CN102020680B - Method for preparing high-purity lactulose - Google Patents
Method for preparing high-purity lactulose Download PDFInfo
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Abstract
The invention relates to the field of the preparation of functional sugar, and relates to a method for preparing high-purity lactulose. The method for preparing the high-purity lactulose comprises the following steps of: preparing lactose solution at the concentration of 15 to 20 percent; adding a boric acid and sodium hydroxide (NaOH) into the solution, and adjusting a reaction to obtain conversion liquid; performing ion exchange sodium ion (Na<+>)-removing treatment on the conversion liquid; decoloring a granular active carbon column; removing the boric acid from the lactose solution to obtain a lactose solution dry substance with the boric acid content of less than 1 mg/kg; concentrating the lactose solution until the concentration is 50 to 60 percent; separating by using a 10-bed continuous chromatographic separation device; and performing aqueous phase crystallization, wherein the cooling speeds are 0.8 DEG C per hour at the temperature of between 60 and 50 DEG C, 1 DEG C per hour at the temperature of between 50 and 30 DEG C and 1.1 DEG C per hour at the temperature of between 30 and 13 DEG C. The conversion rate of the lactulose can be increased, so that the yield of the lactulose products is greatly improved; granular active carbon is decolored; moving bed chromatographic separation is continuously simulated, so continuous chromatographic separation of the high-purity lactulose can be realized, the purity of the lactulose reaches over 92 percent so as to facilitate aqueous phase crystallization; and the purity can reach over 98 percent due to the aqueous phase crystallization.
Description
Technical field
The present invention relates to function sugar preparation field, particularly a kind of preparation method of high purity lactulose.
Background technology
Lactulose is milk ketose, newborn scholar sugar, galactosyl fructoside again, for by semi-lactosi and the fructose synthetic disaccharides with β-1,4 glycosidic link be combined into.Molecular formula is C12H22O11, and molecular weight is 342.Lactulose has good bifidus bacillus value-added functionality, has the intestinal microecology of adjusting equilibrated effect, is having a wide range of applications aspect medicine, food and the animal rearing.Can reduce blood ammonia, catharsis, the treatment constipation also is used for the control of various liver property diseases, aspect food, can also be widely used as low heat value sweeting agent and functional food additives.
The preparation of lactulose can be adopted chemical method or biological process, and wherein using sophisticated method at present is chemical method, is raw material with the lactose normally, isomerization reaction takes place under the catalysis of alkaline reagents generate.In isomerization reaction, DeR can take place in disaccharides, generates monose such as semi-lactosi etc.At present; Mass-produced producer mainly concentrates on abroad, and Belgian Solvay (Su Wei) is maximum in the world lactulose manufacturing firm, mainly as pharmaceutical applications; And Japanese Morinaga (forever gloomy) milk preparation company is another main manufacturer, and its product is mainly used in foodstuff additive.
The chemical method of lactulose prepares in the process; Utilize strong basicity reagent such as sodium hydroxide, Pottasium Hydroxide, calcium hydroxide and strong organic bases amine to wait and carry out isomerization reaction; In these reactions, the amount of monose such as the degraded product semi-lactosi of disaccharides increases greatly, has reduced the yield of lactulose; Reaction product has very heavy color, is difficult to separate and purifying.Utilize weakly alkaline reagent and strong basic ion exchange resin to come the isoversion reaction, unsatisfactory on the productive rate, be not suitable for industriallization.React as the alkaline reagents isoversion with borate and aluminate, meta-aluminate; Because such reagent and lactulose form complex compound; Reaction is carried out to the direction that helps forming lactulose, thereby higher productive rate is arranged, but need to remove borate and aluminate, meta-aluminate.
Utilize the lactulose of chemical method preparation also to contain some other non-functional component, like lactose, semi-lactosi etc., make lactulose purity not high, less than 90%, the existence of these compositions has restricted the application of lactulose in medicine and protective foods industry.Utilize the crystallization property of lactulose; Can prepare highly purified lactulose product with the crystallization of setting out of commercialization lactulose product; But the lactulose product that purity is not high is difficult in the aqueous phase crystallization, and mainly adopts methyl alcohol or ethanol to carry out crystallization operation; Have methyl alcohol in the solid phase prod or alcohol solvent is residual, thereby influence quality product.
Summary of the invention
To the not high and low purity lactulose of existing lactulose production conversion yield liquid crystallization difficulty, the not high lactulose production of finished product purity problem; The invention provides a kind of is raw material with the pure lactose, improves the preparation method of the high purity lactulose of lactulose production conversion yield, raising finished product purity.
The present invention specifically realizes through following measure:
A kind of preparation method of high purity lactulose is characterized in that adopting following steps:
(1) with the lactose be raw material, the preparation lactose solution, concentration is 15wt% ~ 20wt%, adds boric acid by the amount with lactose mol ratio 1:1, stirs, and with 30%NaOH solution adjustment pH to 11.0, reacts 120min under 80 ℃ of conditions, is cooled to 50 ~ 60 ℃ and obtains conversion fluid;
(2) conversion fluid is pumped into to leave in the Amberlite IR-120Na strong acid cation exchange resin column after the activation to hand over handle, resin demand is 2 ~ 4L/kg conversion fluid dry-matter, and circulating temperature is controlled to be 40 ~ 50 ℃, obtains liquid glucose pH and be stopping in 4.5 ~ 6.5 o'clock;
(3) liquid glucose in the step (2) is carried out the decolouring of granulated active carbon post, in order to reach good effect, load Norit 1240Plus type granulated active carbon in the granulated active carbon post, the activated carbon column temperature is 70-80 ℃, and the liquid glucose flow rate control is at 2 ~ 3BV;
(4) liquid glucose after step (3) decolouring is pumped into take off boric acid in the Amberlite IRA96C resin column after the activation and handle, resin demand 3 ~ 5L/kg liquid glucose dry-matter, 40 ~ 50 ℃ of temperature, cyclical operation makes boric acid content less than 1mg/kg liquid glucose dry-matter;
(5) sugar concentration to 50 in the enrichment step (4) ~ 60% injects the post that Amberlite CR1320K type chromatographic grade strong acid sun resin is housed, and adopts continuous simulation mobile bed chromatic partition method; With potassium type ion exchange resin is carrier, uses 10 formula continuous processing chromatographic separation devices to separate, and parameter is set to: resin column internal diameter 120mm; The resin column loading height is 350mm, and simulation resin bed rotating speed is 3 °/min, feeding temperature 60-70 ℃; Charging flow velocity 1.2-1.8L/h, water inlet flow velocity 2-3L/h collects effluent high purity lactulose solution flow velocity 1.4-2.0L/h; Solute is the mixture of lactose and lactulose in the high purity lactulose solution, and concentration is 24-30wt%, eluent flow rate 1.8-2.8L/h; Solute is glucose, semi-lactosi and fructose mixture, and concentration is 17-22wt%;
(6) high purity lactulose solution vacuum concentration to concentration 70%, temperature are 60 ℃, add the lactulose crystal of the weight 0.2%-0.3% that accounts for dry-matter in the solution; Mixing speed 100r/min-300r/min, cooling rate is: 60-50 ℃ is 0.8 ℃/h, 50-30 ℃ is 1 ℃/h; 30-13 ℃ is 1.1 ℃/h, and constant speed stirred 48 hours, and is centrifugal; Obtain the crystallization lactulose, make the solid finished product 35 ~ 40 ℃ of following dryings.
The high purity lactulose solution that liquid glucose that step (4) is obtained and step (5) obtain carries out check and analysis, and analytical procedure is a HPLC, amino chromatographic column, and RI detector, eluent are acetonitrile: water=80:20, flow velocity 1.0ml/min.
Though in product separation purification field; Continuous simulation mobile bed chromatic stripping technique is a kind of commonplace technology of using, but in the separation that continuous simulation mobile bed chromatic stripping technique is applied to lactulose is purified, still need overcome a lot of concrete technical problems; The setting of picture parameter; The control of concentration and flow velocity etc. though some parameter can draw through the experiment of limited number of time, but still have the setting of a lot of parameters to need the concrete use field of technician according to lactulose; The effect that rule of thumb, just can obtain through creative work.
The aqueous crystallization technology also is a kind of general crystallization technique that uses; But separate in the concrete technology of purifying at lactulose; Have only that the purity of lactulose reaches after the certain value in the liquid glucose, the effect that aqueous crystallization just can obtain is through the application of continuous simulation mobile bed chromatic stripping technique; The purity of lactulose is reached more than 92%, make the aqueous crystallization The Application of Technology become possibility.Number of patent application is 201010197402.7; The one Chinese patent application that name is called " a kind of D-seminose preparation technology " discloses a kind of preparation technology of D-seminose; Comprise in this technology earlier through simulation moving-bed separation; Carry out the step of aqueous crystallization again, but D-seminose and lactulose have very big difference, in specific operation process, have the difference of a lot of parameters aspect being provided with; The inventive method reaches more than 98% the purity of crystallization lactulose through rational aqueous crystallization cooling rate is set.
The invention has the beneficial effects as follows:
(1) utilizes alkali/boric acid catalysis system that lactose is carried out isomery and transform, can improve the transformation efficiency of lactose, the yield of lactulose product is improved greatly.
(2) adopt Amberlite IR-120Na strongly acidic cationic exchange resin and Amberlite IRA96C weak anion resin to remove Na
+Ion and boric acid, and the decolouring of granulated active carbon post can reach the purpose that lactulose is refining, decolour, and boric acid content is reduced to below the 1mg/kg, and the renewable use of granulated active carbon helps reducing production costs simultaneously.
(3) adopting Amberlite CR1320K type chromatographic grade strong acid sun resin column to carry out the continuous simulation mobile bed chromatic separates; Through the adjustment of resin column loading height, the control of simulation resin bed rotating speed, input concentration, feeding temperature, charging flow velocity, water inlet flow velocity, effluent flow velocity, the isoparametric adjusting of eluent flow rate; The continuous chromatography of realizing the high purity lactulose separates; Effectively the separating of lactulose and lactose and semi-lactosi in the product liquid, lactulose purity reaches more than 92%, is beneficial to aqueous crystallization.
(4) the higher lactulose liquid product of purity is carried out aqueous crystallization, can avoid the use of the residual problem of pure crystallization lactulose alcohol, product purity reaches more than 98% after the crystallization.
Description of drawings
Accompanying drawing 1 is 10 formula continuous processings of the present invention chromatographic separation device structural representation,
Among the figure: A-J is 10 filled columns, and 1-10 is followed successively by opening for feed, the discharge port of 10 filled columns, and a is the liquid glucose that takes off after boric acid is handled, and b is for flowing out lactose solution, and c is an effluent high purity lactulose solution, and d is an elutriant, and e is a water,
Among the figure, arrow express liquid flow direction.
Embodiment
Embodiment 1:
(1) take by weighing the 10kg high purity lactose, add the lactose solution that deionized water is mixed with concentration 15%, add 1.8kg boric acid, stir, with 30%NaOH solution adjustment pH to 11.0, reaction 120min gets conversion fluid under 80 ℃ of conditions, takes out rapidly and is cooled to 50 ℃;
(2) the back conversion fluid of will lowering the temperature pumps into Amberlite IR-120Na strongly acidic cationic exchange resin is housed; Column internal diameter 250mm, in the chromatography column of high 1500mm, the resin loading height is that 900mm circulates from handing over processing; Circulating temperature is controlled to be 50 ℃, and the pH that ends liquid glucose is controlled to be 4.5;
(3) from handing over the liquid glucose after handling to decolour, adopt Norit 1240Plus type granulated active carbon, activated carbon column internal diameter 250mm, high 1500mm, gac loading height are 1100mm, 77 ℃ of temperature, flow rate control is at 3BV;
(4) liquid glucose after the decolouring pumps into Amberlite IRA96C resin column is housed, column internal diameter 300mm, and high 1500mm, the resin loading height is 1000mm, takes off boric acid and handles, 45 ℃ of temperature, final boric acid content is a 0.56mg/kg liquid glucose dry-matter.Liquid glucose uses performance liquid chromatography to detect after removing boric acid, and the amount of each ingredients constitute total dry matter of liquid glucose is respectively lactulose 76.3%, lactose 12.2%, semi-lactosi 8.5%, other sugar 3.0% (fructose+glucose);
(5) sugar concentration that takes off after boric acid is handled is concentrated into 50%, pumps into 10 formula continuous chromatography separation systems that Amberlite CR1320K type chromatographic grade strong acid sun resin is housed, and is as shown in Figure 2; Resin column internal diameter 120mm, resin column loading height are 350mm, and simulation resin bed rotating speed is 3 °/min; 67 ℃ of feeding temperatures, charging flow velocity 1.8 L/h, water inlet flow velocity 3 L/h; Effluent flow velocity 1.8L/h, eluent flow rate 2.7 L/h get effluent high purity lactulose solution 20.5L; Concentration is 24%, elutriant 30.75L, and concentration is 19%.The high purity lactulose solution is carried out performance liquid chromatography detect, the amount of each ingredients constitute total dry matter of liquid glucose is respectively lactulose 92.3%, lactose 5.1%, other sugar 2.6% of semi-lactosi;
(6) with high purity lactulose solution vacuum concentration to concentration 69%, 60.5 ℃ of temperature are added 12g lactulose crystal; It is 0.8 ℃/h that cooling rate is 60-50 ℃, and 50-30 ℃ is 1 ℃/h, and 30-13 ℃ is 1.1 ℃/h; Stirred 48 hours with the 240r/min constant speed, filter, the crystalline solid that filters out; Vacuum drying oven obtains solid lactulose 4.3kg 38 ℃ of following dryings, utilizes performance liquid chromatography that crystal product is carried out composition analysis, and purity reaches 98.2%.
Embodiment 2:
(1) take by weighing the 10kg high purity lactose, add the lactose solution that deionized water is mixed with concentration 20%, add 1.8kg boric acid, stir, with 30%NaOH solution adjustment pH to 11.0, reaction 120min gets conversion fluid under 80 ℃ of conditions, takes out rapidly and is cooled to 58 ℃;
(2) the back conversion fluid of will lowering the temperature pumps into Amberlite IR-120Na strongly acidic cationic exchange resin is housed; Column internal diameter 250mm, in the chromatography column of high 1500mm, the resin loading height is that 900mm circulates from handing over processing; Circulating temperature is controlled to be 40 ℃, ends liquid glucose pH and is controlled to be 6.5;
(3) from handing over the liquid glucose after handling to decolour, adopt Norit 1240Plus type granulated active carbon, activated carbon column internal diameter 250mm, high 1500mm, gac loading height are 1100mm, and bleaching temperature is 78 ℃, and the feed liquid flow rate control is at 2BV;
(4) liquid glucose after the decolouring pumps into Amberlite IRA96C resin column is housed, column internal diameter 300mm, and high 1500mm, the resin loading height is 1000mm, takes off boric acid and handles, 45 ℃ of temperature, the final content of boric acid is 0.46mg/kg liquid glucose dry-matter.Liquid glucose uses performance liquid chromatography to detect after removing boric acid, and the amount of each ingredients constitute total dry matter of liquid glucose is respectively lactulose 75.8%, lactose 12.7%, semi-lactosi 8.6%, other sugar 2.9% (fructose+glucose);
(5) sugar concentration that takes off after boric acid is handled is concentrated into 60%, pumps into 10 formula continuous chromatography separation systems that Amberlite CR1320K type chromatographic grade strong acid sun resin is housed, and is as shown in Figure 2; Resin column internal diameter 120mm, resin column loading height are 350mm, and simulation resin bed rotating speed is 3 °/min; 62 ℃ of feeding temperatures, charging flow velocity 1.2 L/h, water inlet flow velocity 2 L/h; Effluent flow velocity 1.6 L/h; Eluent flow rate 2.6 L/h, the effluent high purity lactulose solution 20L of concentration 25%, concentration is 18% elutriant 32.5L.The high purity lactulose solution is carried out performance liquid chromatography detect, the amount of each ingredients constitute total dry matter of liquid glucose is respectively lactulose 92.5%, lactose 5.0%, other sugar 2.5% of semi-lactosi;
(6) with high purity lactulose solution vacuum concentration to concentration 70%, 60 ℃ of temperature are added 11g lactulose crystal; It is 0.8 ℃/h that cooling rate is 60-50 ℃, and 50-30 ℃ is 1 ℃/h, and 30-13 ℃ is 1.1 ℃/h; Stirred 48 hours with the 200r/min constant speed, filter, the crystalline solid that filters out; Vacuum drying oven obtains solid lactulose 4kg 37 ℃ of following dryings, utilizes performance liquid chromatography that crystal product is carried out composition analysis, and purity reaches 98.5%.
Claims (2)
1. the preparation method of a high purity lactulose is characterized in that adopting following steps:
(1) with the lactose be raw material, the preparation lactose solution, concentration is 15wt% ~ 20wt%, adds boric acid by the amount with lactose mol ratio 1:1, stirs, and with 30%NaOH solution adjustment pH to 11.0, reacts 120min under 80 ℃ of conditions, is cooled to 50 ~ 60 ℃ and obtains conversion fluid;
(2) conversion fluid is pumped into to leave in the Amberlite IR-120Na strong acid cation exchange resin column after the activation to hand over handle, resin demand is 2 ~ 4L/kg conversion fluid dry-matter, and circulating temperature is controlled to be 40 ~ 50 ℃, obtains liquid glucose pH and be stopping in 4.5 ~ 6.5 o'clock;
(3) liquid glucose in the step (2) is carried out the decolouring of granulated active carbon post;
(4) liquid glucose after step (3) decolouring is pumped into take off boric acid in the Amberlite IRA96C resin column after the activation and handle, resin demand 3 ~ 5L/kg liquid glucose dry-matter, 40 ~ 50 ℃ of temperature, cyclical operation makes boric acid content less than 1mg/kg liquid glucose dry-matter;
(5) sugar concentration to 50 in the enrichment step (4) ~ 60 wt % inject the post that Amberlite CR1320K type chromatographic grade strong acid sun resin is housed, and use 10 formula continuous processing chromatographic separation devices to separate; Parameter is set to: resin column internal diameter 120mm, resin column loading height are 350mm, and simulation resin bed rotating speed is 3 °/min; Feeding temperature 60-70 ℃, charging flow velocity 1.2-1.8L/h, water inlet flow velocity 2-3L/h; Collect effluent high purity lactulose solution flow velocity 1.4-2.0L/h; Concentration is 24-30 wt %, eluent flow rate 1.8-2.8L/h, and concentration is 17-22 wt %;
(6) high purity lactulose solution vacuum concentration to concentration 70 wt %, temperature is 60 ℃, adds the lactulose crystal of the weight 0.2%-0.3% that accounts for dry-matter in the solution; Mixing speed 100r/min-300r/min, cooling rate is: 60-50 ℃ is 0.8 ℃/h, 50-30 ℃ is 1 ℃/h; 30-13 ℃ is 1.1 ℃/h, and constant speed stirred 48 hours, and is centrifugal; Obtain the crystallization lactulose, make the solid finished product 35 ~ 40 ℃ of following dryings.
2. method according to claim 1 is characterized in that loading Norit 1240Plus type granulated active carbon in the step (3) in the granulated active carbon post, and the activated carbon column temperature is 70-80 ℃, and the liquid glucose flow rate control is at 2 ~ 3BV.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102503992A (en) * | 2011-09-20 | 2012-06-20 | 江苏汉斯通药业有限公司 | Preparation method of lactulose concentrated solution |
| CN104059110A (en) * | 2014-06-11 | 2014-09-24 | 江苏汉斯通药业有限公司 | Production process of concentrated solution of lactulose |
| CN104498639B (en) * | 2014-12-10 | 2017-12-05 | 广州双桥股份有限公司 | A kind of production technology of high fructose syrup |
| CN106366137A (en) * | 2016-08-27 | 2017-02-01 | 山东绿健生物技术有限公司 | Desalting and decolorizing method of isomerized lactose liquid |
| CN106318848B (en) * | 2016-10-14 | 2018-05-08 | 山东大学 | A kind of device for being used to remove the D-Fructose in D-Psicose |
| CN108148099B (en) * | 2016-12-05 | 2020-10-30 | 江南大学 | Continuous circulation preparation method of high-purity lactulose solution and product thereof |
| CN107573389A (en) * | 2017-08-03 | 2018-01-12 | 江苏汉斯通药业有限公司 | The preparation method of high-purity lactulose |
| CN113150042B (en) * | 2021-04-16 | 2022-11-08 | 大连美罗中药厂有限公司 | Preparation method of lactulose |
| CN114315920B (en) * | 2021-12-29 | 2023-10-20 | 山东百龙创园生物科技股份有限公司 | Preparation method of isomerized lactose |
| CN114699800A (en) * | 2022-03-23 | 2022-07-05 | 国家能源集团新疆能源有限责任公司 | Method for purifying Si69 stock solution |
| CN115341050B (en) * | 2022-07-17 | 2023-07-28 | 浙江晟格生物科技有限公司 | Lactulose preparation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264763A (en) * | 1978-09-29 | 1981-04-28 | L. Molteni & C. Dei F.Lli Alitti S.P.A. | Process for producing lactulose |
| CN1210863A (en) * | 1997-09-05 | 1999-03-17 | 中国科学院大连化学物理研究所 | Preparation of lactofructose and purifying method |
-
2011
- 2011-01-07 CN CN2011100025306A patent/CN102020680B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264763A (en) * | 1978-09-29 | 1981-04-28 | L. Molteni & C. Dei F.Lli Alitti S.P.A. | Process for producing lactulose |
| CN1210863A (en) * | 1997-09-05 | 1999-03-17 | 中国科学院大连化学物理研究所 | Preparation of lactofructose and purifying method |
Non-Patent Citations (1)
| Title |
|---|
| 于海 等.乳果糖的制备、分离及纯化的研究发展现状.《中国微生态学杂志》.1998,第10卷(第3期),第184页右栏第2段至第186页右栏第2段. * |
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