CN104628793A - Method for isomerizing glucose into fructose in glycerin solvent - Google Patents
Method for isomerizing glucose into fructose in glycerin solvent Download PDFInfo
- Publication number
- CN104628793A CN104628793A CN201510084721.XA CN201510084721A CN104628793A CN 104628793 A CN104628793 A CN 104628793A CN 201510084721 A CN201510084721 A CN 201510084721A CN 104628793 A CN104628793 A CN 104628793A
- Authority
- CN
- China
- Prior art keywords
- fructose
- glucose
- reaction
- hydrotalcite
- turned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a method for isomerizing glucose into fructose in a glycerin solvent, which is environment-friendly, green and efficient. In the glycerin solvent, intermittent reaction on glucose is carried out under the catalysis of a magnalium hydrotalcite catalyst to obtain the fructose. The problem that in an existing alcohol solvent production process, glucose used as a reaction raw material cannot be fully dissolved in a methanol solvent so as to cause low production efficiency is solved.
Description
Technical field
The present invention relates to chemical field, particularly relate to a kind of method preparing platform chemicals with biomass material at biomass solvent system, specifically a kind of method glucose isomerase being turned to fructose in Glycerol solvents.
Background technology
The non-renewable people of impelling of fossil resource pay close attention to biomass energy.5-HMF is a kind of renewable industrial raw material, can produce in a large number from glucose or fructose dehydration reaction.Glucose is the main component of plant, and be also cellulosic structural unit, can obtain glucose by hydrocellulose, namely further dehydration obtains 5-HMF; Also glucose isomerization can be become fructose, then obtain 5-HMF by fructose dehydration.Glucose isomerase is turned to fructose and become exploitation cellulose series biomass resource very important link.The reaction solvent type adopted in known technology is mainly divided into two kinds: one be water as reaction solvent, another kind is exactly organic solvent.But, be no matter the transformation efficiency of glucose, or the yield of fructose is all lower, seriously hinders cellulose series biomass resource industrialized utilization process.
The preparation method of known technology, if I.Delido Vich and R.Palkovits is at <Catalytic activity and stability of hydrophobic Mg – Al hydrotalcites in the continuous aqueous-phase isomerization of glucose into fructose> (Catal.Sci.Technol., 2014, 00, 1 – 8) disclosed in aqueous phase, adopt magnesium aluminum-hydrotalcite (or being called Mg-Al hydrotalcite) to make glucose isomerase turn to fructose for catalyzer, when the aqueous glycerin solution and 1wt% catalyzer (relative to glucose) that adopt 1wt% react 48h at 90 DEG C, inversion rate of glucose is 14%, fructose yield is 12%.Although the method using water as a kind of reaction solvent, can have environmental protection, relatively cheap advantage, reactive behavior is obviously not high, and the yield of fructose is lower, is difficult to realize industrialization.
As Sungdong Yu, catalyzer is made Deng magnesium aluminum-hydrotalcite disclosed in <Isomerization of glucose into fructose over Mg – Al hydrotalcite catalysts> (Catalysis Communications 29 (2012) 63 – 67), at organic solvent N, isomerization reaction is there is in dinethylformamide, the transformation efficiency of the glucose obtained is 49.4%, and fructose yield is 34.6%.Although the inversion rate of glucose of the method and the more previous technology of fructose yield are significantly improved, because DMF belongs to toxic material, to human body and environment all harmful, its industrialization certainly exists many restrictions.
If Ricardo etc. is at <Active Sites in Sn-Beta for Glucose Isomerization to Fructose and Epimerization to Mannose> (ACS Catal.2014,4,2288 – 2297) disclosed in Sn-Beta be catalyzer, in 1% (w/w) glucose solution, isomerization reaction is there is respectively in water and methanol solution, it is better than the reaction effect in water that reaction result shows in methyl alcohol, under optimal conditions, transformation efficiency reaches 23.2%, and fructose yield is 10.3%.But methyl alcohol is very low to the solubleness of glucose, when adding higher raw material, glucose cannot fully be dissolved in methanol solvate, can have impact on reaction efficiency to a certain extent, is also difficult to realize suitability for industrialized production.
For this reason, a kind of not only environmental protection but also economic method for transformation is needed.
Summary of the invention
The object of this invention is to provide a kind of green, environmental protection, efficient method glucose isomerase being turned to fructose in Glycerol solvents.
The object of the present invention is achieved like this: the method that glucose isomerase should be turned to fructose in Glycerol solvents, in Glycerol solvents, glucose carries out rhythmic reaction and obtains fructose under the catalysis of magnesium aluminum-hydrotalcite catalyzer.
As preferably, described glycerol concentration is more than 95wt%.
As preferably, the mol ratio of Mg and Al in described magnesium aluminum-hydrotalcite catalyzer is 1:1 ~ 10:1; Preferred further, the mol ratio of Mg and Al in described magnesium aluminum-hydrotalcite catalyzer is 3:1.
Under guarantee glucose is fully dissolved in the prerequisite of Glycerol solvents, the add-on of glucose is 5 ~ 150wt% of glycerine total amount; The add-on of magnesium aluminum-hydrotalcite is 1 ~ 150wt% of glucose total amount; Temperature of reaction is 80 ~ 150 DEG C.
Under the prerequisite not affecting production efficiency and quality, be production control cost, temperature of reaction be optimized for 90 ~ 120 DEG C.
For ensureing the best catalytic effect of catalyzer, present invention also offers a kind of preparation method of magnesium aluminum-hydrotalcite catalyzer, it adopts coprecipitation method to prepare, and concrete steps are as follows:
(1) Mg (NO that mol ratio is 1:1 ~ 10:1 is accurately taken
3)
26H
2o, Al (NO
3)
39H
2o, mixed dissolution in deionized water, room temperature is accelerated to stir limit below and slowly drip NaOH solution in mixing solutions, be 9 ~ 10 to pH value, continue stir about 15 ~ 25min under dropwising rear room temperature, then in 70 DEG C of oil baths, heat 24h, after completion of the reaction, cooling, suction filtration are washed to neutrality, filter cake in 80 DEG C of vacuum-drying 12h, and grinding obtains white solid powder, i.e. carbonate form hydrotalcite;
(2) by carbonate form hydrotalcite roasting 10h at 500 DEG C in retort furnace, Mg-Al composite oxide is obtained;
(3) sample after roasting is added deionized water vigorous stirring in autoclave, in rare gas element, 60 DEG C of reaction 24h, obtain solid base catalyst after being filtered by reacted solution, afterwards at 80 DEG C of vacuum-drying 12h, get product.
Glycerine, has another name called glycerol, is a kind of reproducible industrial raw material.In traditional saponification industry, it is the principal by product in the steam-cracking process of animal tallow and vegetables oil saponification.In addition, glycerine is the Main By product in production of biodiesel process, accounts for 10% of product gross weight.In recent years, degraded cellulose class material is also had to carry out the report of synthetic glycerine.Therefore, glycerine can be produced by kinds of processes route, is a kind of relatively cheap reproducible chemicals.If glycerine to be used as the solvent of glucose isomerization reaction, obviously can to reduce manufacturing cost, increase economic efficiency.First, glycerine can with glucose with arbitrarily than dissolving each other; Secondly, glycerine is commonly used for foodstuff additive, asepsis environment-protecting; Finally, with water, DMF solvent phase ratio, glucose isomerization reaction activity in glycerine solution is high, obtains higher fructose yield under mild conditions.In sum, Glycerol solvents is adopted to have nontoxic, environmental protection, low production cost, transformation efficiency advantages of higher as the method for transformation of catalysis solvent.
Embodiment
Content of the present invention is described in detail below by way of specific embodiment.In the Glycerol solvents of more than 95wt%, glucose carries out rhythmic reaction under the catalysis of magnesium aluminum-hydrotalcite catalyzer, and isomerization obtains fructose.Wherein, for catalyzer, the mol ratio of Mg, Al content in magnesium aluminum-hydrotalcite can adopt the arbitrary proportion in 1:1 ~ 10:1, and namely Mg is excessive, but after considering the composite factor such as cost, reaction efficiency, is preferably the mol ratio 3:1 of Mg and Al as preferred plan.For isomerization reaction parameter, the add-on of glucose is 5 ~ 150wt% of glycerine total amount; Magnesium aluminum-hydrotalcite add-on is 5 ~ 150wt% of glucose total amount.Temperature of reaction is 80 ~ 150 DEG C, considers, temperature of reaction is optimized for 90 ~ 120 DEG C from factors such as production cost, yield and transformation efficiencys.
One, the preparation of magnesium aluminum-hydrotalcite catalyzer
Magnesium aluminum-hydrotalcite directly can adopt commercially available prod, and the common method of this areas such as coprecipitation method, ion exchange method, hydrothermal synthesis method also can be adopted to prepare voluntarily, and as following employing coprecipitation method prepares magnesium aluminum-hydrotalcite, its concrete steps are:
(1) 4.8g (1.87 × 10 is accurately taken
-2) Mg (NO
3)
26H
2o (M=256.41) and 2.35g (6.26 × 10
-3) Al (NO
3)
39H
2o (M=375.14) mixed dissolution is (mol ratio of Mg and the Al in raw material is about 3:1) in the deionized water of 22ml, 2g (5 × 10
-2) NaOH (M=40) is dissolved in the deionized water of 25ml, separately add 25ml deionized water in there-necked flask, two kinds of solution that under room temperature, slow dropping has prepared are in there-necked flask, accelerate to stir, and the pH value controlling solution in there-necked flask is 9 ~ 10, stir about 15 ~ 25min is continued under dropwising rear room temperature, then in 70 DEG C of oil baths, 24h is heated, after completion of the reaction, cooling, suction filtration are washed to neutrality, filter cake in 80 DEG C of vacuum-drying 12h, grinding obtains white solid powder, and namely Mg-Al ratio is the carbonate form hydrotalcite of 3:1.
(2) by carbonate form hydrotalcite roasting 10h at 500 DEG C in retort furnace, Mg-Al composite oxide is obtained, i.e. Mg (Al) O.
(3) sample after roasting is added deionized water vigorous stirring in autoclave, 60 DEG C of reaction 24h in rare gas element, solid base catalyst is obtained after being filtered by reacted solution, afterwards at 80 DEG C of vacuum-drying 12h, obtain magnesium aluminum-hydrotalcite catalyzer (Mg:Al=3:1).
Two, adopt the reaction of rhythmic reaction catalysis glucose isomerization, concrete steps are as follows:
(1) taking the glucose (M=180) of 100.0mg, the magnesium aluminum-hydrotalcite catalyzer of 10mg and rotor adds in the reaction bottle of 5ml respectively, 1ml (1260mg is added in reaction bottle, relative density 1.26) glycerine solution, sealed vial.In advance during reacting by heating device to 110 DEG C, namely temperature of reaction is 110 DEG C.When temperature of reaction is stabilized in 110 DEG C, reaction bottle is put into reaction heating unit, start timing, carry out glucose isomerization reaction, the reaction times is 2h.
(2) after reaction terminates, collect liquid product, catalyzer is by filtering or centrifugally reclaiming, and filtrate is analyzed by HPLC.Chromatographiccondition is: the rare H of 0.005M
2sO
4as moving phase, differential refraction detector, adopt marker method, ethylene glycol is as internal standard substance.
(glucose) transformation efficiency/%=transforms initial molar weight × 100% dropping into glucose of molar weight/reaction of the glucose fallen
(fructose) yield/%=generates initial molar weight × 100% dropping into glucose of molar weight/reaction of fructose institute consumption of glucose
Molar weight × 100% of glucose is fallen in the molar weight/conversion of (fructose) selectivity/%=generation fructose institute consumption of glucose
The conditions such as other reaction meeting transformationreation time, temperature of reaction, solvents, specific experiment parameter asks for an interview table 1 and table 2..
Each embodiment reaction result is as shown in table 1.
Table 1 is the experimental result of embodiment 1 ~ 7
As shown in Table 1, method of the present invention can realize best transformation efficiency, yield and selective data under the conditions of example 3.
Table 2 is the experimental result of comparative example 1 ~ 4
Note: in comparative example 1 ~ 4, except replacement solvent, other parameters are all identical with embodiment 3.
From table 1,2 test-results, adopt glycerine as after Bound moisture talcum solvent while solvent, can reaction effect be significantly improved within the scope of 90 ~ 120 DEG C.In embodiment 1 ~ 7, the mass ratio of glucose and glycerine is about 0.079, the mass ratio of magnesium aluminum-hydrotalcite and glucose is 0.1, therefore, under guarantee glucose is fully dissolved in the prerequisite of glycerine, the input amount of suitable increase glucose, and the best input amount determining catalyzer by limited number of time experiment, still can realize object of the present invention.
Claims (7)
1. glucose isomerase is turned to a method for fructose in Glycerol solvents, in Glycerol solvents, glucose carries out rhythmic reaction and obtains fructose under the catalysis of magnesium aluminum-hydrotalcite catalyzer.
2. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 1, is characterized in that: described glycerol concentration is more than 95wt%.
3. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 1, is characterized in that: the mol ratio of Mg and Al in described magnesium aluminum-hydrotalcite catalyzer is 1:1 ~ 10:1.
4. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 3, is characterized in that: the mol ratio of Mg and Al in described magnesium aluminum-hydrotalcite catalyzer is 3:1.
5. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 3, is characterized in that: the add-on of glucose is 5 ~ 150wt% of glycerine total amount; The add-on of magnesium aluminum-hydrotalcite is 1 ~ 150wt% of glucose total amount; Temperature of reaction is 80 ~ 150 DEG C.
6. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 5, is characterized in that: described temperature of reaction is 90 ~ 120 DEG C.
7. method glucose isomerase being turned to fructose in Glycerol solvents according to claim 1, is characterized in that: described magnesium aluminum-hydrotalcite catalyzer adopts coprecipitation method preparation, and its step is as follows:
(1) Mg (NO that mol ratio is 1:1 ~ 10:1 is accurately taken
3)
26H
2o, Al (NO
3)
39H
2o, mixed dissolution in deionized water, room temperature is accelerated to stir limit below and slowly drip NaOH solution in mixing solutions, be 9 ~ 10 to pH value, continue stir about 15 ~ 25min under dropwising rear room temperature, then in 70 DEG C of oil baths, heat 24h, after completion of the reaction, cooling, suction filtration are washed to neutrality, filter cake in 80 DEG C of vacuum-drying 12h, and grinding obtains white solid powder, i.e. carbonate form hydrotalcite;
(2) by carbonate form hydrotalcite roasting 10h at 500 DEG C in retort furnace, Mg-Al composite oxide is obtained;
(3) sample after roasting is added deionized water vigorous stirring in autoclave, in rare gas element, 60 DEG C of reaction 24h, obtain solid base catalyst after being filtered by reacted solution, afterwards at 80 DEG C of vacuum-drying 12h, get product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510084721.XA CN104628793A (en) | 2015-02-16 | 2015-02-16 | Method for isomerizing glucose into fructose in glycerin solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510084721.XA CN104628793A (en) | 2015-02-16 | 2015-02-16 | Method for isomerizing glucose into fructose in glycerin solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104628793A true CN104628793A (en) | 2015-05-20 |
Family
ID=53208076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510084721.XA Pending CN104628793A (en) | 2015-02-16 | 2015-02-16 | Method for isomerizing glucose into fructose in glycerin solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104628793A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841521A (en) * | 2020-08-11 | 2020-10-30 | 浙江大学 | Preparation method and application of cellulose-based hydrothermal carbon-supported aluminum catalyst based on swelling regulation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927190A (en) * | 2010-06-30 | 2010-12-29 | 江苏天音化工有限公司 | LDH catalyst for Tishchenko reaction and preparation method thereof |
| CN103007915A (en) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesis of glycerol carbonate and its preparation method and application |
| CN103288887A (en) * | 2013-06-04 | 2013-09-11 | 北京大学 | Method for preparing ketose by utilizing aldose |
| WO2014196861A1 (en) * | 2013-06-06 | 2014-12-11 | Furanix Technologies B.V. | Process for producing a fructoside-containing product |
-
2015
- 2015-02-16 CN CN201510084721.XA patent/CN104628793A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927190A (en) * | 2010-06-30 | 2010-12-29 | 江苏天音化工有限公司 | LDH catalyst for Tishchenko reaction and preparation method thereof |
| CN103007915A (en) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesis of glycerol carbonate and its preparation method and application |
| CN103288887A (en) * | 2013-06-04 | 2013-09-11 | 北京大学 | Method for preparing ketose by utilizing aldose |
| WO2014196861A1 (en) * | 2013-06-06 | 2014-12-11 | Furanix Technologies B.V. | Process for producing a fructoside-containing product |
Non-Patent Citations (1)
| Title |
|---|
| I. DELIDOVICH AND R. PALKOVITS: "《Catalytic activity and stability of hydrophobic Mg–Al hydrotalcites in the continuous aqueous-phase isomerization of glucose into fructose》", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841521A (en) * | 2020-08-11 | 2020-10-30 | 浙江大学 | Preparation method and application of cellulose-based hydrothermal carbon-supported aluminum catalyst based on swelling regulation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10898888B2 (en) | Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid | |
| CN104711007A (en) | Preparation method of aviation kerosene or diesel oil scope liquid alkane | |
| CN104250237B (en) | Method for preparing 5-hydroxymethylfurfural through catalyzing fructose conversion by solid catalyst | |
| CN106905271B (en) | A kind of preparation and application of the heterogeneous catalysis of mesoporous material containing MCM-41 | |
| CN103801282B (en) | A kind of solid base catalyst and Synthesis and applications thereof | |
| CN105664907A (en) | Preparation method of catalyst for synthesizing glycerol carbonate through urea method | |
| CN103694203B (en) | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural | |
| CN106238090A (en) | The preparation of a kind of mesoporous solid base catalyst and the method for catalyzed transesterification biodiesel synthesis | |
| CN107308947A (en) | A kind of biomass slagging is combined mine tailings solid base catalyst and its preparation method and application | |
| CN105056954B (en) | A kind of hydrogenation catalyst and preparation method and application | |
| CN113101941B (en) | Preparation method of cobalt-molybdenum catalyst and application of cobalt-molybdenum catalyst in catalyzing levulinic acid hydrogenation reaction | |
| CN102417493A (en) | Method for preparing 2.5-dimethyl furan through glucose by adopting single-step method | |
| CN102586031A (en) | Ion-liquid-based method for preparing biodiesel | |
| CN109942391A (en) | A method of catalysis oxygen solution lignin preparation is containing vanillic aldehyde and syringaldehyde extract liquor | |
| CN108640892A (en) | A kind of synthetic method of 5 hydroxymethyl furfural | |
| CN110882716B (en) | Preparation method for converting biomass derived furfural into gamma-valerolactone by solid acid catalyst one-pot multi-step catalysis | |
| CN103805343A (en) | Method for continuously producing biodiesel by using two segments of fixed beds | |
| CN104628793A (en) | Method for isomerizing glucose into fructose in glycerin solvent | |
| CN101805381B (en) | Method for directly synthesizing sucrose fatty acid ester by biodiesel and sucrose | |
| CN104624242B (en) | A kind of biodiesel synthesis acidic ion liquid immobilized AlCl_3 catalyst and preparation method thereof | |
| CN110003162A (en) | A method of making catalyst synthesizing annular carbonate with lignin | |
| CN102492558A (en) | Method of preparing biodiesel in ionic liquid | |
| CN108129311B (en) | Method for preparing glycerol carbonate from carbon dioxide and glycerol | |
| CN108424359B (en) | Ruthenium complex in water phase for catalyzing CO2Method for preparing formate/formic acid by hydrogenation reduction | |
| CN102993005A (en) | Method for preparing fatty acid alkyl ester by using long-chain alkyl sulfonic acid functional polyoxometalate as catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150520 |
|
| RJ01 | Rejection of invention patent application after publication |