A continuous co-production system of furfural compounds and carbon-based electrode materials

Abstract

The application provides a continuous co-production system of furfural compounds and carbon-based electrode materials, and belongs to the field of biomass resource utilization, and comprises a hydrothermal module, a heating module, a pyrolysis module and a product processing unit connected in sequence, wherein: the hydrothermal module is used for hydrothermal treatment to obtain a hydrothermal product, the organic layer in the hydrothermal product is separated and recovered to prepare furfural compounds, and the remaining solid-liquid mixture is sent into the heating module to be heated to evaporate water, so that a hydrothermal solid residue is obtained and is sent into the pyrolysis module; the pyrolysis module is used for pyrolysis activation of the hydrothermal solid residue under an inert atmosphere with phosphoric acid as a pore-expanding agent, so that the carbon-based electrode materials are prepared and are discharged after being processed by the product processing unit. The application can realize full utilization of biomass, improve the comprehensive value of products, has high integration degree, can realize continuous production, and is favorable for development and application of the technology for preparing carbon-based electrode materials of alkali metal ion batteries from waste biomass.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of biomass resource utilization, more specifically, it relates to a continuous co-production system of furfural compounds and carbon-based electrode materials. BACKGROUND

[0002] Currently, portable electronic devices and electric vehicles have become an indispensable part of people's lives, and large-scale energy storage is necessary for the future development of renewable energy such as wind power and photovoltaic. Lithium-ion batteries (LIBs) have been widely used in energy storage in recent years due to their high energy density and power density, while sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have similar working principles as LIBs, and sodium and potassium resources are abundant and low-cost, making them ideal alternatives to LIBs. Among them, electrode materials are the core components of alkali metal ion batteries, and their performance plays a crucial role in the performance of the entire battery.

[0003] Carbon materials have been widely studied due to their high specific surface area, adjustable pore structure, and good chemical stability. Typically, carbon materials are prepared from fossil fuels, which have high energy consumption, are harmful to the environment, and are costly. In recent years, the world has increasingly emphasized energy conservation and emission reduction. Biomass, as a renewable and green raw material, has the advantages of abundant resources, environmental protection, and low cost, and its porous or hierarchical porous structure can provide a large amount of accessible surface area and unobstructed transfer path for electrolyte ions. Therefore, biomass-based carbon materials are the most promising electrode materials for alkali metal ion batteries.

[0004] Although there have been studies using rice husk, sugarcane residue, and other biomass to obtain carbon-based materials and use them as electrode materials for alkali metal ion batteries, good reversible capacity, rate performance, and cycle stability have been achieved (Huang et al., New Carbon Materials, 2023); a Chinese patent (CN115594165A) has also disclosed a biomass-based hard carbon material preparation system and method. However, the technology for preparing alkali metal ion battery electrode materials from biomass is currently mainly focused on biomass pyrolysis and carbonization and activation modification research, and there is no complete integrated system that can integrate biomass cleaning, drying, crushing, carbonization, modification, and other units. The existing "carbonization first, then activation" process route and device not only have a complicated carbon-based electrode material preparation process, but also have poor system integration, high energy consumption, and the need for external power and heat supply.

[0005] In addition, the current research on the technology of preparing alkali metal ion battery electrode materials from biomass does not fully consider the composition characteristics of biomass, and does not carry out graded conversion, so as to obtain high-performance carbon-based materials for alkali metal ion batteries while co-producing high-value chemicals or fuels. However, single carbon-based materials are not enough to stimulate capital investment enthusiasm, which seriously hinders the industrialization development of biomass-based alkali metal ion battery electrode materials. Furfural and 5-methylfurfural are important furfural compounds, which can be used to prepare liquid fuels, pharmaceutical intermediates, etc. It has commercial prospects to prepare furfural and 5-methylfurfural by hydrothermal conversion of biomass containing five-carbon sugars and six-carbon sugars. CN108250165A discloses a method for preparing N-(5-methylfurfuryl) aniline and derivatives from biomass carbohydrates. This method uses phosphorous acid to assist hydroiodic acid to mediate fructose and other biomasses to prepare 5-methylfurfural. However, the raw material of hydroiodic acid is not stable and is easy to oxidize, which is not convenient to control. Moreover, the remaining residue still needs to be high-valued.

[0006] In view of the above problems, the development and industrial application of the technology of preparing alkali metal ion battery carbon-based electrode materials from waste biomass are restricted. Therefore, an integrated new system for continuous co-production of furfural compounds and carbon-based electrode materials for alkali metal ion batteries with high integration, low energy consumption and self-supply of heat and electricity is urgently needed. SUMMARY

[0007] In view of the defects of the prior art, the purpose of the present application is to provide a continuous co-production system of furfural compounds and carbon-based electrode materials, which aims to solve the problems of low integration and single product of the existing carbon-based electrode material production system.

[0008] To achieve the above-mentioned purpose, the present application provides a continuous co-production system of furfural compounds and carbon-based electrode materials, which comprises a hydrothermal module, a heating module, a pyrolysis module and a product treatment unit connected in sequence, wherein: the hydrothermal module is used for inputting biomass, phosphorous acid, water, an organic solvent and an iodine-containing reagent and carrying out hydrothermal treatment to obtain a hydrothermal product, at the same time, the organic layer in the hydrothermal product is separated and recovered to prepare furfural compounds, and the remaining solid-liquid mixture is sent to the heating module; the heating module is used for heating the remaining solid-liquid mixture to complete the evaporation of water, so as to recover the iodine-containing reagent and water, thereby obtaining a hydrothermal solid residue containing phosphorous acid and phosphoric acid and sending it to the pyrolysis module; the pyrolysis module is used for pyrolysis activation of the hydrothermal solid residue under an inert atmosphere with phosphoric acid as a pore-expanding agent, thereby preparing carbon-based electrode materials and discharging them after treatment by the product treatment unit.

[0009] As a further preferred, the continuous co-production system further comprises a self-powered module, the self-powered module comprises a combustion power generation assembly and a heat recovery assembly, the combustion power generation assembly is used for combusting combustible gas and liquid oil generated by hydrothermal solid residue pyrolysis to provide power for the continuous co-production system; the heat recovery assembly uses molten salt as a heat storage medium to absorb waste heat of the combustion power generation assembly and provide heat for the continuous co-production system.

[0010] As a further preferred, the product processing unit comprises a cooling module, a cleaning module, a drying module and a discharging module connected in sequence, wherein the cooling module is connected with the pyrolysis module and used for cooling the solid carbon-based product discharged by the pyrolysis module and sending it into the cleaning module; the cleaning module is used for spraying washing liquid to the cooled solid carbon-based product to remove impurities on the surface of the solid carbon-based product and sending it into the drying module; the drying module is used for drying the cleaned solid carbon-based product to obtain carbon-based electrode material and sending it into the discharging module, and the discharging module is used for discharging the carbon-based electrode material.

[0011] As a further preferred, the cleaning module comprises a spraying assembly, a recovery assembly and a hot washing liquid assembly, wherein the spraying assembly comprises a plurality of spiral spraying mechanisms connected in sequence along the material transmission direction, each of the spiral spraying mechanisms comprises a negative pressure cavity, a first centrifugal pump, a spiral fin arranged inside the negative pressure cavity, a washing liquid inlet, a washing liquid spraying port and a filter screen, the outlet of the negative pressure cavity is connected with the first centrifugal pump, the first centrifugal pump is connected with the washing liquid inlet of the previous spiral spraying mechanism to take the cleaning waste liquid of the next spiral spraying mechanism as the washing liquid of the previous spiral spraying mechanism, and the first centrifugal pump of the first spiral spraying mechanism is connected with the recovery assembly; the spiral fin is used for conveying materials; the washing liquid inlet is used for providing washing liquid, which is sprayed through the washing liquid spraying port to remove impurities on the surface of the solid carbon-based product and generate cleaning waste liquid; the filter screen is arranged on the inner wall of the negative pressure cavity and used for sending the cleaning waste liquid into the negative pressure cavity; the inlet of the recovery assembly is connected with the spraying assembly, the outlet thereof is connected with the hot washing liquid assembly, and the recovery assembly is used for heating the sent cleaning waste liquid to recover the modifier and water vapor and sending the water vapor into the hot washing liquid assembly; the outlet of the hot washing liquid assembly is connected with the washing liquid inlet of the last spiral spraying mechanism, and the hot washing liquid assembly is used for mixing the sent water vapor with normal temperature water to obtain washing liquid and sending it into the last spiral spraying mechanism.

[0012] As a further preferred, the hydrothermal module comprises a raw material feeding assembly, a hydrothermal reactor and a furfural recovery assembly, the raw material feeding assembly is connected with the inlet of the hydrothermal reactor for feeding biomass, phosphorous acid and iodine-containing reagent into the hydrothermal reactor; the inlet of the hydrothermal reactor is also connected with the furfural recovery assembly and the heating module for feeding recovered organic solvent, water and iodine-containing reagent into the hydrothermal reactor, and the outlet of the hydrothermal reactor is connected with the furfural recovery assembly and the heating module respectively for feeding the organic solution in the hydrothermal product and the remaining solid-liquid mixture into the furfural recovery assembly and the heating module; the furfural recovery assembly is used for separating and concentrating the fed organic solution to produce furfural compounds, and the recovered organic solvent is fed back to the hydrothermal reactor.

[0013] As a further preferred, the continuous co-production system further comprises a modifier feeding module and a ball milling module arranged between the heating module and the pyrolysis module, one end of the modifier feeding module is connected with the outlet of the heating module, and the other end is connected with the ball milling module for mixing the modifier into the hydrothermal solid residue; the outlet of the ball milling module is connected with the pyrolysis module for mechanically blending the hydrothermal solid residue with the modifier by ball milling and feeding into the pyrolysis module.

[0014] As a further preferred, the raw material feeding assembly and the modifier feeding module have the same structure, and each comprises a material transition chamber, a material feeding chamber and a first screw conveying chamber connected in sequence from top to bottom, wherein the top of the material transition chamber is provided with a first outer door for controlling the feeding of the material, the bottom of the material transition chamber is connected with the material feeding chamber through a first inner door for controlling the feeding of the material into the material feeding chamber, and the material transition chamber is further provided with a first air supplement port and a first air extraction port for vacuumizing the material transition chamber and supplementing inert gas.

[0015] As a further preferred, the heating module and the drying module have the same structure, and each comprises a second screw conveying chamber, a second screw and a first molten salt jacket, the second screw conveying chamber is provided with a gas outlet for guiding out the mixture of water vapor and iodine-containing reagent or water vapor, wherein the gas outlet of the heating module is connected with the hydrothermal module to recover water vapor and iodine-containing reagent; the inside of the second screw conveying chamber is provided with a second screw, and the outside is provided with a first molten salt jacket, the second screw is used for conveying material, and the first molten salt jacket is used for feeding molten salt as a heat source for heating or drying.

[0016] As a further preferred, the pyrolysis module comprises a pyrolysis reaction assembly and a volatile separation assembly, an inlet of the pyrolysis reaction assembly is connected with the heating module for feeding in the hydrothermal solid residue, and an outlet thereof is connected with the volatile separation assembly and the product processing unit respectively for feeding in the volatile generated by the pyrolysis activation of the hydrothermal solid residue and the solid carbon-based product into the volatile separation assembly and the product processing unit respectively; the volatile separation assembly comprises a volatile pipeline, a second molten salt jacket, a condensing tank and a first cooling water jacket, the volatile pipeline is connected with the outlet of the pyrolysis module and extends into the inside of the condensing tank for conveying the volatile to the condensing tank, and the outside of the volatile pipeline is provided with the second jacket for condensing the volatile by using the molten salt; the inside of the condensing tank is provided with the first cooling water jacket for condensing the volatile by using the cooling water, and the condensing tank is provided with a combustible gas outlet and a liquid oil outlet on the upper portion for discharging the product of the volatile condensation.

[0017] As a further preferred, the cooling module comprises a third screw conveying cavity, a third screw, a second cooling water jacket and a third molten salt jacket, one end of the third screw conveying cavity is connected with the pyrolysis module, the other end thereof is connected with the cleaning module, the third screw is arranged in the third screw conveying cavity for pushing the solid carbon-based product; the second cooling water jacket and the third molten salt jacket are arranged outside the third screw conveying cavity for cooling the solid carbon-based product by using the cooling water and the molten salt respectively.

[0018] Overall, compared with the prior art, the above technical scheme conceived by the present application has the following beneficial effects:

[0019] 1. The present application can realize the combined production of biomass and furfural compounds and carbon-based electrode materials by combining hydrothermal treatment and pyrolysis through the sequentially connected hydrothermal module, heating module and pyrolysis module, so as to realize the full utilization of biomass and improve the comprehensive value of products, wherein the hydrothermal module can prepare furfural compounds by stripping five-carbon sugars and / or six-carbon sugars in biomass, and the stripping process has a hole expansion effect, which can make the pores of the hydrothermal residue of biomass more abundant, then the heating module can evaporate the iodine-containing reagent and water by heating to avoid affecting the subsequent pyrolysis process, and finally the pyrolysis module combines pyrolysis and modification to prepare carbon-based electrode materials by using phosphoric acid as a pore-expanding agent for pyrolysis activation of the hydrothermal solid residue, compared with the existing process of carbonization followed by activation, the process is simplified, the production time is reduced, the preparation cost of carbon-based electrode materials can be effectively reduced, the system has high integration, and continuous production can be realized, which is conducive to the development and application of the technology of preparing alkali metal ion battery carbon-based electrode materials from waste biomass;

[0020] 2. In particular, the present application can realize the recycling of energy in pyrolysis volatiles by setting a self-energy supply module, effectively reducing production investment, wherein the combustion power generation assembly can provide power for the continuous cogeneration system by burning the combustible gas and liquid oil generated by the pyrolysis of hydrothermal solid residues, and the heat recovery and utilization assembly can absorb the waste heat generated by the combustion power generation assembly and provide heat for the continuous cogeneration system, thereby reducing the power input in the production process, reducing production cost, and realizing self-supply of energy.

[0021] 3. At the same time, the structure of the cleaning module is optimized, the cleaning waste liquid of the latter spiral spraying mechanism is used as the washing liquid of the former spiral spraying mechanism, cross-flow cascade cleaning is realized, the water footprint of the product is effectively reduced, the energy consumption of distillation recovery of the cleaning waste liquid is saved, and the washing liquid recovery and hot washing liquid cleaning are realized in cooperation with the recovery assembly and the hot washing liquid assembly, which is beneficial to the dissolution and removal of soluble impurities and reduces the consumption of water. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 is the overall structure schematic diagram of the continuous cogeneration system of furfural compounds and carbon-based electrode materials provided by the embodiment of the present application;

[0023] Figure 2 is Figure 1 is the local structure schematic diagram of the raw material feeding assembly or the modifier feeding module in the continuous cogeneration system in the present application;

[0024] Figure 3 is Figure 1 is the local structure schematic diagram of the heating module in the continuous cogeneration system in the present application;

[0025] Figure 4 is Figure 1 is the local structure schematic diagram of the ball milling module in the continuous cogeneration system in the present application;

[0026] Figure 5 is Figure 1 is the local structure schematic diagram of the volatile separation assembly in the continuous cogeneration system in the present application;

[0027] Figure 6 is Figure 1 is the local structure schematic diagram of the cooling module in the continuous cogeneration system in the present application;

[0028] Figure 7 is Figure 1 is the local structure schematic diagram of the spiral spraying mechanism in the continuous cogeneration system in the present application;

[0029] Figure 8 is Figure 1 is the local structure schematic diagram of the recovery assembly in the continuous cogeneration system in the present application;

[0030] Figure 9 is Figure 1 Figure 2 is a schematic diagram of the partial structure of a hot washing liquid assembly in a continuous co-production system.

[0031] Figure 10 is Figure 1 Figure 3 is a schematic diagram of the partial structure of a discharge module in a continuous co-production system.

[0032] In all the drawings, the same reference signs are used to denote the same elements or structures, wherein:

[0033] 1 - hydrothermal module, 2 - heating module, 3 - modifier feeding module, 4 - ball milling module, 5 - pyrolysis module, 6 - cooling module, 7 - cleaning module, 8 - drying module, 9 - discharge module, 10 - self-powered module;

[0034] 101 - first air inlet, 102 - first air outlet, 103 - first outer door, 104 - material transition chamber, 105 - first inner door, 106 - material feeding chamber, 107 - first screw rod, 108 - first screw rod conveying chamber;

[0035] 201 - first molten salt outlet, 202 - second screw rod, 203 - gas guide outlet, 204 - first molten salt jacket, 205 - second screw rod conveying chamber, 206 - first molten salt inlet;

[0036] 401 - air inlet, 402 - inert gas tank, 403 - ball milling tank, 404 - grinding ball;

[0037] 501 - combustible gas outlet, 502 - liquid oil outlet, 503 - volatile fraction pipeline, 504 - second molten salt outlet, 505 - second molten salt inlet, 506 - first cooling water outlet, 507 - volatile fraction outlet, 508 - first cooling water inlet;

[0038] 601 - second cooling water outlet, 602 - third molten salt outlet, 603 - third molten salt inlet, 604 - second cooling water inlet, 605 - third screw rod, 606 - third screw rod conveying chamber;

[0039] 701 - spiral blade, 702 - washing liquid spraying port, 703 - centrifugal pump outlet, 704 - first centrifugal pump, 705 - filter screen, 706 - washing liquid inlet, 707 - negative pressure chamber, 708 - negative pressure chamber outlet, 709 - water vapor guide outlet, 710 - waste water distillation tank, 711 - fourth molten salt outlet, 712 - fourth molten salt inlet, 713 - slag discharge port, 714 - waste water buffer tank inlet, 715 - waste water buffer tank, 716 - pipeline, 717 - water vapor guide inlet, 718 - normal temperature pure water inlet, 719 - hot washing liquid tank, 720 - second centrifugal pump;

[0040] 901 - third cooling water outlet, 902 - fourth screw, 903 - second inner door, 904 - second outer door, 905 - third cooling water inlet, 906 - fourth screw conveying cavity, 907 - to-be-discharged cavity, 908 - second air supplementing port, 909 - second air extracting port, 910 - discharging transition cavity. DETAILED DESCRIPTION

[0041] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0042] As shown in Figure 1 The present application provides a continuous co-production system of furfural compounds and carbon-based electrode materials, which comprises a hydrothermal module 1, a heating module 2, a pyrolysis module 5 and a product processing unit connected in sequence, wherein: the hydrothermal module 1 is used for putting in biomass, phosphorous acid, water, an organic solvent and an iodine-containing reagent and performing hydrothermal treatment to obtain a hydrothermal product, while separating and recovering the organic layer in the hydrothermal product to prepare furfural compounds, and sending the remaining solid-liquid mixture into the heating module 2; the biomass is biomass containing five-carbon sugars and / or six-carbon sugars, the high-silicon biomass includes one or more of diatom, straw, rice husk, bamboo leaf, wheat chaff, reed, reed stalk, peanut shell and tree bark, and the low-silicon biomass includes one or more of sawdust, microalgae and kitchen garbage; in the hydrothermal treatment process, elemental iodine is reduced by phosphorous acid to maintain the content of hydroiodic acid in the solution, so as to prepare furfural compounds and biomass hydrothermal residues with rich pores in the hydrothermal stage, and the hydrothermal peeling of five-carbon sugars and / or six-carbon sugars has a pore expanding effect, which can make the voids of the biomass hydrothermal residues more abundant, thereby facilitating the improvement of the performance of the subsequent carbon-based electrode materials;

[0043] The heating module 2 is used for heating the remaining solid-liquid mixture to complete the evaporation of water, so as to recover the iodine-containing reagent and water, thereby obtaining a hydrothermal solid residue containing phosphorous acid and phosphoric acid and sending it into the pyrolysis module 5; by heating, the iodine-containing reagent including elemental iodine and hydroiodic acid is evaporated, which can avoid the reaction of the iodine-containing reagent with phosphoric acid in the subsequent pyrolysis process to affect the pore expanding effect of phosphoric acid.

[0044] The pyrolysis module 5 is used for pyrolysis activation of the hydrothermal solid residue with phosphoric acid as a pore expander in an inert atmosphere, so as to prepare carbon-based electrode materials and discharge them after being processed by the product processing unit; the carbon-based electrode materials have rich pores, which can effectively improve the performance of alkali metal ion batteries; when silicon-containing biomass is used, the obtained carbon-based electrode materials can be directly used as lithium battery negative materials; when biomass containing five-carbon sugars and / or six-carbon sugars is used, the obtained carbon-based electrode materials need to be mixed with sulfur and heated to be used as lithium-sulfur battery positive materials.

[0045] Further, as shown in Figure 2 The hydrothermal module 1 includes a raw material feeding assembly, a hydrothermal reactor and a furfural recovery assembly. The raw material feeding assembly is connected with the inlet of the hydrothermal reactor for feeding the biomass, the phosphorous acid and the iodine-containing reagent into the hydrothermal reactor. The raw material feeding assembly includes a material transition chamber 104, a material to be fed chamber 106 and a first screw conveying chamber 108 connected in sequence from top to bottom. The top of the material transition chamber 104 is provided with a first outer door 103 for controlling the feeding of the material. The bottom of the material transition chamber 104 is connected with the material to be fed chamber 106 through a first inner door 105 for controlling the feeding of the material into the material to be fed chamber 106. The material transition chamber 104 is also provided with a first air supplement port 101 and a first air extraction port 102 for vacuumizing the material transition chamber 104 and supplementing the inert gas. In operation, the first inner door 105 is opened and closed and the first outer door 103 is opened to feed the material. After the feeding is completed, the first outer door 103 is closed. After the inert gas is extracted for multiple times and supplemented, the first inner door 105 is opened. The material falls from the material transition chamber 104 into the material to be fed chamber 106. Then the material is fed and conveyed to the subsequent processing module at a certain rate in the first screw conveying chamber 108 with the first screw 107. The first screw conveying chamber 108 is provided with the first screw 107 for pushing the material to feed at a certain rate.

[0046] The hydrothermal reactor contains water and an organic solvent. The organic solvent is one or more of benzene, toluene and methyl isobutyl ketone. The inlet of the hydrothermal reactor is connected with the raw material feeding assembly, the furfural recovery assembly and the heating module 2 for feeding the recovered organic solvent, water and the iodine-containing reagent. The outlet of the hydrothermal reactor is connected with the furfural recovery assembly and the heating module 2 for feeding the organic solution in the hydrothermal product and the remaining solid-liquid mixture. During the hydrothermal reaction, the six-carbon sugar component of the biomass in the lower aqueous solution of the hydrothermal reactor is catalytically hydrolyzed and dehydroxylated to obtain 5-methyl furfural by the hydrogen iodide acid generated by the reduction of the phosphorous acid. The five-carbon sugar is catalytically hydrolyzed to furfural. The two kinds of furfural compounds are immediately transferred to the upper organic layer under the stirring and the extraction of the organic solvent. The organic layer is continuously pumped out from the upper side of the hydrothermal reactor into the furfural recovery assembly.

[0047] The furfural recovery assembly is used for separating and concentrating the fed organic solution to obtain the furfural compounds and feeding the recovered organic solvent back to the hydrothermal reactor.

[0048] Further, as shown in Figure 3As shown, the heating module 2 includes a second screw conveying cavity 205, a second screw 202 and a first molten salt jacket 204, the second screw conveying cavity 205 is provided with a gas guide outlet 203 and is connected with the hydrothermal module 1, for guiding the mixture of water vapor and iodine-containing reagent out and returning to the hydrothermal module 1 to recover the water vapor and the iodine-containing reagent; the inside of the second screw conveying cavity 205 is provided with the second screw 202, and the outside is provided with the first molten salt jacket 204, the second screw 202 is used for conveying materials, and the first molten salt jacket 204 is used for introducing molten salt as a heat source for heating or drying, the first molten salt jacket 204 is provided with a first molten salt inlet 206 and a first molten salt outlet 201, the medium-temperature molten salt is sent in from the first molten salt inlet 206, and the low-temperature molten salt after heat exchange flows out from the first molten salt outlet 201.

[0049] Further, as shown in Figure 2 、 4 The continuous co-production system further includes a modifier feeding module 3 and a ball milling module 4 arranged between the heating module 2 and the pyrolysis module 5, one end of the modifier feeding module 3 is connected with the outlet of the heating module 2, and the other end is connected with the ball milling module 4, for mixing the modifier into the hydrothermal solid residue, and for activating the hydrothermal solid residue as a pore-expanding agent during pyrolysis, the structure of the modifier feeding module 3 is the same as that of the raw material feeding assembly, and only the material of the modifier feeding module 3 is the modifier; when the biomass is low-silicon biomass, the modifier is one or more of potassium phosphate, potassium hydroxide, potassium carbonate, potassium bicarbonate and potassium chloride; when the biomass is high-silicon biomass, the modifier is one or more of graphitization catalyst, tin-containing compound and pore-expanding activator, the graphitization catalyst includes one or more of chlorides, nitrates, citrates, oxalates and acetates of iron, cobalt and nickel, the tin-containing compound includes one or more of SnO, SnO2, Sn(OH)2, SnC2O4 and Sn(OH)4, and the pore-expanding activator includes one or more of phosphoric acid, potassium phosphate, potassium hydroxide, potassium carbonate, potassium bicarbonate and potassium chloride.

[0050] The outlet of the ball milling module 4 is connected with the pyrolysis module 5, for mechanically blending the hydrothermal solid residue and the modifier by ball milling and sending them into the pyrolysis module 5, the ball milling module 4 includes a ball milling tank 403 and an inert gas tank 402, the inside of the ball milling tank 403 is provided with grinding balls 404, and the upper part of the ball milling tank 403 is provided with an air blowing inlet 401, for being connected with the inert gas tank 402 to introduce inert gas and carry the powder into the pyrolysis module 5.

[0051] Further, as shown in Figure 5As shown, the pyrolysis module 5 includes a pyrolysis reaction assembly and a volatile separation assembly, the inlet of the pyrolysis reaction assembly is connected with the heating module 2 for feeding in the hydrothermal solid residue, and the outlet thereof is connected with the volatile separation assembly and the product processing unit respectively to send the volatile and the solid carbon-based product generated by the pyrolysis activation of the hydrothermal solid residue into the volatile separation assembly and the product processing unit respectively; the pyrolysis reaction assembly adopts the screw conveying mode to convey and pyrolyze at the same time, and the pyrolysis heat is derived from the molten salt which flows in at high temperature and flows out at medium or low temperature;

[0052] The volatile separation assembly includes a volatile pipeline 503, a second molten salt jacket, a condensing tank and a first cooling water jacket, the volatile pipeline 503 is connected with the outlet of the pyrolysis module 5, the volatile outlet 507 at the bottom of the volatile pipeline 503 extends into the inside of the condensing tank to convey the volatile into the condensing tank; the outside of the volatile pipeline is provided with a second jacket to condense the volatile by using the molten salt, the low-temperature molten salt flows in from the second molten salt inlet 505 and the medium-temperature molten salt flows out from the second molten salt outlet 504; the inside of the condensing tank is provided with a first cooling water jacket to condense the volatile by using the cooling water, the normal-temperature pure water flows in as the cooling water from the first cooling water inlet 508 and flows out in the form of high-temperature water or water vapor from the first cooling water outlet 506; the condensing tank is provided with a combustible gas outlet 501 and a liquid oil outlet 502 to discharge the products of the volatile condensation, including the non-condensable combustible gas and the condensable liquid oil. Through the two-stage cooling design, the pyrolysis volatile is cooled in stages by using the low-temperature molten salt and the normal-temperature pure water, the heat energy is effectively recovered, and the heat energy utilization rate is improved.

[0053] Further, as shown in the figure, Figures 6-10 the product processing unit includes a cooling module 6, a cleaning module 7, a drying module 8 and a discharging module 9 connected in sequence, wherein the cooling module 6 is connected with the pyrolysis module 5 to cool the solid carbon-based product discharged from the pyrolysis module 5 and send it into the cleaning module 7; the cooling module 6 includes a third screw conveying cavity 606, a third screw 605, a second cooling water jacket and a third molten salt jacket, one end of the third screw conveying cavity 606 is connected with the pyrolysis module 5, the other end thereof is connected with the cleaning module 7, the third screw 605 is arranged inside the third screw conveying cavity 606 to push the solid carbon-based product; the second cooling water jacket and the third molten salt jacket are arranged outside the third screw conveying cavity 606, the normal-temperature pure water flows in as the cooling water from the second cooling water inlet 604 and flows out in the form of high-temperature water or water vapor from the second cooling water outlet 601, the low-temperature molten salt flows in from the third molten salt inlet 603 and flows out in the form of medium-temperature molten salt from the third molten salt outlet 602, and then the cooling water and the molten salt are used to cool the solid carbon-based product;

[0054] The cleaning module 7 is used for spraying washing liquid to the cooled solid carbon-based product to remove impurities on the surface of the solid carbon-based product and sending the solid carbon-based product into the drying module 8, and the cleaning module 7 comprises a spraying assembly, a recycling assembly and a hot washing liquid assembly, wherein the spraying assembly comprises a plurality of spiral spraying mechanisms connected in sequence along the material conveying direction, and the direction of liquid transverse flow in the spraying assembly is opposite to the material conveying direction, each spiral spraying mechanism comprises a negative pressure cavity 707, a first centrifugal pump 704, a spiral blade 701 arranged inside the negative pressure cavity 707, a washing liquid inlet 706, a washing liquid spraying port 702 and a filter screen 705, the negative pressure cavity outlet 708 at the bottom of the negative pressure cavity 707 is connected with the first centrifugal pump 704, and the centrifugal pump outlet 703 of the first centrifugal pump 704 is connected with the washing liquid inlet 706 of the previous spiral spraying mechanism, so that the cleaning waste liquid carrying eluate in the next spiral spraying mechanism is sequentially sent into the washing liquid inlet 706 of the previous spiral spraying mechanism through the negative pressure cavity outlet 708, the first centrifugal pump 704 and the centrifugal pump outlet 703, to be used as the washing liquid of the previous spiral spraying mechanism, so as to realize the step-by-step spraying utilization of the washing liquid, and the washing liquid flowing out of the last spiral spraying mechanism is new liquid (pure water); meanwhile, the first centrifugal pump 704 of the first spiral spraying mechanism is connected with the recycling assembly, so as to collect the cleaning waste liquid and send the cleaning waste liquid into the recycling assembly; the spiral blade 701 is used for conveying the material, and the material moves to the next sequence at a certain rate along with the rotation of the spiral blade 701; the washing liquid inlet 706 is used for providing the washing liquid, and the washing liquid is sprayed out through the washing liquid spraying port 702, so as to remove the soluble impurities on the surface of the solid carbon-based product and generate the cleaning waste liquid, and the solid carbon-based product is cleaned by one spiral spraying mechanism, and needs to be sprayed and cleaned by at least three spiral spraying mechanisms; the filter screen 705 is arranged on the inner wall of the negative pressure cavity 707, so as to send the cleaning waste liquid into the negative pressure cavity 707 through the apertures on the filter screen 705 and avoid the solid carbon-based product from entering the negative pressure cavity 707;

[0055] The inlet of the recovery assembly is connected with the spraying assembly, and the outlet is connected with the hot washing liquid assembly for heating the incoming cleaning waste liquid to recover the modifier and water vapor, and sending the water vapor into the hot washing liquid assembly. The recovery assembly comprises a waste water buffer tank 715 and a waste water distillation tank 710. The waste water buffer tank inlet 714 in the upper part of the waste water buffer tank 715 is connected with the centrifugal pump outlet 703 of the first spiral spraying mechanism to collect the cleaning waste liquid into the waste water buffer tank 715. The waste water buffer tank 715 is connected with the waste water distillation tank 710 through a pipeline 716. When the liquid level of the waste water distillation tank 710 is lowered to the lowest liquid level, the cleaning waste liquid is sent from the waste water buffer tank 715 into the waste water distillation tank 710 through the pipeline 716. The outside of the waste water distillation tank 710 is provided with a fourth molten salt jacket. The fourth molten salt inlet 712 of the fourth molten salt jacket is used to introduce medium-temperature molten salt to heat the cleaning waste liquid and change it into low-temperature molten salt flowing out from the fourth molten salt outlet 711. The waste water distillation tank 710 is provided with a water vapor outlet 709 at the top for being connected with the hot washing liquid assembly to discharge the generated water vapor from the water vapor outlet 709 and send it into the hot washing liquid assembly for recovery. The remaining solid residues are discharged from a residue discharge port 713 to recover the modifier.

[0056] The outlet of the hot washing liquid assembly is connected with the washing liquid inlet of the last spiral spraying mechanism for mixing the incoming water vapor with normal-temperature water to obtain washing liquid and send it into the last spiral spraying mechanism. The hot washing liquid assembly comprises a hot washing liquid tank 719 and a second centrifugal pump 720. The hot washing liquid tank 719 is provided with a water vapor guide inlet 717 and a normal-temperature pure water inlet 718. The water vapor guide inlet 717 is connected with the water vapor guide outlet 709 of the recovery assembly. The normal-temperature pure water inlet 718 is used to introduce normal-temperature pure water to mix the water vapor with the normal-temperature pure water to obtain hot washing liquid. Meanwhile, the water vapor guide inlet 717 can also be connected with the first cooling water outlet 506 of the pyrolysis module 5 and the second cooling water outlet 601 of the cooling module 6 to recover and utilize the water vapor generated by the first cooling water jacket and the second cooling water jacket. One end of the second centrifugal pump 720 is connected with the hot washing liquid tank 719, and the other end is connected with the last spiral spraying mechanism to provide hot washing liquid for the spraying assembly. The upper part of the hot washing liquid tank 719 is equipped with a one-way exhaust valve and communicates with inert gas to isolate air and stabilize the liquid level through a liquid level controller and a normal-temperature water inlet control. The space above the liquid level is filled with inert gas.

[0057] The drying module 8 has the same structure as the heating module 2 and is used to dry the cleaned solid carbon-based product to obtain carbon-based electrode material and send it into the discharging module 9. The gas guide outlet 203 of the drying module 8 only discharges water vapor, and the gas guide outlet 203 of the drying module 8 is connected with the water vapor guide inlet 717 of the cleaning module 7 to realize the recovery and utilization of water vapor.

[0058] The discharge module 9 is used for discharging the carbon-based electrode material, which comprises a fourth screw conveying cavity 906, a cavity to be discharged 907 and a discharge transition cavity 910. The inlet of the fourth screw conveying cavity 906 is connected with the outlet of the drying module, so as to send the dried carbon-based electrode material into the fourth screw conveying cavity 906. The outside of the fourth screw conveying cavity 906 is provided with a third cooling water jacket. The third cooling water inlet 905 of the third cooling water jacket is used for passing in cooling water to cool the dried carbon-based electrode material. The generated high-temperature water or water vapor is discharged from the third cooling water outlet 901, which is connected with the water vapor guide inlet 717 of the cleaning module, so as to realize the recycling of the high-temperature water or water vapor. Meanwhile, the inside of the fourth screw conveying cavity 906 is provided with a fourth screw 902, the right side of which is connected with the cavity to be discharged 907, so that the dried carbon-based electrode material is cooled and conveyed at a certain rate along with the rotation of the fourth screw 902, and finally sent into the cavity to be discharged 907. The cavity to be discharged 907 is connected with the discharge transition cavity 910 through the second inner door 903. Meanwhile, the bottom of the discharge transition cavity 910 is provided with the second outer door 904. The discharge transition cavity 910 is also provided with the second air supplementing port 908 and the second air extracting port 909. In working, under the condition that the second inner door 903 is closed, the carbon-based electrode material is conveyed into the cavity to be discharged 907. When the second outer door 904 is closed and the discharge transition cavity 910 completes the inert gas extraction and supplement through the second air extracting port 909 and the second air supplementing port 908, the second inner door 903 is opened. The carbon-based electrode material falls into the discharge transition cavity 910 from the cavity to be discharged 907. When the discharge transition cavity 910 level monitor monitors that the carbon-based electrode material reaches the rated height, the second inner door 903 is automatically closed and the second outer door 904 is opened in turn. The carbon-based electrode material is discharged from the discharge transition cavity 910.

[0059] Further, the continuous co-production system further comprises a self-powered module 10, the self-powered module 10 comprising a combustion power generation assembly and a heat recycling assembly, the combustion power generation assembly being connected with the combustible gas outlet 501 and the liquid oil outlet 502 of the pyrolysis module 5, for combusting the combustible gas and the liquid oil generated by the pyrolysis of the hydrothermal solid residues, so as to provide power for the continuous co-production system; the heat recycling assembly adopts molten salt as a heat storage medium, for absorbing the waste heat of the combustion power generation assembly and providing heat for the continuous co-production system. The medium-temperature molten salt is introduced into the heat recycling assembly, and is changed into high-temperature molten salt by absorbing the waste heat of the combustion power generation assembly, first providing the required heat for the pyrolysis of the hydrothermal solid residues in the pyrolysis reaction assembly, and then being sent into the heating module 2 and the drying module 8 to provide heat for the dried materials, the low-temperature molten salt generated can be used as a cooling medium, and is sent into the cooling module 6 and the cleaning module 7 to be changed into medium-temperature molten salt again and then be sent back to the heat recycling assembly. The low-melting-point molten salt with a use temperature of 60-1000 DEG C is adopted as the heat storage and heat exchange medium, and the heat exchange mechanism of the molten salt with a mode of "high temperature-medium temperature-low temperature-medium temperature-high temperature" is designed, so that the heat energy cascade utilization can be greatly promoted.

[0060] The entire continuous co-production system of the furfural compounds and the carbon-based electrode material has only a gas inlet provided in the ball milling module 4, and the gas inlet is an inert gas with a gas flow transmission function, and only has a gas outlet provided in the pyrolysis module 5, i.e. a pyrolysis volatile discharge pipeline; in order to ensure that the pyrolysis volatiles are discharged from the pyrolysis volatile discharge pipeline, the gas outlet is arranged at the rear end of the screw conveying cavity but has a certain distance from the terminal end, and the carbon-based material conveyed to this position has been completely pyrolyzed, and a negative pressure generating device is further arranged at the terminal end of the pyrolysis volatile discharge pipeline to further promote the timely discharge of the pyrolysis volatiles.

[0061] The production process of the continuous co-production system of the furfural compounds and the carbon-based electrode material provided by the application is described in detail as follows.

[0062] (1) With the help of external power to start continuous co-production system, including with external power to heat pure water, drying, pyrolysis and refrigeration, and drive stirring paddle, screw, screw, centrifugal pump operation, etc., and by inert gas replacement system air, mixed with iodine reagent and phosphorous acid raw materials through the hydrothermal module 1 raw material feeding assembly into the hydrothermal module 1 water, organic solvent hydrothermal reactor containing iodine reagent and phosphorous acid, under the action of the conversion of furfural, 5-methylfurfural and stripping five carbon sugar and / or six carbon sugar hydrothermal solid residue into heating module 2 drying and dehydrating and iodine, the generated furfural, 5-methylfurfural and other furfural compounds are extracted by the organic solvent in the hydrothermal reactor, and the furfural recovery assembly is distilled and concentrated into furfural compound crude product, and the distilled organic solvent is conveyed into the hydrothermal reactor, and the water and iodine vapor in the heating module 2 are returned to the hydrothermal reactor, and the hydrothermal solid residue in the heating module 2 is cooled while adding modifier in the modifier feeding module 3, and is mixed with the modifier in the ball milling module 4, when the particle size of the hydrothermal solid residue mixed with the modifier is reduced to the appropriate size, it is transported into the pyrolysis module 5 by inert gas flow for pyrolysis carbonization in-situ modification, and the obtained solid carbon-based product is cooled in the cooling module 6, and then washed in the cleaning module 7 to remove soluble modifier and its derivatives, and then sequentially passes through the drying module 8 and the discharge module 9, and is further dried and cooled to obtain the carbon-based electrode material, i.e. the negative electrode material of the alkali metal ion battery, and is discharged.

[0063] (2) During the operation of the system, the high temperature volatile matter generated in the pyrolysis module 5 is cooled to combustible gas and liquid oil, which is burned to generate electricity to replace the external power for driving the stirring paddle, screw, screw, centrifugal pump, etc. The high temperature volatile matter, solid carbon-based product heat and combustible gas and liquid fuel combustion waste heat generated by the cold fluid recovery biomass pyrolysis are used to replace the external power for heating pure water, drying and pyrolysis.

[0064] Those skilled in the art will readily understand that the above description is only a preferred embodiment of the present application and is not intended to limit the present application, and any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A continuous co-production system for furfural compounds and carbon-based electrode materials, characterized in that, The continuous co-production system includes a hydrothermal module (1), a heating module (2), a pyrolysis module (5), and a product processing unit connected in sequence. The hydrothermal module (1) is used to feed biomass containing pentose and / or hexose, phosphorous acid, water, organic solvent, and iodine-containing reagent and perform hydrothermal treatment to obtain hydrothermal products. During the hydrothermal process, phosphorous acid is used to reduce elemental iodine to maintain the content of hydroiodic acid in the solution. Then, the organic layer in the hydrothermal product is separated and recovered to obtain furfural compounds, and the remaining solid-liquid mixture is sent to the heating module (2). The heating module (2) is used to heat the remaining solid-liquid mixture until the water is completely evaporated, thereby recovering the iodine-containing reagent and water, thereby obtaining hydrothermal solid residue containing phosphorous acid and phosphoric acid, which is then sent to the pyrolysis module (5). The pyrolysis module (5) is used to pyrolyze and activate the hydrothermal solid residue with phosphoric acid as a pore expander under an inert atmosphere, thereby obtaining carbon-based electrode materials, which are then discharged after being processed by the product processing unit.

2. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 1, characterized in that, The continuous cogeneration system also includes a self-powered module (10), which includes a combustion power generation component and a heat recovery and utilization component. The combustion power generation component is used to burn the combustible gas and liquid oil generated by the pyrolysis of hydrothermal solid residue, thereby providing electricity to the continuous cogeneration system. The heat recovery and utilization component uses molten salt as a heat storage medium to absorb the waste heat of the combustion power generation component and provide heat to the continuous cogeneration system.

3. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 1 or 2, characterized in that, The product processing unit includes a cooling module (6), a cleaning module (7), a drying module (8), and a discharge module (9) connected in sequence. The cooling module (6) is connected to the pyrolysis module (5) and is used to cool the solid carbon-based product discharged from the pyrolysis module (5) and send it to the cleaning module (7). The cleaning module (7) is used to spray the cooled solid carbon-based product with washing liquid to remove impurities on the surface of the solid carbon-based product and send it to the drying module (8). The drying module (8) is used to dry the cleaned solid carbon-based product to obtain carbon-based electrode material and send it to the discharge module (9). The discharge module is used to discharge the carbon-based electrode material.

4. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 3, characterized in that, The cleaning module (7) includes a spray assembly, a recovery assembly, and a hot washing liquid assembly. The spray assembly includes multiple spiral spray mechanisms connected sequentially along the material conveying direction. Each spiral spray mechanism includes a negative pressure chamber (707), a first centrifugal pump (704), and spiral blades (701), a washing liquid inlet (706), a washing liquid spray nozzle (702), and a filter screen (705) disposed inside the negative pressure chamber (707). The outlet of the negative pressure chamber (707) is connected to the first centrifugal pump (704), and the first centrifugal pump (704) is connected to the washing liquid inlet (706) of the preceding spiral spray mechanism, so that the cleaning waste liquid of the subsequent spiral spray mechanism is used as the washing liquid of the preceding spiral spray mechanism. Simultaneously, the first centrifugal pump of the first spiral spray mechanism... 704) is connected to the recovery component; the spiral blade (701) is used to convey materials; the washing liquid inlet (706) is used to provide washing liquid and spray it out through the washing liquid spray nozzle (702) to remove impurities on the surface of solid carbon-based products and generate cleaning waste liquid; the filter screen (705) is set on the inner wall of the negative pressure chamber (707) to send the cleaning waste liquid into the negative pressure chamber (707); the inlet of the recovery component is connected to the spray component, and its outlet is connected to the hot washing liquid component to heat the incoming cleaning waste liquid to recover the modifier and water vapor, and send the water vapor into the hot washing liquid component; the outlet of the hot washing liquid component is connected to the washing liquid inlet of the last spiral spray mechanism to mix the incoming water vapor with room temperature water to obtain washing liquid and send it into the last spiral spray mechanism.

5. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 3, characterized in that, The hydrothermal module (1) includes a raw material feeding component, a hydrothermal reactor, and a furfural recovery component. The raw material feeding component is connected to the inlet of the hydrothermal reactor and is used to feed biomass, phosphorous acid, and iodine-containing reagents into the hydrothermal reactor. The inlet of the hydrothermal reactor is also connected to the furfural recovery component and the heating module (2) and is used to introduce the recovered organic solvent, water, and iodine-containing reagents. The outlet of the hydrothermal reactor is connected to the furfural recovery component and the heating module (2) respectively and is used to feed the organic solution and the remaining solid-liquid mixture in the hydrothermal product. The furfural recovery component is used to separate and concentrate the fed organic solution to obtain furfural compounds and to send the recovered organic solvent back to the hydrothermal reactor.

6. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 5, characterized in that, The continuous co-production system also includes a modifier feeding module (3) and a ball milling module (4) disposed between the heating module (2) and the pyrolysis module (5). One end of the modifier feeding module (3) is connected to the outlet of the heating module (2), and the other end is connected to the ball milling module (4) for mixing modifier into the hydrothermal solid residue. The outlet of the ball milling module (4) is connected to the pyrolysis module (5) for mechanically mixing the hydrothermal solid residue and modifier by ball milling and feeding them into the pyrolysis module (5).

7. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 6, characterized in that, The raw material feeding assembly and the modifier feeding module (3) have the same structure, both including a material transition chamber (104), a material feeding chamber (106) and a first screw conveying chamber (108) connected from top to bottom. The material transition chamber (104) is provided with a first outer door (103) at the top to control the input of materials. The bottom of the material transition chamber (104) is connected to the material feeding chamber (106) through a first inner door (105) to control the material to enter the material feeding chamber (106). At the same time, the material transition chamber (104) is also provided with a first air inlet (101) and a first air extraction port (102) to evacuate the material transition chamber (104) and replenish it with inert gas. The first screw conveying chamber (108) is provided with a first screw (107) inside to convey materials.

8. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 3, characterized in that, The heating module (2) and the drying module (8) have the same structure, both including a second screw conveying chamber (205), a second screw (202) and a first molten salt jacket (204). The second screw conveying chamber (205) is provided with a gas outlet (203) for exporting a mixture of water vapor and iodine-containing reagent or water vapor. The gas outlet (203) of the heating module (2) is connected to the hydrothermal module (1) to recover water vapor and iodine-containing reagent. The second screw conveying chamber (205) is provided with a second screw (202) inside and a first molten salt jacket (204) outside. The second screw (202) is used to convey materials, and the first molten salt jacket (204) is used to introduce molten salt as a heat source for heating or drying.

9. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 3, characterized in that, The pyrolysis module (5) includes a pyrolysis reaction component and a volatile matter separation component. The inlet of the pyrolysis reaction component is connected to the heating module (2) for feeding hydrothermal solid residue. Its outlet is connected to the volatile matter separation component and the product processing unit respectively, so as to send the volatile matter and solid carbon-based products generated by the pyrolysis activation of the hydrothermal solid residue into the volatile matter separation component and the product processing unit respectively. The volatile matter separation component includes a volatile matter pipe (503), a second molten salt jacket, a condenser and a first cooling water jacket. The volatile matter pipe (503) is connected to the outlet of the pyrolysis module (5) and extends into the condenser to transport volatile matter to the condenser. The outer side of the volatile matter pipe is provided with a second jacket to condense the volatile matter using molten salt. The condenser is provided with a first cooling water jacket to condense the volatile matter using cooling water. At the same time, the condenser has a combustible gas outlet (501) and a liquid oil outlet (502) for discharging the condensed volatile matter products.

10. The continuous co-production system of furfural compounds and carbon-based electrode materials as described in claim 3, characterized in that, The cooling module (6) includes a third screw conveying chamber (606), a third screw (605), a second cooling water jacket, and a third molten salt jacket. One end of the third screw conveying chamber (606) is connected to the pyrolysis module (5), and the other end is connected to the cleaning module (7). The third screw (605) is located inside the third screw conveying chamber (606) and is used to push the solid carbon-based product. The second cooling water jacket and the third molten salt jacket are located outside the third screw conveying chamber (606) and use cooling water and molten salt to cool the solid carbon-based material, respectively.

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