CN113636841A - Wood ceramic composite material - Google Patents
Wood ceramic composite material Download PDFInfo
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- CN113636841A CN113636841A CN202110959219.4A CN202110959219A CN113636841A CN 113636841 A CN113636841 A CN 113636841A CN 202110959219 A CN202110959219 A CN 202110959219A CN 113636841 A CN113636841 A CN 113636841A
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Abstract
The invention discloses a wood ceramic composite material, which is prepared by the following method: (1) preparing materials: mixing larch bark powder, modified palygorskite and ferrite solution, stirring to form a wood ceramic powder base, adding a binder, absolute ethyl alcohol and a carbon nitride precursor, continuously stirring, and drying to obtain a mixture; (2) molding: adding the mixture into a preheated mold, hot-press casting, demolding and drying to obtain a blank; (3) and (3) sintering: and sintering the blank in a high-temperature tube furnace to obtain the wood ceramic composite material. The wood ceramic composite material is simple and convenient to manufacture, low in raw material price and good in sewage treatment effect.
Description
Technical Field
The invention belongs to the technical field of ceramic processing, and particularly relates to a wood ceramic composite material.
Background
The wood ceramic is a new type porous carbon material made up by using wood or other wood material and impregnating it in thermosetting resin and vacuum-carbonizing it. The waste wood, crop straw and the like are made into the wood ceramic material, which not only has important significance for reducing environmental pollution, but also can realize resource recycling. The wood ceramic can be used as an adsorption material, a catalyst carrier material, a heat insulation material, a damping material and the like, and has the advantages of light weight, high strength, wear resistance, heat resistance, corrosion resistance and the like. The wood ceramic is used as an adsorbing material, namely the porous structure of the wood ceramic is utilized, so that the wood ceramic has a good adsorbing effect on substances such as heavy metal, phenol and the like in sewage treatment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a wood ceramic composite material.
A preparation method of a wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite powder by a sieve with 80-120 meshes, placing the palygorskite powder in a drying oven to be dried for 20-25h at the temperature of 40-60 ℃ to obtain palygorskite powder, and then mixing larch bark powder, palygorskite powder and 0.02-0.2mol/L ferrite solution according to the mass ratio of (1-5): 1: (5-15), stirring at 500-2000rpm for 10-20min to form a wood ceramic powder base, adding the binder and the absolute ethyl alcohol, continuing stirring for 40-60min, and drying at 40-70 ℃ for 20-30h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol is (7-21): (1-3): 1;
2. molding: adding the mixture into a preheated mold, hot-press molding at 80-120 deg.C and 40-80Mpa, demolding with vaseline as demolding agent, and drying at 100-120 deg.C for 30-40h to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 180 plus 200mL/min for protection, heating to 250 plus 300 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to 400 plus 450 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to the sintering temperature at the speed of 2-4 ℃/h, preserving heat for 3-5h, controlling the sintering temperature to 500 plus 550 ℃, then controlling the cooling speed to 25-50 ℃/h, cooling to 450 plus 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 60-80 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing (20-40) mL, extracting for 30-50min under the ultrasonic conditions of 30-45 ℃, 300-600W and 25-40kHz, filtering to obtain bark residues, and drying the bark residues in an oven at 40-70 ℃ for 48h to obtain larch bark powder.
The ferrous salt is one of ferrous sulfate and ferrous chloride.
The larch bark powder after procyanidin is extracted by the ethanol water solution still contains a large amount of polyphenols, in the ferrous salt solution, due to complexation of the polyphenols and ferrous ions, a large amount of ferrous ions are attached to the surface of the bark powder, and perform ion exchange with cations in a palygorskite structure in the solution, and the intercalation enters into the palygorskite structure layer, so that the connection tightness between the bark powder and the palygorskite is enhanced, the bark powder particles are uniformly coated by the palygorskite particles, the dispersibility of various particles in the solution is improved, the bending strength and the apparent porosity are improved, and the adsorption performance is further improved. On the other hand, in the weakly alkaline environment of the mixture, ferrous ions react to generate FeOOH, including alpha-FeOOH and gamma-FeOOH. In the temperature rising process of the sintering process, part of FeOOH generates magnetic Fe3O4. After the temperature is higher than 300 ℃, the alpha-FeOOH and the gamma-FeOOH lose crystal water to correspondingly generate nonmagnetic alpha-Fe2O3And magnetic gamma-Fe2O3Further, since the lignocellulosic material is carbonized to generate reducing gas such as CO, α -Fe is generated2O3Reducing into an active FeO intermediate, further reducing part of FeO into Fe simple substance, and the other part of FeO and Fe2O3Formation of magnetic Fe3O4. Endows the wood ceramic composite material with magnetism and is convenient to recycle.
The binder is thermosetting phenolic resin and/or hydroxypropyl methyl cellulose. Preferably, the binder is a mixture of thermosetting phenolic resin and hydroxypropyl methylcellulose, and the binder is a mixture of thermosetting phenolic resin and hydroxypropyl methylcellulose in a mass ratio of (2-5): 1.
The palygorskite wood ceramic composite material has various performances superior to those of non-wood ceramic composite materials. As the temperature rises, the larch bark, the palygorskite and the binder can be carbonized, soft amorphous carbon is generated after the larch bark is carbonized, the apparent porosity of the palygorskite-added wood ceramic is obviously improved compared with the wood ceramic without the palygorskite, and the bending strength and the adsorption performance are greatly improved. The larch bark and the binder are carbonized to form rich pores with different pore sizes, and the palygorskite loses zeolite water and crystal water in the structure by heat treatment in the sintering process so as to enhance the adsorption capacity of the palygorskite. Can be partially carbonized at a lower temperature, and part of the carbonized wood ceramic enters pores with larger pore diameters after being melted at a high temperature, and plays a supporting role on the pores after being cooled, so that the density of the prepared wood ceramic is improved, and the bending strength is increased.
The thermosetting phenolic resin has the characteristics of strong binding power, high temperature resistance, high carbon residue rate after pyrolysis and high carbon forming structural strength. Hydroxypropyl methylcellulose (HPMC) is a cellulose ether derivative, is readily soluble in water, and has excellent thickening ability, film-forming properties, dispersibility, and cohesiveness.
The content of lignin in larch bark is greater than that of cellulose and hemicellulose. The lignin is pyrolyzed at the temperature of 250-500 ℃ to generate a large amount of gas, coke is formed, and relatively stable amorphous carbon is formed after the temperature is higher than 500 ℃; the pyrolysis temperature of the cellulose is 325-375 ℃; the pyrolysis temperature of the hemicellulose is 225-350 ℃.
Tests show that when the thermosetting phenolic resin and the hydroxymethyl propyl cellulose are compounded to be used as a binder, the wood ceramic has better various performances. The analysis reason is as follows: when the thermosetting phenolic resin is used alone, the carbonization temperature is 400-500 ℃, and the adhesive strength is still higher at 300 ℃. The wood materials are carbonized at the carbonization temperature to generate porous materials, so that thermosetting phenolic resin is easy to permeate into holes, the mechanical strength of the wood ceramics can be improved after the wood ceramics are cooled, the holes are blocked, the specific surface area of the wood ceramics is reduced, and the adsorption performance is influenced. When the HPMC is used alone, the good dispersibility and film forming property of the HPMC enable the HPMC to be uniformly coated on the surface of the wood ceramic powder-based particles. The carbonization temperature of the HPMC is 280-300 ℃, the HPMC and lignin and hemicellulose in the wood material start to be pyrolyzed at the same time, and holes generated by carbonization of the wood material are not easy to block. But the cellulose is not pyrolyzed yet, and when the pyrolysis temperature of the cellulose is reached, the formed amorphous carbon is soft and loose due to the loss of the caking property of the HPMC, and the strength of the wood ceramic is low. The binder after the thermosetting phenolic resin and the HPMC are compounded participates in the pyrolysis process of the wood material in the whole process, the mechanical strength of the wood ceramic is enhanced, and due to the good dispersibility and film forming property of the HPMC, the blockage of the thermosetting phenolic resin to holes is reduced, the specific surface area of the wood ceramic is increased, and the adsorption performance is improved.
Preferably, the preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite powder by a sieve with 80-120 meshes, placing the palygorskite powder in a drying oven to be dried for 20-25h at the temperature of 40-60 ℃ to obtain palygorskite powder, and then mixing larch bark powder, palygorskite powder and 0.02-0.2mol/L ferrite solution according to the mass ratio of (1-5): 1: (5-15), stirring at 500-2000rpm for 10-20min to form a wood ceramic powder base, adding the binder, absolute ethyl alcohol and the carbon nitride precursor, continuing to stir for 40-60min, drying at 40-70 ℃ for 20-30h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is (7-21): (1-3): 1: (2-5);
2. molding: adding the mixture into a preheated mold, hot-press molding at 80-120 deg.C and 40-80Mpa, demolding with vaseline as demolding agent, and drying at 100-120 deg.C for 30-40h to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 180 plus 200mL/min for protection, heating to 250 plus 300 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to 400 plus 450 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to the sintering temperature at the speed of 2-4 ℃/h, preserving heat for 3-5h, controlling the sintering temperature to 500 plus 550 ℃, then controlling the cooling speed to 25-50 ℃/h, cooling to 450 plus 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The carbon nitride precursor is one of ethylenediamine-carbon tetrachloride, urea, dicyandiamide and melamine.
The carbon nitride precursor takes palygorskite as a template agent to generate graphite phase carbon nitride (g-C)3N4) And the specific surface area is large, so that the adsorption of degradation products and the photocatalytic reaction are facilitated. g-C3N4Has lower forbidden bandwidth and special electronic structure, and has excellent activity in the aspects of hydrogen production by visible light catalysis water, organic pollutant photocatalytic degradation and the like. The wood ceramic composite material has a porous structure and can treat pollutionThe dye can be effectively adsorbed, and can scatter and absorb electromagnetic wave to reduce reflected wave, and carbon nitride (g-C)3N4) The photocatalysis effect of (2) is synergistic with the pollutant, and the water treatment capacity is improved. Furthermore, due to g-C3N4Photocatalytic generation of OH and O2、H2O2And the like, the wood ceramic composite material also shows unusual antibacterial performance under visible light.
In the process of converting the carbon nitride precursor into carbon nitride, Fe elementary substance generated by converting ferrous ions is doped to g-C3N4The frame improves the visible light absorption performance of the material, and after a hole-electron pair is formed in the photocatalytic reaction process, the Fe simple substance is a good electron acceptor, so that electrons can be transferred rapidly, the recombination of the hole and the electrons is effectively reduced, the photocatalytic effect efficiency is further improved, and the degradation performance and the antibacterial property of the material are improved.
Further preferably, the preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: larch bark powder, modified palygorskite and 0.02-0.2mol/L ferrous salt solution are mixed according to the mass ratio of (1-5): 1: (5-15), stirring at 500-2000rpm for 10-20min to form a wood ceramic powder base, adding the binder, absolute ethyl alcohol and the carbon nitride precursor, continuing to stir for 40-60min, drying at 40-70 ℃ for 20-30h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is (7-21): (1-3): 1: (2-5);
2. molding: adding the mixture into a preheated mold, hot-press molding at 80-120 deg.C and 40-80Mpa, demolding with vaseline as demolding agent, and drying at 100-120 deg.C for 30-40h to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 180 plus 200mL/min for protection, heating to 250 plus 300 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to 400 plus 450 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to the sintering temperature at the speed of 2-4 ℃/h, preserving heat for 3-5h, controlling the sintering temperature to 500 plus 550 ℃, then controlling the cooling speed to 25-50 ℃/h, cooling to 450 plus 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The modified palygorskite is prepared by the following method:
crushing the palygorskite, sieving the palygorskite with a sieve of 80-120 meshes, and drying the palygorskite powder in a drying oven at 40-60 ℃ for 20-25h to obtain palygorskite powder; uniformly mixing organic acid and absolute ethyl alcohol, wherein the organic acid is formed by mixing caffeic acid and 5-hydroxybenzene-1, 2, 4-tricarboxylic acid according to the mass ratio of (1-3) to (3); then adding palygorskite powder, performing ultrasonic treatment at 60-70 ℃ for 200min and 20-35kHz and ultrasonic power of 200W and 300W, wherein the mass ratio of the palygorskite powder to the organic acid to the absolute ethyl alcohol is 1 (3-5) to (15-20); after the ultrasonic treatment is finished, adding 2-octyldodecylamine, stirring for 100-150min at 70-80 ℃ and 150rpm, wherein the mass ratio of the 2-octyldodecylamine to the absolute ethyl alcohol is 1 (15-20); filtering and drying to obtain pretreated palygorskite;
adding chitosan into 3-5 wt% acetic acid aqueous solution, stirring for 250-350min at 50-60 ℃ and 150-250rpm, wherein the mass ratio of the chitosan to the acetic acid aqueous solution is 1 (60-80); then adding the pretreated palygorskite and continuing stirring for 250-350min, wherein the mass ratio of the pretreated palygorskite to the chitosan is (8-15): 1; cooling to room temperature, adjusting pH to neutral, filtering, drying, pulverizing, and sieving with 80-120 mesh sieve.
The invention also provides a wood ceramic composite material prepared by the method.
The invention has the beneficial effects that: the wood ceramic composite material has good bending resistance, good sewage treatment effect and easy recovery; the preparation process is simple and convenient, and the cost is low.
Detailed Description
The raw materials used in the examples were as follows:
larch bark, available from yowa water treatment materials ltd, south of the river, specifications: 3-5 cm.
Palygorskite, purchased from a Lingshu county Populus tremula mineral powder processing plant, with an active substance content of 94%.
Ferrous sulfate, CAS number: 7720-78-7.
Thermosetting phenolic resin, available from flame-retardant materials Limited in Xinxiang city, product type: 2130, solid content is more than or equal to 80%, and 4# viscosity cup determination: 90-180 seconds/25 ℃.
Hydroxypropyl methylcellulose, CAS No.: 9004-65-3, available from Hunan Sheng Yuan New building materials Co., Ltd, product type: FQ-100000.
Chitosan, CAS No.: 9012-76-4, the degree of deacetylation is more than or equal to 95%, M.W.20000, and is purchased from Shenzhen, Lijing Biochemical technology Limited.
2-octyldodecylamine, CAS No.: 62281-06-5, available from Zhengzhou alpha chemical Co., Ltd.
5-hydroxybenz-1, 2, 4-tricarboxylic acid, CAS No.: 4961-03-9, available from Shenzhen ai Tuo chemical Co., Ltd.
Caffeic acid, CAS No.: 331-39-5, available from Shanghai Haohong biomedical science and technology, Inc.
Urea, available from Jiangsu Qinghe chemical Co., Ltd, CH4N2The content of O is more than or equal to 99.5 percent.
Example 1
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite with a 100-mesh sieve, placing the palygorskite powder in a drying oven for drying at 50 ℃ for 24 hours to obtain palygorskite powder, and then mixing the larch bark powder, the palygorskite powder and 0.1mol/L ferrous sulfate solution according to a mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding the binder and absolute ethyl alcohol, continuing stirring for 40min, drying in a drying oven at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol is 15: 2: 1;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is a thermosetting phenolic resin.
Example 2
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite with a 100-mesh sieve, placing the palygorskite powder in a drying oven for drying at 50 ℃ for 24 hours to obtain palygorskite powder, and then mixing the larch bark powder, the palygorskite powder and 0.1mol/L ferrous sulfate solution according to a mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding the binder and absolute ethyl alcohol, continuing stirring for 40min, drying in a drying oven at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol is 15: 2: 1;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is hydroxypropyl methyl cellulose.
Example 3
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite with a 100-mesh sieve, placing the palygorskite powder in a drying oven for drying at 50 ℃ for 24 hours to obtain palygorskite powder, and then mixing the larch bark powder, the palygorskite powder and 0.1mol/L ferrous sulfate solution according to a mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding the binder and absolute ethyl alcohol, continuing stirring for 40min, drying in a drying oven at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol is 15: 2: 1;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is thermosetting phenolic resin and hydroxypropyl methyl cellulose, and the mass ratio of the thermosetting phenolic resin to the hydroxypropyl methyl cellulose is 4: 1.
Example 4
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite with a 100-mesh sieve, placing the palygorskite powder in a drying oven for drying at 50 ℃ for 24 hours to obtain palygorskite powder, and then mixing the larch bark powder, the palygorskite powder and 0.1mol/L ferrous sulfate solution according to a mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding a binder, absolute ethyl alcohol and a carbon nitride precursor, continuously stirring for 40min, placing in a drying oven for drying at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is 15: 2: 1: 3;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is thermosetting phenolic resin and hydroxypropyl methyl cellulose, and the mass ratio of the thermosetting phenolic resin to the hydroxypropyl methyl cellulose is 4: 1.
The carbon nitride precursor is urea.
Comparative example 1
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: mixing larch bark powder and water according to a mass ratio of 3: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding the binder and absolute ethyl alcohol, continuing stirring for 40min, drying in a drying oven at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol is 15: 2: 1;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is a thermosetting phenolic resin.
Comparative example 2
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: crushing palygorskite, sieving the palygorskite with a 100-mesh sieve, placing the palygorskite powder in a drying oven for drying at 50 ℃ for 24 hours to obtain palygorskite powder, and mixing larch bark powder, palygorskite powder and water according to a mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding a binder, absolute ethyl alcohol and a carbon nitride precursor, continuously stirring for 40min, placing in a drying oven for drying at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is 15: 2: 1: 3;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is thermosetting phenolic resin and hydroxypropyl methyl cellulose, and the mass ratio of the thermosetting phenolic resin to the hydroxypropyl methyl cellulose is 4: 1.
The carbon nitride precursor is urea.
Example 5
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: mixing larch bark powder, modified palygorskite and 0.1mol/L ferrous sulfate solution according to the mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding a binder, absolute ethyl alcohol and a carbon nitride precursor, continuously stirring for 40min, placing in a drying oven for drying at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is 15: 2: 1: 3;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is thermosetting phenolic resin and hydroxypropyl methyl cellulose, and the mass ratio of the thermosetting phenolic resin to the hydroxypropyl methyl cellulose is 4: 1. The carbon nitride precursor is urea.
The modified palygorskite is prepared by the following method:
crushing the palygorskite, sieving the palygorskite with a 100-mesh sieve, and drying the palygorskite powder in a drying oven at 50 ℃ for 24 hours to obtain palygorskite powder; uniformly mixing organic acid and absolute ethyl alcohol, wherein the organic acid is formed by mixing caffeic acid and 5-hydroxybenzene-1, 2, 4-tricarboxylic acid according to the mass ratio of 2: 3; then adding palygorskite powder, and carrying out ultrasonic treatment at 67 ℃ for 180min at the ultrasonic frequency of 30kHz and the ultrasonic power of 250W, wherein the mass ratio of the palygorskite powder to the organic acid to the absolute ethyl alcohol is 1:3: 16; after the ultrasonic treatment is finished, adding 2-octyldodecylamine, and stirring for 120min at 73 ℃ and 120rpm, wherein the mass ratio of the 2-octyldodecylamine to the absolute ethyl alcohol is 1: 16; filtering and drying to obtain pretreated palygorskite;
adding chitosan into 3.5 wt% acetic acid aqueous solution, and stirring at 55 ℃ and 200rpm for 300min, wherein the mass ratio of the chitosan to the acetic acid aqueous solution is 1: 65; adding pretreated palygorskite and continuing stirring for 300min, wherein the mass ratio of the pretreated palygorskite to the chitosan is 9: 1; cooling to room temperature, adjusting pH to neutral, filtering, drying, pulverizing, and sieving with 100 mesh sieve. The COD adsorption of the wood ceramic composite obtained in example 5 was determined to be 75.93% by referring to the test method in test example 4.
Comparative example 3
The preparation method of the wood ceramic composite material comprises the following steps:
1. preparing materials: mixing larch bark powder, modified palygorskite and 0.1mol/L ferrous sulfate solution according to the mass ratio of 3: 1: 7, mixing, stirring at 1000rpm for 10min to form a wood ceramic powder base, adding a binder, absolute ethyl alcohol and a carbon nitride precursor, continuously stirring for 40min, placing in a drying oven for drying at 60 ℃ for 24h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is 15: 2: 1: 3;
2. molding: adding the mixture into a preheated mold, hot-press molding at 100 deg.C and 50Mpa, demolding with vaseline as demolding agent, and drying in a forced air drying oven at 105 deg.C for 36 hr to obtain a blank;
3. and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 200mL/min for protection, heating to 300 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, heating to a sintering temperature at the speed of 4 ℃/h, preserving heat for 4h, controlling the sintering temperature to be 550 ℃, then controlling the cooling speed to be 50 ℃/h, cooling to 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
The preparation method of the larch bark powder comprises the following steps:
pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 70 wt% ethanol water solution according to a feed-liquid ratio of 1 g: mixing 30mL of the above materials, extracting at 40 deg.C under 300W and 30kHz ultrasonic conditions for 35min, filtering to obtain bark residue, and oven drying the bark residue in a 60 deg.C oven for 48h to obtain Larix Gmelini bark powder.
The binder is thermosetting phenolic resin and hydroxypropyl methyl cellulose, and the mass ratio of the thermosetting phenolic resin to the hydroxypropyl methyl cellulose is 4: 1. The carbon nitride precursor is urea.
The modified palygorskite is prepared by the following method:
crushing the palygorskite, sieving the palygorskite with a 100-mesh sieve, and drying the palygorskite powder in a drying oven at 50 ℃ for 24 hours to obtain palygorskite powder; adding chitosan into 3.5 wt% acetic acid aqueous solution, and stirring at 55 ℃ and 200rpm for 300min, wherein the mass ratio of the chitosan to the acetic acid aqueous solution is 1: 65; adding palygorskite powder, and continuously stirring for 300min, wherein the mass ratio of the palygorskite powder to the chitosan is 9: 1; cooling to room temperature, adjusting pH to neutral, filtering, drying, pulverizing, and sieving with 100 mesh sieve. The COD adsorption of the wood ceramic composite obtained in comparative example 3 was determined to be 74.60% by reference to the test method in test example 4.
Test example 1
The sintered wood ceramic composite material is not all carbon, but essentially belongs to a carbon/carbon composite material or a carbon material, and the residual carbon rate is one of important performance indexes. The higher the carbon residue rate, the more environment-friendly the preparation process of the material is. And (3) respectively weighing the mass of the green body obtained after the step 2 molding in the examples and the comparative examples and the mass of the wood ceramic composite material obtained after the step 3 sintering, and testing the carbon residue rate of the wood ceramic composite material in each example.
In the formula: m1-the quality of the green body obtained after moulding;
M2-the quality of the wood ceramic composite material obtained after sintering.
TABLE 1 residual carbon rate of the Wood-ceramic composite Material
| Residual carbon ratio (%) | |
| Example 1 | 43 |
| Example 2 | 41 |
| Example 3 | 48 |
| Example 4 | 52 |
| Comparison ofExample 1 | 38 |
| Comparative example 2 | 48 |
The carbon residue rate of the palygorskite wood ceramic composite material is higher than that of the non-wood ceramic composite material, the compounding of the thermosetting phenolic resin and the HPMC is favorable for improving the carbon residue rate, and the carbon residue rate is improved after the carbon nitride precursor is added.
Test example 2
And (3) apparent porosity testing: the apparent porosity of the adsorbent is a main factor for determining the adsorption performance, and generally, the higher the apparent porosity, the better the adsorption performance.
The test method is as follows:
drying the wood ceramic composite material at 100 ℃ to constant weight, cooling in a dryer and weighing to obtain the mass M of the wood ceramic composite material in the air1(ii) a Putting the wood ceramic composite material into a beaker, vacuumizing and keeping for 5min, slowly injecting distilled water into the beaker within 5min until the wood ceramic composite material is completely submerged, keeping the vacuum for 5min, taking the beaker and the wood ceramic composite material out of the vacuum environment and standing for 30min, hanging the wood ceramic composite material at a balance weighing end by using fine metal wires to ensure that the wood ceramic composite material is completely submerged and does not contact with the wall and the bottom of the beaker containing the distilled water, and weighing the mass M of the wood ceramic composite material when the wood ceramic composite material is immersed in the distilled water2(ii) a Finally, taking out the wood ceramic composite material, carefully wiping redundant liquid drops on the surface of the wood ceramic composite material by using a towel saturated with distilled water, taking care not to suck out the liquid in the air holes, and immediately weighing to obtain M3。
TABLE 2 apparent porosity of the Wood-ceramic composites
| Apparent porosity (%) | |
| Example 1 | 30 |
| Example 2 | 29 |
| Example 3 | 36 |
| Example 4 | 41 |
| Comparative example 1 | 26 |
| Comparative example 2 | 37 |
Test example 3
The bending strength is tested according to GB/T4741-1999 ceramic material bending strength test method. The specific operation is as follows:
(1) drying the wood ceramic composite material in a drying oven at 110 ℃ to constant weight, and naturally cooling the wood ceramic composite material in a dryer to room temperature;
(2) the wood ceramic composite material is placed on a supporting knife edge of a bending strength testing machine, the length of the wood ceramic composite material outside the supporting knife edge is 10mm, the two supporting knife edges are ensured to be on the same plane and parallel to each other, and the loading knife edge is positioned in the middle of the two supporting knife edges;
(3) starting a bending strength testing machine, loading at a constant speed of 20N/s on average until the composite material is damaged, and recording the maximum load of the wood ceramic composite material when the composite material is damaged;
(4) the width and thickness of the fracture part of the wood ceramic composite material are measured by a vernier caliper to be accurate to 0.1 mm.
In the formula: f-maximum load, N;
l is the distance between two supporting knife edges, mm;
b, the width of the fracture of the wood ceramic composite material is mm;
h-the thickness of the end opening of the wood ceramic composite material, mm.
TABLE 3 flexural Strength of Wood-ceramic composites
| Bending strength (MPa) | |
| Example 1 | 4.78 |
| Example 2 | 4.53 |
| Example 3 | 5.32 |
| Example 4 | 5.90 |
| Comparative example 1 | 3.57 |
| Comparative example 2 | 5.12 |
Test example 4
Testing the treatment capacity of the wood ceramic composite material on urban sewage:
respectively crushing the wood ceramic composite materials of all the examples, sieving the crushed materials with a 200-mesh sieve, putting 0.5g of the crushed materials into a 150mL conical flask filled with 50mL of effluent of a secondary sedimentation tank of a sewage treatment plant, sealing the conical flask, putting the sealed conical flask into a 25 ℃ constant temperature oscillator, oscillating the sealed conical flask at 150rpm for 24 hours, then carrying out centrifugal separation to obtain supernatant, and carrying out suction filtration on the supernatant through a 0.45-micron filter membrane to obtain a treated water sample.
(1) Respectively testing the Chemical Oxygen Demand (COD) and NH of the water sample before treatment and the water sample after treatment of each wood ceramic composite material3N, concentration of total P, calculating adsorption rate. The specific test method is carried out according to CJ/T51-2018 urban wastewater quality standard test method: measuring COD by potassium dichromate spectrophotometry; ascorbic acid reduction molybdenum blue spectrophotometry to measure total P; NH measurement by adopting nano-reagent spectrophotometry3-N。
In the formula: rho1Before treatment, the concentration of the measured component of the water sample is mg/L;
ρ2the concentration of the measured component of the processed water sample is mg/L.
(2) The killing effect of the wood ceramic composite materials on heat-resistant escherichia coli groups in sewage is tested. The test is carried out according to an enzyme substrate method in CJ/T51-2018 urban wastewater quality standard test method, and the quantitative characterization of the heat-resistant Escherichia coli group in the wastewater treated by the wood ceramic composite material is carried out according to a 51-hole quantitative disc method. Strain: escherichia coli (ATCC 25922).
TABLE 4 treatment of municipal sewage with wood-ceramic composite
Compared with the wood ceramic without the palygorskite, the wood ceramic added with the palygorskite has obviously improved apparent porosity and greatly improved bending strength and adsorption performance. The larch bark and the binder are carbonized to form rich pores with different pore diameters, the palygorskite can lose zeolite water and crystal water in the structure by heat treatment in the sintering process so as to enhance the adsorption capacity of the palygorskite, the palygorskite can be partially carbonized at a lower temperature, part of the palygorskite enters pores with larger pore diameters after being melted at a high temperature, and the palygorskite plays a supporting role after being cooled, so that the density of the prepared wood ceramic is improved, and the bending strength is increased.
The addition of ferrous ions enhances the connection tightness of the bark powder and the palygorskite, ensures that the bark powder particles are uniformly coated by the palygorskite particles, improves the dispersibility of various particles in the solution, and is beneficial to improving the bending strength and the apparent porosity so as to improve the adsorption performance.
The binder after the thermosetting phenolic resin and the HPMC are compounded participates in the pyrolysis process of the wood material in the whole process, the mechanical strength of the wood ceramic is enhanced, and due to the good dispersibility and film forming property of the HPMC, the blockage of the thermosetting phenolic resin to holes is reduced, the specific surface area of the wood ceramic is increased, and the adsorption performance is improved.
After adding the carbon nitride precursor, the carbon nitride precursor generates graphite phase carbon nitride (g-C) by taking palygorskite as a template agent3N4) And the specific surface area is large, so that the adsorption of degradation products and the photocatalytic reaction are facilitated. On one hand, the physical adsorption effect of the wood ceramic porous structure on pollutants promotes the pollutants to be more rapidly adsorbed with g-C3N4Contacting; on the other hand, the g-C is enhanced due to the scattering and absorption of light by the porous structure3N4The light utilization efficiency of the catalyst can more effectively catalyze and degrade organic pollutants, anddue to g-C3N4Photocatalytic generation of OH and O2、H2O2And the like, and the antibacterial performance is achieved. In the process of converting the carbon nitride precursor into carbon nitride, Fe elementary substance generated by converting ferrous ions is doped to g-C3N4The frame improves the visible light absorption performance of the material, and after a hole-electron pair is formed in the photocatalytic reaction process, Fe simple substance can rapidly transfer electrons, effectively reduce the recombination of the hole and the electron, further improve the photocatalytic effect efficiency, and improve the degradation performance and antibacterial property of the material.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. The wood ceramic composite material is characterized by being prepared by the following method:
(1) preparing materials: larch bark powder, modified palygorskite and 0.02-0.2mol/L ferrous salt solution are mixed according to the mass ratio of (1-5): 1: (5-15), stirring at 500-2000rpm for 10-20min to form a wood ceramic powder base, adding the binder, absolute ethyl alcohol and the carbon nitride precursor, continuing to stir for 40-60min, drying at 40-70 ℃ for 20-30h to obtain a mixture, wherein the mass ratio of the wood ceramic powder base to the binder to the absolute ethyl alcohol to the carbon nitride precursor is (7-21): (1-3): 1: (2-5);
(2) molding: adding the mixture into a preheated mold, hot-press molding at 80-120 deg.C and 40-80Mpa, demolding with vaseline as demolding agent, and drying at 100-120 deg.C for 30-40h to obtain a blank;
(3) and (3) sintering: and putting the blank body into a high-temperature tube furnace, introducing nitrogen at the flow rate of 180 plus 200mL/min for protection, heating to 250 plus 300 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to 400 plus 450 ℃ at the speed of 1-2 ℃/min, preserving heat for 25-30min, heating to the sintering temperature at the speed of 2-4 ℃/h, preserving heat for 3-5h, controlling the sintering temperature to 500 plus 550 ℃, then controlling the cooling speed to 25-50 ℃/h, cooling to 450 plus 500 ℃, and naturally cooling along with the furnace to obtain the wood ceramic composite material.
2. The wood ceramic composite of claim 1, wherein the modified palygorskite is prepared by a method comprising:
crushing the palygorskite, sieving the palygorskite with a sieve of 80-120 meshes, and drying the palygorskite powder in a drying oven at 40-60 ℃ for 20-25h to obtain palygorskite powder; uniformly mixing organic acid and absolute ethyl alcohol, wherein the organic acid is formed by mixing caffeic acid and 5-hydroxybenzene-1, 2, 4-tricarboxylic acid according to the mass ratio of (1-3) to (3); then adding palygorskite powder, performing ultrasonic treatment at 60-70 ℃ for 200min and 20-35kHz and ultrasonic power of 200W and 300W, wherein the mass ratio of the palygorskite powder to the organic acid to the absolute ethyl alcohol is 1 (3-5) to (15-20); after the ultrasonic treatment is finished, adding 2-octyldodecylamine, stirring for 100-150min at 70-80 ℃ and 150rpm, wherein the mass ratio of the 2-octyldodecylamine to the absolute ethyl alcohol is 1 (15-20); filtering and drying to obtain pretreated palygorskite;
adding chitosan into 3-5 wt% acetic acid aqueous solution, stirring for 250-350min at 50-60 ℃ and 150-250rpm, wherein the mass ratio of the chitosan to the acetic acid aqueous solution is 1 (60-80); then adding the pretreated palygorskite and continuing stirring for 250-350min, wherein the mass ratio of the pretreated palygorskite to the chitosan is (8-15): 1; cooling to room temperature, adjusting pH to neutral, filtering, drying, pulverizing, and sieving with 80-120 mesh sieve.
3. The lignocellulosic composite of claim 1 wherein the binder is a thermosetting phenolic resin and/or hydroxypropyl methylcellulose.
4. The wood-ceramic composite material of claim 1, wherein the ferrous salt is one of ferrous sulfate and ferrous chloride.
5. The wood-ceramic composite material of claim 1, wherein the larch bark powder is prepared by a method comprising: pulverizing larch bark, sieving with a 100-mesh sieve, mixing with 60-80 wt% ethanol water solution according to a feed-liquid ratio of 1 g: (20-40) mL, extracting for 30-50min under the ultrasonic conditions of 30-45 ℃, 300-DEG F, 600W and 25-40kHz, filtering to obtain bark residues, and drying the bark residues in an oven at 40-70 ℃ for 48h to obtain larch bark powder.
6. The method of claim 1, wherein the carbon nitride precursor is one of ethylenediamine-carbon tetrachloride, urea, dicyandiamide, and melamine.
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| AU2005201974A1 (en) * | 2005-05-11 | 2006-11-30 | Xuegang Chen | Methods of processing palygorskite or sepiolite for prevention and treatment of algal blooms |
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| CN108658599A (en) * | 2018-06-29 | 2018-10-16 | 佛山市陵谐环保科技有限公司 | A kind of preparation method of porous bionical wooden class ceramics |
| CN110252379A (en) * | 2019-07-10 | 2019-09-20 | 西北师范大学 | A kind of preparation and application of palygorskite/graphite-phase carboritride composite material |
| CN111018036A (en) * | 2019-12-18 | 2020-04-17 | 安徽江赫科技有限公司 | Preparation method of composite domestic sewage treatment agent |
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| AU2005201974A1 (en) * | 2005-05-11 | 2006-11-30 | Xuegang Chen | Methods of processing palygorskite or sepiolite for prevention and treatment of algal blooms |
| CN102188952A (en) * | 2011-05-12 | 2011-09-21 | 西北师范大学 | Multifunctional palygorskite base adsorbing material |
| CN108658599A (en) * | 2018-06-29 | 2018-10-16 | 佛山市陵谐环保科技有限公司 | A kind of preparation method of porous bionical wooden class ceramics |
| CN110252379A (en) * | 2019-07-10 | 2019-09-20 | 西北师范大学 | A kind of preparation and application of palygorskite/graphite-phase carboritride composite material |
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