Manufacturing method and apparatus for producing 5-hydroxymethylfurfural in a connected manner

Abstract

The present invention relates to the fields of catalytic chemistry and biomass resource utilization, and particularly to a production method and apparatus for continuously producing 5-hydroxymethylfurfural. This production method uses saccharide biomass, a solvent, an auxiliary agent, and an acid catalyst as raw materials, uniformly mixes them to obtain an aqueous phase material, pre-heats the aqueous phase material, then puts it into multi-stage reaction equipment, and cools and separates the product obtained by the reaction to obtain the 5-hydroxymethylfurfural. The apparatus of the present invention can accommodate both a simple aqueous phase system and a two-phase system, controls the production process using a fully automated program, is equipped with an on-line monitoring system, and can monitor the production status of HMF in real time. At the same time, in the production process of 5-hydroxymethylfurfural, the problem that black corrosion products are likely to clog the tubes due to the generation of a large amount of humins can be effectively solved, the production rate is high, and this apparatus has broad development prospects for the large-scale industrial production of 5-hydroxymethylfurfural in the future.

Description

Technical Field

[0001] The present invention relates to the fields of catalytic chemistry and biomass resource utilization, and particularly to a production method and apparatus for continuously producing 5-hydroxymethylfurfural.

Background Art

[0002] 5-Hydroxymethylfurfural (HMF) is an important intermediate compound connecting biomass and chemical industrial raw materials. Through chemical reactions such as hydrogenation, oxidation, etherification, and esterification, a series of other new furan derivatives with high added value, such as 2,5-furandicarboxylic acid and 2,5-tetrahydrofuran dimethanol, can be synthesized, and it has extremely great application prospects and value.

[0003] Currently, the production methods of 5-hydroxymethylfurfural mainly include: (1) a method of directly dehydrating using fructose for production; (2) a method of producing by isomerizing glucose and then dehydrating; (3) a method of synthesizing 5-hydroxymethylfurfural after hydrolyzing cellulose. However, in the synthesis process of 5-hydroxymethylfurfural, a large amount of Humins is generated, and its polymerization form is complex. For example, there are etherification reactions between HMF molecules, acetalization reactions between HMF molecules, and esterification reactions between HMF and levulinic acid, formic acid, etc. Along with this, the corresponding black rot substances also exhibit various forms such as thin and small soft particles, hard particle-like substances, soft mass-like blocks, and sparse cotton-like shapes. At the stage of high-temperature reaction, the solubility of the black rot substances is relatively high, but when cooled and the temperature is lowered, the solubility of the high-molecular substances decreases, and most of them will precipitate, settle, or adhere as solid or semi-solid black rot substances. Especially in a simple aqueous phase system, with the increase in the amount of water, the humins structure becomes very dense, showing black and hard lumps, which extremely easily clog the tubes and make it difficult to flow through. In a batch kettle reaction, the influence of black rot substances on the production process is relatively small, but in the development of a continuous flow reaction process, many challenges are faced. For example, when producing HMF by reaction in a conventional continuous fixed bed, the generated black rot substances are extremely likely to adhere to the surface of the catalyst, reducing the activity of the catalyst and ultimately deactivating the catalyst. On the other hand, if this black rot substance accumulates for a long time, it may completely clog the tubes, elbows, valves, etc., making production impossible. Therefore, preventing black rot substances from clogging the tubes is an urgent problem to be solved in realizing the continuous production of HMF.

[0004] Therefore, in view of the deficiencies of the prior art as described above, the present invention provides a production method and apparatus for continuously producing 5-hydroxymethylfurfural.

Summary of the Invention

[0005] (1) Problems to be Solved by the Invention The present invention aims to provide a manufacturing method and apparatus for continuously manufacturing 5-hydroxymethylfurfural so as to solve the problems that the tube is prone to clogging and continuous production is difficult in the production process of 5-hydroxymethylfurfural.

[0006] (2) Means for Solving the Problems To solve the above problems, the present invention provides an apparatus for continuously manufacturing 5-hydroxymethylfurfural, comprising: a raw material transportation system including an aqueous phase material transportation unit for transporting an aqueous phase material; a first cleaning system respectively connected to the outlet of the raw material transportation system together with the aqueous phase material transportation unit and used for cleaning when the material is clogged or discharged; a heat source system connected to the outlet of the raw material transportation system via a first tube and used for heating the raw material; a modular reaction equipment system connected to the outlet of the heat source system via a second tube and incorporating a raw material reaction tube unit, a temperature-sensitive control unit, and a pressure-sensitive control unit; a cooling system connected to the outlet of the modular reaction equipment system via a third tube and used for cooling the product in the modular reaction equipment system; and a control system respectively connected to the aqueous phase material transportation unit, the first cleaning system, the heat source system, the temperature-sensitive control unit, the pressure-sensitive control unit, and the cooling system so as to perform intelligent control of feeding, automatic cleaning of equipment, temperature, pressure, emergency start-up, and emergency stop, thereby providing an apparatus for continuously manufacturing 5-hydroxymethylfurfural.

[0007] Furthermore, the raw material transportation system further comprises an organic phase material transportation unit connected to its outlet for transporting an organic material.

[0008] Furthermore, the modular reaction equipment system includes a plurality of modular reaction equipments. The temperature-sensitive control unit is a temperature sensor, and the pressure-sensitive control unit is a pressure sensor. The modular reaction equipment is provided with a built-in raw material reaction tube unit, a temperature sensor, and a pressure sensor. A polytetrafluoroethylene inner tube is lined throughout the raw material reaction tube unit, and a temperature sensor and a pressure sensor are built into the raw material reaction tube unit. The temperature sensor and the pressure sensor are respectively connected to a control system, a heating element is provided in the raw material reaction tube unit, and the heating element is connected to the control system.

[0009] Furthermore, it further includes a second cleaning system, and a plurality of modular reaction equipments are installed in series or in parallel in this order. The modular reaction equipment further includes a first cleaning three-way valve and a second cleaning three-way valve. The first cleaning three-way valve and the second cleaning three-way valve are respectively installed at positions close to the inlet of the raw material reaction tube unit and positions close to the outlet of the raw material reaction tube unit. The first cleaning three-way valve is connected to the second cleaning system, and the first cleaning three-way valve and the second cleaning three-way valve are respectively connected to the control system.

[0010] Furthermore, the online monitoring system further includes a connected UV online detector and a sampling probe. The sampling probe is installed in a tube at the outlet of the cooling system. The UV online detector is used to detect the sample sent from the sampling probe and feedback the detection data to the control system so as to adjust the flow rate of the initial material. The UV online detector is connected to the control system. The preheating system is connected to the cooling system so as to recover the residual heat exchanged by the cooling system. The preheating system is connected to the heat source system so as to supply heat to the heat source system.

[0011] Furthermore, the first cleaning system is a cleaning module comprising a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order. The outlet of the cleaning pump is connected to the first tube at the outlet of the raw material transportation system, and the inlet of the recovery pump is connected to the outlet of the modularized reaction equipment system or the outlet of the cooling system.

[0012] Furthermore, the second cleaning system is a cleaning module comprising a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order.

[0013] The outlet of the cooling system is connected to an extraction device, and the extraction device, the separation device, and the reaction product distillation device are connected in this order.

[0014] The outlet of the cleaning pump is connected to the first cleaning three-way valve of the raw material reaction tube unit, and the inlet of the recovery pump is connected to the second cleaning three-way valve of the raw material reaction tube unit. Alternatively, the outlet of the cleaning pump is connected to the inlet of the cooling system, and the inlet of the recovery pump is connected to the outlet of the cooling system. Alternatively, the outlet of the cleaning pump is connected to the inlet of the extraction device, and the inlet of the recovery pump is connected to the outlet of the extraction device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the separation device, and the inlet of the recovery pump is connected to the outlet of the separation device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the reaction product distillation device, and the inlet of the recovery pump is connected to the outlet of the reaction product distillation device.

[0015] Furthermore, the second cleaning system is a cleaning module including a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order.

[0016] The outlet of the cooling system is connected to an extraction device via a fourth tube, the extraction device is connected to a separation device via a fifth tube, the separation device is connected to a reaction product distillation device via a sixth tube, and the outlet of the reaction product distillation device is connected to a seventh tube.

[0017] A seventh three-way valve having a cleaning inlet of a seventh three-way valve is provided in the fourth tube. An eighth three-way valve having a cleaning outlet of an eighth three-way valve and a ninth three-way valve having a cleaning inlet of a ninth three-way valve are provided in the fifth tube. A tenth three-way valve having a cleaning outlet of a tenth three-way valve and an eleventh three-way valve having a cleaning inlet of an eleventh three-way valve are provided in the sixth tube. A twelfth three-way valve having a cleaning outlet of a twelfth three-way valve is provided in the seventh tube.

[0018] The cleaning inlets of the seventh three-way valve, the ninth three-way valve, and the eleventh three-way valve are respectively connected to a liquid inlet main pipe via liquid inlet branch pipes, and the cleaning outlets of the eighth three-way valve, the tenth three-way valve, and the twelfth three-way valve are respectively connected to a liquid outlet main pipe via liquid outlet branch pipes.

[0019] The outlet of the cleaning pump is connected to the liquid inlet main pipe, and the inlet of the recovery pump is connected to the liquid outlet main pipe.

[0020] Furthermore, the cleaning module is connected to the cleaning liquid storage device and further includes a heating device for heating the liquid in the cleaning liquid storage device. The cooling system is a cooling tank having an elongated body with an intermediate layer. The cooling tank is provided with a cooling coil tube inside, a relief port is provided at the upper part of the waist of the body, a timed material outlet is provided below the waist, and the bottom is a material outlet with an inverted taper shape. A back pressure valve is provided on the body, and a safety valve, a pressure sensor and a temperature sensor are further provided on the body.

[0021] On the other hand, the present invention provides a manufacturing method for continuously manufacturing 5-hydroxymethylfurfural, comprising: a step of uniformly mixing saccharide biomass, a solvent, an auxiliary agent and an acid catalyst as raw materials to obtain an aqueous phase material; a step of preheating the aqueous phase material and then putting it into a multi-stage reaction equipment, and cooling and separating the obtained product to obtain 5-hydroxymethylfurfural.

[0022] Furthermore, the raw materials include organic materials. The organic materials and the aqueous phase material are respectively transported to the multi-stage reaction device by different pumps. The temperature of the preheating is 60°C to 90°C, and the operating temperature of the multi-stage reaction device is 120°C to 160°C. The concentration of the saccharide biomass is 10 to 400 g / L, and the saccharide biomass is at least one of glucose, fructose, sucrose, maltose, and fructose grape syrup. The auxiliary agent is at least one of polyethylene glycol, choline chloride, and ionic liquid. The organic solvent of the organic phase is at least one of dimethyl carbonate, diethyl carbonate, 4-methyl-2-pentanone, tetrahydrofuran, and butanol.

[0023] (3) Beneficial effects As described above, according to the above configuration of the present invention, the following advantages exist.

[0024] The present invention can accommodate both a simple aqueous phase and a two-phase system, control the production process using a fully automated process, be equipped with an online monitoring system to monitor the production status of HMF in real time, and when problems occur in the temperature, pressure, and production yield of the system, it can initiate corresponding solutions on its own to save manpower.

[0025] In addition, the present invention effectively solves the problem that black rotten substances generated due to the generation of a large amount of humins in the actual production process of 5-hydroxymethylfurfural are likely to clog the tubes. That is, on the one hand, by adding an auxiliary agent from the raw material side, the aggregation of black rotten substances is suppressed, preventing clogging caused by the aggregation of black rotten substances into blocks. On the other hand, by modularizing the design of the reaction equipment and adopting the design of tacks in the cooling process, it is possible to effectively prevent the tubes from being clogged due to the precipitation of black rotten substances during the cooling process. Also, even if the tubes are clogged, the clogged module can be quickly replaced, and the clogged unit can be individually connected to a cleaning device for cleaning, saving the shutdown inspection time and not delaying the production of the factory. From this, it can be seen that this device has broad development prospects for the large-scale industrial production of 5-hydroxymethylfurfural in the future.

Brief Description of the Drawings

[0026]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Embodiments for Carrying Out the Invention

[0027] Hereinafter, embodiments of the present invention will be described in more detail with reference to the drawings and examples. The following detailed description of the examples and the drawings are for illustratively explaining the principle of the present invention and do not limit the scope of the present invention. That is, the present invention is not limited to the described examples.

[0028] In order to more clearly understand the above objects, features, and advantages of the present invention, the aspects of the present invention will be further described below. Note that the examples and features in the examples of the present invention can be combined with each other as long as they do not conflict.

[0029] In the following description, many specific details are described to make the present invention easier to understand. However, the present invention may be implemented in a manner different from the aspects described herein. It goes without saying that the examples in the specification are only some examples of the present invention and not all examples.

[0030] Hereinafter, preferred embodiments of the present invention will be described in detail based on examples. It should be understood that the presentation of the following examples is for illustrative purposes only and is not intended to limit the scope of the present invention. Those skilled in the art can make various modifications and substitutions to the present invention without departing from the gist and spirit of the present invention.

[0031] The experimental methods used in the following examples are conventional methods unless otherwise specified.

[0032] The materials, reagents, etc. used in the following examples can be commercially available unless otherwise specified.

[0033] On one side, as shown in FIGS. 1 and 2, the present invention includes a raw material transportation system including an aqueous phase material transportation unit for transporting an aqueous phase material, A first cleaning system that is respectively connected to the outlet of the raw material transportation system together with the aqueous phase material transportation unit and is used for cleaning when the material is clogged or discharged. A heat source system connected to the outlet of the raw material transportation system via a first tube and used for heating the raw material, A modular reaction equipment system connected to the outlet of the heat source system via a second tube and incorporating a raw material reaction tube unit, a temperature-sensitive control unit, and a pressure-sensitive control unit, A cooling system connected to the outlet of the modular reaction equipment system via a third tube and used for cooling the product in the modular reaction equipment system, Provided is an apparatus for continuously producing 5-hydroxymethylfurfural, comprising a control system connected to the aqueous phase material transportation unit, the first cleaning system, the heat source system, the temperature-sensitive control unit, the pressure-sensitive control unit, and the cooling system respectively, so as to perform intelligent control of feed, automatic cleaning of equipment, temperature, pressure, emergency startup, and emergency stop.

[0034] Furthermore, the raw material transportation system further comprises an organic phase material transportation unit connected to its outlet for transporting organic materials.

[0035] Preferably, the inorganic phase material transportation unit is an aqueous phase pump, the organic phase material transportation unit is an organic pump, and the first cleaning system is a cleaning pump. More preferably, the aqueous phase pump, the organic pump, and the cleaning pump are all high-pressure pumps.

[0036] In addition, when there is only an aqueous phase material in the transported material, the aqueous phase pump operates and the organic pump closes, but when there are both an aqueous phase material and an organic material in the transported material, both the aqueous phase pump and the organic pump operate. When cleaning is required due to blockage in the system, the cleaning pump is turned on, and when the system is operating normally, the cleaning pump is turned off. When the system detects that the pressure exceeds the upper limit value of the reaction pressure, the aqueous phase pump and the organic phase pump are closed, the cleaning pump is turned on, and the tube cleaning mode is entered to prevent further deposition in the system of black corrosive substances.

[0037] Furthermore, the modular reaction equipment system includes a plurality of modular reaction equipments. The temperature-sensitive control unit is a temperature sensor, and the pressure-sensitive control unit is a pressure sensor. The modular reaction equipment is provided with a built-in raw material reaction tube unit, a temperature sensor, and a pressure sensor. The entire inside of the raw material reaction tube unit is lined with a polytetrafluoroethylene inner tube, and a temperature sensor and a pressure sensor are built into the raw material reaction tube unit. The temperature sensor and the pressure sensor are respectively connected to a control system, and a heating element is provided in the raw material reaction tube unit.

[0038] Note that the modular design of the reaction equipment means modularly designing the filling area of the conventional reaction fixed bed catalyst or the material countercurrent (cocurrent) reaction area, that is, the core area of such dehydration reaction.

[0039] Preferably, the plurality of modular reaction equipments may be installed in series or in parallel in this order according to the requirements of the actual production capacity.

[0040] Preferably, the material reaction tube system includes a reaction coil tube, a three-way valve and a valve for inserting into the tube, a feed pump, and a three-way valve and a valve for flowing out of the tube.

[0041] In order to better prevent blockage in the system, the arrangement method of the tubes in the modular reaction equipment is in the form of a coil tube, and it is preferable that the liquid is transported from top to bottom.

[0042] While suppressing blockage of the black rot food on the wall and blockage of the tube, and at the same time enhancing the acid corrosion resistance of the tube, the entire inside of the reaction tube is lined with a polytetrafluoroethylene inner tube, and a plurality of temperature sensors and pressure sensors are built in to feedback the real-time situation of the raw materials in the tube, for example, so that adjustments can be made immediately when abnormalities occur.

[0043] Furthermore, the cooling system is a cooling tank having an elongated main body with an intermediate layer. The cooling tank is provided with a cooling coil tube inside, a relief port is provided at the upper part of the waist of the main body, a timed material outlet is provided below the waist, and the bottom is a tapered material outlet. A back pressure valve is provided on the main body, and a safety valve, a pressure sensor and a temperature sensor are further provided on the main body.

[0044] Note that according to the structure of the cooling tank, it can be divided into two forms. One is to adopt nitrogen gas filling to ensure a certain pressure in the system and discharge materials regularly, and the other is to relieve the liquid after cooling and ensure a certain pressure in the system through the back pressure valve.

[0045] Furthermore, the second cleaning system is further provided. The modular reaction equipment further includes a first cleaning three-way valve and a second cleaning three-way valve. The first cleaning three-way valve and the second cleaning three-way valve are respectively installed at positions close to the inlet and the outlet of the raw material reaction tube unit. The first cleaning three-way valve is connected to the second cleaning system, and the first cleaning three-way valve and the second cleaning three-way valve are respectively connected to the control system.

[0046] The three-way valves at the inlet and outlet of the raw material reaction tube unit are used to transport materials during the normal operation of the reaction equipment and to flow the cleaning liquid in case of blockage in the equipment.

[0047] Furthermore, the first cleaning system is a cleaning pump or a cleaning module. The cleaning module includes a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order. The outlet of the cleaning pump is connected to the first tube at the outlet of the raw material transportation system, and the inlet of the recovery pump is connected to the outlet of the modularized reaction equipment system or the waste discharge port of the cooling system. The recovery pump is used to transport the extracted cleaning liquid to the buffer tank, and the buffer tank performs primary filtration and debris removal.

[0048] As shown in Figure 4, the second cleaning system is a cleaning module including a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order.

[0049] The outlet of the cooling system is connected to an extraction device, and the extraction device, a separation device, and a reaction product distillation device are connected in this order. Also, as follows, a plurality of connection arrangement methods with the cleaning pump and the recovery pump are provided.

[0050] The outlet of the cleaning pump is connected to the first cleaning three-way valve of the raw material reaction tube unit, and the inlet of the recovery pump is connected to the second cleaning three-way valve of the raw material reaction tube unit. Alternatively, the outlet of the cleaning pump is connected to the inlet of the cooling system, and the inlet of the recovery pump is connected to the outlet of the cooling system. Alternatively, the outlet of the cleaning pump is connected to the inlet of the extraction device, and the inlet of the recovery pump is connected to the outlet of the extraction device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the separation device, and the inlet of the recovery pump is connected to the outlet of the separation device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the reaction product distillation device, and the inlet of the recovery pump is connected to the outlet of the reaction product distillation device.

[0051] As shown in FIG. 5, the second cleaning system is a cleaning module including a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order.

[0052] The outlet of the cooling system is connected to the extraction device via a fourth tube, the extraction device is connected to the separation device via a fifth tube, the separation device is connected to the reaction product distillation device via a sixth tube, and the outlet of the reaction product distillation device is connected to a seventh tube.

[0053] The fourth tube is provided with a seventh three-way valve having a cleaning inlet of the seventh three-way valve. The fifth tube is provided with an eighth three-way valve having a cleaning outlet of the eighth three-way valve and a ninth three-way valve having a cleaning inlet of the ninth three-way valve. The sixth tube is provided with a tenth three-way valve having a cleaning outlet of the tenth three-way valve and an eleventh three-way valve having a cleaning inlet of the eleventh three-way valve. The seventh tube is provided with a twelfth three-way valve having a cleaning outlet of the twelfth three-way valve.

[0054] The cleaning inlets of the seventh three-way valve, the ninth three-way valve, and the eleventh three-way valve are respectively connected to the main liquid inlet pipe through liquid inlet branch pipes, and the cleaning outlets of the eighth three-way valve, the tenth three-way valve, and the twelfth three-way valve are respectively connected to the main liquid outlet pipe through liquid outlet branch pipes.

[0055] The outlet of the cleaning pump is connected to the main liquid inlet pipe, and the inlet of the recovery pump is connected to the main liquid outlet pipe.

[0056] With the above connection arrangement, when a certain equipment needs to be cleaned, open the valves close to both sides of this equipment and close the valves on both sides of other equipment, so as to transport the cleaning liquid from the cleaning pump to the main liquid inlet pipe, enter the equipment through the corresponding liquid inlet branch pipe, then extract the cleaning waste liquid from the equipment to the liquid outlet branch pipe with the recovery pump, put the cleaning waste liquid from the liquid outlet branch pipe into the main liquid outlet pipe, then return it from the main liquid outlet pipe to the recovery pump, and finally perform the next waste liquid cleaning and recovery utilization process.

[0057] Furthermore, the cleaning module is connected to the cleaning liquid storage device and further includes a heating device for heating the liquid in the cleaning liquid storage device. During the production process of 5-hydroxymethylfurfural, black rotten substances often solidify and adhere to the surface of the equipment and are difficult to remove with cleaning liquid at normal temperature. In order to enhance the cleaning effect, the black rotten substances can be softened and dissolved by heating the cleaning liquid. Therefore, a heating device for heating the liquid in the cleaning liquid storage device is introduced.

[0058] In the above embodiment, in order to ensure the quality and service life of the cleaning liquid and realize the recycling of the cleaning liquid, a cleaning liquid solvent distillation device and a cleaning liquid recovery device for secondary treatment of the cleaning liquid are introduced. A heating module is installed in this cleaning liquid solvent distillation device, and impurities and residues in the cleaning liquid can be removed through heating and distillation operations, the cleaning liquid can be purified, and its service life can be extended.

[0059] Furthermore, the rear end of the regular material outlet of the cooling tank is connected to an extraction device via a fourth tube, the extraction device is connected to a separation device via a fifth tube, the separation device is connected to a reaction product distillation device via a sixth tube, and the outlet of the reaction product distillation device is connected to a seventh tube.

[0060] Since valves are installed in the fourth tube, the fifth tube, the sixth tube, and the seventh tube, the extraction device, the separation device, and the reaction product distillation device can be cleaned individually.

[0061] Furthermore, it further includes an online monitoring system including a connected UV online detector and a sampling probe. The sampling probe is installed in the tube at the outlet of the cooling system, and the UV online detector is used to detect the sample sent from the sampling probe and feedback the detection data to the control system so as to adjust the flow rate of the initial material.

[0062] Furthermore, it further includes a preheating system connected to the cooling system so as to recover the residual heat exchanged by the cooling system. The preheating system is connected to a heat source system so as to supply heat to the heat source system.

[0063] The heat source of the reaction equipment is derived from the steam generated in the heat source system. Automatic temperature control is realized by adjusting the opening degree of the valve with the built-in temperature control sensor, and the tubes connecting the reaction equipment are insulated with heat preservation cotton.

[0064] According to the example of the present disclosure, the cleaning liquid in the cleaning liquid storage device contains various cleaning agents having a strong dissolving ability for black rot food generated in the production process of HMF. The composition of the cleaning liquid includes various commercially available cleaning agents with high fume removal effects, fume removers, etc., and also includes organic solvents. Therefore, when selecting the cleaning liquid, it may be a combination of one or more of the cleaning agent, the fume remover, and the organic solvent.

[0065] In this embodiment, the organic solvent is at least one of organic solvents such as fluorocarbon-based organic solvents, halogenated hydrocarbon-based organic solvents, alcohol-based organic solvents, amide-based organic solvents, ester-based organic solvents, and furan-based organic solvents.

[0066] The organic solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, dichlorodifluoromethane, monofluorotrichloromethane, trichlorotrifluoroethane, tetrachloroethylene, methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, polyethylene glycol, glycerin, N,N-dimethylformamide, N,N-dimethylacetamide, methyl acetate, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran, 4-methyl-2-pentanone, dimethyl carbonate, diethyl carbonate, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, and acetone.

[0067] When the cleaning waste removal system operates, the formulated cleaning liquid is atomized and filled into the modular reaction equipment to be cleaned at a certain temperature and pressure, circulated back and forth for 5 to 120 minutes, then cleaned with an organic solvent and water in this order, and the equipment can be used again.

[0068] In this embodiment, the certain temperature includes room temperature to 150 °C, and the certain pressure includes 0.1 to 2 MPa.

[0069] On the other hand, the present invention provides a production method for continuously producing 5-hydroxymethylfurfural, which includes a step of uniformly mixing saccharide biomass, a solvent, an auxiliary agent, and an acid catalyst as raw materials to obtain an aqueous phase material, and a step of preheating the aqueous phase material, then putting it into a multi-stage reaction equipment, reacting, cooling, and separating the obtained product to obtain 5-hydroxymethylfurfural.

[0070] Furthermore, the raw material includes an organic material. The organic material and the aqueous phase material are respectively transported to a multi-stage reactor by different pumps. The temperature of the preliminary heating is 60°C to 90°C, and the operating temperature of the multi-stage reactor is 120°C to 160°C.

[0071] Furthermore, the concentration of the saccharide biomass is 10 to 400 g / L, and the saccharide biomass is at least one of glucose, fructose, sucrose, maltose, and fructose syrup. The co-agent is at least one of polyethylene glycol, choline chloride, and ionic liquid. The organic solvent of the organic phase is at least one of dimethyl carbonate, diethyl carbonate, 4-methyl-2-pentanone, tetrahydrofuran, and butanol.

[0072] In addition, the co-agent plays a role in improving the selectivity of 5-hydroxymethylfurfural and suppressing the block generation of black rot food.

[0073] Preferably, the solvent is water.

[0074] Preferably, the acid catalyst is a homogeneous acid and includes inorganic acids and organic acids. More preferably, the inorganic acid is at least one of sulfuric acid, hydrochloric acid, and phosphoric acid, and the organic acid is at least one of methanesulfonic acid, p-toluenesulfonic acid, tartaric acid, and citric acid.

[0075] Example 1 As shown in FIG. 1, the method for producing biphasic 5-hydroxymethylfurfural according to the present invention is as follows.

[0076] 60 kg of fructose, 400 kg of water, 1.8 kg of phosphoric acid, and 20 kg of polyethylene glycol 4000 were weighed and stirred and dissolved to obtain an aqueous phase raw material, and a dimethyl carbonate solvent was used as the organic phase.

[0077] It reacted in the equipment shown in Fig. 1. In the case of normal operation, nitrogen gas was filled to keep the system pressure above 0.8 MPa, and the system was maintained between 140 °C and 150 °C with heat source steam. The organic phase dimethyl carbonate solvent was transported at a rate of 1 L / min by the organic pump 2, and the aqueous phase raw material was transported at a rate of 0.5 L / min by the aqueous phase pump 1. The washing pump 3 was closed. Both the organic phase and the aqueous phase were mixed and then fed into the primary reaction equipment 6 through the heat exchanger 4, which is a heat source system, and the first three-way valve 5. The material obtained in the primary reaction equipment 6 was fed into the secondary reaction equipment 9 through the second three-way valve 7 and the third three-way valve 8 in this order. The material obtained in the secondary reaction equipment 9 was fed into the tertiary reaction equipment 12 through the fourth three-way valve 10 and the fifth three-way valve 11 in this order. The material obtained in the tertiary reaction equipment 12 was fed into the cooling tank 14 through the sixth three-way valve 13.

[0078] After the material obtained by the reaction was put into the cooling tank 14, the material was cooled to 60 °C - 80 °C in the cooling tank. A nitrogen gas filling port 25 was provided at the upper part of the side of the cooling tank to fill nitrogen gas to maintain the system at a certain system pressure. The system pressure was under automatic control, and a gas backpressure valve 15 was provided at the outlet of the cooling tank. A coolant discharge port 27 was opened at the lower part of the side of the cooling tank. The discharge port discharged the material at regular intervals. After discharging the material, it was transported to an extraction device 29 for extracting the reaction product, a separation device 32 for further separating the target product and other impurities, and a reaction product distillation device 35 for purifying and refining the product. Finally, high-purity 5-hydroxymethylfurfural was obtained. Each device played a different role throughout the manufacturing process. A waste discharge port 26, which was mainly used for discharging the deposited black rotten substances, was also opened at the bottom of the cooling tank.

[0079] In the case of normal operation of the equipment, the valves of the cleaning inlets 16, 17, 18 of the three-way valve in front of the reaction equipment are in the closed state, and the valves of the cleaning inlets (outlets) 19, 20, 21 of the three-way valve behind the reaction equipment are in the closed state. Steam heat source inlets 22, 23, 24 are respectively provided in the reaction equipment 6, 9, 12. When a little blockage occurs in the reaction equipment connected in series, the reaction equipment can be replaced with the same module. If it is necessary to replace the secondary reaction equipment 9, one corresponding tube of the three-way valve at the feed port of the preliminary reaction equipment is connected to the second cleaning inlet 19 of the three-way valve, and one corresponding tube of the three-way valve at the discharge port is connected to the fifth three-way valve 11. After the connection is completed, only the corresponding valve needs to be switched, ensuring the smooth operation of the reaction equipment. Also, it is very convenient to clean the secondary reaction equipment 9. Connect the tube of the cleaning inlet 17 of the third three-way valve corresponding to the cleaning pump, close the valve at the inlet of the third three-way valve 8 and the valve at the outlet of the fourth three-way valve 10, and only open the valve of the cleaning inlet tube 17 of the third three-way valve and the cleaning outlet 20 of the fourth three-way valve. It can be cleaned separately and then used preliminarily.

[0080] By measuring and analyzing the mixture after the reaction, the molar yield of 5-hydroxymethylfurfural was 50%.

[0081] Example 2 As shown in Figure 2, the method for producing simple aqueous-phase 5-hydroxymethylfurfural according to the present invention is as follows.

[0082] Weigh 60 kg of fructose, 400 kg of water, 1.8 kg of phosphoric acid, and 20 kg of polyethylene glycol 4000, stir and dissolve them to obtain an aqueous-phase raw material.

[0083] The reaction was carried out with the equipment shown in Fig. 2. In the case of normal operation, the back pressure valve 15 was adjusted to a pressure of 0.8 MPa, and the system was maintained between 140 °C and 150 °C with the heat source steam. The aqueous phase raw material was transported at a rate of 1.5 L / min by the aqueous phase pump 1, and the organic pump 2 and the washing pump 3 were closed. The aqueous phase material passed through the heat exchanger 4 and the first three-way valve 5 in this order and entered the primary reaction equipment 6. The material obtained in the primary reaction equipment 6 passed through the second three-way valve 7 and the third three-way valve 8 in this order and entered the secondary reaction equipment 9. The material obtained in the secondary reaction equipment 9 passed through the fourth three-way valve 10 and the fifth three-way valve 11 in this order and entered the tertiary reaction equipment 12. The material obtained in the tertiary reaction equipment 12 passed through the sixth three-way valve 13 and entered the cooling tank 14.

[0084] After entering the cooling tank 14, the material was cooled to 60 °C - 80 °C in the cooling tank. A relief port was provided at the upper part of the side of the cooling tank, and the upper-stage cooling liquid was led to the storage tank through the back pressure valve 15 in a relief manner. The discharge port 27 at the lower part of the side of the cooling tank was an emergency discharge port and was in a closed state during normal operation. A waste discharge port 26 mainly used for discharging the deposited black rotten substances was also opened at the bottom of the cooling tank.

[0085] Steam heat source inlets 22, 23, and 24 were provided in the reaction equipment 6, 9, and 12 respectively. If a slight blockage occurred in the serially connected reaction equipment, the reaction equipment could be replaced with the same module. If it was necessary to replace the secondary reaction equipment 9, one tube corresponding to the three-way valve at the feed port of the spare reaction equipment was connected to the washing inlet 19 of the second three-way valve, and one tube corresponding to the three-way valve at the discharge port was connected to the fifth three-way valve 11. After the connection was completed, only the corresponding valve needed to be switched, ensuring the smooth operation of the reaction equipment. Also, it was very convenient to clean the secondary reaction equipment 9. The tube at the washing inlet 17 of the third three-way valve was connected corresponding to the washing pump, the valves at the inlet of the third three-way valve 8 and the outlet of the fourth three-way valve 10 were closed, and only the valves at the washing inlet tube 17 of the third three-way valve and the washing outlet 20 of the fourth three-way valve needed to be opened. It could be cleaned separately and then used preliminarily.

[0086] By measuring and analyzing the mixture after the reaction, the molar yield of 5-hydroxymethylfurfural was 43%.

[0087] The cleaning of black rot food includes the cleaning of the entire device and the individual cleaning of certain equipment in the device. Hereinafter, the processes of the overall cleaning and the individual cleaning of certain equipment will be described in detail.

[0088] Figure 3 shows the cleaning of the entire plurality of modular reaction facilities 100 (that is, the primary reaction facility 6, the secondary reaction facility 9, and the tertiary reaction facility 12). Specifically, first, the cleaning pump 3 atomizes water at a certain pressure and sprays it into the heat exchanger 4, the first three-way valve 5, and the reaction facilities 6, 9, 12 to wash and remove most of the reaction solution and lumpy black rot food. The recovery pump 42 sends the waste liquid from the cleaning outlet (inlet) 21 of the sixth three-way valve to the buffer tank 41 and the cleaning liquid solvent distillation device 40 to discharge waste water and debris, and puts the filtered cleaning liquid into the cleaning liquid recovery device 39, and then from the cleaning liquid recovery device 39 into the cleaning liquid storage device 38. Then, an organic solvent such as an amide-based or ketone-based or alcohol-based or ester-based one is used, or a small amount of detergent 0.1 - 5% is added, or a fume remover 0.1 - 5% is further added, stirred and uniformly mixed, then the mixed liquid is heat-treated by the heating device 43, and then high-pressure cleaning is performed, repeating for 5 - 120 minutes. Then, using a single type of organic solvent, it is heated to about 100 °C and high-pressure cleaning is performed, repeating for 5 - 120 minutes. Finally, high-pressure cleaning is performed with tap water, repeating for 5 - 120 minutes to restore the system, and then continue to be put into use. In this process, the organic solvents are collected according to types, respectively recovered into the cleaning liquid recovery device 39, and then formulated and used again.

[0089] Figures 4 and 5 show the individual cleaning of the extraction device 29, the separation device 32, and the reaction product distillation device 35. When cleaning the extraction device 29 individually, open the cleaning inlet 28 of the seventh three-way valve and the cleaning outlet 30 of the eighth three-way valve, close the valves of the cleaning inlets 16, 17, 18 of the three-way valves in front of the reaction equipment and the valves of the cleaning out (in)lets 19, 20, 21 of the three-way valves behind the reaction equipment, and close the cleaning inlet 31 of the ninth three-way valve, the cleaning outlet 33 of the tenth three-way valve, the cleaning inlet 34 of the eleventh three-way valve, and the cleaning outlet 36 of the twelfth three-way valve. First, operate the cleaning pump 3 to atomize water at a certain pressure, spray it into the extraction device 29, and wash away the reaction liquid and lumpy black rotten food in the extraction device 29. Use the recovery pump 42 to put the waste liquid from the cleaning outlet 30 of the eighth three-way valve into the buffer tank 41 and the cleaning liquid solvent distillation device 40, discharge the waste water and scraps, put the filtered cleaning liquid into the cleaning liquid recovery device 39, and then put it from the cleaning liquid recovery device 39 into the cleaning liquid storage device 38. Then, use an organic solvent such as an amide-based or ketone-based or alcohol-based or ester-based one, or add a small amount of detergent of 0.1 - 5%, or further add an oil fume remover of 0.1 - 5%, stir and mix uniformly, then heat-treat the mixture with the heating device 43, and then perform high-pressure cleaning, repeating it for 5 - 120 minutes. Then, use a single type of organic solvent, heat it to about 100 °C and perform high-pressure cleaning, repeating it for 5 - 120 minutes. Finally, perform high-pressure cleaning with tap water, repeat it for 5 - 120 minutes to restore the system, and then continue to use it. In this process, collect the organic solvents according to their types, recover them into the cleaning liquid recovery device 39 respectively, and then mix and use them again.

[0090] The process of cleaning the separation device 32 and the reaction product distillation device 35 alone is the same as the cleaning process of the extraction device 29, so the description is omitted. Also, in this application, the heat exchanger 4 may be cleaned, and the heat exchanger 4 is connected to the liquid inlet main pipe and the liquid outlet main pipe through tubes.

[0091] Note that the present invention is not limited to the specific processes and structures described above and shown in the figures. Also, for simplicity, the detailed description of known method technologies is omitted here.

[0092] The above description is only an example of the present application and is not limited to the present application. For those skilled in the art, the present application can be subject to various modifications and changes without departing from the scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the scope of the claims of the present application.

Description of Reference Numerals

[0093] 1 - aqueous phase pump; 2 - organic pump; 3 - cleaning pump; 4 - heat exchanger; 5 - first three-way valve; 6 - primary reaction equipment; 7 - second three-way valve; 8 - third three-way valve; 9 - secondary reaction equipment; 10 - fourth three-way valve; 11 - fifth three-way valve; 12 - tertiary reaction equipment; 13 - sixth three-way valve; 14 - cooling tank; 15 - back pressure valve; 16 - cleaning inlet of the first three-way valve; 17 - cleaning inlet of the third three-way valve; 18 - cleaning inlet of the fifth three-way valve; 19 - cleaning outlet (inlet) of the second three-way valve; 20 - cleaning outlet (inlet) of the fourth three-way valve; 21 - cleaning outlet (inlet) of the sixth three-way valve; 22 - heat source inlet of the primary reaction equipment; 23 - heat source inlet of the secondary reaction equipment; 24 - heat source inlet of the tertiary reaction equipment; 25 - nitrogen gas filling port of the cooling tank; 26 - waste discharge port of the cooling tank; 27 - coolant discharge port of the cooling tank; 28 - cleaning inlet of the seventh three-way valve; 29 - extraction device; 30 - cleaning outlet of the eighth three-way valve; 31 - cleaning inlet of the ninth three-way valve; 32 - separation device; 33 - cleaning outlet of the tenth three-way valve; 34 - cleaning inlet of the eleventh three-way valve; 35 - reaction product distillation device; 36 - cleaning outlet of the twelfth three-way valve; 38 - cleaning liquid storage device; 39 - cleaning liquid recovery device; 40 - solvent distillation device of the cleaning liquid; 41 - buffer tank; 42 - recovery pump; 100 - modular reaction equipment.

Claims

1. A raw material transportation system including an aqueous phase material transportation unit for transporting an aqueous phase material, A first cleaning system respectively connected to the outlet of the raw material transportation system together with the aqueous phase material transportation unit and used for cleaning during material clogging and material discharge, A heat source system connected to the outlet of the raw material transportation system via a first tube and used for heating the raw material, A modular reaction equipment system connected to the outlet of the heat source system via a second tube and incorporating a raw material reaction tube unit, a temperature-sensitive control unit and a pressure-sensitive control unit, A cooling system connected to the outlet of the modular reaction equipment system via a third tube and used for cooling the product in the modular reaction equipment system, A control system respectively connected to the aqueous phase material transportation unit, the first cleaning system, the heat source system, the temperature-sensitive control unit, the pressure-sensitive control unit and the cooling system so as to perform intelligent control of salary, automatic cleaning of equipment, temperature, pressure, emergency startup and emergency stop, characterized in that the device for producing 5-hydroxymethylfurfural is connected.

2. The device according to claim 1, characterized in that the raw material transportation system further comprises an organic phase material transportation unit connected to its outlet for transporting an organic material.

3. The modular reaction equipment system includes a plurality of modular reaction equipments. The temperature-sensitive control unit is a temperature sensor, the pressure-sensitive control unit is a pressure sensor. The modular reaction equipment comprises a built-in raw material reaction tube unit, a temperature sensor and a pressure sensor. The entire inside of the raw material reaction tube unit is lined with a polytetrafluoroethylene inner tube, and the temperature sensor and the pressure sensor are built in the raw material reaction tube unit. The temperature sensor and the pressure sensor are respectively connected to the control system. A heating element is provided in the raw material reaction tube unit, and the heating element is connected to the control system. The device according to claim 1 is characterized in that.

4. Further comprising a second cleaning system, a plurality of modular reaction facilities are installed in series or in parallel in this order, the modular reaction facilities further comprising a first cleaning three-way valve and a second cleaning three-way valve, the first cleaning three-way valve and the second cleaning three-way valve being installed at positions close to the inlet and the outlet of the raw material reaction tube unit respectively, the first cleaning three-way valve being connected to the second cleaning system, and the first cleaning three-way valve and the second cleaning three-way valve being connected to a control system respectively. The apparatus according to claim 3, characterized in that.

5. Further comprising an on-line monitoring system and a preheating system, the on-line monitoring system comprising a connected UV on-line detector and a sampling probe, the sampling probe being installed in a tube at the outlet of the cooling system, the UV on-line detector being used to detect a sample sent from the sampling probe and feedback detection data to the control system so as to adjust the flow rate of the initial material, the UV on-line detector being connected to the control system, the preheating system being connected to the cooling system so as to recover the residual heat exchanged by the cooling system, and the preheating system being connected to the heat source system so as to supply heat to the heat source system. The apparatus according to claim 1, characterized in that.

6. The first cleaning system is a cleaning module comprising a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank and a recovery pump, among which the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank and the recovery pump are connected in series via tubes in this order, the outlet of the cleaning pump being connected to a first tube at the outlet of the raw material transport system, and the inlet of the recovery pump being connected to the outlet of the modular reaction facility system or the discharge outlet of the cooling system. The apparatus according to claim 1, characterized in that.

7. The second cleaning system is a cleaning module comprising a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order. The outlet of the cooling system is connected to an extraction device, and the extraction device, a separation device, and a reaction product distillation device are connected in this order. The outlet of the cleaning pump is connected to the first cleaning three-way valve of the raw material reaction tube unit, and the inlet of the recovery pump is connected to the second cleaning three-way valve of the raw material reaction tube unit. Alternatively, the outlet of the cleaning pump is connected to the inlet of the cooling system, and the inlet of the recovery pump is connected to the outlet of the cooling system. Alternatively, the outlet of the cleaning pump is connected to the inlet of the extraction device, and the inlet of the recovery pump is connected to the outlet of the extraction device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the separation device, and the inlet of the recovery pump is connected to the outlet of the separation device. Alternatively, the outlet of the cleaning pump is connected to the inlet of the reaction product distillation device, and the inlet of the recovery pump is connected to the outlet of the reaction product distillation device. The device according to claim 4, characterized in that.

8. The second cleaning system is a cleaning module comprising a cleaning pump, a cleaning liquid storage device, a cleaning liquid recovery device, a cleaning liquid solvent distillation device, a buffer tank, and a recovery pump. Among these, the cleaning pump, the cleaning liquid storage device, the cleaning liquid recovery device, the cleaning liquid solvent distillation device, the buffer tank, and the recovery pump are connected in series via tubes in this order. The outlet of the cooling system is connected to the extraction device via a fourth tube, the extraction device is connected to the separation device via a fifth tube, the separation device is connected to the reaction product distillation device via a sixth tube, and the outlet of the reaction product distillation device is connected to a seventh tube. The fourth tube is provided with a seventh three-way valve having a cleaning inlet of the seventh three-way valve. The fifth tube is provided with an eighth three-way valve having a cleaning outlet of the eighth three-way valve and a ninth three-way valve having a cleaning inlet of the ninth three-way valve. The sixth tube is provided with a tenth three-way valve having a cleaning outlet of the tenth three-way valve and an eleventh three-way valve having a cleaning inlet of the eleventh three-way valve. The seventh tube is provided with a twelfth three-way valve having a cleaning outlet of the twelfth three-way valve. The cleaning inlets of the seventh three-way valve, the ninth three-way valve, and the eleventh three-way valve are respectively connected to a liquid inlet main pipe via liquid inlet branch pipes. The cleaning outlets of the eighth three-way valve, the tenth three-way valve, and the twelfth three-way valve are respectively connected to a liquid outlet main pipe via liquid outlet branch pipes. The device according to claim 4, characterized in that an outlet of the cleaning pump is connected to the liquid inlet main pipe, and an inlet of the recovery pump is connected to the liquid outlet main pipe.

9. The cleaning module is connected to the cleaning liquid storage device and further includes a heating device for heating the liquid in the cleaning liquid storage device. The cooling system is a cooling tank having an elongated main body with an intermediate layer. The cooling tank is provided with a cooling coil tube inside, a relief port is provided at the upper part of the waist of the main body, a timed material outlet is provided below the waist, and the bottom is a reverse tapered material outlet. A back pressure valve is provided on the main body, and a safety valve, a pressure sensor, and a temperature sensor are further provided on the main body. The device according to any one of claims 6 - 8, characterized in that.

10. A step of uniformly mixing saccharide biomass, a solvent, an auxiliary agent, and an acid catalyst as raw materials to obtain an aqueous phase material. A step of preheating the aqueous phase material and then putting it into a multi-stage reaction equipment, reacting, cooling, and separating the obtained product to obtain 5-hydroxymethylfurfural. A manufacturing method for continuously manufacturing 5-hydroxymethylfurfural, characterized by including.

11. The raw materials include organic materials. The organic materials and the aqueous phase materials are respectively transported to a multi-stage reactor by different pumps. The temperature of the preheating is 60°C to 90°C, the operating temperature of the multi-stage reactor is 120°C to 160°C, the concentration of the saccharide biomass is 10 to 400 g / L, the saccharide biomass is at least one of glucose, fructose, sucrose, maltose, and fructose syrup, the auxiliary agent is at least one of polyethylene glycol, choline chloride, and ionic liquid, and the organic solvent in the organic phase is at least one of dimethyl carbonate, diethyl carbonate, 4-methyl-2-pentanone, tetrahydrofuran, and butanol. The manufacturing method according to claim 10, characterized in that.

Images