DE2031252A1 - Process for the crystallization of glucose, fructose or mixtures of glucose and fructose - Google Patents

Description

DR. E. WIEGAND DIPL-ING W. NiEMANM 2031252

PHONE! 55 54 7 "8000 MÖNCHEN 15, 2Ί, June 1970

TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

W. 14917/70 - Ko / Ne

Teikoku hormones Mfg. Co., Ltd. Tokyo (Japan)

and

Japan Chemurgy Co., Ltd. • Yokohama-shi (Japan)

Process for the crystallization of glucose, fructose or mixtures of glucose and fructose

The invention relates to a method for crystallization of glucose, fructose or mixtures of the two from solutions of mixed sugars, the glucose and fructose contain.

In particular, the invention relates to a method for crystallizing glucose, fructose or mixtures of the two, with a specifically combined system as the crystallization medium, namely a combination of one liquid polyhydric alcohol and a liquid monohydric alcohol Alcohols is applied.

109808/1291

Attempts to crystallize glucose, fructose, or mixtures of the two from mixed sugars that Contain glucose and fructose, for example invert sugar, using alcohols as crystallization media are already known.

For example, US Pat. No. 2,357,838 describes a process in which a mixture of a concentrated syrup of invert sugar and ethanol with a concentration of at least 90 % is stirred at a high speed of at least 200 revolutions / min. is subjected to crystallization of glucose and the resulting mother liquor is concentrated while distilling off the contents of ethanol and water, whereupon fresh ethanol is added to the system and the same stirring is applied at high speed, whereby the fructose crystallizes within a very short time . However, if the sucrose or sucrose is not completely inverted, only a fructose syrup of low purity is obtained in the process described above, as indicated in the US patent. However, in practice, it is difficult to obtain a completely converted invert sugar, that is, an invert sugar free from any impurities, on an industrial scale. Furthermore, mixing a concentrated syrup of invert sugar with ethanol in a homogeneous manner and stirring the mixture at high speed is industrially very difficult, if not practically entirely impossible. The process cannot therefore be carried out successfully on an industrial scale.

In French patent 1 563 168 is a Process described in which invert sugar is concentrated in vacuo, this in anhydrous methanol or dehydrated

109808/1291. BAD ORlGiNAL

Monoethyl ether of ethylene glycol is dissolved, for this purpose seed crystals of glucose or fructose to the subsequent Crystallization of glucose and fructose can be added or mixed seeds of glucose and fructose are added to the system to crystallize the mixture of the two will. This method can be advantageous in that crystalline glucose, fructose, or mixtures of the two can be separated from the mixed sugar solution by a simple crystallization process, however, the Amount of crystallized sugar in each individual crystallization operation generally low. To the finally achievable yield of crystalline sugar from As a result, to increase the starting material, the crystallization process has to be repeated several times. Furthermore, the process requires that the water content of the supersaturated solution during the crystallization the fructose is kept at 1% or less. This requirement brings with it the inconvenience that at the time of fructose crystallization from the mother liquor, from which the glucose has crystallized, special water removal devices to remove the Water content of the crystallization medium required and that at the time of crystallization of the sugar from the mother liquor, the mother liquor is definitely concentrated must become. ■

It has now been found that with a combination me- ■ medium from a liquid monohydric alcohol and a liquid polyhydric alcohol a distinctly superior crystallization medium for glucose and fructose is obtained, when these sugars are mixed out in crystallized form Sugars that contain the two sugars listed. simple crystallization measures should be separated

109808/129 1. _BAD original

r-τΛ that using this combination medium, the sugars can be obtained in practically pure form without the need for severe restrictions with regard to the process conditions or the above disadvantages occurring and that a higher yield is obtained in each individual crystallization operation.

According to the invention, there is a method for crystallizing glucose, fructose or mixtures of the both from solutions of mixed sugars that. Containing glucose and fructose, the crystallization of these sugars in the presence of a combination medium of a liquid polyhydric alcohol and a liquid, monohydric alcohol, which is used as a crystallization medium is carried out.

As mixed sugars containing glucose and fructose, all of the mixed sugars contained in ' generally in the form of a syrup, d. H. as an aqueous solution, such as. B. invert sugar, isomerized Sugar, compound sugar obtained by isomerization of glucose, honey and the like are used as raw materials will. These industrial compound sugars usually contain other impurities than that listed sugars, for example other sugars, amino acids, organic acids, oxidized derivatives of sugars, inorganic materials and the like. The presence of these impurities is not relevant to the present process harmful. To illustrate some of the mixed Sugar listed below:

1 09808/129 1

Invert sugar

'Glucose 4-5-50% by weight

Fructose. 45 - 50% by weight

Sucrose 0-10% by weight

Isomerized sugar (as a solid)

Glucose 50 - 90% by weight

Fructose 5- 45% by weight

Mannose 5-15% by weight

Honey (as sugar)

• Glucose 45% by weight

Fructose 50 wt.%

Other sugars 5% by weight

According to the invention, these mixed sugars that Glucose and fructose contain, in the form of supersaturated solutions in the mixed solvent from the liquid polyvalent Alcohol and the liquid monohydric alcohol used. As liquid polyhydric alcohols, for example, di- or trihydric aliphatic alcohols, such as glycerine, glycerine monoalkyl ether or alkylene glycol or polyalkylene glycols of the general formula

HO (RO) _n H,

wherein R is an alkylene group preferably having 2 to 4 carbon atoms and η is an integer not lower than 1, preferably from 1 to 4, including e.g. B. propylene glycol, Ethylene glycol, diethylene glycol and irethylene glycol belong to be used. The most preferred In the context of the invention, polyhydric alcohols are, in order of importance, propylene glycol and glycerol

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and ethylene glycol.

The ArI; of the monohydric liquid alcohol is not critical, but those having boiling points at atmospheric pressure of not higher than 200 ° C are normally preferred. Such monohydric alcohols can be aliphatic monohydric alcohols corresponding to the formula E OH, in which R is an alkyl group, for example methanol, ethanol, propanol and the like. And mono- or polyalkylene glycol monoalkyl ethers corresponding to the formula R "R ¹¹ O (RO ^ ₁ H, where R "denotes an alkyl group and R an alkylene group, for example ethylene glycol monoethyl ether, diethylene glycol monomethyl ether and the like. The monohydric alcohols which allow an even easier crystallization process and are therefore preferred are those corresponding to the general formula

^C n ^H 2n ₊ i ^0H '

where η is an integer from 1 to 5, for example Methyl alcohol, ethyl alcohol, tropyl alcohol, butanol and amyl alcohol. Also the known denatured alcohols, for example Ethanol denatured with methanol, ethanol denatured with ethyl acetate, denatured with IsoproparcL Ethanol, ethanol denatured with benzene, ethanol denatured with methyl ethyl ketone, and the like are as liquid monohydric alcohols can be used.

Particularly preferred combinations of the crystallization media according to the invention are ethanol with propylene glycol or glycerin. The obtained crystalline glucose, fructose or mixed crystals thereof using the above combination medium can advantageously to be used to food and differentiate

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hereby completely different from those as they do with methanol can be obtained as a crystallization medium.

The quantitative ratio of the mixed alcohol solvent to the sugar mixture varies depending on such factors as the ratio of the polyhydric alcohol to the monohydric alcohol in the mixed solvent, the Temperature conditions in the dissolution and crystallization operations and the type of that to be crystallized Sugar. In general, however, it is preferred that the amount of mixed alcohol solvent at the time the crystallization 0.1 to 20 times the weight of the Sugar is. For fructose, a range of 0.1 to 10 times the weight is preferred, while 0.1 to 20 times the weight Weight is suitable for the crystallization of glucose. If a crystalline mixture of the two is desired, the suitable amount of the mixed solvent is in the range of 0.1 to 10 times the weight of the sugar. A special one preferred ratio is in the range of 0.3 to 2 times the weight of the sugar in each case.

The amount of the polyhydric alcohol in the mixed alcohol solvent varies considerably depending on the ratio of the total solvent to sugar. This means that the amount of the polyhydric alcohol can be varied within a wide range without deleteriously affecting the present process. For example, the polyhydric alcohol can make up 1 to 80% of the volume of the total mixed alcohol solvent. For the purposes of the invention, it is particularly preferred to use 5 to 60 % by volume of polyhydric alcohol, based on the total alcohol solvent. In the presence of an extremely small amount of the polyhydric alcohol in the solvent system, the elution of the sugar into the alcohol

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"Dragonfly system increased remarkably, however, the -following löiiaiidlimg "complicates the system unnecessarily. DeslialO are favorably at least 1% of the total alcohol used in the form of polyhydric alcohol. If egg polyhydric alcohol is more than 80%, this will The solvent is viscous and there are difficulties in handling.

The supersaturated mixed sugar solution can contain water to such an extent that calibrate, there are no disturbances in the crystallization of the sugar, for example not more than 15% by weight of the sugar mixture and not more than 5% by weight of the total solution ". If, on the other hand, the water content of the supersaturated mixed sucking solution is decreased to below 1.5% by weight, selective crystallization will be carried out the sugar unstable and the control of the sugar crystallization rate difficult within the certain area v.drd. Generally speaking, therefore, contain the supersaturated mixed sugar solutions preferably 1.5 to 5% by weight of water at the time of crystallization «,

If the mixed sugar solution containing glucose and fructose As an aqueous solution ordered, it is also possible according to the invention to reduce the water content to the above To reduce the listed area after adding the liquid polyhydric alcohol, for example by means of a distillation under atmospheric pressure or under reduced pressure, by spray drying and the like ,, which is followed by a dissolution of the mixture obtained in the liquid monohydric alcohol, so that the supersaturated Mixed sugar solution is formed »This execution horn! is advantageous in that the water from the aqueous solution used as the starting material is the mixed sugar

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the sugar can be removed without damaging it. This procedure is of particular benefit to isolation of glucose and fructose from a mixed syrup, such as honey, Date syrup, molasses, or invert sugar, such as those in the Sugar industry obtained or obtained as a by-product, and syrup, such as isomerized sugar, applied. In this embodiment, the amount of the liquid added to the solution or the syrup of the mixed sugar can be polyhydric alcoholss the total amount or a * part of the polyhydric alcohol required to crystallize the sugar Alcohol it be. Usually it is preferred that at least 10% by weight of polyhydric alcohol be used on the starting mixed sugar. The concentration temperature is variable as a function of time, with temperatures usually in the range of JO to 120 ° C and preferably 4-0 to 100 ° C can be used.

If the mixed sugar is in the form of a crystallized In a mixture or as a melt, it can be dissolved directly in the mixed solvent with heating and forms the supersaturated solution. The solution can also be through the steps of adding water within that specified quantitative range to the solid mixed sugar, further addition of the polyhydric alcohol to this, heating of the System with the formation of a homogeneous aqueous solution of the mixed sugar and addition of the monohydric alcohol of the solution.

According to the present invention, the crystalline glucose, crystalline fructose or a crystalline Mix the two if desired from the supersaturated solution obtained in this way can be crystallized from the monovalent in the mixed solvent Alcohol and polyhydric alcohol mixed sugar "consists.

109808/1291

The crystallization temperature is not subject to any particular restriction as long as it is below the boiling point of the solvent and is sufficient that the sugar is supersaturated in the solution. The preferred crystallization temperature varies considerably depending on the kind of sugar to be crystallized. In general, however, the range from -20 to 7-0 ° C is suitable. The pH of the supersaturated solution should be at the time. point of crystallization preferably in the area of the _h . The neutral point. However, the solution should not be acidic, since this would result in disadvantageous side reactions.

According to a preferred practical embodiment the invention can be made by dissolving the mixed sugar, containing glucose and fructose, in a combination medium of liquid polyhydric alcohol and liquid monohydric alcohol solution formed the crystalline mixture of glucose and fructose under such temperature and concentration conditions sufficient to form a supersaturated solution of the mixed sugar in the presence of seed crystals or through suitable crystallization measures, like drilling, are formed.

f. The amount of mixed seed crystals of glucose and fructose to be added can vary within a considerably wide range, depending on the rate of crystallization and the size of the crystals formed, normally in the range from 0.05 to 1% by weight, based on Sugar, is preferred. In the crystallization of the mixture of glucose and fructose, the crystallization temperature is favorably between 0 and 50 ° C, in particular between 10 and ° C. If you work in this way, practically the entire

109808/1291

Sugar, excluding the dissolved sugar at the chosen one Temperature, crystallized out within, for example, 1 to 5 days. Since the dissolved sugar is usually only a fairly small amount, the yield is practically quantitative. The crystalline mixture of glucose and fructose is then passed through by the mother liquor suitable solid-liquid separators, for example Centrifugation, filtration and the like., Separated. This is done through a single crystallization operation a crystalline mixture of practically pure glucose and fructose in yields up to 90 to 98% of the sugar content of the starting mixed sugar isolated.

The mother liquor, from which the crystalline mixture of glucose and fructose was isolated and obtained, can be discarded or can be returned to the production stage of the supersaturated mixed sugar solution, which is a continuous production of the crystalline mixture of glucose and fructose allowed. In the latter embodiment can practically the entire sugar content of the starting mixed sugar finally as a crystalline mixture can be obtained from glucose and fructose. According to the optimal embodiment according to the invention, crystalline glucose and fructose, each in a practically pure form, can be used made by dissolving the mixed sugar, which contains fructose and glucose, in a combination medium of liquid polyhydric alcohol and liquid monohydric alcohol © can be separated by the following steps: (a) Adding crystalline glucose to the solution as seed crystals among those to form a supersaturated one Glucose solution sufficient temperature and concentration conditions so that the glucose from the

109808/129 1

BATH ORIGINAL

Solution crystallized out, and

(Id) adding crystalline fructose to the solution :, as seed crystals among those responsible for the formation of an Hb; saturated fructose solution sufficient temperature and concentration conditions, whereby the crystalline fructose precipitates out of the solution,; ; being the order of performing the foregoing. Steps (a) and (b) can be carried out in a desired manner. , ·

In the above practical embodiment, The order of crystallization of each sugar from the supersaturated mixed sugar solution is not important. If. z. B. crystalline glucose is added as seed crystals to the supersaturated mixed sugar solution, the glucose crystallizes out, and if seed crystals out If fructose are present, fructose crystallizes out.

According to one embodiment of the invention, seed crystals of glucose are first added to the supersaturated mixed sugar solution. The appropriate amount of the seed crystals varies considerably depending on the crystallization rate and the size of the crystals to be formed, normally an addition of 0.05 to Λ wt.% Of the seed crystals, based on the sugars' kergehalt, is preferred. The maximum crystallization of the glucose is reached after 1 to 5 days from the time of addition. Then, the formed glucose crystals are separated from the mother liquor by any suitable solid-liquid separation means such as centrifugation, filtration and the like. As a result, a glucose with a purity of at least 80% up to 95 % is isolated in excellent yields, such as 60 to 85%, of the total glucose contained in the mixed sugar. The crystallization of the glucose will

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preferably "carried out at temperatures between ⁰ and 70 ° C.

If the mother liquor from which the crystallized glucose was removed, from a supersaturated fructose solution there is, seed crystals of fructose are added to this, whereby the selective crystallization of the Yields fructose. The preferred amount of the fructose seed crystals is within the range already indicated. Since the mother liquor from which the glucose was removed occasionally still contains small amounts of glucose, which have remained unseparated, it is advantageous to either heat this crystalline glucose by heating the Mother liquor to a temperature higher than the crystallization point of glucose, i.e. H. such a temperature, at which the glucose concentration in the liquid comes to lie below the saturation point, or by filtering of the liquid or to make it disappear. <»

Although it is possible to heat the mother liquor from which the glucose has been removed, in order to obtain some of the monohydric alcohol or part thereof and of Distill water, reducing the extent of supersaturation As the fructose in the liquid rises, such a concentration process is usually within the limits of the present invention is not required.

The crystallization of the fructose is carried out by adding preferably 0.05 to 1% by weight of seed crystals Fructose running. The temperature of the system at 'the Crystallization of the fructose is preferably in the range from -20 to 50 ° 0 · Under these conditions, the Crystallization of fructose the maximum quantitative Value within 1 to 2 days. This creates a fructose

10980871291

isolated with a purity of at least 80 % up to 98 % in high yield of 40 to 85% to the total fructose in the mixed sugar. The isolation yields of glucose and fructose from the mixed sugar are of course influenced by the composition of the mixed sugar, but the purity and yield of glucose and fructose obtained according to the process according to the invention far exceed those of the conventional processes. This can be seen clearly from the following examples.

The mother liquor, from which glucose and fructose are separated and obtained can continuously follow the above crystallization treatments described either as it is or after being returned to the manufacturing stage be subjected to the supersaturated mixed sugar solution.

For example, with invert sugar, in which the quantitative ratio of fructose to glucose is 1: 1, the number of operations required for complete crystallization of glucose and fructose from this in the above-mentioned continuous procedure according to the following formula:

Number of circuits =

crystalline crystalline

GIu- +ized fructo-

cose (Ge se

weight) (weight)

According to the present process, virtually all of the glucose and fructose can ultimately be effectively removed from the Mixed sugar can be separated with as few operations as normally 1.2 to 1.9, calculated according to the above Formula, d. that is, with a very small amount of recirculation.

109808/1291

According to a further embodiment of the invention, seed crystals of fructose are first added to a supersaturated mixed sugar solution and the fructose crystallizes. The crystallization is carried out in the same way as that of the glucose, but the composition of the solution and the temperature for the crystallization of the fructose are suitably selected in the manner set out above. As a result, a fructose with a purity of 80 to 85 % can be obtained in a yield of 10 to 35%.

Seed crystals of the glucose are then added to the mother liquor remaining after the fructose has been separated off in order to bring about the crystallization of the glucose, optionally after heating to dissolve any remaining crystalline fructose or to distill off part of the monohydric alcohol or the monohydric alcohol and water . As a result, glucose with a purity of 80 to 95% and a yield of 75 to 90 % is obtained. The mother liquor remaining after the fructose and glucose have been separated off can be returned to the production stage of the supersaturated mixed sugar solution.

The optimal conditions for the successive and alternating crystallization of glucose and fructose according to the invention are, for example, the following:

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■ Hi. -

■ IC

Table I.

Crystallization

first

second

third

Starting mix
sugar 60 - 65% 40 - 45% 15 - 20% Ethanol 20 - 25 % 40 - 45 % 60 '- 70 % Propylene glycol 8th - 2U 70 20 - 25 % 25 - 30% water 1.5 - 3 % 1.5 - 4.5% 2.0 - 5.5% Temperature at
d. Kristalli
sation of
glucose 70 ° - 30 ⁰ C 60 ° - 20 ⁰ C 40 ° - O ⁰ C Temperature at
d. Kristalli
sation of
Fructose 40 ° - 10 ⁰ C 40 ° - O ⁰ C 30 ° - -20 ⁰ C

According to the present invention, under Use of a combination medium of polyhydric alcohol and monohydric alcohol glucose and fructose selectively and are alternately crystallized from the mixed sugar. Also crystalline mixtures of glucose and fructose can be obtained in high yield. Furthermore, the obtained glucoses, fructoses and crystalline mixtures the two are of a purity higher than that which could be obtained by the usual methods, and they are obtained in far higher yields.

The greatest advantage of the present method lies in the fact that in the above alternating Crystallization operation after centrifugal or filter separation in the first crystallization stage formed crystals, mother liquor remained in the second crystallization stage as it is without any Intermediate treatment can be used. In comparison

109808/1 291

to the usual procedures where the mother liquor was concentrated in each pail or troublesome water removal steps was subjected, it clearly emerges that essential superiority of the present procedure.

The successive alternating crystallization without any intermediate treatment of the mother liquor can repeated a few times, as follows from Example 1.

An important technical finding was also made found during these repeated crystallizations from the same system during numerous operations, ν Of the constituents of mixed sugar, fructose in particular is highly reactive with alcohol and shows a tendency towards the formation of fructosides as a reaction product during the operation described above with the alcohols used as solvents, even in the absence of any catalyst. Because the solubility If the fructose in the fructosides is high, the fructosides that are present often result in reductions in the Fructose yield. This by-product can easily be formed by means of thin-layer chromatography determine. If z. B. a system of ethanol and fructose is left to stand after adding a mineral acid, is the formation of ethyl fructoside in the form of two Spots with a greater E "value than that of the D-fructose observed in the thin layer chromatogram (Silica gel, solvent: ethyl acetate: isopropyl alcohol : Water = 6: 2: i). In some cases it will be accurate the same substance among those listed above Crystallization conditions formed.

To inhibit this side reaction and increase the yield To increase the sugar components, the following measures

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took recommended:

(1) If an aqueous solution of the mixed sugar, which is mixed with polyhydric alcohol, should be concentrated, the concentration temperature should "to be chosen at the lowest possible value and a treatment at high temperature" at, low Water content should only be used during the minimum possible. . Time.

_k (2) Especially in the glucose crystallization

level, an unnecessarily high temperature should be avoided

will.

The present process is also extremely valuable as a process unit in the production or refining of fructose in particular. As already stated, the fructose crystallization according to the invention can be applied to mixed sugars which contain fructose and glucose in a ratio of 1: 1. This means that in practice it becomes possible to refine a raw fructose of low purity, which was previously impossible. Typically, the fructose by crystallization W was lization from ethanol refined, but was in this case if not amounted to the glucose content of the crude to be refined fructose 10% or less, in other words, when the purity of fructose was not at least 90%, with the glucose, which is more difficult to dissolve, initially crystallizes out, making efficient refining of the fructose impossible. The glucose is normally contained in fructose as an impurity component. Therefore, if in the usual production of fructose a fructose with a purity of below 90% was obtained, it became the initial stage of the production.

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management management. In contrast, according to the present process, practically pure fructose can even be obtained from invert sugar, ie a raw fructose with 50 % purity, and even fructoses with extremely low purity can be refined according to the invention, as can be seen from the following examples.

As a second advantage, the glucose crystallization stage according to the invention serves as a more effective and simpler process for removing the glucose and consequently for enriching the fructose component for the purpose of fructose production compared to all known processes. In the previously known processes for removing glucose by crystallization, the removal efficiency for a working cycle was at most about 50% of the total glucose content. On the other hand, up to 85 % of the glucose present can be removed using one working cycle with the present method. The present method is thus very effective.

The invention thus provides a very advantageous process for fructose production when it is in combination with known processes for the production of fructose, for example the bromine oxidation process, carried out in practice will.

As far as described, each process unit is itself valuable for the purpose of fructose production. The crystallization conditions in each process unit are perfect same as "those involved in the alternating crystallization process were specified.

Those obtainable by the process according to the invention Materials Glucose, fructose and crystalline mixtures of the two can be used in the fields of food, Pharmaceuticals and as industrial materials, if necessary after, after-treatment, \ d.e washing,! Drying or re-

109 808/129 1

crystallization can be used.

The following working examples serve for further Explanation of the Invention »wherein the percentages are by weight unless otherwise specified. .

example 1

To 240 kg of a 50% aqueous solution of invert sugar was added 15 kg of propylene glycol, followed by concentration under reduced pressure. 137 kg of a concentrate with a residual water content of 2.2% were obtained, which were thoroughly mixed with 50 l of anhydrous ethanol. The water content of the system was adjusted to 1.9% and the homogeneous mixture was admixed with 500 g of crystalline glucose as seed crystals and left to stand at 40 ° C. for 48 hours with stirring. Subsequently, the system was brought into a state suitable for crystal recovery from the viewpoint of both purity and quantity. The crystals formed were separated off from the centrifuge, 38 kg of crystalline glucose with a value (a) _D = + 43 ° being obtained.

500 g of crystalline fructose were added as seed crystals to the mother liquor obtained with a water content of 2.64 % and the system was left to stand for 48 hours at 20 ° C. with stirring. As a result, the optimum state for obtaining fructose was obtained, both in terms of purity and quantity. The crystals formed were separated off on the centrifuge, 35 kg of crystalline fructose with a Vert (oc) _D = -88 ° being obtained.

Then 200 g of crystalline glucose were added to the mother liquor, from which the crystalline fructose

I 09808/129 1

had been obtained (water content 3 »15%) and the system "Let stand at 30 ° C for 48 hours with stirring, whereby the optimal state for crystallization of the glease is obtained both in terms of purity and quantity became. The crystals formed were then separated off on the centrifuge, with 12 kg of crystalline glucose with a value (a) jj - + 4-7 ° ■ were obtained.

Again 200 g of crystalline fructose were added to the remaining mother liquor (water content 3 * 66%) as seed crystals added and the system allowed to stand for 48 hours at 20 ° C with stirring. Then was the optimal one Condition for the recovery of crystalline fructose, both in terms of purity and quantity, is achieved and the formed Crystals were separated on the centrifuge. This resulted in 8.2 kg of crystalline fructose with a value (a) ^ °° = -90 ° obtained.

The remaining mother liquor with a water content of 4.16 % was left to stand and a crystal mixture of fructose and glucose formed. By centrifugal separation of the crystals formed, 15 kg of the crystal mixture of glucose and fructose with a value of p ° = -24 ° were obtained.

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Table IA

CD GO CD CD

First crystallization

Second crystallization

Third crystallization

Crystalline glucose

Vas s result d. Crystal

lization _ training

systerns r ^^ O prey

(kg)

1.90 3.15

+43

+ 47 °

Crystalline fructose

Water content
d.crystalline

lization- ^ Aussystems

2.64
3.66

(α)

-88 '

-90 ^c

(kg)

35
8.2

Crystalline mixture of glucose and fructose

Water content

d.Krist-

lization

loot systems

4.16

20 L

-24 '

Yield kg

Example 2

This example shows the production of glucose and fructose from invert sugar as the starting material, with ethylene glycol, diethylene glycol, triethylene glycol, glycerol ether and glycerol being used as polyhydric alcohols in each experiment and initially the glucose crystalline. was sated. 50 to 85 g of the polyhydric alcohols specified above were added to each 1 kg of an aqueous invert sugar solution with a concentration of 50 ° / ° to 290 ecm of anhydrous ethanol was added, followed by thorough stirring and cooling to room temperature. At room temperature, 6 g of anhydrous crystalline glucose was added to the system as seed crystals and the system was allowed to stand with slow stirring. After 48 hours, the pure glucose crystals reached the maximum amount After which it was centrifuged to separate the crystalline glucose from the mother liquor. To the liquid was added 1.2%, based on total sugar, of crystalline fructose as seed crystals, which was again allowed to stand with slow stirring the fructose crystals of high purity d as maximum, whereupon they were centrifuged off from the mother liquor. The ethanol was recovered from the liquid and the above procedures repeated. The total number of cycles required for complete recovery of the desired sugar was 1.7 to 2.2. The results are shown in Table II below.

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■ Polyvalent alcohol Ethylene
glycol Table II Triethylene monomethyl-
glycol glycerin ether Invert
sugar Glycerin
(84%) From gang mat eri al Invert
sugar Diethylene
glycol Invert
sugar 1000 Invert
sugar Source material as
50% aqueous
Solution (g) 1000 Invert
sugar 1000 50 1000 Polyvalent alcohol
(ε) 55 1000 65 570 85 Weight of the
liquid (g) 555 70 576 285 585 109 Ethanol (ecm) 270 584 290 290 OO Crystallized glucose 290 + 20 ° OO (α) § °° + 30 ° + 32 ° 76 + 39 ° Purity (%) 85 + 35 ° 86 152 91 ro
CD Amount (g) 154 87 176 61 156 ^ ~ * Yield (%) 62 182 70 63 Crystallized fructose 73 - 78 ° _(α) 20 ° -78 ° - 78 ° 91 - 80 ° Purity (%) 91 -80 ° 91 78 92 Amount (g) 112 92 112 31 77 Yield (%) 45 116 45 2.2 A 31 Number of circuits (approx.) 1.8 46 1.7 2.1 1.7

K) CD OJ

Example 3

In this example, the relationship between the yield and purity of the products glucose and fructose versus the quantitative ratio of ethanol to propylene glycol, which form the combination medium, is shown when an aqueous sugar solution of 30 % fructose and 70 % glucose and an aqueous invert sugar solution according to the invention be treated. The results are listed as Runs 1-7.

150 to 800 g of propylene glycol were added to each 1 kg of the above materials in a concentration of 50 % , and the water content of each system was reduced to 2% by weight by concentration in vacuo. 200 to 500 ecm of anhydrous ethanol was added to the concentrate, mixed thoroughly and cooled to room temperature. Then 6 g of anhydrous, crystalline glucose was added thereto as seed crystals, whereupon the mixture was left to stand with slow stirring. After 48 hours, the amount of pure glucose crystals had reached its maximum, whereupon the centrifuge was used to separate the crystalline glucose and the mother liquor. 1.2%, based on the total sugar content, of crystalline fructose were added as seed crystals to the liquid, which was again allowed to stand with slow stirring. After 4-8 hours the formation of pure fructose crystals reached the maximum. Then the system was separated into crystalline fructose and mother liquor on the centrifuge. The ethanol was recovered from the system and the above procedures repeated. The cycle numbers required for complete extraction of the sugar were between 1.5 and 1.9. The results are summarized in Table III.

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Trial no. From gangmat eri al

Starting material as a 50% aqueous solution (g).

Propylene glycol (more than 98 % 1 (g)

Weight of concentrated liquid (g) ethanol (ecm) Crystallized glucose

Z> Purity (%) 'Quantity (g) Yield (%) Crystallized fructose

Purity (%) Amount (g) Yield (%) Number of cycles (approx.)

Table III 3
Invert
sugar 4th
Invert
sugar 5
Fructose 30%
Glucose 70 # 6th
Invert
sugar 1
Invert
sugar 2
Invert
sugar 1000 1000 " 1000 1000 ^% 1000 1000 250 300 150 200 150 200 785
250 820
500 675
• 500 720
400 680
300 740
400 + 32 ° + 38 ° + 39 ° + 32 ° + 28 °. . + 42 ° 86
180
73 91
160
64 91
265
76 81
290
83 84
200
80 93
165
66 -82 ° -78 ° -68 °. - -70 ° -76 ° -80 ° 98
125
50
1.9 91
150
60
1.8. 84
78
52
1.6 85
60
46
1.7 ' 89
158
63
1.6 92 ·
130
52
1.5

Invert sugar

1000 200

725 300

+39 ^C

275

-70 ^c

1.6

TO CD CO

Cn

Example 4

In this example, an experiment is described "at

the propylene glycol was halved in as little as 10% or slightly more of the total sugar and glucose initially from the starting material that contained fructose and glucose, for example invert sugar, was crystallized out.

60 g of propylene glycol were added to each Λ kg of an aqueous invert sugar solution with a concentration of 50 % and the water content of the system was reduced to 3 % by concentration in vacuo. 290 ecm of anhydrous ethanol were added to 575 g of the concentrate, mixed thoroughly and cooled to room temperature. 6g of anhydrous crystalline glucose was added to the system as seed crystals, and the system was allowed to stand with slow stirring. After 48 hours the formation of the pure glucose crystals had reached the maximum and the crystalline glucose was separated on the centrifuge. 17 g of glucose with a value (oc) jj = + were obtained. To the remaining mother liquor, 3 g of crystalline eructose were added as seed crystals and the system was allowed to stand with slow stirring. ITacii 48 hours the pure fructose had reached the maximum amount, after which the system was separated into crystalline fructose and mother liquor on the centrifuge. The crystalline product with a value (α) ™ = -82 ° was 150 g. The ethanol was obtained from the mother liquor and the concentrate was again subjected to the above treatments. The number of cycles required for complete extraction of the sugar was about 1.7 *

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BATH ORIGINAL

Example 5

To 1 kg of an aqueous invert sugar solution with a

Concentration of 50 % , 60 g of propylene glycol were added and the water content was reduced to 2.5 % by concentration in vacuo. 280 ecm of anhydrous ethanol were added to 570 g of the concentrate, which was then mixed thoroughly and cooled to 40 ° C + 2 ° C At this temperature, 6 g of anhydrous crystalline glucose was added to the system as seed crystals, and it was kept for 72 hours

f allowed to stand slowly stirring, the formation of the

pure glucose crystals reached the maximum in the system, which were separated on the centrifuge. There were 215 g crystalline glucose with a value (α) · η = + 38 ° was obtained.

3 g of crystalline fructose were added as seed crystals to the remaining mother liquor, whereupon slowly Stirring was left to stand. The formation of the pure fructose crystals reached the maximum value after 24 hours. The fructose was separated off on the centrifuge, 183 g of crystals with a value (α) ^ ° = -82 ° being obtained became.

The ethanol was utterlauge from the remaining ⁿ

t obtained and the concentrate mixed with 1 kg of an aqueous invert sugar solution with a concentration of 50 % , whereupon 25 g of propylene glycol were added and concentrated in vacuo to a water content of 2% . 330 ecm of anhydrous ethanol were added to 660 g of the concentrate and stirred thoroughly. The mixture was then cooled to 40 ° C. - 2 ° C. and 6 g of anhydrous, crystalline glucose were added as seed crystals. It was left to stand for 72 hours with slow stirring, after which the formation of the pure glucose crystals reached the maximum value, whereupon the crystals were then separated on the centrifuge.

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the. The yield was 240 g with a value (oc) ^ = +38

3 g of crystalline were added to the remaining mother liquor Fructose was added and then the system was allowed to stand with slow stirring. After 24 hours the formation reached of the pure fructose crystals the maximum, whereupon the Crystals were separated on centrifuge. 230 g one crystalline product with a Vert (a) | j = -82 ° obtain.

The above procedures were repeated with the mixture of the starting invert sugar with the previously obtained film of recrystallization of glucose and fructose. The average yields of crystalline fructose and glucose were each about 47 to 48 % of the starting material (total amount of mixed sugar).

Example 6 -

In this example, three types of starting materials were used for the production of glucose, that is, invert sugar, a mixed sugar containing 70% glucose and 30% fructose, and a mixed sugar containing 30 % glucose and 70 % fructose.

150 to 300 g of the polyhydric alcohol listed in Table IV were added to each 1 kg of starting material with a solids content of 50 %. Then each system was concentrated in vacuo to a water content of 3 % and 200 to 500 ecm anhydrous ethanol were added to the concentrate, mixed thoroughly and cooled to tree temperature. Then 6 g of anhydrous crystalline glucose was added to the system, followed by standing with slow stirring. After 48 hours, the formation of pure glucose crystals reached the maximum and then the crystals became from the mother liquor

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separated on the centrifuge. 50 to 290 g of crystalline glucose with a value (a) _D = + 32 ° to + 4-2 ° were obtained. The experimental values and results are given in Table IV.

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OO
O
OO

Propylene
glycol Table IV Ethylene
glycol Triethylene
glycol Propylene propylene
glycol glycol 6th Propy
lengly
col Polyvalent alcohol Propylene
glycol 3 4th 5 Invert
sugar 7th Trial no. Invert
sugar 2 Fructose
30 p / c
glucose
70 % Fructose
30 %
glucose
70% Fructose
70 %
glucose
30 % Invert
sugar Source material Fructose
30%
glucose
70 %

Source material as

50% aqueous solution 1000

(G)

Amount of polyhydric alcohol (g). 60

Weight of concentrated liquid. (G) 580

Ethanol (ecm) 290

Crystallized glucose

Purity (%) 95

Quantity (g) .192

Yield (%) 77

1000 60

575 290

81

290

1000

60

1000

70

575 * 580 290 290 + 32 ° +34 81 86 285 285 81 81

1000
80

600
300

+30 ^C

84
50
33

1000 100

. 615 310

+ 38 °

188

1000 250

780 390

+ 41 °

93 160

Example 7

»
This example explains the embodiment

where first fructose from the raw material of the mixed sugar is crystallized out.

60 g of propylene glycol were added to 1 kg of an aqueous invert sugar solution with a concentration of 50% and the water content of the system is reduced to 2.% by concentration in a vacuum. To 580 g of the concentrate were 290 ecm of anhydrous ethanol added, mixed thoroughly and cooled to room temperature. Then 6 g of crystalline fructose was added to the system as seed crystals, followed by allowing it to stand with slow stirring The formation of pure fructose crystals reached its maximum for 48 hours. The fructose crystals were on the Centrifuge obtained and 85 g of a product with a Vert (oc) ^ = -70 ° obtained. From the remaining mother liquor the ethanol was recovered and the concentrate was concentrated in vacuo to 4-75 g. 240 ecm of anhydrous were added to this concentrate Ethanol was added, followed by thorough mixing and cooling. Then 5 S became crystalline glucose added to the system, which was then allowed to stand with slow stirring. After 48 hours the

™ Formation of the glucose crystals the maximum and the crystals were separated on the centrifuge. 185 g

PqO

crystalline glucose with a value (α) ί = +39 obtained.

The mother liquor, from which the ethanol was removed, was repeatedly subjected to the above procedures.

Example 8

To 1000 g of an aqueous solution of raw fructose with 60 % fructose and 40 % glucose, their sugar content

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75 % ", 150 g of propylene glycol was added. The water content was reduced to 2% by concentration in vacuo and 950 g of concentrate was obtained. To the concentrate was added 65 cc of anhydrous ethanol, followed by thorough mixing and cooling to tree temperature. The system was turned on Then left to stand for 24 hours in the presence of fructose crystals as seed crystals, after which the formation of the fructose crystals reached the maximum. 160 g of crystalline fructose were obtained with a value (a) ^ ° = -75 °. The yield was 35% based on the fructose content of the starting material.

Example 9

60 g of propylene glycol were added to 1 kg of invert sugar with a concentration of 50 %. The water content of the system was reduced to 3 % by concentration in vacuo and 580 g of concentrate was obtained. 290 cc of anhydrous ethanol was added to the concentrate, followed by thorough mixing and cooling to room temperature. Then, 6 g of crystalline fructose was added to the system as seed crystals, and the system was allowed to stand while stirring slowly. After 48 hours, the formation of pure Fri reached uctosekristallen the maximum and the crystals were separated from the mother liquor in the centrifuge.

This gave 85 g of crystals with a value (cOjj = -70. The yield was 34 %, based on the fructose content of the starting material.

Example 10

To 1 kg of an aqueous I'ructose solution with 90 % fructose and 10 % glucose, the sugar content of which was 75%, were

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140 g propylene glycol added. The system was in vacuum concentrated and 925 g of a concentrate with a water

obtained water content of 2 % . 460 cc of anhydrous ethanol was added to the concentrate, then mixed thoroughly and allowed to cool to room temperature. The system was left to stand for 24 hours in the presence of fructose crystals as seed crystals, the formation of pure fructose reaching the maximum. The crystals were separated from the mother liquor on the centrifuge, washed with about 200 ecm of anhydrous ethanol and dried. This gave 572 g of purified fructose with a value (cc) ™ = -91 °. The yield was 85 % of the fructose content of the starting material.

Example 11

I) First crystallization

80 g of propylene glycol were added to 1 kg of invert sugar with a water content of 60 % , and the system was concentrated in vacuo to obtain 495% of a concentrated syrup with a moisture content of 3%. 150 ecm of anhydrous alcohol were added to the syrup and the syrup was stirred, a homogeneous solution being obtained with cooling. After the temperature of the mixed syrup dropped to 40 ° C, 2 g of glucose crystals and 2 g of fructose crystals were added to the syrup as seed crystals, and the syrup was stirred at a speed of 8 revolutions / min at room temperature. After 70 hours the system was separated into the crystals and liquid on the centrifuge. The separated crystals were sufficiently washed with 200 ecm of anhydrous alcohol, and the crystallized mixture of glucose and. Get fructose.

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Yield of dried mixture

(crystallized glucose-fructose) 360 g

Yield, based on starting

material. 90 %

Optical rotation of the crystallizing? O °

th mixture ( ^α )

II) Second and subsequent crystallization From the liquid obtained on the centrifuge the alcohol was removed by distillation in vacuo. To 112 g of the mixture of propylene glycol and the Sugars not formed into crystals, which remained after the distillation, were mixed with 1 kg of invert sugar a water content of 60% and 10 g of propylene glycol were added and the crystallization operation is repeated in the same manner as in the first crystallization process. the Values for the second and the subsequent crystallizations for the crystallized mixture of glucose and fructose were the following:

yield

Crystallization ζ v / ei te third fourth fifth Dried mixture
(crystallized glucose
and fructose) 395 396 394- 395 Yield based on
used material 98.7 99.1 98.5 98.7 Optical rotation of the
Crystals (oc) 20 °
D. -19.0 -20.0 -19.5 -19.5

As can be seen from this experiment, the yields are on the crystallized mixture of glucose and fructose, based on the material used, practically quantitative.

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Example 12

I) First crystallization

To 1 kg of invert sugar having a water content of 60 % (moisture), 70 g of glycerin was added and the system was concentrated to 3% moisture by distillation in vacuo, whereby 4-92 g of concentrated syrup were obtained. 150 ecm of anhydrous alcohol was added to this syrup and the system was stirred to form a homogeneous solution, which was cooled and left to stand. When the temperature of the mixed system was 40 ° C, 2 g of glucose and 26 fructose were added as seed crystals, and the system was stirred at a speed of 8 revolutions / min at room temperature. After 50 hours, the separation into crystals and liquid was carried out on the centrifuge.

The resulting crystals were sufficiently washed with 200 cc of anhydrous alcohol, and this crystallized Obtained mixture of glucose and fructose with the following values.

Yielding dried mixture (crystallized glucose-fructose) 34-0 g

Yield, based on the material used 85 %

Optical rotation of the mixture ^ ⁰ ^ D ⁼ -8> 0 °

II) Second crystallization

The alcohol was removed from the liquids separated off on the centrifuge during the first crystallization by distillation in vacuo. To 132 g of the mixture of glycerine and sugar, ie non-formed crystals, ie dissolved sugar), which remained after the distillation, 1 kg of invert sugar with a moisture content of 60 % and 10 g of glycerine were added, whereupon the

10 9 8 0 8/1291

same crystallization as in the first crystallization process took place.

The mixture of the crystals of glucose-fructose obtained in the second crystallization was mixed with the following yields and properties are obtained i

Yield of dried mixture (crystallized glucose-fructose) 39Og

Yield, based on the material used, 97%

Optical rotation of the mixture (° 0i) = -18> 2 °

Example i5

To 1 kg of an invert sugar having 60 % moisture content, 120 g of propylene glycol was added and the system was concentrated in vacuo to a moisture content of 3% to obtain 50 g of concentrated syrup. 150 ecm of anhydrous alcohol were added to this syrup and the system was stirred while cooling to 40 ° C. To this system, 2 g of glucose crystals and 2 g of fructose crystals were added as seed crystals, and the system was stirred at a speed of 8 revolutions / min. After 90 hours, the separation into crystals and liquid took place on the centrifuge. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol, and after drying, the mixture of the crystals of glucose-fructose having the following values was obtained.

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Yield of the dried mixture (crystallized glucose-fructose) 259 g

Yield, based on the material used, 74%

Optical rotation of the crystals ^ ^α ^ τ \ ⁼ + 4 · »2 °

As can be seen from this experiment, the crystallized amount of fructose was reduced by the additional increase in propylene glycol, but repeated use of this mother liquor according to Example ΛΛ resulted in a quantitative yield of the mixture of glucose-fructose crystals, based on the material used.

Example 14-

To 1 kg of invert sugar having a moisture content of 60 % , 40 g of propylene glycol was added, and the system was concentrated in vacuo to a moisture content of 3%, whereby 4-60 g of the concentrated syrup was obtained. 150 ecm of anhydrous alcohol were added to this syrup concentrate and the system was stirred homogeneously at 60 to 70 ° C. At 40 ° C, 2 g of glucose crystals and 2 g of fructose crystals were added as seed crystals to this homogeneous mixture.

The mixture was then kept at 35 ° C and that System stirred for 40 hours and then at a speed of 8 revolutions / min, under slower Cooling to 20 ° C stirred.

After 70 hours since the addition of glucose and fructose, the system on the centrifuge turned into crystals and liquid separated. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol and after drying, the mixture of glucose

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Obtained fructose crystals with the following values.

Yield of dried mixture
(crystallized glucose-fructose) 378 g

Yield drawn on used
Material 95 %

Optical rotation of the mixture ( ^a )

The above mother liquor could be used repeatedly as in Example 11.

Example 15

80 g of propylene glycol were added to 1 kg of an aqueous solution of mixed sugars containing 12% glucose and 28 % fructose. The system was concentrated by vacuum distillation to a moisture content of 2% and thereby obtain 495 S concentrated syrup. 200 ecm of anhydrous alcohol were added to the syrup concentrate and the system was cooled to 40 ° C., while it was left to stand while stirring. To this end, 2 g of glucose crystals and 2 g of fructose crystals were added as seed crystals and the system was stirred at a speed of 8 revolutions per hour. After 70 hours the system was separated into crystals and liquid on the centrifuge. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol and dried.

Yield of the dried mixture
(crystallized glucose-fructose) 365 p

optical rotation of the mixture. (a) ^ = + 13.0 °

The liquid separated on the centrifuge was as in Example 11 used repeatedly.

109808/1291 'BAD ORIGINAL

Example 16

80 g of propylene glycol were added to 1 kg of an aqueous solution of granulated sugar with a content of 12% glucose and 28% fructose. The system was concentrated to a moisture content of 2 % by distillation in vacuo to obtain 4-95 g of concentrated syrup. 200 ecm of anhydrous alcohol were added to the syrup concentrate and the system was cooled to 4-0 ° C. with stirring, while it was left to stand. To this end, 2 g of glucose crystals and 2 g of fructose crystals were added as seed crystals and the system was stirred at a speed of 8 revolutions / min. After 80 hours * the system was separated into crystals and liquid on the centrifuge. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol and then dried.

Yield of the dried mixture (crystallized glucose-fructose) 520 g

PO O

Optical rotation of the mixture ( ⁰ ^ D ⁼ "^

The liquid separated off on the centrifuge could again be used repeatedly as in Example 11.

Example 17

To 1 kg of an aqueous solution of mixed sugars containing 12 % glucose and 12 % fructose was added 70 g of glycerol. The system was concentrated to a moisture content of 2 % by distillation in vacuo and 4-95 g of a concentrated syrup was obtained. 200 ecm of anhydrous alcohol were added to the syrup concentrate

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sets and the system is cooled to 40 ° C with stirring and allowed to stand. For this purpose, 2 g of glucose crystals and 2 g of fructose crystals added and the mixture in a Speed of 8 revolutions / min, stirred. After 70 hours the system turned into crystals on the centrifuge and liquid separated. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol and then dried.

Yield of the dried mixture (crystallized glucose-fructose) 350 g

Optical rotation of the mixture (cc) ™ = + 11 °

The liquid separated off on the centrifuge could be used repeatedly as in Example 11.

Example 18

To 1 kg of an aqueous solution of mixed sugars containing 12 % glucose and 28% fructose was added 70 g of glycerin. The system was concentrated by distillation in vacuo and 495 g of a concentrated syrup was obtained. 200 ecm of anhydrous alcohol were added to the syrup concentrate. The system was cooled to 40 ° C. with stirring and left to stand. For this purpose, 2 g of glucose crystals and 2 g of fructose crystals were added as seed crystals and the system at a speed of 8 revolutions / min. touched. After 80 hours the system was separated into crystals and liquid on the centrifuge. The separated crystals were sufficiently washed with 200 cc of anhydrous alcohol and then dried. .

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Yield of dried mixture (crystallized glucose-fructose) 310 g *

Optical rotation of the mixture ( ^a ); n ⁼ ~ 38

The liquid separated on the centrifuge could can be used repeatedly as in Example 11.

Example 19

55 g of ethylene glycol were added to 1 kg of invert sugar with a water content of 50 % , whereupon it was concentrated in vacuo to a water content of 2.5%. This gave 565 g of concentrate. The concentrate was mixed thoroughly with 280 ecm anhydrous ethanol and cooled to room temperature. Then, 3 ½ each of crystalline glucose and crystalline eructose were added as seed crystals, and the system was allowed to stand for 72 hours with stirring until the crystallization reached the maximum. The system was then centrifuged and separated into crystals and mother liquor. The crystalline product with a value (a) p = -17 ° was 480 g, the yield based on the starting material being 96 % . The mother liquor from which the ethanol had been removed was added to 1 kg of invert sugar with a water content of 50 % . Fifteen grams of ethyl glycol was added to the loss replenishment system and again concentrated in vacuo. When the above process was repeated, a crystalline mixture of fructose and glucose was obtained in a yield of more than 99 %, based on the starting invert sugar.

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Example 20 . -

90 g of propylene glycol were added to 1 kg of an invert sugar with a water content of 50%, whereupon the mixture was concentrated in vacuo to a water content of 3 ° / ° . As a result, 610 g of the concentrated liquid was obtained. The liquid was mixed thoroughly with 120 ecm anhydrous propyl alcohol and cooled to room temperature. Then 3 g each of crystalline glucose and fructose were added to the mixture as seed crystals and then left to stand for 72 hours with stirring until the crystallization reached the maximum. The system was then separated into crystals and mother liquor on the centrifuge. This gave -400 g of a crystalline product with a value (α) ί = +9. The mother liquor, from which the propyl alcohol had been removed, was added to 1 kg of invert sugar with a water content of 50 % and to this a further 10 g of propylene glycol was added to make up for the loss * The water content of the system was again reduced by concentration in vacuo and the above Crystallization treatment carried out. In this repeated execution, practically more than 99 % of the invert sugar material used as the starting material was obtained in the form of a crystalline mixture of fructose and glucose.

Example 21

100 g of propylene glycol were added to 1 kg of an invert sugar with a water content of 50 % , whereupon it was concentrated in vacuo to a water content of 3 %. This gave 670 g of concentrate, which was then thoroughly mixed with 120 ecm of anhydrous n-butyl alcohol

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and cooled to room temperature. Then were 5 g each of crystalline glucose and crystalline Fructose was added as seed crystals and the system was left to stand for 72 hours with stirring, "until crystallization had reached the maximum. Then 420 g crystals with a value (a) ^ = + 5 ° were separated on the centrifuge. The mother liquor from which the butyl alcohol was removed became 1 kg of invert sugar with a water content of 50% were added and further 10 g of propylene glycol added to supplement the loss, whereupon the concentration in the vacuum to reduce the water content again took place.

By repeating the above processes, significantly more than 99 % of the invert sugar material used as the starting material was obtained in the form of a crystalline mixture of fructose and glucose.

Example 22

20 g of propylene glycol were added to 1 kg of invert sugar with a water content of 50 % , whereupon it was concentrated in vacuo to a water content of 5%. 520 g of the concentrated liquid obtained in this way were thoroughly mixed with 200 ecm of anhydrous methanol, cooled to room temperature and mixed with 3 g each of crystalline glucose and crystalline fructose as seed crystals. The system was left with stirring for 72 hours until crystallization reached the maximum. The separation on the centrifuge gave 3 ^ 0 g of crystalline product with a value (α) £ = + 15 °. The remaining mother liquor, from which the methanol was removed, was added to 1 kg of invert sugar with a water content of 50 % . Furthermore, 5 S propylene glycol

109808/1 291

to supplement the loss, whereupon it was again concentrated in vacuo to reduce the water content to 3%. By this repetition of the above process were more as a 99 ° / ° of serving as a starting material Invertzuckermaterials in form of a crystalline mixture of fructose and glucose significantly.

Example 23

70 g of diethylene glycol were added to 1 kg of an invert sugar with a water content of 50 % , whereupon it was concentrated in vacuo to reduce the water content to 3 %. This gave 584 g of the concentrated liquid, which was mixed thoroughly with 290 ecm of anhydrous ethanol and cooled to room temperature. Then, 3 g each of crystalline glucose and crystalline fructose was added to the system as seed crystals, followed by standing for 72 hours with stirring. The crystallization then reached its maximum and the crystals were separated from the mother liquor on the centrifuge. 485 g of crystals with a value (α) ρ = -17 ° were obtained, which corresponds to a yield of 97% of the starting material. The mother liquor, from which the ethanol was obtained, was added to 1 kg of an invert sugar with a water content of 50 %, and 18 g of diethylene glycol were added to make up for the loss. When the above procedures were repeated, substantially more than 99% was obtained in the form of a crystalline mixture of fructose and glucose.

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Example 24

65 g of iriethylene glycol were added to 1 kg of an invert sugar with a water content of 50 % , whereupon the mixture was concentrated in vacuo to a water content of 3 %. This gave 570 g of concentrated liquid, which was thoroughly mixed with 290 ecm of anhydrous ethanol, cooled to room temperature and treated with 3 g each of crystalline glucose and crystalline fructose as seed crystals. The mixture was then left to stand while stirring for 72 hours, whereupon the amount of crystallization reached the maximum, whereupon the mother liquor was separated off on the centrifuge. 455 g of crystals with a value (a) p = -15 ° were obtained, which corresponds to a yield of 91 % of the starting material. The mother liquor, from which the ethanol had been removed, was added to 1 kg of an invert sugar with a water content of 50% and 15 g3toL ethylene glycol was added to the system, whereupon it was again concentrated in vacuo to reduce the water content. By repeating the above procedures, substantially more than 99 % of the starting material was obtained in the form of a crystalline mixture of fructose and glucose.

Example 25

50 g of glycerol-oc-monomethyl ether were added to 1 kg of an invert sugar with a water content of 50%, whereupon it was concentrated in vacuo to a water content of 3%. 560 g of the concentrate obtained were then thoroughly mixed with 280 ecm of anhydrous ethanol and cooled to room temperature. Then 3 g each of crystalline glucose and fructose were added to the

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System added as seed crystals, followed by 72 hours left to stand _# was. After the crystallization had reached the maximum, the crystals were separated from the mother liquor on the centrifuge. 452 g of crystals with a value (a) β = -15 were obtained, which corresponds to a yield of 90 % of the starting material. The mother liquor, from which the ethanol had been removed, was added to 1 kg of an inverter with a water content of 50 % and 11 g of glycerol-a-monoethyl ether was added to make up for the loss, which was then again concentrated in vacuo. When the above process was repeated, significantly more than 99% of the invert sugar material used as the starting material was obtained in the form of a crystalline mixture of fructose and glucose.

Example 26

Examples 26, 27 and 28 describe experiments where the importance of the respective proportions from fructose and glucose in the starting material and the polyhydric alcohol to that from monohydric alcohol, polyhydric Alcohol and a small amount of water built-up mixed solvents were investigated.

To 110 g invert sugar with a sugar content of 90% and a water content of 10% were 100 g of propylene glycol added and mixed thoroughly. 1000 ecm of anhydrous ethanol were added to the mixture and then 1 g each of crystalline glucose and crystalline fructose was added to the system as seed crystals. The system was left to stand for 24 hours with stirring, where the crystallization reached the maximum. The crystals were separated on the centrifuge and following

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Get results:

Amount of crystals formed 7 ^ g Optical rotation of the crystals ( ⁰ ^ D yield of crystals 75%

Example 27.

To a homogeneous mixture of 110 g invert sugar with a sugar content of 90% and a water content of 10% with 10Og propylene glycol became 2000 ecm anhydrous Ethanol and 1 g each of crystalline glucose and crystalline fructose as seed crystals in the above given order were added, whereupon the mixture was stirred and left to stand for 24 hours at room temperature became. The crystallization reaches the maximum and the Crystals were deposited on the centrifuge, with the following results.

Amount of crystals formed 20 g

PqO

Optical rotation of the crystals ( ^α ) τ) ^{= + z} * -9 ° Yield of crystals 20 %

Example 28

To a homogeneous mixture of 125 g of invert sugar with a sugar content of 80 % and a water content of 20 % with 100 g of propylene glycol, 5000 ecm of anhydrous ethanol and 2 g each of crystalline glucose and crystalline fructose were added in the order given above, followed by stirring and was allowed to stand at room temperature for about 24 hours. The crystallization reached the maximum and the crystals

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-49 - ■■ 2037252

were separated on the centrifuge * with the following results received:

• Amount of crystals formed 10 g Optical rotation of the crystals (α yield of crystals 10 %

Example 29

200 g of propylene glycol were added to 1 kg of a 50% aqueous solution of invert sugar, whereupon it was concentrated in vacuo to reduce the water content to 3%. 730 g of the concentrate obtained in this way were thoroughly mixed with 170 ecm of n-butyl alcohol and cooled to barely any temperature. At this temperature, 6 g each of anhydrous crystalline glucose and crystalline fructose were added to the system as seed crystals, followed by allowing to stand with slow stirring. After 48 hours crystallization peaked and the crystals were separated on the centrifuge. .

Quantity of crystals 400 g

Optical rotation of the crystals ( ^α ) τι "~? ° Yield of the crystals 80 %

Example 30

250 g of propylene glycol were added to 1 kg of a 50% aqueous invert sugar solution, which was then concentrated in vacuo to a water content of 3%. 800 g of the concentrate obtained were mixed thoroughly with 200 ecm of Ieoamyl alcohol and cooled to room temperature.

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Then, 3 g each of anhydrous crystalline glucose and crystalline fructose were added to the system as seed crystals added, whereupon left to stand with slow stirring became. After 48 hours, crystallization reached this Maximum and the crystals were separated on the centrifuge.

Quantity of crystal parts 280 g

g Optical rotation of the crystals (a) | °° = + 22 °

Yield of crystals 56%

Example 51

For 1 kg of a 50% aqueous invert sugar solution 210 g of propylene glycol were added, whereupon the mixture was concentrated in vacuo to a water content of 3%. 750 g of the concentrate obtained were thoroughly with 175 ecm η-amyl alcohol mixed and cooled to room temperature. 3 g of anhydrous crystalline glucose were then added in each case and crystalline fructose was added to the system as seed crystals, followed by standing with gentle stirring became. After 48 hours, crystallization reached this Maximum and the crystals were separated on the centrifuge.

Quantity of crystals 300 g

Optical rotation of the crystals ( ⁰ ^ D ^{= +} ^ 5 ° yield of the crystals 60%.

Example 32

To 1 kg of a 50% aqueous solution of invert ' sugar were added to 200 g of propylene glycol, whereupon im

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Was reduced in vacuo to a water content of 3 % , 740 g of the concentrate obtained were thoroughly mixed with 150 ecm of n-amyl alcohol and cooled to 40 to 45 ° C. Then 6 g of anhydrous crystalline glucose was added to the system as seed crystals, followed by standing at that temperature with gentle stirring. After 48 hours, the formation of the pure glucose crystals reached the maximum and the crystals were separated off on the centrifuge. 170 g of a crystalline glucose with a Vert. (Cc) - = + 51 ° were obtained, which corresponds to a yield of 64%.

Example 33

200 g of propylene glycol were added to 1 kg of a 50% aqueous invert sugar solution, which was then concentrated in vacuo to a water content of 3%. 740 g of the concentrate obtained were mixed thoroughly with 220 ecm of isoamyl alcohol and cooled to 40 to 45 ° G. Then 6 g of anhydrous, crystalline glucose were added as seed crystals, which were then left to stand at the stated temperature with gentle stirring. After 48 hours, the crystallization of the pure glucose reached the maximum and the crystals were separated on the centrifuge. 170 g of glucose crystals with a Vert (cc) _D = + 51 ° were obtained, which corresponds to a yield of 64%.

Example 34

200 g of propylene glycol were added to Λ kg of a 50% aqueous invert sugar solution, whereupon the mixture was concentrated in vacuo to a water content of 3%. 735 g

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of the concentrate obtained was thoroughly mixed with 250 cc of n-butyl alcohol were mixed and cooled to 40 to 45 ° C _β Then, 6 g of anhydrous crystalline glucose was added to the system as seed crystals, to which was allowed to stand at the specified temperature with gentle stirring "After reaching 48 hours the formation of pure glucose crystals reached the maximum and the crystals were separated on the centrifuge. 160 g of crystalline glucose with a value (a) ^ = + 35 ° were obtained. The mother liquor separated off on the centrifuge was cooled to room temperature and 3 g of crystalline fructose were added as seed crystals. - After standing for 48 hours with gentle stirring, the formation of the pure fructose crystals reached the maximum and the crystals were separated on the centrifuge. 120 g of crystalline fructose with a V / ert (a) ^ = -80 ° were obtained. The mother liquor from which the n-butyl alcohol had been removed was used in repeating the above procedures.

Example 35

50 g of propylene glycol were added to 1 kg of a 50% aqueous invert sugar solution, whereupon the mixture was concentrated in vacuo to a water content of 3%. 580 g of the concentrate obtained in this way were mixed thoroughly with 200 ecm of anhydrous methanol and cooled to room temperature. Then 6 g of anhydrous, crystalline glucose were added to the system as seed crystals. After the mixture was then left to stand for 48 hours with gentle stirring, the formation of pure glucose crystals reached its maximum and the crystals were separated from the mother liquor on the centrifuge. Included

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■ - 53 -

were 163 S crystalline glucose with a value (a) | °° = + 43 ° obtained.

Mother liquor was cooled to room temperature and to this 3 g of crystalline fructose were added as seed crystals, whereupon left to stand with gentle stirring became. After 48 hours, the formation of pure pruetose crystals peaked and the crystals became separated on the centrifuge. 135 g of crystalline fructose with a value (α) ί = -80 were obtained. The mother liquor from which the methanol was removed became by repeating the above Process used again.

Example 36

In this example dates were used as the starting material for fructose and glucose.

10 kg of dried edible dates from Iraq were taken heated to 90 ° C. with 40 l of water for 8 hours, then cooled to room temperature and centrifuged to remove insoluble material. To what remained Material was added to 200 grams of calcium hydroxide, followed by stirred thoroughly and allowed to stand for 3 hours. The system was centrifuged again and removes the insoluble material. The mother liquor was neutralized with sulfuric acid and continued to one acidified pH in the region of 2, which was then left to stand for about 15 hours. It was turned on the centrifuge is separated and the mother liquor is deacidified and desalinated with an ion exchange resin. The received Date sugar solution was decolorized with activated charcoal and made odorless and cleaned.

BAD ORlGINAL.

109B08712Ö I

800 g of propylene glycol were added to the refined date sugar solution, whereupon it was concentrated in vacuo to reduce the water content to 3%. 5 kg of the concentrate obtained were mixed homogeneously with 2000 ecm of anhydrous ethanol and cooled to room temperature. Then 30 g each of anhydrous, crystalline glucose and crystalline fructose were added to the system as seed crystals and the system under. left to stand with gentle stirring. After 72 hours, the crystallization reached the maximum and the crystals formed were separated off on the centrifuge.

Quantity of crystals 2100 g

Optical rotation of the crystals ( ⁰ ^ D * °

Yield of crystals: = «

of the sugar contained in the dates

example y ?

According to this example, honey is used as the starting material.

To a homogeneous mixture of 1 kg of honey (clover honey) and 3 l of water, sulfuric acid was added to adjust the pH to 1 to 2 was added and the system was left to stand at room temperature for 15 hours. Then became the sulfuric acid is neutralized with calcium hydroxide and the pH is increased to around 10. Then the system became centrifuged to remove the insoluble material and dealkalized the mother liquor with an ion exchange resin and desalted, followed by refining with activated carbon by decolorization and odor removal.

IO.li.öe / 129 I BAD ORIGINAL

140 g of propylene glycol were added to the refined honey, after which it was concentrated in vacuo to reduce the water content to 3%. This gave 800 g of a concentrate which was mixed homogeneously with 400 ecm of anhydrous alcohol and cooled to room temperature. Then 6 g each of anhydrous, crystalline glucose and crystalline fructose were added to the system as seed crystals, which was then allowed to stand with gentle stirring. Crystallization reached its maximum after 72 hours, after which the crystals were separated on the centrifuge.

Quantity of crystal parts 440 g

Optical rotation of the crystals ^ ^α ^ Yield of crystals =

used sugar

Example ff 8

This example describes an experiment where the crystallization of glucose and fructose crystals from the mixed solution of the starting material in a mixed solvent of polyhydric alcohol and monohydric alcohol is carried out under low temperature conditions.

125 g of propylene glycol were added to 500 g of an invert sugar with a sugar content of 50 % and a water content of 50 % , whereupon it was concentrated in vacuo to reduce the water content to 2.0%. 390 g of the concentrate obtained were thoroughly mixed with 500 ecm of anhydrous ethanol and cooled to room temperature. Thereupon 6 g became crystalline

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Glucose added as seed crystals. The system was left to stand with vigorous stirring for 60 hours, the temperature finally being lowered to 0 ° C at a uniform rate. a) ^ ⁰ = + 40 ° were obtained «

To the mother liquor, 3 g of crystalline fructose were added as seed crystals, followed by 60 hours | was left to stand and the temperature in a uniform ' Speed starting at room temperature until finally -10 ° C was lowered »After the crystallization When the fructose reached the maximum, the separation was carried out on the centrifuge. Thereby 15Ο g crystalline fructose with a value (a) ^ - -75 ° obtained.

Example 39

In this example, attempts are described "in which denatured ethanols are used as monohydric alcohol were used.

90 g of propylene glycol were added to 1 kg of a 50% aqueous invert sugar solution J) , whereupon the mixture was concentrated in vacuo to a water content of 2 %. 620 g of the concentrate obtained were thoroughly mixed with 250 ecm of an anhydrous alcohol which contained a denaturant, and 6 g of anhydrous, crystalline glucose were added as seed crystals to the system, whereupon at 4-0 to 4-5 ° C. for 48 hours was allowed to stand with gentle stirring. The formation of pure glucose crystals reached its maximum, whereupon centrifugation was carried out. 160 to 179 g of crystals with a value (a) ^ ⁰ = + 37 ° to + 45 ° were obtained _o

109808/1291

The remaining mother liquor was to about 30 bis Cooled 10 ° C and add 3 g of crystalline fructose as Seed crystals were added and the mixture was left to stand for 48 hours with gentle stirring. The formation of the pure fructose crystals reached the maximum and the system was centrifuged. 115 to 135 S became crystalline Obtain fructose with a value (cc) | j = -80 ° to -88 °. The denatured ethanol was obtained from the remaining mother liquor.

The above procedures were repeated with the addition of propylene glycol loss. The results are included in Table V.

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Table V

Modifier Methanol Benzene, toluene Ethyl methyl
ether ethyl- ^
ketone ' 3.8 Gaso
lin Kerosene ethyl
acetate Pyridine Amount of modes
fizierers (g) 8.8 2.5 2.5 8.8 250 8.0 2.5 8.8- 1.5 Anhydrous
Ethanol (ecm) 250 250 250 250 250 250 25O 250 glucose 170 O
to Yield (g) 160 • 175 175 165 ₊ 41 ° 179 175 170 172 f808 Optical rotation
_(n n2O ° ₊ 45 ° + 40 ° + 40 ° + 42 ° + 37 ° + 39 ° + 45 °. + 44 ° Fructose 130 Ό ¹
CD Yield (g) 115 135 135 130 137 135 130 125 _ *. Optical rotation

-88

-82 ° -82 ° -83 ° -84 °

-80 ° -82 °

-88

-88

Claims

1. Process for the crystallization of glucose, fructo se or mixtures thereof, characterized in that the crystallization in the presence of a combination medium from a liquid polyhydric alcohol and a liquid monohydric alcohol as a crystallization medium is carried out.

2. The method according to claim 1, characterized in that that glycerine, propylene glycol and / or ethylene glycol is used as the liquid polyhydric alcohol.

5 ·. Method according to claim 1 or 2, characterized in that that as a liquid monohydric alcohol, an alcohol according to the formula

where η is an integer from 1 "to 5 is used.

4. The method according to claim 1 to 3 »characterized in that the liquid polyhydric alcohol is used in an amount of 2 to 80 VpI.% Of the total alcohol in system i .

5. Method according to claim 1 to 4-, characterized in that that an amount of the combination medium in the range of 0.1 to 20 times the weight of the mixed sugar for Time of crystallization is applied.

6. The method according to claim Λ to 5> characterized in that the crystallization is carried out at temperatures in the range from -20 ° C to 70 ° C.

7 · The method according to claim 1 to 6, characterized in that the liquid polyhydric alcohol to a

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Claims (2)

aqueous solution of mixed sugars containing glucose and fructose is added, the system is concentrated until the water content of the solution is reduced to not more than 15% by weight, based on sugar, the mixture obtained is dissolved in a liquid monohydric alcohol and the crystallization is carried out from this solution. 8. "The method according to claim 7ν, characterized in that the concentration is carried out at a temperature not higher than 100 ° C. 9 · Method for obtaining a crystalline mixture of glucose and fructose from a mixed sugar solution, characterized in that to one by dissolving a mixed sugar containing glucose and fructose, in a combination medium of a liquid polyhydric alcohol and a liquid monohydric alcohol, a crystalline mixture of glucose and fructose is added as seed crystals under temperature and concentration conditions sufficient to form a supersaturated solution of the mixed sugar, and the crystalline mixture of glucose and fructose is formed 10. The method according to claim 9 »characterized in that the crystalline mixture of glucose and fructose is formed at temperatures in the range from 0 ° C to 50 ° C. 11. Method for obtaining crystalline fructose from a mixed sugar Solution, characterized in that crystalline fructose as seed crystals under sufficient temperature and concentration conditions to make the solution supersaturated with respect to a solution formed by dissolving a mixed sugar containing fructose and glucose in a combination medium of a liquid polyhydric alcohol and a liquid monohydric alcohol to make the fructose is added and the fructose is crystallized from the solution. 10 9 8 0 8/1291 1. 2. The method according to claim 11, characterized in that that the fructose is at a temperature in the range of ■. ■ -20 ° C to 50 ° 0 is crystallized. 13 · Process for obtaining crystalline. glucose from a mixed sugar solution, characterized in that to one by dissolving a mixed sugar, the fructose and contains glucose, in a combination medium of a liquid polyhydric alcohol and a liquid monohydric alcohol Alcohol-formed solution crystalline glucose, as seed crystals under sufficient temperature and Concentration conditions to make the solution supersaturated to make visible the glucose is added and the crystalline glucose is crystallized from the solution. 14. The method according to claim 13, characterized in that the glucose at temperatures in the range of 0 ° 0 to 70 ° C is crystallized. 15 · Process for the separation of glucose and fructose each in practically pure form from a mixed sugar, characterized in that the sugars from a through Dissolving a mixed sugar containing fructose and glucose in a combination medium of a liquid one polyhydric alcohol and a liquid monohydric alcohol I hol formed solution according to the following stages '(■ a) and (b) are separated by (a) Crystalline glucose to the solution as seed crystals under sufficient temperature and concentration conditions is added to the supersaturation of the solution with respect to the glucose and the glucose out of the solution is crystallized and '·. '- (b) Crystalline fructose to the solution as seed crystals under sufficient temperature and concentration conditions to supersaturate the solution with respect to the Fructose is added and the fructose crystallizes 109808/1291 is sated, where the order in which steps (a) are carried out and (b) can be done as desired. 10980Θ / 1291