CN1177586A - Preparation method for D-mannitol - Google Patents

Preparation method for D-mannitol Download PDF

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CN1177586A
CN1177586A CN 97106616 CN97106616A CN1177586A CN 1177586 A CN1177586 A CN 1177586A CN 97106616 CN97106616 CN 97106616 CN 97106616 A CN97106616 A CN 97106616A CN 1177586 A CN1177586 A CN 1177586A
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glucose
seminose
usp mannitol
fructose
preparation
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CN1060756C (en
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于家波
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Abstract

The preparation method of mannitol includes the following steps: (a) making glucose solution pass through the process of chemical isomerization to obtain mixed solution of glucose and mannitose; (b) making obtained mixed solution of glucose and mannitose pass through immobilized glucose isomerase column bed to produce mannitose-fructose-glucose solution X1; (c) making glucose solution X1 pass through the process of hydrogenation treatment to obtain the mannitol-enriched solution. Said preparation method is convenient and economic, and its mannitol yield is higher.

Description

The preparation method of N.F,USP MANNITOL
The present invention mainly be a kind of be raw material with glucose, produce the preparation technology of N.F,USP MANNITOL and the Sorbitol Solution USP be rich in N.F,USP MANNITOL.
D-N.F,USP MANNITOL, formal name used at school is six alcohol, are widely used in industries such as medicine, food, chemical industry, can also be as the low heat value sweeting agent.The production of N.F,USP MANNITOL the earliest adopts the natural extract method to extract from marine plants such as sea-tangle marine alga.N.F,USP MANNITOL also can pass through D-seminose or the chemosynthesis of D-fructose shortening.In theory, pure D-seminose hydrogenation can obtain 100% N.F,USP MANNITOL, and D-fructose hydrogenation can obtain 50% sorbyl alcohol and 50% N.F,USP MANNITOL.It is the sucrose hydrolysis product that the U.S. begins to adopt Nulomoline the fifties, and shortening prepares N.F,USP MANNITOL, is reported under the neutrallty condition as U.S. Patent No. 2759024, to the Nulomoline hydrogenation, contains the N.F,USP MANNITOL of 24～26% (butts) in the alcohol mixture approximately.Under alkaline condition or adopt catalysts selective that Nulomoline is carried out hydrogenation, can improve the content of N.F,USP MANNITOL in the alcohol mixture, as United States Patent(USP) Nos. 3,329,729,3,763,246,3,725,199, the content of N.F,USP MANNITOL can reach 30～36%, 27～31% and 28～29% respectively.Though under alkaline condition, the yield of N.F,USP MANNITOL increases, the decomposition reaction of sugar also increases greatly.
The Bilik of Czech in 1972 has reported under acidic conditions, is catalyzer with the molybdate, and glucose can be converted into the D-seminose, and transformation efficiency is about 25% (Chem.Zvesti., 26,183-186 (1972)).1975, people such as the Walter.M.Kruse of the U.S. improved this method, and were used for producing N.F,USP MANNITOL, and the content of N.F,USP MANNITOL can reach about 30%.United States Patent(USP) Nos. 4083881 and 4173514 has reported that respectively glucose produces 28～36% seminose earlier through the molybdate katalysis, residue glucose is through the glucose isomer enzyme effect, part generates fructose, with above-mentioned mixed sugar liquid hydrogenation, can obtain being rich in the alcohol mixture solution of N.F,USP MANNITOL, the crystallization of mannitol yield can reach 40～42%.
1988, Japanese Patent JP03258437 studied glucose in methanol solution, was catalyzer with the organic amine, and the isomerization back end hydrogenation prepares the method for N.F,USP MANNITOL, dissolving 40.8 gram CaCl2H in 200 gram methyl alcohol 2O and 50 gram glucose add 24.3 gram quadrols simultaneously, and 53 ℃ of isomerization 10 minutes contain 35.0% seminose in the solution, and 42.9% fructose and 15.1% glucose after hydrogenation, refining, the crystallization, can get 26 gram N.F,USP MANNITOL.Though this method N.F,USP MANNITOL yield is higher, owing to adopted organic solvent, and need to add a large amount of calcium salt and organic amine, cause very big difficulty to product purification.Japanese Patent JP.04368347 has reported glucose through molybdate catalysis, after the part isomery turns to seminose, with Pb 2+Type or Cu 2+The storng-acid cation exchange resin fixed bed separates mixing sugar solution, and the solution concentration back end hydrogenation that will be rich in seminose then prepares N.F,USP MANNITOL.Though this method technology is simpler, but because glucose and seminose are all aldose and pyranose form six-membered ring structure, the only chirality difference of second carbon, so character is very approaching, separation difficulty, resin isolation efficient is low, need a large amount of resins, it is rarer to separate back solution, and the rate of recovery of seminose is also lower, in addition, contain small amounts of Pb in the solution of separation back 2+, Cu 2+Etc. heavy metal ion, need to increase an one-step refining step.The patent EP580490 of France ROQUETTE company has reported the new operational path of strip adoption high fructose syrup production N.F,USP MANNITOL, glucose content is lower than 15% high fructose syrup, adopt seminose fructose allomerase to carry out isomerization, produce 15～29% seminose, syrup after the isomerization is carried out chromatographic separation, the component that obtains being rich in the component of seminose and be rich in fructose, the component isomerization again of fructose will be rich in, and the component that will be rich in seminose carries out hydrogenation, adopts this method to produce 1 kilogram of N.F,USP MANNITOL and only produces 0.43 kilogram 85% sorbyl alcohol.This method has adopted chromatographic separation twice, once is the high fructose syrup of preparation fructose content more than 85%, and another time is to seminose enrichment in the syrup after the isomerization.The dilution that chromatographic separation caused need be evaporated a large amount of water, and simultaneously, seminose fructose allomerase is suitability for industrialized production not as yet, costs an arm and a leg, and has limited the application of this method.
The purpose of this invention is to provide a kind of high yield and the easy N.F,USP MANNITOL production method that is easy to get.
Present method is raw material with glucose, obtains the N.F,USP MANNITOL of high yield by following four steps: at first be catalyzer with the molybdate (a), under acidic conditions, the glucose moiety isomery turned to seminose; (b), generate the mixing solutions of glucose-seminose-fructose with the mixing solutions of glucose-seminose post bed by the fixation glucose allomerase; (c) adopt fixed bed or continuous chromatography to separate the mixing solutions X that obtains being rich in seminose-fructose above-mentioned mixing solutions 1With the solution X that is rich in glucose 2, with X 2Get back to (b) isomerization again; (d) with X 1The high pressure shortening obtains to be rich in the solution of N.F,USP MANNITOL.
The N.F,USP MANNITOL production technique that relates among the present invention, the first step is under acidic conditions, the glucose catalytic isomerization is turned to the mixing solutions of glucose and seminose, the concentration of glucose solution can be 40～70wt%, after adding the molybdate dissolving, regulate PH to 2.0-5.0, temperature of reaction is 90-160 ℃, reaction times is 10 minutes-3 hours, and the rising of reaction times with temperature of reaction reduces.
The pH value of glucose solution and temperature of reaction have bigger influence to the speed and the transformation efficiency of isomerization reaction.The pH value of isomerization reaction can be 2.0-5.0, and pH value is too high, and speed of response slows down, and pH value is low excessively, can cause the decomposition and the oligomerisation of glucose, makes the liquid glucose color burn.The adjusting of sugar soln pH value can be adopted hydrochloric acid or sulfuric acid.The temperature of reaction rising, reaction is accelerated, and the reaction times shortens, and the transformation efficiency of seminose rises, and for example, under the normal pressure, 95～98 ℃ were reacted 2.5～3.0 hours, and mannose content can reach 29% (butt); 135 ℃ were reacted 10 minutes, and mannose content can reach 34% (butt).When temperature of reaction is higher than 160 ℃, can cause that sugar decomposes rapidly, darkens reaction soln.
Catalyst for reaction can adopt ammonium molybdate, Sodium orthomolybdate, molybdic acid or molybdic oxide etc.With the increase of catalyst levels, speed of response increases, but the also corresponding increase of side reactions such as breakdown of glucose.More suitable molybdate consumption is 0.05～0.3wt% of glucose over dry content.
Glucose after the isomerization-seminose mixing solutions, the rare glucose that goes out with chromatographic separation, i.e. X 2, be diluted to 45～50wt% after, carry out refinement treatment, to remove molybdate catalyst and other impurity.Syrup decolorization can adopt gac or decolorizing resin, and the sugar soln after the decolouring is handled by storng-acid cation exchange resin and weak base anion-exchange resin, removes the ion in the solution.
Second step that relates to technology among the present invention is for above-mentioned glucose-seminose mixing solutions, by common fixation glucose allomerase post bed, makes that remaining glucose moiety is converted into fructose in the solution.
Adopt fixation glucose amylase (as the SweetzymeT of Denmark NOVO company), residue glucose moiety in the solution is converted into fructose, and suitable operational condition is: 55～65 ℃ of temperature of reaction, syrup pH7.0-7.5, syrup concentration 45～55wt%, fructose content is lower than 5% (butt), adds MgSO in every liter of sugar soln 47H 2O 0.4～1.5 gram, with the raising enzymic activity, and anti-Ca short of money 2+Restraining effect to enzymic activity.Syrupy flow velocity keep 1～1.5 times of column volume/hour, make glucose in the syrup maintain 42～44% to the transformation efficiency of fructose.
The 3rd of related technology the step obtained being rich in the mixing solutions X of seminose and fructose for the mixing solutions that will contain seminose-fructose-glucose carries out chromatographic separation among the present invention 1With the solution X that is rich in glucose 2Though,, use be common fixed bed and chromatography separating method, this step is that prior art does not relate to.
The high fructose syrup of fructose content 42% prepares fructose content 90% through chromatographic separation the technology of high fructose syrup is quite ripe.Because configuration and character are very approaching, separating of glucose and seminose is the comparison difficulty.N.F,USP MANNITOL preparation technology's characteristics are less demanding to the separation degree of seminose and glucose among the present invention, and the content that separates seminose in the glucose component of back is not had particular requirement.With X 1Be concentrated into 20-30%, with Ca 2+The type storng-acid cation exchange resin is a stationary phase, resin is preferably the chromatography resin (as the PCR series chromatography resin of Britain Purolite company) of equal grain, moving phase is pure water or deionized water, can adopt fixed bed, and analog stream movable bed or continuous chromatography device separate.The peak sequence of three kinds of sugar is followed successively by: glucose, seminose and fructose.By chromatographic separation, mixing sugar solution is divided into two portions: the component X that is rich in seminose and fructose 1With the component X that is rich in glucose 2, the fructose content (butt) that separates in the glucose component of back should be lower than 8%, is preferably lower than 5%.Tripping device preferably adopts continuous separation device (as the CSEP of U.S. Advanced Separation TechnologiesInc. R), easy to operate, production concentration is higher, X 2Component is got back to (b) fructose isomerization again.
The final step of technology involved in the present invention will be for being rich in the component X of fructose and seminose 1The high pressure catalytic hydrogenation.X after the chromatographic separation 1Component concentration is about 12～20%, this solution evaporation is concentrated into contain dry-matter 20-30wt%, adds hydrogenation catalyst, for example Raney nickel or platinum group supported catalyst heat, and stir, under 100-160 ℃, reacted 1.0-3.0 hour, pressure is that conventional hydrogenation pressure gets final product.In the solution, the N.F,USP MANNITOL that consists of 60-70wt% of dry-matter and the sorbyl alcohol of 30-40wt%, above-mentioned alcohol mixture solution pass through refining, concentrated post crystallization behind the hydrogenation.The crystallization yield of N.F,USP MANNITOL can reach 58-65%, and fusing point is greater than 165 ℃.
Better when D-glucose solution of the present invention adds pH=3.0-4.0 after the molybdate catalyst dissolving, temperature of reaction is controlled in the 95-140 ℃ of scope better.
Glucose isomerase turns to the seminose catalyst system therefor, also disposable load type catalyzer, and the carrier of loaded catalyst can adopt Al 2O 3, porous inorganic materials such as molecular sieve are preferably Al 2O 3, molybdate preferably adopts ammonium molybdate.Pickling process is adopted in the preparation of loaded catalyst, the consumption of ammonium molybdate is the 5-25wt% of carrier consumption, be preferably 10-20wt%, dipping catalyzer well in 300-600 ℃ of roasting promptly, maturing temperature is preferably 350-450 ℃, loaded catalyst can adopt fixed bed type reactor, makes glucose solution pass through reaction bed continuously; Also can adopt and stir axe formula reactor, after reaction finishes, adopt standing sedimentation or filtering recovering catalyst, adopt loaded catalyst, can significantly reduce the consumption of molybdate, in reaction process, can adopt relatively large catalyzer, thereby shorten the reaction times greatly and reduce byproduct of reaction, do not have molybdate in the reaction soln, can reduce the gac and the ion exchange resin consumption of refining usefulness.
The active constituent of loaded catalyst better is (NH4) 6Mo 7O 244H 2O.
Be the essential step that improves yield separating of glucose, seminose and fructose in the technology of the present invention, do not have in the prior art to relate to this step process, and three kinds of mixing sugar can adopt the fixed bed of prior art when separating, and perhaps the continuous chromatography method all can.
The inventive method adopts four steps, makes N.F,USP MANNITOL from glucose, has overcome many deficiencies that prior art exists, for example increase of sugar decomposition reaction, and the product purification difficulty is separated numerous and diversely, and productive rate is low, and cost is high.Effective conversion and the separating of three step of the present invention by first, second step, make last seminose and fructose hydrogenation after the N.F,USP MANNITOL yield improve greatly.The inventive method is not high to equipment requirements, and each goes on foot the reaction conditions maturation, and gained produces Lu compared with prior art, productive rate height not only, and technology is simple, and cost also reduces greatly.
Figure one is glucose after the mixing sugar solution separating, seminose, fructose content.
The following examples will help to describe better and understand the present invention.
Embodiment 1
Take by weighing 1.4 kilogram of one water crystallization glucose (moisture about 9%, back with), be dissolved in the 700ml water, add 3.5 gram (NH then 4) 6Mo 7O 244H 2O after the dissolving, regulates pH to 3.4 with 10% dilute sulphuric acid, is heated to 95～98 ℃ of stirring reactions 2.5 hours.Sampling, with the content of efficient liquid phase chromatographic analysis seminose and glucose, chromatographic column is Sugar-Pak II (waters), and detector is a differential refraction detector, and moving phase is ultrapure water.Below, the detection of sugar and alcohol is all the same.By analysis, mannose content is 29.31% in the solution, glucose content is 69.79%, above-mentioned solution is with the rare glucose solution (glucose 70.1% after separating, seminose 23.5%, fructose 6.2%) it is about 48% to be diluted to concentration, adds 1% activated carbon decolorizing, then by Zeo-karb (H +) and anionite-exchange resin (OH -) handle.
Liquid glucose after refining with 1% NaOH solution adjusting pH to 7.5, under 58 ℃, by fixation glucose allomerase post bed (NOVO isomerase SweetzymeT), is contained seminose 29.08%, fructose 30.75%, glucose 41.09% in the epimerized sugar liquid.
The separation of mixed sugar liquid adopts the stainless steel column of internal diameter 20cm strap clamp cover to finish, and stationary phase is the PCR-642 Ca type chromatography resin of Britain Purolite company, and bed height is 120cm, and each inlet amount 250ml squeezes into 60 ℃ of thermostat(t)ed waters in the resin column chuck.Moving phase is 60 ℃ of deionized waters, elution speed be 0.5BV (bed volume) per hour, collect eluate, every 150ml is as a sample.Glucose in the sample, seminose and fructose content are seen figure one.
With among the figure one 2 #-6 #Number sample merge X 2, mean concns is 9.93%, and wherein glucose content is 69.44% (butt, down together), and mannose content is 23.80%, and fructose content is 6.76%.Again returned for second step after concentrating and carry out isomerization (part solution can be used to the mixing solutions that alkene is released glucose-seminose).With among the figure 7 #-11 #Number sample merge X 1, mean concns is 10.10%, and wherein glucose content is 11.56%, and mannose content is 34.75%, and fructose content is 53.68%.Is 25% to carry out hydrogenation with the solution concentration that is rich in seminose and fructose to Bx.
With the X after concentrating 1Solution 600ml (containing dry-matter 151 grams) regulates pH to 8.0 with 10%NaOH, adds 60 gram Raney nickel catalyzators, and 130 ℃, hydrogen pressure 45kg/cm 2Down, hydrogenation is 2 hours in 2 liters autoclave.The mixing solutions of hydrogenation is through activated carbon decolorizing, sun (H +), cloudy (OH -) after the ion exchange resin treatment, with pure content in the efficient liquid phase chromatographic analysis alcohol mixture, wherein sorbyl alcohol is 38.35%, N.F,USP MANNITOL is 61.49%, with the crystallization of alcohol mixture solution concentration, be total to such an extent that N.F,USP MANNITOL crystal 85.6 restrains, the yield of N.F,USP MANNITOL is 56.7% (with respect to D-glucose).
Embodiment 2
Take by weighing 1.2 kilogram of one water crystallization glucose, be dissolved in the 500ml water, add 1.2 gram (NH 4) 6Mo 7O 244H 2After the O dissolving, regulate pH to 3.5, add in 2 liters the autoclave, be heated with stirring to 135 ℃ with 10% dilute sulphuric acid, kept 10 minutes, cooling discharging, mannose content is 34.12% in the solution, glucose 65.28%, sugar soln is diluted to about 48% decolouring, ion exchange treatment.Regulate pH to 7.5 with 1% NaOH, under 58 ℃, by fixation glucose allomerase post bed, flow out in the solution and contain glucose 38.89%, fructose 28.64%, seminose 32.25% with 1.1BV/ hour flow velocity.
Above-mentioned sugar soln adopts the continuous chromatography tripping device L100C type CSEP of U.S. AST company RSeparate, every resin column filling PCR-642Ca type chromatography resin 360ml, 30 posts are adorned 10.8 liters of resins altogether.Wherein 1 #The mouth water inlet, 15 #The mouth charging, 5 #Mouth and 26 #Fructose and seminose component X are rich in the mouth discharging after the separation 1Concentration is 15.4%, and wherein glucose content 7.82%, seminose 35.86%, and fructose 58.04% is rich in glucose component X 2Concentration is 12.8%, and wherein glucose content 66.76%, seminose 29.06%, fructose 4.18%.
With X 1Component is concentrated into 25% (BX), gets 600ml (containing dry-matter 153 grams) mixing sugar solution such as embodiment 1 and carries out hydrogenation, and is refining, crystallization contains N.F,USP MANNITOL 64.91% in the alcohol mixture solution, sorbyl alcohol 34.88%, be total to such an extent that N.F,USP MANNITOL crystal 92.0 restrains after the crystallization, 166 ℃ of fusing points, yield are 60.14%.
Embodiment 3
Take by weighing 1.0 kilogram of one water crystallization glucose, add the 1000ml water dissolution, add 25 gram MoO 3/ r-Al 2O 3Catalyzer, 95～98 ℃ of stirring reactions 1.5 hours contain seminose 31.29%, glucose 68.87% in the mixed sugar liquid.With above-mentioned solution with activated carbon decolorizing, ion exchange treatment.Press embodiment 1, the glucose moiety isomery is turned to fructose, contain glucose 39.18% in the mixing sugar solution, fructose 29.64%, seminose 31.33%.
Above-mentioned liquid glucose is according to embodiment 1, adopts fixed bed to separate, and is rich in after the separation in the mixing solutions of seminose and fructose to contain glucose 8.78%, seminose 37.14%, fructose 54.08%.Get 600ml solution (containing dry-matter 148 grams) hydrogenation, refining, contain N.F,USP MANNITOL 64.08% in the mixing solutions, sorbyl alcohol 35.64% is total to such an extent that N.F,USP MANNITOL crystal 91.8 restrains after the crystallization, and 165 ℃ of fusing points, yield are 62%.

Claims (7)

1. the preparation method of a D-N.F,USP MANNITOL, it is characterized in that its mainly by following four the step preparation technology:
(A) the D-glucose solution is under acidic conditions, under 90～160 ℃ of the temperature, is catalyzer with the molybdate, and part is converted into the D-seminose;
(B) mixed sugar liquid that (A) obtained, will remain glucose moiety and be converted into fructose under 55～65 ℃ by fixation glucose allomerase post bed;
(C) mixed sugar liquid that (B) is obtained adopts fixed bed or continuous chromatography to separate, and obtains being rich in the component X of seminose and fructose 1With the component X that is rich in glucose 2, with X 2Return (B) isomerization again;
(D) to being rich in the component X of seminose and fructose 1After concentrating, the high pressure shortening gets alcohol mixture behind the hydrogenation, and refining, concentrated post crystallization is isolated N.F,USP MANNITOL;
The actual conditions of above-mentioned preparation process (A) is:
The concentration of D-glucose solution is 40-70wt%, and acidic conditions is PH=2.0-5.0, and the consumption of molybdate is the 0.05-0.30wt% of amount of dry matter, 10 minutes-3 hours reaction times;
The actual conditions of (B) is in the above-mentioned preparation process:
Temperature of reaction 55-65 ℃, syrup pH=7.0-7.5, syrup concentration 45-55wt% adds MgSO in every liter of liquid glucose 47H 2The O0.4-1.5 gram, 1-1.5 times of column volume of syrup flow velocity/hour;
The actual conditions of (D) is in the above-mentioned preparation process:
X 1Be concentrated into 100-160 ℃ of 20-30% hydrogenation temperature, reaction times 1.0-3.0 hour.
2. the preparation method of D-N.F,USP MANNITOL according to claim 1 is characterized in that the PH=3.0-4.0 after the D-glucose solution adds the molybdate catalyst dissolving, and temperature of reaction is better at 95-140 ℃.
3. the preparation method of D-N.F,USP MANNITOL according to claim 1, it is characterized in that the D-glucose solution can be converted into the D-seminose in loading type molybdate catalyst lower section, wherein the consumption of molybdate is the 5-25wt% of carrier consumption, and the carrier of loaded catalyst is the porous inorganic material.
4. the preparation method of D-N.F,USP MANNITOL according to claim 3 is characterized in that in the loaded catalyst that it is 10-20wt% that the consumption of molybdate is preferably the carrier consumption.
5. the preparation method of D-N.F,USP MANNITOL according to claim 3, the carrier that it is characterized in that loaded catalyst can be Al 2O 3Or molecular sieve.
6. the preparation method of D-N.F,USP MANNITOL according to claim 3, the active constituent that it is characterized in that loaded catalyst is (NH preferably 4) 6Mo 7O 244H 2O.
7. the preparation method of D-N.F,USP MANNITOL according to claim 1 is characterized in that the enrichment of seminose and fructose can be with the fixed bed or the continuous chromatography method of Ca type chromatography resin.
CN97106616A 1997-09-19 1997-09-19 Preparation method for D-mannitol Expired - Fee Related CN1060756C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851689A (en) * 2010-06-11 2010-10-06 谭卫星 Preparation process of D-mannose
CN103288887A (en) * 2013-06-04 2013-09-11 北京大学 Method for preparing ketose by utilizing aldose
CN103831122A (en) * 2014-01-30 2014-06-04 内蒙古民族大学 Mixed catalyst for enhancing conversion rate of glucose to mannose
CN104151369A (en) * 2014-08-01 2014-11-19 山东福田药业有限公司 Preparation method of lyxose and application thereof
CN105255961A (en) * 2015-10-22 2016-01-20 邓和超 Isomerization method for glucose in fructose production process
CN108579747A (en) * 2018-02-28 2018-09-28 浙江工业大学 A kind of preparation method of fructose hydrogenation copper base catalyst

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5277007A (en) * 1975-12-19 1977-06-29 Towa Kasei Kogyo Kk Method of producing aqueous hexose and hexoseealcohol containing solution
JP2979442B2 (en) * 1991-06-18 1999-11-15 東和化成工業株式会社 Method for producing mannit and mannose

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851689A (en) * 2010-06-11 2010-10-06 谭卫星 Preparation process of D-mannose
CN101851689B (en) * 2010-06-11 2012-01-11 谭卫星 Preparation process of D-mannose
CN103288887A (en) * 2013-06-04 2013-09-11 北京大学 Method for preparing ketose by utilizing aldose
CN103288887B (en) * 2013-06-04 2016-01-27 北京大学 A kind of method being prepared ketose by aldose
CN103831122A (en) * 2014-01-30 2014-06-04 内蒙古民族大学 Mixed catalyst for enhancing conversion rate of glucose to mannose
CN103831122B (en) * 2014-01-30 2017-01-18 内蒙古民族大学 Mixed catalyst for enhancing conversion rate of glucose to mannose
CN104151369A (en) * 2014-08-01 2014-11-19 山东福田药业有限公司 Preparation method of lyxose and application thereof
CN105255961A (en) * 2015-10-22 2016-01-20 邓和超 Isomerization method for glucose in fructose production process
CN108579747A (en) * 2018-02-28 2018-09-28 浙江工业大学 A kind of preparation method of fructose hydrogenation copper base catalyst

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