Method and apparatus for the continuous production of 5-hydroxymethylfurfural

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 novel furan derivatives with high added value, such as 2,5-furandicarboxylic acid and 2,5-tetrahydrofurandimethanol, can be synthesized, and it has extremely great application prospects and value.

[0003] Currently, there are three main methods for producing 5-hydroxymethylfurfural: (1) direct dehydration using fructose, (2) isomerization of glucose followed by dehydration, and (3) hydrolysis of cellulose followed by synthesis of 5-hydroxymethylfurfural. However, the synthesis process of 5-hydroxymethylfurfural generates a large amount of humins, and its polymerization form is complex, including etherification reactions between HMF molecules, acetalization reactions between HMF molecules, and esterification reactions between HMF and levulinic acid, formic acid, etc. Consequently, the corresponding black erosions exhibit various forms, such as fine, small, soft particles, hard particulate matter, soft clump-like blocks, and loose, cotton-like material. At the high-temperature reaction stage, the solubility of the black erosions is relatively high, but as the temperature is lowered by cooling, the solubility of the polymer decreases, and most of it precipitates, settles, or adheres as solid or semi-solid black erosions. In particular, in simple aqueous systems, increasing the water volume causes the humins structure to become very dense, resulting in the formation of hard, black lumps that easily clog tubes and make communication difficult. While the impact of black erosion on the production process is relatively small in batch-type kettle reactions, many challenges arise in the development of continuous flow reaction processes. For example, when producing HMF by reaction in a conventional continuous fixed bed, the generated black erosion adheres very easily to the catalyst surface, reducing catalyst activity and ultimately inactivating the catalyst. On the other hand, if this black erosion accumulates for a long time, it can completely clog tubes, elbows, valves, etc., potentially making production impossible. Therefore, preventing black erosion from clogging tubes is an urgent problem that must be solved in order to realize continuous production of HMF.

[0004] Therefore, in view of the shortcomings of the prior art described above, the present invention provides a manufacturing method and apparatus for the continuous production of 5-hydroxymethylfurfural. [Overview of the project]

[0005] (1) Problems that the invention aims to solve The present invention aims to provide a method and apparatus for the continuous production of 5-hydroxymethylfurfural, in order to solve the problem that tubes tend to clog during the production process of 5-hydroxymethylfurfural, making continuous production difficult.

[0006] (2) Means for solving the problem To solve the above problems, the present invention provides an apparatus for the continuous production of 5-hydroxymethylfurfural, A raw material transport system including an aqueous material transport unit for transporting aqueous material, A first cleaning system, which is connected to the outlet of the raw material transport system along with the aqueous phase material transport unit and used for cleaning when material is clogged or discharged, A heat source system used for heating raw materials is connected to the outlet of the raw material transport system via a first tube, A modular reaction equipment system is connected to the outlet of the heat source system via a second tube and incorporates a raw material reaction tube unit, a temperature-sensitive control unit, and a pressure-sensitive control unit. A cooling system is connected via a third tube to the outlet of the modularized reaction equipment system and used for cooling the products within the modularized reaction equipment system. The present invention provides an apparatus for the interconnected production of 5-hydroxymethylfurfural, comprising a control system connected to the aqueous phase material transport unit, a first cleaning system, a heat source system, a temperature-sensitive control unit, a pressure-sensitive control unit, and a cooling system, respectively, to intelligently control the supply and equipment, automatic cleaning, temperature, pressure, emergency start, and emergency stop.

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

[0008] Furthermore, the modularized reaction equipment system includes multiple modularized reaction equipment units. The temperature-sensitive control unit is a temperature sensor, and the pressure-sensitive control unit is a pressure sensor. The modularized reaction equipment includes a built-in raw material reaction tube unit, a temperature sensor, and a pressure sensor. The entire raw material reaction tube unit is lined with polytetrafluoroethylene inner tubes, and the temperature sensor and pressure sensor are built into the raw material reaction tube unit. The temperature sensor and pressure sensor are each connected to a control system, and a heating element is provided in the raw material reaction tube unit, which is connected to the control system.

[0009] Furthermore, a second cleaning system is further provided, and multiple modularized reaction units are installed in this order in series or in parallel. The modularized reaction unit further comprises 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 installed near the inlet and near the outlet of the raw material reaction tube unit, respectively, with the first cleaning three-way valve connected to the second cleaning system, and the first and second cleaning three-way valves connected to a control system, respectively.

[0010] Furthermore, the online monitoring system further comprises a connected UV online detector and a sampling probe, the sampling probe being installed in a tube at the outlet of the cooling system, and the UV online detector being used to detect the sample sent from the sampling probe and to feed the detection data back to the control system to adjust the initial material flow rate. The UV online detector is connected to the control system. The preheating system is connected to the cooling system to recover the residual heat exchanged by the cooling system. The preheating system is connected to the heat source system 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and 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 transport 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and recovery pump are connected in series via tubes in this order.

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

[0014] The outlet of the washing pump is connected to the first washing three-way valve of the raw material reaction tube unit, and the inlet of the recovery pump is connected to the second washing three-way valve of the raw material reaction tube unit. Alternatively, the outlet of the washing 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 washing 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 washing 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 washing 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 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and 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] The fourth tube is provided with a seventh three-way valve having a flush inlet for a seventh three-way valve. The fifth tube is provided with an eighth three-way valve having a flush outlet for an eighth three-way valve and a ninth three-way valve having a flush inlet for a ninth three-way valve. The sixth tube is provided with a tenth three-way valve having a flush outlet for a tenth three-way valve and an eleventh three-way valve having a flush inlet for an eleventh three-way valve. The seventh tube is provided with a twelfth three-way valve having a flush outlet for a twelfth three-way valve.

[0018] The flush inlets of the seventh, ninth, and eleventh three-way valves are each connected to the main liquid inlet via liquid inlet branch pipes, and the flush outlets of the eighth, tenth, and twelfth three-way valves are each connected to the main liquid outlet 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 fluid storage device and further includes a heating device for heating the liquid in the cleaning fluid storage device. The cooling system is a cooling tank having a body with an elongated intermediate layer. The cooling tank has a cooling coil tube inside, a relief port at the top of the waist of the body, a timed material outlet below the waist, and a reverse tapered material outlet at the bottom. The body is provided with a back pressure valve, and the body is further provided with a safety valve, a pressure sensor, and a temperature sensor.

[0021] On the other hand, the present invention is a method for producing 5-hydroxymethylfurfural in conjunction, A process of uniformly mixing sugar biomass, solvent, auxiliary agent, and acid catalyst as raw materials to obtain an aqueous phase material, The present invention provides a method for producing 5-hydroxymethylfurfural in a linear fashion, comprising the steps of: preheating the aqueous phase material, then placing it in a multi-stage reaction apparatus, and cooling and separating the product obtained by the reaction to obtain 5-hydroxymethylfurfural.

[0022] Furthermore, the raw materials include organic materials. The organic materials and the aqueous phase materials are transported to a multi-stage reactor using different pumps. The preheating temperature is 60°C to 90°C, and the operating temperature of the multi-stage reactor is 120°C to 160°C. The concentration of the sugar biomass is 10 to 400 g / L, and the sugar biomass is at least one of glucose, fructose, sucrose, maltose, and fructose-glucose 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, the above configuration of the present invention offers the following advantages.

[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, provide an online monitoring system to monitor the production status of HMF in real time, and when problems occur in the system temperature, pressure, and production yield, it can initiate corresponding solutions by itself, saving manpower.

[0025] In addition, the present invention effectively solves the problem that blackened and decayed substances generated by the large amount of humins generated 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 blackened and decayed substances is suppressed, preventing clogging caused by the aggregation of blackened and decayed 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 clogging due to the precipitation of blackened and decayed 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 stop 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] It is a drawing schematically showing the pressure of the nitrogen gas filling and maintaining system of the manufacturing apparatus according to Example 1 of the present invention. [Figure 2] It is a drawing schematically showing the pressure of the liquid backpressure valve maintaining system for the manufacturing apparatus according to Example 2 of the present invention. [Figure 3] It is a schematic configuration diagram of the cleaning of the modular reaction equipment and the entire cooling system according to the present invention. [Figure 4] It is a schematic diagram of the connection structure for individually cleaning the extraction device according to the present invention. [Figure 5] It is a schematic diagram of the connection structure for individually cleaning each equipment according to the present invention.

Modes for Carrying Out the Invention

[0027] Embodiments of the present invention will be described in further detail below with reference to the drawings and examples. The following detailed description of embodiments and drawings are for illustrative purposes only to illustrate the principles of the present invention, but do not limit the scope of the invention. That is, the present invention is not limited to the embodiments described.

[0028] To provide a clearer understanding of the above-mentioned objectives, features, and advantages of the present invention, embodiments of the present invention will be further described below. The embodiments and features of the present invention can be combined with each other, provided they do not conflict.

[0029] The following description provides many specific details to facilitate a thorough understanding of the present invention, but the invention may be implemented in embodiments other than those described herein. It goes without saying that the examples in the specification are only some, not all, embodiments of the present invention.

[0030] Preferred embodiments of the present invention will be described in detail below based on the examples. It should be understood that the following examples are presented for illustrative purposes only and are 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, as long as they do not depart from the spirit and essence of the invention.

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

[0032] Unless otherwise specified, the materials, reagents, etc., used in the following examples are commercially available.

[0033] As one aspect, the present invention includes a raw material transport system that includes an aqueous material transport unit for transporting aqueous material, as shown in Figures 1 and 2. A first cleaning system, which is connected to the outlet of the raw material transport system along with the aqueous phase material transport unit and used for cleaning when material is clogged or discharged, A heat source system used for heating raw materials is connected to the outlet of the raw material transport system via a first tube, A modular reaction equipment system is connected to the outlet of the heat source system via a second tube and incorporates a raw material reaction tube unit, a temperature-sensitive control unit, and a pressure-sensitive control unit. A cooling system is connected via a third tube to the outlet of the modularized reaction equipment system and is used to cool the products within the modularized reaction equipment system. The present invention provides an apparatus for the interconnected production of 5-hydroxymethylfurfural, comprising a control system connected to the aqueous phase material transport unit, a first cleaning system, a heat source system, a temperature-sensitive control unit, a pressure-sensitive control unit, and a cooling system, respectively, to intelligently control the supply and equipment, automatic cleaning, temperature, pressure, emergency start, and emergency stop.

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

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

[0036] If only aqueous phase material is being transported, the aqueous phase pump will operate and the organic pump will close. However, if both aqueous and organic material are being transported, both the aqueous and organic pumps will operate. If cleaning is required due to clogging in the system, the cleaning pump will be turned on, and if the system is operating normally, the cleaning pump will be turned off. If the system detects that the pressure has exceeded the upper limit of the reaction pressure, it will close the aqueous and organic phase pumps, turn on the cleaning pump, and enter tube cleaning mode to prevent further accumulation of black corrosion in the system.

[0037] Furthermore, the modularized reaction equipment system includes multiple modularized reaction equipment units. The temperature-sensitive control unit is a temperature sensor, and the pressure-sensitive control unit is a pressure sensor. The modularized reaction equipment includes 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 polytetrafluoroethylene inner tubes, and the temperature sensor and pressure sensor are built into the raw material reaction tube unit. The temperature sensor and pressure sensor are each connected to a control system, and a heating element is provided in the raw material reaction tube unit.

[0038] Furthermore, modular design of reaction equipment refers to modularizing the core areas of the dehydration reaction, such as the packing area for the fixed-bed catalyst or the reverse (forward) material flow reaction area.

[0039] Preferably, the plurality of modularized reaction equipment may be installed in series or in parallel in this order, depending on the actual production capacity requirements.

[0040] Preferably, the material reaction tube system includes a reaction coil tube, a three-way valve and valves inserted into the tube, a supply pump, and a three-way valve and valves for discharge from the tube.

[0041] To better prevent clogging in the system, it is preferable that the arrangement of tubes in the modular reaction equipment be in a coil tube configuration, with the liquid being transported from top to bottom.

[0042] To suppress wall and tube clogging caused by black corrosion and to enhance the acid corrosion resistance of the tubes, the entire inside of the reaction tube is lined with a polytetrafluoroethylene inner tube. In addition, multiple temperature and pressure sensors are built in to provide real-time feedback on the raw material conditions inside the tube, allowing for immediate adjustments if, for example, an abnormality occurs.

[0043] Furthermore, the cooling system is a cooling tank having a body with an elongated intermediate layer. The cooling tank has a cooling coil tube inside, a relief port at the top of the waist of the body, a time-regulating material outlet below the waist, and a reverse tapered material outlet at the bottom. The body is provided with a back pressure valve, and is further provided with a safety valve, a pressure sensor, and a temperature sensor.

[0044] Furthermore, the cooling tanks can be divided into two types based on their structure. One type employs nitrogen gas filling to ensure a constant pressure in the system and discharge the material at regular intervals, while the other type relieves the liquid after cooling and ensures a constant pressure in the system through a back pressure valve.

[0045] Furthermore, the modularized reaction apparatus further comprises a second cleaning system. The modularized reaction apparatus further comprises 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 installed near the inlet and near the outlet of the raw material reaction tube unit, respectively, with the first cleaning three-way valve connected to the second cleaning system, and the first cleaning three-way valve and the second cleaning three-way valve each connected to a 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 normal operation of the reaction equipment and to flush cleaning solution in the event of clogging in the equipment.

[0047] Furthermore, the first cleaning system is a cleaning pump or cleaning module. The cleaning module comprises 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and 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 transport 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, where initial filtration and debris removal are performed.

[0048] As shown in Figure 4, 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and recovery pump are connected in series via tubes in this order.

[0049] The outlet of the cooling system is connected to the extraction device, and the extraction device, separation device, and reaction product distillation device are connected in this order. Furthermore, multiple connection arrangements for the washing pump and recovery pump are provided as follows.

[0050] The outlet of the washing pump is connected to the first washing three-way valve of the raw material reaction tube unit, and the inlet of the recovery pump is connected to the second washing three-way valve of the raw material reaction tube unit. Alternatively, the outlet of the washing 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 washing 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 washing 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 washing 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 Figure 5, 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. In this module, the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and recovery pump are connected in series via tubes in this order.

[0052] 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.

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

[0054] The flush inlets of the seventh, ninth, and eleventh three-way valves are each connected to the main liquid inlet via liquid inlet branch pipes, and the flush outlets of the eighth, tenth, and twelfth three-way valves are each connected to the main liquid outlet via liquid outlet branch pipes.

[0055] 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.

[0056] With the above connection configuration, when a piece of equipment needs to be cleaned, the valves closest to both sides of that equipment are opened, and the valves on both sides of other equipment are closed. This transports the cleaning fluid from the cleaning pump to the main inlet pipe, which then enters the equipment via the corresponding branch inlet pipe. Subsequently, the recovery pump extracts the cleaning wastewater from the equipment into the branch outlet pipe, which then flows into the main outlet pipe. Finally, the wastewater is returned from the main outlet pipe to the recovery pump, and the next wastewater cleaning and recovery process is carried out.

[0057] Furthermore, the cleaning module is connected to the cleaning fluid storage device and further includes a heating device for heating the liquid in the cleaning fluid storage device. During the manufacturing process of 5-hydroxymethylfurfural, black corrosion often solidifies and adheres to the surface of the equipment, and is difficult to remove with cleaning fluid at normal temperatures. To enhance the cleaning effect, the black corrosion can be softened and dissolved by heating the cleaning fluid. Therefore, a heating device for heating the liquid in the cleaning fluid storage device has been introduced.

[0058] In the above embodiment, a cleaning solution solvent distillation apparatus and a cleaning solution recovery apparatus were introduced to perform secondary treatment of the cleaning solution in order to ensure the quality and service life of the cleaning solution and to enable the recycling of the cleaning solution. A heating module is installed in this cleaning solution solvent distillation apparatus, and impurities and residues in the cleaning solution can be removed by heating and distillation operations, thereby purifying the cleaning solution and extending its service life.

[0059] Furthermore, the rear end of the time-controlled 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, fifth, sixth, and seventh tubes, the extraction apparatus, separation apparatus, and reaction product distillation apparatus can be cleaned individually.

[0061] Furthermore, it includes an online monitoring system that 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, and the UV online detector detects the sample sent from the sampling probe and is used to feed the detection data back to the control system to adjust the initial material flow rate.

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

[0063] The heat source for the reaction equipment is derived from steam generated by the heat source system. Automatic temperature control is achieved by adjusting the valve opening using a built-in temperature control sensor, and the tubes connecting the reaction equipment are insulated with heat-insulating cotton.

[0064] According to the example disclosed herein, the cleaning solution in the cleaning solution storage device contains various cleaning agents that have a strong dissolving ability against black corrosion generated during the HMF manufacturing process. The composition of the cleaning solution includes various cleaning agents and oil fume removers that are commonly sold commercially and have high oil fume removal effects, as well as organic solvents. Therefore, when selecting a cleaning solution, one or more combinations of cleaning agents, oil fume removers, and organic solvents may be used.

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

[0066] The organic solvent is at least one of the following: 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, or acetone.

[0067] When the cleaning debris removal system is activated, the formulated cleaning solution is atomized and filled into the modular reaction equipment to be cleaned at a constant temperature and pressure. After circulating it back and forth for 5 to 120 minutes, the equipment is cleaned in the order of organic solvent and water, after which it can be used again.

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

[0069] On the other hand, the present invention provides a step of uniformly mixing sugar biomass, a solvent, an auxiliary agent, and an acid catalyst as raw materials to obtain an aqueous phase material, The present invention provides a method for producing 5-hydroxymethylfurfural in a linear fashion, comprising the steps of: preheating the aqueous phase material, then placing it in a multi-stage reaction apparatus, and cooling and separating the product obtained by the reaction to obtain 5-hydroxymethylfurfural.

[0070] Furthermore, the raw materials include organic materials. The organic materials and the aqueous phase materials are transported to a multi-stage reactor using different pumps. The preheating temperature 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 sugar biomass is 10 to 400 g / L, and the sugar biomass is at least one of glucose, fructose, sucrose, maltose, and fructose-glucose liquid sugar. 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.

[0072] Furthermore, the aforementioned auxiliary agent plays a role in improving the selectivity of 5-hydroxymethylfurfural and suppressing the formation of black corrosion blocks.

[0073] Preferably, the solvent is water.

[0074] Preferably, the acid catalyst is a homogeneous phase acid and includes an inorganic acid and an organic acid. 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 Figure 1, the method for producing a two-phase 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 are mixed and stirred to dissolve, and this mixture is used as the aqueous phase raw material, with dimethyl carbonate solvent as the organic phase.

[0077] The reaction took place in the apparatus shown in Figure 1. Under normal operation, nitrogen gas was filled to maintain the system pressure at 0.8 MPa or higher, and the system temperature was maintained between 140°C and 150°C using a 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, and both the organic and aqueous phases were mixed before being fed into the primary reaction facility 6 via the heat exchanger 4, which is the heat source system, and the first three-way valve 5. The material obtained in the primary reaction facility 6 was fed into the secondary reaction facility 9 via the second three-way valve 7 and the third three-way valve 8 in that order. The material obtained in the secondary reaction facility 9 was fed into the tertiary reaction facility 12 via the fourth three-way valve 10 and the fifth three-way valve 11 in that order. The material obtained in the tertiary reaction facility 12 was fed into the cooling tank 14 via the sixth three-way valve 13.

[0078] The material obtained from the reaction was placed in a cooling tank 14, where it was cooled to 60°C to 80°C. A nitrogen gas filling port 25 was provided at the top of the side of the cooling tank, and nitrogen gas was used to maintain the system at a constant system pressure. The system pressure was automatically controlled, and a gas back pressure valve 15 was provided at the outlet of the cooling tank. A coolant outlet 27 was provided at the bottom of the side of the cooling tank, which discharged the material at regular intervals. After the material was discharged, it was transported to an extraction device 29 for extracting the reaction products, a separation device 32 for further separating the target product from other impurities, and a reaction product distillation device 35 for purifying and refining the product. Each device played a different role throughout the manufacturing process, ultimately yielding high-purity 5-hydroxymethylfurfural. A waste material outlet 26 was also provided at the bottom of the cooling tank, primarily used for discharging accumulated black corrosion.

[0079] Under normal operation, the valves 16, 17, and 18 of the three-way valve cleaning inlets in front of the reactor are closed, and the valves 19, 20, and 21 of the three-way valve cleaning outlets (inlets and outlets) behind the reactor are closed. Reactors 6, 9, and 12 are equipped with steam heat source inlets 22, 23, and 24, respectively. If a slight blockage occurs in a reactor connected in series, it can be replaced with the same module. For example, if it is necessary to replace the Class II reactor 9, one corresponding tube of the three-way valve at the supply port of the backup reactor is connected to the cleaning inlet 19 of the second three-way valve, and one corresponding tube of the three-way valve at the outlet is connected to the fifth three-way valve 11. After completing the connections, the corresponding valves are simply switched, ensuring smooth operation of the reactor. Furthermore, it is also very convenient for cleaning the Class II reaction equipment 9. Simply connect the cleaning inlet 17 tube of the third three-way valve to the cleaning pump, close the inlet valve of the third three-way valve 8 and the outlet valve of the fourth three-way valve 10, and open the cleaning inlet tube 17 of the third three-way valve and the cleaning outlet 20 of the fourth three-way valve. It can then be used for preliminary cleaning after being cleaned independently.

[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 5-hydroxymethylfurfural in a simple aqueous phase according to the present invention is as follows.

[0082] The aqueous phase raw material is made by mixing 60 kg of fructose, 400 kg of water, 1.8 kg of phosphoric acid, and 20 kg of polyethylene glycol 4000, and dissolving them together.

[0083] The reaction was carried out using the equipment shown in Figure 2. Under normal operation, the back pressure valve 15 was adjusted to 0.8 MPa, the system was maintained between 140°C and 150°C with 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 washing pump 3 were closed. The aqueous phase material was fed into the Class 1 reaction facility 6 via the heat exchanger 4 and the first three-way valve 5 in that order. The material obtained in the Class 1 reaction facility 6 was fed into the Class 2 reaction facility 9 via the second three-way valve 7 and the third three-way valve 8 in that order. The material obtained in the Class 2 reaction facility 9 was fed into the Class 3 reaction facility 12 via the fourth three-way valve 10 and the fifth three-way valve 11 in that order. The material obtained in the Class 3 reaction facility 12 was fed into the cooling tank 14 via the sixth three-way valve 13.

[0084] After being placed in the cooling tank 14, the material was cooled to 60°C to 80°C in the cooling tank. A relief port is provided at the top of the side of the cooling tank, allowing the upper cooling liquid to be relieved and passed through the back pressure valve 15 to the storage tank. An emergency outlet 27 is located at the bottom of the side of the cooling tank and is closed during normal operation. A waste material outlet 26 is also provided at the bottom of the cooling tank, primarily used for discharging accumulated black corrosion.

[0085] Reactor units 6, 9, and 12 are equipped with steam heat source inlets 22, 23, and 24, respectively. If a slight blockage occurs in a series-connected reactor, it can be replaced with the same module. For example, if it is necessary to replace the Class II reactor unit 9, one tube corresponding to the three-way valve at the supply port of the backup reactor is connected to the cleaning inlet 19 of the second three-way valve, and one tube corresponding to the three-way valve at the outlet is connected to the fifth three-way valve 11. After completing the connections, it is simply a matter of switching the corresponding valves, ensuring smooth operation of the reactor. It is also very convenient for cleaning the Class II reactor unit 9. The tube at the cleaning inlet 17 of the third three-way valve is connected to the cleaning pump, the inlet valve of the third three-way valve 8 and the outlet valve of the fourth three-way valve 10 are closed, and the valves at the cleaning inlet tube 17 of the third three-way valve and the cleaning outlet 20 of the fourth three-way valve are opened. It can then be cleaned independently and used as a backup.

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

[0087] The cleaning of black corrosion includes cleaning the entire apparatus and cleaning specific components within the apparatus individually. The following describes the processes of cleaning the entire apparatus and cleaning specific components in detail.

[0088] Figure 3 shows the cleaning of the entire modularized reaction equipment 100 (i.e., primary reaction equipment 6, secondary reaction equipment 9, and tertiary reaction equipment 12). Specifically, first, water is atomized at a constant pressure by the cleaning pump 3 and sprayed into the heat exchanger 4, the first three-way valve 5, and the reaction equipment 6, 9, and 12 to clean and remove most of the reaction liquid and lumpy black corrosion. The waste liquid is then fed from the cleaning outlet (inlet) 21 of the sixth three-way valve by the recovery pump 42 into the buffer tank 41 and the cleaning liquid solvent distillation apparatus 40, where wastewater and debris are discharged. The filtered cleaning liquid is then fed into the cleaning liquid recovery apparatus 39, and from the cleaning liquid recovery apparatus 39 into the cleaning liquid storage apparatus 38. Subsequently, an organic solvent such as an amide, ketone, alcohol, or ester is used, or a small amount of detergent (0.1-5%) is added, or an additional 0.1-5% of an oil fumes remover is added, and after stirring to ensure uniform mixing, the mixture is heated in a heating device 43, followed by high-pressure washing, which is repeated for 5-120 minutes. Then, a single type of organic solvent is used, heated to approximately 100°C, and high-pressure washing is repeated for 5-120 minutes. Finally, high-pressure washing with tap water is repeated for 5-120 minutes to restore the system, after which it is used again. During this process, the organic solvents are collected by type and recovered in the cleaning solution recovery device 39, and then recombined for use.

[0089] Figures 4 and 5 show the individual cleaning of the extraction unit 29, the separation unit 32, and the reaction product distillation unit 35. When cleaning the extraction unit 29 individually, the cleaning inlet 28 of the 7th three-way valve and the cleaning outlet 30 of the 8th three-way valve are opened, the valves at the cleaning inlets 16, 17, and 18 of the three-way valves in front of the reaction equipment and the valves at the cleaning outlets 19, 20, and 21 of the three-way valves behind the reaction equipment are closed, and the cleaning inlet 31 of the 9th three-way valve, the cleaning outlet 33 of the 10th three-way valve, the cleaning inlet 34 of the 11th three-way valve, and the cleaning outlet 36 of the 12th three-way valve are closed. First, the cleaning pump 3 is operated to atomize water at a constant pressure and spray it into the extraction unit 29 to clean and remove the reaction liquid and lumpy black corrosion inside the extraction unit 29. The waste liquid is fed from the cleaning outlet 30 of the eighth three-way valve by the recovery pump 42 to the buffer tank 41 and the cleaning solution solvent distillation apparatus 40, where wastewater and debris are discharged. The filtered cleaning solution is then fed into the cleaning solution recovery apparatus 39, and from the cleaning solution recovery apparatus 39 to the cleaning solution storage apparatus 38. Subsequently, an organic solvent such as an amide, ketone, alcohol, or ester type is used, or a small amount of detergent (0.1-5%) or an oil fumes remover (0.1-5%) is added, and after stirring to ensure uniform mixing, the mixture is heated in the heating apparatus 43, followed by high-pressure washing, which is repeated for 5-120 minutes. After that, a single type of organic solvent is used, heated to approximately 100°C, and high-pressure washing is repeated for 5-120 minutes. Finally, high-pressure washing is performed with tap water, repeated for 5-120 minutes to restore the system, and then it is continued for use. During this process, the organic solvents are collected by type and recovered in the cleaning solution recovery apparatus 39, and then recombined for use.

[0090] The process of cleaning the separation device 32 and the reaction product distillation device 35 individually is the same as the cleaning process of the extraction device 29, so the explanation is omitted. In addition, the heat exchanger 4 may also be cleaned in this invention, as the heat exchanger 4 is connected to the liquid inlet main pipe and the liquid outlet main pipe via a tube.

[0091] Furthermore, the present invention is not limited to the specific processes and structures described above and shown in the figures. Also, for simplicity, a detailed description of known methods and techniques is omitted here.

[0092] The above description is merely an example of the present application and is not limited to the present application. Various modifications and changes can be made to those skilled in the art, as long as they do not depart from the scope of the present invention. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of the claims. [Explanation of Symbols]

[0093] 1. Water phase pump; 2. Organic pump; 3. Washing pump; 4. Heat exchanger; 5. First three-way valve; 6. Class 1 reactor; 7. Second three-way valve; 8. Third three-way valve; 9. Class 2 reactor; 10. Fourth three-way valve; 11. Fifth three-way valve; 12. Class 3 reactor; 13. Sixth three-way valve; 14. Cooling tank; 15. Back pressure valve; 16. Washing inlet for the first three-way valve; 17. Washing inlet for the third three-way valve; 18. Washing inlet for the fifth three-way valve; 19. Washing outlet (inlet / outlet) for the second three-way valve; 20. Washing outlet (inlet / outlet) for the fourth three-way valve; 21. Washing outlet (inlet / outlet) for the sixth three-way valve; 22. Inlet for the heat source of the Class 1 reactor; 23- Heat source inlet for Class II reactor; 24- Heat source inlet for Class III reactor; 25- Nitrogen gas filling port for cooling tank; 26- Waste material outlet for cooling tank; 27- Coolant outlet for cooling tank; 28- Cleaning inlet for 7th three-way valve; 29- Extraction device; 30- Cleaning outlet for 8th three-way valve; 31- Cleaning inlet for 9th three-way valve; 32- Separation device; 33- Cleaning outlet for 10th three-way valve; 34- Cleaning inlet for 11th three-way valve; 35- Reaction product distillation device; 36- Cleaning outlet for 12th three-way valve; 38- Cleaning liquid storage device; 39- Cleaning liquid recovery device; 40- Solvent distillation device for cleaning liquid; 41- Buffer tank; 42- Recovery pump; 100- Modular reactor.

Claims

1. A raw material transport system including an aqueous material transport unit for transporting aqueous material, A first cleaning system, which is connected to the outlet of the raw material transport system along with the aqueous phase material transport unit and used for cleaning when material is clogged or discharged, A heat source system used for heating raw materials is connected to the outlet of the raw material transport system via a first tube, A modular reaction equipment system is connected to the outlet of the heat source system via a second tube and incorporates a raw material reaction tube unit, a temperature-sensitive control unit, and a pressure-sensitive control unit. A cooling system is connected via a third tube to the outlet of the modularized reaction equipment system and is used to cool the products within the modularized reaction equipment system. The system includes a control system connected to the aqueous phase material transport unit, a first cleaning system, a heat source system, a temperature-sensitive control unit, a pressure-sensitive control unit, and a cooling system, respectively, for the purpose of introducing aqueous phase material into the raw material transport system, and for controlling the automatic cleaning, temperature, pressure, emergency start, and emergency stop of the equipment. The modularized reaction equipment system includes multiple modularized reaction equipment, the temperature-sensitive control unit is a temperature sensor, the pressure-sensitive control unit is a pressure sensor, and the modularized reaction equipment comprises a built-in raw material reaction tube unit, a temperature sensor, and a pressure sensor, the entire raw material reaction tube unit is lined with polytetrafluoroethylene inner tubes, the temperature sensor and pressure sensor are built into the raw material reaction tube unit, the temperature sensor and pressure sensor are connected to the control system, the raw material reaction tube unit is provided with a heating element, and the heating element is connected to the control system. The modular reaction equipment further comprises a second cleaning system, and multiple modular reaction equipment are installed in this order in series or in parallel, and the modular reaction equipment further comprises a first cleaning three-way valve and a second cleaning three-way valve, with the first cleaning three-way valve and the second cleaning three-way valve installed near the inlet and near 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, 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, wherein the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and recovery pump are connected in series via tubes in this order. 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. The fourth tube is provided with a seventh three-way valve having a flush inlet for the seventh three-way valve, the fifth tube is provided with an eighth three-way valve having a flush outlet for the eighth three-way valve and a ninth three-way valve having a flush inlet for the ninth three-way valve, the sixth tube is provided with a tenth three-way valve having a flush outlet for the tenth three-way valve and an eleventh three-way valve having a flush inlet for the eleventh three-way valve, and the seventh tube is provided with a twelfth three-way valve having a flush outlet for the twelfth three-way valve, The flush inlet of the seventh three-way valve, the flush inlet of the ninth three-way valve, and the flush inlet of the eleventh three-way valve are each connected to the main liquid inlet pipe via liquid inlet branch pipes, and the flush outlet of the eighth three-way valve, the flush outlet of the tenth three-way valve, and the flush outlet of the twelfth three-way valve are each connected to the main liquid outlet pipe via liquid outlet branch pipes. 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. An apparatus for continuously producing 5-hydroxymethylfurfural, characterized by individually cleaning the extraction apparatus, the separation apparatus, and the reaction product distillation apparatus.

2. The apparatus according to claim 1, wherein the raw material transport system further comprises an organic phase material transport unit connected to its outlet for transporting organic materials.

3. The apparatus according to claim 1, wherein 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, wherein the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and 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 transport 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.

4. 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, wherein the cleaning pump, cleaning liquid storage device, cleaning liquid recovery device, cleaning liquid solvent distillation device, buffer tank, and recovery pump are connected in series via tubes in this order. The outlet of the cooling system is connected to the extraction device, and the extraction device, separation device, and reaction product distillation device are connected in this order. The apparatus according to claim 1, characterized in that the outlet of the washing pump is connected to the first washing three-way valve of the raw material reaction tube unit and the inlet of the recovery pump is connected to the second washing three-way valve of the raw material reaction tube unit, or the outlet of the washing 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, or the outlet of the washing 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, or the outlet of the washing 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, or the outlet of the washing 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.

5. The cleaning module is connected to the cleaning liquid storage device and further comprises a heating device for heating the liquid in the cleaning liquid storage device, and the cooling system is a cooling tank having a body with an elongated intermediate layer, the cooling tank having a cooling coil tube inside, the body having a relief port, the body having a timed material outlet, the bottom having a reverse tapered material outlet, the body having a back pressure valve, the body having a safety valve, a pressure sensor and a temperature sensor, as described in any one of claims 1 to 4.

6. A step of obtaining an aqueous phase material by uniformly mixing sugar biomass, a solvent, an auxiliary agent and an acid catalyst as raw materials using the apparatus described in any one of Claims 1-4, A method for continuously producing 5-hydroxymethylfurfural, characterized by comprising the step of preheating the aqueous phase material, then placing it in a multi-stage reaction apparatus, and cooling and separating the product obtained by the reaction to obtain 5-hydroxymethylfurfural.

7. The manufacturing method according to claim 6, characterized in that the raw materials include an organic material, the organic material and the aqueous phase material are transported to a multi-stage reactor by different pumps, the preheating temperature is 60°C to 90°C, the operating temperature of the multi-stage reactor is 120°C to 160°C, the concentration of the sugar biomass is 10 to 400 g / L, the sugar biomass is at least one of glucose, fructose, sucrose, maltose, and fructose-glucose liquid sugar, the auxiliary agent is at least one of polyethylene glycol, choline chloride, and ionic liquid, and the organic solvent of the organic phase is at least one of dimethyl carbonate, diethyl carbonate, 4-methyl-2-pentanone, tetrahydrofuran, and butanol.

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