CN111760557A - Magnetic lignin graphene oxide composite aerogel - Google Patents
Magnetic lignin graphene oxide composite aerogel Download PDFInfo
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- CN111760557A CN111760557A CN202010616583.6A CN202010616583A CN111760557A CN 111760557 A CN111760557 A CN 111760557A CN 202010616583 A CN202010616583 A CN 202010616583A CN 111760557 A CN111760557 A CN 111760557A
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- 229920005610 lignin Polymers 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 27
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- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 6
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
- 231100000719 pollutant Toxicity 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims abstract description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000000352 supercritical drying Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000002431 foraging effect Effects 0.000 description 3
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- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000219000 Populus Species 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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Abstract
The invention provides a magnetic lignin/graphene oxide composite aerogel and a preparation method thereof. The preparation method reserves the advantages of high specific surface area, light weight, high adsorbability and the like of the phenolic aerogel, enhances the network structure, improves the brittleness problem, endows the phenolic aerogel with the characteristics of high surface activity, biodegradability and easy quick separation and absorption by a magnet, has the advantages of low cost, high strength, extremely high porosity and the like, and has wide application prospect when being used as an adsorbent for absorbing pollutants such as heavy metal ions, organic molecules and the like.
Description
Technical Field
The invention belongs to the field of aerogel material preparation, and particularly relates to a magnetic lignin graphene oxide composite aerogel.
Background
With the increasing world energy crisis and the worsening of the environment, people are increasingly aware of the importance of resource utilization and environmental protection, and the human world is facing severe resource, energy and environmental challenges. Therefore, more and more people are looking to utilize renewable biomass resources. Lignin is a natural high molecular organic compound widely existing in nature, the content of the lignin is second to that of cellulose, but only a small part of the lignin is effectively utilized. Therefore, the utilization of the lignin and the related products thereof has great economic value and environmental protection significance.
The aerogel is a novel nano porous material taking a solid as a framework and gas as a dispersion medium, and has the characteristics of low thermal conductivity, low density, high porosity, high adsorbability and the like. The biomass-based organic aerogel is low in cost and strong in environmental friendliness. The magnetic aerogel has aerogel performance and magnetic response performance, has wide research prospect, and particularly has unique advantages in the aspect of adsorbing pollutants such as heavy metal ions, organic molecules and the like.
However, in the prior art, the synthesized phenolic aerogel has low mechanical property, high brittleness, easy pulverization and poor degradability, does not conform to the concept of green chemistry, and greatly limits the application range of the phenolic aerogel. The traditional adsorbent is not easy to recover after being added into an adsorption system, and can cause secondary pollution.
Disclosure of Invention
The invention provides a magnetic lignin graphene oxide composite aerogel and a preparation method thereof, wherein lignin with a sulfonic acid group is used, so that the adsorption capacity of the aerogel is improved. The magnetic lignin graphene oxide composite aerogel provided has better mechanical property, good adsorption effect on heavy metal ions, organic molecules and other pollutants, easy separation and reutilization, and solves the problems of high cost and non-degradable base material of the traditional aerogel.
The preparation method of the magnetic lignin graphene oxide composite aerogel provided by the invention comprises the following steps:
1) dissolving modified lignin in a resorcinol solution, adding nano ferroferric oxide and graphene oxide, performing ultrasonic treatment, adding a formaldehyde solution, uniformly stirring, adding a catalyst, performing ultrasonic dispersion, stirring and dissolving to obtain a composite sol;
the modified lignin is obtained by extracting 40-60-mesh poplar wood chips with p-toluenesulfonic acid with the mass concentration of 80%, wherein the extraction temperature is 80 ℃, and the extraction time is 20 min.
The solid-to-liquid ratio of the added amount of the modified lignin to the resorcinol solution is 1:3-1: 10;
the mass ratio of the resorcinol to the formaldehyde is 1:2, and the mass ratio of the addition amount of the graphene oxide to the resorcinol is 1:10-1: 50;
the catalyst is any one of sodium carbonate, calcium hydroxide and sodium hydroxide.
2) Placing the composite sol in a closed container, and carrying out solution gel reaction under the condition of high-temperature water bath to obtain a gel primary material;
the water bath temperature is 70-90 ℃, and the water bath time is 4-8 h.
3) Aging the gel primary material, then placing the gel in a closed container, and soaking the gel in a solvent for solvent exchange to obtain a fully aged gel material;
the aging treatment is natural aging treatment or acid aging treatment;
one specific scheme is that 5 percent of dilute trifluoroacetic acid solution or acetic acid solution is used for aging treatment, the aging treatment time is 1-2 days, and the solvent is replaced every 12 hours;
the solvent used in the solvent exchange is deionized water or organic solvents such as acetone, ethanol and the like, the exchange time is 2-3 days, and the solvent is replaced every 12 hours.
4) Drying the gel to obtain a composite aerogel material;
the drying is carried out under the conditions of 40 ℃ and 10-12kPa2After supercritical drying or freezing completely, freeze-drying at-60 deg.C.
Compared with the prior art, the invention has the beneficial effects that:
(1) the aerogel prepared by the invention solves the problem of high brittleness of phenolic aerogel, has a better net structure and higher adsorbability and strength, and has magnetic performance, so that the phenolic aerogel is favorable for recovery and reuse. The raw materials adopted by the invention are easy to obtain and have lower price, the lignin is fully reused as a biomass energy source, and the aerogel retains the biodegradability of the biomass resource, is green and economic and belongs to an environment-friendly type.
(2) The capability of the aerogel for adsorbing heavy metal ions and organic dyes in wastewater is improved, and the magnetic nano ferroferric oxide particles can be uniformly attached to the modified lignin with a three-dimensional network structure through high-speed stirring.
(3) The addition of the magnetic nano ferroferric oxide particles changes the hydrophilicity and hydrophobicity of the aerogel and enhances the hydrophobicity of the aerogel.
Drawings
FIG. 1 is an infrared characterization image of the extracted modified lignin in an example of the present invention.
Fig. 2 is an infrared characterization image of an example synthetic magnetic aerogel of the present invention.
Detailed Description
The modified lignin and the graphene oxide can be used for strengthening the network structure of the aerogel and enhancing the strength of the magnetic aerogel, and the synthesized magnetic aerogel has a 3D (three-dimensional) porous structure with high specific surface area and high porosity, is high in surface activity, strong in adsorption capacity, good in hydrophobicity and excellent in magnetic performance.
The present invention will be described in detail with reference to examples.
Example 1:
1. compared with the common lignin, the modified lignin has more active groups such as hydroxyl groups in the molecular structure, and the content of the active groups is increased, so that the capability of the aerogel for adsorbing heavy metal ions in wastewater can be improved.
The specific preparation method of the modified lignin comprises the following steps:
accurately weighing 3g of modified lignin, placing the modified lignin in a beaker, dissolving the modified lignin in 100g of 10% resorcinol solution, then adding 20g of formaldehyde solution, then adding 0.5g of nano ferroferric oxide, 1g of graphene oxide and 0.5g of sodium carbonate, placing the beaker in an ultrasonic instrument for ultrasonic dispersion for 20min, stirring the mixture for 1.5h by using a stirrer, placing the composite sol in a closed container, and carrying out 80 ℃ constant temperature water bath for 4h to obtain a gel primary material;
2. placing the gel primary material in a beaker, soaking the gel primary material in a 5% diluted trifluoroacetic acid solution for aging treatment for 1 day, and replacing the solvent once every 8-12 h;
3. placing the gel in a beaker, soaking the gel in acetone for solvent exchange for 2 days, and replacing the solvent once every 12 h;
4. drying the gel at 40 deg.C under 10-12kPa with CO2And (5) performing supercritical drying to obtain the aerogel.
The obtained aerogel was subjected to a nitrogen adsorption test at 77K using a fully automatic specific surface area and pore size analyzer. From the measured adsorption isotherms, the BET test method was used to calculate the specific surface area, which is the specific surface area of the aerogel prepared in this example: 132.6625m2Per g, pore volume 0.7311cm3/g。
Compared with the aerogel without the graphene oxide, the mechanical property of the aerogel obtained by the method is obviously improved. When graphene oxide is not added, the aerogel is high in brittleness and easy to break during compression; after the graphene oxide is added, the aerogel is extruded for many times, and the surface morphology of the aerogel is still intact.
After a water drop is dropped on the surface of the aerogel, the water drop is in a substantially spherical state, has a contact angle of 120 degrees and is not wetted, and is a typical hydrophobic aerogel.
Example 2:
1. extracting modified lignin from poplar chips by using an acid solution mixed by p-toluenesulfonic acid and formic acid, and specifically comprising the following steps of:
accurately weighing 2g of modified lignin and 10g of resorcinol, stirring and dissolving, adding 100ml of deionized water and 20g of formaldehyde solution, stirring and dissolving, then adding 0.3g of nano ferroferric oxide, 0.5g of graphene oxide and 0.4g of sodium hydroxide, ultrasonically dispersing for 20min, stirring with a stirrer for 1h, and uniformly stirring the system to obtain a composite sol;
2. placing the composite sol in a high-temperature reaction kettle, sealing the reaction kettle, and placing the reaction kettle in a drying oven to react for 12 hours at the temperature of 80 ℃ to obtain a gel primary material;
3. placing the gel primary material at room temperature for natural aging treatment for 2 days; placing the gel in ethanol for solvent exchange for 3 days, and replacing the solvent every 24 h;
4. drying the gel at 40 deg.C under 10-12kPa with CO2And (5) performing supercritical drying to obtain the aerogel.
Example 3:
1. weighing 3g of sodium lignosulfonate, placing the sodium lignosulfonate in a beaker, dissolving the sodium lignosulfonate in 100g of 10% resorcinol solution, adding 20g of formaldehyde solution and 0.8g of graphene oxide, placing the mixture in an ultrasonic instrument for ultrasonic dispersion for 20min, adding 0.5g of sodium carbonate, stirring the mixture for 1.5h by using a magnetic stirrer to enable the mixture to react fully, placing the mixture in a closed container, and carrying out 80 ℃ constant-temperature water bath for 4h to obtain a gel primary material;
2. placing the gel primary material at room temperature for natural aging treatment for 2 days;
3. soaking the gel in acetone, performing solvent exchange for 2 days, and replacing the solvent every 12 h;
4. and drying the gel at normal pressure under the drying condition of 60 ℃ to obtain the aerogel.
5. The shrinkage of the aerogel obtained by the normal pressure drying mode is far larger than that of the aerogel obtained by supercritical drying, and the density reaches 1g/cm3Above, and aerogel specific surface area<10m2(ii) in terms of/g. Supercritical drying is therefore preferred for the aerogel drying mode.
Example 4:
1. extracting modified lignin from a pulp board by using p-toluenesulfonic acid, weighing 3g of lignin, placing the lignin in a beaker, dissolving the lignin in 100g of 10% resorcinol solution, adding 20g of formaldehyde solution, adding 0.5g of nano ferroferric oxide and 0.8g of graphene oxide, placing the beaker in an ultrasonic instrument for ultrasonic treatment for 20min to uniformly disperse lignin and other substances, adding 0.5g of sodium hydroxide serving as a catalyst, stirring the mixture for 1.5h by using a magnetic stirrer, placing the mixture in a closed container, and performing constant-temperature water bath at 80 ℃ for 4h to obtain a gel primary material;
2. placing the gel primary material in a 5% acetic acid solution water bath at 40 ℃ for aging treatment for 2 days, and replacing the solution every 24 hours;
3. soaking the gel in deionized water, performing solvent exchange for 2 days, and replacing the solvent every 12 h;
4. and (3) placing the sample in a refrigerator for 8h until the sample is completely frozen, and freeze-drying the gel under the freezing condition of-58 ℃ to obtain the aerogel.
Example 5
100ml of 100mg/L Pb were taken2+In a 250 ml conical flask, the solution is diluted with 0.1 mol.L-1HCL solution or 0.1 mol. L-1NaOH solution is used for adjusting the pH value of the solution, 30mg of the magnetic aerogel prepared in the embodiment 1 is added, the conical flask is placed in a shaking table to enable the aerogel to be uniformly dispersed in the solution, the solution is kept stand for 8 hours, magnetic separation and recovery are carried out under the action of an external loading magnetic field, and Pb in supernate after the adsorption of the aerogel is detected2+The concentration of the magnetic aerogel to Pb is obtained through calculation2+The adsorbed amount of (A) was 232.81mg/g, and the adsorbed amount was 71.82%.
The aerogel still keeps integrity and good mechanical strength after adsorption is finished, and can be recycled for recycling and absorption. The adsorption capacity of the aerogel decreases with increasing cycle times. But after repeating the adsorption five times, the aerogel is adsorbed to Pb2+The adsorption amount of (A) is still maintained at 60% or more.
The results of the tests showed that the aerogels prepared in examples 2 to 4 also had similar effects to those of example 1.
In addition to the above examples, the present invention is capable of other embodiments. The above embodiments are only exemplary embodiments, and are not intended to limit the present invention, and all technical solutions formed by equivalent substitutions or equivalent transformations are within the scope of the present invention.
Claims (10)
1. The magnetic lignin graphene oxide composite aerogel is characterized in that the preparation method of the magnetic lignin graphene oxide composite aerogel is as follows:
1) dissolving modified lignin in a resorcinol solution, adding nano ferroferric oxide and graphene oxide, performing ultrasonic treatment, adding a formaldehyde solution, uniformly stirring, adding a catalyst, performing ultrasonic dispersion, stirring and dissolving to obtain a composite sol;
wherein the modified lignin is extracted from wood chips by using p-toluenesulfonic acid;
2) placing the composite sol in a closed container, and carrying out solution gel reaction under the condition of high-temperature water bath to obtain a gel primary material;
3) aging the gel primary material, then placing the gel in a closed container, and soaking the gel in a solvent for solvent exchange to obtain a fully aged gel material;
4) and drying the gel to obtain the composite aerogel material.
2. The magnetic lignin-graphene oxide composite aerogel according to claim 1, wherein the solid-to-liquid ratio of the added amount of the modified lignin in 1) to the resorcinol solution is 1:3-1: 10.
3. The magnetic lignin graphene oxide composite aerogel according to claim 1, wherein the mass ratio of resorcinol to formaldehyde in 1) is 1:2, and the mass ratio of the added amount of graphene oxide to resorcinol is 1:10-1: 50.
4. The magnetic lignin-graphene oxide composite aerogel according to claim 1, wherein the catalyst in 1) is any one of sodium carbonate, calcium hydroxide and sodium hydroxide.
5. The magnetic lignin-graphene oxide composite aerogel according to claim 1, wherein the water bath temperature in 2) is 70-90 ℃, and the water bath time is 4-8 h.
6. The magnetic lignin-graphene oxide composite aerogel according to claim 1, wherein the aging treatment in 3) is natural aging treatment or acid aging treatment.
7. The magnetic lignin-graphene oxide composite aerogel according to claim 1, wherein the aging treatment is a natural aging treatment or an acid aging treatment.
8. The magnetic lignin-graphene oxide composite aerogel according to claim 7, wherein the acid aging treatment is performed by using a 5% diluted trifluoroacetic acid solution or acetic acid solution, the aging treatment time is 1-2 days, and the solvent is replaced every 12 h.
9. The magnetic lignin graphene oxide composite aerogel according to claim 1, wherein the drying in 4) is performed at 40 ℃ under 10-12kPa by CO2After supercritical drying or freezing completely, freeze-drying at-60 deg.C.
10. The application of the magnetic lignin graphene oxide composite aerogel described in claim 1 in preparation of adsorbents of heavy metal ions or organic molecular pollutants.
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