CN104045670B - A kind of preparation method of mannose - Google Patents
A kind of preparation method of mannose Download PDFInfo
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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
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- phosphomolybdic acid
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- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 21
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 23
- 239000008103 glucose Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 35
- 229910052792 caesium Inorganic materials 0.000 claims description 29
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 10
- -1 cesium compound Chemical class 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 5
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 230000001131 transforming effect Effects 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- ATZQZZAXOPPAAQ-UHFFFAOYSA-M caesium formate Chemical compound [Cs+].[O-]C=O ATZQZZAXOPPAAQ-UHFFFAOYSA-M 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 230000004913 activation Effects 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000011949 solid catalyst Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000009508 confectionery Nutrition 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 229930091371 Fructose Natural products 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GZCGUPFRVQAUEE-KVTDHHQDSA-N aldehydo-D-mannose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O GZCGUPFRVQAUEE-KVTDHHQDSA-N 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-RWOPYEJCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 240000007154 Coffea arabica Species 0.000 description 2
- 244000241257 Cucumis melo Species 0.000 description 2
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- 229920002752 Konjac Polymers 0.000 description 2
- 229920000161 Locust bean gum Polymers 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 241000206572 Rhodophyta Species 0.000 description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000010420 locust bean gum Nutrition 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 210000004493 neutrocyte Anatomy 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000029663 wound healing Effects 0.000 description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- 244000202285 Acrocomia mexicana Species 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 206010063560 Excessive granulation tissue Diseases 0.000 description 1
- PNNNRSAQSRJVSB-SLPGGIOYSA-N Fucose Natural products C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C=O PNNNRSAQSRJVSB-SLPGGIOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 102000004195 Isomerases Human genes 0.000 description 1
- 108090000769 Isomerases Proteins 0.000 description 1
- 108010064983 Ovomucin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 102000005686 Serum Globulins Human genes 0.000 description 1
- 108010045362 Serum Globulins Proteins 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical class [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 210000001126 granulation tissue Anatomy 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002703 mannose derivatives Chemical class 0.000 description 1
- 150000002704 mannoses Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 206010034674 peritonitis Diseases 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000004730 pulsed amperometry Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000019254 respiratory burst Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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
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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