CN113145032B - Method and system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation - Google Patents

Method and system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation Download PDF

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CN113145032B
CN113145032B CN202110468414.7A CN202110468414A CN113145032B CN 113145032 B CN113145032 B CN 113145032B CN 202110468414 A CN202110468414 A CN 202110468414A CN 113145032 B CN113145032 B CN 113145032B
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CN113145032A (en
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胡松
雷志文
任强强
吴紫月
张嘉琳
向军
苏胜
汪一
江龙
徐俊
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • C—CHEMISTRY; METALLURGY
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/10—Treatment of sludge; Devices therefor by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention discloses a method and a system for preparing carbon aerogel and fuel gas by the cooperation of agricultural wastes and sludge, wherein the method comprises the following steps: step 1, pyrolyzing dry sludge to obtain pyrolysis volatile components, pyrolysis coke and pyrolysis oil; step 2, carrying out co-hydrothermal reaction on the agricultural wastes and the pyrolysis oil to obtain co-hydrothermal reaction liquid and hydrogel, drying the hydrogel to obtain aerogel, and centrifuging, filtering and gasifying the co-hydrothermal reaction liquid to obtain gaseous reaction oil; step 3, putting the aerogel into a first pyrolysis furnace and carrying out carbonization reaction to obtain carbon aerogel and carbonization reaction gas; and 4, mixing the nickel-based catalyst and the pyrolytic coke, putting the mixture into a second pyrolysis furnace, sending pyrolysis volatile components, gaseous reaction oil and carbonization reaction gas, carrying out catalytic reaction, and obtaining fuel gas. According to the method, the sludge pyrolysis oil is used as a nitrogen source, the nitrogen in the sludge pyrolysis oil is migrated into the hydrogel to prepare the nitrogen-doped carbon aerogel by adopting a co-hydrothermal reaction, and the high-quality fuel gas is prepared by using the products of all the steps.

Description

Method and system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation
Technical Field
The invention relates to the technical field of carbon aerogel and fuel gas preparation, in particular to a method and a system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner.
Background
With the rapid development of economy and agriculture in China, the annual output of agricultural wastes is increased year by year, wherein the annual output of shaddock peels is about 70 ten thousand tons, the annual output of bagasse is about 700 ten thousand tons, the annual output of corncobs is about 4500 ten thousand tons, and the same with the promotion of urbanization, the output of municipal sludge is also increased rapidly, so that the problem of how to treat the two wastes in a green, environment-friendly and resource manner becomes increasingly important and severe.
The introduction of nitrogen atoms can improve the properties of the carbon aerogel, particularly the improvement on the adsorption capacity and the electrochemical performance. At present, pure substances with high nitrogen content, such as melamine, urea, ammonia water, pyridine and the like, are usually used as nitrogen sources in the preparation process of the nitrogen-doped biomass-based carbon aerogel, so that the large-scale application of the nitrogen-doped carbon aerogel is limited to a great extent.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner.
A method for preparing carbon aerogel and fuel gas by the cooperation of agricultural wastes and sludge comprises the following steps:
step 1, pyrolyzing dry sludge to obtain pyrolysis volatile components, pyrolysis coke and pyrolysis oil;
step 2, carrying out hydrothermal reaction on agricultural wastes and the pyrolysis oil obtained in the step 1 to obtain hydrothermal reaction liquid and hydrogel, drying the obtained hydrogel to obtain aerogel, centrifuging the hydrothermal reaction liquid to obtain an oil-water suspension, filtering the oil-water suspension to obtain oil, and heating the oil to gasify to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace and carrying out carbonization reaction in an inert atmosphere to obtain carbon aerogel and carbonization reaction gas;
and 4, mixing a nickel-based catalyst and the pyrolytic coke obtained in the step 1, putting the mixture into a second pyrolysis furnace, sending the pyrolysis volatile component obtained in the step 1, the gaseous reaction oil generated in the step 2 and the carbonization reaction gas obtained in the step 3 into the second pyrolysis furnace, and carrying out catalytic reaction in the second pyrolysis furnace to obtain fuel gas.
Specifically, in the step 1, the water content of the dry sludge is lower than 15%, and the conditions for feeding the dry sludge into the sludge pyrolysis furnace for pyrolysis are as follows: under the condition that inert gas is fed into the sludge pyrolysis furnace at the flow rate of 20-200mL/min, the temperature in the sludge pyrolysis furnace is increased from room temperature to 600-1000 ℃ at the temperature rise rate of 5-20 ℃/min, and the temperature is maintained for 80-120min so that the dry sludge undergoes pyrolysis reaction.
In the step 2, the hydrothermal reaction solution is centrifuged, filtered and gasified to obtain a light component in the hydrothermal reaction solution, namely gaseous reaction oil, which specifically comprises aliphatic hydrocarbon, aromatic hydrocarbon, esters, aldehyde, ketone, carboxylic acid, phenol, alcohol and nitrogen-containing compounds.
Specifically, in the step 3, the method for obtaining the aerogel after drying the hydrogel comprises vacuum drying, freeze drying and normal pressure drying, wherein the vacuum drying is to dry the pre-frozen hydrogel for 12-24 hours under the conditions of less than 100Pa and at the temperature of 80-120 ℃; freeze drying, namely freeze drying the pre-frozen hydrogel for 24-36 hours in an environment with the vacuum degree below 100Pa, the temperature of a cold trap between-50 ℃ and-40 ℃ and the temperature between-10 ℃ and-5 ℃; drying under normal pressure without freeze-drying treatment, and drying the obtained hydrogel in a drying air-blast box at 70-90 deg.C for 12-24 h.
Specifically, the inert atmosphere in step 3 includes a nitrogen atmosphere, an argon atmosphere, and a carbon dioxide atmosphere.
Preferably, the content of nitrogen element in the carbonized aerogel obtained in the step 3 is 3-5.5%, and the density is 20-80mg/cm3Specific surface area of 600-1200m2The pore size distribution is 2.5-30nm, and the porosity is 80-90%.
Preferably, the composition of the fuel gas obtained in the step 4 comprises H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 15.84-17.32MJ/Nm3。
Preferably, the agricultural waste used in step 2 comprises one or more of a combination of shaddock peel, bagasse, watermelon peel and corn cobs.
Preferably, the raw material ratio of the hydrothermal reaction in the step 2 is that the mass-volume ratio of the agricultural wastes to the pyrolysis oil is 0.05-0.2 g/mL.
Preferably, the step 2 is carried out for a hydrothermal reaction 180-600min under the conditions of a stirring speed of 100-400r/min and a temperature of 140-200 ℃.
Preferably, the carbonization reaction conditions in step 3 are as follows: under the condition of introducing inert gas into the first pyrolysis furnace at the flow rate of 20-160mL/min, the temperature in the first pyrolysis furnace is increased from room temperature to 600-1000 ℃ at the temperature increase rate of 5-50 ℃/min, and then the temperature is maintained for 80-120 min.
Preferably, in the step 4, the mass ratio of the nickel-based catalyst to the pyrolytic coke is 1: 5-15, the mass volume ratio of the nickel-based catalyst and the pyrolysis volatile component fed into the second pyrolysis furnace is 0.1-0.25g/L, and the volume ratio of the pyrolysis volatile component, the carbonization reaction gas and the gaseous reaction oil fed into the second pyrolysis furnace is 2-4:3-5: 1-2.
Preferably, the pyrolysis volatile components, the gaseous reaction oil and the carbonization reaction gas in the second pyrolysis furnace in the step 4 are catalytically reacted for 60-120min at the temperature of 800-.
The utility model provides a system for agricultural discarded object is with mud preparation carbon aerogel and gas in coordination, includes mud pyrolysis device, hydrothermal reaction unit, drying device, first pyrolysis oven and second pyrolysis oven altogether, the feed inlet of mud pyrolysis device is used for sending into dry mud to its inside, the pyrolysis oil export of mud pyrolysis device with hydrothermal reaction unit's feed inlet intercommunication altogether, hydrothermal reaction unit's feed inlet altogether still is used for sending into agricultural discarded object to its inside, hydrothermal reaction unit's aquogel discharge gate altogether with drying device's feed inlet intercommunication, drying device's discharge gate and inert gas air feeder respectively with first pyrolysis oven inside intercommunication, the pyrolysis coke export of mud pyrolysis device and catalyst feedway's discharge gate communicate with two interfaces of tee bend respectively, the gas outlet of first pyrolysis oven, And a volatile component outlet of the sludge pyrolysis device and the rest interface of the tee joint are respectively communicated with the inside of the second pyrolysis furnace, and a reaction liquid outlet of the co-hydrothermal reaction device is communicated with the inside of the second pyrolysis furnace after sequentially passing through the centrifuge, the filter and the gasification device.
According to the method, the sludge pyrolysis oil is used as a nitrogen source, the nitrogen in the sludge pyrolysis oil is transferred into hydrogel by adopting a co-hydrothermal reaction to prepare the nitrogen-doped carbon aerogel, and the pyrolysis coke is used as a carrier of the nickel-based catalyst to perform catalytic reaction with the sludge pyrolysis volatile component, the gaseous reaction oil and the carbonization reaction gas generated in the carbonization reaction process of the aerogel to obtain high-quality fuel gas, so that agricultural wastes and sludge are utilized in an environment-friendly and resource-oriented manner;
the carbonized aerogel prepared by the method for preparing the carbon aerogel and the fuel gas by the agricultural waste and the sludge in a synergistic manner has the nitrogen element content of 3-5.5 percent and the density of 20-80mg/cm3Specific surface area of 600-1500m2The pore size distribution is 2.5-30nm, the porosity is 80-90%, and the catalyst has the characteristics of high nitrogen content, small density, high specific surface area and good electrochemical performance;
the components of the fuel gas prepared by the method for preparing the carbon aerogel and the fuel gas by using the agricultural waste and the sludge in a synergistic manner comprise H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 15.84-17.32MJ/Nm3。
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings. The detailed description of the present invention is given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a schematic flow chart of a method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation according to an embodiment of the invention;
FIG. 2 is a schematic structural diagram of a system for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation according to an embodiment of the present invention;
FIG. 3 is a scanning electron micrograph of the aerogel prepared in example 3 of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The principles and features of the present invention are described below in conjunction with the accompanying fig. 1-3, which are provided by way of example only to illustrate the present invention and not to limit the scope of the present invention. The invention is described in more detail in the following paragraphs by way of example with reference to the accompanying drawings. Advantages and features of the present invention will become apparent from the following description and from the claims. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The dry sludge in the following examples is naturally dried in a sewage treatment plant for 5 days and then put into sludge drying equipment for drying until the water content of the sludge is lower than 15%, so that the energy is saved.
Example 1
Referring to fig. 1, an embodiment 1 of the present application is provided, which provides a method for preparing carbon aerogel and fuel gas by using agricultural waste and sludge in a synergistic manner, comprising the following steps:
step 1, putting dry sludge into a sludge pyrolysis furnace, and pyrolyzing the sludge in the sludge pyrolysis furnace for 80min under the conditions that the flow of inert gas is 20mL/min and the temperature is 600 ℃ to obtain pyrolysis volatile components, pyrolysis oil and pyrolysis coke;
step 2, mixing the washed watermelon peel and the pyrolysis oil obtained in the step 1 in a ratio of 1 g: feeding the pyrolysis oil and the watermelon peel into a hydrothermal device according to a proportion of 5mL, preserving the heat of the pyrolysis oil and the watermelon peel for 180min under the conditions that the stirring speed is 100r/min and the temperature is 140 ℃ to perform hydrothermal reaction to obtain hydrogel and hydrothermal reaction liquid, pre-freezing the obtained hydrogel for 20min, then putting the hydrogel into a freeze drying device, performing freeze drying for 24h under the environment that the vacuum degree is below 100Pa, the temperature of a cold trap is-50 to-40 ℃ and the temperature is-10 to-5 ℃ to obtain aerogel, centrifuging the obtained hydrothermal reaction liquid for 15min at the rotating speed of 8000r/min of a centrifuge to obtain oil-water suspension, filtering the oil-water suspension to obtain oil liquid floating on the surface, heating the oil liquid to 80 ℃ and then gasifying the oil liquid to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace, introducing inert gas into the first pyrolysis furnace at a speed of 20mL/min, controlling the temperature in the first pyrolysis furnace to rise from room temperature to 600 ℃ at a heating rate of 5 ℃/min, and preserving heat for 80min, wherein the aerogel generates a carbonization reaction in the first pyrolysis furnace, and a carbonized aerogel and a carbonization reaction gas are obtained;
and 4, mixing 1g of nickel-based catalyst and 15g of the pyrolytic coke obtained in the step 1, putting the mixture into a second pyrolysis furnace, feeding the pyrolytic volatile matter obtained in the step 1 into the second pyrolysis furnace at a flow rate of 10L/min, feeding carbonization reaction gas at a flow rate of 15L/min, feeding gaseous reaction oil generated in the step 2 at a flow rate of 5L/min, and carrying out catalytic reaction at the temperature of 800 ℃ for 60min to obtain fuel gas.
A sample of the carbon aerogel prepared in step 3 of this example was removed and the density measured to be about 80mg/cm3The graphitization degree of the carbon material is calculated to be more than 60 percent through X-ray diffraction detection analysis, and a nitrogen absorption desorption instrument detectorThe specific surface area is calculated to reach 600m2The volume of the doped nitrogen is 3 wt% detected by an element analyzer.
In this example, the fuel gas sample prepared in step 4 mainly includes H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 15.84MJ/Nm3。
Example 2
Embodiment 2 provides a method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner, which specifically comprises the following steps:
step 1, putting dry sludge into a sludge pyrolysis furnace, and pyrolyzing the sludge in the sludge pyrolysis furnace for 80min under the conditions that the flow of inert gas is 80mL/min and the temperature is 800 ℃ to obtain pyrolysis volatile components, pyrolysis oil and pyrolysis coke;
step 2, mixing the cleaned shaddock peel and the pyrolysis oil obtained in the step 1 in a ratio of 1 g: feeding 15mL of the pyrolysis oil and shaddock peel into a hydrothermal device, keeping the temperature of the pyrolysis oil and the shaddock peel at the stirring speed of 300r/min and the temperature of 180 ℃ for 420min to perform hydrothermal reaction to obtain hydrogel and hydrothermal reaction liquid, pre-freezing the obtained hydrogel for 20min, then putting the hydrogel into a freeze-drying device, freeze-drying the hydrogel for 36h in an environment with the vacuum degree of below 100Pa, the cold trap temperature of-50 to-40 ℃ and the temperature of-10 to-5 ℃ to obtain aerogel, and centrifuging, filtering and gasifying the obtained hydrothermal reaction liquid to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace, introducing inert gas into the first pyrolysis furnace at a speed of 80mL/min, controlling the temperature in the first pyrolysis furnace to rise from room temperature to 800 ℃ at a heating rate of 20 ℃/min, and preserving heat for 80min, wherein the aerogel generates a carbonization reaction in the first pyrolysis furnace, and a carbonized aerogel and a carbonization reaction gas are obtained;
and 4, mixing 3g of nickel-based catalyst and 30g of the pyrolytic coke obtained in the step 1, putting the mixture into the second pyrolysis furnace, feeding the pyrolytic volatile matter obtained in the step 1 into the second pyrolysis furnace at a flow rate of 15L/min, feeding carbonization reaction gas at a flow rate of 20L/min, feeding gaseous reaction oil at a flow rate of 8L/min, and carrying out catalytic reaction at the temperature of 1000 ℃ for 80min to obtain fuel gas.
The carbon aerogel sample prepared in step 3 of this example was removed and had a density of about 60mg/cm3The graphitization degree of the carbon material is calculated to be more than 60 percent through X-ray diffraction detection and analysis, and the specific surface area is 823m through detection and calculation of a nitrogen absorption and desorption instrument2The volume ratio/g, the porosity of 86 percent and the pore size distribution are 2.5-30nm, and the doping amount of nitrogen element detected by an element analyzer is 4.12wt percent.
In this example, the fuel gas sample prepared in step 4 mainly includes H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 16.24MJ/Nm3。
Example 3
Embodiment 3 provides a method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner, which specifically comprises the following steps:
step 1, putting dry sludge into a sludge pyrolysis furnace, and pyrolyzing the sludge in the sludge pyrolysis furnace for 100min under the conditions that the flow of inert gas is 100mL/min and the temperature is 1000 ℃ to obtain pyrolysis volatile components, pyrolysis oil and pyrolysis coke;
step 2, mixing the washed corncobs and the pyrolysis oil obtained in the step 1 in a ratio of 1 g: feeding 20mL of the mixed solution into a co-hydrothermal device, keeping the temperature of pyrolysis oil and corncobs at 200 ℃ for 300min at a stirring speed of 300r/min to perform co-hydrothermal reaction to obtain hydrogel and co-hydrothermal reaction liquid, placing the obtained hydrogel into a vacuum drier for 25min, performing vacuum drying in an environment with a vacuum degree of below 100Pa and a temperature of 80 ℃ for 24h to obtain aerogel, and centrifuging, filtering and gasifying the obtained co-hydrothermal reaction liquid to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace, introducing inert gas into the first pyrolysis furnace at a speed of 100mL/min, controlling the temperature in the first pyrolysis furnace to rise from room temperature to 1000 ℃ at a heating rate of 30 ℃/min, and preserving the temperature for 100min, wherein the aerogel generates a carbonization reaction in the first pyrolysis furnace, and a carbonized aerogel and a carbonization reaction gas are obtained;
and 4, mixing 5g of nickel-based catalyst and 25g of the pyrolytic coke obtained in the step 1, putting the mixture into the second pyrolysis furnace, feeding the pyrolytic volatile matter obtained in the step 1 into the second pyrolysis furnace at a flow rate of 20L/min, feeding carbonization reaction gas at a flow rate of 25L/min, feeding gaseous reaction oil generated in the step 2 at a flow rate of 10L/min, and performing catalytic reaction at 1200 ℃ for 120min to obtain fuel gas.
The carbon aerogel sample prepared in step 3 of this example was removed and had a density of about 20mg/cm3The graphitization degree of the carbon material is calculated to be more than 60% through X-ray diffraction detection and analysis, and the specific surface area is calculated to be 1200m through detection of a nitrogen absorption and desorption instrument2The volume ratio/g, the porosity of 90 percent and the pore size distribution are 2.5-30nm, and the doping amount of nitrogen element detected by an element analyzer is 5.5wt percent.
In this example, the fuel gas sample prepared in step 4 mainly includes H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 17.32MJ/Nm3。
Example 4
Embodiment 4 provides a method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner, which specifically comprises the following steps:
step 1, putting dry sludge into a sludge pyrolysis furnace, and pyrolyzing the sludge for 80min in the sludge pyrolysis furnace under the conditions that the flow of inert gas is 120mL/min and the temperature is 800 ℃ to obtain pyrolysis volatile components, pyrolysis oil and pyrolysis coke;
step 2, mixing the washed bagasse and the pyrolysis oil obtained in the step 1 in a ratio of 1 g: feeding 15mL of the mixed solution into a co-hydrothermal device, keeping the temperature of pyrolysis oil and bagasse for 600min under the conditions of stirring at the speed of 400r/min and the temperature of 200 ℃ to perform co-hydrothermal reaction to obtain hydrogel and co-hydrothermal reaction liquid, putting the obtained hydrogel into a drying air blowing device, drying at the temperature of 80 ℃ to obtain aerogel, and centrifuging, filtering and gasifying the obtained co-hydrothermal reaction liquid to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace, introducing inert gas into the first pyrolysis furnace at a speed of 160mL/min, controlling the temperature in the first pyrolysis furnace to rise from room temperature to 1000 ℃ at a heating rate of 50 ℃/min, and keeping the temperature for 120 min;
and 4, mixing 5g of nickel-based catalyst and 25g of the pyrolytic coke obtained in the step 1, putting the mixture into a second pyrolysis furnace, feeding the pyrolytic volatile matter obtained in the step 1 into the second pyrolysis furnace at a flow rate of 20L/min, feeding carbonization reaction gas at a flow rate of 25L/min, feeding the gaseous reaction oil obtained in the step 2 at a flow rate of 10L/min, and carrying out catalytic reaction at 1200 ℃ for 120min to obtain fuel gas.
The carbon aerogel sample prepared in step 3 of this example was removed and had a density of about 65mg/cm3The graphitization degree of the carbon material is more than 60 percent calculated by X-ray diffraction detection and analysis, and the specific surface area is 840m calculated by detection of a nitrogen absorption and desorption instrument2The volume ratio/g, the porosity of 84 percent and the pore size distribution are 2.5-30nm, and the doping amount of nitrogen element detected by an element analyzer is 3.2wt percent.
In this example, the fuel gas sample prepared in step 4 mainly includes H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 16.89MJ/Nm3。
Example 5
As shown in fig. 2, the present embodiment provides a system for preparing carbon aerogel and fuel gas by cooperating agricultural waste and sludge, specifically including a sludge pyrolysis device 1, a hydrothermal reaction device 2, a drying device 3, a first pyrolysis furnace 4 and a second pyrolysis furnace 5, a feed port of the sludge pyrolysis device 1 is used to feed dry sludge into the sludge pyrolysis device 1, a pyrolysis oil outlet of the sludge pyrolysis device 1 is communicated with a feed port of the hydrothermal reaction device 2, a feed port of the hydrothermal reaction device 2 is further used to feed agricultural waste into the hydrothermal reaction device, a hydrogel discharge port of the hydrothermal reaction device 2 is communicated with a feed port of the drying device 3, a discharge port of the drying device 3 and an inert gas feeding device are respectively communicated with the first pyrolysis furnace 4, a pyrolysis coke outlet of the sludge pyrolysis device 1 and a discharge port of a nickel-based catalyst feeding device are respectively communicated with two ports of a tee joint, the inert gas feeding device, the gas outlet of the first pyrolysis furnace 4, the volatile matter outlet of the sludge pyrolysis device 1 and the rest interface of the tee joint are respectively communicated with the inside of the second pyrolysis furnace 5, and the reaction liquid outlet of the hydrothermal reaction device 2 is communicated with the inside of the second pyrolysis furnace 5 after sequentially passing through a centrifuge 6, a filter 7 and a gasification device 8.
The pyrolysis coke sent out from the pyrolysis coke outlet of the sludge pyrolysis device 1 is mixed with the nickel-based catalyst and then sent into the second pyrolysis furnace 5, so that the pyrolysis coke is used as a carrier of the nickel-based catalyst to enable pyrolysis volatile components, carbonization reaction gas and gaseous reaction oil of the sludge to perform catalytic reaction in the second pyrolysis furnace 5 to generate high-quality fuel gas.
As shown in fig. 3, in this embodiment, the first pyrolysis furnace 4 and the second pyrolysis furnace 5 are connected into a whole and form a two-stage pyrolysis furnace, the second pyrolysis furnace 5 is disposed above the first pyrolysis furnace 4, the lower end of the second pyrolysis furnace 5 is communicated with the upper end of the first pyrolysis furnace 4, and the carbonization reaction gas generated in the carbonization reaction process of the aerogel in the second pyrolysis furnace 4 flows into the second pyrolysis furnace 5 through the upper end of the first pyrolysis furnace 4.
This application agricultural waste still includes sludge drying device 9 with the system of mud preparation carbon aerogel and gas in coordination, sludge drying device 9 sets up pyrolysis oven 1's feed inlet department, sludge drying device 9 is used for sending into the dry mud that the water content is less than 15% to pyrolysis oven 1.
The device is characterized by further comprising a washing device 10, wherein the washing device 10 is arranged at a feeding hole of the hydrothermal reaction device 2, the feeding hole of the washing device 10 is used for feeding agricultural wastes into the washing device 10, after the agricultural wastes are fed into the washing device 10 and cleaned, the washing device 10 feeds clean agricultural wastes into the hydrothermal reaction device 2, and normal operation of the hydrothermal reaction is guaranteed.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; the present invention may be readily implemented by those of ordinary skill in the art as illustrated in the accompanying drawings and described above; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention without departing from the scope of the invention as defined by the appended claims; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner is characterized by comprising the following steps of:
step 1, pyrolyzing dry sludge to obtain pyrolysis volatile components, pyrolysis coke and pyrolysis oil;
step 2, carrying out hydrothermal reaction on agricultural wastes and the pyrolysis oil obtained in the step 1 to obtain hydrothermal reaction liquid and hydrogel, drying the obtained hydrogel to obtain aerogel, centrifuging the hydrothermal reaction liquid to obtain an oil-water suspension, filtering the oil-water suspension to obtain oil, and heating the oil to gasify to obtain gaseous reaction oil;
step 3, putting the aerogel obtained in the step 2 into a first pyrolysis furnace and carrying out carbonization reaction in an inert atmosphere to obtain carbon aerogel and carbonization reaction gas;
and 4, mixing a nickel-based catalyst and the pyrolytic coke obtained in the step 1, putting the mixture into a second pyrolysis furnace, sending the pyrolysis volatile component obtained in the step 1, the gaseous reaction oil generated in the step 2 and the carbonization reaction gas obtained in the step 3 into the second pyrolysis furnace, and carrying out catalytic reaction in the second pyrolysis furnace to obtain fuel gas.
2. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner according to claim 1, wherein the content of nitrogen in the carbonized aerogel obtained in the step 3 is 3-5.5%, and the density is 20-80mg/cm3Specific surface area600-1200m2The pore size distribution is 2.5-30nm, and the porosity is 80-90%.
3. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation with claim 1, wherein the component of the fuel gas obtained in the step 4 comprises H2、CO、CO2、CH4And C2H4The heat value of the fuel gas is 15.84-17.32MJ/Nm3。
4. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation as claimed in claim 1, wherein the agricultural wastes used in the step 2 comprise one or more of a combination of shaddock peel, bagasse, watermelon peel and corncob.
5. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner according to claim 1, wherein the raw material ratio of the hydrothermal reaction in the step 2 is that the mass-to-volume ratio of the agricultural wastes to the pyrolysis oil is 0.05-0.2 g/mL.
6. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner as claimed in claim 1, wherein the hydrothermal reaction is carried out for 180-600min under the conditions of a stirring speed of 100-400r/min and a temperature of 140-200 ℃ in the step 2.
7. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation as claimed in claim 1, wherein the carbonization reaction conditions in the step 3 are as follows: under the condition of introducing inert gas into the first pyrolysis furnace at the flow rate of 20-160mL/min, the temperature in the first pyrolysis furnace is increased from room temperature to 600-1000 ℃ at the temperature increase rate of 5-50 ℃/min, and then the temperature is maintained for 80-120 min.
8. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in a synergistic manner according to claim 1, wherein in the step 4, the mass ratio of the nickel-based catalyst to the pyrolytic coke is 1: 5-15, the mass volume ratio of the nickel-based catalyst and the pyrolysis volatile component fed into the second pyrolysis furnace is 0.1-0.25g/L, and the volume ratio of the pyrolysis volatile component, the carbonization reaction gas and the gaseous reaction oil fed into the second pyrolysis furnace is 2-4:3-5: 1-2.
9. The method for preparing carbon aerogel and fuel gas by using agricultural wastes and sludge in cooperation as claimed in claim 1, wherein the pyrolysis volatile components, the gaseous reaction oil and the carbonization reaction gas in the second pyrolysis furnace in the step 4 are subjected to catalytic reaction for 60-120min at the temperature of 800-1200 ℃.
10. The utility model provides a system for agricultural waste prepares carbon aerogel and gas with mud in coordination, a serial communication port, including mud pyrolysis device (1), hydrothermal reaction unit (2), drying device (3), first pyrolysis oven (4) and second pyrolysis oven (5) altogether, the feed inlet of mud pyrolysis device (1) is used for sending into dry mud to its inside, the pyrolysis oil export of mud pyrolysis device (1) with hydrothermal reaction unit's (2) feed inlet intercommunication altogether, hydrothermal reaction unit's (2) feed inlet still is used for sending into agricultural waste to its inside altogether, hydrothermal reaction unit's (2) hydrogel discharge gate altogether with drying device's (3) feed inlet intercommunication, drying device's (3) discharge gate and inert gas air supply device respectively with inside intercommunication of first pyrolysis oven (4), the pyrolysis coke export of mud pyrolysis device (1) and catalyst feedway's discharge gate respectively with two three-way two The connector is communicated, the inert gas feeding device, the gas outlet of the first pyrolysis furnace (4), the volatile matter outlet of the sludge pyrolysis device (1) and the rest connector of the tee joint are respectively communicated with the inside of the second pyrolysis furnace (5), and the reaction liquid outlet of the hydrothermal reaction device (2) is communicated with the inside of the second pyrolysis furnace (5) after sequentially passing through the centrifuge (6), the filter (7) and the gasification device (8).
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CN108439400A (en) * 2018-03-23 2018-08-24 武汉科技大学 A kind of N doping bagasse active carbon and preparation method thereof
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JPS58114800A (en) * 1981-12-28 1983-07-08 Ishikawajima Harima Heavy Ind Co Ltd Treatment for sludge
JPH0523699A (en) * 1991-05-13 1993-02-02 Kouyuu Kk Method and agent for treating industrial waste
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