CN104045670B - A kind of preparation method of mannose - Google Patents

A kind of preparation method of mannose Download PDF

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CN104045670B
CN104045670B CN201310082764.5A CN201310082764A CN104045670B CN 104045670 B CN104045670 B CN 104045670B CN 201310082764 A CN201310082764 A CN 201310082764A CN 104045670 B CN104045670 B CN 104045670B
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cesium
acid
mannose
preparation
phosphomolybdic acid
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CN104045670A (en
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杜昱光
刘启顺
陈玮
岳敏
崔刚
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Jiao Siming
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DALIAN GLYCOBIO Co Ltd
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Abstract

The present invention relates to a kind of method for efficiently preparing mannose, specifically with phosphomolybdate as solid catalyst, efficient catalytic glucose conversion prepares mannose.The technology raw material that the present invention is provided is extensively, cheap;Process is simple, separation are simply, catalyst is repeatable utilizes, and whole production cost is lower, with very strong competitiveness.

Description

A kind of preparation method of mannose
Technical field
The present invention relates to a kind of method for efficiently preparing mannose, i.e., with water insoluble phosphomolybdic acid cesium salt as solid catalysis Agent, efficient catalytic glucose prepares mannose, and phosphomolybdic acid caesium is repeatable to be utilized.Present invention process is simple, transformation efficiency is high, process Green, low production cost.
Technical background
Mannose molecules formula is C6H12O6, it is the isomers of glucose, it is naturally occurring six carbon aldose, in nature It is present in dom nut, yeast, red algae, coffee grounds, serum globulins, ovomucoid tuberculosis bar in the form of glycan extensively Bacterium.There are a large amount of galactomannans in carob bean gum and melon bean gum.Mannose is a large amount of in the form of Glucomannan in konjaku In the presence of.Additionally, mannose is present in certain plants pericarp such as orange peel on a small quantity with free state, in the fruit such as peach, apple.
Mannose can suppress inflammatory reaction during wound healing, reduce the quantity of neutrophil leucocyte in wound fluid, subtract The growth of few scar granulation tissue, can suppress the oxidative burst of neutrophil leucocyte;The derivative of mannose is to peritonitis, adjuvanticity Arthritis, inflammation during wound healing has antiinflammatory action.But, the maximum application field of current mannose is Hydrogenation for sweet dew Alcohol.
The technology for preparing mannose at present mainly has following several, and one is by corozo of the hydrolysis containing mannosan Son, yeast, red algae, coffee grounds, carob bean gum, melon bean gum, konjaku etc. are then peeled off preparing mannose, and the raw material of the method comes Source is limited, causes small scale, and production cost is high;Two is to prepare mannose by fucose isomerase isomery fructose, and the method enzyme is not It is easy to get expensive to, fructose starting materials, industrial prospect is not good.Production now is upper main using molybdic acid or molybdate isomery grape Sugared system prepares mannose(Chinese Patent Application No.:201110340562;201010197402), but molybdic acid or ammonium molybdate can be molten Yu Shui, as catalyst reaction it is complete after, separate difficult, and can not reuse, increased production cost.Solid catalyst has The characteristics of efficiency high, process green, after the completion of reaction, in that context it may be convenient to which separating catalyst and reaction solution, separation process are more simple Single, catalyst is reusable, it is possible to decrease production cost.
The content of the invention
It is an object of the invention to provide the technology that a kind of solid catalyst efficient catalytic transforming glucose prepares mannose, Present invention process is simple, transformation efficiency is high, process is green, low production cost, can overcome that raw material in current technique is rare, separate It is difficult.Production cost problem high.
To achieve the above object, the technical solution adopted by the present invention is:
A kind of preparation method of mannose, with water insoluble phosphomolybdic acid caesium as catalyst, at 60-180 DEG C, in water phase Transforming glucose prepares mannose.
The phosphomolybdic acid caesium preparation process is as follows:Phosphomolybdic acid is soluble in water, make the mass concentration 0.1- of phosphomolybdic acid in water 50%, add the cesium salt of 0.1-5 times of phosphomolybdic acid molal quantity or containing cesium compound, stirred 0.1-24 hours at 10-100 DEG C, filtering Obtain solid phosphomolybdic acid cesium salt.
Cesium salt is cesium carbonate, cesium chloride, cesium nitrate, cesium sulfate, cesium iodide, cesium bromide, cesium formate containing cesium compound The mixture of one or two or more kinds.
Can be dried at 10-150 DEG C 0.5-24 hours using preceding, described solid phosphomolybdic acid cesium salt, be then more than Activated 0.5-20 hours at 150-800 DEG C.
The mass concentration of the glucose is 1%-50%, and phosphomolybdic acid caesium consumption is the 0.1%-100% of glucose quality.
The glucose solution before the reaction, can use proton acid for adjusting pH to 1-6.9, and Bronsted acid is hydrochloric acid, sulfuric acid, phosphorus One kind of acid, acetic acid, nitric acid, formic acid, hydrobromic acid etc. or two kinds of mixtures.
After the completion of reaction, phosphomolybdic acid caesium is gone out by filtering or centrifugation, phosphomolybdic acid caesium is reusable.
After the completion of reaction, after phosphomolybdic acid caesium is separated, the mannose and glucose in solution are separated, then sweet dew Sugar crystallization can prepare mannose sterling.
The invention has the advantages that
Sweet dew is prepared preparing mannose and enzyme process isomery fructose relative to from the natural living resources containing mannosan Sugar, raw materials of glucose wide material sources of the invention, price is lower, preparation process efficiency high, so that production cost is lower.It is relative with The molybdate such as molybdic acid or ammonium molybdate prepares mannose for catalyst isomery glucose, and the present invention is with phosphomolybdic acid caesium as solid catalysis Agent, separation simpler, process is more green, catalyst is repeatable utilizes, so that production cost is lower.
From the above it can be seen that the technology raw material sources for preparing mannose that the present invention is provided are extensively, it is cheap;Technique Simply, the repeatable utilization of simple, catalyst is separated, whole production cost is lower, with very strong competitiveness.
Brief description of the drawings:
Fig. 1 is the reaction solution analysis collection of illustrative plates of HPLC of embodiment 8, and previous peak is glucose, and latter peak is sweet dew Sugar, it can be seen that the generation without other impurities.
Specific embodiment
The preparation of the phosphomolybdic acid caesium of embodiment 1(1:1)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.163g cesium carbonates, stir 8 hours, production Yellow-green precipitate, aging 20 hours, is filtrated to get precipitation, in 50 DEG C of drying, in 300 DEG C of calcinations 2 hours, obtains the catalysis of phosphomolybdic acid caesium Agent 1.92g.
The preparation of the phosphomolybdic acid caesium of embodiment 2(1:2)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.325g cesium carbonates, stir 8 hours, production Yellow-green precipitate, aging 20 hours, overanxious precipitation, in 50 DEG C of drying, in 300 DEG C of calcinations 2 hours, obtained phosphomolybdic acid cesium-promoted catalyst 1.98g。
The preparation of the phosphomolybdic acid caesium of embodiment 3(1:3)
Take 1.88g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.488g cesium carbonates, stir 8 hours, production Yellow-green precipitate, aging 20 hours, overanxious precipitation, in 50 DEG C of drying, in 300 DEG C of calcinations 2 hours, obtained phosphomolybdic acid cesium-promoted catalyst 2.05g。
The preparation (1 of the phosphomolybdic acid caesium of embodiment 4:2)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.36g cesium sulfates, stir 8 hours, production Yellow-green precipitate, aging 20 hours, overanxious precipitation, in 50 DEG C of drying, in 300 DEG C of calcinations 2 hours, obtained phosphomolybdic acid cesium-promoted catalyst 1.95g。
The preparation of the phosphomolybdic acid caesium of embodiment 5(1:3)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.5g cesium chlorides, stir 8 hours, production is yellow Green precipitate, aging 20 hours, overanxious precipitation, in 50 DEG C of drying, in 300 DEG C of calcinations 2 hours, obtained phosphomolybdic acid cesium-promoted catalyst 2.02g。
The preparation of the phosphomolybdic acid caesium of embodiment 6(1:2)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.39g cesium nitrates, stir 8 hours, production Yellow-green precipitate, aging 20 hours, filtering precipitation, in 110 DEG C of dryings 5 hours, in 300 DEG C of calcinations 2 hours, phosphomolybdic acid caesium urge Agent 1.96g.
The preparation of the phosphomolybdic acid caesium of embodiment 7(1:2)
Take 1.82g phosphomolybdic acids (with anhydrous calculating) to be dissolved in 20mL water, add 0.334g cesium hydroxides, stir 8 hours, it is raw Produce light-yellow precipitate, aging 20 hours, filtering precipitation, in 110 DEG C of dryings 5 hours, in 300 DEG C of calcinations 2 hours, phosphomolybdic acid caesium Catalyst 1.94g.
It is prepared by the mannose of embodiment 8
Take 30g glucose to be dissolved in 100mL water, the catalyst for adding 0.3g embodiments 1 to prepare, adjusted with the hydrochloric acid of 2mol/L PH to 3, is reacted 4 hours at 120 DEG C, and reaction solution is analyzed with HPLC, and mannose yield is 28%.
The reaction solution HPLC of Fig. 1 embodiments 8 analyzes collection of illustrative plates, analysis condition:Dionex pulsed amperometries, CarboPacTM PA10 posts;Detection temperature:30 degree;Mobile phase:18mmol/L NaOH, 1mL/min;Sample size:10ul.
It is prepared by the mannose of embodiment 9
Take 30g glucose to be dissolved in 100mL water, the catalyst for adding 0.3g embodiments 2 to prepare, adjusted with the sulfuric acid of 2mol/L PH to 3, is reacted 4 hours at 130 DEG C, and reaction solution is analyzed with HPLC, and mannose yield is 27%.
It is prepared by the mannose of embodiment 10
Take 30g glucose to be dissolved in 100mL water, the catalyst for adding 0.3g embodiments 5 to prepare, adjusted with the hydrochloric acid of 2mol/L PH to 3, is reacted 3 hours at 140 DEG C, and reaction solution is analyzed with HPLC, and mannose yield is 30%.
The mannose of embodiment 11 is isolated and purified
5Kg crystal glucose purified waters are diluted to mass concentration concentration 30%, are carried out using the method for embodiment 8 different Structure, HPLC detection mannoses yield 27.8%.After foregoing gained isomery mixed liquor is filtered, enter into Simulation moving bed Row separating-purifying, obtains component B1 and the component A1 rich in glucose rich in mannose.Component A1 returns to Simulation moving bed system System is circulated utilization, the content 91.2% of mannose in component B1.Through flush distillation, concentration is 55%, Ran Houjia to component B1 Enter 18g activated carbon to be decolourized, through desolventing technology after, carry out double evaporation-cooling, obtain the feed liquid that concentration is 92%.The feed liquid is entered Row aqueous crystallization.Falling temperature gradient control in crystallization process:0~12 hour, 0.5 DEG C was dropped per hour;13~24 hours, per hour 0.8 DEG C of drop;After 24 hours, 1.0 DEG C are dropped per hour, until being down to 20~30 DEG C, through centrifuge refining after crystallizing 86 hours, obtain Crude crystalline D-MANNOSE C1 weights 2.75Kg.Absolute ethyl alcohol with consumption as the 28% of wet product sweet dew sugar weight is to thick D-MANNOSE Carry out immersion in 20 minutes refined, the crystallization D-MANNOSE finished product 2.54Kg of content 99.4% is obtained after drying, product yield is 50.7%.
By above embodiment as can be seen that the method for preparing mannose of present invention raising, is solid with phosphomolybdic acid caesium Body catalyst effect catalysis glucose conversion prepares mannose, and raw material sources are extensively, cheap;Process is simple, separate it is simple, urge Agent is repeatable to be utilized, and whole production cost is lower, with very strong competitiveness.

Claims (8)

1. a kind of preparation method of mannose, it is characterised in that:With water insoluble phosphomolybdic acid caesium as catalyst, at 60-180 DEG C Under, transforming glucose prepares mannose in water phase, the glucose solution before the reaction, with proton acid for adjusting pH to 1-6.9.
2. preparation method according to claim 1, it is characterised in that:
The phosphomolybdic acid caesium preparation process is as follows:Phosphomolybdic acid is soluble in water, make the mass concentration 0.1-50% of phosphomolybdic acid in water, Add the cesium salt of 0.1-5 times of phosphomolybdic acid molal quantity or containing cesium compound, stirred 0.1-24 hours at 10-100 DEG C, be filtrated to get Solid phosphomolybdic acid cesium salt.
3. preparation method according to claim 2, it is characterised in that:Cesium salt or containing cesium compound be cesium carbonate, cesium chloride, The mixture of one or two or more kinds of cesium nitrate, cesium sulfate, cesium iodide, cesium bromide, cesium formate.
4. preparation method according to claim 2, it is characterised in that:
Dried at 10-150 DEG C 0.5-24 hours using preceding, described solid phosphomolybdic acid cesium salt, then more than 150-800 DEG C Lower activation 0.5-20 hours.
5. preparation method according to claim 1, it is characterised in that:The mass concentration of the glucose is 1%-50%, Phosphomolybdic acid caesium consumption is the 0.1%-100% of glucose quality.
6. preparation method according to claim 1, it is characterised in that:The Bronsted acid be hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, Nitric acid, formic acid, one kind of hydrobromic acid or two kinds of mixtures.
7. preparation method according to claim 1, it is characterised in that:
After the completion of reaction, phosphomolybdic acid caesium is gone out by filtering or centrifugation, phosphomolybdic acid caesium is reusable.
8. preparation method according to claim 1, it is characterised in that:
After the completion of reaction, after phosphomolybdic acid caesium is separated, the mannose and glucose in solution are separated, then mannose knot Crystalline substance can prepare mannose sterling.
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CN104447888B (en) * 2014-12-04 2017-08-01 青岛蜜福堂健康科技有限公司 A kind of preparation method and applications of psicose

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US5049375A (en) * 1989-05-31 1991-09-17 Kao Corporation Oral compositions containing colloidal fluoride
EP0710501A2 (en) * 1994-10-31 1996-05-08 Cerestar Holding Bv Catalyst regeneration
CN101851689A (en) * 2010-06-11 2010-10-06 谭卫星 Preparation process of D-mannose
CN102329340A (en) * 2011-11-01 2012-01-25 青岛明月海藻集团有限公司 Method for preparing D-mannose
CN102627564A (en) * 2012-03-25 2012-08-08 聊城大学 Green method for nitrifying benzene with nitric acid to prepare nitrobenzen
CN102883804A (en) * 2010-02-15 2013-01-16 卡吉尔公司 Epimerisation of saccharides

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4029878A (en) * 1975-05-19 1977-06-14 Ici United States Inc. Process for preparing mannitol from glucose
US5049375A (en) * 1989-05-31 1991-09-17 Kao Corporation Oral compositions containing colloidal fluoride
EP0710501A2 (en) * 1994-10-31 1996-05-08 Cerestar Holding Bv Catalyst regeneration
CN102883804A (en) * 2010-02-15 2013-01-16 卡吉尔公司 Epimerisation of saccharides
CN101851689A (en) * 2010-06-11 2010-10-06 谭卫星 Preparation process of D-mannose
CN102329340A (en) * 2011-11-01 2012-01-25 青岛明月海藻集团有限公司 Method for preparing D-mannose
CN102627564A (en) * 2012-03-25 2012-08-08 聊城大学 Green method for nitrifying benzene with nitric acid to prepare nitrobenzen

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Effective date of registration: 20231227

Address after: No. 34, Building 8, Bajiao South Road, Shijingshan District, Beijing, 100043

Patentee after: Jiao Siming

Address before: Room 2301, Building A, Xinghai Building, No. 595 Zhongshan Road, Dalian City, Liaoning Province, 116023

Patentee before: DALIAN GLYCOBIO Co.,Ltd.