CN105001279A - Method for preparation of Palatinitol by catalytic hydrogenation of isomaltulose - Google Patents
Method for preparation of Palatinitol by catalytic hydrogenation of isomaltulose Download PDFInfo
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- CN105001279A CN105001279A CN201510361774.1A CN201510361774A CN105001279A CN 105001279 A CN105001279 A CN 105001279A CN 201510361774 A CN201510361774 A CN 201510361774A CN 105001279 A CN105001279 A CN 105001279A
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- palatinose
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- nickel
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- hydroxyl isomaltulose
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Abstract
The invention discloses a method for preparation of Palatinitol by catalytic hydrogenation of isomaltulose. The method includes: mixing isomaltulose with water according to certain ratio, then putting the mixture into a high pressure reaction kettle to react with hydrogen under a temperature of 110-120DEG C, a hydrogenation pressure of 0.5-0.7MPa and a reaction pH value of 5.0-6.0 in the presence of a catalyst so as to obtain Palatinitol. The catalyst is independently researched, developed and compounded, and is a mixture of a skeletal nickel catalyst and a nickel-copper catalyst in a weight ratio of 1:1-1:0.5, wherein the weight of the mixture of the skeletal nickel catalyst and the nickel-copper catalyst accounts for 1%-2% of the weight of isomaltulose. The invention aims to provide the safe Palatinitol preparation method with mild reaction conditions and high conversion rate.
Description
Technical field
The present invention relates to aldose and ketose shortening field, specifically a kind of method being prepared hydroxyl isomaltulose by Palatinose by shortening.
Background technology
The existing method preparing hydroxyl isomaltulose by shortening by Palatinose adopts the Palatinose produced after sucrose enzyme process isomery to be hydrogenating materials mostly, α-D-glucofuranose base-1 is hydroconverted under nickel catalyzator, high temperature, condition of high voltage, 6-D-sorbyl alcohol (GPS) and α-D-glucofuranose base-1,1-D-N.F,USP MANNITOL (GPM), in resultant of reaction, these two kinds of sugar alcohols wait a mole mixing (collection of illustrative plates has two peaks), is referred to as hydroxyl isomaltulose.What tradition hydrogenation technique adopted is adopt skeleton nickel single catalyst, need carry out the method for high pressure, high temperature, high-speed stirring for improving speed of response, transformation efficiency also only has 97-98%, and machine utilization is large, safety operation risk is high, so that domestic hydroxyl isomaltulose manufacturer is fewer.
Summary of the invention
The object of the present invention is to provide a kind of reaction conditions gentle, transformation efficiency high, the hydroxyl isomaltulose preparation method of safety.
Concrete technical scheme of the present invention is: a kind of method being prepared hydroxyl isomaltulose by Palatinose by shortening, join after Palatinose is mixed by a certain percentage with water in autoclave, under catalyzer existent condition, obtain hydroxyl isomaltulose with hydrogen reaction.Concrete technology parameter:
Temperature of reaction: 110 ~ 120 DEG C;
Hydrogenation pressure: 0.5 ~ 0.7MPa;
Mixing speed: 200-300r/ divides
PH value in reaction: 5.0-6.0;
Catalyzer is for composite voluntarily before facing production, and formula is independent research: the mixture of skeletal nickel catalyst and nickel-copper catalyst, and wherein the weight of the mixture of skeletal nickel catalyst and nickel-copper catalyst is 1% ~ 2% of Palatinose weight; The part by weight of skeletal nickel catalyst and nickel-copper catalyst is 1:1 ~ 1:0.5.
Prepare in the method for hydroxyl isomaltulose at above-mentioned Palatinose by shortening, described Palatinose and the part by weight of water are 1:1 ~ 1.4:1.
Prepare in the method for hydroxyl isomaltulose at above-mentioned Palatinose by shortening, the reaction times is 0.5 ~ 1 hour, and the transformation efficiency of Palatinose is greater than 99.8%.
Prepare in the method for hydroxyl isomaltulose at above-mentioned Palatinose by shortening, the control method of described pH value is: the mixing solutions of Palatinose and water is 5.0-6.0 by being adjusted to pH value with 2wt% liquid caustic soda or 2wt% hydrochloric acid.
Prepare in the method for hydroxyl isomaltulose at above-mentioned Palatinose by shortening, also comprise by single-action high dense evaporation, spray drying granulation after reaction terminates and be packaged to be finished solid hydroxyl isomaltulose.
Compared with prior art, beneficial effect of the present invention is:
The present invention adopts the special catalyst compounded of independent research, hydrogenation reaction pressure is made to be reduced to 0.5-0.7Mpa from tradition from 10-12Mpa, temperature of reaction DEG C is reduced to 110-120 from tradition from 130-145, mixing speed divides from traditional 700-800r/ and is reduced to 200-300r/ and divides, transformation efficiency brings up to 99-99.5% from former 97-98%, overhaul of the equipments by once delay original half a year to annual annually, improve equipment operation ratio, along with reaction conditions becomes gentle, alleviate machine utilization, improve processing safety, product purity is higher.Skeletal nickel catalyst and nickel-copper catalyst effectively can improve transformation efficiency, make reaction conditions gentle, reduce production difficulty, improve processing safety.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail, but does not form any limitation of the invention.
embodiment 1
1, take the Palatinose 1200g that purity is 98wt%, the 1200g that adds water is to autoclave, and dissolve allotment into about 2000Ml, 50% solution, obtains syrup;
2, take skeletal nickel catalyst 8g, nickel-copper catalyst 6g, adds in syrup and stirs evenly, and in reaction process, stirring velocity is 200-300r/min; Wherein, skeletal nickel catalyst is the Raney's nickel that the triumphant Chemical Industry Science Co., Ltd of upper Hisoon produces, nickel-method for preparing copper catalyst as The Journal of Catalysis 81,204-13, described in 1983.
3, regulate syrup pH value to 5.0-6.0 with 2% liquid caustic soda and 2% hydrochloric acid;
4, carry out airtight test to autoclave, be filled with hydrogen pressure to 1MPa after passed examination, in cyclic permutation 3 detection hydrogen, oxygen is extremely lower than 0.3%, and being then filled with hydrogen is 0.6MPa;
5, heating is started.Design temperature 100 DEG C, closes when temperature reaches 100 DEG C and adds hot key.Control temperature of reaction 110-120 DEG C.
6, pressurize hydrogenation.Careful adjustment reaction pressure 0.6Mpa, along with the continuous hydrogenation of Palatinose in reaction process, hydrogen is consumed and pressure drop, opens hydrogen valve pressurising again to 0.6Mpa when dropping to 0.5Mpa, so constantly repeats hydrogenation until hydrogen pressure no longer drops to reaction end after pressurising.Close hydrogen inlet valve.
7, continue out stirring, stop heating.Open blow-off valve, carefully get about 50ml sample and detect reducing sugar lower than 0.04% for qualified to laboratory, PH about 7, confirm that reaction terminates.1 hour reaction times.
8, lower the temperature; Connect coil pipe water coolant, be cooled to 95 DEG C.
9, flash distillation discharge; Keep opening stirring, carefully open blow-off valve; Collect resultant of reaction.
10, nitrogen replacement; After operation terminates, open nitrogen valve, as above-mentioned 4th step replacement reaction kettle 3 times, the sampling of notice laboratory, detect examination quick-fried without blast for qualified.Reactor is used time adjustable pressure 1Mpa not, and nitrogen is with pressure deposits for band.
11, the resultant of reaction of step 9 is concentrated into concentration be after 85wt% through single-action standard pan about 110 DEG C evaporation concentration, removing portion of water wherein, concentration rises to 95 ~ 96% by about 85%, obtains the high dense syrup of hydroxyl isomaltulose.
12, the high dense syrup of hydroxyl isomaltulose after the high dense evaporation concentration of single-action; be injected in fixed fluidized bed spray drying granulation machine by gas stream atomizer; be dried to moisture <0.5%; and obtain solid Isomalt, then enter in Vibratingfluidbeddrier and finally dry and cool.
13, the solid Isomalt after drying-granulating is filled in special packing bag by automatic ration and obtains finished solid hydroxyl isomaltulose.
The purity of hydroxyl isomaltulose is 99.8%, and the content of reducing sugar is 0.08%.
Embodiment 2:
Substantially identical with embodiment 1, different places is, Palatinose is 1400g, and water is 1000g; Skeletal nickel catalyst 18.5g, nickel-copper catalyst 9.5g.Skeletal nickel catalyst is the Raney's nickel that the triumphant Chemical Industry Science Co., Ltd of upper Hisoon produces, and nickel-method for preparing copper catalyst is described in Chinese patent application CN201310028518.1, and ambrose alloy ratio is 1:1.
In step 6, careful adjustment reaction pressure 0.7Mpa, along with the continuous hydrogenation of Palatinose in reaction process, hydrogen is consumed and pressure drop, opening hydrogen valve pressurising again when dropping to 0.55Mpa to 0.7Mpa, so constantly repeating hydrogenation until hydrogen pressure no longer drops to reaction end after pressurising.Close hydrogen inlet valve.
The purity of hydroxyl isomaltulose is 99.84%, and the content of reducing sugar is 0.05%.
detection method
the detection of hydroxyl isomaltulose:high performance liquid chromatography
Chromatographic condition:
Moving phase: through the ultrapure water of 0.45 μm of filtering vacuum suction filtration;
Chromatographic column: 300*7.8mmCOREGEL-87C post;
Flow velocity: 0.5-0.8ml/min;
Column temperature: 60-85 DEG C;
Sampling volume: 20 μ L;
Standard substance prepare:
Take a certain amount of hydroxyl isomaltulose standard substance, N.F,USP MANNITOL standard substance and sorbyl alcohol standard substance to be dissolved in the water, to obtain Palatinose alcoholic solution that concentration is 20mg/ml and the N.F,USP MANNITOL mark solution that concentration is 0.1mg/mL and Sorbitol Solution USP;
Preparation of samples:
Take about 1000mg sample, in 50mL volumetric flask, use water constant volume.
Measure
Inject standardized solution and the sample solution of same volume respectively, the peak area of record GPS, GPM, N.F,USP MANNITOL, sorbyl alcohol, calculates the content of GPS and GPM.
the mensuration of reducing sugar:
Take 3.3g sample in iodine flask, add 25ml water, slowly add dissolving, add 20ml alkalescence Cuprocitrol test solution and several granulated glass spherees, after heated solution is about 4min, solution comes to life, keep boiling 3min, after rapid cooling, add acetic acid solution and the 20.0ml of 100ml dilution, 0.025mol/l iodine titration solution, while rock solution, while add 25ml dilute hydrochloric acid solution, when after resolution of precipitate, with the iodine liquid that the titration of 0.05mol/L Sulfothiorine is unnecessary, when nearly titration end point, add 2ml, the Starch Indicator of 1%, the Sulfothiorine volume consumed is no less than 12.8ml.
Above-describedly be only preferred embodiment of the present invention, all do within the scope of the spirit and principles in the present invention any amendment, equivalently to replace and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. prepared a method for hydroxyl isomaltulose by Palatinose by shortening, join after Palatinose is mixed with water in autoclave, under catalyzer existent condition, obtain hydroxyl isomaltulose with hydrogen reaction, it is characterized in that:
Temperature of reaction: 110 ~ 120 DEG C;
Hydrogenation pressure: 0.5 ~ 0.7MPa;
Mixing speed: 200-300r/ divides;
PH value in reaction: 5.0-6.0;
Catalyzer is: the mixture of skeletal nickel catalyst and nickel-copper catalyst, and wherein the weight of the mixture of skeletal nickel catalyst and nickel-copper catalyst is 1% ~ 2% of Palatinose weight; The part by weight of skeletal nickel catalyst and nickel-copper catalyst is 1:1 ~ 1:0.5.
2. Palatinose according to claim 1 prepares the method for hydroxyl isomaltulose by shortening, it is characterized in that, described Palatinose and the part by weight of water are 1:1 ~ 1.4:1.
3. Palatinose according to claim 2 prepares the method for hydroxyl isomaltulose by shortening, it is characterized in that, the reaction times is 0.5 ~ 1 hour, and the transformation efficiency of Palatinose is greater than 99.8%.
4. Palatinose according to claim 2 prepares the method for hydroxyl isomaltulose by shortening, it is characterized in that, the control method of described pH value is: the mixing solutions of Palatinose and water is 5.0 ~ 6.0 by being adjusted to pH value with 2wt% liquid caustic soda or 2wt% hydrochloric acid.
5. Palatinose according to claim 2 prepares the method for hydroxyl isomaltulose by shortening, it is characterized in that, also comprises by single-action high dense evaporation, spray drying granulation and be packaged to be finished solid hydroxyl isomaltulose after reaction terminates.
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| CN201510361774.1A CN105001279B (en) | 2015-06-26 | 2015-06-26 | The method that isomalt is prepared by catalytic hydrogenation by isomaltoketose |
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| CN201510361774.1A CN105001279B (en) | 2015-06-26 | 2015-06-26 | The method that isomalt is prepared by catalytic hydrogenation by isomaltoketose |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969824A (en) * | 2016-07-25 | 2016-09-28 | 山东百龙创园生物科技有限公司 | Preparation method of palatinitol |
| CN110813297A (en) * | 2019-10-15 | 2020-02-21 | 厦门大学 | Synthesis method of sugar alcohol |
Citations (6)
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|---|---|---|---|---|
| US4117173A (en) * | 1975-05-06 | 1978-09-26 | Suddeutsche Zucker-Aktiengesellschaft | Use of glucopyranosido-1,6-mannitol as a sugar substitute |
| US6103894A (en) * | 1997-01-17 | 2000-08-15 | Sudzucker Aktiengesellschaft | Process for the hydrogenation of sugars |
| US20040002597A1 (en) * | 1999-03-16 | 2004-01-01 | Sudzucker Aktiengesellschaft | Catalytic process for the modification of carbohydrates, alcohols, aldehydes or polyhydroxy compounds |
| WO2008077640A1 (en) * | 2006-12-22 | 2008-07-03 | Cargill, Incorporated | A process for the hydrogenation of a sugar or sugar mixture |
| CN101597309A (en) * | 2009-06-30 | 2009-12-09 | 广西投资集团维科特生物技术有限公司 | A kind of method of producing hydroxyl isomaltulose by Palatinose |
| CN103055870A (en) * | 2013-01-24 | 2013-04-24 | 中国科学院青岛生物能源与过程研究所 | Nickel/copper catalyst and preparation method thereof, and method for directly preparing 1,2-hexanediol from cellulosan by using nickel/copper catalyst |
-
2015
- 2015-06-26 CN CN201510361774.1A patent/CN105001279B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117173A (en) * | 1975-05-06 | 1978-09-26 | Suddeutsche Zucker-Aktiengesellschaft | Use of glucopyranosido-1,6-mannitol as a sugar substitute |
| US6103894A (en) * | 1997-01-17 | 2000-08-15 | Sudzucker Aktiengesellschaft | Process for the hydrogenation of sugars |
| US20040002597A1 (en) * | 1999-03-16 | 2004-01-01 | Sudzucker Aktiengesellschaft | Catalytic process for the modification of carbohydrates, alcohols, aldehydes or polyhydroxy compounds |
| WO2008077640A1 (en) * | 2006-12-22 | 2008-07-03 | Cargill, Incorporated | A process for the hydrogenation of a sugar or sugar mixture |
| CN101597309A (en) * | 2009-06-30 | 2009-12-09 | 广西投资集团维科特生物技术有限公司 | A kind of method of producing hydroxyl isomaltulose by Palatinose |
| CN103055870A (en) * | 2013-01-24 | 2013-04-24 | 中国科学院青岛生物能源与过程研究所 | Nickel/copper catalyst and preparation method thereof, and method for directly preparing 1,2-hexanediol from cellulosan by using nickel/copper catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969824A (en) * | 2016-07-25 | 2016-09-28 | 山东百龙创园生物科技有限公司 | Preparation method of palatinitol |
| CN110813297A (en) * | 2019-10-15 | 2020-02-21 | 厦门大学 | Synthesis method of sugar alcohol |
| CN110813297B (en) * | 2019-10-15 | 2021-04-30 | 厦门大学 | Synthesis method of sugar alcohol |
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| CN105001279B (en) | 2018-07-17 |
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Denomination of invention: Preparation of isomaltulose alcohol from isomaltulose by catalytic hydrogenation Effective date of registration: 20220523 Granted publication date: 20180717 Pledgee: China Co. truction Bank Corp Zhaoqing branch Pledgor: ZHAOQING CORUSCATE BIOLOGICAL TECHNOLOGY CO.,LTD. Registration number: Y2022980006098 |