CN1042237C - Integrated process for producing crystalline fructose - Google Patents

Abstract

The present invention discloses an integrated method for producing crystalline fructose and liquid phase sweetening agents. For example, corn syrup containing high fructose can be obtained from material feeding liquid containing dextrose. A part of dextrose isomerism in the material feeding liquid is converted into fructose, the obtained dextrose/fructose flow is separated for producing high fructose flow of which a part of fructose is crystallized out, and residual mother liquid after crystallisation and the liquid flow containing the dextrose are mixed for producing liquid phase sweetening agents.

Description

Produce the method for liquid sweetener and crystal diabetin

The present invention relates to table sugar.More particularly, it relates to the fructose that the isomerization by dextrose obtains.Relevant especially is the syrupy method of producing anhydrous crystal fructose simultaneously and mainly being made up of fructose and dextrose.

Also relevant especially is to come the method for crystal diabetin and the method for producing purified and spissated fructose syrups by the cooling fructose soln in the different steps generation supersaturation in various degree of crystal growth.

Liquid phase fructose product

Fructose is that a kind of the high evaluation is the monose of nutritive sweetener.The fructose of mass selling is that the principal mode from product is that the W-Gum of the high maize treacle of fructose content (HFCS) obtains in this country.Commercial syrupy fructose content is 42% to 90wt% (hereinafter, comprise claims, " dsb " meaning is the weight in dried solids) in dried solids [(dsb)].Residuum mainly is a dextrose.The HFCS that is commonly used to place of sucrose in soft drink typically contains 55% fructose, 41% dextrose and 4% high-grade carbohydrate (all being the percentage ratio of dsb).This syrupy solid contents approximately is 77wt% usually.

On technical scale, the production of HFCS begins with the enzymatically liquefying of purified farinaceous size.In the U.S., the main source of raw material is the W-Gum that obtains by wet milling process.Yet, also can adopt the starch of the suitable purity that obtains from other source.

In typical method, at first, at high temperature by boiling with the farinaceous size gelatinization.Then by starch liquefacation and the dextrinization with gelatinization in the successive two-step reaction of heat-stable α-Dian Fenmei.The product of this reaction is the dextrin hydrolysis product of the soluble 6-15 of having dextrose equivalent (DE), is suitable for the subsequent saccharification step.

After the liquefaction-dextrinization, regulate the PH and the temperature of 10-15DE hydrolysate and carry out saccharification.In saccharifying, the enzyme effect by glucoamylase further is hydrolyzed to dextrose with hydrolysate.Although saccharification can be finished with intermittent reaction, in most of modernized factories, carry out in a continuous manner.In the continuous conversion reaction, after adjusting PH and the temperature, then in the 10-15DE hydrolysate, add glucoamylase.The carbohydrate of the saccharification liquid of typical high dextrose content is formed: 94-96% dextrose, 2-3% maltose, 0.3-0.5 trisaccharide maltose and the senior carbohydrate of 1-2% (all being the percentage ratio of dsb).This product typically contains the dry-matter of 25-37%.Then with the refining dextrose raw material that is used for isomerization reaction with production of the hydrolysate of this high dextrose content.

Because it is very low requiring the color of finished product HFCS and ash content, it is essential that preparation is used for isomerized high-quality dextrose raw material.In order effectively to utilize immobilized isomerase enzyme post, also need highly purified raw material.

Use immobilized isomerase enzyme post some months continuously.In the meantime, a large amount of dextrose raw materials pass through pillar.The unusual impurity of low levels in raw material, for example the reduction of enzymic activity can be assembled and cause to ash content, metal ion and/or protein.Because these reasons, with the dextrose feed purification to color 0.1 (CRA * 100), electric conductivity 5-10 micro-ohm.

For isomerization, the fluid evaporator of that carbon is handled, filtering and deionized high dextrose content is to suitable solid contents.In addition, by adding magnesium ion raw material is carried out chemical treatment, the magnesium ion of adding has not only activated immobilized isomerase, and has suppressed the effect of any remaining calcium ion competitively, and calcium ion is the strong inhibitor of isomerase.

The isomerization reaction that some dextroses are converted into fructose is normally carried out on the dry-matter of being made up of 94-96% (dsb) dextrose and the senior carbohydrate of 4-6% (dsb) is the liquid stream of 40-50%.The PH of liquid stream is 7.5-8.2 in the time of 25 ℃, and under 55-65 ℃ of effect that is placed on isomerase 1/2 to 4 hour.

Conversion of glucose is that fructose is reversible reaction, is approximately 1.0 at 60 ℃ of its equilibrium constants.Therefore, people wish that the content that obtains fructose when balance is approximately 47-48%, and balance is from successive 94-96% dextrose raw material.Yet, near the isomerization reaction speed of trim point be so slow so that when the inversion quantity of about 42% fructose modestly termination reaction to reach the real reaction device residence time.

In specific isomerization post (immobilized isomerase post), the conversion rate that dextrose (glucose) is converted into fructose is proportional with the enzymic activity of immobilized isomerase.This activity weakens so that almost exponential manner is overtime.When pillar is new and active high right, the flow velocity that feedstream is crossed pillar compares higher, because need the short residence time reach 42% fructose content.Along with pillar work-ing life increases, the flow by pillar must reduce pro rata so that the long residence time to be provided, and the activity that compensation reduces is so that reach the constant transformation efficiency.

In actual production,, used the parallel operation of a plurality of isomerization posts to come to be reduced to minimum produce fluctuation with regard to capacity and transformation efficiency.In this arrangement, each isomerization post can be independent of other pillar basically to be operated.Because evaporation and other are finished the needs of operation, must remain on the variation of the total flux of isomerization post in the narrow relatively scope.In actual production, can not be always accurately dominant discharge obtain 42% fructose stream, but this can be easily on average to reach.

In such method, one of most important operational variable is the PH of isomerization post inside.Operation PH is the compromise between the PH of maximum activity (typically about PH8) and the highest stabilizing (typically PH7.0-7.5) normally.This variable Yin Wendu 60 ℃ of left and right sides raw material PH is unstable, and this is true and complicated.Certain decomposes generation, has produced acidic by-products, the decline of PH when this decomposition has caused that logistics is by the isomerization post in operating process.

After the isomerization, typical manufacture method adopts makes with extra care and polishes the 42%HFCS product for the second time.When raw material was kept for some time under higher PH and temperature, some other colors had appearred during chemical treatment and isomerization.Product also contains some ash contents that get from the pharmaceutical chemicals that adds for isomerization.Remove this color and ash content by regenerative carbon and ion exchange system.Typically purified 42%HFCS is evaporated to 71% solids preparation shipping then.

It generally is known using the activated carbon affination syrup.U.S. Patent No. 1,979,781 (Van Sherpenberg) disclose living syrup (that is, discord glucose syrup or discord invert syrup blended syrup) with 60 ℃ of Brixs (60% dried solids) and the mixing of 1-2wt% activated carbon and be heated to 134 ℃ very short for some time.The liquid glucose that it is 10-60wt%, particularly 20-56wt% at 52 to 93 ℃ of solid contents that U.S. Patent No. 2,763.580 (Zabor) mainly discloses with activated carbon treatment (for example, sugarcane, beet or primverose).This patent disclosure under a certain concentration or condition, carry out after the partially disposed, under higher concentration (obtaining) or other condition, finish this processing by evaporation.

The patent that the various maize treacle that contain fructose with production are target discloses by way of parenthesis that carbon is handled and the concentrated subsequently aqueous solution with different fructose concentration (dsb) and different dried solid contents.U.S. Patent No. 3,383,245 (people such as Scallet) and No.3,690,948 people such as () Katz disclose carbon and have handled the syrup that contains fructose, and this syrup contains the fructose of about 20% (dsb), and about 40% is dried solids, concentrate this syrup (for example, by being evaporated to the dried solids of 70-83%) subsequently.

United States Patent (USP) N.3,684,574 people such as () Katz disclose carbon and have handled and contain about 20% (dsb) fructose, solids is low to 20% syrup, subsequently heavy syrup.U.S. Patent No. 4,395,292 people such as () Katz disclose past fractional column and have sent into by carbon treatment the 10-70% that contains, and the fructose of preferred 40% dried solids and the mixture of dextrose also concentrate the extract that contains fructose.This patent disclosure can obtain containing the extract that surpasses 90% fructose, and an embodiment (embodiment 7) disclosed, the charging fractionation that will contain 40% dried solids in this embodiment obtains a kind of cut that contains 100% (dsb) fructose, and dried solids is 9%.

The HFCS product that obtains from isomerization reaction typically contains 42% fructose, the dextrose of 52% end conversion and about 6% oligosaccharides.Because reason discussed above, this product has been represented the fructose of the actual maximum that can obtain by isomerization.In order to obtain having the more product of high content fructose, need optionally to concentrate fructose.Many common isolation technique are not suitable for this purpose, because they are not easy to distinguish two substantially the same isomer of molecular size.Yet, fructose preferably with different positively charged ions, for example calcium ion forms mixture.Utilized this difference to come the separation method of developing industry.

For large scale purification fructose, the present spendable two kinds of different commercial runs that have basically.In these two methods, the resin of preferred cationic form is used for the packed bed system.Method adopts and causes selectively the inorganic resin of molecular absorption fructose (referring to " The Sarex Process for theFractionation of High Fructose Corn Syrup " Abstracts of the Institute of ChemicalEngineers of R.J.Jensen, 85th National Meeting, Philadelphia, Pa., 1978).

The chromatographic separation of using organic resin is that the basis of second kind of industrial process for separating is (referring to K.Venkatasubramanian, " Integration of Large ScaleProduction and Purification of Biomolecules ", Enzyme Engineering, 6:37-43,1982).When the aqueous solution of dextrose and fructose (for example 42% HFCS) was sent into separator column, resin was with fructose fixed degree big than dextrose.With deionization and remove the water of oxygen as eluant.Typically, be separated in low cross-linking, finish in the pillar of fine-meshed poly styrene sulfonate Zeo-karb filling, using calcium is preferred salt form.The enriched product that contains about 90% fructose is meant highly enriched fructose maize treacle (VEFCS).This VEFCS cut can mix with 42% HFCS feed material, obtains the product that the fructose resultant is 42%-90%.These products are most typical to be 55% spissated fructose maize treacle, is called as EFCS or 55EFCS sometimes.U.S. Patent No. 4,395,292 (people such as Katz) disclose a mixture fructose and dextrose and have been fractionated into various cuts, merge spissated fructose cut and produce the syrupy embodiment (embodiment 1) that contains 55.8% (dsb) fructose.This embodiment also discloses the single cut of the fructose (for example 75.1% (dsb)) that contains high density (dsb) and discloses the cut (for example, 64.5% (dsb) and 58.2% (dsb) fructose) that merges the fructose that contains low concentration.

Other raffinate stream is a thing that needs important consideration in the processing sepn process.Usually, the raffinate stream that is rich in dextrose is circulated to the isomerization column system, this dextrose charging further is converted into 42% HFCS.Can cycle through separator to keep a high solids content and to reduce the use of water with containing dextrose and fructose and fructose content that the contain raffinate stream higher than the fructose content of charging.The raffinate stream that is rich in oligosaccharides can be circulated to the saccharification system.

Since water is as the elution medium, it has very big influence to the whole evaporation load of system.Very low solids concentration has increased the danger of microbial contamination in system.Therefore, the most important design variable of arranging whole process economy is the yield that improves solids under acceptable purity condition to greatest extent, and the diluting effect with the eluant resin is reduced to minimum simultaneously.In order to obtain the service efficiency that best yield must improve charging and water to greatest extent.Yield is important to reducing new isomerized expense.

Comprise circulating technology in order to reach the spendable means of these targets, make resin mutually balanced more and in pillar, increase a plurality of inlet points and exit point with distribution more suitable in the packed column.These methods can be used for increasing purity and yield.

In the intermittent type fractionating system, a little tangible increase of the charging purity of fractional column that is to say, higher fructose content has caused a large amount of raisings of producing owing to increased yield under given product purity.In actual production, this may be interpreted as the ratio that improves the sugared volume of sending in each loop cycle unit volume resin to greatest extent, reduce the ratio of the required water column of each loop cycle unit volume resin to greatest extent, and carry out fluid distribution carefully pillar.

Solid phase fructose product

Many methods of crystal diabetin are known.For example, can prepare crystal diabetin by add raw spirit in syrup, this syrup gets (people such as Bates, Natl.Bur.Std.Circ.C440,399,1942) from the acid hydrolysis synanthrin.At United States Patent (USP) 2,354,664 have described from dextrose and have prepared fructose, United States Patent (USP) 2,729, and 587 have described by enzymatic conversion and have prepared fructose from sucrose.

Fructose forms orthogonal disphenoid prism in alcohol, this prism is in approximately 103-105 ℃ of decomposition.Also know semihydrate and dihydrochloride dihydrate crystal form, but preferably avoid forming these types because they than anhydrous form more moisture absorption and fusing point near room temperature.These character make these crystallized form intractable of fructose.

Prepare solvent crystallization fructose (SCF) by a kind of method, organic solvent in the method, for example Denatured alcohol mixes with high fructose content materials flow (95%dsb).Crystallization when this logistics is cooled off when it forms purified crystal diabetin.Product centrifugation from mother liquor is come out.Desolventizing is also dry.

United States Patent (USP) 4,199,374 have described the method for a kind of SFC of preparation.Fructose crystallizes out from the ethanolic soln of VEFCS.Microlite inoculation solution with fructose or glucose.By filtering, centrifugation or other means are collected crystal.Clean these crystal and drying under vacuum with alcohol then.In this method, must carefully control pure and mild syrupy water content to obtain free-pouring thin fructose crystals.

Can also produce a kind of exsiccant fructose sweeting agent (DFS) simply.In the DFS. method, the logistics of the high fructose content that will obtain from fractionation is sieved in the classifier that comprises sieve and shredder then at the rotatory drier inner drying.United States Patent (USP) 4,517,021 has described granular, the hemicrystalline a kind of solid fructose of preparation, and this fructose contains the water that is less than about 2%wt.This patent disclosure the product of about 60wt% be crystal diabetin, being less than 35wt% is amorphous fructose.Using rotary dryer, is 50-80 ℃ air with starting temperature.Part solid fructose product can be recycled as crystallisation initiator.

A unfavorable factor of DFS method is that this product can not be called pure fructose, because it is full sugar product, does not satisfy food, and pharmaceutical chemicals, pharmacopeia are to the regulation of " fructose ".And it is not a holocrystalline, and easier moisture absorption is therefore more difficult than crystal diabetin under wet condition.

Also can use aqueous methods to produce crystal diabetin.Typical water-containing crystal fructose method is from the incoming flow of high fructose content, make its cooling in case from solution crystal diabetin.Many data have been described such method.

At United States Patent (USP) 3,513, in 023, obtaining crystalline from the aqueous solution (minimum 95%ds) of fructose does not have Fruit candy.The PH of solution must be at 3.5-8.0.Concentrating fructose soln under vacuum is 2-5% up to water content.This solution is cooled to 60-85 ℃, with crystal diabetin inoculation, high degree of agitation when temperature remains on 60-85 ℃.The patentee points out, slowly the cooling back produces ingot, can break or grind this ingot into pieces, and subsequent drying produces thickness not, free-pouring, very thin crystalline powder.This method of it is said avoids forming glassy product, general this product that produces when such fructose soln is concentrated under vacuum and allows to cool off in due form.

At United States Patent (USP) 3,883, in 365, be the aqueous solution crystal diabetin of fructose from the fructose/glucose sugar and the 90-99% (dsb) of 90% dry-matter.Saturated this solution (58-65 ℃).By the fructose crystals crystal diabetin from solution that adds even size.Reduce to minimum by keeping the suitable weak point of the distance of crystal seed between mutually and keeping degree of supersaturation new crystalline to be formed at 1.1.-1.2.When carrying out crystallization, increase the volume of solution continuously or step by step.The best PH of fructose soln is 5.0.It is reported that the crystalline average mean crystal size that obtains like this is the 200-600 micron.With centrifugal method isolation of crystalline from this solution.

United States Patent (USP) 3,928,062 disclose by the inoculation solution obtain anhydrous fructose crystals, this solution contains the full sugar that comprises 88-99% fructose of 83-95.5% (butt).By cooling solution or finish crystallization simply under atmospheric pressure by vapourisation under reduced pressure water.By in certain fructose concentration and temperature range, finishing the formation that semihydrate and dihydrate have been avoided in crystallization.This scope is in the supersaturation zone that is lower than the point that hemihydrate begins to crystallize out.It is said and after first crystallization, can repeatedly use this mother liquor to come another batch of crystallization crystal in the same manner without any handling.Use a kind of massecuite of form realize crystal seed as going into, prepared beforehand is good in the fructose soln by crystal is suspended in for this massecuite.

At United States Patent (USP) 4,199, in 373, by with 2-15wt% levulose seed crystal inoculation fructose syrups (88-96%dsb) and allow the syrup of inoculation to be lower than to leave standstill under the about 10-32 of 70% temperature ℃ to produce crystal diabetin in relative humidity.Crystallization needs 2-72 hour.The crystallized product that obtains by this method is big sheet.

United States Patent (USP) 4,164,429 have described a kind of method and apparatus of production crystalline seed.Adopt a series of centrifugation to select kind of a crystalline substance from the solution of inoculation, this kind crystalline substance falls in the predetermined size range.

The crystallization cooling curve

Cooling off saturated or oversaturated solution comes crystallization that yes is known from its material that comes.

We know that also saturated the or supersaturated solution of naturally cooling often causes serious nucleus to form, and this nucleus forms the wide granularities substep that does not expect to have in a large number to crystallized product is provided.For example, at Encyclopedia of Chemical Technology Vol.7, pp.243-285 (Kirk-Othmer, Ed.John Wiley ﹠amp; Sons N.Y.3rd ed., 1979) crystalline is discussed, point out naturally cooling cooling stages caused in early days comprise that thus a large amount of nucleus forms in the supersaturation peak.This article instruction, by following a kind of cooling curve of control, the supersaturation that can keep constant basis is controlled nucleus thus and is formed within the acceptable range.Fig. 5 is the replica that is published in the cooling curve of nature in this piece works and control.

Various content of the present invention is discussed below tout court.1. production associating, multiple fructose sweeting agent

On the one hand, the present invention relates generally to the numerous sweeting agents that contain fructose of combination producing.

A. sweeting agent of production liquid phase simultaneously and crystal diabetin

In a special aspects, the present invention relates to produce crystal diabetin and the method for the liquid phase sweeting agent formed by fructose and dextrose, comprising:

Crystal diabetin production is contained the mixture of crystal diabetin and mother liquor in the aqueous solution of fructose;

Fractional crystallization fructose from mother liquor; With

Dextrose and mother liquor mix produces the liquid phase sweeting agent that contains dextrose and fructose.

During from aqueous solution production crystalline sucrose, the general practice is that crystal is taked multiple, and successive takes out the impurity in the concentrated mother liquor, and this impurity is meant molasses.These molasses are general very impure so that its only useful value of making animal fodder additives or fermentation media.U.S. Patent No. 3,928,062 instruction is reused the mother liquor that obtains from the fructose crystallization and is come the more fructose crystals of crystallization.Use the yield of the fructose crystals that general crystallization technique obtains from the crystal that once takes out lower, with with isomerization with separate maize treacle and obtain containing the relevant difficulty of crystallizer charging of high density fructose, this makes and makes Recycling Mother Solution seem very necessary by continuous taking-up fructose crystals.Yet, come combination producing crystal diabetin and liquid phase sweeting agent to allow people obtain two kinds of high-quality sweeting agents by in mother liquor, adding dextrose.This allows people to improve the yield of useful fructose as sweeting agent to greatest extent conversely, therefore proves that isomerized difficulty is justified.Yet this method is brought the loss of yield in separation really, and isolating general purpose is to remove dextrose to prepare the crystallizer charging, therefore adds dextrose toward mother liquor and has lost the enriching section that reaches by separation.

In a special embodiment of this respect of the present invention, the present invention relates to produce crystal diabetin and contain dextrose and the method for the logistics of fructose from the incoming flow that contains dextrose, comprising:

A part of dextrose is produced first dextrose that contains dextrose and fructose/fructose materials flow in the isomerization incoming flow;

First dextrose/fructose stream is divided into first incoming flow and second incoming flow;

Separate first incoming flow and produce high fructose logistics;

Fructose production in the high fructose logistics of crystallization is contained the mixture of crystal diabetin and mother liquor;

Fractional crystallization fructose from mother liquor; With

The mother liquor of at least a portion and second incoming flow mix the ratio of producing fructose and dextrose than second dextrose/fructose logistics that first dextrose/the fructose logistics is high.(be meant the logistics that contains dextrose and fructose as comprising the term " dextrose, fructose logistics " that uses in claims hereinafter.)

At a related aspect, the method that the present invention relates to produce crystal diabetin He contain the liquid phase sweeting agent of fructose comprises:

Fructose production in the crystal diabetin aqueous solution is contained the mixture of crystal diabetin and mother liquor;

Fractional crystallization fructose from mother liquor; With

The liquid phase sweeting agent that contains fructose is produced in the further crystallization that is suppressed in the mother liquor.

Remaining mother liquor is the saturated solution of fructose after the crystallization.Prior art, for example United States Patent (USP) 3,928, and 062 has instructed reusable mother liquor to come the more crystal of crystallization.In order to produce more crystal, must heat saturated mother liquor and concentrate and obtain suitable oversaturated fructose soln, be implemented in the crystallization in the mother liquor thus.Found and the more multicrystal crystallization of its realization, it would be better to and suppress further crystallization, can use mother liquor production fluid in next life phase sweeting agent like this.As noted above, mother liquor is the saturated solution of fructose.In order to prevent the precipitation of fructose crystals in processing, transportation and/or storage process, must take steps to suppress the crystallization of fructose in the mother liquor.This one side of the present invention is relevant with top a first aspect of the present invention, has avoided further crystallization.Yet this on the one hand may not need the loss of separation yield, does not need to add dextrose because suppress further crystallization, that is to say, it is the fructose purity of the mother liquor of benchmark that water dilutes simply that mother liquor is enough to suppress crystallization and can not water down with dried solids.

B. the separating for several times of high fructose content sweeting agent

At related aspect, the present invention relates to a kind of method of producing multiple fructose sweeting agent, at least a dextrose and the fructose of containing of said sweeting agent, this method comprises:

Separating the incoming flow that contains dextrose and fructose becomes a kind of raffinate that is rich in dextrose, and a kind of extracting solution of low fructose content and a kind of extracting solution of high fructose content, the extracting solution of said high fructose content are the fructose greater than about 90% (dsb); With,

The dextrose component that the extracting solution of low fructose content and the dextrose concentration (dsb) that has are higher than the extracting solution of said low fructose content is mixed production fluid in next life sweeting agent mutually.

" fructose sweeting agent " comprises any sweeting agent that contains fructose in context, no matter fructose is in solution, and dispersive, amorphous still crystalline.For example, the extracting solution production of available high fructose content contains fructose, the syrup of crystal diabetin or hypocrystalline fructose, wherein the fructose of at least a portion be amorphous solid mutually in.

The dextrose syrup of separating isomerismization promptly contains the syrup of fructose and dextrose, produces the fructose sweeting agent generally by adopting dextrose raffinate and fructose extracting solution and the remaining separated product that circulates to finish.For example, U.S. Patent No. 4,395, yet 292 point out preferred such operational condition ', by adopting two kinds of extracting solutions, a kind of concentration of fructose.(dsb) higher (promptly, the extracting solution of high fructose content), (dsb) is lower for a kind of concentration of fructose, can obtain having the fructose extracting solution of greater concn and (for example not increasing the attached collection degree of resolving the isomerization raw material and the problem that all are relevant with it than single extracting solution, the separating power that reduces because the bigger evaporation load that the elution water that increases brings and/or since increase separate the deleterious pressure decline that need bigger elution water flow velocity causes).

The extracting solution Billy who utilizes low fructose content with the narrow range of the fructose of high fructose content (promptly, the extracting solution of use low fructose content is produced crystal diabetin can be very difficult), but can use fructose raising wherein to contain the still less fructose content of the maize treacle of fructose, for example, by with isomerized maize treacle (for example, 42% fructose maize treacle) mixes the maize treacle (for example, 55% fructose maize treacle) of producing high fructose content.

In the particularly preferred embodiment in this respect, use the extracting solution of high fructose content to prepare the crystallizer charging that crystal diabetin is used.Correspondingly, on the one hand, this invention relates to the method for producing crystal diabetin and containing the liquid phase sweeting agent of dextrose and fructose, comprising:

Divide clutch to have the logistics of dextrose and fructose to become the raffinate that is rich in dextrose, the extracting solution of low fructose content and the extracting solution of high fructose content;

The aqueous solution crystal diabetin that obtains from the extracting solution of high fructose content; With

The dextrose component that the extracting solution of low fructose content and dextrose concentration (dsb) are higher than the extracting solution of low fructose content is mixed and is produced the liquid phase sweeting agent that contains dextrose and fructose.

This embodiment particularly advantageous because suitable from the aqueous solution crystal diabetin usually required fructose concentration (dsb) to such an extent as to very highly separate the dextrose/fructose incoming flow that gets from isomerization method to produce single extracting solution be unpractiaca.In other words, produce and to have enough high fructose purity, can be used as the required parsing degree of the single extract of crystallizer charging and reduce separating power and/or increase other and separate relevant difficulty, to such an extent as to such parsing is unpractiaca through regular meeting.

Adopt two kinds of extracting solutions of high fructose content and low fructose content and use separately their parents respectively the possible shortcoming of production crystallization sweeting agent and liquid phase sweeting agent be that the quantity of fructose in the extracting solution of low fructose content that can be used for improving the fructose content of isomerization maize treacle is lacked than available amount in the single fructose extracting solution with the attached collection degree of identical parsing.Therefore, the fructose total amount (dsb) that can be used as the utilization of liquid phase sweeting agent has reduced.This shortcoming improves by utilizing the mother liquor that gets from the part fructose of the extracting solution of crystallization high fructose content.In other words, in a particularly preferred embodiment, mix the mother liquor that contains fructose, the extracting solution of low fructose content and isomerized maize treacle prepare liquid phase sweeting agent (for example, 55% fructose maize treacle).II. variable supersaturation cooling curve

On the other hand, this invention relates to the method for producing crystal diabetin from the solution that contains fructose, comprising:

With initial rate of cooling, cool off said solution to the initial temperature scope;

With the medium rates lower, cool off said solution then to intermediate temperature range than initial rate; With

Last with the final speed faster than medium rates, cool off said solution to the outlet temperature scope.

Fig. 5 demonstrates the typical cooling curve that is used for crystallisation process, and curve A is the naturally cooling curve. and curve B is in order to reach the oversaturated control curve of constant basis.Fig. 4 is a variable saturated cooling curve of the present invention.The contrast of two figure demonstrates tangible difference between ordinary curve and the curve of the present invention.

Use the rate of cooling in intercooling stage slower than initial and final speed nucleus spontaneous in solution is formed and the solution that causes by heat in the degraded of fructose be reduced to bottom line especially at initial cooling stages.The minimizing that nucleus forms has caused the crystallized product that more distributes near uniform grain sizes, the minimizing of heat collapse increased the yield of fructose crystals and mother liquor and reduced the content of degraded product impurity in mother liquor, improved its utilization as the fructose source of liquid phase sweeting agent thus.III. handle the syrup of the high fructose content of purifying low-solid content by carbon

On the other hand, the present invention relates to prepare the method for spissated fructose soln, comprise

Obtain fructose concentration greater than the about dried solids concentration of 75wt% (dsb) less than 40% fructose soln;

Make said solution and the purified fructose soln of activated carbon contact preparation; With

Evaporate said purified solution to dried solids concentration greater than 40%.

With the refining said syrup of activated carbon treatment syrup generally is known, found in the presence of activated carbon, fructose syrups with high density (dsb) fructose should have formation that low relatively solids concentration reduces by product (for example, two fructose), this by product can reduce the fructose that exists in the syrup, inhibition is crystal diabetin from syrup, and/or influences syrupy or by the sensory qualities of the sweeting agent of syrup preparation.The table II demonstrated with activated carbon with the table III and contact the influence that solids concentration forms two fructose in the syrup of high fructose content (95+%dsb) in for some time.

At a related aspect, the invention still further relates to the method for producing crystal diabetin, comprising:

Separate the logistics that contains dextrose and fructose, produce the logistics that contains greater than the high fructose content of 90% (dsb) fructose;

The logistics of said high fructose content is contacted with activated carbon, produce purified fructose logistics;

Evaporate said purified fructose logistics then, produce the solution of fructose; With

The fructose of crystallization in said fructose water solution.

Contact has earlier guaranteed to contact under relatively low solid content with the order of the logistics of evaporating high fructose content subsequently to be carried out, because when from the separator column elution, the general solid content of the extracting solution of high fructose content is low.

At another related aspect, the present invention relates to produce the method for crystal diabetin, comprising:

Fructose production in the crystal diabetin solution contains crystal diabetin and the mixture of the mother liquor be made up of fructose;

Fractional crystallization fructose from mother liquor;

The fructose of the said mother liquor of at least a portion and the liquid mixing that contains water are formed the lower fructose soln of solid content (for example, be less than about 70% dried solids);

The lower fructose soln of said solid content is contacted with activated carbon; With

Evaporate the lower fructose soln of said solid content and form the higher fructose soln of solid content.

In a particularly preferred embodiment, the mother liquor that the fructose crystallization is got and liquid, aqueous (for example, tap water, tap water, carbohydrate syrup is as 42% fructose maize treacle and analogue) mix and reduce solid content, this is blended in activated carbon treatment and before being evaporated to higher solids content subsequently and carries out.Can use the solution of the higher solids content of gained in many ways, for example, as the crystallizer charging, the maize treacle sweeting agent of high fructose content or produce its production logistics, all these benefit from the advantage that reduces the solids concentration generation of mother liquor before with activated carbon treatment and evaporation subsequently discussed above.

Fig. 1 demonstrates each step of producing 42%HFCS and 55%HFCS (EFCS) from starch with ordinary method.

Fig. 2 demonstrates associating, uses the method for Starch Production crystal diabetin and EFCS.

Fig. 3 shows out the method for illustrating in greater detail in Fig. 2.

Fig. 4 is the graphic representation of the massecuite temperature of typically variable supersaturation cooling program of the present invention to the postvaccinal time.

Fig. 5 be in discontinuous crystallizer naturally cooling curve (curve A) and both temperature of constant supersaturation cooling curve (curve B) to the graphic representation of time.

An important feature of the present invention is the synergy that obtains when producing anhydrous crystal fructose (ACF) and EFCS together.The yield of the fructose crystals that obtains from the fructose massecuite is about 40-55% typically, for example is 45%.Long crystallization time can increase yield, but only is under the condition that consumes throughput.Therefore, by the fructose crystallization with not only for the ACF crystallization processes provides the fructose charging, but also can accept the amorphous fructose that obtains from ACF technology and do not have the method for the adverse consequences significant advantage of having joined together.

In some crystal diabetin production methods of prior art, the amorphous part of circulation in whole crystallisation process.This method, the problem of bringing are the by products that does not expect to have, and for example two fructose, 5-(methylol)-2-furfural (HMF) and senior carbohydrate trend increase in recycle stream gradually, because crystallization mainly selects fructose to carry out.As a result, to such an extent as to recycle stream is got by by-product contamination terribly must clear out it from system and with the loss of a large amount of fructose.

The invention solves the problem of byproducts build-up, method is that the solution phase materials (mother liquor) that stays after the fructose crystallization is incorporated in the technology of the liquid phase sweeting agent of producing high fructose content.By this way, unwanted by product does not concentrate in that part of the method for the associating of producing ACF, but removes from that system continuously.This needs of having avoided containing the fructose purge flow of uniting are kept at fructose in the product that economic worth is more arranged thus.

Referring to Fig. 1, producing 55%HFCS (EFCS) as can be seen need have a separation (fractionation) step on stream.Usually, need fractionation to prepare fructose content and be higher than about 48% syrup.For crystal diabetin, preferably contain syrup greater than 95% fructose (dsb).Although can obtain lower yield from the fructose that contains than this solution crystallization fructose that lacks, with regard to economically, this method is undesirable.

It is known providing the isolation technique of 95+% fructose logistics from the charging that contains about 42% (dsb) fructose (the typical output that obtains from the dextrose isomerization).Therefore, can obtain the ACF incoming flow from do not improve substantially or do not have the improved EFCS technology at all.Most preferably, as known in the prior art, separation system is a mimic mobile bed chromatic type.

Referring now to Fig. 2,, will the details of integrated process be described.As shown in " the main conversion/refining " that indicates in the grid, use conventional as described above enzyme method technique at first starch to be converted into dextrose.Isomerization

Isomerization steps adopts enzyme that dextrose is converted into fructose.Be fixed on enzyme on the carrier and be fixed in the pillar (isomerization post) and when using up, be replaced.An advantage of the invention is that it allows effectively to utilize the allomerase of increased number in the isomerization post.Because to the changes of seasons of EFCS (55% fructose) demand, buy the isomerization throughput that the producer that extra allomerase satisfies high demand must bear annual increasing amount, even when his EFCS production also be like this when low-level relatively.By optionally using disclosed integrated processes here, when to the demand of EFCS product when big, by arriving the EFCS production line with the logistics that distributes more high fructose content in the series of separate post (train), when the EFCS demand is hanged down, by adopt the above-mentioned logistics of major part in ACF produces, the producer can utilize the isomerization of increasing amount expeditiously.Like this, can effectively utilize the whole year in the isomerization ability that increases and invest.Separate

Be separated in to contain in a series of of resin or one group of container and carry out, this resin sequential operation separates the dextrose in the syrup incoming flow with fructose.Incoming flow and elution current are sent in this series, the product of one or more high fructose contents stream, high dextrose raffinate stream, and/or the raffinate stream of one or more high oligosaccharide content is by extraction.As shown at Fig. 3, the logistics of high dextrose content is circulated to isomerization is converted into fructose, and the logistics of high fructose content enters the ACF part of technology or mixes and produce EFCS.

Weigh separating power by the fructose percentage ratio in charging flow velocity, the product logistics and the fructose rate of recovery in the logistics.To a specific fructose content (dsb), separating power is high more, and the fructose transformation efficiency that needs in isomerization is low more.Therefore, in order to reduce the expense of allomerase composition, preferably separate continuously with the ability of maximum.

In order to obtain actual crystallizer yield from ACF technology, separated product must be the fructose more than about 90% (dsb), preferably more than the fructose of 95% (dsb).Because it is higher than the fructose of in EFCS technology 90% (dsb) of normal separation, thereby must use the special operational condition of conventional separation system, this condition can cause the separating power that reduces.These conditions are: 1) slow down the syrup feeding rate and the ratio that do not change elution water improve resolve and/or 2) increase elution water ratio and improve parsing.These operational conditions have the shortcoming that reduces product output and/or add the water that must remove subsequently, bear the expense of additional energy at least.Yet, a preferable scheme is arranged.

Will understand that as those skilled in the art when the aqueous solution that contains dextrose and fructose passed through suitable chromatographic column, two kinds of materials at least by part separately.In order to realize separating, must carry out appropriate shunting to the effluent of pillar so that separate required cut.The part of shunting typically refers to " cut "." narrow fraction " contains the effluent composition of less volume than " wide fraction ".Therefore, according to purity, make separation optimizing to special kind by taking out suitable narrow fraction.To the common compromise selection of getting narrow fraction from effluent is the whole recovery that influence selected kind unfriendly.

Found to take out suitable narrow fraction the product stream of the separation system by producing EFCS from common process, can obtain preferably 95+% (dsb) fructose logistics as the crystal diabetin part charging of disclosed technology.Particularly preferred a kind of such fractionating system has description in the U.S. Patent application of owning together (application number 861,026, the applying date 5/8/86) of John F.Rasche application, this patent application is entitled as " mimic mobile bed chromatic tripping device ".The disclosed instruction of this patent combination expressly in the present invention.

When adopting chromatographic separation equipment mentioned above in separation system of the present invention, preferred working method is that the ratio of eluant and charging is increased to about 2.0 from about 1.7.The syrup charging of preferably approximately 60%wt dry-matter, temperature remain on about 60 ℃.

The raffinate stream that obtains from separation system is used for separately the mode of extracting solution stream and pro rata distributes to be similar to.Like this can be the logistics partitioning cycle that is rich in oligosaccharides relatively to the saccharification system, deliver to independent, special-purpose saccharification system, perhaps from system, clear out.

Do not having removing or circulation oligosaccharides to the situation of saccharification system, the unique channel of discharging oligosaccharides from system is an extracting solution stream, because typical isomerization does not act on oligosaccharides.Therefore, being circulated to oligosaccharides in the raffinate stream of isomerization system does not only change and is retained in the charging by the isomerization system and turn back in the separation system.

Oligosaccharides is unwanted in extracting solution stream, because use the charging of the sort of liquid stream of at least a portion as the fructose crystallising part of technology, the crystallization of fructose is preferably finished from the solution that contains minimum other carbohydrate.Therefore similarly, oligosaccharides is unwanted in by the liquid phase sweeting agent of explained hereafter of the present invention, can remove limited amount such oligosaccharides only from system by liquid product.

An additional advantage is to have by the liquid stream that is rich in oligosaccharides is circulated to the saccharification system from separation system.Such liquid flows that dry matter content is low relatively typically, and prevailing approximately is 10%d.s., promptly contains the water of about 90%wt.Typically must be diluted before saccharification from the starch syrup that the liquefaction/dextrinization of technology partly obtains.Water in oligosaccharides liquid stream can replace the water as the starch syrup thinner of at least a portion, has preserved water thus generally and has reduced the required steam capability of system.Mix

In conventional EFCS technology, the extracting solution of the high fructose content that gets from separation and isomerized product (typically 42-48% (dsb) fructose) are mixed the required fructose content (EFCS is 55% (dsb)) that obtains final product.In integrated processes of the present invention, mix the dry-matter that contains to get from the centrifugation step of crystallization processes in addition and be approximately 83%, the about fructose of 88-92% (dsb), the mother liquor of preferred 90-92% (dsb) fructose.This brings additional handiness to technology, because can mix the charging of polishing step as EFCS to various liquid streams, mixing wherein typically ion-exchange, carbon is handled, and is evaporated to the part that 77% dry-matter is produced as the EFCS of routine then.Dotted line among Fig. 3 has been pointed out blended, and some select possibility.Certainly, the overall material balance of system is depended in the final selection of mixed solution stream.

Except regulating very a spot of hydrochloric acid or the SODA ASH LIGHT 99.2 of PH, in ACF technology, there is not chemical substance to be added in the liquid stream of high fructose content, so in ACF technology, do not produce a large amount of new trace constituents.In the evaporation step of carbon treating processes and crystallizer charging processing, can produce colour solid, HMF and two fructose.Yet, can remove these compounds by final carbon in EFCS technology and ion exchange treatment.

Because can under high dry matter content, operate most of steps of all fructose technology, suppressed microbial growth, this should no longer be main problem.As a result, the amount of acetaldehyde does not increase significantly and can reduce by final ion-exchange and last evaporation, if necessary.

The fructose charging PH of crystallizer regulates

The PH preferably approximately PH3.7 of fructose water solution that has found therefrom to obtain fructose crystals is to about PH4.3, although have opposite instruction (referring to, for example United States Patent (USP) 3,883,365).In order to reduce the formation of two fructose acid anhydrides to greatest extent, need the PH of the fructose charging of correct crystallization control device.The existence of having found two fructose acid anhydrides in crystallizer causes lower crystallizer yield, unfriendly the distribution of the fructose crystals granularity of influence formation.It is believed that the formation speed minimum of acid anhydride in the scope of PH3.7-4.3.On this scope and under acid anhydride is formed speed higher.Believe that further higher pH value is beneficial to the formation that color forms thing.

Embodiment

PH studies by as described below to the solubleness of fructose with to the influence that impurity in containing in the syrup of about 95% fructose of dried solids produces.The syrup of being studied is those representatives as the charging of the fructose crystallising part of disclosed technology.

In the sample of VEFCS (90% fructose dsb), add the syrup that crystal diabetin production contains about 95% (dsb) fructose.Subsequently with as syrup is handled being entitled as " carbon processing " disclosed grain active carbon.Therefore, with same way as this syrup is handled charging as crystallizer.

The PH of above-mentioned syrupy aliquots containig is adjusted to 3.94, is evaporated to the high solid thing at 73 ℃.2 liters of such high solid thing syrup are put in the flask that has stirring of sealing and soaked and remain in about 55 ℃ water bath with thermostatic control in temperature.This sample (" sample of PH4 ") continuously stirring in thermostatic bath is prepared second sample (about 5 hours) simultaneously.

The PH of the aliquots containig of second 95% fructose syrups is adjusted to 5.48, is evaporated to the high solid thing at 77 ℃.The evaporation of this evaporite ratio PH4 sample is finished slowlyer.Put into 2 liters of these sample crystalline substances (" sample of PH5.5 ") in flask sealing, that have stirring and soak in the water bath with thermostatic control that is placed with the PH4 sample.

Regulate after the temperature to 55.5 ℃ of water-bath, add 50 in two samples to restrain levulose seed crystals.Continuously stirring is 60 hours under constant temperature.This be disclosed here in ACF technology syrupy about crystallizer residence time.

To resultant massecuite take a sample, centrifugation, mother liquor and charging syrup sample are analyzed together.During the analytical data of gained is listed in the table below.

Table 1

Raw material reaches equilibrated

Single acid anhydride (%dsb) 0.27 0.24 nd*, 0.48 solids (% by weight) 89.79 89.13 88.90 88.86HMF (ppm dsb) 71 4.03 25.9 6.58 acetaldehyde (ppb total amount) 104 48 58 66 furfurals (ppm dsb) nd8 nd* 0.29 0.44 color (RBU unit), 14.0 39.6 50.7 163.1 solubility---7.64 7.60 (g fructose/g water) supersaturation----1.0 1.0*nd: do not detect of pH4 pH5.5 pH4 pH5.5 fructose (%dsb) 95.81 95.86 95.33 95.24 fructose (%dsb) 96.08 96.10 95.33 95.72 hydrolysis subsequently

Before the hydrolysis of sample and the difference of fructose analysis afterwards calculate single acid anhydride.Calculate the solubleness of fructose from the solid contents of fructose analysis (before the hydrolysis) and sample.Two kinds of sample solutions all crystallization go out some fructose with equilibrium establishment.

The increase of color is more much more than what find in the PH4 sample in the PH5.5 sample.More color will cause the yield of lower crystallization processes, because need repeatedly wash centrifugal cake.Yet might increase mother liquor purified needs.

Two samples demonstrate similar single acid anhydride in the process of preparation charging increases (0.27%dsb compares at PH5.5 with 0.24%dsb at PH4); Yet the result of liquid chromatography research shows at PH5.5 and has formed more DFA.

Say that briefly the PH4 sample demonstrates less colorant and forms, and demonstrates the minimizing of total acetaldehyde.Its solubleness is not different significantly with the PH5.5 sample.Therefore, as its result who hangs down color content, with regard to product yield and mother liquor quality, the PH4 charging syrup of ACF technology is better than the PH5.5 raw material.Low PH reduces to the formation of color and fructose minimum significantly and solubleness is had inappreciable influence.

As shown in FIG. 3, carry out the PH adjusting after fractionation and before the carbon processing easily.This position in technology, the viscosity of fructose soln is relatively low, therefore relatively easily reaches solution and is used for regulating the acid of PH or the thorough mixing of alkali.Many known bronsted lowry acids and bases bronsted lowries that are fit to this purpose are arranged in the prior art.Particularly preferably be with hydrochloric acid (HCl) and reduce PH, with anhydrous sodium carbonate (NaCO ₃, " SODA ASH LIGHT 99.2 ") and improve PH.Carbon is handled

Preferably before passing through evaporation concentration, handle 95+% (dsb) the fructose incoming flow of crystallization processes with carbon.The purpose that carbon is handled is to remove the crystalline impurity that disinthibites.Another purpose be remove the quality that influences mother liquor unfriendly and thereby make its impurity that can not use as the component of liquid phase sweeting agent, as colour solid, HMF, furfural and acetaldehyde.The preferred kryptol of using is finished the carbon processing, and usage quantity is approximately the 1-3% dry-matter, perhaps uses powdery carbon, and typically the consumption than kryptol is low.Preferred syrupy temperature is about 71 ℃, and syrup typically contains the 15-30%wt dry-matter, and preferably approximately 20%wt is to about 25%wt dry-matter.

Carbon is handled after separation and is carried out the most favourable before the evaporation at once.Found under low solids concentration, to carry out carbon and handled that to make the fructose loss be that the amount of two fructose is lower than 0.5%.Carry out after evaporation if carbon is handled, can expect to have fructose loss greater than 2.5%.Syrup temp should be approximately 71 ℃ (with 60 ℃ of comparisons), preventing microbial growth in the carbon adsorber, and can reduce syrupy viscosity and obtains the diffusion in carbon granule preferably.

Embodiment

The amount of two fructose that detection forms at least 95% (dsb) of different solid contents fructose water body lotion.In preceding two tests, in flask, the aqueous solution and 2.7% kryptol (in the dried solids of the kryptol of the dried solids weight of the aqueous solution) mixed and be incorporated in 71 ℃

Stirred 24 hours.In the time of 0,6,14 and 24 hour, take out two fructose that sample detection wherein contains.The results are shown in following table:

The table II

Two fructose (%dsb) are in difference

Amount in the solution of content dry-matter:

Dried solids: the 25%ds 50%ds time (hour) 0 0.25 0.47 6 0.32 0.8514 0.38 1.6224 0.78 1.94

Top data show that two fructose form faster (fast nearly 4 times) in the solution of 50% dry-matter than in the solution of 25% dry-matter.

Ensuing 4 experiments to be operated plant-scale carbon in the plug flow mode and are handled and take and design in order to simulate, and promptly allow to detect the formation of two fructose in the dynamic flow system of comparing with the static system of the flask that has stirring.

Two 12 inches glass column serial operation provides the residence time of about 20 hours syrup charging.Pillar soaks in adjustable water-bath with the coil pipe of the stainless steel tube of the weak point that is used for preheated feed.

In order to simulate counter-current flow at the carbon of plateau, at first pillar is operated to standard state and partly consumes carbon, with new second pillar of granular activated charcoal filling, promptly place about 2 inches fresh carbon then in the outlet of this pillar.

Use this device to check four different conditions; (each condition kryptol that regulate, new)

At 60 ℃ of 70% dry-matter

At 71 ℃ of 70% dry-matter

At 71 ℃ of 50% dry-matter

At 71 ℃ of 25% dry-matter

With successive charging and listed each condition 36 hours above the not cyclical operation, the quantity of two fructose in 0,6,14,24 and 36 hour pillar effluent is listed in the table below:

The table III

Two fructose quantity in the solution of different solid contents: temperature: 60 ℃ of 71 ℃ of dried solids: the 70%ds 25%ds 50%ds 70%ds time (hour) 0 0.32 0.32 0.35 0.32 6 0.83----1.614 0.26 0.92 0.95--24 0.39 0.61 1.35 1.8336 0.24 0.64 1.72 2.24

As if though the formation at 70%ds, 60 ℃ of two fructose does not have problems, lower temperature means the danger that has increased microorganism growth and higher sugar slurry viscosity.Show that in the test of 71 ℃ of two higher solids content (50% and 70%ds) content of two fructose continues to increase in large quantities in time, although the same with the time of carbon processing to being heated of adopting of all samples.If do not wish to be subjected to the constraint of any particular theory, possible explanation is by the material that carbon is removed from the aqueous solution forming of two fructose to be carried out catalysis and/or help catalysis, so this material has caused in using the process of carbon fructose to be converted into the increase of two fructose speed in the accumulation on the carbon.

Can use a strainer that stops carbon to remove any carbon granules in liquid stream to the syrup that leaves the carbon post.It is important effectively filtering, because any insolubles that enters into crystallizer will be by the centrifugal quality that enters into crystal diabetin and directly influence product.

Prepare the liquid phase sweeting agent owing to mix non crystallized fructose, carbon is handled the quality that has improved the sort of material equally.Owing to normally EFCS being carried out the carbon processing, when reaching final product, it is made with extra care by twice carbon processing from the centrifugal mother liquor that obtains in last (promptly mixing the back) near technological process.Crystallizer charging vaporizer

Crystalline power is that syrup by the cooling high fructose content is to the supersaturation effect of the point of the temperature of saturation that is lower than it.The saturation curve of fructose (concentration is to temperature of saturation) is very steep.In order to reach the scope of theoretical crystallizer yield at 40-55%, 40-48% for example, fructose charging syrup needs about 7-13 ℃ cooling, for example 8 ℃ cooling.

In evaporation step, remove heavy syrup that point that extremely fructose will crystallize out from solution when it cools off that anhydrates from the charging syrup.The vaporizer preferred design becomes syrupy pyrolytic damage minimum and operates concentrated solution with this understanding.The mode of preferable generation evaporation is a two-step approach.At first the charging syrup is concentrated in the 6-passage tube-type down-flow evaporator with multiple-effect and machinery recompression.About 95+% of 20% to about 25wt% (dsb) fructose liquid stream that obtains from the carbon treatment step is approximately 88 ℃ in temperature, and the about 3.7-of PH about 4.3 delivers in the vaporizer.This step output be the syrup that contains the about 65wt% dry-matter of about 55%-.

In second evaporation step, the output object of the first step to be delivered to disc type rise in the film single-effect evaporator, this vaporizer is approximately being operated under the about 24 inch Hg vacuum of 23-.The output object in second step is about 79 ℃ of about 74-, contains the syrup of about 88-90% (wt) dry-matter.Vaporizer is operated under about 26 inch Hg vacuum, and the product temperature is approximately about 66 ℃ of 60-like this, makes the loss of fructose be reduced to minimum thus.

The main standard of crystallizer charging evaporator designs and operation is with the standard concentrated solution to syrupy pyrolytic damage minimum.To the syrupy disagreeable pyrolytic damage of crystallizer charging is the conversion that minimizing fructose of yield in crystallizer becomes two fructose.High temperature, high density and in vaporizer long residence time help the formation of two fructose.Because concentration is fixing basically, should select to design that the residence time in vaporizer is reduced to minimum temperature and syrup with operational condition.

Suitable vaporizer for example tube type falling-film and disc type climbing-film evaporator is known in the art.Crystallization

The crystallization of fructose can be finished in partial or continuous crystallizer.With the successive crystallization merits and demerits is arranged all in batches.Batch crystallization has very big handiness when producing different crystal size distributions, and can be more prone to and regulate apace the abnormality of technology.Yet, batch crystallization have lower crystallizer productivity (charging, discharging and in crystallizer inoculation need to).Distribute more difficult by batch grain size number that production is consistent.It needs bigger raw material and massecuite hold tank so that keep the batch cycle time to the shortest, and it need prepare independent cooling system for each crystallizer.Continuous crystallisation has opposite merits and demerits.

Crystallization can be finished with single job or multi-pass operations.Yet preferred single job.Every batch only can reach 88% yield according to estimates, and the crystallization time ratio is crystallization operation long 87% for the second time.And because the high-grade sugar of high level, from mother liquor that crystallization obtains second time thickness more, the slurry density (the crystal poundage of every pound of massecuite) of crystalline massecuite is lower for the second time.These two factor trends reduce centrifugal productivity.

Utilize mother liquor on a big chunk, to depend on the purity of mother liquor as the stock blend of liquid phase sweeting agent.Depend on multiple factor though can tolerate the accurate content of the by product that is present in the mother liquor or from mother liquor, effectively removes, must take steps to be reduced to the formation of the by product in the technology crystallising part minimum.Because fructose is mainly selected in crystallization, by product trends towards concentrating with each continuous crystallisation operation in mother liquor.Therefore, problem has been aggravated under crystalline situation repeatedly, and the amount of by product forces a upper limit often for the crystalline number of times in mother liquor, and in fact this numerical value adopt in process integration.

Found in crystallisation process repeatedly, colorant, ash content, HMF, the amount of furfural and acetaldehyde all is tending towards increasing in mother liquor.In these impurity, what colorant increased is the fastest, so the determinative of its crystallization number of times that normally can effectively adopt.

Keep the appropriate action of mother liquor purity to comprise that careful control evaporation, carbon are handled and crystallization condition for example PH, temperature and the residence time.Preferred condition is discussed in this paper is exclusively used in the paragraph of each processing step.

Before entering crystallizer, preferably the syrup charging of crystallizer is cooled to about 60 ℃.In order to produce the crystal diabetin of 40-48% theoretical yield, it should contain minimum 95% (dsb) fructose and solid content is 88.5-89.7wt% (standard is 89%d.s.b).

The inoculation of every batch of material and and crystal seed thoroughly mix.Inoculation temp (about 57 ℃) is based on the dry-matter percentage of estimating and the fructose percentage of the every batch of crystallizer.In case syrup and crystal seed thoroughly mix, should analyze every batch sample and determine actual temperature of saturation.The cooling system that should regulate crystallizer makes every batch of raw material enter the supersaturation scope of 1.00-1.05 (based on the concentration of fructose).If massecuite has been lower than this scope, do not form but nucleus also occurs, cooling should continue.

Nucleus form be a crystal from liquid, the process that generates in oversaturated solution (gel) or the saturated vapo(u)r (cloud).Crystal produces plaing on the micro-foreign matter of nucleus effect.These foreign matters are provided by impurity usually.Crystal produces in the very zonule of parent phase at first, acts in the parent phase by increase then to increase.In the methods of the invention, it is unwanted that nucleus forms, and is stranded for it causes the generation of small-crystalline particulate.And if significantly nucleus forms generation, crystal size distributes will be out of control.Because these reasons are preferably used crystal seed.

By the massecuite refrigerative speed process of crystallization control indirectly, according to the set-point that predetermined cooling curve is regulated water coolant, making the supersaturation amount is 1.0-1.35, for example 1.0-1.3.

More preferably actual measurement degree of supersaturation is so that the process of direct crystallization control.Can estimate degree of supersaturation from the initial dry-matter percentage that only provides and the dry-matter percentage of the percentile mother liquor of fructose.Utilize the supersaturation data, can determine to continue batch process or improve rate of cooling so that keep required degree of super saturation according to predetermined cooling curve.

Producing preferred method of crystalline comprises, at the about 3.7-of PH about 4.3, about 59 ℃ of the about 54-of temperature inoculates 95+% (dsb) fructose syrups that contains the about 90wt% dry-matter of about 88%-with the crystal seed of the about 250 microns about 10wt% of about 7-of the about 150-of average particle size.There is the syrup of inoculation the cooling of control that the fructose in the solution is crystallized out then.

Cooling can be finished by following: syrup is cooled to 46 ℃ with the speed of about 0.5 ℃/hr from about 59 ℃; Syrup is cooled to 30 ℃ with the speed of the about 1.5 ℃/hr of about 1.0-from 46 ℃.When the suggestion syrup temp is higher than about 46 ℃, keep the supersaturation amount to be lower than about 1.17; If syrup temp is lower than about 46 ℃, keep the supersaturation amount to be lower than about 1.25.Maximum temperature head is preferably about 10 ℃ between refrigerant and the massecuite.The generation that too high temperature head can cause nucleus to form.

Yet cooling is preferably at least three phases and is controlled with different speed.For example, during the starting stage, when syrup temp be about 59 and about 52 ℃ between the time, with about 1.0 and about 1.5 ℃/hr between speed finish cooling, the supersaturation amount remains below about 1.20.During critical stage, when syrupy temperature be about 52 and about 43 ℃ between the time, rate of cooling preferably about 0.5 is to about 1.0 ℃/hr, and keeps the supersaturation amount to be lower than about 1.17.During quick thoroughly cooling stages, when syrup temp is between about 43 ℃ and about 30 ℃ the time, speed of cooling preferably about 1.5 is to about 2.5 ℃/hr, and keeps the supersaturation amount to be lower than about 1.25.

Found that preferred method of cooling comprises that the automatic control that the continuous monitor of supersaturation amount is attached to coolant water temperature gets on.In most preferred method, data processor receives continuously about massecuite temperature, coolant water temperature and oversaturated information.Data processor uses this information to come the rate of cooling of controlled chilling water temperature and massecuite then.Data processor compile is gone up the critical temperature (T ') that program at first is cooled to massecuite to be scheduled to from its inoculation temp (Ts) with the rate of cooling of 2.5 ℃/hr.(pre-determine critical temperature from the fructose percentage and the percentile calculating of dry-matter of crystallizer charging, reach 1.17) in the oversaturated amount of this temperature.Program provides with the rate of cooling of 1 ℃/hr cooling massecuite from T ' to 46 ℃ then, is cooled to outlet temperature (typically being 30 ℃) with the rate of cooling of 1.5 ℃/hr from 46 ℃.Yet program has compensation to stop excessive nucleus to form.At first, program guarantees that under any circumstance any time massecuite of cooling period and the temperature head between the water coolant can not surpass preset temperature (being typically about-10 ℃).The second, program guarantees that under any circumstance oversaturated amount of any time during cooling can not surpass predetermined value (being generally 1.28).Above-described concrete temperature and speed can change to some extent makes one group of specific crystallization condition reach optimizing and not have the over-drastic cut-and-try work.The principal element that influences temperature is the total surface area of total dried solid contents (%ds) and crystal seed.For example, increasing dried solid contents will shift to scope more preceding in the cooling curve to critical stage, and vice versa.The total surface area that reduces crystal seed by the quantity that reduces the crystal seed that adds will enlarge critical stage, and vice versa.The kinetics of crystallization supersaturation

The function that in kinetics of crystallization, growth velocity is a concentration power--ratio of concentration in mother liquor and the concentration that exists under that temperature when balance--.

Supersaturation is that a kind of of concentration power measures.There are many modes to define supersaturation.Concerning the fructose crystallization, found with water to be that the supersaturation that the basis defines is the most reliable to the process of controlling batch operation.Therefore, supersaturation is defined as in oversaturated syrup the ratio of fructose gram number in the gram number of fructose in every gram water and the every gram water that obtains when the balance:

Ideally, should regulate the supersaturation amount that rate of cooling is in batches controlled mother liquor.Concerning the crystallization of fructose, the supersaturation scope of having found 1.0-1.30 has produced the acceptable yield of crystalline in desired particle size range.The supersaturation amount that is lower than this scope has caused the prolongation of cooling time in batches, and has caused serious nucleus to form above 1.35 supersaturation amount.

Nucleus forms

Selecting aspect the supersaturation target value balance method is arranged.Fructose seems the metastable state zone that none can be seen, and also, does not have nucleus to form the supersaturation scope that takes place therein.Existing crystalline growth always produces (nucleus formation) competition with new crystalline.Owing to increased the supersaturation amount, crystal growth rate has increased, but the speed that nucleus forms has also increased.Target is to find out the supersaturation amount that produces required crystal size in favourable economically cycling time.

It is " spray " or " quenching " formula that the top nucleus of mentioning forms.As above mentioned, the fructose crystallization nucleus that invariably accompanies forms.Quenching formula nucleus forms and can take place along with the beginning of inoculation in batches.Estimate that this causes owing to inoculation temp is low.Form if nucleus takes place, preferably massecuite is heated to remove nucleus.In case nucleus dissolves, can begin to cool down.

The preferred method of avoiding quenching formula nucleus to form is that the inoculation back keeps the supersaturation amount to be lower than 1.30.A large amount of nucleus forms will increase the viscosity of massecuite greatly, make centrifugation very difficult owing to increased clean-up time greatly.From the more difficult drying of the isolated fine crystals of massecuite and be very easy to be tending towards the cohesion.A large amount of nucleus form the product that causes unwanted little average mean crystal size.

Found that for the fructose crystallization 95 gallons every batch syrup in 100 gallons of crystallizers needs about 30 to about 80 hours refrigeration cycle, usually about 35 to 40 hours refrigeration cycle.During that stage, preferably with multiple, preferably with three kinds of different speed cool syrup.The requirement of different cooling rate is the nonlinear result of fructose crystallization.Various speed is corresponding to the growth of desired different steps during cooling.

The temperature range that initial cooling relates to is until about 49 ℃.The target cooling range is about 1 to 4 ℃/hr; Typical speed is 2 ℃/hr, and this speed makes this stage need 4 to 6 hours, preferably approximately 8 hours.In the meantime, growth almost all takes place on nucleus, and the density of slurry is set up very slowly.A large amount of thermal loads of water coolant come from the sensible heat of removing.

The batch-wise nucleus forms and can take place in this zone.Yet, to have only when inoculation temp when too low or supersaturation surpasses 1.3, this phenomenon just can take place.

In " critical stage ", growth velocity has increased by 2 to 4 times.Slurry density increases fast, and new crystal produces and be grown to serve as required size range.The competition process of crystal growth and nucleus form and have all accelerated.

Can not clearly define this regional boundary line.Best estimation is that it is between 49 ℃ and 43 ℃.In this zone, need carefully, out of hand because nucleating process is easy to occupy an leading position.By keeping the supersaturation amount (1.05-1.20) of appropriateness, found and can remain on nucleus formation in the acceptable limit.Slower rate of cooling is the optimal way of control degree of super saturation.Rate of cooling is approximately 0.5-3.0 ℃/hr in this zone, the rate of cooling of general recommendations 0.5-1.5 ℃/hr.With this speed, estimate that the time of critical stage is about 10-40 hour, preferably approximately 18-22 hour.

In some cases, high saturation capacity can not cause nucleus to form.In the sort of situation, further cooling can cause the formation of fructose semihydrate.This carbohydrate occurs like the needle-like crystal form, this is crystal formation have very high viscosity (＞800, slurry 000Cps).This slurry of centrifugation is unpractical, and even can make crystallizer transmission excess load.Semihydrate can detect during the crystal inspection of routine, and this check should be carried out at whole thorough cooling stages.

Finish critical stage, the enough height of the density of slurry does not have nucleus to form so that rate of cooling to be provided faster.At this fast thorough cooled region, coolant water temperature can descend apace.About 1-7 ℃/hr of suggestion massecuite rate of cooling, preferably approximately 1-4 ℃/hr.From 43 ℃ be cooled to final approximately 38-40 ℃ the about 3-12 of needs hour, typically 8-12 hour.Can cool off faster and do not have nucleus to form, but growth do not catch up with, behind batchwise operation, stay higher supersaturation amount.Some remaining supersaturation can be removed by massecuite being placed in mixing tank or the mixing tank for some time.

Though cooling can be finished than at the commitment of batchwise operation quickly at fast thorough cooling stages, a restriction is arranged to allowing the temperature difference between great water coolant and the sugared person of outstanding talent.Do not know the exact value of this restriction, but rate of cooling should not produce greater than the about 15 ℃ massecuite and the temperature difference between the cooling surface.Can cause the pollution of nucleus formation and cooling surface greater than 15 ℃ the temperature difference.Inoculation

Inoculation temp can obtain from the temperature of saturation of crystallizer mother liquor completely.In order to obtain this data, can adopt syrupy liquid chromatography of charging and refractive index.Use syrupy fructose percentage of charging and dry-matter percentage to calculate fructose concentration.Inoculation should for example be finished in the 1.0-1.10 scope greater than 0.96 supersaturation scope.

Most preferred crystal seed is the drying crystalline fructose of the about 100-400 micron of average mean crystal size.The charge amount of suggestion 1-20% (dsb).Charge amount depends on the required granularity in final product.Do everything possible crystal seed is added to and make crystal seed uniform distribution in crystallizer in the whole crystallizer.As above mentioned, United States Patent (USP) 4,164,429 have described the method and apparatus of production crystalline seed.

Preferably finish inoculation by at first crystal seed and fructose charging syrup being mixed the fluid soup compound that obtains joining in the crystallizer.This has the effect of regulating seed surface.The preparation crystal seed is also the formation of bubble in crystallizer reduces to minimum in when inoculation in syrup.Bubble is the position that possible nucleus forms.

Consistent inoculation mainly is to provide identical surface-area for the growth of fructose crystalline.The ratio of surface-area and volume generally reduces along with the increase of granularity, increases the granularity of crystal seed, needs the greater weight crystal seed to obtain required surface-area.

Another method is, can leave the residuum of about 5-30% in crystallizer, and preferably approximately 10-20% plays crystal seed.This step has littler labour intensity than the dry crystal seed of use, but produces the crystal size distribution of a broad, in the residuum that has been removed during centrifugal and drying step because tiny fructose is retained in.Had to subsequently it is ground bigger crystal with the standard that satisfies the final product crystal size with this method.

Preferred step is also to add hot molass except residuum.Hot molass will improve the temperature of massecuite residuum to the temperature of saturation of estimating (about 56 ℃), and the syrup of charging simultaneously is cooled to inoculation temp.Some crystal mass in this process, have probably been lost.The fact of even now, final seed density preferably should be at least in the scopes of 2-10% (dsb).The key component of this operation is the outlet temperature that is reached by charging syrup and massecuite residuum.This should produce 1.00 to 1.10 supersaturation amount.In this scope, the generation that crystal seed loss can be reduced to minimum and make nucleus seldom.

Embodiment

In the popular response device of pilot scale form, use that to contain dry-matter be that the charging syrup of 95.82% (dsb) fructose of 89.60% carries out the fructose crystallization.The crystallizer that adopts has a central shaft agitator.Reach cooling by the inner fins that is connected on the central shaft.Crystallizer almost is equipped with 102 gallons syrup.Begin to finish cooling in about 40 hours from inoculation.Yet, when this stage finishes, stay a lot of supersaturation (1.17).Regulate every batch amount by ensuing oversaturated change.

Be equipped with crystal seed by grinding crystallized product by 2A Fitzmill sieve series.Screen the material that grinds by 55 mesh sieves with by 100 mesh sieves.The mean particle size of crystal seed is 161 microns.Direct syrup in crystallizer adds dry crystal seed.

The table IV provides the actual cooling program that uses in crystallisation process.Supersaturation increases up to maximum value 1.26 in first operating process of 18 hours.It drops to approximately 1.17 then, and remains in the thorough refrigerative residuum.

Table the IV stage begin temperature end temp rate of cooling (from the hours of inoculation beginning) (℃) (℃) (°F/hr) 2.0-10.8 56 50 1.2510.8-20.8 50 44 0.9820.8-30.8 44 38 1.1130.8-40.8 38 30 1.46

Product crystalline mean particle size is 268 microns.The crystal yield that calculates according to syrupy fructose content is 46%.Separate

From mother liquor separating levulose crystalline preferred method is to carry out centrifugation with centrifugal basket drier.Find 14 " * 6 " 4 gallons massecuite can be separated in about 10-15 minute in the whizzer.Comprise during this period of time with warm water (49-93 ℃) washing 1 to 3 time, typically 2 times.Higher temperature of washing water can cause the dissolving of more fructose and the loss of yield.The washing water yield that suggestion is calculated according to the massecuite amount is 1-5%.Can use the deionization washing water.The PH of preferred washing water is in the scope of about PH3-5.

The preferred operations condition of using centrifugal basket drier to remove crystal diabetin from mother liquor comprises; About 1400 separating factor (g force), about 3 inches of the thick about 2-of cake, the moisture of cake calculate about 0.7-about 1.5% by water and product purity about more than 99.5%, more preferably about more than 99.8.The moisture of cake and purity are considered to produce the major criterion of not agglomeration and stable product.

Be preferably in washed product cake in the whizzer before removing.Preferred washing is the water with the about 1-about 1.5% that calculates according to the weight that installs to the massecuite in the whizzer, about 82 ℃ of the about 66-of water temperature.Use this method, find that typically the loss of material in the washing is about 5-about 10%.Can circulate contain dissolved fructose washing water to removing impurity and spissated again subsequently carbon treatment step.Dry

In this process, can adopt various types of moisture eliminators.Fluidized bed dryer, vibrating fluid bed dryer, disc type and spin drier all are fit to.Preferably, by the variable screw spreader of speed the wet cake metering that obtains from centrifugation is sent to the successive mixing tank.Dry-matter was metered on the wet cake up to 4: 1 with the standard ratio by choke formula handling machinery (preventing bypass air).Fully effect in mixing tank is with thorough mixing dry material and wet stock.Then the blended cake is moved on in the moisture eliminator.

Preferred concurrent drying cake is to avoid the superheated product.At first by the air in the borosilicate cleaning filtration room of estimating can 95% to remove 0.5 micron particle.Then air heating is produced 71 ℃ to the inlet at moisture eliminator when mixing with the waste gas that comes out from water cooler

The temperature of air.

Product leaves moisture eliminator and is transported in the water cooler at about 54 ℃.The product of manipulated variable not refrigeration cycle to the inlet of moisture eliminator wet centrifugal cake is handled.The variable of most critical is the moisture of the cake of coming in moisture eliminator operation.If moisture is too high, moisture eliminator will produce product spherical and cohesion.By the dry material circulation and the cake that wets than may command moisture.Although the ratio of 2: 1 the dry material circulation and the cake that wets is suitable for the crystal that forms usually, the crystal centrifugation well that produces nucleus, need 3: 1 recently avoid cohesion.

Preferably in spin drier that centrifugal biscuit is dry, the moisture of fructose crystals reduced to be lower than about 0.1wt%.Found in moisture eliminator, will form agglomerate if the moisture content of centrifugal cake surpasses about 1.5wt%.As above mention, can use the centrifugal cake moisture of dry labor thing cycle control.Suggestion does not allow the product temperature above about 60 ℃.Preferred moisture eliminator operational condition is: about 121 ℃ of the about 77-of intake air temperature, about 93 ℃ of more preferably about 77-; About 63 ℃ of the about 54-of outlet air temperature; About 57 ℃ of the about 52-of product temperature; With the product moisture content less than about 0.1%, be more preferably less than about 0.07%.Regulate

Found will produce at the lay up period fructose crystals and consolidate piece if when also hot, store fructose crystals.In dextrose and sucrose production, exist identical phenomenon.Though do not verify accurate mechanism, expection moves on to less crystalline moisture from macrocrystal and can cause further crystallization on the border.This is the temperature contrast or the result of moisture difference, and both generations are not in equilibrium state because of crystal.Experiment shows, product is dried to very low moisture (about 0.05%) and product is cooled to room temperature will produce free-pouring product.In order to balance each other with the fructose crystals that contains 0.05% moisture, 21 ℃ air must have and is lower than 50% relative humidity.

Rotary water cooler with counter-flow air proves effective to this purpose very much.With (adjusting) air cooling product crystal of refrigerated, dehumidifying to being lower than about 24 ℃, more preferably about 22 ℃.The temperature of the cooling air of suggestion inlet is lower than about 21 ℃ and relative humidity and is lower than about 40%.The residence time in water cooler should be enough to guarantee to regulate suitably crystal.The moisture content of preferred final product is less than about 0.07%.

The final product for preparing given granularity by screening and/or grinding.The extension of product is at high temperature stored and will be caused caking and color problem, even it is stored in the sack of waterproof.Should be at storehouse reservation under the humidity condition of control.Mix

In whizzer, can return the EFCS part of technological process from the isolating mother liquor of crystallized product.

Except mixing with mother liquor that stays behind the fractional crystallization fructose and dextrose, used water is diluted mother liquor simply and is produced VEFCS.

After isolating crystal diabetin, after mother liquor and dextrose or the solution that contain dextrose can be mixed, produce the liquid phase sweeting agent 55%HFCS (EFCS) for example that contains dextrose and fructose at last.As shown in Figure 3, many liquid streams that contain dextrose be transported to last, before the completion procedures and the mother liquor mixing.Consideration by material balance limits the selection of tool body fluid flow, and target is a required fructose content in final liquid phase sweeting agent.Concerning integrated process, this amount is modal will to be 55% (dsb) fructose.If enough fructose is arranged in mother liquor, even can use dextrose product stream (typically 94-96% (dsb) dextrose) mixing that obtains from saccharification to be input to the EFCS completion procedures.

Another method is to dilute mother liquor production fluid in the next life phase sweeting agent that typically contains 90-92% (dsb) fructose simply for water.If the fructose of wanting to keep mother liquor to contain is liquid state, dilution is taked in suggestion, because if solution is not diluted to the saturation point that is lower than all temperature that may run into, extra fructose might crystallize out from mother liquor.Except water, other suitable diluent comprises for example syrupy living production fluid flow of dextrose syrup, HFCS, EFCS, VEFCS and this class of the carbohydrate aqueous solution.Other is suppressed at, and fructose crystalline means comprise in the isolating mother liquor: take measures to prevent and reduce water from solution evaporation and mix and suppress the crystalline additive.

It is to produce amorphous or hemicrystalline fructose sweeting agent that the another kind of isolating mother liquor or its part is used.A kind of method of finishing this is that mother liquor is dispersed on the edible granular solids thing, and dry then this dispersion is produced the sweeting agent that contains amorphous or hypocrystalline form fructose.The preferred food grain solids that is used for this purpose is a crystal diabetin.

United States Patent (USP) 4,517,021 has described a kind of method of producing the hypocrystalline fructose composite.The instruction of this patent expressly is combined in the content disclosed by the invention for reference.Can use the moisture fructose syrups of isolating mother liquor of the present invention, can use crystal diabetin as crystallisation initiator as that method.Therefore, provide a kind of production crystal diabetin here, hypocrystalline fructose and the integrated processes that contains one or more liquid phase sweeting agents of fructose.

According to the requirement of United States Patent (USP) regulations, the description of front is used for description and interpretation specific embodiment of the present invention.Yet, many improvement in the equipment that is proposed, composition and method and to change will be possible, only otherwise deviate from scope and spirit of the present invention, this will be readily apparent to persons skilled in the art.Following claims can be interpreted as comprising all such improvement and change.

Claims (11)

1. a production contains the method for the liquid sweetener of fructose and dextrose, and said method comprises from the aqueous solution crystal diabetin that contains fructose and add dextrose in the solution of fructose dilution.

2. as desired method in claim 1, the water solution flow that wherein contains fructose and dextrose is divided into first and second liquid stream, the said first liquid flow point is flowed from the liquid of producing high fructose content, from said high fructose content liquid stream crystal diabetin, flow combination to the liquid stream and said second liquid of the high fructose content of small part fructose dilution.

3. as desired method in claim 2, the water solution flow that wherein contains fructose and dextrose produces by following method: the aqueous solution that contains dextrose is handled, the wherein a part of dextrose of isomerization obtains the described aqueous solution that contains fructose and dextrose.

4. as desired method in any one claim of claim 1 to 3, wherein produce the fructose crystallization at PH3.7-4.3.

5. as desired method in any one claim of claim 1 to 3, wherein before the fructose crystallization, the aqueous solution that contains fructose is carried out carbon handle, carry out the solvent evaporation step then.

6. as desired method in any one claim of claim 1 to 3, wherein separate the aqueous solution that contains fructose and dextrose and produce the solution that is rich in dextrose, first solution and second solution that contains fructose that contain fructose, the fructose content of said second solution that contains fructose is bigger than the fructose content of said first solution that contains fructose, wherein the solution crystallization fructose that obtains from said second solution or from second solution and wherein toward said first solution and toward dextrose concentration (dsb) than the solution that adds the fructose dilution of gained in the big aqueous solution that contains dextrose of said first solution.

7. as desired method in claim 6, wherein the aqueous solution that contains fructose and dextrose is divided into first and second liquid stream, wherein the said first liquid stream is separated with the fructose crystallization treatment and wherein the said second liquid stream is added in the solution of said first solution and said fructose dilution as the said aqueous solution that contains dextrose and go.

8. produce crystal diabetin and the method that contains the liquid phase sweeting agent of fructose for one kind, comprising:

Crystal diabetin production contains the mixture of crystal diabetin and mother liquor in the aqueous solution of fructose;

Fractional crystallization fructose from mother liquor; With

The liquid phase sweeting agent that contains fructose is produced in the further crystallization that is suppressed in the mother liquor.

9. method of producing crystal diabetin comprises:

Separate the liquid stream that contains dextrose and fructose and produce the liquid stream that contains greater than the high fructose content of 90% (dsb) fructose;

The liquid stream of said high fructose content is contacted with activated carbon produce purified fructose and flow;

Evaporate said purified fructose stream and produce fructose soln; With

Crystal diabetin in said fructose soln.

10. method of producing crystal diabetin comprises:

Crystal diabetin production is contained crystal diabetin and the mixture that contains the mother liquor of fructose in the solution of fructose;

From mother liquor fractional crystallization fructose;

The fructose of the said mother liquor of at least a portion and liquid, aqueous mixing are formed fructose soln than low-solid content;

Said fructose soln than low-solid content is contacted with activated carbon; With

Evaporate the said fructose soln that forms higher solids content than the fructose soln of low-solid content.

11. a method of producing crystal diabetin by fructose soln comprises:

Cool off said solution to an initial temperature scope with initial rate of cooling;

Cool off said solution to an intermediate temperature range with the medium rates slower then than initial rate; With

At last cool off said solution to an outlet temperature scope with the final speed faster than medium rates.

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