Process and apparatus for the spray synthesis of 5-hydroxymethylfurfural

Abstract

The application provides a method and device for spray synthesis of 5-hydroxymethylfurfural. The method comprises the following steps: preheating a reaction liquid to a preset temperature, wherein the reaction liquid comprises an aqueous phase mixture and an organic solvent, the aqueous phase mixture is configured by a saccharide compound, a catalyst and an aqueous phase solvent according to a preset proportion; a high-speed spray device sprays the aqueous phase mixture and the organic solvent into a pipeline reactor after atomization, so that the saccharide compound, the catalyst and the organic solvent can be mixed and homogenously reacted in the form of microparticles to obtain 5-hydroxymethylfurfural; a reflux circulating pump pumps the mixed liquid of the aqueous phase mixture and the organic solvent with a preset proportion at a tail end into a head end, so that the aqueous phase mixture and the organic solvent can be mixed and homogenously reacted again to obtain 5-hydroxymethylfurfural. The application has the advantages of safety, high efficiency, intelligent control, low investment and the like, and provides a new technical implementation scheme for industrial production of 5-hydroxymethylfurfural.

Description

Technical Field

[0001] This invention relates to the fields of catalytic chemistry and biomass resource utilization technology, and more specifically, to a method and apparatus for spray synthesis of 5-hydroxymethylfurfural. Background Technology

[0002] 5-Hydroxymethylfurfural (HMF), as an important platform compound linking biomass and chemicals, has attracted much attention in recent years and has now become one of the most promising emerging chemicals.

[0003] 5-Hydroxymethylfurfural (HMF) is produced by the dehydration of sugars under the action of a catalyst. Pipeline reactors are a good choice for the production of 5-hydroxymethylfurfural due to their small reaction volume, continuous reaction, and high relative safety.

[0004] HMF can typically be synthesized in either a pure aqueous system or an aqueous / organic solvent system. Literature indicates that the dispersion of the carbohydrates, catalyst, and organic solvent significantly affects HMF synthesis. In a two-phase system, higher dispersion of the carbohydrates and organic solvent allows HMF generated in the aqueous phase to be immediately extracted into the adjacent organic solvent, thus protecting it and effectively preventing rehydration or condensation reactions, thereby greatly reducing the consumption of already generated HMF.

[0005] However, although sugars have excellent solubility in water, their solubility in organic solvents is greatly reduced, making good dispersion a major problem in industrial production. Summary of the Invention

[0006] (a) Technical problems to be solved

[0007] The present invention aims to solve the technical problems of low solubility and poor homogeneity of sugars in the organic phase during the production of 5-hydroxymethylfurfural.

[0008] (II) Technical Solution

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] In a first aspect, the present invention provides a method for spray synthesis of 5-hydroxymethylfurfural, comprising the following steps:

[0011] The reaction solution is preheated to a preset temperature. The reaction solution includes an aqueous mixture and an organic solvent. The aqueous mixture is prepared by a carbohydrate compound, a catalyst, and an aqueous solvent in a preset ratio.

[0012] The high-speed spraying device simultaneously atomizes the aqueous mixture and the organic solvent and sprays them into the pipeline reactor, so that the carbohydrate compound, the catalyst and the organic solvent can be mixed and homogenized in the form of microparticles to obtain 5-hydroxymethylfurfural.

[0013] A reflux pump pumps a predetermined ratio of the aqueous mixture and the organic solvent, located at the tail end of the pipeline reactor, back into the head end of the pipeline reactor, so that the aqueous mixture and the organic solvent can be mixed and homogenized again to obtain 5-hydroxymethylfurfural.

[0014] Preferably, the preset temperature is 90℃~200℃.

[0015] Preferably, the preset ratio is 0-50%.

[0016] Preferably, the carbohydrate compound includes at least one of fructose, glucose, sucrose, maltose, polyfructose, high-fructose corn syrup, inulin, and cellulose, and the mass fraction of the carbohydrate compound in the aqueous solvent is 1 wt% to 60 wt%.

[0017] Preferably, the catalyst comprises an acid catalyst and an oxidation catalyst, and the mass fraction of the catalyst is 0.1 wt% to 20 wt% of the total mass of the aqueous mixture.

[0018] Preferably, the organic solvent includes at least one of dimethyl carbonate, diethyl carbonate, valerate, acetone, 4-methyl-2-pentanone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

[0019] Secondly, the present invention provides an apparatus for the spray synthesis of 5-hydroxymethylfurfural, the apparatus comprising a pipeline reactor, a high-speed spraying device, a reflux pipe, a post-treatment system, a discharge pipe, and a reflux circulation pump; the high-speed spraying device is located at the beginning of the pipeline reactor and is used to simultaneously atomize the aqueous mixture and the organic solvent and spray them into the pipeline reactor, so that the reaction solution can be mixed and homogenized in the form of microparticles to obtain 5-hydroxymethylfurfural; the reflux pipe connects the beginning and end of the pipeline reactor; the post-treatment system is used to process the reaction solution... The reactor is processed to obtain 5-hydroxymethylfurfural; the discharge pipe is connected to the tail end of the pipeline reactor and the post-treatment system; a reflux circulation pump is connected to the reflux pipe and the discharge pipe respectively. The reflux circulation pump is used to pump a predetermined proportion of the aqueous mixture and the organic solvent located at the tail end back into the head end through the reflux pipe, so that the aqueous mixture and the organic solvent can be mixed and homogenized again to obtain 5-hydroxymethylfurfural, and the remaining reaction liquid located at the tail end is pumped into the post-treatment system through the discharge pipe.

[0020] Preferably, the discharge pipe is equipped with a valve and a back pressure valve.

[0021] Preferably, the total residence time of the reaction solution in the pipeline reactor and the reflux pipe is 20-120 min.

[0022] Preferably, the pipeline reactor has a temperature control module for adjusting the reaction temperature of the reaction liquid.

[0023] (III) Beneficial Effects

[0024] The above-described technical solution of the present invention has at least the following advantages:

[0025] This invention utilizes a high-speed spray device for feeding, enabling the mixing and homogenization of carbohydrate compounds, catalysts, and organic solvents in the form of microparticles to obtain 5-hydroxymethylfurfural. By atomizing the reaction solution into small particles, a larger specific surface area and an unstable material state are created, thereby enhancing the catalytic conversion effect of the catalyst on the carbohydrate feedstock.

[0026] Meanwhile, the reaction liquid at the tail end of the tubular reactor continues to circulate under the action of a reflux pump, which better promotes stirring and homogenization, facilitating the complete conversion of residual sugars. Furthermore, the use of reflux circulation effectively increases the length and volume of the tubular reactor, significantly reducing its investment cost.

[0027] The method and apparatus for spray synthesis of 5-hydroxymethylfurfural provided by this invention have the advantages of safety, high efficiency, intelligent control, and low investment, providing a new technical implementation plan for the industrial production of 5-hydroxymethylfurfural. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0029] Figure 1 This is a schematic diagram of the apparatus for spray synthesis of 5-hydroxymethylfurfural provided in an embodiment of the present invention.

[0030] The labels for the attached figures are as follows:

[0031] 1. Pipeline reactor; 2. High-speed spray equipment; 3. Return pipe; 4. Post-treatment system; 5. Discharge pipe; 6. Return circulation pump; 7. Aqueous phase mixture flow; 8. Organic phase material flow; 11. Head end; 12. Tail end; 31. Return valve; 51. Valve; 52. Back pressure valve. Detailed Implementation

[0032] To better understand the above-mentioned objectives, features, and advantages of the present invention, the solutions of the present invention will be further described below. It should be noted that, unless otherwise specified, the embodiments of the present invention and the features thereof can be combined with each other.

[0033] Many specific details are set forth in the following description in order to provide a full understanding of the invention, but the invention may also be practiced in other ways different from those described herein; obviously, the embodiments in the specification are only some embodiments of the invention, and not all embodiments.

[0034] The embodiments of the present invention will be described in further detail below with reference to the examples. The detailed description of the following examples is used to illustrate the principles of the present invention, but should not be used to limit the scope of the present invention, that is, the present invention is not limited to the described embodiments.

[0035] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0036] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0037] like Figure 1 As shown, this embodiment of the invention provides an apparatus for the spray synthesis of 5-hydroxymethylfurfural. The apparatus includes a pipeline reactor 1, a high-speed spraying device 2, a reflux pipe 3, a post-treatment system 4, a discharge pipe 5, and a reflux circulation pump 6. The high-speed spraying device 2 is located at the beginning 11 of the pipeline reactor 1 and is used to simultaneously atomize the aqueous mixture and organic solvent and spray them into the pipeline reactor 1, allowing the aqueous mixture and organic solvent to mix and homogenize in the form of microparticles to obtain 5-hydroxymethylfurfural. The reflux pipe 3 is connected to the beginning of the pipeline reactor 1. 11 and tail end 12; post-treatment system 4 is used to treat the reaction solution to obtain 5-hydroxymethylfurfural; discharge pipe 5 connects the tail end 12 of pipeline reactor 1 to post-treatment system 4; reflux circulation pump 6 is connected to reflux pipe 3 and discharge pipe 5 respectively. Reflux circulation pump 6 is used to pump the reaction solution at the tail end 12 in a preset proportion back into the head end 11 through reflux pipe 3 so that the reaction solution can be mixed and homogenized again to obtain 5-hydroxymethylfurfural, and the remaining reaction solution at the tail end 12 is pumped into post-treatment system 4 through discharge pipe 5.

[0038] In one embodiment, the discharge pipe 5 is equipped with a valve 51 and a back pressure valve 52. Valve 51 controls the discharge of the reaction liquid. The reflux circulation pump 6 pumps the reaction liquid out through the discharge pipe 5, and after being depressurized by the back pressure valve 52, it enters the post-processing system 4 for post-processing. In one embodiment, the reflux pipe 3 is equipped with a reflux valve 31.

[0039] In one embodiment, the total residence time of the reaction liquid in the tubular reactor 1 and the return pipe 3 is 20-120 min.

[0040] In one embodiment, the pipeline reactor 1 has a temperature control module for regulating the reaction temperature of the reaction liquid. Specifically, in this embodiment, the pipeline reactor 1 is a pipeline reactor with a large length-to-diameter ratio, possessing functions such as heating, heat preservation, and cooling. The heating function of the temperature control module can be achieved by controlling the steam volume and the opening of the steam valve, while cooling can be achieved through cooling water circulation. Furthermore, to facilitate the control of the reaction temperature, insulation measures are required for the outer perimeter of both the pipeline reactor 1 and the return pipe 3.

[0041] This invention also provides a method for spray synthesis of 5-hydroxymethylfurfural, comprising the following steps:

[0042] The reaction solution is preheated to a preset temperature. The reaction solution includes an aqueous mixture and an organic solvent. The aqueous mixture is prepared by mixing carbohydrates, a catalyst, and an aqueous solvent in a preset ratio. It should be noted that the aqueous mixture and the organic solvent are continuously fed. The device provided by this invention is applied to a continuous reaction system.

[0043] The high-speed spray device 2 atomizes the aqueous mixture and organic solvent simultaneously and sprays them into the pipeline reactor 1, so that the carbohydrates, catalyst and organic solvent can be mixed and homogenized in the form of microparticles to obtain 5-hydroxymethylfurfural; specifically, the nozzle on the high-speed spray device 2 is a tapered pipe that gradually narrows to become a spray nozzle.

[0044] The reflux pump 6 pumps a mixture of aqueous phase material and organic solvent in a preset ratio, located at the tail end 12 of the pipeline reactor 1, back into the head end 11 of the pipeline reactor 1, so that the aqueous phase material and organic solvent can be mixed and homogenized again to obtain 5-hydroxymethylfurfural.

[0045] In one embodiment, the preset temperature is 90°C to 200°C.

[0046] In one embodiment, the preset ratio is 0-50%. Specifically, the parameters such as the reflux circulation frequency of the reflux reaction liquid, the diameter and length of the reflux pipe 3, and the reflux flow rate are determined based on parameters such as the feed flow rate of the aqueous mixture, the feed flow rate of the organic solvent, the residence time of the reaction liquid in the pipeline reactor 1, and the degree of reaction.

[0047] In one embodiment, the carbohydrate compound includes at least one of fructose, glucose, sucrose, maltose, polyfructose, high-fructose corn syrup, inulin, and cellulose, and the mass fraction of the carbohydrate compound in the aqueous solvent is 1 wt% to 60 wt%.

[0048] In one embodiment, the catalyst comprises an acid catalyst and an oxidizing catalyst, wherein the mass fraction of the catalyst is 0.1 wt% to 20 wt% of the total mass of the aqueous mixture.

[0049] In one embodiment, the organic solvent includes at least one selected from dimethyl carbonate, diethyl carbonate, valproic acid, acetone, 4-methyl-2-pentanone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane.

[0050] The following is a specific embodiment provided by the present invention:

[0051] Weigh 40 kg of 4-methyl-2-pentanone (organic solvent), 10 kg of crystalline fructose (carbohydrate), 10 kg of deionized water (aqueous solvent), and 1 kg of hydrochloric acid (catalyst). Stir and dissolve them evenly to prepare an aqueous mixture for later use.

[0052] During the reaction, a high-pressure aqueous phase pump extracts the aqueous phase mixture, forming an aqueous phase mixture stream 7, which is then pumped into the high-speed spray device 2. The flow rate of the aqueous phase mixture stream 7 is 20 ml / min. A high-pressure organic pump extracts the organic solvent, forming an organic phase material stream 8, which is also pumped into the high-speed spray device 2. The flow rate of the organic phase material stream 8 is 40 ml / min. Specifically, the organic phase material stream 8 is positioned around the aqueous phase mixture stream 7. Both the aqueous phase mixture stream 7 and the organic phase material stream 8 are simultaneously atomized at high speed through the nozzles of the high-speed spray device to increase the mixing contact area between the two materials, ensuring sufficient contact. After the aqueous mixture and organic solvent are preheated to 100°C, they are atomized by the nozzles of the high-speed spray device 2 and then enter the tubular reactor 1. The temperature of the tubular reactor 1 is set to 130°C, and the designed residence time in the tubular reactor 1 is 20 minutes. Afterwards, 10% of the reaction liquid at the tail end 12 is pumped into the head end 11 through the reflux circulation pump 6 and the reflux pipe 3. The remaining 90% of the reaction liquid at the tail end 12 enters the post-treatment system 4 through valve 51 and back pressure valve 52 to complete the reaction process of 5-hydroxymethylfurfural. Samples are taken from the temporary storage tank of the post-treatment system 4 for HPLC detection of the concentration of 5-hydroxymethylfurfural (in this embodiment, 5-hydroxymethylfurfural is detected using Waters 2695 and 2487 liquid chromatographs, and quantification is performed using the external standard method), according to the formula: The yield of 5-hydroxymethylfurfural was calculated to be 63%, the conversion rate of fructose was 87%, and the selectivity of 5-hydroxymethylfurfural was 72.4%.

[0053] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for spray synthesis of 5-hydroxymethylfurfural, characterized in that, Includes the following steps: The reaction solution is preheated to a preset temperature, wherein the reaction solution includes an aqueous mixture and an organic solvent, the aqueous mixture is prepared by a carbohydrate compound, a catalyst and an aqueous solvent in a preset ratio, and the preset temperature is 90℃~200℃; A high-speed spraying device simultaneously atomizes the aqueous mixture and the organic solvent and sprays them into a pipeline reactor, so that the carbohydrate compound, the catalyst and the organic solvent can be mixed and homogenized in the form of microparticles to obtain 5-hydroxymethylfurfural. A reflux pump pumps a predetermined proportion of the aqueous mixture and the organic solvent, located at the tail end of the pipeline reactor, back into the head end of the pipeline reactor, so that the aqueous mixture and the organic solvent can be mixed and homogenized again to obtain 5-hydroxymethylfurfural. The predetermined proportion is 0-50%. The total residence time of the reaction solution in the pipeline reactor and the reflux pipe is 20-120 minutes.

2. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 1, characterized in that, The carbohydrate compound is selected from at least one of fructose, glucose, and sucrose, and the mass fraction of the carbohydrate compound in the aqueous solvent is 1 wt% to 60 wt%.

3. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 1, characterized in that, The catalyst is selected from acid catalysts, and the mass fraction of the catalyst is 0.1wt% to 20wt% of the total mass of the aqueous mixture.

4. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 1, characterized in that, The organic solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, 4-methyl-2-pentanone, and 2-methyltetrahydrofuran.

5. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 1, characterized in that, An apparatus for the spray synthesis of 5-hydroxymethylfurfural, the apparatus comprising: Pipeline reactor; A high-speed spraying device is located at the beginning of the pipeline reactor and is used to simultaneously atomize the aqueous mixture and the organic solvent and spray them into the pipeline reactor, so that the reaction liquid can be mixed and homogenized in the form of microparticles to obtain 5-hydroxymethylfurfural. A reflux pipe connects the beginning and end of the pipeline reactor; A post-processing system is used to treat the reaction solution to obtain 5-hydroxymethylfurfural; The discharge pipe connects the tail end of the pipeline reactor to the post-treatment system; A reflux circulation pump is connected to the reflux pipe and the discharge pipe, respectively. The reflux circulation pump is used to pump a mixture of the aqueous phase mixture and the organic solvent in a preset ratio located at the tail end back into the head end through the reflux pipe, so that the aqueous phase mixture and the organic solvent can be mixed and homogenized again to obtain 5-hydroxymethylfurfural, and the remaining reaction liquid located at the tail end is pumped into the post-treatment system through the discharge pipe.

6. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 5, characterized in that, The discharge pipe is equipped with a valve and a back pressure valve.

7. The method for spray synthesis of 5-hydroxymethylfurfural as described in claim 5, characterized in that, The pipeline reactor has a temperature control module, which is used to adjust the reaction temperature of the reaction liquid.

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