DE2038230A1 - Process for the production of lactulose and lactobionic acid from lactose - Google Patents

Description

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Hayashibara Oompana July 31, 1970

Okayama / Japan ^{SJ / Hu}

"hao

Process for the production of lactulose and lactobionic acid from lactose

The invention relates to the production of lactulose and lactobionic acid from lactose.

It is well known that lactulose is not found in nature. Montgomery succeeded. 1930 the synthesis of lactulose by isomerization of lactose using the Lobry-ae-Bruyn E reaction. Here, after evaporation, the seaction solution is used the lactulose crystallized out by the addition of methanol and the remaining lactose is deposited as aldonic acid by oxidation with bromine «for di® ÜJechnik this is it Method ©, however, too complicated and not economically feasible, as the following additional Te rf Areas levels are required are: eretea »dae Entferaen dta. excess bro "s with eintr Silbersttlfatlöeong and .des r * etll © 3sea silver, »it • Ehwfligitr acid; swti'ttne dit IiolieEHHg tor.- IDafeteilos © durcb. Mtthanoltxtrakticni ame dtr .roatXiehn lismage -Bio iu's'bsute amounts sudtfli aar 15%.

. ■. ' . ' ■ 109810/2291 ■ ■■ ■■ '

Attempts have also been made to isomerize the lactose using sodium or ammonium hydroxide! But here too the iaaslbsttt® was only a little over 10? £ _o Finally, B “Kahn et al. won lactuose from lactose via the! -Cp-IEoIyI) -IaCtO-sylamine using the Amadori reaction, but after this one still achieved more uneconomical processes also ■ no better yield «,

The task of the present invention was zttgra & d © 3Li © g®a & © in the development of an economically applicable one in Seatrnik Process for obtaining pure I ^ ktulos © xmd reiner Lactobionic acid.

The method according to the invention is dadurcli gakenaseichnetg that man

(a) Lactose in an alkaline medium au. Jiaktalos © isom © risi © rt ₂

(b) the non-isomerized Terbried.® Laktos © by means of lactose Belbydrogenase to LaktobionäßE © osydi © rt and se if necessary. "wan of lactulose miife1S © lg basic ©»

uad / od @ r dinreh lallsa as tesi

Ba ia Sitafe (a) seki? mim di © halft © äos lafette © ® © isomerized ₉ io'fe aatiai? g®iiäS di® Ast des

derer Bedemteago WaisQff Ämserfeiag dos WE3i3teEÄs ₉ ifersr gerlngsa SBslielik © it l @ i <skf aaösglQfealligiert ?,

_ 3 -

if desired, most of the remaining lactose
by evaporation of the isomerization solution sum crystallized and then the lactose still remaining in the isomerization solution are oxidized. Then can

easy
the unaffected lactulose 'are separated off.

Experiments with different enzyme strains of the genus Pseudomonas showed that those from P. graveolens (IK) 3460). or.P. Fragi (NRBL 23) extractable enzymes most completely convert aldoses, especially lactose, into the corresponding bionic acids _? - on the other hand, surprisingly no action at all on ketoses such as lactulose. The enzymes mentioned are therefore particularly suitable for the specific oxidation of lactose in the presence of lactulose, especially since only extremely small amounts of inorganic and organic for cultivating these enzymes
Nutrients required and these easily after oxidation
are removable; The calcium compound used by di® to adjust the pH forms the Ealziumbionat, which is deposited in the subsequent precipitation stage.

Wi® stated, the lactobionic acid obtained is either as basic calcium salis easily precipitated or by absorption to a basic ion exchange resin after separating the metal ions Can be isolated as free acid by means of an ion exchange resin. A complete separation of the bionic acid is achieved by using both methods. Regardless of whether you can the bionic acid is obtained as calcium salt or as frei® acid,

... 4. 109810/2231

is the fact that Laktulos © isolates on the same side as an important economic benefit of the invention to evaluate.

Furthermore, part _{9 is} that the two reaction products with. A similar degree of unity is obtained ₅ because it is based on a commercially available lactose ₉ which is obtained from milk whey with a purity of over 99% «.

(a). The isomerization stage.,

The Lobry-de-Bruyn action, using a basic catalyst that causes the isomerization of lactose to lactulose, is the simplest method for this purpose. The isomerization ex 'takes place when strongly basic aqueous lactose solutions are heated, which contain, for example, potassium ₉ - calcium =' ₉ sodium and ammonium hydroxide or strongly basic anion storage resins. It is well known that sugars are unstable at high alkalinity, especially at high temperatures, and oxidative degradation occurs quickly. If, however, one gives a catalyst, there are a multitude of possibilities ^ which depend on the production equipment or other conditions ^ above all whether the leaction in the case of high Semperatnir-eB. - should "run over" in a short time or at a lower temperature,

While the previous Yer £ ®hx @ D. at

were dupchführung over a longer® time _s where © is comparable

109810/228 1. »-. 5

■ - 5 -

only minor degradation took place, the inventors also led. Experiments at high temperatures and short reaction times, whereby one the oxidative degradation depending on the given The amount of alkali and the temperature level. TJm To avoid contact with air and to be able to heat it for a short time, the sugar solutions flow at a constant speed cooled by a reaction tube in which it is heated and were neutralized. 20% lactose solutions were used with 1.5% Ca (OH) ρDi © results are shown in the following table:

Heating time 5 min 10 min 15 minutes 3 days 36 (1.5) ■
4-5 (4) 43 (D Heating temp. ° G Degree of isomerization (loss of degradation) in % 35
80
100 30 (1.5)

Lactose concentrations of 20 to 40% have been found suitable. Low Isomerisationstemperatüren are indeed preferable because at temperatures above 80 ⁰ C to prevent sugar losses an unusually short duration of treatment would require only a few minutes "When Eeaktion at low temperatures but would, for example, be allowed to stand 0.13% strength alkaline solutions 3 to 4 days . The trials at

10 9810/2291

high temperatures were "at an alkalinity of from 1 to and a pH of 9 to 10 is performed, - wherein the Zuckerver--" losses during brief heating about 1 to $ 2 were} although a vivid coloration occurred ₈ reaches © the Xsomeri "sationsgrad 30 up to 40 ^ (the latter was determined by the gystein-HoSCX-Garbazol method) _o The isoiaerized sugar obtained was quickly cooled and poured into a fakua container in which the reaction liquid was neutralized with v @ reL hydrochloric acid or sulfuric acid * § the calcium sulfate formed was filtered off. Sodium chloride and ammonium sulfate used in the following cultivation or in the enzymatisehen reaction farbig® leaktionsgemische wmrd @ n ced using granulated carbon © layers eatfärtto laalysen se that lactulose was formed najtesia su H-Qfa Nebea kl@in.en amounts of degradation products "; besides, unreacted lactose remained in large quantities.

h If this Bohprodukt is treated with © IAEE loBsaa.ras'te.iiseMaaE '^, we obtain a syrup ax greater than Sue @ Iekto® © ₉ which is useful as a sweetener "A © Jfcbtr®nmmg the aicht isomerized lactose through. Inskristelli8ier © a dei? © ingedampften syrup® increases your taste © | Such® syrups sometimes contain over

Instead of metal and lüB © aiiiafe.jteoxii. @ M Isis see ion exchange lifearae. as "basieefee den; in this case" aam alber- © ia © läagei? ©

108810/2291 '"-. ..". 7

_ τρ _

time and higher temperatures. Hence, this method has the following Disadvantages

1) The need to circulate the solution while avoiding contact with air in order to prevent oxidation of the air Sugar;

2) the reduction of the alkalinity of the ion exchanger by the acid formed %

3) reducing the number of reuse cycles themselves Use of comparatively heat-resistant resins.

"Amberlite EA-OO" was used as the basic resin. at one circulation at 70 ° C and a duration of over 5 h received one in a 30% lactose solution without contact with air Degree of isomerization of over $ 30 έ »

(b). The oxidizing pins.

How to separate the isomerized lactose solution is carried out stated above, according to the invention by enzymatic oxidation. Bas can either by gjcydafcion the remaining lactose to Lactobionic acid under cultivation of Pseudomonas strains Lactose-DehydrogeBase - generate on the isoiaerized solution as a source of coal «Or the isomerized lactose solutions are dehydrated enx ^ matically. The action is particularly useful from. Strains of the Pseudomonas GattuBg to 5 to 10% isomerized Laktoaelöimg with exposure and addition of a Nitrogen source, such as swollen shark extract fc, and smaller

109810/2291. ...8th

Amounts of inorganic salts. The enzyme cells obtained in the aforementioned culture brewers are 20 to 30% strength isomerized lactose solution added. In case of oxidation with ventilation, movement and avoidance of a drop in pH in the presence of basic substances such as calcium carbonate, the remaining lactose is oxidized to lactobionic acid, with a small loss of ketosis. The turnover time is' 10 to 20 h. The degree of oxidation was determined by quantitative analyzes of the amounts of calcium bionate formed.

(c). The preparation stage.

From the oxidation mixture, the calcium is first obtained by means of strongly acidic exchange resins removed. Using the acidity of the bionic acid, its isolation is then carried out Absorption on weakly basic ion exchange resins can be carried out by removing the absorbate from the exchanger with strong Dissolved alkalis and in the resulting solution of the alkali metal salts of bionic acid with strong acidic ions

pure

Exchange resins cleans ^ the bionic acid sets free. Another possibility of separation consists in precipitating the basic calcium salt of bionic acid from the concentrated solution, which is made alkaline by the slow addition of calcium hydroxide. The crystals formed are decomposed with sulfuric acid, after which first the calcium sulfate formed and then the remaining sulfate ions are removed from the solution by adding a small amount of barium salt. After removal of the remaining metal ions by a cation exchanger

1098 1 η / 2 29 1 * 9

the free bionic acid is obtained in a pure state.

Me matter liquid, from which the bionic acid as such or when calcium salt was removed, is acidic and basic Replacement resins purified to obtain pure lactulose. On the other hand, it is in the oxidation stage. (b) received raw mixture of lactulose and lactobionic acid after cleaning with activated charcoal and strongly acidic ion exchange resin too Can be used directly as an acidic sweetener as a food additive.

Although the bisaccharide lactulose as 4-0-ß-D-galactopyranosyl- ^

(B-fructose) physical properties similar to cane sugar has, its sweetness, as already mentioned, is much milder and finer, whereas that of conventional sweeteners, such as glucose, eructose, honey and corn syrup, especially cane sugar, has a certain irritating effect and is monotonous, but is not mild. High concentrations of the usual sugars cause crystallization} and they are all digestible and have essential nutritional values. Lately exists but increased demand from the pharmaceutical and cosmetic industry for sweeteners with better, more refined and lasting sweetness and corresponding taste and for indigestible food additives with no caloric value.

The following properties of lactulose are important for their use in food:

10 109810/2291 "

1. Lactulose does not give food and drinks

However, hot and undesirable sweetness such as Bokra.cker ₉ can also be used together with drill sugar in foods and beverages to weaken the pickling effect of botossueker, which gives the foods a more sophisticated and refined sweetness.

2. lactulose gives food lajad drinks a ER- ψ creased viscosity and solid products a nice shine, while glucose and viscosity Iruktose act shexabsetzend.

5. _s which are heavily sweetened with lactulose With food and drink _t yet neither crystallization nor cloudiness caused by crystallization occurs, as is the case when using Bohrsueker and glucose as a sweetener. Becomes lactulose at the same time as

If sugar or glucose is used, crystallization occurs 'This sugar prevents and increases the shelf life.

4. Lactulose has flavor and feneis.tigk © it®e: ßb.alten & e Properties that make the foods spiked with Laktnios © and drinks get a consistent taste and sweetness «

5. Because lactulose undergoes hydrolysis

Animal body is not absorbed »is it a calorie-free, but a means of giving a "body". IfaJ ^ ranks

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ac «I»

and drinks that only contain this sweetener, are to be described as calorie-free products.

The testing of the lactulose-containing products showed the following:

(1). Results of community exams in which thirty Examiner every paired comparison test with cane sugar, Repeated glucose and lactulose five times each at concentration levels of 35 »20 and 10 $, respectively, confirmed that the sweetening power of lactulose is weaker than that of cane sugar, but as strong as that of glucose, however the quality is milder and more refined than that of cane sugar. The scheme was obtained:

Cane sugar ^ * lactulose = »glucose ^> Lactose.

(2). The lactulose, which is completely soluble in mass, crystallizes very bad even at high concentrations. When adding 10% lactulose to a 70% concentrate of cane sugar and glucose is not observed to crystallize out, although solutions that only contain drilling sugar or glucose crystallize out after a short time.

(3). Test conditions! Be the comparative test Hydrolysis resistance!

- ... 12 10981 n / 2 291.

Temperature 40 ⁰ C

pH ABC

5 * 0 6.0 7 ₉ 5

Eeakti ons sub strat: '. End 1% 5 ml

0.1 M buffer solution for (A), (B) 4 ml acetate

(C) 4 ml Mcllvaine reagent enzyme solution 1 ml.

The reducing and total sugar were determined immediately by the Schoorl method; after hydrolysis at 100 ⁰ C with 1 ml of 25% HGL is neutralized for 1 hour. The tests showed the following;

Lactose, its breakdown as a control for the effects was chosen from rhyzops and glucoamylases, disintegrated in 5 h. 100% "Decomposed when exposed to invertase cane sugar completely in 15 min «When using an extract of porcine pancreas, maltose completely decayed after 26 hours. In all three cases, lactulose itself persisted an exposure time of 120 h undecomposed.

(4). For comparative testing of the absorbability of lactulose In the digestive organs of higher animals, the following work was carried out:

In closed on both sides. Intestinal parts of live rabbits, The 24 h did not get anything to eat, 50 ml of 20% solutions, on the one hand of lactulose, on the other hand injected by cane sugar. 90% of the injected pipe

10 °

suckers were absorbed in a few hours, by contrast Lactulose showed no sign of absorption.

(5). The stability of lactulose at different pH was tested under the following conditions:

End value of the sugar concentration 0.02 $ pH end value of the 0.02 M buffer solution 2.0 to 10.0 temperature 98 ⁰ C.

After checking the changes in the content of reduced sugar (R) and total sugar (G) in the samples taken at intervals according to the Somog ^ i-Efelson method, the initial concentration was set at 100. To 1 ml Beaktionsflüsaigkeit 0.5 ml of a 5% strength "3a HOl added, then the mixture was 4-5 min to 100 ⁰ C and kept neutralized with 0.5 al NaQH" The determination of the 'Gesamfczukkers performed according to the Somoggi-Helson -Method and the results were expressed as total sugar values (G) »The results are shown in the following table.

109 8.10 / 2291

pH after 12 h Heating time 1 2, in H .5, 8th 0
0 12th at first 2 , 3 100 102
100 5 103
101 107
102 0 110
103 2.0 4th , 0 E.
G 101 101
100 99 ₉ 5 100
100 100
102 4.0 6th , 5 R.
G 100 100
102 98.0 99
98 99.5
97.8 6.0 8th , 2 E.
G 105 104
91 103
84 _$ 0 104
80, 103
75 ₉ 3 9.0 E.
G 3

Be seen from the table holding to 8.0 Laktuloselösmngen können§ value of the hydrolysis; b @ ± m to move »

That in a pH range of 3 ^ 0 © hm © decomposition 12 h at 98 ⁰ G g © pH 2 is subject to an extremely small 9 ₃ O, lactulose has a tendency to decrease

As stated above, Laktuloseignet for! Numerous © © rfrischand © haltigea drinks ^, v ± ® GoIa ₀ Apples lactulose with de-r Schnack »In lactic acid and yoghurt, harmonized improves the GesckaaeL · Schnack. In natural as Süßmitt ©! especially ge beverage® ο in carbonic acid · =

lachöalpis, gat ait d © 3? Hil © is.säur-e, ver

Lactic acid © n ₉ artificial fruit juices

... 15

10 9 810/229

and fruit juice concentrates, lactulose preserves the fresh Fruit flavor and gives the products a refreshing Sweet. Small additions of lactulose to alcoholic beverages of the Western and Japanese types, such as beer and wine, showed a great improvement in taste and "body". Even high levels of lactulose in highly concentrated juices do not cause the sweetener to crystallize. Especially in the cases in which artificial sweeteners are not used is appropriate, the above advantage of lactulose is of particular importance.

The mild sweetness and high flavor-retaining property of lactulose makes them particularly applicable in ice cream, ice candies, effervescent soft drinks and frozen desserts as well as fruit preserves and Tomatensau ^c s. In ice cream, lactulose achieves a higher melting point, an increase in flowability (over run) and softness.

Lactulose can be used very well in Japanese and Western confectionery products to prevent it from sagging, drying out or crystallizing out, and to achieve it of the desired moisture content. For the preparation of low-calorie food, e.g. half of the © of the necessary sugar replaced by lactulose. At a If a few percent lactulose is added to bread and baked goods, the lactulose in the end products remains undecomposed. at Baked goods, such as biscuits and biscuits, are great causes of lactulose

... 16 1 0 9fi 1 Π / v? 9 ι ■

■ - 16 -

desirable beautiful baking colors, while moisture resistance the lactulose reduces deformation and breakage and the yield improves »

Lactulose gives jellies a refined sweetness «, increases the taste, makes the staining durable, extends the transparency and prevents excessive drying out or plasmolysis and that brings about a permanent preservation of the original freshness. Lactulose gives different creams one delicate sweetness and a mild palatability Lactulose e.g. in candy, chocolate fillings, chewing gum and caramels a change in the conventional pronounced sweetness, amplifies and improves the aftertaste.

Example 1.

(a) A solution of 1 g of lactose in 5 1 of water is made after addition of 6 g OaO incubated for 4 days at 35 ° O until the optical rotation becomes almost constant. The decolorized and purified isomerized solution is then evaporated in vacuo, whereupon the crystallized out Lactose is filtered off and washed.

(b) The mother liquor combined with the washing liquids is _{adjusted to a content of 10%, neutralized with GO 2} , heated after the addition of 1% liquid corn swell, 0.2% urea, 0.05% KH ₂ PO ₄ and 0.025 % MgSO ₄ .7H ₂ O in the autoclave

... 17 1 Ü ¹ JH 1 Π / '"2 9 1

and then adds 2.5% separately sterilized GaCO ^. Then Pseudomonas graveolens (Ii ¹ O 3460) is inoculated and cultured for 50 h at 30 ⁰ O with aeration and stirring at 400 rev / min, centrifuged and then the cells enzyme and used as a dehydrogenase for further oxidation of lactose.

(c) The centrifuged culture broth is decolorized, filtered, evaporated and made weakly alkaline by adding saturated cold water, whereby the basic calcium salt of lactobionic acid precipitates. After filtering off, this is suspended in three times the amount of water, slowly diluted sulfuric acid is added to the ^{suspension and the calcium sulfate formed is filtered off, while the remaining calcium ions are removed from the I 1} Xltrat by means of a strongly acidic exchange resin ("Amberlite IE 120") and by means of small amounts of a basic one Exchange resin ("Amberlite IE 400") the excess sulfuric acid ions are removed. Lactobionic acid is then obtained as a syrup by acuume evaporation; a content of 98% bionic acid plus small amounts of lactose, lactulose, etc. is determined by paper chromatography. Yield 13% _s calculated on starting lactose.

(d) The filtrate obtained above under (c) after separating off the calcium bionate is freed as far as possible from calcium ions by saturation with Cog, then by means of a three-bed exchange resin system ("Amberlite IJ 120, IM 69, IH 120 and IP 4- 11 ") decolorized and evaporated. The lactulose obtained

109810/2291 ... 18

is 99% pure and hardly contains any lactose. Yield 40% ₉ be calculated on the starting lactose.

Example 2.

^{(a) 1 l of a 15% lactose solution is kept at 35 0} O for 4 days after adding 200 ml of ammonia water (spec »G-ew« 0 ^ 88) until the optical rotation remained constant.

(b) After adjusting the isomerized solution to pH 5j8 with sulfuric acid, adding O ₉ 5% liquid corn swelling, 0.06% EH ₂ PO ₄ and 0.025% MgSO ^ .THgO and sterilizing, the solution was inoculated with Pseudomonas fragi (ISEL 25) and cultivated with aeration and adjustment of the pH with CaCO ^ according to Example 1.

(c) After separating the Zetl © n ₉ GaGQ ^ ^ ₉ GASO etc. is di © ■ feurbrühe evaporated _s with concentrated © ® © Kalkwass? sctefaeh alkaliseli g © _f isacht the auskristallisi rt © © "basisciiG Kalziombionat abgescJaleudertj washed and g @ 5iäß Example 1 au one of aadereia Garboasäur ^ a free lactobionic Ausbeuts VJ ^L% j calculated on Ausgangslatefcos ©"

(d) Slide under (e) removed © schloud © rt ©

line with the tfascliflüssigk © It © a iron H @ t> allioa © a ₉ r © stliöb. © r Bionaäur © ism. by means of a bread tank ^ AustaTa Han asMlt © ia © ag @ lbli © hoa Bisap ₉ dop

with

ssweif

set at uad_ under

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Seeding crystals and stirring is cooled. Lactulose yield Crystals 38%, calculated on the starting lactose.

Example 3 «

2 liters of a 15% lactose solution are treated after adding 2 g of GaO for 3 to 4 days at 35 ° C., then _{neutralized with CO 2} and decolorized with activated charcoal; then the solution of 37 g OaOO ^ 1 1 solution and 5 g of the separated cells according to Example 1 enzyme is added, and the oxidized 15 with aeration and vigorous stirring at 30 ⁰ C. After decolorization and separation of the calcium ions by means of exchange resin ("Amberlite IR J adsorption of lactobionic acid on a weakly basic ion exchange resin (" Amberlite IRA 69 ")» decolorization by passing over a mixed-bed exchange resin ("AmberliteIR 120 and IRA 4-11") and evaporation pure lactone-free lactulose is obtained, yield 38%, calculated on the starting lactose.

The adsorbed lactobionic acid is eluted with sodium hydroxide solution, leads the sodium bionate formed through a strongly acidic one Exchange resin tower ("Amberlite IR 120") and recover the free acid in syrup form after evaporation. Yield 47% calculated on Starting lactose.

example A-.

A 30% lactose solution is used continuously adjusted to pH 10.0 with sodium hydroxide solution and by 5 min

... 20 1 093 1.Q / '>? .9 1

Long heating at 95 ° C continuously isomerized, then rapidly cooled, neutralized with HGl, decolorized by passing through a 4 m high layer of granulated activated carbon and desalinated with ion exchange resin. Contains the isomerized yellowish syrup containing about 40% lactulose, it provides a 1Oxigen content a "is 2 ₈ 5% GACO ₅ and 10 g sugar 200 of the enzyme cells obtained according to Example 1 mg to and oxidized for 20 hours at 30 ⁰ C. with aeration and stirring, with most of the lactone being converted to -.

The heated reaction solution, decolorized with activated charcoal, is freed from calcium ions using a strongly acidic ion exchange resin ("Amberlite IE: 120") and from lactobionic acid using a weakly basic ion exchange resin ("Amberlite IEA. 69"). The lactobionic acid worked up according to Example 3 is recovered. pure in a yield of 52% ₉ calculated on the starting lactose, whereas the acid-free lactulose solution, after decolorization and cleaning in a mixed bed system containing strongly acidic and strongly basic ion exchange resins, is converted into a colorless syrup which, in addition to lactulose, contains less than 1% lactose . Yield 37% * calculated on starting lactose.

Example 5.

A 25% lactose solution _s rough air was removed by boiling, allowed to stand at 70 ⁰ C by a Ohirm _s of a large amount of a basic ion exchange resin © ®. ("Amberlite JR 400")

109310 /?.? 91. ... 21

was filled, circulate, where "with the sugar oxidation if possible was prevented by introducing air. In 5 ms 7 h the degree of isomerization reached 32%. It was then removed with activated carbon and in the mixed-bed resin system ("Amberlite IE 12C and IE 411 "). The very sweet syrup obtained was worked up according to Example 4. Yield of lactulose 30%, of lactobionic acid 57% »calculated on initial lactose.

Application forms of the invention are obtained below Lactulose for the preparation of food and beverages is described in more detail.

(A) Making a carbonated beverage.

The batch for 10 l of a cider drink was: lactulose 700 g

Saccharin 12 g

Table salt 2g

Citric acid etc. 60 g flavor 50 ml.

After completely dissolving in the precalculated amounts of water and saturating with CO ₂ , the drink, which had a refreshing sweetness, was filled into bottles. The new sweetener harmonized well with the sourness and the sweetener of the approach and gave the latter a delicate sweetness and freshness. In addition, it is about a completely calorie-free drink.

... 22 109810/2291

(B) Preparation of an orange syrup. The approach consisted of 1OOO

750 l of a 60% lactulose solution 79 1 of an orange juice thickened to the fifth part

40 kg of citric acid
5 1 orange base
2.5 1 orange essence.

In this mixture, lactulose increases the acidity and the inherent taste of the oranges, thus harmonizing with their aroma and preventing crystallization and cloudiness of the still further thickened juice.

(0) Preserving mandarins »

Hit 100 kg of one containing 60 kg of lactulose and 30 g of saccharin Syrups are peeled and doused in mandarins usually sterilized. lactulose gives them the desired shine; their mild sweetness harmonizes well with sourness of the fruits as well as emphasizes and preserves their aroma. A low-calorie food is obtained.

(D) Preparation of tomato sauce.

To 10 1 tomato puree, obtained by crushing toai & ten, Straining the pulp "and thickening it to 40 to 50% was prepared, were admitted:

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800 g dry lactulose

100 g table salt ■

100 g of 30% acetic acid

50 g onion ^.

12 g cinnamon
5 g of clove oil
2 g spice mixture
2 g mace
1 g red pepper.

The mixture was thickened to a density of 1.128. The product retained its lively luster and color. Lactulose gave it a mild sweetness and enhanced its fresh aroma.

(E) Making ice cream.

A mixture of

30 parts by weight "Skin milk" 15 "" fresh cream with 4-5% fat 5 ^ä "lactulose and
0.5 "" cellulose glycolate

are with 50 parts by weight. Milk intimately mixed at 50 to 75 ° C, then heated to 60 to 65 ° 0 and filtered. The included Fats are harmonized with an emulsifier (a harmonizer), whereby the mixture expands strongly (the over run increases). This is followed by distillation at 70 ° C. for 30 minutes, then cooled at Let stand 3 to 5 G and freeze. The exquisitely edible and tasty product has a

10 981 η / 9 291

... 24

frozen desserts desired refined SUBE _{9 has} a relatively high melting point and an improved expansion capacity (to over-run property) ι the properties are comparable to those obtained ,, upon application of Eohrucker "

(F) Preparation of sand cake ("Gastella") "

One made by ordinary mixing
1000 g eggs
500g flour
100 g lactulose
50 g honey

The prepared dough is placed on iron sheets covered with a thin layer of paper and baked in the oven at 180 to 190 ° C Baked to the desired color = the lactulose gives the cake an excellent baking color. »Its structure consists of fine, uniform grains of the desired elasticity » Its moisture and original softness can be retained for a long time, i.e. a reduction and drying out of the cake is completely prevented, moreover the taste and aroma are enhanced to a greater extent by lactulose than by rice syrup, honey or other sweeteners »

(G) Manufacture of soft biscuits »
A dough batch consisting of;

.. »25 1 0 8 8-1'η / ■? 2 9 1

100 Weight Tin. flour 40 Il π Lactulose 15th It Il concentrated milk 10 H Il butter 10 Π Il Shortening 8th Il Il Eggs 6th Il Il strength ο, 5 " Il baking powder ο, 3 " Il Table salt

was mixed with an appropriate amount of water until the mixture has a rag-like firmness. After punching is baked 10 minutes in an oven whose temperature at the inlet 270 °, at the exit 130 ⁰ O. The light-colored biscuits obtained had a uniform luster, color, shape and a slightly dry, delicate structure which is easily loosened by the saliva *.

(H) Preparation of strawberry jelly.

To a hot syrup consisting of

80 kg of an 80% lactulose solution 11.4 kg of one thickened to 1/10 and 121 g

Citric acid containing strawberry juice 10 kg of a 4 # pectin solution,

was heated by mixing with a pectin solution at 80 ⁰ O and pH 3.1 and then evaporated in vacuo at 103 ⁰ O. The juice, gelatinized in the desired. Weis ·· This was over-.

1098in / '22'91

surprising, since a usual gelatinization with less than 50% Cane sugar does not take place, so that excessively sweet products are obtained. Neither decomposition nor plasmolysis the lactulose through the berry acids takes place «

(J) Making butter cream.

An aqueous solution of 1.1 kg of a dry mixture 95% lactulose and 5% lactose are steamed to a syrup and stir in 100 ml of baking oil in portions. As soon as the mixture has reached a smooth state with gloss and color, small amounts of aroma and alcohol are added Drinks too. The product has a very delicate taste and a mild sweetness and is excellent for decorating Cakes etc. suitable.

(K) Preparation of gastard krem.

199 g of lactulose and 8 g of table salt are first stirred into 1 kg of corn starch, then with 2.8 kg of eggs and finally mixed with 10 l of fresh milk. After gentle heating, the starch gelatinizes completely. Once ".If the product opaque, 'it is cooled and mixed with flavoring"Eb's not overly sweet and has a consistent smoothness, "therefore lactulose various sweetening Kuchan suitable _o

(L) Making Hard Boabona ^. -; ■ -. ^;

To a solution of. 60 6 © fj _o !! & o lsi stall sugar vm & 20 wt. TIn ₀

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Corn syrup is put in 20 parts by weight. Lactulose to ₉ evaporates the syrup in a vacuum to a moisture content of 1 to 1.5% at a temperature of 130 ° G and mixes 0.8 parts by weight after cooling. Citric acid as well as color and flavor too. By guiding the mass at 80 ⁰ O between a sieve and a roller, the moldings are formed in which lactulose weakens the harsh sweetness of the drilling sugar, prevents the latter from crystallizing and improves the clarity and quality of the candies.

(M) Production of chocolate ball cores.

The malleable mass obtained according to the above procedure is deformed into grains and then cooled or by vacuum expansion deformed into spheres. In both cases, the structure is used as a core for coating with chocolate mass Chocolate products. The kernels have a mild taste ^ no excessive sweetness and harmonize with the chocolate mass.

(N) Making condensed milk.

Once at 110 to 130 ⁰ O sterilized fresh milk with controlled fat content lactulose is added and evaporated, then cooled to below 15 ° 0, so that the lactose forms microcrystals having 15%; the lactulose prevents the lactose from crystallizing out. The product consists of 70% fat, 45% lactulose, 29% milk solids, 14% lactose, 7% protein, 1.5% ash and 25% water. It has a cream color and shine

1 0 38 "l Π / ■ *> 2 9 T ... 28

- 28 desired viscosity. And an excellent structure.

(0) Production of chewing gum .

In 20 parts by weight. molten rubber mass are 10 to 30 parts by weight. Cane sugar powder, 50 to 70 parts by weight. Lactulose and Λ part by weight Flavor kneaded in. The mixture obtained is shaped into sheets of suitable strength and shape and dried overnight. The lactulose content maintains the taste and gives the product a refreshing aftertaste.

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Claims (1)

ZELLRNTiN L KUYKcN ** ? 'j i'r. c K *:> 22 ... '■■■■ · July 51, 1970 SJ / Hu hao 7111 Claims Process for the production of lactulose and lactobionic acid made of lactose, characterized by it, that he (a) lactose isomerized to lactulose in an alkaline medium, (b) the lactose that has not been isomerized by means of Lactose dehydrogenase is oxidized to lactobionic acid and this if necessary. of the lactulose by means of basic ion resin exchangers and / or by precipitation as basic Separates calcium salt. 2. The method according to claim 1, characterized in that, uses alkali metal or ammonium hydroxide or a strongly basic resin as an isomerization agent. 3. The method according to claim 1 and 2, characterized g # _t denotes that culturing the lactose DehydrogenaB © in Isomerisationsgemisch or cells "ines - * eat speaking Enaymeteisiiea 109810/2291 4. The method according to claim 1 to 5, characterized in that that the lactose dehydrogenase-forming strains Pseudomonas graveolens (IFO 3460) or Pseudomonas fragi (NEEL 25) applies. 10 98