CN113636536B - Method for co-producing biomethane by hydrothermal carbonization of wood fiber wastes - Google Patents
Method for co-producing biomethane by hydrothermal carbonization of wood fiber wastes Download PDFInfo
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Abstract
The invention discloses a method for co-producing biomethane by hydrothermal carbonization of wood fiber wastes, which is characterized in that choline chloride and ferric chloride are added into water to form an autocatalytic dissolution system, so that the hydrothermal carbonization reaction temperature is obviously reduced, the process energy consumption is reduced, the specific surface area of hydrothermal carbon can be increased, and the adsorption capacity of the hydrothermal carbon is improved. Meanwhile, while solid carbon is obtained, acid-rich micromolecule liquid products are generated, and the products are inoculated into anaerobic fermentation strains to quickly generate biological methane. Compared with other synergistic methods such as acid-base pretreatment and the like, the method has the advantages of simple process, better sustainability and larger application potential.
Description
Technical Field
The invention belongs to the field of organic solid waste resource utilization, and particularly relates to a method for co-producing biomethane by hydrothermal carbonization of wood fiber waste.
Background
Hydrothermal carbonization is an important way for recycling organic solid wastes, is widely concerned due to the advantages of mild reaction conditions, strong raw material adaptability and the like, and hydrothermal carbon has proved to have the characteristics of high carbon content, low oxygen content, strong hydrophobicity, high calorific value, energy density and the like, and can be used in the fields of carbon fixation, soil improvement, solid fuels, adsorption, catalysis and the like. Organic solid waste that has been currently reported for hydrothermal carbonization and carbonization temperatures thereof are: mushroom dregs, such as edible mushroom dregs 200-250 ℃ (CN 104312590A), biogas dregs 200-240 ℃ (CN 111847938A), algae dregs algae mud 160-220 ℃ (CN 105668564A), vegetable and fruit peel, such as cane shoot 150-350 ℃ (CN 106044745B), shaddock peel 230 ℃ (CN 112547009A), shinyleaf yellowhorn 200-240 ℃ (CN 106044745B), longan core 160-320 ℃ (CN 10596503962A), watermelon peel 170 ℃ (CN 109503526B), sludge and feces, such as municipal sludge 200-260 ℃ (CN 10987676770A), municipal refuse 250-400 ℃ (CN 10610667461B), livestock and poultry feces 200-350 ℃ (CN 110523767A), and wood fiber, such as Chinese hemp stalk 74747409A, chinese soapberry dregs CN 200-200 ℃ (CN 1101947095B), chinese hemp stalk 1101105241160 ℃ (CN 11012A), wheat straw 112112220-11269290 ℃ and CN 110753220 (CN 1117095B). Although the hydrothermal reaction temperature of the prior art is greatly reduced compared with that of the prior art for preparing the carbon by pyrolysis (300-800 ℃), the carbonization temperature is still higher, and the reduction of the energy consumption in the carbonization process has great significance for improving the economic efficiency of resource utilization of the organic solid waste. Chinese patent CN109628499A discloses a high-temperature hydrothermal method for improving the biogas production of garden wastes, which is to pretreat garden waste raw materials or/and other lignocellulose biomass by using water and choline chloride as reaction solutions, remove lignin to the maximum extent under the condition of retaining fermentable sugars such as cellulose, hemicellulose and the like, and obviously improve the fermentation efficiency of biogas of the garden wastes, thereby realizing the high-efficiency energy conversion of the garden wastes, but does not relate to the hydrothermal carbonization of organic solid wastes.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for preparing hydrothermal carbon by hydrothermal carbonization of wood fiber wastes.
The second purpose of the invention is to provide the application of the method for preparing the hydrothermal carbon by the hydrothermal carbonization of the wood fiber wastes in the preparation of the biomethane
The above purpose of the invention is realized by the following technical scheme:
a method for preparing hydrothermal carbon by hydrothermal carbonization of wood fiber wastes is characterized by mixing choline chloride and water according to a mass ratio of 2-5: 10 to 20g/ml is mixed with agricultural and forestry waste and FeCl is added 3 Reacting for 3-9 h at 140-180 ℃ in a high-pressure reaction kettle; after the reaction is finished, carrying out solid-liquid separation, and drying the solid product to obtain the agricultural and forestry waste hydrothermal carbon.
The choline chloride-water-ferric chloride-based autocatalytic dissolution system provided by the invention can realize high-efficiency carbonization of the lignocellulose component at low temperature, remarkably reduce the carbonization reaction temperature, reduce the process energy consumption, improve the specific surface area of the hydrothermal carbon and improve the adsorption capacity of the hydrothermal carbon. Meanwhile, while solid carbon is obtained, acid-rich micromolecule liquid products are generated, and further, biological methane can be generated through rapid anaerobic fermentation.
Preferably, said FeCl 3 The addition amount of the catalyst is 1-4 g/g material.
Further preferably, the FeCl 3 The addition amount of the catalyst is 2-4 g/g material.
Preferably, the solid-to-liquid ratio is 1.
Preferably, the mass ratio of the choline chloride to the water is 2-3.
Preferably, the reaction is carried out at 160-180 ℃ for 3-5.
Preferably, the stirring speed of the high-pressure reaction kettle is 200-400 rpm.
Further preferably, the solid-liquid ratio is 1.
The invention also provides application of any one of the methods in preparation of biomethane, wherein liquid products obtained after solid-liquid separation are inoculated into anaerobic fermentation strains for biological fermentation to obtain biomethane.
Compared with the prior art, the invention has the following beneficial effects:
according to the hydrothermal carbon preparation method, choline chloride and ferric chloride are added into water to form an autocatalytic dissolution system, so that the carbonization reaction temperature can be remarkably reduced, the process energy consumption is reduced, the specific surface area of the hydrothermal carbon can be increased, and the adsorption capacity of the hydrothermal carbon is improved. Meanwhile, while solid carbon is obtained, acid-rich micromolecule liquid products are generated, and the products are inoculated into anaerobic fermentation strains to quickly generate biological methane. Compared with other synergistic methods such as acid-base pretreatment and the like, the method has the advantages of simple process, better sustainability and larger application potential.
Detailed Description
The present invention will be further described with reference to the following specific examples, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Mixing choline chloride and water according to a mass ratio of 5:1, adding garden waste according to a solid-liquid ratio of 1 to 20 (g/ml), and adding FeCl 3 2g/g of catalyst, the reaction conditions in a high-pressure reaction kettle are 140-9 h, the stirring speed of the reaction kettle is 200rpm, after the reaction is finished, the solid-liquid mixture is filtered and separated, and the solid product is dried to obtain the gardenThe waste hydrothermal carbon has an adsorption capacity of 118mg/g for methylene blue, the same raw materials are used for preparing carbon under the conventional hydrothermal condition (only pure water and the same reaction conditions are used), the adsorption capacity of the methylene blue is only 21mg/g, the same raw materials are directly pyrolyzed to prepare carbon (800-1 h in a tubular furnace and under the nitrogen flow), and the adsorption capacity of the methylene blue is 98mg/g. Liquid products produced in the conventional hydrothermal carbon preparation process are rich in furan or benzene ring compounds such as furfural, 5-hydroxymethylfurfural and coumarin, and need to be subjected to complex directional catalytic reforming for utilization, a pyrolytic carbon liquid product is bio-oil with more complex components, the liquid product obtained by the method is rich in small molecular acid, wherein acetic acid is 5.4g/l, formic acid is 3.5g/l, and levulinic acid is 1.5g/l, the product is easier to be directly and mildly converted by microorganisms, anaerobic fermentation strains are directly inoculated according to a method reported in the literature (Bioresource. Technol.2018,55, 205-212), and the biomethane can be obtained after fermentation for 5 hours.
Example 2
Mixing choline chloride and water according to a mass ratio of 3:1, adding garden waste according to a solid-liquid ratio of 1 to 15 (g/ml), and adding FeCl 3 The method comprises the following steps of preparing 3g/g of a material by using a catalyst in a high-pressure reaction kettle under the reaction condition of 160-5 h, stirring the reaction kettle at the rotating speed of 400rpm, filtering and separating a solid-liquid mixture after the reaction is finished, drying a solid product to obtain the hydrothermal carbon of the garden waste, wherein the adsorption capacity of the carbon to methylene blue is 141mg/g, the same raw materials are used for preparing the carbon under the conventional hydrothermal condition (only pure water and the other reaction conditions are the same), the adsorption capacity of the methylene blue is only 34mg/g, the same raw materials are directly pyrolyzed to prepare the carbon (a tubular furnace is 800-1 h, nitrogen flow), and the adsorption capacity of the methylene blue is 98mg/g. Liquid products produced in the conventional hydrothermal carbon preparation process are rich in furan or benzene ring compounds such as furfural, 5-hydroxymethylfurfural and coumarin, and need complicated directional catalytic reforming for utilization, and a pyrolytic carbon liquid product is bio-oil with more complicated components, the liquid product obtained by the method is rich in small molecular acid, wherein the acetic acid is 6.2g/l, the levulinic acid is 1.8g/l, the formic acid is 0.6g/l, and the glycolic acid is 0.2g/l, so that the product is easier to be directly and mildly converted by microorganisms, anaerobic fermentation strains are directly inoculated according to a method reported in the literature (Bioresource, technol.2018,55, 205-212), and the biomethane can be obtained after fermentation for 3h.
Example 3
Choline chloride and water are mixed according to the mass ratio of 2:1, adding garden waste according to a solid-liquid ratio of 1 to 10 (g/ml), and adding FeCl 3 4g/g of catalyst is put in a high-pressure reaction kettle under the reaction condition of 180-3 h, the stirring speed of the reaction kettle is 300rpm, after the reaction is finished, solid-liquid mixture is filtered and separated, a solid product is dried to obtain the hydrothermal carbon of the garden waste, the adsorption quantity of the carbon to methylene blue is 169mg/g, the same raw materials are used for preparing the carbon under the conventional hydrothermal condition (pure water, the other reaction conditions are the same), the adsorption quantity of the methylene blue is only 40mg/g, the same raw materials are directly pyrolyzed to prepare the carbon (a tubular furnace is 800-1 h, nitrogen flow), and the adsorption quantity of the methylene blue is 98mg/g. Liquid products produced in the conventional hydrothermal carbon preparation process are rich in furan or benzene ring compounds such as furfural, 5-hydroxymethylfurfural and coumarin, and need complicated directional catalytic reforming for utilization, and a pyrolytic carbon liquid product is bio-oil with more complicated components, the liquid product obtained by the method is rich in small molecular acid, wherein 10.4g/l of acetic acid, 3.5g/l of levulinic acid, 0.8g/l of formic acid and 0.7g/l of glycolic acid are easy to directly and mildly convert by microorganisms, anaerobic fermentation strains are directly inoculated according to a method reported in the literature (Bioresource, technol.2018,55, 205-212), and biomethane can be obtained after 2h of fermentation.
Comparative example 1
The effects of different treatment conditions on the elemental composition, BET specific surface area and total pore volume of the samples were compared. Wherein GW: garden waste; GHC op : choline chloride/water/FeCl 3 The system has a solid-liquid ratio of 1 to 10g/ml, and the mass ratio of choline chloride to water is 2 3 The adding amount of the catalyst is 4g/g of material, and the reaction condition is that the reaction is carried out for 3 hours at 180 ℃; reference GHC op The temperature, time and solid-to-liquid ratio conditions are that GHC-1 is a single hydrothermal system; GHC-2 is choline chloride/water system.
The results are shown in Table 1, along with untreated material GW and carbon GHC-1 from a single hydrothermal system and carbon GHC-2,GHC from a choline chloride/water system op Under the condition, the content, specific surface area and total pore volume of the charcoal element of the biological charcoal are greatly improved, which is beneficial to improving the adsorption capacity.
Table 1 elemental composition, BET specific surface area and Total pore volume of the samples
Comparative example 2
By comparing the influence of different metal salt promoters on the adsorption performance of the hydrothermal carbon. Conditions are as follows: 1g/g of garden waste, wherein the solid-liquid ratio is 1. The results show that when FeCl is used 3 The adsorption capacity of the prepared biochar to methylene blue is maximum when the temperature is 180 ℃ and 5 hours.
TABLE 2 influence of various metal salt co-catalysts on adsorption performance of hydrothermal charcoal
The above examples and comparative examples prove that an autocatalytic dissolution system is formed by adding choline chloride-ferric chloride into water, the temperature of the hydrothermal carbonization reaction of the wood fiber raw material is remarkably reduced, the carbonization efficiency of garden waste is improved, the problems of high energy consumption, poor carbon adsorption capacity and the like of the existing hydrothermal carbonization technology are solved, and meanwhile, the hydrothermal carbonization liquid product can be quickly started to generate the biological methane by being inoculated with an anaerobic fermentation strain, so that the application prospect is wide.
Claims (3)
1. A method for preparing hydrothermal carbon by hydrothermal carbonization of wood fiber wastes is characterized by mixing choline chloride and water according to a mass ratio of 2 3 Reacting for 3 hours at 180 ℃ in a high-pressure reaction kettle; after the reaction is finished, carrying out solid-liquid separation, and drying a solid product to obtain the agricultural and forestry waste hydrothermal carbon; the FeCl 3 The amount of catalyst added was 4g/g of batch.
2. The method of claim 1, wherein the stirring speed of the autoclave is 200 to 400rpm.
3. The method of any one of claims 1 to 2, wherein the liquid product after solid-liquid separation is inoculated into an anaerobic fermentation strain for biological fermentation to obtain the biomethane.
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| CN105883753A (en) * | 2016-06-03 | 2016-08-24 | 浙江科技学院 | Preparation method and application of bamboo shoot shell biochar |
| CN106065332A (en) * | 2016-06-03 | 2016-11-02 | 浙江科技学院 | A kind of method and the application that utilize pomelo peel hydro-thermal carbonization to prepare charcoal |
| CN109628499A (en) * | 2019-01-16 | 2019-04-16 | 中国科学院广州能源研究所 | It is a kind of for improving the high temperature hydrothermal method of garden waste generation combustion gas |
| CN110358599A (en) * | 2019-07-15 | 2019-10-22 | 北京科技大学 | A kind of agriculture and forestry organic waste material dealkalize charing method based on hydro-thermal reaction |
| CN110510613A (en) * | 2019-08-29 | 2019-11-29 | 东北大学 | A kind of preparation method of two-dimensional metallic carbonitride MXene |
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| US10549997B2 (en) * | 2016-11-07 | 2020-02-04 | Council Of Scientific & Industrial Research | Process for the production of graphene sheets with tunable functionalities from seaweed promoted by deep eutectic solvents |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105883753A (en) * | 2016-06-03 | 2016-08-24 | 浙江科技学院 | Preparation method and application of bamboo shoot shell biochar |
| CN106065332A (en) * | 2016-06-03 | 2016-11-02 | 浙江科技学院 | A kind of method and the application that utilize pomelo peel hydro-thermal carbonization to prepare charcoal |
| CN109628499A (en) * | 2019-01-16 | 2019-04-16 | 中国科学院广州能源研究所 | It is a kind of for improving the high temperature hydrothermal method of garden waste generation combustion gas |
| CN110358599A (en) * | 2019-07-15 | 2019-10-22 | 北京科技大学 | A kind of agriculture and forestry organic waste material dealkalize charing method based on hydro-thermal reaction |
| CN110510613A (en) * | 2019-08-29 | 2019-11-29 | 东北大学 | A kind of preparation method of two-dimensional metallic carbonitride MXene |
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