CN113750917B - High-elasticity high-temperature-resistant aerogel and preparation method thereof - Google Patents
High-elasticity high-temperature-resistant aerogel and preparation method thereof Download PDFInfo
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- CJVHHQFFITZLKX-UHFFFAOYSA-N (2-formylphenyl) methyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1C=O CJVHHQFFITZLKX-UHFFFAOYSA-N 0.000 claims abstract description 25
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
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- 238000001035 drying Methods 0.000 claims description 23
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- 238000009849 vacuum degassing Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
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- 238000010992 reflux Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 239000001301 oxygen Substances 0.000 description 4
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- 229920006395 saturated elastomer Polymers 0.000 description 3
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- OZRNSSUDZOLUSN-LBPRGKRZSA-N dihydrofolic acid Chemical compound N=1C=2C(=O)NC(N)=NC=2NCC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OZRNSSUDZOLUSN-LBPRGKRZSA-N 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001243 protein synthesis Methods 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a high-elasticity high-temperature-resistant aerogel and a preparation method thereof, and relates to the technical field of aerogel materials. The modified biochar is utilized to prepare aerogel through the steps of low-temperature baking, carbon dioxide microwave heating, ultrasonic treatment, static directional freeze drying, vacuum sublimation and the like in sequence, so that a porous three-dimensional network structure is formed, and the aerogel is endowed with oil absorption and high elasticity; the modified biochar is prepared from porous nano biochar, amino hydroxynaphthalene and methoxycarbonyl salicylaldehyde, and antibacterial groups and hydrophobic groups are introduced to jointly act to inhibit bacterial growth, so that the aerogel has antibacterial property. The high-elasticity high-temperature-resistant aerogel prepared by the invention has the effects of oil absorption, bacteriostasis and cyclic utilization.
Description
Technical Field
The invention relates to the technical field of aerogel materials, in particular to a high-elasticity high-temperature-resistant aerogel and a preparation method thereof.
Background
Once the carbon aerogel material appears, the carbon aerogel material is in great interest of researchers in countries around the world, and is different from other aerogels, the carbon aerogel has the characteristics of high temperature resistance, warmth retention and the like, but is deficient in bacteriostasis, high elasticity and the like.
The synthesis of such materials is currently generally based on sol-gel reactions of phenolic solutions. The preparation method has various problems that (1) phenolic resin nanoparticle units are obtained by sol reaction, and then the units are crosslinked by gelation reaction to form a three-dimensional nano network, and the formed nano carbon nanoparticle units are non-porous or quasi-non-porous. (2) The sol-gel reaction is usually carried out in a stationary closed vessel, which makes it difficult to rapidly conduct heat during polymerization, and dangerous explosion occurs during process amplification. (3) Most of the carbon aerogel precursors obtained after the sol-gel reaction have low mechanical strength and cannot bear strong capillary shrinkage force generated in the solvent drying process under normal pressure, so that the solvent is usually removed by adopting supercritical drying or freeze drying and other technologies which are complicated in process and high in cost. (4) Aerogel materials obtained through sol-gel reaction are generally in a block shape, and cannot meet the diversified requirements of application. Based on this, we have invented a high elasticity high temperature resistant aerogel.
Disclosure of Invention
The invention aims to provide a high-elasticity high-temperature-resistant aerogel and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the high-elasticity high-temperature-resistant aerogel is characterized by mainly comprising the following preparation steps of:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.2-0.3 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.005-0.01 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 70-75 ℃, and fermenting for 20-25 d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure into a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 2-4 min, heating to 250-300 ℃, preserving heat for 30-40 min, and cooling to room temperature to obtain hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 10-15 min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 5-10 min, starting microwaves, and activating for 15-25 min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in 4-6 times of ultrapure water of the modified biochar, stirring at 1000-1200 rpm for 30-40 min to obtain modified biochar hydrogel, and then placing the modified biochar hydrogel in an ultrasonic crusher for 1-3 h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 50-60 min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying at-45 ℃ and 0.01MPa for 50-60 hours to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.6-1.0 m, and the distance is 1-3 m.
Further, the heating speed in the step (2) is 15-25 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 100-110 ℃, adding amino hydroxynaphthalene with the mass of 0.7-0.9 times of that of the porous nano-charcoal, stirring for 15-25 min at 1000-1500 rpm, adding hydrazine hydrate with the mass of 1.7-1.85 times of that of the porous nano-charcoal and hydrochloric acid with the mass fraction of 20% with the mass of 2.0-2.1 times of that of the porous nano-charcoal, heating to 70-90 ℃, adding ethylene glycol with the mass of 44.5-44.7 times of that of the porous nano-charcoal, stirring and dissolving, heating to 120-130 ℃, reacting for 5-7 h, cooling in an ice water bath at 0 ℃ for 25-30 min, suction filtering, and drying at room temperature for 8-10 h to obtain the nitrified nano-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with 157-158 times of the nitrile biochar, heating to 120-130 ℃, stirring for 30-40 min, adding methoxycarbonyl salicylaldehyde with 0.8-1.0 times of the nitrile biochar, stirring at a speed of 100-120 rpm, carrying out reflux reaction for 1-3 h, cooling to room temperature, standing for 20-25 h, carrying out suction filtration, and drying at room temperature for 10-12 h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is-120 to-100 ℃, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (6) is the horizontal direction, and the frequency is 60-70 kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 60-100 parts of livestock manure, 45-70 parts of amino hydroxy naphthalene and 50-75 parts of methoxycarbonyl salicylaldehyde.
Compared with the prior art, the invention has the following beneficial effects:
The modified biochar is sequentially subjected to baking, microwave heating, ultrasonic treatment, static directional freeze drying, vacuum sublimation and the like to prepare the aerogel, so that the aerogel has the effects of high-efficiency oil absorption, bacteriostasis and cyclic utilization.
Firstly, preparing modified biochar from porous nano biochar, amino hydroxynaphthalene and methoxycarbonyl salicylaldehyde; after the hydroxyl of the amino hydroxynaphthalene is condensed with the hydroxyl on the surface of the porous nano charcoal, the amino of the amino hydroxynaphthalene is changed into hydrazine group, and the hydrazine group and the aldehyde group of methoxycarbonyl salicylaldehyde generate a Schiff base structure; the Schiff base group is similar to pteridine in dihydrofolate molecules in bacteria, and competes for inhibiting bacterial protein synthesis, preventing bacterial growth and reproduction, and enabling the aerogel to have antibacterial effect; methoxycarbonyl salicylaldehyde has an electron-withdrawing effect, improves the activity strength of Schiff base groups, enhances the antibacterial property of aerogel, and meanwhile, when bacterial cell membranes are broken, hydrophobic ester groups of methoxycarbonyl salicylaldehyde permeate into hydrophobic areas inside bacteria to change the permeability of the cell membranes, so that bacterial contents are escaped, and the antibacterial property of the aerogel is facilitated.
Secondly, taking pretreated livestock manure as a raw material, and baking at a low temperature by limiting oxygen to prepare a hydrophobic solid, so that the aerogel has an oil absorption effect; the porous nano biochar is prepared by heating carbon dioxide through microwaves, so that a mutually communicated micropore-mesopore-macropore multilayer structure is formed, oil can be diffused inwards from the surface of the porous nano biochar, and the oil absorption effect of aerogel is improved; after preparing modified biochar from porous nano biochar, preparing the modified biochar into gel, and then performing low-frequency ultrasonic treatment to change hydroxyl groups on the surface of the modified biochar into free radicals, so that organic matters in sewage can be degraded, aggregation of oxygen-enriched substances is reduced, bacterial reproduction is inhibited, and the antibacterial property of aerogel is facilitated; preparing the modified biochar into porous aerogel through static directional freeze drying and vacuum sublimation; the modified biochar generates ice crystals along the freezing direction, and simultaneously, as the electrostatic field direction is perpendicular to the freezing direction, part of the modified biochar deflects towards the electrostatic field direction to form dendrites, so that each layer is mutually entangled and crosslinked to form a three-dimensional reticular structure, the aerogel is endowed with higher elasticity, adsorbed oil can be extruded and recycled, and the effect of recycling the aerogel is realized.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the method in detail, and the method for testing each index of the high-elasticity high-temperature resistant aerogel prepared in the following examples is as follows:
Oil absorption: taking the examples and the comparative examples with the same size, completely immersing the examples and the comparative examples in an oil-water mixture, wherein the volume ratio of diesel oil to water in the oil-water mixture is 1:1, rapidly taking out and weighing the mixture after the mixture reaches a saturated state, and calculating the saturated adsorption quantity; saturated adsorption amount= (weight after adsorption-weight before adsorption)/weight before adsorption.
Circularity: 80 compression experiments were performed to measure the 80 th adsorption amount by taking the same size examples as the comparative examples.
Bacteriostasis: the antibacterial effect test is carried out by taking the examples with the same size and the comparative examples, and the method is referred to GB/T209444.3 evaluation of antibacterial property of textiles.
Example 1
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.2 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.005 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 70 ℃, and fermenting for 20d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 2min, heating to 250 ℃, preserving heat for 30min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 10min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 5min, starting microwaves, and activating for 15min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in 4 times of ultrapure water of the modified biochar, stirring at 1000rpm for 30min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 1h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 50min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 50 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.6m, and the distance is 1m.
Further, the heating speed in the step (2) is 15 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 100 ℃, adding amino hydroxynaphthalene with the mass of 0.7 times of that of the porous nano-charcoal, stirring at 1000rpm for 15min, adding hydrazine hydrate with the mass of 1.7 times of that of the porous nano-charcoal and hydrochloric acid with the mass fraction of 20% with the mass of 2.0 times of that of the porous nano-charcoal, heating to 70 ℃, adding ethylene glycol with the mass of 44.5 times of that of the porous nano-charcoal, stirring and dissolving, heating to 120 ℃, reacting for 5h, cooling for 25min in an ice water bath at 0 ℃, carrying out suction filtration, and drying at room temperature for 8h to obtain the nitrified nano-charcoal;
b. placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157 times of that of the nitrile biochar, heating to 120 ℃, stirring for 30min, adding methoxycarbonyl salicylaldehyde with the mass of 0.8 time of that of the nitrile biochar, stirring at the speed of 100rpm, carrying out reflux reaction for 1h, cooling to room temperature, standing for 20h, carrying out suction filtration, and drying at room temperature for 10h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 120 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (6) is the horizontal direction, and the frequency is 60kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 60 parts of livestock manure, 45 parts of amino hydroxy naphthalene and 50 parts of methoxycarbonyl salicylaldehyde.
Example 2
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.3 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.01 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 75 ℃, and fermenting for 25 days to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 4min, heating to 300 ℃, preserving heat for 40min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 15min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 10min, starting microwaves, and activating for 25min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in ultrapure water which is 6 times of the modified biochar, stirring at 1200rpm for 40min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 3h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 60min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying at-45 ℃ and 0.01MPa for 60 hours to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 1.0m, and the distance is 3m.
Further, the heating speed in the step (2) is 25 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 110 ℃, adding amino hydroxynaphthalene with the mass of 0.9 times of that of the porous nano-charcoal, stirring at 1500rpm for 25min, adding hydrazine hydrate with the mass of 1.85 times of that of the porous nano-charcoal and hydrochloric acid with the mass fraction of 20% with the mass of 2.1 times of that of the porous nano-charcoal, heating to 90 ℃, adding ethylene glycol with the mass of 44.7 times of that of the porous nano-charcoal, stirring and dissolving, heating to 130 ℃, reacting for 7h, cooling for 30min in an ice water bath at 0 ℃, carrying out suction filtration, and drying at room temperature for 10h to obtain the nitrified bio-charcoal;
b. placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with 158 times of the nitrile biochar, heating to 130 ℃, stirring for 40min, adding methoxycarbonyl salicylaldehyde with 1.0 times of the nitrile biochar, stirring at the speed of 120rpm, carrying out reflux reaction for 3h, cooling to room temperature, standing for 25h, carrying out suction filtration, and drying at room temperature for 12h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is-100 ℃, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (6) is the horizontal direction, and the frequency is 70kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 100 parts of livestock manure, 70 parts of amino hydroxy naphthalene and 75 parts of methoxycarbonyl salicylaldehyde.
Example 3
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 3min, heating to 276 ℃, preserving heat for 33min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 14min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 6min, starting microwaves, and activating for 18min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in ultrapure water which is 5.2 times of the modified biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 2.5h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the heating speed in the step (2) is 17 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 106 ℃, adding amino hydroxynaphthalene with the mass of 0.8 times of that of the porous nano-charcoal, stirring at 1398rpm for 20min, adding hydrazine hydrate with the mass of 1.79 times of that of the porous nano-charcoal, hydrochloric acid with the mass fraction of 2.06 times of that of the porous nano-charcoal being 20%, heating to 83 ℃, adding ethylene glycol with the mass of 44.61 times of that of the porous nano-charcoal, stirring and dissolving, heating to 127 ℃, reacting for 6.5h, cooling in an ice water bath at 0 ℃ for 28min, carrying out suction filtration, and drying at room temperature for 9h to obtain the nitrified bio-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157.6 times of that of the nitrile biochar, heating to 127 ℃, stirring for 36min, adding methoxycarbonyl salicylaldehyde with the mass of 0.91 times of that of the nitrile biochar, stirring at the speed of 116rpm, carrying out reflux reaction for 2h, cooling to room temperature, standing for 24h, carrying out suction filtration, and drying at room temperature for 11.5h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (6) is the horizontal direction, and the frequency is 65kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure, 52 parts of amino hydroxy naphthalene and 60 parts of methoxycarbonyl salicylaldehyde.
Comparative example 1
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in an oven at 105 ℃, drying for 6 hours, sealing and placing in a crucible, heating to 865 ℃, carbonizing for 60 minutes, cooling to room temperature, washing with 10% hydrochloric acid for 5 times, washing with deionized water for 9 times, placing in the oven, drying at 60 ℃ for 3 hours, and grinding into biochar capable of passing through a 100-mesh sieve;
(3) Placing the biochar into a ball mill for ball milling for 14min, wherein the ball-material ratio is 3:1, then placing the biochar into a quartz fixed bed reactor, introducing carbon dioxide for 6min, starting microwaves, and activating for 18min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in ultrapure water which is 5.2 times of the modified biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 2.5h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 106 ℃, adding amino hydroxynaphthalene with the mass of 0.8 times of that of the porous nano-charcoal, stirring at 1398rpm for 20min, adding hydrazine hydrate with the mass of 1.79 times of that of the porous nano-charcoal, hydrochloric acid with the mass fraction of 2.06 times of that of the porous nano-charcoal being 20%, heating to 83 ℃, adding ethylene glycol with the mass of 44.61 times of that of the porous nano-charcoal, stirring and dissolving, heating to 127 ℃, reacting for 6.5h, cooling in an ice water bath at 0 ℃ for 28min, carrying out suction filtration, and drying at room temperature for 9h to obtain the nitrified bio-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157.6 times of that of the nitrile biochar, heating to 127 ℃, stirring for 36min, adding methoxycarbonyl salicylaldehyde with the mass of 0.91 times of that of the nitrile biochar, stirring at the speed of 116rpm, carrying out reflux reaction for 2h, cooling to room temperature, standing for 24h, carrying out suction filtration, and drying at room temperature for 11.5h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (6) is the horizontal direction, and the frequency is 65kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure, 52 parts of amino hydroxy naphthalene and 60 parts of methoxycarbonyl salicylaldehyde.
Comparative example 2
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure into a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 3min, heating to 276 ℃, preserving heat for 33min, and cooling to room temperature to obtain biochar;
(3) Placing the biochar into an organic solution to prepare modified biochar;
(4) Soaking the modified biochar in ultrapure water which is 5.2 times of the modified biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 2.5h to obtain ultrasonic modified biochar;
(5) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the heating speed in the step (2) is 17 ℃/min.
Further, the preparation method of the modified biochar in the step (3) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 106 ℃, adding amino hydroxynaphthalene with the mass of 0.8 times of that of the porous nano-charcoal, stirring at 1398rpm for 20min, adding hydrazine hydrate with the mass of 1.79 times of that of the porous nano-charcoal, hydrochloric acid with the mass fraction of 2.06 times of that of the porous nano-charcoal being 20%, heating to 83 ℃, adding ethylene glycol with the mass of 44.61 times of that of the porous nano-charcoal, stirring and dissolving, heating to 127 ℃, reacting for 6.5h, cooling in an ice water bath at 0 ℃ for 28min, carrying out suction filtration, and drying at room temperature for 9h to obtain the nitrified bio-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157.6 times of that of the nitrile biochar, heating to 127 ℃, stirring for 36min, adding methoxycarbonyl salicylaldehyde with the mass of 0.91 times of that of the nitrile biochar, stirring at the speed of 116rpm, carrying out reflux reaction for 2h, cooling to room temperature, standing for 24h, carrying out suction filtration, and drying at room temperature for 11.5h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (4) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical die in the step (5) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (5) is the horizontal direction, and the frequency is 65kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure, 52 parts of amino hydroxy naphthalene and 60 parts of methoxycarbonyl salicylaldehyde.
Comparative example 3
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 3min, heating to 276 ℃, preserving heat for 33min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 14min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 6min, starting microwaves, and activating for 18min to obtain porous nano biochar;
(4) Soaking porous nano biochar in 5.2 times of ultrapure water of the porous nano biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 2.5h to obtain ultrasonic modified biochar;
(5) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the heating speed in the step (2) is 17 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the power of the ultrasonic crusher in the step (4) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical die in the step (5) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (5) is the horizontal direction, and the frequency is 65kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure.
Comparative example 4
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 3min, heating to 276 ℃, preserving heat for 33min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 14min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 6min, starting microwaves, and activating for 18min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking modified biochar in 5.2 times of ultrapure water of the modified biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, placing into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, placing into a cold source, directionally freezing, and applying an electrostatic field during freezing to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the heating speed in the step (2) is 17 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 106 ℃, adding amino hydroxynaphthalene with the mass of 0.8 times of that of the porous nano-charcoal, stirring at 1398rpm for 20min, adding hydrazine hydrate with the mass of 1.79 times of that of the porous nano-charcoal, hydrochloric acid with the mass fraction of 2.06 times of that of the porous nano-charcoal being 20%, heating to 83 ℃, adding ethylene glycol with the mass of 44.61 times of that of the porous nano-charcoal, stirring and dissolving, heating to 127 ℃, reacting for 6.5h, cooling in an ice water bath at 0 ℃ for 28min, carrying out suction filtration, and drying at room temperature for 9h to obtain the nitrified bio-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157.6 times of that of the nitrile biochar, heating to 127 ℃, stirring for 36min, adding methoxycarbonyl salicylaldehyde with the mass of 0.91 times of that of the nitrile biochar, stirring at the speed of 116rpm, carrying out reflux reaction for 2h, cooling to room temperature, standing for 24h, carrying out suction filtration, and drying at room temperature for 11.5h to obtain the modified biochar.
Further, the inner cavity of the cylindrical die in the step (5) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the application direction of the electrostatic field in the step (5) is the horizontal direction, and the frequency is 65kV/m.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure, 52 parts of amino hydroxy naphthalene and 60 parts of methoxycarbonyl salicylaldehyde.
Comparative example 5
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 3min, heating to 276 ℃, preserving heat for 33min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid into a ball mill for ball milling for 14min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid into a quartz fixed bed reactor, introducing carbon dioxide for 6min, starting microwaves, and activating for 18min to obtain porous nano biochar;
(4) Placing the porous nano biochar into an organic solution to prepare modified biochar;
(5) Soaking the modified biochar in ultrapure water which is 5.2 times of the modified biochar, stirring at 1137rpm for 34min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 2.5h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 56min, pouring into a cylindrical mold, and placing on a cold source for directional freezing to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the heating speed in the step (2) is 17 ℃/min.
Further, the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
Further, the preparation method of the modified biochar in the step (4) comprises the following steps:
a. Placing porous nano-charcoal into a stirrer, heating to 106 ℃, adding amino hydroxynaphthalene with the mass of 0.8 times of that of the porous nano-charcoal, stirring at 1398rpm for 20min, adding hydrazine hydrate with the mass of 1.79 times of that of the porous nano-charcoal, hydrochloric acid with the mass fraction of 2.06 times of that of the porous nano-charcoal being 20%, heating to 83 ℃, adding ethylene glycol with the mass of 44.61 times of that of the porous nano-charcoal, stirring and dissolving, heating to 127 ℃, reacting for 6.5h, cooling in an ice water bath at 0 ℃ for 28min, carrying out suction filtration, and drying at room temperature for 9h to obtain the nitrified bio-charcoal;
b. Placing the nitrile biochar into a round-bottom flask, adding absolute ethyl alcohol with the mass of 157.6 times of that of the nitrile biochar, heating to 127 ℃, stirring for 36min, adding methoxycarbonyl salicylaldehyde with the mass of 0.91 times of that of the nitrile biochar, stirring at the speed of 116rpm, carrying out reflux reaction for 2h, cooling to room temperature, standing for 24h, carrying out suction filtration, and drying at room temperature for 11.5h to obtain the modified biochar.
Further, the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
Further, the inner cavity of the cylindrical mold in the step (6) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure, 52 parts of amino hydroxy naphthalene and 60 parts of methoxycarbonyl salicylaldehyde.
Comparative example 6
The preparation method of the high-elasticity high-temperature-resistant aerogel mainly comprises the following preparation steps:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.24 times of the livestock manure, uniformly stirring, adding strains with the mass of 0.0078 times of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 73 ℃, and fermenting for 24d to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in an oven at 105 ℃, drying for 6 hours, sealing and placing in a crucible, heating to 865 ℃, carbonizing for 60 minutes, cooling to room temperature, washing with 10% hydrochloric acid for 5 times, washing with deionized water for 9 times, placing in the oven, drying at 60 ℃ for 3 hours, and grinding into biochar capable of passing through a 100-mesh sieve;
(3) Soaking biochar in 5.2 times of ultrapure water of the biochar, stirring at 1137rpm for 34min to obtain biochar hydrogel, placing into a vacuum drying oven, vacuum degassing at 100Pa and 40deg.C for 56min, pouring into a cylindrical mold, and placing into a cold source for directional freezing to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying for 56 hours at the temperature of minus 45 ℃ and the pressure of 0.01MPa to obtain the high-elasticity high-temperature-resistant aerogel.
Further, the auxiliary materials in the step (1) are one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
Further, the height of the compost in the step (1) is 0.8m, and the distance is 1.2m.
Further, the inner cavity of the cylindrical die in the step (3) is 10mm multiplied by 15mm; the temperature of the directional freezing device is 116 ℃ below zero, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
Further, the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 80 parts of livestock manure.
Effect example
The following table 1 shows the results of performance analysis of the high-elasticity high-temperature-resistant aerogel using examples 1 to 6 of the present invention and comparative examples.
TABLE 1
From comparison of experimental data of examples 1 to 3 with comparative example 6, it was found that hydrophobic solids were produced using low temperature baking and microwave heating while improving the pore structure to impart oil absorption to the aerogel; applying an electrostatic field in the directional freeze-drying process to crosslink the modified biochar with each other to form a three-dimensional network structure with high elasticity; amino hydroxynaphthalene and methoxycarbonyl salicylaldehyde are utilized to modify biochar, antibacterial groups and hydrophobic groups are introduced to inhibit bacterial growth under the synergistic effect, and simultaneously, the excessive hydroxyl groups are changed into free radicals by ultrasonic treatment, so that organic matters are degraded, and the antibacterial property of the aerogel is improved; from comparison of experimental data of examples 1 to 3 and comparative example 1, it can be found that if the biochar is prepared by conventional pyrolysis without low-temperature baking, moisture and oxygen cannot be replaced, so that the biochar does not have hydrophobicity, thereby affecting the oil absorption of aerogel; from the comparison of the experimental data of examples 1 to 3 and comparative example 2, it can be found that if the carbon dioxide microwave is not used to heat the biochar, a multi-layer pore structure can not be generated on the surface and in the interior, so that the oil can only adhere to the surface and can not diffuse into the interior, thereby affecting the oil absorption of the aerogel; from the comparison of the experimental data of examples 1 to 3 and comparative example 3, it can be found that the antibacterial groups cannot be introduced to destroy the cell growth without using the amino hydroxynaphthalene and methoxycarbonyl salicylaldehyde modified biochar, and meanwhile, the hydrophobic groups cannot be introduced to permeate into the bacterial hydrophobic area, so that the bacteriostasis of the aerogel is affected; from comparison of experimental data of examples 1 to 3 and comparative example 4, it can be found that if modified biochar is not subjected to ultrasonic treatment, redundant hydroxyl groups cannot be changed into free radicals, organic matters in sewage cannot be degraded, oxygen-enriched substances cannot be reduced, and microorganisms are bred, so that the bacteriostasis of aerogel is reduced; from comparison of experimental data of examples 1 to 3 and comparative example 5, it can be found that if an electrostatic field is not applied during the freezing process, the modified biochar cannot be guided to deflect, so that the interlayer modified biochar cannot be crosslinked with each other, and a three-dimensional network structure cannot be formed, so that the aerogel is not elastic, cannot rebound after multiple compressions, and cannot adsorb greasy dirt in sewage, so that the aerogel cannot achieve the effect of multiple recycling.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The preparation method of the high-elasticity high-temperature-resistant aerogel is characterized by mainly comprising the following preparation steps of:
(1) Collecting livestock manure, adding auxiliary materials with the mass of 0.2-0.3 times of that of the livestock manure, uniformly stirring, adding strains with the mass of 0.005-0.01 times of that of the livestock manure, uniformly stirring, composting in a pretreatment shed, controlling the fermentation temperature to be 70-75 ℃, and fermenting for 20-25 days to obtain pretreated livestock manure;
(2) Placing pretreated livestock manure in a fixed bed pyrolysis device, heating to 100 ℃ under nitrogen atmosphere, preserving heat for 2-4 min, heating to 250-300 ℃, preserving heat for 30-40 min, and cooling to room temperature to obtain a hydrophobic solid;
(3) Placing the hydrophobic solid in a ball mill for ball milling for 10-15 min, wherein the ball-material ratio is 3:1, then placing the hydrophobic solid in a quartz fixed bed reactor, introducing carbon dioxide for 5-10 min, starting microwaves, and activating for 15-25 min to obtain porous nano biochar;
(4) Placing porous nano-charcoal into a stirrer, heating to 100-110 ℃, adding amino hydroxynaphthalene with the mass of 0.7-0.9 times of that of the porous nano-charcoal, stirring at 1000-1500 rpm for 15-25 min, adding hydrazine hydrate with the mass of 1.7-1.85 times of that of the porous nano-charcoal and hydrochloric acid with the mass fraction of 20% with the mass of 2.0-2.1 times of that of the porous nano-charcoal, heating to 70-90 ℃, adding ethylene glycol with the mass of 44.5-44.7 times of that of the porous nano-charcoal, stirring and dissolving, heating to 120-130 ℃, reacting for 5-7 h, cooling in an ice water bath at 0 ℃ for 25-30 min, suction filtering, and drying at room temperature for 8-10 h to obtain the nitrilized bio-charcoal; placing the nitrile biochar in a round-bottom flask, adding absolute ethyl alcohol with the mass of 157-158 times of that of the nitrile biochar, heating to 120-130 ℃, stirring for 30-40 min, adding methoxycarbonyl salicylaldehyde with the mass of 0.8-1.0 times of that of the nitrile biochar, stirring at a speed of 100-120 rpm, carrying out reflux reaction for 1-3 h, cooling to room temperature, standing for 20-25 h, carrying out suction filtration, and drying at room temperature for 10-12 h to obtain modified biochar;
(5) Soaking the modified biochar in 4-6 times of ultrapure water of the modified biochar, stirring at 1000-1200 rpm for 30-40 min to obtain modified biochar hydrogel, and placing the modified biochar hydrogel in an ultrasonic crusher for 1-3 h to obtain ultrasonic modified biochar;
(6) Placing the ultrasonic modified biochar into a vacuum drying oven, vacuum degassing at 100Pa and 40 ℃ for 50-60 min, pouring into a cylindrical mold, placing on a cold source for directional freezing, and applying an electrostatic field in the freezing process to obtain frozen solid; and (3) placing the frozen solid in a freeze dryer, and performing vacuum freeze drying at-45 ℃ and 0.01MPa for 50-60 hours to obtain the high-elasticity high-temperature-resistant aerogel.
2. The method for preparing the high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the auxiliary material in the step (1) is one or more of leaves, straw or dry soil; the strain is one or more of cellulose, catabolic enzyme, protease, depeptidase or amylase.
3. The method for preparing the high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the height of the compost in the step (1) is 0.6-1.0 m, and the interval is 1-3 m.
4. The method for preparing the high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the heating speed in the step (2) is 15-25 ℃/min.
5. The method for preparing a high-elasticity high-temperature resistant aerogel according to claim 1, wherein the flow rate of the carbon dioxide in the step (3) is 0.1L/min; the microwave frequency was 900W.
6. The method for preparing a high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the power of the ultrasonic crusher in the step (5) is 600W, the frequency is 40kHz, and the temperature is 20 ℃.
7. The method for producing a highly elastic high temperature resistant aerogel according to claim 1, wherein the cavity size of the cylindrical mold in step (6) is 10mm x 15mm; the temperature of the directional freezing device is-120 to-100 ℃, the cold source is the combination of liquid nitrogen and ethanol, and the freezing direction is vertical upwards.
8. The method for preparing a high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the application direction of the electrostatic field in the step (6) is a horizontal direction, and the frequency is 60-70 kV/m.
9. The preparation method of the high-elasticity high-temperature-resistant aerogel according to claim 1, wherein the high-elasticity high-temperature-resistant aerogel prepared by the preparation method of the high-elasticity high-temperature-resistant aerogel comprises the following raw materials in parts by weight: 60-100 parts of livestock manure, 45-70 parts of amino hydroxynaphthalene and 50-75 parts of methoxycarbonyl salicylaldehyde.
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