CN109879838B - Method and device for preparing 5-hydroxymethylfurfural from high fructose corn syrup - Google Patents
Method and device for preparing 5-hydroxymethylfurfural from high fructose corn syrup Download PDFInfo
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Abstract
The invention discloses a method and a device for preparing 5-hydroxymethylfurfural from high fructose corn syrup, which take the high fructose corn syrup as a raw material and acid as a catalyst, and respectively convert fructose and glucose in the high fructose corn syrup into the 5-hydroxymethylfurfural through continuous step-by-step reaction in an aqueous solution. Aiming at the condition difference of fructose and glucose conversion in the high fructose corn syrup, the invention adopts a mode of connecting double reaction kettles in series, fructose and glucose are respectively converted into 5-hydroxymethylfurfural through continuous stepwise reaction in aqueous solution, pure organic solvent is added in the reaction process, and 5-hydroxymethylfurfural in the reaction system is transferred to an organic layer in real time to extract 5-hydroxymethylfurfural in real time, so that the yield of 5-hydroxymethylfurfural is further improved, the continuously extracted organic solvent is recycled through reduced pressure distillation, and the water phase can be reused for many times after impurities are removed by an adsorption tower, so that the production cost is effectively reduced on one hand, the discharge of three wastes is reduced on the other hand, and the environmental protection pressure in the production process is reduced.
Description
Technical Field
The invention relates to the field of chemistry and chemical engineering, in particular to a method and a device for preparing 5-hydroxymethylfurfural from high fructose corn syrup.
Background
5-hydroxymethyl furfural is an important organic chemical intermediate obtained by dehydrating hexose, and is one of important bridge compounds for connecting biomass and organic chemicals. The 5-hydroxymethylfurfural contains various groups such as aldehyde group, hydroxyl group, furyl group and the like, and can be used for producing various bulk organic chemicals such as polyester monomers, fuel additives, biological fuels, essences, spices and the like.
At present, 5-hydroxymethylfurfural is mainly produced by dehydrating a saccharide compound under the acid catalysis condition, wherein fructose is the most suitable raw material for preparing 5-hydroxymethylfurfural, but the fructose is high in price and high in cost; when glucose is used as a raw material, an isomerization catalyst needs to be added into a system, so that the system is complex and the yield is relatively low. Therefore, the method has great limitation in adopting fructose and glucose as raw materials.
Disclosure of Invention
The invention aims to provide a method and a device for preparing 5-hydroxymethylfurfural from high fructose corn syrup, wherein glucose and fructose in the high fructose corn syrup are respectively converted into the 5-hydroxymethylfurfural by adopting a mode of connecting double kettles in series, and the optimal conversion result is achieved by setting the conditions of each reaction kettle, so that higher yield is obtained.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing 5-hydroxymethylfurfural from high fructose corn syrup takes the high fructose corn syrup as a raw material and acid as a catalyst, and fructose and glucose in the high fructose corn syrup are respectively converted into the 5-hydroxymethylfurfural through continuous stepwise reaction in an aqueous solution.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the high fructose corn syrup is an industrial product which meets the regulation of the national standard GB/T20882-2007.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the total mass fraction of fructose and glucose in the aqueous solution is 10-45%.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the continuous step-by-step reaction is carried out in a reaction kettle I and a reaction kettle II which are connected in series.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: high fructose corn syrup is added into the reaction kettle I, acid B is used as a catalyst, and the reaction temperature is 80-140 DEGoC, the average residence time of the aqueous solution is 10-120 min; in the reaction kettle II, L acid is used as a catalyst, and the reaction temperature is 140-oAnd C, the average residence time of the aqueous solution is 30-240 min.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the acid B is phosphoric acid, sulfuric acid, hydrochloric acid or acetic acid, and the concentration of the acid B in the aqueous solution is 0.001-2 mol/L; the L acid is aluminum chloride, zinc chloride or stannic chloride, and the concentration of the L acid in the aqueous solution is 0.01-2.5 mol/L.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the generated 5-hydroxymethylfurfural is extracted by an organic solvent in real time, and the method for extracting in real time comprises the steps of adding a pure organic solvent in the reaction process and transferring the 5-hydroxymethylfurfural in the reaction system to an organic layer in real time.
As a further optimization of the method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the invention: the organic solvent is one or more of dichloromethane, trichloromethane, ethyl acetate, n-butanol, toluene, n-hexane, n-heptane, butyl acetate, methyl tert-butyl ether, isopropyl ether and isobutanol, and the average residence time of the organic phase is 0.02-2 times of the average residence time of the aqueous phase.
The utility model provides a device by high fructose syrup preparation 5-hydroxymethyl furfural, including reation kettle I, reation kettle II, divide liquid tower I, divide liquid tower II, reduced pressure distillation tower adsorption tower, wherein, the reaction liquid in reation kettle I divides liquid through dividing liquid tower I, the organic phase of dividing liquid tower I passes through the pipeline and gets into reduced pressure distillation tower, the aqueous phase of dividing liquid tower I passes through the pipeline and gets into reation kettle II, the reaction liquid in reation kettle II divides liquid through dividing liquid tower II, the aqueous phase of dividing liquid tower II gets into the adsorption tower and gets into reation kettle I after removing impurity, the organic phase of dividing liquid tower II passes through the pipeline and gets into reduced pressure distillation tower, the organic phase of reduced pressure distillation tower passes through the pipeline and flows back to reation kettle I and reation kettle II.
Advantageous effects
Firstly, the raw material used by the preparation method is high fructose corn syrup, the high fructose corn syrup is a sucrose substitute prepared by hydrolyzing corn starch, the production of the high fructose corn syrup is not limited by regions and seasons, and the raw material is easy to obtain;
the preparation method of the invention has simple equipment, short process flow, and low cost which is only slightly higher than glucose and far lower than crystalline fructose, especially the high fructose corn syrup contains a large amount of fructose, and is an ideal raw material for producing 5-hydroxymethylfurfural;
thirdly, the preparation method of the invention adopts a continuous extraction process to transfer the generated 5-hydroxymethylfurfural out of the reaction system, thereby further improving the yield of the 5-hydroxymethylfurfural.
And fourthly, the organic solvent continuously extracted in the preparation method is recycled through reduced pressure distillation, and the water phase can be repeatedly utilized after impurities are removed through an adsorption tower, so that the production cost is effectively reduced, the discharge of three wastes is reduced, and the environmental protection pressure in the production process is reduced.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to the present invention;
the labels in the figure are: 1. reation kettle I, 2, reation kettle II, 3, divide liquid tower I, 4, divide liquid tower II, 5, the distillation column of reducing pressure, 6, adsorption column.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is further illustrated below with reference to specific examples.
Example 1
As shown in figure 1, 0.25L of HCl and 0.75L of MIBK with the concentration of 0.5mol/L are added into a reaction kettle I1 in advance; ZnCl is added into the reaction kettle II 2 in advance20.25L of 0.25mol/L aqueous solution, MIBK0.75L. The temperature of the reaction kettle I1 and the temperature of the reaction kettle II 2 are respectively controlled to be 100oC and 180oC. A glucose fructose syrup solution (type F55, HCl pH = 0.3) containing 25% of fructose and glucose in total mass fraction and MIBK were pumped into a continuous reaction vessel I1, with an aqueous solution residence time of 60min and an organic phase residence time of 6 min. And simultaneously, taking out the reaction liquid in the continuous reaction kettle I1 to a liquid separation tower I3 by using a pump. And transferring the organic phase after liquid separation to a reduced pressure distillation tower 5 for reduced pressure distillation to obtain a crude product of 5-hydroxymethylfurfural, and recycling the organic phase MIBK. The water phase in the liquid separation tower I3 is adjusted to ZnCl2The mixture is injected into a continuous reaction kettle II 2 after the concentration is 0.25 mol/L. The retention time of the aqueous solution in the reaction kettle II 2 is 60min, the retention time of the organic phase is 6min, and the reaction liquid is introduced into a liquid separation tower II 4. And transferring the organic phase after liquid separation to a reduced pressure distillation tower 5 for reduced pressure distillation to obtain a crude product of 5-hydroxymethylfurfural, and recycling the organic phase MIBK. And removing impurities from the water phase in the liquid separation tower II 4 through an adsorption tower 6, and preparing the high fructose corn syrup reaction liquid with the total sugar mass fraction of 25%. After the reaction, the gas phase purity of the crude 5-hydroxymethylfurfural is 90.2 percent, 0.502kg of crude 5-hydroxymethylfurfural is obtained by 1.000kg of F55 type high fructose corn syrup, and the yield is 86.3 percent.
Example 2
The present embodiment is different from embodiment 1 in that: in this example, the B acid previously added to reactor I1 was HCl of a concentration of 0.75mol/LThe L acid added into the reactor II 2 is ZnCl with the concentration of 0.05mol/L2And the organic phase MIBK is replaced by toluene, and the residence time of the toluene in the bicontinuous reaction kettle is 10 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 72 percent through continuous reaction.
Example 3
The present embodiment is different from embodiment 1 in that: in this example, the B acid previously charged in reactor I1 was HCl of a concentration of 0.25mol/L, and the L acid charged in reactor II 2 was ZnCl of a concentration of 0.15mol/L2And replacing the organic phase MIBK with CH2Cl2，CH2Cl2The residence time in the bicontinuous reaction kettle is 10 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 76% through continuous reaction.
Example 4
The present embodiment is different from embodiment 1 in that: in this example, the L acid previously added to reaction vessel II 2 was ZnCl at a concentration of 0.75mol/L2And the residence time of the organic phase in the bicontinuous reaction kettle is 5 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 88 percent through continuous reaction.
Example 5
The present embodiment is different from embodiment 1 in that: in this example, the L acid previously added to reaction vessel II 2 was ZnCl at a concentration of 0.75mol/L2And the retention time of the organic phase in the reaction kettle I1 is 15 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 82 percent through continuous reaction.
Example 6
The present embodiment is different from embodiment 1 in that: in this example, the L acid previously added to reaction vessel II 2 was ZnCl at a concentration of 0.5mol/L2And the retention time of the organic phase in the reaction kettle I1 is 30min, and the retention time in the reaction kettle II 2 is 15 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 81 percent through continuous reaction.
Example 7
The present embodiment is different from embodiment 1 in that: in this example, the L acid previously added to reaction vessel II 2 was ZnCl at a concentration of 0.5mol/L2And the residence time of the organic phase in the bicontinuous reaction kettle is 10 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 82 percent through continuous reaction.
Example 8
The present embodiment is different from embodiment 1 in that: in this example, the total concentration of fructose and glucose in the reaction mixture was 35%, the acid B previously added to reactor I1 was HCl of a concentration of 0.2mol/L, the temperature of reactor I1 was 90 ℃, and the acid L added to reactor II 2 was ZnCl of a concentration of 0.5mol/L2The temperature of the reaction kettle II 2 is unchanged, the organic phase is replaced by toluene, the residence time of the toluene in the reaction kettle I1 is 50min, and the residence time of the water phase in the reaction kettle I1 is 100 min; the residence time of the toluene in the reaction vessel II 2 was 50min, and the residence time of the aqueous phase in the reaction vessel II 2 was 180 min. Finally, the yield of the crude 5-hydroxymethylfurfural is 77 percent through continuous reaction.
Example 9
The present embodiment is different from embodiment 1 in that: the total concentration of fructose and glucose in the reaction solution of this example was 15%, and the amount of B acid previously added to reaction vessel I1 was H at a concentration of 1.2mol/L3PO4The temperature of the reaction kettle I1 is 120 ℃, and the L acid added into the reaction kettle II 2 is AlCl with the concentration of 1.0mol/L3The temperature of the reaction kettle II 2 is unchanged, the residence time of the organic phase in the reaction kettle I1 is 20min, and the residence time of the water phase in the reaction kettle I1 is 40 min; the retention time of the organic phase in the reaction kettle II 2 is 10min, and the retention time of the water phase in the reaction kettle II 2 is unchanged. Finally, the yield of the crude 5-hydroxymethylfurfural is 71 percent through continuous reaction.
Example 10
The present embodiment is different from embodiment 1 in that: in this example, the B acid previously added to reaction vessel I1 was H at a concentration of 0.5mol/L2SO4L acid added into the reaction kettle II 2 is SnCl with the concentration of 0.5mol/L2The residence time of the organic phase in the reaction kettle I1 is 20min, the residence time in the reaction kettle II 2 is 12min, and the residence time of the aqueous phase in the reaction kettle II 2 is 100 min. Finally pass throughThe continuous reaction gave a crude 5-hydroxymethylfurfural yield of 82%.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A method for preparing 5-hydroxymethylfurfural from high fructose corn syrup is characterized by comprising the following steps: the method comprises the following steps of taking high fructose corn syrup as a raw material and acid as a catalyst, respectively converting fructose and glucose in the high fructose corn syrup into 5-hydroxymethylfurfural through continuous stepwise reaction in an aqueous solution, and specifically, preparing the high fructose corn syrup by the following device: the device comprises a reaction kettle I (1), a reaction kettle II (2), a liquid separation tower I (3), a liquid separation tower II (4) and an adsorption tower (6) of a reduced pressure distillation tower (5), wherein reaction liquid in the reaction kettle I (1) is subjected to liquid separation through the liquid separation tower I (3), an organic phase of the liquid separation tower I (3) enters the reduced pressure distillation tower (5) through a pipeline, a water phase of the liquid separation tower I (3) enters the reaction kettle II (2) through a pipeline, reaction liquid in the reaction kettle II (2) is subjected to liquid separation through the liquid separation tower II (4), a water phase of the liquid separation tower II (4) enters the adsorption tower (6) to remove impurities and then enters the reaction kettle I (1), an organic phase of the liquid separation tower II (4) enters the reduced pressure distillation tower (5) through a pipeline, and the organic phase of the reduced pressure distillation tower (5) flows back to the reaction kettle I (1) and the reaction kettle II (2) through pipelines;
the continuous step-by-step reaction is carried out in a reaction kettle I (1) and a reaction kettle II (2) which are connected in series;
high fructose corn syrup is added into the reaction kettle I (1), acid B is used as a catalyst, the reaction temperature is 80-140 ℃, and the average residence time of the aqueous solution is 10-120 min; in the reaction kettle II (2), L acid is used as a catalyst, the reaction temperature is 140 ℃ and 190 ℃, and the average residence time of the aqueous solution is 30-240 min;
the acid B is phosphoric acid, sulfuric acid, hydrochloric acid or acetic acid, and the concentration of the acid B in the aqueous solution is 0.001-2 mol/L; the L acid is aluminum chloride, zinc chloride or stannic chloride, and the concentration of the L acid in the aqueous solution is 0.01-2.5 mol/L.
2. The method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to claim 1, wherein: the high fructose corn syrup is an industrial product which meets the requirements specified in the national standard GB/T20882-2007.
3. The method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to claim 1, wherein: the total mass fraction of fructose and glucose in the aqueous solution is 10-45%.
4. The method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to claim 1, wherein: the generated 5-hydroxymethylfurfural is extracted by an organic solvent in real time, and the method for extracting in real time comprises the steps of adding a pure organic solvent in the reaction process and transferring the 5-hydroxymethylfurfural in the reaction system to an organic layer in real time.
5. The method for preparing 5-hydroxymethylfurfural from high fructose corn syrup according to claim 4, wherein: the organic solvent is one or more of dichloromethane, trichloromethane, ethyl acetate, n-butanol, toluene, n-hexane, n-heptane, butyl acetate, methyl tert-butyl ether, isopropyl ether and isobutanol, and the average residence time of the organic phase is 0.02-2 times of the average residence time of the aqueous phase.
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