CN112063387B - Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof - Google Patents
Lignosulfonate-phenolic resin-based carbon aerogel microsphere and preparation method and application thereof Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 81
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 74
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 34
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 27
- 239000002689 soil Substances 0.000 claims abstract description 27
- 150000002989 phenols Chemical class 0.000 claims abstract description 18
- -1 aldehyde compound Chemical class 0.000 claims abstract description 17
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- 238000006243 chemical reaction Methods 0.000 claims description 31
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- 235000019483 Peanut oil Nutrition 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
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- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
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- 230000001681 protective effect Effects 0.000 claims description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 2
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 2
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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 6
- 239000003054 catalyst Substances 0.000 description 6
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- 238000000034 method Methods 0.000 description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000003911 Arachis Nutrition 0.000 description 1
- 241000220438 Arachis Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
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- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种木质素磺酸盐‑酚醛树脂基炭气凝胶微球及其制备方法和应用。将木质素磺酸盐、酚类化合物、醛类化合物及多胺类化合物溶于水中，得到水相；将水相与非水溶性油相混合，在搅拌条件下进行聚合反应，聚合反应完成后，过滤分离，所得固体产物经过水封老化、干燥，得到干凝胶微球；所述干凝胶微球经过炭化处理，洗涤，即得具有宏观粒度小，微观孔结构发达，比表面积大，且含有极性基团和类分子印迹特异结构的木质素磺酸盐‑酚醛树脂基炭气凝胶微球，该炭气凝胶微球材料可以用于重金属的选择性高效吸附，特别适合用于重金属污染土壤修复，且炭气凝胶微球的制备原料来源广泛、成本低廉，有利于大规模生产和应用。The invention discloses a lignosulfonate-phenolic resin-based carbon aerogel microsphere and a preparation method and application thereof. Dissolve lignosulfonate, phenolic compound, aldehyde compound and polyamine compound in water to obtain an aqueous phase; mix the aqueous phase with the water-insoluble oil phase, carry out a polymerization reaction under stirring conditions, and after the polymerization reaction is completed , filtration and separation, the obtained solid product is water-sealed, aged and dried to obtain xerogel microspheres; the xerogel microspheres are carbonized and washed to obtain a small macroscopic particle size, a developed microscopic pore structure, and a large specific surface area. Moreover, lignosulfonate-phenolic resin-based carbon aerogel microspheres containing polar groups and molecular imprint-like specific structures can be used for selective and efficient adsorption of heavy metals, and are especially suitable for It is suitable for the remediation of heavy metal contaminated soil, and the preparation of carbon aerogel microspheres has a wide range of raw materials and low cost, which is conducive to large-scale production and application.
Description
Technical Field
The invention relates to a carbon aerogel microsphere material, in particular to a lignosulfonate-phenolic resin based carbon aerogel microsphere material which is synthesized by oil-water two-phase suspension polymerization, has a microsphere shape, a large specific surface area, developed pores and a molecular imprinting specific structure, and also relates to application of the lignosulfonate-phenolic resin based carbon aerogel microsphere material in heavy metal polluted soil remediation, belonging to the field of ecological environment treatment.
Background
Unlike common bulk aerogels, microspherical aerogels, also called aerogel microspheres, also called micro aerogels, are a special new material, are constructed by nanoscale materials, have micron-sized dimensions (usually between 1-1000 μm), and simultaneously have a three-dimensional network porous structure as large as macro bulk aerogels. The aerogel is prepared into aerogel microspheres, so that the potential application range of the aerogel can be expanded, such as superabsorbents, medicine/catalyst carriers, functional composite particles, permeable membranes and the like. This is due to the fact that aerogel microspheres have a range of superior properties compared to aerogel blocks, such as: as a catalyst carrier, the catalyst has larger specific surface area and can provide more active reaction centers; as a filler, the resin composition has good fluidity, is easy to uniformly disperse, and is not easy to cause stress concentration. Therefore, the use efficiency of the aerogel can be greatly improved and the application field of the aerogel can be widened. Due to the characteristics (high porosity, network structure, etc.) of aerogels, aerogel microspheres are not easily obtained by conventional machining. Thus, rather than first preparing a large block of aerogel and then preparing aerogel microspheres by machining, microspherical aerogels are generally prepared in situ. Generally, aerogel microspheres are generally prepared by first preparing organic/hydrogel microspheres by an emulsion method, a spray method, or a ball drop method, and then by supercritical CO2And replacing the solvent in the microspheres with air by drying, freeze drying and other drying modes, thereby obtaining the aerogel microspheres with complex open-cell structures.
Lignin is the most abundant natural organic high molecular compound except cellulose. The lignin is a complex three-dimensional phenolic polymer formed by connecting phenylpropane units through C-C bonds or C-O-C bonds, has phenolic properties and is extremely cheap, and simultaneously has high reaction activity because the lignin contains various active functional groups such as carboxyl, carbonyl, hydroxyl and the like. Thus making use ofThe lignin can be used for preparing cheap, green and environment-friendly biomass charcoal aerogel. The lignin-based carbon aerogel has a unique three-dimensional network structure, and has excellent performance, low density and high specific surface area. Due to excellent performance, the lignin-based carbon aerogel has good application prospects in catalyst carriers, supercapacitors and other aspects. Zainol ("Synthesis and catalysis of carbon cryogel from lignin-fural mixtures for Biodeiesel production", Zainol. M, et al, Bioresource Technology, 2015, 190:44.) and the like, lignin, furfural are also used as raw materials, sol-gel is carried out under the catalysis of sulfuric acid, and lignin-furfural carbon aerogel is finally prepared through freeze drying and carbonization treatment. The specific surface area of the carbon aerogel reaches 330.4m2The oleic acid has high thermal stability, has great potential on the aspect of esterifying free fatty acid into biodiesel, and has high oleic acid conversion rate of 98.1 percent. Zapata-Benabihe et al ("Activated carbon bio-xenogel as electrolytes for super catalysts applications", Zapata-Benabihe, et al, Procedia Engineering, 2016, 148:18-24.) uses lignin as a precursor, partially substituted for resorcinol, sol-gel with formaldehyde under NaOH catalysis, via H3PO4Activating to prepare lignin-resorcinol-formaldehyde carbon aerogel. The activated carbon aerogel has high activity, heterogeneous micropore size distribution, specific capacitance of 234.2F/g and good electrochemical performance. Chen et al ("Preparation and catalysis of organic aerogels by the lignin-resorcinol-formaldehyde copolymer", CHEN F, et al, Bioresources, 2011, 6(2): 1262-. The results show that: when the mass fraction of the lignin reaches 50%, the density of the carbon aerogel is lowest and is as low as 0.244g/cm3When the mass fraction of lignin is high, LRF carbon aerogel cannot be prepared.
Although the development of the carbon aerogel microsphere technology is mature day by day, a plurality of challenges still exist in the aspects of technology and application, such as high manufacturing cost, long synthesis period and the like, so that the commercial popularization of the carbon aerogel microsphere is greatly limited, and related reports that the carbon aerogel microsphere is used for soil heavy metal pollution remediation are rarely reported at present.
Disclosure of Invention
Aiming at the problems of serious soil heavy metal pollution and shortage of high-performance environment functional materials in the prior art, the invention aims to provide a powder carbon aerogel microsphere material which has a developed pore structure and a large specific surface area, contains polar groups and a molecular imprinting-like specific structure, has selective and efficient adsorption on heavy metals, and is particularly suitable for a heavy metal polluted soil remediation material.
The second purpose of the invention is to provide a preparation method of the lignosulfonate-phenolic resin-based carbon aerogel microspheres, which is simple in process, low in cost and beneficial to large-scale production.
The third purpose of the invention is to provide an application of the carbon aerogel microsphere material in the aspect of repairing heavy metal contaminated soil, the carbon aerogel microsphere is easy to mix and mix with soil uniformly, the occurrence form of heavy metal with high content in the heavy metal contaminated soil can be converted from a weak acid extractable state with high biological effectiveness to a residue state with low biological effectiveness, and the carbon aerogel microsphere material can be added into the heavy metal contaminated soil to obviously improve the soil matrix.
In order to realize the technical purpose, the invention provides a preparation method of lignosulfonate-phenolic resin-based carbon aerogel microspheres, which is characterized in that lignosulfonate, a phenolic compound, an aldehyde compound and a polyamine compound are dissolved in water to obtain a water phase; mixing the water phase with the water-insoluble oil phase, carrying out polymerization reaction under the stirring condition, filtering and separating after the polymerization reaction is finished, and carrying out water seal aging and drying on the obtained solid product to obtain dry gel microspheres; and carbonizing and washing the xerogel microspheres to obtain the product.
The reaction raw materials adopted by the invention have good water solubility, can be fully dissolved in aqueous solution, and can be crosslinked with polyamine compounds under the condition of full dissolution to form a three-dimensional network structure with certain strength, meanwhile, the three-dimensional network structure can be converted into micron-scale solid gel by suspension polymerization in oil-water two phases, and the framework structure of the crosslinked phenolic resin can be maintained after high-temperature carbonization, so that the three-dimensional carbon aerogel microspheres can be obtained.
The key point of the invention is that lignosulfonate is adopted to partially replace phenolic substances in a phenolic resin reaction system, metal ions of lignosulfonate can be doped in a carbon aerogel microsphere precursor space structure, a carbon aerogel microsphere precursor containing the metal ions is formed through oil-water two-phase microemulsion gel reaction, the metal ions are removed through solid-liquid separation, gel aging, carbonization and other modes, the carbon aerogel microsphere has a specific structure similar to molecular imprinting while the carbon aerogel microsphere with micron scale is obtained, the selective adsorption of certain metal ions can be realized, metal plays a role in high-temperature pore forming under high-temperature conditions, the pore structure of the carbon aerogel microsphere is improved, and the carbon aerogel microsphere with developed pores and higher specific surface is obtained.
As a preferable mode, the lignosulfonate includes at least one of sodium lignosulfonate, calcium lignosulfonate, iron lignosulfonate, zinc lignosulfonate, and manganese lignosulfonate. By selecting lignosulfonate with different metal cations, molecular imprinting-like specific structures with different sizes can be left on the carbon aerogel microspheres, so that selective adsorption of certain heavy metal ions in soil can be realized. Such as sodium ions, calcium ions, iron ions and the like which are typical univalent, divalent and trivalent metal ions respectively, the ionic radii are different, and the selective adsorption of the carbon aerogel microspheres on heavy metal ions can be realized by reasonably selecting lignosulfonate corresponding to metal cations with different ionic radii. The lignosulfonate is also a good surfactant, and is beneficial to the generation of microspherical gel.
As a preferred embodiment, the phenolic compound comprises phenol and/or resorcinol. These phenolic compounds are common phenolic resin raw materials.
As a preferred embodiment, the aldehyde compound includes formaldehyde and/or furfural. These aldehyde compounds are common phenolic resin raw materials.
In a preferred embodiment, the polyamine compound includes at least one of diethylenetriamine, triethylenetetramine, and hexamethylenetetramine. The polyamine compounds are not only good catalysts for synthesizing the phenolic resin, but also used as a cross-linking agent, so that the phenolic resin is cross-linked into a three-dimensional network structure.
Preferably, the mass of the polyamine compound is 0.5-20% of the total mass of the lignosulfonate, the phenolic compound, the aldehyde compound and the polyamine compound; more preferably 1% to 7%.
As a preferable scheme, the mass of the lignosulfonate is 1-50% of the total mass of the lignosulfonate and the phenolic compound; more preferably 10% to 40%.
As a preferable scheme, the mass ratio of the phenolic compound to the aldehyde compound is 10: 1-1: 10; more preferably 3:1 to 1: 3.
Preferably, the total mass of the lignosulfonate, the phenolic compound, the aldehyde compound and the polyamine compound is 1-60% of the mass of the water phase; more preferably 20 to 50%.
As a preferred embodiment, the water insoluble oily phase is mineral oil and/or arachis oil.
Preferably, the volume ratio of the oil phase to the water phase is 10:1 to 1: 10. The O/A ratio is more preferably 5:1 to 1: 1.
As a preferred embodiment, the polymerization conditions are: the reaction temperature is 40-90 ℃, the stirring speed is 10-1000 r/min, and the reaction time is 10-600 min. The reaction time is more preferably 100 to 300 min. The stirring speed is further preferably 200-800 r/min, and the size of the gel microspheres can be regulated and controlled to a certain extent through the stirring speed.
As a preferred scheme, the aging condition is as follows: sealing in water, and preserving heat for 1-10 days at the temperature of 40-90 ℃. The reaction time is more preferably 4 to 6 days. The gel microspheres after aging can be subjected to freeze drying, vacuum drying, supercritical drying and the like to obtain dry gel, and the gel microspheres prepared by the method have a strong three-dimensional structure and can be directly obtained by vacuum drying.
As a preferable scheme, the carbonization conditions are as follows: and preserving the heat for 1 to 24 hours at the temperature of 300 to 1000 ℃ in a protective atmosphere. The protective atmosphere is generally an inert atmosphere, and an inert atmosphere such as nitrogen or argon can be selected. The reaction temperature is preferably 300-800 ℃, and the reaction time is preferably 3-6 h. Under the optimal temperature, a large amount of polar groups remained on the carbon aerogel microspheres can be ensured.
As a preferable scheme, the carbonized product can be washed by water or placed in inorganic dilute acid to be oscillated for 1-48 h. The inorganic dilute acid can be one or a mixture of more of dilute hydrochloric acid, dilute nitric acid and dilute sulfuric acid. In a more preferable scheme, the concentration of the dilute acid is generally 0.2-2 mol/L. The oscillation time is preferably 8-24 h. The washing process mainly washes out metal ions in the carbon aerogel microspheres to obtain a specific structure similar to molecular imprinting.
The invention also provides a lignosulfonate-phenolic resin based carbon aerogel microsphere which is obtained by the preparation method.
As a preferable scheme, the particle size distribution of the lignosulfonate-phenolic resin-based carbon aerogel microspheres is 10-2000 mu m, and the specific surface area is 400-1200 m2Per g, pore volume of 2.4cm3/g～3.6cm3Is/g and has a molecular imprinting structure. Further preferably, the specific surface area is 800 to 1000m2/g。
The invention also provides application of the lignosulfonate-phenolic resin-based carbon aerogel microspheres as a heavy metal polluted soil repairing material. The lignosulfonate-phenolic resin-based carbon aerogel microspheres are added in the heavy metal contaminated soil, so that the stabilization of heavy metal ions can be realized, and the lignosulfonate-phenolic resin-based carbon aerogel microspheres have good water and fertilizer retention effects and can improve the soil structure.
As a preferable scheme, the doping proportion of the carbon aerogel microspheres in the heavy metal contaminated soil is not higher than 10%. Preferably 1 to 5%, more preferably 2 to 4%.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the preparation method of the carbon aerogel microspheres provided by the invention has the advantages of simple process, no generation of harmful wastes and mild reaction conditions, is used for partially replacing phenolic substances with lignosulfonate with wide sources to produce the carbon aerogel microspheres with micron scale, and is suitable for large-scale production of carbon aerogel microsphere materials.
2. The carbon aerogel microspheres provided by the invention have selectivity on target metal repair, can be subjected to targeted design, synthesis and adjustment aiming at the heavy metal pollution characteristics, and can be used for synthesizing carbon aerogels with different molecular imprinting by adopting different lignosulfonate parts to replace classified substances so as to achieve the optimal repair effect.
3. The carbon aerogel microspheres provided by the invention have ultralow density and larger specific surface area, have a similar molecular imprinting specific structure and have a selective and specific remediation effect on heavy metal pollution, and provide a basis and reference for realizing the remediation of the heavy metal polluted soil due to long-term effectiveness and stability of the remediation effect on the soil heavy metal pollutants and the improvement effect on the soil matrix.
4. The carbon aerogel microspheres provided by the invention are simple in use method, small in addition amount in heavy metal contaminated soil, small in soil capacity increase and have the potential of recycling.
Drawings
FIG. 1 is a scanning electron micrograph of the carbon aerogel microspheres prepared in example 2.
FIG. 2 is an infrared spectrum of the lignosulfonate-phenolic resin prepared in example 2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1 (control experiment)
In a 250mL three-necked flask, 12.98g of resorcinol, 4g of hexamethylenetetramine and 18.97mL of formaldehyde are added, deionized water is added to the mixture to reach 40mL, and the mixture is stirredAfter homogenization, 120ml of peanut oil is poured in, stirring is continued at 300r/min, and heating is started. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 100 min. After the reaction is finished, brown yellow solid particles are presented, and after filtration, the yellow solid is taken out to be sealed by water and aged for 5d at 80 ℃. Washing residual peanut oil on the surface after ageing is finished, heating for 4 hours at 800 ℃ in a tubular furnace in the nitrogen atmosphere after vacuum drying, and taking out black solids after cooling to obtain the carbon aerogel microspheres without print marks. The carbonization yield of the carbon aerogel is as follows: 53.5%, average particle diameter of 120 μm, specific surface area of 470m2Per g, average pore diameter: 438nm, pore volume: 2.11cm3/g。
Example 2
Adding 8.98g of resorcinol, 4.02g of sodium lignosulfonate, 4g of hexamethylenetetramine and 18.97mL of formaldehyde into a 250mL three-neck flask, adding deionized water to a constant volume of 40mL, uniformly stirring, pouring 120mL of peanut oil, continuously stirring at 450r/min, and starting heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 100 min. After the reaction is finished, brown yellow solid particles are presented, and after filtration, the yellow solid is taken out to be sealed by water and aged for 5d at 80 ℃. And washing residual peanut oil on the surface after ageing is finished, heating for 4 hours at 300 ℃ in a tubular furnace in the nitrogen atmosphere after vacuum drying, taking out black solid after cooling, and washing with pure water until the pH value is constant to obtain the carbon aerogel microspheres with sodium ion imprinting. The carbonization yield of the carbon aerogel is as follows: 51.3%, an average particle diameter of 78 μm and a specific surface area of 615m2Per g, average pore diameter: 1317nm, pore volume: 3.11cm3/g。
FIGS. 1 and 2 are SEM electron micrograph and IR spectra, respectively, of example 2. The spherical chain structure formed by connecting the carbon aerogel spheres can be clearly seen from an electron microscope atlas, and the spherical chain structure has obvious spherical characteristics and pores formed by the spherical chain; it can be observed from an infrared spectrum that the carbonized aerogel microspheres still retain surface functional groups such as hydroxyl, imino, carboxyl and the like, and the existence of the functional groups also provides sufficient reaction sites for the adsorption of heavy metal ions in soil remediation.
Example 3
9.02g of resorcinol, 3.98g of zinc lignosulfonate, 2g of hexamethylenetetramine and 18.97mL of formaldehyde are added into a 250mL three-neck flask, deionized water is added to the mixture to reach a constant volume of 40mL, the mixture is uniformly stirred, 120mL of peanut oil is poured into the mixture, the mixture is continuously stirred at a speed of 600r/min, and heating is started. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 100 min. After the reaction is finished, brown yellow solid particles are presented, and after filtration, the yellow solid is taken out to be sealed by water and aged for 5d at 80 ℃. And washing residual peanut oil on the surface after ageing is finished, heating the peanut oil for 4 hours at 800 ℃ in a tubular furnace in the nitrogen atmosphere after vacuum drying, taking out black solid after cooling, washing the black solid with 1mol/L hydrochloric acid for three times to remove zinc ions, and washing the black solid with pure water until the pH value is constant to obtain the carbon aerogel microspheres with zinc ion imprinting. The carbonization yield of the carbon aerogel is as follows: 52.7%, an average particle diameter of 42 μm, and a specific surface area of 862m2Per g, average pore diameter: 1425nm, pore volume: 3.32cm3/g。
Example 4
Adding 7.87g of resorcinol, 5.03g of iron lignosulfonate, 3g of diethylenetriamine and 18.97mL of formaldehyde into a 250mL three-neck flask, adding deionized water to a constant volume of 40mL, uniformly stirring, pouring 140mL of peanut oil, continuously stirring at 600r/min, and starting heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 150 min. After the reaction is finished, brown yellow solid particles are presented, and after filtration, the yellow solid is taken out, sealed by water and aged for 4 days at 85 ℃. And washing residual peanut oil on the surface after aging is finished, heating the peanut oil for 4 hours at 700 ℃ in a tubular furnace in the nitrogen atmosphere after vacuum drying, taking out black solid after cooling, washing the black solid for three times by using hydrochloric acid, and washing the black solid by using pure water until the pH value is constant to obtain the carbon aerogel microspheres with the iron ion imprinting. The carbonization yield of the carbon aerogel is as follows: 53.3%, average particle diameter of 86 μm, specific surface area of 892m2Per g, average pore diameter: 1625nm, pore volume: 3.38cm3/g。
Example 5
Adding 3.22g of resorcinol, 8.85g of zinc lignosulfonate, 2g of hexamethylenetetramine and 18.97mL of formaldehyde into a 250mL three-neck flask, adding deionized water to a constant volume of 40mL, uniformly stirring, pouring 120mL of peanut oil, continuously stirring at 300r/min, and starting heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 90 ℃ for 200 min. After the reaction is finished, solid particle gel cannot be formed due to the high concentration of the lignosulfonate.
Example 6
The carbon aerogel microspheres prepared in example 3 were doped into a heavy metal contaminated soil matrix according to different proportions, water was periodically added to maintain the water content at 20%, a soil matrix culture experiment was performed at room temperature, and the specific measurement results after 120 days are shown in table 1.
TABLE 1 basic physicochemical Properties of the different formulations
The table shows that the carbon aerogel microspheres can effectively adsorb Pb and Zn in the heavy metal contaminated soil, the leaching concentration reduction effect on Zn is more obvious, the volume weight of the soil is reduced, and the pH value of the soil is increased.
Example 7
3g of the carbon aerogel microspheres prepared in examples 3 and 4 were added to 200ml of 1mol/L CuSO4、PbSO4And ZnSO4Stirring and mixing the solution for a certain time, wherein the removal rate of Cu, Pb and Zn heavy metal ions in the carbon aerogel microspheres in the embodiment 3 is more than 95%, and the removal rate of the carbon aerogel microspheres in the embodiment 4 is about 70%; the same amount of carbon aerogel microspheres prepared in example 3 was added while containing CuSO4、PbSO4And ZnSO4The Zn ion removal rate of the mixed solution (1 mol/L) is higher than 95 percent and obviously higher than that of Cu and Pb (40 percent of Cu and 65 percent of Pb).
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