration, and long residence time in the evaporator. Since concentration is essentially fixed, design and operating conditions should be chosen to minimize temperature and residence time of the syrup in the evaporator.
  • Suitable evaporators such as the tube-type falling film and the plate-type rising film are generally known in the art.
  • Crystallization of fructose may be accomplished in either batch or continuous crystallizers.
  • Batch crystallization has greater flexibility in producing different crystal size distributions, and can adjust for process upsets more easily and quickly.
  • batch crystallization has lower crystallizer productivity (time required to load, unload, and seed the crystallizer); it is more difficult to produce a consistent crystal size distribution from batch to batch; it requires larger storage tanks for feed and for massecuite in order to keep batch cycle times to a minimum; and, it requires individual cooling systems for each crystallizer.
  • Continuous crystallization has the opposite advantages and disadvantages.
  • Crystallization may be accomplished in either a single pass or multiple passes. Single pass, however, is preferred. It is estimated that only 88% of the yield per batch would be achieved and crystallization time would be 87% longer for second pass crystallization. Moreover, the mother liquor from a second pass crystallization is more viscous due to greater levels of higher saccharides and slurry density (mass crystal per unit mass massecuite) is lower for second pass massecuite. Both these factors tend to reduce centrifuge productivity.
  • the utility of the mother liquor as blend stock for a liquid-phase sweetener depends in large part on the purity of the mother liquor. While the precise levels of by-products that can be tolerated in, or efficiently removed from, the mother liquor will depend upon a variety of factors, steps should be taken to minimize the formation of by-products in the crystallization portion of the process. Inasmuch as crystallization is essentially selective for fructose, by-products tend to become concentrated in the mother liquor with each successive crystallization pass. Thus, the problem is exacerbated in the case of multiple pass crystallizations and the level of by-products in the mother liquor will often impose an upper limit on the number of crystallization passes which may actually be employed in the integrated process.
  • Appropriate measures to maintain the purity of the mother liquor include careful control of evaporation, carbon treatment, and crystallization conditions such as pH, temperature, and residence times. Preferred conditions are discussed in the sections of this disclosure devoted to the various steps of the process.
  • Syrup feed to the crystallizer is preferably cooled to approximately 60 ° C (140 ° F) before entering the crystallizer.
  • dsb 95% fructose
  • the batch is seeded and thoroughly mixed with the seed crystals.
  • the seeding temperature (approximately 57.2 ° C (135 ° F)) is based on the estimated percent d.s. and percent fructose of the crystallizer batch.
  • a sample of the batch should be analyzed to determine the actual saturation temperature.
  • the cooling system of the crystallizer should be adjusted to bring the batch into the supersaturation range 1.00-1.05 (based on fructose concentration). If the massecuite is already below this range, but nucleation has not occurred, cooling should continue.
  • Nucleation is a process by which crystals are formed from liquids, supersaturated solutions (gels), or saturated vapors (clouds).
  • a crystal originates on a minute trace of a foreign substance acting as a nucleus. These are often provided by impurities. Crystals form initially in tiny regions of the parent phase and then propagate into it by accretion. In the process of the subject invention, nucleation is undesirable inasmuch as it gives rise to a produce of small crystal size. Moreover, control of the crystal size distribution is lost if appreciable nucleation occurs. For these reasons, the use of seed crystals is preferred.
  • the progress of the crystallization can be controlled indirectly by the rate of massecuite cooling, the setpoint for the cooling water being adjusted according to predetermined cooling curve such that the supersaturation level is 1.0 to 1.35, e.g. 1.0 to 1.3.
  • supersaturation is actually measured in order to directly control the progress of the crystallization.
  • Supersaturation can be estimated from percent d.s. of the mother liquor alone given the initial percent d.s. and percent fructose.
  • a decision can be made whether to continue a batch on a predetermined cooling curve or to modify the cooling rate so as to maintain the desired degree of supersaturation.
  • One preferred way of effecting crystallization comprises seeding a 95+% (dsb) fructose syrup having about 88 to about 90 percent by weight dry substance, a pH of about 3.7 to about 4.3, and a temperature of about 54.4 ° C to about 58.9 ° C (about 130 to about 138 ° F) with about 7 to about 10% by weight of seed crystals having a mean particle size of about 150 to about 250 micrometers.
  • the seeded syrup is then subjected to controlled cooling to cause the fructose in solution to crystallize out.
  • the cooling can be accomplished as follows: from a syrup temperature of about 58.9 ° C to about 46.1 ° C (about 138 to about 115 ° F) the syrup is cooled at a rate of about 0.28C ° /hour (about 0.5F ° /hr); from about 46.1 ° C to about 30 ° C (about 115 to about 86 ° F) the syrup is cooled at the rate of about 0.56 to 0.83C ° /hour (about 1.0 to about 1.5F ° /hr). It is recommended that the supersaturation level be maintained below about 1.17 when the syrup temperature is above about 46.1 ° C (115 ° F) and maintained below about 1.25 if the syrup temperature is below about 46.1 ° C (115 ° F).
  • the maximum temperature difference between the coolant and the massecuite is preferably about 5.6C ° (10F ° ). Too high a temperature difference may cause nucleation to occur.
  • cooling is controlled at differing rates in at least three periods.
  • the cooling is accomplished at a rate between about 0.56 and about 0.83C ° /hour (about 1.0 and about 1.5F ° /hr) and the supersaturation level is maintained below about 1.20.
  • the cooling rate is preferably about 0.28 to about 0.56 C ° /hour (about 0.5 to about 1.0F ° /hr) and the supersaturation level is maintained below about 1.17.
  • the cooling rate is preferably about 0.83 to about 1.39C ° /hour (about 1.5 to about 2.5F ° /hr) and the supersaturation level is maintained below about 1.25.
  • a preferred means of cooling involves coupling a continuous monitor of the level of supersaturation to an automatic control of the cooling water temperature.
  • a data processor continuously receives information about massecuite temperature, cooling water temperature and supersaturation. The processor then uses this information to control the cooling water temperature and thus, the rate of cooling of the massecuite.
  • the data processor is programmed to first cool the massecuite from its seeding temperature (T s ) to a predetermined critical temperature (T') at 1.39C ° /hour (2.5F ° /hr).
  • the critical temperature is predetermined by calculating from the % fructose and % ds of the crystallizer feed the temperature at which the level of supersaturation will reach 1.17).
  • the program then provides for cooling of the massecuite from T' to 46.1 ° C (115 ° F) at 0.56C ° /hour (1F ° /hr) and from 46.1 ° C (115 ° F) to final temperature (typically 30 ° C (86 ° F)) at 0.83C ° (1.5F ° /hr).
  • the program has overrides to prevent excessive nucleation.
  • the program provides that, in any event, the temperature difference between the massecuite and cooling water will not at any time during cooling exceed a predetermined temperature (typically about 7.8C ° (14F ° )).
  • a predetermined temperature typically about 7.8C ° (14F ° )
  • the program provides that, in any event, the level of supersaturation will not at any time during cooling exceed a predetermined value (typically 1.28).
  • the particular temperatures and rates described above may be varied to optimize the curve for a given set of crystallization conditions without undue experimentation.
  • the major factors which affect the temperatures are the total dry solids level (% ds) and the total surface area of the seed. For example, increasing the dry solids level will move the critical period to a range earlier in the cooling curve and vice versa. Decreasing the total surface area of the seed, e.g. by decreasing the amount of seed loaded, will broaden the critical period, and vice versa.
  • the growth rate is a function of a concentration driving force--the concentration present in the mother liquor versus the concentration that would be present at that temperature at equilibrium.
  • the batch cooling rate should be adjusted to control the supersaturation level of the mother liquor.
  • the supersaturation range 1.0-1.30 produces an acceptable yield of crystals in the desired size range.
  • Supersaturation levels below this range result in extended batch cooling times while supersaturation levels in excess of 1.35 result in severe nucleation.
  • the nucleation referred to above is the "shower” or "shock" type.
  • fructose crystallization is always accompanied by nucleation.
  • Shock nucleation can occur at the start of the batch upon occur at the start of the batch upon seeding. It is contemplated that this is due to a low seeding temperature. If nucleation occurs, the massecuite should preferably be heated to remove the nuclei. Once the nuclei have been dissolved, cooling can begin.
  • a preferred method of avoiding shock nucleation is to maintain the supersaturation level below 1.30 after seeding. Massive nucleation will greatly increase the viscosity of the massecuite, making centrifuging very difficult by greatly increasing the purge time. Fine crystals separated from the massecuite are much more difficult to dry and tend to agglomerate more easily. Massive nucleation gives rise to a product with undesirably small mean crystal size.
  • Initial cooling covers the temperature range down to about 48.9 ° C (120 ° F).
  • the target cooling range is about 0.56 to 2.22C ° /hour (about 1 to 4F ° /hr); the typical rate is 1.11C ° /hour (2F ° per hour), which makes this period require four to six hours, preferably about eight hours.
  • growth occurs almost entirely on the seed crystals and slurry density builds slowly. Most of the heat load on the cooling water comes from removal of sensible heat.
  • Nucleation of the batch can occur in this region; however, this will occur only if the seeding temperature is too low or supersaturation exceeds 1.3.
  • this region is not clearly defined. Best estimates place it between 48.9 ° C and 43.3 ° C (120 and 110 ° F). Caution is required in this region inasmuch as nucleation processes can easily dominate and get out of control. By maintaining a moderate level of supersaturation (1.05 - 1.20), it has been found that nucleation can be kept within acceptable limits. A slower cooling rate is the preferred way to control the degree of supersaturation. In this region a cooling rate of about 0.28 to 1.67 C ° /hour (about 0.5 to 3.0F ° /hr), typically a 0.28 to 0.83 C ° /hour (0.5 to 1.5F ° /hr) cooling rate, is recommended. At this rate the estimated time in the Critical Period is about 10-40 hours, preferably about 18-22 hours.
  • fructose hemihdyrate In some situations, high supersaturation levels may not result in nucleation. In that case, further cooling could lead to the formation of fructose hemihdyrate.
  • This species occurs in the form of needle-shaped crystals which form a slurry having a very high viscosity (above 800 Pa.s (>800,000 cps)). This slurry is impractical to centrifuge and may even overload the crystallizer drive. The hemihydrate can be detected during routine crystal inspections which should be conducted throughout the cooldown period.
  • the slurry density is high enough to support a faster cooling rate without nucleating. In this rapid cooldown region the cooling water temperature can be dropped rapidly. Massecuite cooling rates of from about 0.56 to 3.89 C ° /hour (about 1 to 7F ° /hr, preferably about 0.56 to 2.22 C ° /hour (about 1-4F ° /hr), are recommended. To cool from 43.3 ° C (110 ° F) to a final temperature of about 37.8 to 23.9 ° C (about 100-75 ° F) will require about 3-12, typically 8-12, hours.
  • More rapid cooling can be done without nucleation, but the growth does not keep pace and one may be left with a higher level of supersaturation at the end of the batch.
  • Some residual supersaturation can be relieved by placing the massecuite in a mingler or a mixer tank for a period of time.
  • the seeding temperature may be derived from the saturation temperature of the full crystallizer mother liquor. To obtain this information, a liquid chromatogram of the feed syrup and the refractive index can be taken. The percent fructose and the percent d.s. of the feed syrup are then used to calculate a fructose concentration. Seeding should be accomplished in the supersaturation range of greater than 0.96, e.g. 1.0 to 1.10.
  • the seed is dried crystalline fructose having a mean crystal size of about 100-400 microns.
  • a 1 to 20% (dsb) loading is recommended. The loading depends upon the particle size desired in the final product. Seed should be added to the full crystallizer with every effort made to distribute the seed uniformly in the crystallizer.
  • U.S. Patent 4,164,429 describes a process and apparatus for producing crystallization seeds.
  • Seeding is preferably accomplished by first mixing the seed crystals with fructose feed syrup to obtain a liquid slurry for addition to the crystallizer. This has the effect of conditioning the surfaces of the seed crystals. Preparing the seed crystals in syrup also minimizes the formation of bubbles in the crystallizer upon seeding. Bubbles are a possible site of nucleation.
  • Consistent seeding is largely a matter of providing the same surface area for growth of fructose crystals. Since the surface-area-to-volume ratio of seed crystals generally decreases with increasing particle size, if the size of the seed crystals is increased, a grater weight of seed crystals is required to obtain the desired surface area.
  • a heel of about 5 to 30%, preferably about 10 to 20%, may be left in the crystallizer to act as seed, This procedure is much less labor intensive than using dry seed, but produces a broader distribution of crystal sizes since fine particles remain in the heel which would otherwise have been removed during the centrifuging and drying steps. With this method larger crystals are obtained which may subsequently have to be ground in order to meet final product crystal size specifications.
  • the preferred procedure is to add hot syrup on top of the heel.
  • the hot syrup will raise the temperature of the massecuite heel to the estimated saturation temperature (approximately 56.1 ° C (133 ° F)) while the feed syrup is cooled to seeding temperature. Some crystal mass is probably lost during this process.
  • the final seed density should preferably be at least in the range of 2 to 10% (dsb).
  • the critical portion of this operation is the final temperature reached by the feed syrup and the massecuite heel. This should result in supersaturation levels of 1.00 to 1.10. In this range the loss of seed will be minimized and the production of nuclei will be small.
  • a fructose crystallization was conducted using a feed syrup comprising 95.82% (dsb) fructose at 89.60% dry substance in a pilot scale version of a conventional crystallizer.
  • the crystallizer employed had a center shaft agitator. Cooling was achieved through internal fins attached to the center shaft. The crystallizer was nearly filled with 386 L (102 gallons) of syrup. Cooling was accomplished in about 40 hours from seeding; however, considerable supersaturation (1.17) remained at the end of the period. The batch was monitored by following the change in supersaturation.
  • Seed was prepared by grinding crystalline product through a 2A Fitzmill screen. The ground material was screened through a 55-mesh screen and through a 100-mesh screen. The seed had a mean size of 161 microns. Dry seed was added directly to the syrup in the crystallizer.
  • Table IV presents the cooling program actually used during the crystallization. Supersaturation rose during the first 18 hours of the run to a maximum of 1.26. It then dropped to around 1.17 where it remained throughout the remainder of the cool-down. Period (hrs since seeding) Starting Temp in ° C ( ° F) Ending Temp in ° C ( ° F) Cooling Rate in C ° /hr (F ° /hr) 2.0 - 10.8 56.4 (133.5) 50.3 (122.5) 0.69 (1.25) 10.8 - 20.8 50.3 (122.5) 44.3 (111.7) 0.54 (0.98) 20.8 - 30.8 44.3 (111.7) 38.1 (100.6) 0.62 (1.11) 30.8 - 40.8 38.1 (100.6) 30.0 (86.0) 0.81 (1.46)
  • the product crystals had a mean size of 268 microns.
  • the crystal yield was 46% based on the fructose content of the syrup.
  • a preferred method of separating fructose crystals from the mother liquor is centrifugation in a basket centrifuge. It has been found that about 15 L (4 gallons) of massecuite in a 35.6 cm x 15.2 cm (14" x 6") centrifuge can be separated in about 10-15 minutes. This period includes one to three, typically two, washes with warm water (48.9 to 93.3°C (120-200°F)). Higher washwater temperatures may result in a greater dissolution of fructose and loss of yield. Recommended washwater amounts are 1-5% based on massecuite charge. Deionized washwater can be used. It is preferred that the pH of the washwater be in the range of about pH 3 to 5.
  • Preferred operating conditions for a basket centrifuge used to remove crystalline fructose from the mother liquor include: a g force of about 1400, a cake thickness of about 5 to about 7.6 cm (about 2 to about 3 inches); cake moisture between about 0.7 and about 1.5 percent by water; and a product purity above about 99.5%, more preferably above about 99.8%. Cake moisture and purity are believed to be important criteria for producing a nonagglomerated and stable product.
  • the product cake is preferably washed in the centrifuge prior to removal.
  • a preferred wash is water at a temperature between about 65.6°C and about 82.2°C (about 150 and about 180°F) in a quantity of about 1 to about 1.5 percent by weight of the massecuite charged to the centrifuge. Using this method, loss of the product in the wash has typically been found to be about 5 to about 10%. Washwater containing dissolved fructose may be recycled to the carbon treatment step for impurity removal and subsequent reconcentration.
  • a variety of dryer types may be employed in the process. Fluidized bed dryers, vibrating fluidized bed dryers, tray and rotary dryers are all suitable.
  • wet cake from the centrifuge is metered into a continuous mixer through a variable speed screw conveyor.
  • Dry recycle material is metered in through a choked conveyor (to prevent air bypassing) at a nominal ratio up to 4:1 over the wet cake. Action in the mixer must be sufficient to thoroughly blend the wet and dry materials. The blended cake is then removed to the dryer.
  • the cake is dried cocurrently to avoid overheating the product.
  • Room air should first be cleaned by passage through an ultrafine borosilicate filter rated for 95% removal of 0.5-micron particles. The air is then heated to a temperature which, when mixed with the exhaust air from the cooler, produces 71.1 ° C (160 ° F) air at the dryer inlet.
  • the product leaves the dryer at about 54.4 ° C (130 ° F) and is conveyed to the cooler.
  • a controlled amount of the produce is recycled without cooling to the dryer inlet for treating wet centrifuge cake.
  • the most critical variable in dryer operation is moisture of the incoming cake. If the moisture is too high, the dryer will produce balls and agglomerated product.
  • the moisture may be controlled by the ratio of dry recycle to wet cake. Although a 2:1 ratio of dry recycle to wet cake is usually satisfactory for well-developed crystals, nucleated crystals will not centrifuge well and may require a 3:1 ratio to avoid agglomeration.
  • the centrifuge cake is preferably dried in a rotary dryer to reduce the moisture of the fructose crystals to below about 0.1 percent by weight. It has been found that if the moisture content of the centrifuge cake exceeds approximately 1.5 percent by weight, lumps will form in the dryer. As noted above, dry product recycle may be used to control the centrifuge cake moisture. It is recommended that the product temperature not be allowed to exceed about 60 ° C (140 ° F).
  • Preferred dryer operating conditions are: an inlet air temperature of about 76.7 to about 121.1 ° C (about 170 to about 250 ° F), more preferably about 76.7 to about 93.3 ° C (about 170 to about 200 ° F); an outlet air temperature of about 54.4 to about 62.8 ° C (about 130 to about 145 ° F); a product temperature of about 51.7 to about 57.2 ° C (about 125 to about 135 ° F); and, a product moisture content of less than about 0.1%, more preferably less than about 0.07%.
  • a rotary cooler with countercurrent air works well for this purpose.
  • Refrigerated, dehumidified (conditioned) air is used to cool the product crystals to below about 23.9°C (75°F), more preferably about 22.2°C (72°F). It is recommended that the inlet cooling air have a temperature below about 21.1°C (70°F) and a relative humidity below about 40%. Retention time in the cooler should be sufficient to assure that the crystals are properly conditioned.
  • the final product moisture content is preferably less than about 0.07%.
  • the final product may be sized by screening and/or grinding. Prolonged storage of product at high temperatures will cause caking and color problems evenif it is stored in moisture barrier bags. Warehousing should be done under controlled humidity conditions.
  • the mother liquor separated from the crystalline product in the centrifuge may be returned to the EFCS portion of the process.
  • the mother liquor may simply be diluted with water to produce a VEFCS.
  • the mother liquor may be mixed with dextrose or dextrose-containing solutions to ultimately produce a liquid-phase sweetener comprising dextrose and fructose such as 55% HFCS (EFCS).
  • EFCS 55% HFCS
  • a number of dextrose-containing streams may be blended with the mother liquor prior to input to the final finishing operations.
  • the choice of particular stream or streams will be dictated by mass balance considerations, the goal being the desired fructose level in the final liquid phase sweetener product. Most commonly for the integrated process this level will be 55% (dsb) fructose. If sufficient fructose is available in the mother liquor, it is even possible to use the dextrose product stream from saccharification (typically 94-96% (dsb) dextrose) to blend for input to EFCS finishing.
  • the mother liquor which is typically 90-92% (dsb) fructose may simply be diluted with water to produce a liquid-phase sweetener. Dilution is recommended if it is desired to maintain the fructose contained in the mother liquor in the liquid inasmuch as additional fructose would likely crystallize from the mother liquor if the solution is not diluted to below the saturation point for all temperatures likely to be encountered.
  • suitable diluents include aqueous saccharide solutions such as dextrose syrups, HFCS, EFCS, VEFCS, and production streams for such syrups.
  • Other means for inhibiting the crystallization of fructose in the separated mother liquor include measures for preventing or reducing the evaporation of water from the solution and the incorporation of crystallization-inhibiting additives.
  • Another use for the separated mother liquor or a portion thereof is production of a non-crystalline or a semi-crystalline fructose sweetener.
  • One way of accomplishing this is to disperse the mother liquor on an edible, particulate solid and then drying the dispersion to produce a sweetener comprising fructose in an amorphous or semi-crystalline form.
  • a preferred edible, particulate solid for this purpose is crystalline fructose.

Claims (24)

  1. Verfahren zur Herstellung eines flüssigen, Fructose und Dextrose umfassenden Süßungsmittels, bei dem man Fructose aus einer Fructose-haltigen wässrigen Lösung kristallisiert und zu der Fructose-abgereicherten Lösung Dextrose gibt.
  2. Verfahren nach Anspruch 1, bei dem ein Strom einer Fructose- und Dextrose-haltigen wässrigen Lösung in einen ersten und einen zweiten Strom aufgeteilt wird, der erste Strom unter Herstellung eines hochfructosehaltigen Stroms fraktioniert wird, Fructose aus dem hochfructosehaltigen Strom kristallisiert wird und zumindest ein Teil des Fructose-abgereicherten hochfructosehaltigen Stroms mit dem zweiten Strom vereinigt wird.
  3. Verfahren nach Anspruch 2, bei dem eine Dextrose-haltige wässrige Lösung zur Isomerisierung eines Teils der darin enthaltenen Dextrose behandelt wird, wobei die Fructose- und Dextrose-haltige wässrige Lösung erhalten wird.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem die Kristallisation der Fructose in einem einzigen Durchgang erfolgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, bei dem die Fructose-Kristallisation bei einem pH-Wert von 3,7 bis 4,3 erfolgt.
  6. Verfahren nach einem der Ansprüche 1 bis 5, bei dem die Fructose-Kristallisation durch Abkühlen der Fructose-haltigen Lösung von einer Temperatur von mehr als 54,4°C erfolgt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem die Fructose-Kristallisation durch Abkühlen der Fructose-haltigen Lösung von einer Temperatur von etwa 60°C auf eine Temperatur von etwa 48,9°C mit einer Geschwindigkeit von 0,56 bis 2,22°C/h erfolgt.
  8. Verfahren nach einem der Ansprüche 1 bis 7, bei dem vor der Kristallisation der Fructose aus der Fructose-haltigen wässrigen Lösung diese einer Kohlenstoffbehandlung und dann Lösungsmittelverdampfungsschritten unterworfen wird.
  9. Verfahren nach Anspruch 8, bei dem die Fructose-haltige wässrige Lösung, die der Kohlenstoffbehandlung unterworfen wird, eine Fructose-Konzentration von mehr als 75%, bezogen auf die Trockenmasse, aufweist und der Kohlenstoffbehandlung durch Kontakt mit Aktivkohle unterworfen wird.
  10. Verfahren nach Anspruch 9, bei dem die Fructose-haltige wässrige Lösung, die der Kohlenstoffbehandlung unterworfen wird, eine Trokkenmassekonzentration von weniger als 40% aufweist und die Lösung nach der Kohlenstoffbehandlung einer Lösungsmittelverdampfung unterworfen wird, wobei eine Fructose-haltige wässrige Lösung mit einer Trockenmassekonzentration von mehr als 40% erhalten wird.
  11. Verfahren nach Anspruch 9 oder 10, bei dem die Fructose-haltige Lösung eine Trockenmassekonzentration von weniger als 50% aufweist und beim Kontakt mit der Aktivkohle eine Temperatur von mehr als 60°C aufweist.
  12. Verfahren nach einem der Ansprüche 1 bis 11, bei dem eine Fructose- und Dextrose-haltige wässrige Lösung fraktioniert wird, wobei eine Dextrose-angereicherte Lösung, eine erste Fructose-haltige Lösung und eine zweite Fructose-haltige Lösung erhalten werden, wobei die zweite Fructose-haltige Lösung einen Fructosegehalt aufweist, der größer als der der ersten Fructose-haltigen Lösung ist, und wobei Fructose aus der zweiten Lösung oder einer daraus gewonnenen Lösung kristallisiert wird und die erhaltene Fructoseabgereicherte Lösung zu der ersten Lösung und zu einer Dextrose-haltigen wässrigen Lösung mit einer größeren Dextrose-Konzentration, bezogen auf die Trockenmasse, als die erste Lösung gegeben wird.
  13. Verfahren nach Anspruch 12, bei dem die Fraktionierung so erfolgt, dass eine zweite Fructose-haltige Lösung mit einem Fructose-Gehalt von mindestens 90%, bezogen auf die Trockenmasse, erhalten wird.
  14. Verfahren nach Anspruch 12 oder 13, bei dem eine Fructose- und Dextrose-haltige Lösung in einen ersten und einen zweiten Strom aufgeteilt wird, wobei der erste Strom einer Fraktionierung und Fructose-Kristallisation unterworfen wird und wobei der zweite Strom zu der ersten Lösung und der Fructose-abgereicherten Lösung als der Dextrose-haltigen wässrigen Lösung gegeben wird.
  15. Verfahren nach einem der Ansprüche 1 bis 13, bei dem das so hergestellte flüssige Fructose- und Dextrose-haltige Süßungsmittel einen Fructose-Gehalt von mindestens 55%, bezogen auf die Trockenmasse, aufweist.
  16. Verfahren nach Anspruch 1, bei dem eine Dextrose-haltige wässrige Lösung mit der Fructose-abgereicherten Lösung gemischt wird, und das erhaltene Gemisch einer Kohlenstoffbehandlung und Lösungsmittelverdampfung unterworfen wird, wobei eine Dextrose- und Fructose-haltige wässrige Lösung erhalten wird.
  17. Verfahren nach Anspruch 16, bei dem die Dextrose-haltige wässrige Lösung ein hochfructosehaltiger Maisstärkezuckersirup ist und das erhaltene Gemisch eine Fructose-Konzentration von etwa 55%, bezogen auf die Trockenmasse, aufweist.
  18. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Fructose-Kristallisation durch Abkühlen erfolgt und während des Abkühlens die Temperaturerniedrigungsgeschwindigkeit verringert und anschließend erhöht wird.
  19. Verfahren nach Anspruch 18, bei dem die Temperaturerniedrigungsgeschwindigkeit bei etwa 48,8°C verringert und anschließend bei etwa 43,3°C erhöht wird.
  20. Verfahren nach Anspruch 18 oder 19, bei dem die Temperaturerniedrigungsgeschwindigkeit von einem Wert im Bereich von 0,55 bis 2,22°C/h auf einen Wert im Bereich von 0,28 bis 1,67°C/h verringert und anschließend auf einen Wert im Bereich von 0,55 bis 3,89°C/h erhöht wird.
  21. Verfahren nach einem der vorhergehenden Ansprüche, bei dem nach der Fructose-Kristallisation die kristallisierte Fructose aus der Fructose-abgereicherten Lösung entfernt wird und eine Fructose-Kristallisation in der Fructose-abgereicherten Lösung inhibiert wird.
  22. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Kristallisation der Fructose nach einem Verfahren erfolgt, bei dem man:
    einen Dextrose und Fructose umfassenden Strom fraktioniert, wobei ein hochfructosehaltiger Strom mit mehr als 90%, bezogen auf die Trockenmasse, Fructose erhalten wird;
    den hochfructosehaltigen Strom mit Aktivkohle in Kontakt bringt, wobei ein gereinigter Fructose-Strom erhalten wird;
    den gereinigten Fructose-Strom eindampft, wobei eine Fructose-Lösung erhalten wird; und
    Fructose in der Fructose-Lösung kristallisiert.
  23. Verfahren nach einem der Ansprüche 1 bis 21, bei dem man:
    Fructose in einer Fructose-Lösung kristallisiert, wobei ein Gemisch erhalten wird, das kristalline Fructose und Fructose-umfassende Mutterlauge umfaßt;
    kristalline Fructose von der Mutterlauge abtrennt;
    zumindest einen Teil der Fructose der Mutterlauge mit einer wässrigen Flüssigkeit mischt, wobei eine Fructose-Lösung mit geringerem Feststoffgehalt erhalten wird;
    die Fructose-Lösung mit geringerem Feststoffgehalt mit Aktivkohle in Kontakt bringt; und
    die Fructose-Lösung mit geringerem Feststoffgehalt eindampft, wobei eine Fructose-Lösung mit höherem Feststoffgehalt erhalten wird.
  24. Verfahren nach einem der Ansprüche 1 bis 21, bei dem die Kristallisation von Fructose aus einer Fructose-Lösung nach einem Verfahren erfolgt, bei dem man:
    die Lösung über einen Anfangstemperaturbereich mit einer Anfangsabkühlgeschwindigkeit abkühlt;
    die Lösung dann über einen Zwischentemperaturbereich mit einer Zwischengeschwindigkeit abkühlt, die langsamer als die Anfangsgeschwindigkeit ist; und
    die Lösung über einen Endtemperaturbereich mit einer Endgeschwindigkeit abkühlt, die schneller als die Zwischengeschwindigkeit ist.
EP93301559A 1987-02-02 1993-03-01 Fruktose und Dextrose enthaltender flüssiger Süssstoff Expired - Lifetime EP0613953B1 (de)

Priority Applications (18)

Application Number Priority Date Filing Date Title
US07/747,773 US5230742A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and high-fructose, liquid-phase sweetener
US07/747,775 US5234503A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and a high-fructose, liquid-phase sweetener
US07/747,764 US5350456A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and a high fructose, liquid-phase sweetener
EP93301560A EP0613954B1 (de) 1991-08-20 1993-03-01 Kristallisation von Fruktose
DE69321456T DE69321456T2 (de) 1991-08-20 1993-03-01 Kristallisation von Fruktose
EP93301559A EP0613953B1 (de) 1991-08-20 1993-03-01 Fruktose und Dextrose enthaltender flüssiger Süssstoff
ES93301559T ES2126627T3 (es) 1991-08-20 1993-03-01 Edulcorante liquido que contiene fructosa y dextrosa.
DE69323414T DE69323414T2 (de) 1991-08-20 1993-03-01 Fruktose und Dextrose enthaltender flüssiger Süssstoff
AT93301560T ATE171982T1 (de) 1991-08-20 1993-03-01 Kristallisation von fruktose
ES93301560T ES2124283T3 (es) 1991-08-20 1993-03-01 Cristalizacion de fructosa.
AT93301559T ATE176503T1 (de) 1991-08-20 1993-03-01 Fruktose und dextrose enthaltender flüssiger süssstoff
AU33991/93A AU662391B2 (en) 1991-08-20 1993-03-04 Fructose and dextrose containing liquid sweetener
ZA931871A ZA931871B (en) 1991-08-20 1993-03-16 Integrated process for producing crystalline fructose
CA002091706A CA2091706A1 (en) 1991-08-20 1993-03-16 Integrated process for producing crystalline fructose
JP07412893A JP3399576B2 (ja) 1991-08-20 1993-03-31 結晶フルクトースを生産するための一体化プロセス
HU9301156A HUT67470A (en) 1991-08-20 1993-04-19 Integrated process for producing crystalline fructose
BR9301098A BR9301098A (pt) 1991-08-20 1993-05-17 Processo integrado para produção de frutose cristalina
GR990400653T GR3029569T3 (en) 1991-08-20 1999-03-04 Fructose and dextrose containing liquid sweetener.

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
US07/747,764 US5350456A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and a high fructose, liquid-phase sweetener
US07/747,775 US5234503A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and a high-fructose, liquid-phase sweetener
US07/747,773 US5230742A (en) 1987-02-02 1991-08-20 Integrated process for producing crystalline fructose and high-fructose, liquid-phase sweetener
EP93301559A EP0613953B1 (de) 1991-08-20 1993-03-01 Fruktose und Dextrose enthaltender flüssiger Süssstoff
EP93301560A EP0613954B1 (de) 1991-08-20 1993-03-01 Kristallisation von Fruktose
AU33991/93A AU662391B2 (en) 1991-08-20 1993-03-04 Fructose and dextrose containing liquid sweetener
CA002091706A CA2091706A1 (en) 1991-08-20 1993-03-16 Integrated process for producing crystalline fructose
ZA931871A ZA931871B (en) 1991-08-20 1993-03-16 Integrated process for producing crystalline fructose
JP07412893A JP3399576B2 (ja) 1991-08-20 1993-03-31 結晶フルクトースを生産するための一体化プロセス
HU9301156A HUT67470A (en) 1991-08-20 1993-04-19 Integrated process for producing crystalline fructose
BR9301098A BR9301098A (pt) 1991-08-20 1993-05-17 Processo integrado para produção de frutose cristalina

Publications (2)

Publication Number Publication Date
EP0613953A1 EP0613953A1 (de) 1994-09-07
EP0613953B1 true EP0613953B1 (de) 1999-02-03

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP93301559A Expired - Lifetime EP0613953B1 (de) 1987-02-02 1993-03-01 Fruktose und Dextrose enthaltender flüssiger Süssstoff
EP93301560A Expired - Lifetime EP0613954B1 (de) 1987-02-02 1993-03-01 Kristallisation von Fruktose

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP93301560A Expired - Lifetime EP0613954B1 (de) 1987-02-02 1993-03-01 Kristallisation von Fruktose

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EP (2) EP0613953B1 (de)
JP (1) JP3399576B2 (de)
AT (2) ATE171982T1 (de)
AU (1) AU662391B2 (de)
BR (1) BR9301098A (de)
CA (1) CA2091706A1 (de)
DE (2) DE69321456T2 (de)
ES (2) ES2126627T3 (de)
GR (1) GR3029569T3 (de)
HU (1) HUT67470A (de)
ZA (1) ZA931871B (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR0103406A (pt) 2001-08-15 2004-05-04 Getec Guanabara Quimica Ind S Processo de produção de frutose cristalina de elevada pureza utilizando xarope com baixo teor de frutose originária de sacarose, e produto obtido
FI115919B (fi) * 2002-06-27 2005-08-15 Danisco Sweeteners Oy Menetelmä kiteytysinhibiittoreiden poistamiseksi monosakkaridisokeriliuoksista
KR101217137B1 (ko) * 2012-03-05 2012-12-31 한국생산기술연구원 프록토오스를 포함하는 옥수수시럽으로부터 5-히드록시메틸-2-푸르푸랄을 제조하는 방법
CN104837376A (zh) * 2012-08-20 2015-08-12 天然成分有限责任公司 从水果中制备糖产品的方法
CN103146849B (zh) * 2013-03-25 2014-01-08 保龄宝生物股份有限公司 小麦为原料联产结晶果糖与果葡糖浆及小麦淀粉制备方法
KR20210096688A (ko) 2015-02-24 2021-08-05 테이트 앤드 라일 인그리디언츠 어메리카즈 엘엘씨 알룰로스 시럽
KR101695831B1 (ko) 2015-05-15 2017-01-12 주식회사 삼양사 감미질 및 결정화가 개선된 사이코스 혼합당 조성물
US11254959B2 (en) 2016-05-23 2022-02-22 Annikki Gmbh Process for the conversion of sugars
KR102065155B1 (ko) * 2016-12-08 2020-02-11 주식회사 삼양사 사이코스의 제조방법
FR3061413B1 (fr) 2017-01-05 2021-08-27 Roquette Freres Procede de fabrication de cristaux de d-allulose
FR3061414B1 (fr) 2017-01-05 2021-07-16 Roquette Freres Sirops cristallisables de d-allulose
KR102004940B1 (ko) * 2017-06-30 2019-07-29 주식회사 삼양사 감미료 알룰로스를 제조하는 방법

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2007971A (en) * 1926-11-29 1935-07-16 Richard F Jackson Process of making sugar products
FR1534746A (fr) * 1966-04-29 1968-08-02 Boehringer & Soehne Gmbh Procédé d'obtention de fructose à l'état cristallisé
US3883365A (en) * 1972-01-04 1975-05-13 Suomen Sokeri Oy PH adjustment in fructose crystallization for increased yield
US3816175A (en) * 1972-07-03 1974-06-11 Suomen Sokeri Oy Process for formation of crystalline fructose-glucose blends
JPS5239901B2 (de) * 1973-02-12 1977-10-07
US4199373A (en) * 1979-04-13 1980-04-22 Chimicasa Gmbh Process for the manufacture of crystalline fructose
US4517021A (en) * 1983-10-28 1985-05-14 A. E. Staley Manufacturing Company Semi-crystalline fructose
US4634472A (en) * 1985-08-23 1987-01-06 A. E. Staley Manufacturing Company Enrichment of fructose syrups
US5047088A (en) * 1989-06-30 1991-09-10 A. E. Staley Manufacturing Company Method for crystallization of fructose

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AU662391B2 (en) 1995-08-31
BR9301098A (pt) 1994-11-29
ZA931871B (en) 1993-10-06
ES2126627T3 (es) 1999-04-01
ATE171982T1 (de) 1998-10-15
DE69323414T2 (de) 1999-06-10
DE69321456D1 (de) 1998-11-12
ES2124283T3 (es) 1999-02-01
EP0613953A1 (de) 1994-09-07
ATE176503T1 (de) 1999-02-15
HU9301156D0 (en) 1993-07-28
EP0613954A1 (de) 1994-09-07
JPH06277099A (ja) 1994-10-04
GR3029569T3 (en) 1999-06-30
CA2091706A1 (en) 1994-09-17
DE69321456T2 (de) 1999-06-17
AU3399193A (en) 1994-09-15
JP3399576B2 (ja) 2003-04-21
EP0613954B1 (de) 1998-10-07
DE69323414D1 (de) 1999-03-18
HUT67470A (en) 1995-04-28

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