Glycosyl biomass energy conversion system and method

Abstract

The application provides a sugar-based biomass energy conversion system and method, and relates to the technical field of new energy and sugar-based biomass resource utilization.The application integrates a catalytic oxidation reactor, a formic acid decomposition reactor, a fuel cell and a heat energy management and circulation unit into a closely coupled sugar-based biomass energy conversion system, realizes efficient circulation and utilization of matter and energy in the sugar-based biomass energy conversion system, and improves the energy utilization efficiency and operation economy in the process of converting the sugar-based biomass into electric energy.

Description

Technical Field

[0001] This invention relates to the field of new energy and glycosylated biomass resource utilization technology, and in particular to a glycosylated biomass energy conversion system and method. Background Technology

[0002] Glyco-based biomass energy is an important renewable energy source, and how to efficiently and economically convert it into electricity is a current research hotspot. Existing technological pathways are mainly divided into direct utilization (such as microbial fuel cells) and indirect utilization (such as hydrogen production followed by power generation). Direct utilization pathways suffer from low efficiency, low power density, and poor stability. Indirect utilization pathways are typically complex and energy-intensive. For example, glyco-based biomass gasification for hydrogen production requires high temperature and pressure conditions, resulting in high costs; after glyco-based biomass is catalytically oxidized to formic acid, low-concentration formic acid solutions often need to be separated and purified through extraction or distillation to meet commercial requirements, but this process is very energy-intensive; catalytically converting biomass into liquid intermediates such as formic acid, and then decomposing formic acid to produce hydrogen under mild conditions, theoretically has advantages, but if the generated hydrogen-containing gas contains impurities (such as CO), it can deactivate the anode catalyst of conventional low-temperature fuel cells, and purifying the hydrogen further increases system complexity. Even with more robust fuel cells (such as high-temperature proton exchange membrane fuel cells, HT-PEMFC), the large amount of waste heat generated, if not effectively utilized, will reduce the overall energy efficiency of the system.

[0003] In summary, existing glyco-based biomass power generation technologies suffer from drawbacks such as demanding reaction conditions, low system integration, lack of internal energy and material circulation, reliance on external energy input, and high operating costs. Therefore, there is an urgent need for a glyco-based biomass energy conversion system that improves energy utilization efficiency and operational economics. Summary of the Invention

[0004] In view of this, the present invention provides a glycosyl biomass energy conversion system and method, the technical problem to be solved being: how to improve the energy utilization efficiency and operational economy in the process of converting glycosyl biomass into electrical energy.

[0005] On one hand, the present invention provides a glyco-based biomass energy conversion system, comprising: a pretreatment unit for pretreating glyco-based biomass raw materials to obtain intermediate raw materials; a catalytic oxidation reactor connected to the pretreatment unit, wherein the catalytic oxidation reactor contains an oxidation catalyst for catalytically oxidizing the glyco-based biomass in the intermediate raw materials under a first temperature condition to generate a liquid containing formic acid; a formic acid decomposition reactor connected to the catalytic oxidation reactor, wherein the formic acid decomposition reactor contains a decomposition catalyst for catalytically decomposing the liquid containing formic acid under a second temperature condition to generate a hydrogen-containing gas; a fuel cell, wherein its anode is connected to the formic acid decomposition reactor for generating electricity using the hydrogen-containing gas; a thermal energy management and circulation unit for recovering waste heat generated during the operation of the fuel cell and supplying the waste heat to the catalytic oxidation reactor and / or the formic acid decomposition reactor to provide or supplement heat for the reactions therein; and a water management unit for collecting water vapor generated by the catalytic oxidation reactor and water generated by the fuel cell, and recycling at least a portion of the collected water back to the pretreatment unit and / or the catalytic oxidation reactor.

[0006] Optionally, the oxidation catalyst is Keggin-type phosphomolybdic acid.

[0007] Optionally, the first temperature condition is 60℃~100℃.

[0008] Alternatively, the oxidant in the catalytic oxidation reactor may be air or oxygen.

[0009] Optionally, the decomposition catalyst is any one of palladium-based alloy, ruthenium-based alloy, iridium-based alloy, or bimetallic alloy catalyst.

[0010] Optionally, the second temperature condition is 20℃~100℃.

[0011] Optionally, the thermal management and circulation unit includes a heat transfer medium pipeline and a heat exchange element; the heat exchange element is disposed in the cooling circuit of the fuel cell and is used to heat the heat transfer medium flowing through it; the heat transfer medium pipeline delivers the heated heat transfer medium to the heating jacket or coil of the catalytic oxidation reactor and / or the formic acid decomposition reactor.

[0012] Optionally, the water management unit includes a water storage tank, a condenser, and a water pump connected in sequence; the condenser is used to condense water vapor in the exhaust gas from the catalytic oxidation reactor; the water storage tank is used to collect the water condensed by the condenser and the water generated by the fuel cell power generation; and the water pump is used to transport the water formed after the water vapor is condensed.

[0013] Optionally, the operating temperature of the fuel cell is 160℃~250℃, and the fuel cell is a high-temperature proton exchange membrane fuel cell.

[0014] Optionally, a material circulation pump is also provided between the formic acid decomposition reactor and the catalytic oxidation reactor. The material circulation pump is used to output the oxidation catalyst input into the formic acid decomposition reactor to the catalytic oxidation reactor.

[0015] On the other hand, the present invention provides a method for converting glyco-based biomass energy, comprising the following steps: S100, preparing glyco-based biomass raw materials into intermediate materials; S200, catalytically oxidizing the intermediate materials with an oxidant in the presence of an oxidation catalyst and at a reaction temperature of 60°C to 100°C to generate a liquid containing formic acid; S300, catalytically decomposing the liquid containing formic acid in the presence of a decomposition catalyst and at a reaction temperature of 20°C to 100°C to generate hydrogen-containing gas; S400, passing the hydrogen-containing gas into the anode of a fuel cell to generate electricity through an electrochemical reaction; S500, recovering the waste heat generated during the fuel cell power generation process, and using the recovered waste heat to provide or supplement heat for the catalytic oxidation reaction and / or catalytic decomposition reaction; S600, collecting the water vapor generated by the catalytic oxidation reaction and the water generated by the fuel cell power generation, and recycling at least a portion of the collected water for the preparation of intermediate materials and / or the catalytic oxidation reaction.

[0016] Optionally, in step S500, the recovered waste heat is preferentially used for catalytic oxidation reaction, and secondarily for catalytic decomposition reaction.

[0017] The implementation of this invention offers the following advantages: by integrating a catalytic oxidation reactor, a formic acid decomposition reactor, a fuel cell, and a thermal management and recycling unit into a tightly coupled glyco-based biomass energy conversion system, efficient recycling of matter and energy within the system is achieved. Specifically, firstly, by incorporating oxidation and decomposition catalysts into the glyco-based biomass energy conversion system, both the catalytic oxidation and decomposition steps can be carried out under milder conditions compared to traditional methods, avoiding the high-temperature and high-pressure requirements of traditional methods and significantly reducing energy consumption and equipment requirements for these two steps. Secondly, by integrating a high-temperature fuel cell into the glyco-based biomass energy conversion system, the waste heat generated by the fuel cell is higher than the temperature required for the catalytic oxidation and decomposition reactions of glyco-based biomass. The thermal management and recycling unit supplies the waste heat from the fuel cell to the catalytic oxidation and decomposition of glyco-based biomass, greatly reducing dependence on external heat sources. Simultaneously, the water management unit recovers and reuses the water generated within the glyco-based biomass energy conversion system for the process of preparing intermediate materials from glyco-based biomass raw materials, reducing the consumption of external water resources and maintaining the water balance of the glyco-based biomass energy conversion system. Ultimately, through the combination and synergy of the aforementioned technical features, the beneficial effects of improving energy utilization efficiency and operational economy in the process of converting glycosyl biomass into electricity were achieved. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the connection of a glycosyl biomass energy conversion system in one embodiment;

[0019] Figure 2 In one embodiment, Keggin-type phosphomolybdicavanadate after 1-6 cycles 31 P-spectrum nuclear magnetic resonance spectrum;

[0020] Figure 3 In one embodiment, Keggin-type phosphomolybdicavanadate after 1-6 cycles 51 The nuclear magnetic resonance spectrum of the V spectrum;

[0021] Figure 4 In one embodiment, the infrared spectrum of Keggin-type phosphomolybdic vanadate after 1 to 6 cycles;

[0022] Figure 5 In one embodiment, the Raman spectra of Keggin-type phosphomolybdic vanadate after 1 to 6 cycles;

[0023] Figure 6 This is a schematic diagram illustrating the effect of phosphomolybdic acid concentration on the relative yield of each component during the catalytic oxidation reaction in one embodiment.

[0024] Figure 7 This is a schematic diagram illustrating the effect of temperature on the relative yields of various components during a catalytic oxidation reaction in one embodiment.

[0025] Figure 8 This is a schematic diagram illustrating the effect of reaction time on the relative yield of each component during the catalytic oxidation reaction in one embodiment.

[0026] In the picture:

[0027] 1. Pretreatment unit; 2. Catalytic oxidation reactor; 3. Formic acid decomposition reactor; 4. Fuel cell; 5. Energy storage battery; 6. Oxidation chamber; 7. First heat exchanger; 8. Heater; 9. Material circulation pump; 10. Condenser; 11. Water storage tank; 12. Second heat exchanger. Detailed Implementation

[0028] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments. The step numbers in the following embodiments are only for ease of explanation and do not limit the order of the steps. The execution order of each step in the embodiments can be adapted according to the understanding of those skilled in the art.

[0029] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the embodiments of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any or all possible combinations of one or more of the associated listed items.

[0030] In the following description, when referring to the accompanying drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with this application. Rather, they are merely examples of apparatuses and methods consistent with some aspects of this application as detailed in the appended claims. In the description of this application, it should be understood that the terms "first," "second," "third," etc., are used only to distinguish similar objects and are not necessarily used to describe a specific order or sequence, nor should they be construed as indicating or implying relative importance. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0031] Furthermore, in the description of this application, unless otherwise stated, "multiple" means two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0032] Example 1

[0033] In this embodiment, as Figure 1 The illustrated glycosyl biomass energy conversion system includes:

[0034] Pretreatment unit 1 is used to prepare intermediate materials from glyco-based biomass raw materials;

[0035] The catalytic oxidation reactor 2 is connected to the pretreatment unit 1. The catalytic oxidation reactor 2 contains an oxidation catalyst, which is used to catalytically oxidize the glycosyl biomass in the intermediate material under a first temperature condition to generate a liquid containing formic acid (HCOOH).

[0036] Formic acid decomposition reactor 3 is connected to catalytic oxidation reactor 2. Formic acid decomposition reactor 3 contains a decomposition catalyst, which is used to catalytically decompose liquid containing formic acid under a second temperature condition to generate hydrogen-containing gas.

[0037] Fuel cell 4, whose anode is connected to formic acid decomposition reactor 3, is used to generate electricity using hydrogen-containing gas;

[0038] The thermal energy management and circulation unit is used to recover the waste heat generated during the operation of the fuel cell 4 and supply the waste heat to the catalytic oxidation reactor 2 and / or the formic acid decomposition reactor 3 to provide or supplement heat for the reactions therein.

[0039] A water management unit is used to collect water vapor generated by the catalytic oxidation reactor 2 and water generated by the fuel cell 4, and to reuse at least a portion of the collected water for the pretreatment unit 1 and / or the catalytic oxidation reactor 2.

[0040] In this embodiment, the pretreatment unit 1 is specifically used to crush and homogenize the glycosyl biomass, remove impurities and form powder, and mix the powder with water to prepare a uniform intermediate material.

[0041] In this embodiment, the catalytic oxidation reactor 2 is a reaction vessel / tank, and its outer shell is equipped with a heating jacket, while the interior is loaded with an oxidation catalyst. Air or oxygen is introduced into the catalytic oxidizer to oxidize the glycosyl biomass component in the intermediate material into a formic acid-rich liquid under mild conditions at a first temperature.

[0042] In this embodiment, the outer shell of the formic acid decomposition reactor 3 is also provided with a heating jacket, and the interior is loaded with a decomposition catalyst for decomposing formic acid, which is used to catalytically decompose the above-mentioned liquid containing formic acid into a mixture of hydrogen (H2) and carbon dioxide (CO2).

[0043] In this embodiment, fuel cell 4 utilizes the aforementioned H2 and CO2 mixture to undergo an electrochemical reaction with air to generate electrical energy. Fuel cell 4 can operate stably under a wide temperature range of 60°C to 250°C.

[0044] In this embodiment, the thermal energy management and circulation unit is used to recover the waste heat generated during the power generation process of the fuel cell 4 and conduct it to the heating jacket of the catalytic oxidation reactor 2 and / or the formic acid decomposition reactor 3 to provide or supplement the required heat for the oxidation reaction and / or decomposition reaction.

[0045] In this embodiment, the thermal energy management and circulation unit includes a heat medium pipeline and a heat exchange element; the heat exchange element is disposed in the cooling circuit of the fuel cell 4 and is used to heat the heat medium flowing through it; the heat medium pipeline is used to connect the heat exchange element, the cooling circuit of the fuel cell 4, and the jackets of the formic acid decomposition reactor 3 and the catalytic oxidation reactor 2, thereby realizing the circulation of the heat medium.

[0046] In this embodiment, as Figure 1 As shown, the heat transfer medium (such as heat transfer oil, steam or water) of the thermal energy management and circulation unit flows through the cooling circuit of fuel cell 4 to absorb waste heat, and is then pumped by the heat transfer medium to the heating jackets of each catalytic oxidation reactor 2 and formic acid decomposition reactor 3 to release heat, so as to realize the on-demand and cascaded utilization of thermal energy.

[0047] In this embodiment, fuel cell 4 is a high-temperature proton exchange membrane fuel cell. Each bipolar plate in its stack is provided with a cooling channel independent of the H2, O2 (or air) flow channels. The cooling channels of several bipolar plates are connected in sequence to form the cooling channel of the fuel cell stack.

[0048] In this embodiment, the cooling circuit of the high-temperature proton exchange membrane fuel cell includes a cathode exhaust gas cooling channel and a built-in cooling channel in the fuel cell stack.

[0049] In this embodiment, the heat exchange elements include a first heat exchanger 7, a second heat exchanger 12, and cooling channels for the fuel cell stack 4. The second heat exchanger 12 is used to recover waste heat carried by the exhaust gas generated at the cathode of the fuel cell 4; the first heat exchanger 7 is used to recover waste heat carried by the exhaust gas emitted from the oxidation chamber 6; and the cooling channels within the bipolar plates are used to recover waste heat generated by the reaction of hydrogen with the high-temperature proton exchange membrane within the stack.

[0050] Specifically, the second heat exchanger 12 is connected to the exhaust gas cooling channel. The heat medium undergoes its first heat exchange with the high-temperature exhaust gas generated at the cathode within the second heat exchanger 12, thereby condensing the exhaust gas at the cathode and recovering waste heat from the exhaust gas. The heat medium then passes through the stack cooling channel, where the stack temperature is higher than the heat medium temperature, thus reheating the heat medium. The heat medium then flows through the first heat exchanger 7, which is connected to the outlet of the oxidation chamber 6. The residual H2 discharged from the anode of the fuel cell 4 enters the oxidation chamber 6 and is completely oxidized to H2O, releasing heat. This heat is used to reheat the heat medium a third time in the first heat exchanger 7, ensuring that the temperature of the heat medium meets the temperature requirements of the catalytic oxidation reactor 2 and the formic acid decomposition reactor 3.

[0051] In this embodiment, the water management unit includes a water storage tank 11, a condenser 10, and a water pump connected in sequence; the condenser 10 is used to condense water vapor in the gas discharged from the catalytic oxidation reactor 2; the water storage tank 11 is used to collect the water condensed by the condenser 10 and the water generated by the fuel cell 4; the water pump is used to transport the water formed after the water vapor is condensed or the water generated by the fuel cell 4.

[0052] In this embodiment, the water management unit is used to manage the water generated during the catalytic oxidation process, the water lost during the aeration process, and the water generated during the reaction of the fuel cell 4 through the condenser 10, the water storage tank 11, and the water pump, so as to maintain the water balance of each part of the system.

[0053] In this embodiment, as Figure 1As shown in the figure, the black arrows indicate the flow direction of materials, the orange arrows indicate the flow direction of heat medium, the red arrows indicate the flow direction of water (water vapor, liquid water), the green arrows indicate the reflux direction of phosphomolybdic acid, and the blue arrows indicate the flow direction of electrical energy.

[0054] Specifically, the direction of material flow is as follows:

[0055] Glycosyl biomass is input from the input end of pretreatment unit 1, and the output end of pretreatment unit 1 is connected to catalytic oxidation reactor 2, thereby conveying the intermediate material formed after pretreatment to catalytic oxidation reactor 2. Catalytic oxidation reactor 2 is a jacketed reactor, and the inner cavity of the reactor includes three inlet ends and two outlet ends. The first inlet end of the inner cavity of the reactor is used to input the intermediate material, the second inlet end is used to input air or oxygen, and the third inlet end is connected to a material circulation pump 9, which is used to transport the phosphomolybdic vanadate solution in formic acid decomposition reactor 3 to catalytic oxidation reactor 2 for recycling. The intermediate material is catalytically oxidized by liquid phosphomolybdic vanadate to formic acid in catalytic oxidation reactor 2. One outlet end of the reactor cavity is connected to formic acid decomposition reactor 3 and inputs the mixture of formic acid and phosphomolybdic vanadate into formic acid decomposition reactor 3, and the other outlet end is connected to the inlet end of condenser 10, which is used to discharge N2 that does not participate in the reaction or CO2 generated by catalytic oxidation from the oxidant (air) and condense and recover the water vapor therein. The formic acid decomposition reactor 3 is also a jacketed reactor. The inner cavity of the formic acid decomposition reactor 3 includes one inlet end and two outlet ends. The inlet end of the inner cavity of the formic acid decomposition reactor 3 is connected to one outlet end of the inner cavity of the catalytic oxidation reactor 2. The CO2 and H2 produced by the decomposition in the formic acid decomposition reactor 3 are transported to the fuel inlet end of the fuel cell 4 through one outlet end. The other outlet end of the formic acid decomposition reactor 3 is connected to the inlet end of the material circulation pump 9, allowing the material circulation pump 9 to transport the unreacted phosphomolybdenum vanadium acid solution from the formic acid decomposition reactor 3 to the catalytic oxidation reactor 2 for recycling. CO2 and H2 are input to the anode of the fuel cell 4, constituting the feedstock for power generation. The fuel outlet end of the fuel cell 4 after the anode reaction is connected to the oxidation chamber 6. The oxidation chamber 6 is used to oxidize the unreacted H2 discharged from the fuel cell 4, thereby generating H2O and CO2 that are harmless to the atmosphere and can be directly emitted. The cathode of the fuel cell 4 is used to discharge the exhaust gas (high-temperature water vapor) produced by the internal reaction of the fuel cell 4.

[0056] In this embodiment, as Figure 1The high-temperature proton exchange membrane fuel cell shown delivers electrical energy to the energy storage battery 5 for storage, and then transmits it to the user end via the energy storage battery 5. The user end of the energy storage battery 5 can be powered by external electricity, or it can supply power to the heater 8 (if it is an electric heater 8), the material circulation pump 9, or the water pump, further improving the energy utilization efficiency and the economic efficiency of the glyco-based biomass energy conversion system.

[0057] Specifically, the flow direction of the hot coal (in this embodiment, steam) is as follows:

[0058] The water vapor in the heat transfer medium pipeline first exchanges heat with the exhaust gas generated during power generation at the cathode of fuel cell 4 in the second heat exchanger 12, thus initially heating the water vapor used as the heat transfer medium. The initially heated heat transfer medium is then input into the cooling channel of the bipolar plates in fuel cell 4, where the heat generated during power generation is transferred to the heat transfer medium, causing secondary heating of the fuel. The secondary-heated heat transfer medium is then transported to the first heat exchanger 7, where the residual H2 discharged from the anode of fuel cell 4 reacts exothermically in the oxidation chamber 6, further heating the heat transfer medium in the first heat exchanger 7. The tertiary-heated heat transfer medium is then transported to the jacket inlet of catalytic oxidation reactor 2 and formic acid decomposition reactor 3, thereby raising the temperature of the inner cavity of catalytic oxidation reactor 2 to meet the temperature requirements of the catalytic oxidation reaction process. The exhaust gas from the cathode of fuel cell 4 is cooled into liquid water after absorbing heat from the heat transfer medium in the second heat exchanger 12, and then pumped to the water storage tank 11 by a water pump (not shown in the figure). The water stored in the water storage tank 11 can be discharged directly or used to replenish the heat transfer medium.

[0059] In this embodiment, a heater 8 is also provided between the heat medium pipeline of the catalytic oxidation reactor 2 and the first heat exchanger 7. The heater 8 is used to provide auxiliary heating to the heat medium when the temperature of the heat medium cannot meet the temperature of the catalytic oxidation reaction.

[0060] In this embodiment, the oxidation catalyst is Keggin-type phosphomolybdic vanadate (HPA). By using the phosphomolybdic vanadate catalyst, the direct oxidation of glycosyl biomass to formic acid is achieved at normal pressure and low temperature (i.e., the first temperature condition, 60℃~100℃), thereby avoiding the high temperature and high pressure conditions required by traditional thermochemical pathways (such as gasification and pyrolysis) and the resulting tar problem.

[0061] It should be noted that the process of oxidizing glycosyl biomass with phosphomolybdic vanadate is complex due to the homogeneity of phosphomolybdic vanadate as a catalyst, making its recovery and reuse relatively complicated. The traditional method involves pressure swing distillation of a mixture of phosphomolybdic vanadate and formic acid to separate the formic acid from the phosphomolybdic vanadate. However, pressure swing distillation requires high temperatures (higher than the decomposition temperature of formic acid in this application) and high pressures (higher than the atmospheric pressure in this application), resulting in high energy consumption during the separation of formic acid and phosphomolybdic vanadate.

[0062] Therefore, this application also proposes a method for separating a mixed solution of formic acid and phosphomolybdic vanadate, by decomposing formic acid, thereby separating formic acid as a gaseous product from phosphomolybdic vanadate.

[0063] Specifically, in this embodiment, glucose is used as an example of glycosyl biomass, and Keggin-type phosphomolybdic vanadate is used as HPA-2 (two vanadium atoms, with the vanadium in the +5 valence, and the molecular formula: H5PV2Mo). 10 O 40 For example, the reaction formula for the direct oxidation of glucose by HPA-2 is:

[0064] 6H5PV2Mo 10 O 40 + C6H 12 O6→6 HCOOH+ 6 H5PV2Mo 10 O 39 (Vanadium is oxidized to a tetravalent state)

[0065] Re-oxidation process:

[0066] 2H5PV2Mo 10 O 39 + O2→2H5PV2Mo 10 O 40 ;

[0067] However, in a one-pot reaction, the above two steps occur simultaneously. The reactive oxygen species (ROS) generated during the re-oxidation process can directly react with glucose and its degradation intermediates, triggering side reactions.

[0068] C6H 12 O6 + ROS → 6CO2 + 6H2O;

[0069] The CO2 yield is not constant; in a one-pot reaction, it is approximately 40%–60%, depending on factors such as the amount of glucose added and aeration conditions. Water is also generated. If a chemical chain oxidation method is used, the CO2 yield will drop below 5%.

[0070] In this embodiment, aeration refers to adding air or oxygen as an oxidant to the catalytic oxidation reactor 2.

[0071] In this embodiment, the operating conditions of the catalytic oxidation reactor 2 are: atmospheric pressure, reaction temperature of 60℃~100℃, and oxidant is air or oxygen.

[0072] In this embodiment, the operating temperature of fuel cell 4 is 160°C to 250°C, which is a high-temperature proton exchange membrane fuel cell.

[0073] In this embodiment, a material circulation pump 9 is also provided between the formic acid decomposition reactor 3 and the catalytic oxidation reactor 2. The material circulation pump 9 is used to output the oxidation catalyst input into the formic acid decomposition reactor 3 to the catalytic oxidation reactor 2.

[0074] Specifically, the catalytic reaction conditions of phosphomolybdic vanadate as a catalyst are atmospheric pressure and low temperature. Its reaction temperature is lower than the waste heat generated by the power generation process of fuel cell 4. By using the waste heat generated by the power generation of fuel cell 4 to heat the catalytic oxidation reactor 2, the heat supply for the catalytic oxidation process is realized, and the waste heat waste of the power generation of fuel cell 4 is reduced.

[0075] In this embodiment, the decomposition catalyst in the formic acid decomposition reactor 3 is a palladium-based alloy, ruthenium-based alloy, or iridium-based alloy catalyst, and the operating temperature of the formic acid decomposition reactor 3 is 20℃~100℃.

[0076] Specifically, addressing the high energy consumption issue in the separation and purification of low-concentration formic acid, this invention aims to enable the formic acid hydrogen production step to be carried out at low temperatures (20℃~100℃) by selecting palladium-based alloys, ruthenium-based alloys, iridium-based alloys, or bimetallic alloys as catalysts. This eliminates the energy-intensive formic acid separation and purification step, simplifies the process, and reduces costs. Furthermore, palladium-based alloys, ruthenium-based alloys, iridium-based alloys, or bimetallic alloys all possess excellent resistance to poisoning and corrosion as catalysts. They also do not react with the oxidation catalyst (phosphomolybdic acid), ensuring that phosphomolybdic acid does not affect the formic acid decomposition process after entering the formic acid decomposition reactor 3. This also ensures the stability of phosphomolybdic acid, allowing it to be recycled back to the catalytic oxidation reactor 2 and continue to serve as an oxidation catalyst.

[0077] Preferably, the decomposition catalyst is any one of palladium-rhodium, palladium-gold, palladium-iridium, or bimetallic alloy (e.g., Pd-Au / C) catalysts with a double core-shell structure.

[0078] This invention integrates the three processes of biomass oxidation to produce an intermediate (formic acid), hydrogen production from the intermediate, and power generation via fuel cell 4 into a single, coupled design, achieving highly efficient recycling of matter and energy within the glyco-based biomass energy conversion system. Specifically, waste heat generated during power generation via fuel cell 4 is recovered and used to heat the formic acid decomposition and the catalytic oxidation reaction of glyco-based biomass, achieving cascaded energy utilization. Simultaneously, water recycling through a water management unit reduces the glyco-based biomass energy conversion system's consumption of external water sources, significantly reducing dependence on external heat and water sources, making the glyco-based biomass energy conversion system more thermodynamically and materially self-consistent and efficient.

[0079] Example 2:

[0080] This embodiment provides a method for converting glycosyl biomass energy, based on Embodiment 1.

[0081] In this embodiment, the glycosyl biomass energy conversion method includes the following steps:

[0082] S100. Prepare intermediate materials from glyco-based biomass raw materials; specifically, the intermediate materials are materials from crushed glyco-based biomass.

[0083] S200. In the presence of an oxidation catalyst and at a reaction temperature of 60℃~100℃, the intermediate material is subjected to a catalytic oxidation reaction with an oxidant to generate a liquid containing formic acid.

[0084] S300. In the presence of a decomposition catalyst and at a reaction temperature of 20℃~100℃, a liquid containing formic acid is subjected to a catalytic decomposition reaction to generate hydrogen-containing gas.

[0085] S400, Hydrogen-containing gas is introduced into the anode of fuel cell 4 to generate electricity through an electrochemical reaction;

[0086] S500 recovers the waste heat generated during the power generation process of fuel cell 4 and uses the recovered waste heat to provide or supplement heat for catalytic oxidation and / or catalytic decomposition reactions;

[0087] S600 collects water vapor generated by the catalytic oxidation reaction and water generated by the fuel cell 4 for power generation, and reuses at least a portion of the collected water for the preparation of intermediate materials and / or the catalytic oxidation reaction.

[0088] In this embodiment, in step S500, the recovered waste heat is preferentially used for catalytic oxidation reaction, and secondarily for catalytic decomposition reaction.

[0089] Example 3

[0090] This embodiment provides a specific implementation scheme for a glycosyl biomass energy conversion system, based on any of the above embodiments.

[0091] In this embodiment, the glycosylated biomass in the glycosylated biomass energy conversion system is glucose.

[0092] In this embodiment, the pretreatment unit 1 is used to prepare the biomass raw materials into intermediate materials in slurry form.

[0093] In this embodiment, the reaction conditions were as follows: glucose, 0.5 mol / L; reaction temperature, 95℃; reaction time, 8h; aeration rate, 200 ml / min (O2); reaction liquid volume, 0.25 L.

[0094] In this embodiment, the oxidation catalyst is specifically Keggin-type phosphomolybdic acid, and the effect of catalyst concentration on glucose oxidation is as follows: Figure 6 As shown, when the HPA concentration is between 0.1 mol / L and 0.2 mol / L, the generation of byproducts (other liquid phases) can be significantly reduced, while the relative yield of formic acid increases. At an HPA concentration of 0.1 mol / L, the products in other liquid phases are minimal, while at an HPA concentration of 0.2 mol / L, the relative yield of formic acid is maximum. Therefore, in this embodiment, to balance the relative yield of formic acid and the relative yield of byproducts, an HPA concentration of 0.15 mol / L is selected.

[0095] In this embodiment, the catalyst in the formic acid decomposition reactor 3 is 5 wt% Pd-Au / C (meaning that the mass fraction of Pd-Au in Pd-Au / C is 5 wt%).

[0096] In this embodiment, as Figure 7 As shown, with increasing temperature, the relative yield of formic acid gradually increases, while the yields of other liquid phase products decrease. The relative yield of formic acid reaches its maximum at 95°C, while the relative yields of other liquid phases reach their minimum. Therefore, in this embodiment, the reaction temperature of the catalytic oxidation reactor 2 is set to 95°C.

[0097] In this embodiment, the effect of reaction time on the catalytic oxidation of glucose is as follows: Figure 8 As shown, the relative yield of formic acid gradually increases with increasing reaction time, while the relative yields of other liquid phases gradually decrease, reaching a maximum at 8 hours. With further increases in reaction time, although the products of other liquid phases decrease further, formic acid gradually decomposes into CO2 or other gases. Therefore, this embodiment selects an optimal reaction time of 8 hours.

[0098] In this embodiment, the nuclear magnetic resonance spectrum of biomass after catalytic oxidation by phosphomolybdic acid is as follows: Figure 2 and Figure 3 As shown in the figure, HPA-1 to HPA-5 represent Keggin-type phosphomolybdic vanadate containing 1 to 5 vanadium atoms, respectively, and ED-0 to 6 represent HPA being used as a catalyst 0 to 6 times. From... Figure 2 and Figure 3 As can be seen from this, during the catalytic oxidation reaction of Keggin-type phosphomolybdic vanadate, even with the increase of the number of cycles, the Keggin-type phosphomolybdic vanadate after 1 to 6 cycles... 31 P spectrum and 51 The peak intensities corresponding to HPA-1 to HPA-5 were detected in the NMR spectra of the V spectrum, and no chemical shift occurred.

[0099] In this embodiment, the infrared and Raman spectra of Keggin-type phosphomolybdic vanadate after 1-6 cycles are as follows: Figure 4 and Figure 5 As shown, with the increase of the number of cycles, the wavenumber and Raman shift of Keggin-type phosphomolybdic vanadate did not change significantly at different cycles.

[0100] comprehensive Figures 2-5 It can be seen that the Keggin-type phosphomolybdic vanadate maintains good stability during the catalytic oxidation of glycosyl biomass under the parameter conditions of this embodiment and is not affected by the reactants.

[0101] In this embodiment, formic acid is catalytically decomposed at 20°C to 100°C using a decomposition catalyst, thereby decomposing formic acid into gaseous CO2 and H2. This achieves the separation of formic acid as a gaseous product from phosphomolybdic vanadate with low energy consumption, enabling the recovery and reuse of phosphomolybdic vanadate in a more economical way. At the same time, the hydrogen produced by the decomposition of formic acid is also used as a reactant in a high-temperature proton exchange membrane fuel cell.

[0102] Specifically, the pretreatment unit 1 is a high-speed pulverizer and a mixing tank with a stirrer, used to pulverize the lumpy or granular glucose raw material and mix it with water to form a uniform intermediate material.

[0103] In this embodiment, the catalytic oxidation reactor 2 is connected to the mixing tank of the pretreatment unit 1 via pipelines and a water pump.

[0104] Specifically, the catalytic oxidation reactor 2 is a reaction vessel with a heating jacket. The interior of the catalytic oxidation reactor 2 contains an oxidation catalyst, which is used to catalytically oxidize the biomass in the intermediate material under a first temperature condition to produce a liquid containing formic acid.

[0105] In this embodiment, the formic acid decomposition reactor 3 and the catalytic oxidation reactor 2 are connected by pipelines.

[0106] The catalytic oxidation reactor and the formic acid decomposition reactor are equipped with jacketed reaction vessels heated by heat media such as steam, and are commercially available products. Meanwhile, the first heat exchanger and the second heat exchanger can be commercially available products such as tube sheet heat exchangers or shell and tube heat exchangers.

[0107] It should be noted that the pretreatment unit, catalytic oxidation reaction, formic acid reactor, fuel cell, heat exchange element and condenser and other components can be commercially available models or other models known to those skilled in the art. Their specific structure is not the technical solution claimed in this application or essential, and will not be described in detail here.

[0108] The above is a detailed description of the preferred embodiments of the present invention. However, the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention. All such equivalent modifications or substitutions are included within the scope defined by the claims of this application.

Claims

1. A method for converting glycosyl biomass energy, characterized in that, Includes the following steps: S100, Prepare intermediate materials from glycosyl biomass raw materials; S200. In the presence of an oxidation catalyst and at a reaction temperature of 60℃~100℃, the intermediate material is subjected to a catalytic oxidation reaction with an oxidant to generate a liquid containing formic acid. The oxidation catalyst is Keggin-type phosphomolybdic vanadate, and the concentration of the oxidation catalyst is 0.1mol / L~0.2mol / L. The catalytic oxidation reaction is carried out under normal pressure. S300. Under the conditions of the presence of a decomposition catalyst and a reaction temperature of 20℃~100℃, the liquid containing formic acid is subjected to a catalytic decomposition reaction to generate hydrogen-containing gas. The decomposition catalyst is any one of palladium-based alloy, ruthenium-based alloy, iridium-based alloy catalyst or bimetallic alloy catalyst. S400, The hydrogen-containing gas is introduced into the anode of the fuel cell (4) to generate electricity through an electrochemical reaction; S500, recover the waste heat generated during the power generation process of the fuel cell (4), and use the recovered waste heat to provide or supplement heat for the catalytic oxidation reaction and / or the catalytic decomposition reaction; S600, collect the water vapor generated by the catalytic oxidation reaction and the water generated by the fuel cell (4) for power generation, and reuse at least a portion of the collected water for the preparation of the intermediate material and / or the catalytic oxidation reaction.

2. The method for converting glycosyl biomass energy according to claim 1, characterized in that, In step S500, the recovered waste heat is preferentially used for the catalytic oxidation reaction, and secondarily for the catalytic decomposition reaction.

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