Industrial production device and method for carbonized polymer points
By heating the reaction in a tower reactor and using solvent for purification, the problem of low yield and high cost of carbonized polymer dots is solved, efficient industrial production of carbonized polymer dots is achieved, the process is simplified and the product quality is improved. quality.
Patent Information
- Application Number
- CN202411403625.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-09
- Publication Date
- 2025-01-21
AI Technical Summary
In the prior art, the yield of the carbonized polymer point is relatively low, the cost is high, and industrial production is difficult to achieve.
Using raw material A as the carbon source and raw material B as the nitrogen source, the reaction is heated at 140~220°C in a tower reactor. After obtaining the crude product, the solvent is dissolved and centrifuged, and the solvent is removed by standing and vacuum distillation to obtain Carbonized polymer dots.
It achieves high-yield and low-cost industrial production of carbonized polymer dots, simplifies the purification process, avoids complex steps such as dialysis and freeze-drying, and improves the quality and stability of the product.
Smart Images
Figure CN119330340A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of nano material production, and in particular to an industrial production device and method for carbonized polymer dots. Background Art
[0002] With the development of nanotechnology, the synthesis, performance and application of nanomaterials have become a research hotspot due to their small size and unique properties. In the field of oilfield development, nanomaterials, as a new type of economical and efficient high-temperature, high-mineralization, low-permeability reservoir material, have broad application prospects in improving oil recovery. Carbonized polymer dots are a new type of carbon nanomaterial with a size of 1~100nm and fluorescent emission ability. Due to their low toxicity, good biocompatibility and luminescence stability, carbonized polymer dots have shown great application potential in the fields of bioimaging, fluorescent sensing and optoelectronic energy.
[0003] However, currently, carbonized polymer dots are mainly produced by hydrothermal method in a high-temperature and high-pressure reactor, and the preparation process is relatively complicated. The product refining and purification process involves dialysis, freeze drying and other steps, resulting in low yield and high cost, and industrial production is still difficult to achieve. In view of these problems, it is necessary to provide a production device and method of carbonized polymer dots to overcome the shortcomings of the existing technology and promote its industrialization process. Summary of the invention
[0004] In view of the technical problems existing in the background technology, the present application provides an industrial production device and method for carbonized polymer dots, aiming to solve the technical problems of low yield, high cost and difficulty in industrial production.
[0005] In a first aspect, the present invention provides an industrial production method of carbonized polymer dots, comprising the following steps: S1. Mix raw material A and raw material B in a mass ratio of (0.5-2):(0.5-3), and then heat and react at 140-220° C. for 8-16 hours to obtain a crude product, wherein raw material A includes one or more of fructose, galactose, sucrose, salicylic acid, and benzoic acid, and raw material B includes one or more of n-decanol, dodecanol, tetradecanol, n-decylamine, dodecylamine, and tetradecylamine; S2. Dissolve the crude product in step S1 with a solvent, remove the residue by centrifugation to obtain a liquid phase, let the liquid phase stand to separate the solvent containing the product from the excess raw materials, separate the solvent containing the product, and then remove the solvent by reduced pressure distillation to obtain carbonized polymer dots.
[0006] In the technical solution of the embodiment of the present application, raw material A is used as a carbon source and raw material B is used as a nitrogen source to prepare carbonized polymer dots. Carbonized polymer dots are a type of spherical carbon nanoparticles with a size of 1 to 100 nm, which are mainly composed of a highly graphitized carbon core and surface functional groups.
[0007] The groups in raw materials A and B are dehydrated, condensed and carbonized at high temperature to form a highly cross-linked carbon core. Hydrophilic groups and hydrophobic polymer chains are distributed on the surface of the carbon core, which gives the carbonized polymer dots of the present application unique amphiphilic properties. They can be dissolved in both aqueous and organic phases and can be extracted and purified by using poor solvents for the raw materials. Therefore, refined carbide polymer dots can be obtained without the need for dialysis and freeze-drying steps.
[0008] Preferably, the solvent includes one or more of toluene, xylene, methanol, ethanol, cyclohexane, chloroform and acetone.
[0009] In the technical solution of the embodiment of the present application, raw materials A and raw materials B are insoluble in the solvent, and the carbonized polymer product is soluble in the solvent. Excess raw materials A and raw materials B can be removed by extraction, which is simple to operate and suitable for industrial production.
[0010] Preferably, the volume ratio of the crude product to the solvent is (0.5-2):(10-30).
[0011] In a second aspect, an embodiment of the present application provides an industrial production device for carbonized polymer dots, including a feed tank, a feed metering pump, a tower reactor, a discharge metering pump, a solvent stirring buffer tank, a centrifugal solid-liquid separator, a liquid phase separation buffer tank, a vacuum distillation tower and a product tank arranged in series, the solvent stirring buffer tank is connected to a solvent feed pipe, the centrifugal solid-liquid separator is provided with a first liquid phase discharge port and a first solid phase discharge port, the first liquid phase discharge port is connected to the liquid phase separation buffer tank, the first solid phase discharge port is connected to a residue tank, and the vacuum distillation tower is connected to a solvent recovery tank; The device is used to implement an industrial production method of carbonized polymer dots.
[0012] In the technical solution in the embodiment of the present application, raw material A and raw material B are placed in a feed tank and mixed to obtain a mixed liquid, and the mixed liquid is pumped into a tower reactor by a feed metering pump for reaction to obtain a crude product of carbonized polymer dots, and the discharge port of the tower reactor is connected to a solvent stirring buffer tank containing a solvent through a discharge metering pump, and the crude product is dissolved in the solvent stirring buffer tank, the carbonized polymer dots are dissolved in the solvent, and raw material A and raw material B are insoluble in the solvent; the crude product and the solvent mixed liquid enter a centrifugal solid-liquid separator, and the solid residue is centrifuged and separated, and the solid residue is removed from the first The solid phase discharge port is discharged into the residue tank, and the liquid phase is discharged from the first liquid phase discharge port into the liquid phase separation buffer tank, in which the carbonized polymer dots are extracted, and the raw materials A and B that are insoluble in the solvent are separated from the solvent containing the carbonized polymer dots to remove excess raw materials A and B; the solvent containing the carbonized polymer dots is discharged into the vacuum distillation tower, and the vacuum distillation is performed to remove the solvent to obtain a solid phase carbonized polymer dot product, and the solvent is cooled by a condenser and collected in a solvent recovery tank, and the solvent in the solvent recovery tank can be recycled as a reaction solvent.
[0013] Preferably, the tower reactor comprises a tank body and several layers of rectangular reactors, and the several rectangular reactors are evenly fixedly connected in the tank body in the vertical direction. The rectangular reactor is 100~150cm long, 70~120cm wide, and 10~15cm high. A feed pipe and a discharge pipe are respectively provided on both sides of each rectangular reactor. The feed pipe is connected to the feed tank through a feed metering pump. The feeding rate of the feed metering pump is 0.5~5L / min. The discharge pipe is connected to the solvent stirring buffer tank through a discharge metering pump.
[0014] In the technical solution in the embodiment of the present application, a multi-layer rectangular reactor is provided in the tower reactor, which has the advantage of forming a larger reaction interface, improving the uniformity of raw material distribution, ensuring that the carbonized polymer dots can be completely carbonized during the preparation process, and improving the yield of the carbonized polymer dots; and each rectangular reactor has a separate feed pipe and discharge pipe, which can be adjusted according to different product demand, which is convenient and efficient.
[0015] Preferably, the thickness of the raw material in the rectangular reactor is 0.3-1.2 cm.
[0016] In the technical solution in the embodiment of the present application, a raw material thickness of 0.3~1.2cm is beneficial to accelerate the reaction rate so that the carbonized polymer dots can be completely carbonized during the preparation process; too large a thickness is not conducive to heat transfer, resulting in a lower raw material conversion rate and a too low yield of carbonized polymer dots.
[0017] Preferably, 30 to 40 layers of rectangular reactors are arranged in the tank body.
[0018] Preferably, a heating device and an automatic temperature control system are provided outside the tank body of the tower reactor.
[0019] Preferably, a stirring mechanism is provided in the solvent stirring buffer tank, and the rotation speed of the stirring mechanism is 100-200 rpm.
[0020] Preferably, the operating temperature of the vacuum distillation tower is 25~200°C, the operating pressure is -0.1~1MPa, and the vacuum distillation tower is provided with a second solid phase discharge port and a second liquid phase discharge port, the second solid phase discharge port is connected to the product tank, and the second liquid phase discharge port is connected to the solvent recovery tank.
[0021] Different from the existing technical solutions, the beneficial effects of this application include: 1. The present application uses raw material A as a carbon source and raw material B as a nitrogen source to prepare carbonized polymer dots. The groups in raw materials A and B are dehydrated, condensed and carbonized at high temperature to form highly cross-linked carbon cores. Hydrophilic groups and hydrophobic polymer chains are distributed on the surface of the carbon core, thereby giving the carbonized polymer dots of the present application unique amphiphilic properties and being soluble in both aqueous and organic phases. Compared with traditional carbonized polymer dots that are only soluble in aqueous or organic phases, the carbonized polymer dots in the present application can be soluble in both aqueous and organic phases. The carbonized polymer dots can be extracted and purified by using poor solvents of the raw materials, without the need for purification steps such as dialysis and freeze-drying, which can greatly reduce the difficulty of industrialization and production costs.
[0022] 2. The reaction device in the present application is simple in design, easy to operate and maintain, and is conducive to promotion and application. The tower reactor contains multi-layer rectangular reactors. The thickness of the raw materials in the rectangular reactor is 0.3~1.2cm. The multi-layer rectangular reactor can form a larger reaction interface, improve the uniformity of the distribution of the raw materials in the tower reactor, ensure that the carbonized polymer dots can be completely carbonized during the preparation process, and improve the yield of the carbonized polymer dots; the smaller raw material thickness in the rectangular reactor is conducive to accelerating the reaction rate, and too large a thickness is not conducive to heat transfer, resulting in a decrease in the raw material conversion rate and a too low yield of the carbonized polymer dots; and each rectangular reactor has a separate feed port and a discharge port, which can be adjusted according to different product demand, which is convenient and efficient.
[0023] 3. The industrial production method of carbonized polymers of the present application not only includes the synthesis and purification of carbonized polymer dots, but also covers solvent recovery, solving the problems of low yield and high cost faced by industrial production. Compared with the synthesis method of the prior art, this production method can realize the industrial-scale production of carbonized polymer dots, and has a simple process flow, high reaction efficiency, low production cost, and uniform and stable product quality.
[0024] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings used in the present application. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.
[0026] Figure 1 This is a schematic diagram of the structure of an industrial production device for carbonized polymer dots in an embodiment of the present application; Figure 2 This is a transmission electron microscope characterization image of the carbide polymerization point in Example 1 of the present application; Figure 3 This is a transmission electron microscope characterization image of the carbide polymerization point in Example 2 of the present application; Figure 4 This is a transmission electron microscope characterization image of the carbide polymerization point in Example 3 of the present application.
[0027] Description of reference numerals: In the figure, 1. feed tank; 2. feed metering pump; 3. tower reactor; 31. tank body; 32. rectangular reactor; 33. feed pipe; 34. discharge pipe; 4. discharge metering pump; 5. solvent stirring buffer tank; 6. centrifugal solid-liquid separator; 61. first liquid phase discharge port; 62. first solid phase discharge port; 7. liquid phase separation buffer tank; 8. vacuum distillation tower; 81. second liquid phase discharge port; 82. second solid phase discharge port; 9. product tank; 10. residue tank; 11. solvent recovery tank. DETAILED DESCRIPTION
[0028] The following embodiments of the technical solution of the present application will be described in detail in conjunction with the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present application, and are therefore only used as examples, and cannot be used to limit the scope of protection of the present application.
[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by technicians in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" in the specification and claims of this application and the above-mentioned figure descriptions and any variations thereof are intended to cover non-exclusive inclusions.
[0030] In the description of the embodiments of the present application, the technical terms "first", "second", etc. are only used to distinguish different objects, and cannot be understood as indicating or implying relative importance or implicitly indicating the number, specific order or primary and secondary relationship of the indicated technical features. In the description of the embodiments of the present application, the meaning of "multiple" is more than two, unless otherwise clearly and specifically defined.
[0031] Reference to "embodiments" herein means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described herein may be combined with other embodiments.
[0032] In the description of the embodiments of the present application, the term "and / or" is only a description of the association relationship of the associated objects, indicating that there may be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.
[0033] In the description of the embodiments of the present application, the term "multiple" refers to more than two (including two). Similarly, "multiple groups" refers to more than two groups (including two groups), and "multiple pieces" refers to more than two pieces (including two pieces).
[0034] In the description of the embodiments of the present application, unless otherwise clearly specified and limited, technical terms such as "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, and it can be the internal connection of two elements or the interaction relationship between two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood according to the specific circumstances.
[0035] At present, carbonized polymer dots are mainly prepared by hydrothermal method in a high-temperature and high-pressure reactor, and the preparation process is relatively complicated. The product refining and purification process involves dialysis, freeze-drying and other steps, resulting in low yield and high cost, making industrial production difficult to achieve.
[0036] In a first aspect, the present invention provides an industrial production method of carbonized polymer dots, comprising the following steps: S1. Mix raw material A and raw material B in a mass ratio of (0.5-2):(0.5-3), and then heat and react at 140-220° C. for 8-16 hours to obtain a crude product, wherein raw material A includes one or more of fructose, galactose, sucrose, salicylic acid, and benzoic acid, and raw material B includes one or more of n-decanol, dodecanol, tetradecanol, n-decylamine, dodecylamine, and tetradecylamine; S2. Dissolve the crude product in step S1 with a solvent, remove the residue by centrifugation to obtain a liquid phase, let the liquid phase stand to separate the solvent containing the product from the excess raw materials, separate the solvent containing the product, and then remove the solvent by reduced pressure distillation to obtain carbonized polymer dots.
[0037] In the technical solution of the embodiment of the present application, raw material A is used as a carbon source and raw material B is used as a nitrogen source to prepare carbonized polymer dots. Carbonized polymer dots are a type of spherical carbon nanoparticles with a size of 1 to 100 nm, which are mainly composed of a highly graphitized carbon core and surface functional groups.
[0038] Carbonized polymer dots are prepared using raw material A as a carbon source and raw material B as a nitrogen source. The groups in raw materials A and raw material B are dehydrated, condensed and carbonized at high temperature to form a highly cross-linked carbon core. Hydrophilic groups and hydrophobic polymer chains are distributed on the surface of the carbon core, thereby giving the carbonized polymer dots of the present application unique amphiphilic properties and being soluble in both aqueous and organic phases.
[0039] Preferably, the solvent includes one or more of toluene, xylene, methanol, ethanol, cyclohexane, chloroform and acetone.
[0040] In the technical solution of the embodiment of the present application, raw materials A and raw materials B are insoluble in the solvent, and the carbonized polymer product is soluble in the solvent. Excess raw materials A and raw materials B can be removed by extraction, which is simple to operate and suitable for industrial production.
[0041] Preferably, the volume ratio of the crude product to the solvent is (0.5-2):(10-30).
[0042] In a second aspect, the present application provides an industrial production device for carbonized polymer dots, such as Figure 1 As shown, it includes a feed tank 1, a feed metering pump 2, a tower reactor 3, a discharge metering pump 4, a solvent stirring buffer tank 5, a centrifugal solid-liquid separator 6, a liquid phase separation buffer tank 7, a vacuum distillation tower 8 and a product tank 9 arranged in series, the solvent stirring buffer tank 5 is connected to a solvent feed pipe 33, the centrifugal solid-liquid separator 6 is provided with a first liquid phase discharge port 61 and a first solid phase discharge port 62, the first liquid phase discharge port 61 is connected to the liquid phase separation buffer tank 7, the first solid phase discharge port 62 is connected to a residue tank 10, and the vacuum distillation tower 8 is connected to a solvent recovery tank 11; The device is used to implement the industrial production method of carbonized polymer dots as claimed in any one of claims 1 to 3.
[0043] Preferably, the tower reactor 3 includes a tank body 31 and several layers of rectangular reactors 32, and the several rectangular reactors 32 are evenly fixedly connected in the tank body 31 along the vertical direction. The rectangular reactor 32 is 100~150cm long, 70~120cm wide, and 10~15cm high. A feed pipe 33 and a discharge pipe 34 are respectively provided on both sides of each rectangular reactor 32. The feed pipe 33 is connected to the supply tank 1 through a feed metering pump 2. The feeding rate of the feed metering pump 2 is 0.5~5L / min. The discharge pipe 34 is connected to the solvent stirring buffer tank 5 through a discharge metering pump 4.
[0044] In the technical solution of the embodiment of the present application, a feed metering pump 2 is used to pump the mixed liquid of raw material A and raw material B into the tower reactor 3, the feeding rate of the feed metering pump 2 is 0.5~5L / min, and the mixed liquid is evenly input into each rectangular reactor 32 through the feed pipe 33, and the liquid phase thickness in each rectangular reactor 32 is controlled to be 0.3~1.2cm; the heating device is turned on until it rises to 140~220℃, and the crude product is obtained after the reaction for 8~16h.
[0045] A discharge pipe 34 is provided on the rectangular reactor 32 of the tower reactor 3, and the discharge pipe 34 is connected to the feed port of the solvent stirring buffer tank 5 containing the solvent. The solvent stirring buffer tank 5 is provided with a solvent feed pipe 33 for adding solvent to the solvent stirring buffer tank 5. After the reaction liquid in the rectangular reactor 32 is input into the solvent stirring buffer tank 5, the stirring device is turned on. The volume ratio of the crude product of carbonized polymer dots to the solvent is (0.5~2):(10~30), and the stirring rate is controlled to be 500~1000rpm. The stirring is performed for 2~5h to fully mix the crude product with the solvent, and the generated carbonized polymer dots are dissolved in the solvent. The unreacted raw materials A and raw materials B are insoluble in the solvent.
[0046] The discharge port of the solvent stirring buffer tank 5 is connected to the feed port of the centrifugal solid-liquid separator 6. The mixed liquid in the solvent stirring buffer tank 5 is input into the centrifugal solid-liquid separator 6. The centrifugal solid-liquid separator 6 is turned on. The rotation speed of the centrifugal solid-liquid separator 6 is 5000~10000rpm, and the centrifugation time is 10~30min. After the centrifugation is completed, the solid phase enters the residue tank 10 from the first solid phase discharge port 62, and the liquid phase enters the liquid phase separation buffer tank 7 through the first liquid phase discharge port 61.
[0047] The liquid phase separated by centrifugation is allowed to stand in the liquid phase separation buffer tank 7 to separate the solvent from the unreacted raw material A and raw material B, to separate the solvent containing the product, and to remove the excess raw material A and raw material B.
[0048] A solvent outlet is provided on the liquid phase separation buffer tank 7, and the solvent outlet is connected to the vacuum distillation tower 8. The solvent containing the product is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 80-100°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the vacuum distillation tower 8; the solvent enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the solvent recovery tank 11 after liquefaction, and the solid phase is collected in the product tank 9. The solvent in the solvent recovery tank 11 can be recycled as a reaction solvent.
[0049] Preferably, the thickness of the raw material in the rectangular reactor 32 is 0.3-1.2 cm.
[0050] In the technical solution in the embodiment of the present application, a raw material thickness of 0.3~1.2cm is beneficial to accelerate the reaction rate so that the carbonized polymer dots can be completely carbonized during the preparation process; too large a thickness is not conducive to heat transfer, resulting in a lower raw material conversion rate and a too low yield of carbonized polymer dots.
[0051] Preferably, 30 to 40 layers of rectangular reactors 32 are arranged in the tank body 31 .
[0052] Preferably, a heating device and an automatic temperature control system are provided outside the tank body 31 of the tower reactor 3 .
[0053] In the technical solution of the embodiment of the present application, the heating device can be a heating plate or heating wire arranged on the tank body 31 of the tower reactor 3 and an automatic temperature control system of the electric heating device, which adopts a programmed temperature increase method to increase the temperature at a rate of 1~5℃ / min until it reaches 140~220℃.
[0054] Preferably, a stirring mechanism is provided in the solvent stirring buffer tank 5, and the rotation speed of the stirring mechanism is 100-200 rpm.
[0055] Preferably, the operating temperature of the vacuum distillation tower 8 is 25~200°C, and the operating pressure is -0.1~1MPa. The vacuum distillation tower 8 is provided with a second solid phase discharge port 82 and a second liquid phase discharge port 81. The second solid phase discharge port 82 is connected to the product tank 9, and the second liquid phase discharge port 81 is connected to the solvent recovery tank 11.
[0056] Some specific embodiments are listed below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. If specific techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be obtained commercially.
[0057] 1. Preparation method Example 1 In Example 1, raw material A is salicylic acid and raw material B is dodecylamine. Carbonized polymer dots are produced using an industrial device and method for carbonizing polymer dots of the present invention, including the following steps: 2.5 kg of salicylic acid and 3 L of dodecylamine were put into the feed tank 1, mixed and added through a metering pump at a feeding rate of 2 L / min, and the liquid phase thickness in each rectangular reactor 32 was controlled to be 0.5 cm; the temperature was raised at a rate of 1.5 ° C / min by programmed heating, and the temperature was raised to 190 ° C after 2 hours. After reacting for 8 hours, 3 L of crude product was obtained; the crude product was connected to the feed port of the solvent stirring tank, 60 L of toluene solvent was added, the stirring rate was controlled to 500 rpm, and stirred for 2 hours; after the dissolution was completed, the discharge port of the solvent stirring buffer tank 5 was connected to the feed port of the centrifugal solid-liquid separator 6, and the centrifugal solid-liquid separation device was turned on. The rotation speed of the centrifugal solid-liquid separator 6 was 5000 rpm, and the centrifugation time was 10 minutes. After the centrifugation was completed, The solid phase enters the residue tank 10 from the solid phase discharge port, and the yield of the residue is 2%. The liquid phase enters the liquid phase separation buffer tank 7 through the liquid phase discharge port, and is allowed to stand to allow the excess raw materials and the solvent containing the product to separate, and the solvent containing the product is separated; the solvent containing the product in the liquid phase separation buffer tank 7 is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 80°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the condenser of the vacuum distillation tower 8; the solvent in the solvent containing the product enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the toluene solvent recovery tank 11 after liquefaction, and the solvent recovery rate is 93.72%. The solid phase is collected in the product tank 9. The transmission electron microscope characterization image of the carbonized polymer dots prepared in this embodiment is as shown in FIG. Figure 2 As shown, the yield of carbonized Pdots was 90.43%.
[0058] Example 2 In Example 2, raw material A is galactose and raw material B is dodecanol. Carbonized polymer dots are produced using an industrial device and method for carbonizing polymer dots of the present invention, including the following steps: 20 kg of galactose and 30 L of dodecanol were put into the feed tank 1, mixed and added through a metering pump at a feeding rate of 1 L / min, and the liquid phase thickness in each rectangular reactor 32 was controlled to be 0.3 cm; the temperature was raised at a rate of 2 ° C / min by programmed heating, and the temperature was raised to 160 ° C after 1.5 hours, and 45 L of crude product was obtained after 12 hours of reaction; the crude product was connected to the feed port of the solvent stirring tank, 450 L of xylene solvent was added, the stirring rate was controlled to 800 rpm, and stirred for 5 hours; after dissolution, the solvent stirring buffer tank 5 was discharged The inlet is connected to the feed inlet of the centrifugal solid-liquid separator 6, and the centrifugal solid-liquid separator is turned on. The speed of the centrifugal solid-liquid separator 6 is 8000rpm, and the centrifugal time is 20min. After the centrifugation is completed, the solid phase enters the residue tank 10 from the solid phase discharge port, and the residue yield is 3.46%. The liquid phase enters the liquid phase separation buffer tank 7 through the liquid phase discharge port, and is allowed to stand to allow the excess raw materials and the solvent containing the product to be separated, and the solvent containing the product is separated; the liquid phase in the solvent separation buffer tank containing the product is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 85°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the condenser of the vacuum distillation tower 8; the solvent in the product solvent enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the toluene solvent recovery tank 11 after liquefaction, and the solvent recovery rate is 92.89%. The solid phase is collected in the product tank 9, and the transmission electron microscope characterization image of the carbonized polymer dots prepared in this embodiment is as shown in Figure 3 As shown, the yield of carbonized Pdots was 91.58%.
[0059] Example 3 In Example 3, the raw material A is benzoic acid and the raw material B is dodecylamine. The industrial device and method for carbonizing polymer dots of the present invention are used to produce carbonized polymer dots, including the following steps: 50L of benzoic acid and 50L of dodecylamine were put into the feed tank 1, mixed and added through a metering pump at a feeding rate of 5L / min, and the liquid phase thickness in each rectangular reactor 32 was controlled to be 0.8cm; the temperature was raised at a rate of 2°C / min by a programmed temperature rise method, and the temperature was raised to 200°C after 2h, and 92L of crude product was obtained after the reaction for 12h; the crude product was connected to the feed port of the solvent stirring tank, 920L of cyclohexane solvent was added, the stirring rate was controlled to be 1000rpm, and the stirring was completed for 5h; after the dissolution was completed, the discharge port of the solvent stirring buffer tank 5 was connected to the feed port of the centrifugal solid-liquid separator 6, the centrifugal solid-liquid separation device was turned on, the rotation speed of the centrifugal solid-liquid separator 6 was 9000rpm, the centrifugation time was 30min, and the centrifugation was completed. After that, the solid phase enters the residue tank 10 from the solid phase discharge port, and the yield of the residue is 4.95%. The liquid phase enters the liquid phase separation buffer tank 7 through the liquid phase discharge port, and is allowed to stand to allow the excess raw materials and the solvent containing the product to be separated, and the solvent containing the product is separated; the solvent containing the product in the liquid phase separation buffer tank 7 is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 75°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the condenser of the vacuum distillation tower 8; the solvent in the liquid phase enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the toluene solvent recovery tank 11 after liquefaction, and the solvent recovery rate is 93.25%. The solid phase is collected in the product tank 9. The transmission electron microscope characterization image of the carbonized polymer dots prepared in this embodiment is as shown in FIG. Figure 4 As shown, the yield of carbonized Pdots was 89.72%.
[0060] Example 4 In Example 4, the raw material A is benzoic acid and the raw material B is dodecylamine. The industrial device and method for carbonizing polymer dots of the present invention are used to produce carbonized polymer dots, including the following steps: 20L of benzoic acid and 20L of dodecylamine were put into the feed tank 1, mixed and added through a metering pump at a feeding rate of 5L / min, and the liquid phase thickness in each rectangular reactor 32 was controlled to be 1.2cm; the temperature was raised at a rate of 2°C / min by a programmed temperature rise method, and the temperature was raised to 200°C after 2h, and 36L of crude product was obtained after the reaction for 12h; the crude product was connected to the feed port of the solvent stirring tank, 360L of cyclohexane solvent was added, the stirring rate was controlled to be 1000rpm, and the stirring was carried out for 5h; after the dissolution was completed, the discharge port of the solvent stirring buffer tank 5 was connected to the feed port of the centrifugal solid-liquid separator 6, and the centrifugal solid-liquid separation device was turned on, the rotation speed of the centrifugal solid-liquid separator 6 was 9000rpm, and the centrifugal time was 30min After centrifugation, the solid phase enters the residue tank 10 from the solid phase discharge port, and the residue yield is 9.63%. The liquid phase enters the liquid phase separation buffer tank 7 through the liquid phase discharge port, and is allowed to stand to allow excess raw materials and the solvent containing the product to separate, and the solvent containing the product is separated; the solvent containing the product in the liquid phase separation buffer tank 7 is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 75°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the vacuum distillation tower 8; the solvent in the liquid phase enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the toluene solvent recovery tank 11 after liquefaction, and the solvent recovery rate is 92.79%. The solid phase is collected in the product tank 9, and the yield of carbonized polymer dots is 88.94%.
[0061] Comparative Example 1 In Comparative Example 1, raw material A is citric acid and raw material B is potassium dihydrogen phosphate, which are placed in 40 mL of deionized water, and then the solution is placed in a high-temperature and high-pressure reactor, placed in an oven at 200°C for hydrothermal reaction for 12 hours, and the product is centrifuged at 9000 rpm for 15 minutes to remove the black precipitate. The yellow supernatant is collected and freeze-dried, and the freeze-dried product is redispersed in water, dialyzed for 48 hours using a dialysis bag with a molecular weight cutoff of 1000Da, and freeze-dried after dialysis to obtain carbonized polymer dots.
[0062] Comparative Example 1 is a conventional method for preparing carbonized polymer dots. The raw materials A and B used and the obtained carbonized polymer dots are all soluble in polar solvents, but insoluble in non-polar solvents. The carbonized polymer dots cannot be refined by extraction, and the crude product needs to be refined and purified by freeze drying and dialysis, which cannot be applied to large-scale industrial production.
[0063] Comparative Example 2 In Comparative Example 2, raw material A is benzoic acid, and raw material B is dodecylamine. 50L of benzoic acid and 50L of dodecylamine are put into a feed tank 1, mixed and fed by a metering pump, the feeding rate is 5L / min, and the liquid phase thickness in each rectangular reactor 32 is controlled to be 3.0cm; the temperature is raised at a rate of 2°C / min by a programmed temperature rise method, and the temperature is raised to 200°C after 2h. After reacting for 12h, 52L of crude product is obtained; the crude product is connected to the feed port of the solvent stirring tank, 520L of cyclohexane solvent is added, the stirring rate is controlled to 1000rpm, and stirring is carried out for 5h; after dissolution is completed, the discharge port of the solvent stirring buffer tank 5 is connected to the feed port of the centrifugal solid-liquid separator 6, the centrifugal solid-liquid separator is turned on, and the centrifugal solid-liquid separator is centrifuged to separate the solid and liquid. The rotation speed of the separator 6 is 9000rpm, and the centrifugation time is 30min. After the centrifugation, the solid phase enters the residue tank 10 from the solid phase discharge port, and the residue yield is 20.34%. The liquid phase enters the liquid phase separation buffer tank 7 through the liquid phase discharge port; the liquid phase in the liquid phase separation buffer tank 7 is added to the vacuum distillation tower 8, the evaporator and the heating device are turned on, and the heating temperature is set to 75°C. At the same time, heat transfer oil is introduced into the vacuum distillation tower 8, and circulating water is introduced into the vacuum distillation tower 8; the solvent in the liquid phase enters the condenser in the vacuum distillation tower 8 after vaporization, and is collected in the toluene solvent recovery tank 11 after liquefaction, and the solvent recovery rate is 89.73%. The solid phase is collected in the product tank 9, and the yield of carbonized polymer dots is 49.69%.
[0064] The liquid phase thickness in the rectangular reactor 32 in Comparative Example 2 is 3.0 cm. The liquid phase thickness is too high, resulting in a reduced raw material conversion rate. The yield is only 49.69%, which is much lower than the yields in Examples 1 to 4.
[0065] It should be noted that the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same structure as the technical idea and exerting the same effect within the scope of the technical solution of the present application are all included in the technical scope of the present application. In addition, without departing from the scope of the main purpose of the present application, various modifications that can be thought of by those skilled in the art to the embodiments and other methods of combining some of the constituent elements in the embodiments are also included in the scope of the present application.
Claims
1. An industrial production method of carbonized polymer dots, characterized in that: The steps include: S1. Mix raw material A and raw material B in a mass ratio of (0.5-2): (0.5-3), and then heat and react at 140-220° C. for 8-16 hours to obtain a crude product, wherein the raw material A comprises one or more of fructose, galactose, sucrose, salicylic acid, and benzoic acid, and the raw material B comprises one or more of n-decanol, dodecanol, tetradecanol, n-decylamine, dodecylamine, and tetradecylamine; S2. Dissolving the crude product in step S1 with a solvent, removing the residue by centrifugation to obtain a liquid phase, allowing the liquid phase to stand to separate the solvent containing the product from the excess raw materials, separating the solvent containing the product and then removing the solvent by reduced pressure distillation to obtain carbonized polymer dots.
2. The industrial production method of carbonized polymer dots according to claim 1, characterized in that: The solvent includes one or more of toluene, xylene, methanol, ethanol, cyclohexane, chloroform and acetone.
3. The industrial production method of carbonized polymer dots according to claim 1, characterized in that: The volume ratio of the crude product to the solvent is (0.5~2):(10~30).
4. An industrial production device for carbonized polymer dots, characterized in that: The invention comprises a feed tank (1), a feed metering pump (2), a tower reactor (3), a discharge metering pump (4), a solvent stirring buffer tank (5), a centrifugal solid-liquid separator (6), a liquid phase separation buffer tank (7), a vacuum distillation tower (8) and a product tank (9) arranged in series, wherein the solvent stirring buffer tank (5) is connected to a solvent feed pipe (33), the centrifugal solid-liquid separator (6) is provided with a first liquid phase discharge port (61) and a first solid phase discharge port (62), the first liquid phase discharge port (61) is connected to the liquid phase separation buffer tank (7), the first solid phase discharge port (62) is connected to a residue tank (10), and the vacuum distillation tower (8) is connected to a solvent recovery tank (11); The device is used to perform the industrial production method of carbonized polymer dots as described in any one of claims 1 to 3.
5. The industrial production device of carbonized polymer dots according to claim 4, characterized in that: The tower reactor (3) comprises a tank body (31) and a plurality of layers of rectangular reactors (32). The plurality of rectangular reactors (32) are evenly and fixedly connected in the tank body (31) along the vertical direction. The rectangular reactors (32) are 100 to 150 cm long, 70 to 120 cm wide, and 10 to 15 cm high. A feed pipe (33) and a discharge pipe (34) are provided on both sides of each rectangular reactor (32). The feed pipe (33) is connected to the feed tank (1) via a feed metering pump (2). The feed rate of the feed metering pump (2) is 0.5 to 5 L / min. The discharge pipe (34) is connected to the solvent stirring buffer tank (5) via a discharge metering pump (4).
6. The industrial production device of carbonized polymer dots according to claim 5, characterized in that: The thickness of the raw material in the rectangular reactor (32) is 0.3-1.2 cm.
7. The industrial production device of carbonized polymer dots according to claim 5, characterized in that: The tank body (31) is provided with 30 to 40 layers of rectangular reactors (32).
8. The industrial production device of carbonized polymer dots according to claim 5, characterized in that: The tank body (31) of the tower reactor (3) is provided with a heating device and an automatic temperature control system on the outside.
9. The industrial production device of carbonized polymer dots according to claim 4, characterized in that: The solvent stirring buffer tank (5) is provided with a stirring mechanism, and the rotation speed of the stirring mechanism is 100-200 rpm.
10. The industrial production device of carbonized polymer dots according to claim 4, characterized in that: The vacuum distillation tower (8) has an operating temperature of 25-200° C. and an operating pressure of −0.1-1 MPa. The vacuum distillation tower (8) is provided with a second solid phase discharge port (82) and a second liquid phase discharge port (81). The second solid phase discharge port (82) is connected to a product tank (9), and the second liquid phase discharge port (81) is connected to a solvent recovery tank (11).