CN111876160B - A kind of carbon aerogel material and its preparation method and application as heavy metal contaminated soil remediation material - Google Patents
A kind of carbon aerogel material and its preparation method and application as heavy metal contaminated soil remediation material Download PDFInfo
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 64
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 30
- 239000002689 soil Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005067 remediation Methods 0.000 title claims abstract description 11
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims description 37
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 22
- 229920001568 phenolic resin Polymers 0.000 claims description 22
- 239000005011 phenolic resin Substances 0.000 claims description 22
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000000499 gel Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 239000011592 zinc chloride Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011240 wet gel Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 229960004011 methenamine Drugs 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 20
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 229920003986 novolac Polymers 0.000 abstract description 10
- 239000004964 aerogel Substances 0.000 abstract description 7
- 150000003841 chloride salts Chemical class 0.000 abstract description 7
- 239000003337 fertilizer Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- -1 phenolic aldehyde Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGXAGETVRDOQFP-UHFFFAOYSA-N 2,6-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(O)=C1C=O DGXAGETVRDOQFP-UHFFFAOYSA-N 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 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
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000004021 humic acid Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (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)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种炭气凝胶材料及其制备方法和作为重金属污染土壤修复材料的应用，该炭气凝胶材料的制备方法是以线性酚醛树脂为原料，金属氯化盐为模板，利用线性酚醛树脂交联形成凝胶和利用金属氯化盐形成印迹，获得具有孔结构发达，比表面积大，且含有极性基团和具有类似分子印迹特异性结构的炭气凝胶材料，该炭气凝胶材料可以实现重金属选择性吸附，且具有良好的保水保肥性能，可改善土壤容重，特别适合用于重金属污染土壤修复。The invention discloses a carbon aerogel material, a preparation method thereof, and an application as a heavy metal polluted soil remediation material. The preparation method of the carbon aerogel material uses novolac resin as a raw material, metal chloride salt as a template, and uses Novolac resin is cross-linked to form gel and metal chloride salt is used to form imprinting to obtain carbon aerogel materials with developed pore structure, large specific surface area, polar groups and specific structures similar to molecular imprinting. Aerogel materials can achieve selective adsorption of heavy metals, have good water and fertilizer retention properties, can improve soil bulk density, and are especially suitable for heavy metal-contaminated soil remediation.
Description
Technical Field
The invention relates to a carbon aerogel material, in particular to a method for synthesizing the carbon aerogel material with a similar molecular imprinting specific structure by a molecular imprinting and template method, and also relates to application of the carbon aerogel material in heavy metal polluted soil remediation, belonging to the field of ecological environment management.
Background
The carbon aerogel is a special carbon foam material, and has the excellent performances of low density, large specific surface area, controllable pore structure, good conductivity and the like due to the unique three-dimensional network structure. Resorcinol-formaldehyde (RF) carbon aerogels were first prepared by Lawrence Livermore national laboratories in the United states in 1989 and have been of interest to researchers. The carbon aerogel is a novel nano-scale porous carbon material, and is obtained by replacing liquid in a gel structure with gas and carbonizing at high temperature under the condition of not damaging an organic hydrogel structure. As the second main category of aerogels following inorganic aerogels, carbon aerogels have not only aerogel lightweightThe carbon aerogel has the characteristics of porosity, low density, high specific surface area and the like, has the advantages of high temperature resistance, acid and alkali resistance and the like of the carbon material, is the only conductive aerogel, and has good application prospect in the research fields of thermal, acoustic, electrical, catalysis and the like. Carbon aerogels started relatively late, but developed very rapidly. With the progress of research, the preparation raw materials are converted from the traditional phenolic aldehyde prepolymer to the renewable biomass materials with wide sources, the drying method is expanded to supercritical drying, freeze drying and normal-pressure drying, the carbonization modes comprise high-temperature carbonization and hydrothermal carbonization, and the application of the method also extends to the fields of adsorption, electrochemistry, carriers, hydrogen storage and the like. The carbon aerogel has excellent performance, so that the carbon aerogel has good application prospects in the aspects of catalyst carriers, supercapacitor electrode materials, adsorbents and the like. The carbon aerogel material has excellent performance in the aspects of adsorbing organic pollutants and heavy metals, so that the carbon aerogel material can be possibly applied to the field of soil ecological environment restoration. He and the like take lignocellulose as raw materials to prepare cellulose-based carbon aerogel with developed pore structure and higher specific surface area, and the cellulose-based carbon aerogel is applied to adsorbing Cr in sewage6+99 percent of Cr in chromium ion solution with the concentration of 1.0mg/L can be adsorbed and removed within 50min6+("Aerogels from quaternary ammonium-functionalized cellulose nanoparticles for rapid removal of Cr (VI) from water", He X, et al, Carbohydrate Polymers,2014,111: 683-687). The adsorption performance of carbon xerogel to o-dichlorobenzene and humic acid is researched by the Huangyan of Zhejiang university, and the result shows that the carbon xerogel to o-dichlorobenzene with different catalyst dosage has good adsorption effect, and the adsorption of humic acid depends on the specific surface area of the carbon xerogel (research on characteristic pollutants in slightly polluted water by carbon xerogel adsorption and catalytic oxidation treatment, "Huangyan and the like, Zhejiang university, 2010: 5-62). Li academic good nickel doping is carried out on carbon aerogel to prepare magnetic carbon adsorption material with uniform structure, and Pb is treated at room temperature2+The adsorption capacity of the material reaches 62.5mg/g, and the material can reach adsorption saturation in 50 minutes (the preparation of spherical carbon aerogel based magnetic adsorption material, good Lischao and the like, metal functional material, 2013, 20(2): 12-15). Doping titanium with m-benzene in Liuling of Beijing chemical universityThe carbon aerogel in the diphenol-formaldehyde system is used for water electro-adsorption desalination, and the carbon aerogel is doped with 20 percent TiO2When a 4000mg/L NaCl solution is treated, the adsorption capacity can reach 20mg/g, the solution can still be regenerated after multiple times of adsorption, and the cycle performance is good (research on the electro-adsorption desalting performance of a carbon aerogel electrode, Liuling and the like, functional materials 2012, 43(3): 320-324). Although the development of the carbon aerogel technology is mature, the carbon aerogel technology still has many challenges in the aspects of technology and application, such as high manufacturing cost, long synthesis period and the like, so that the commercialization popularization of the aerogel is greatly limited.
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 the carbon aerogel material which has a developed pore structure, a large specific surface area, polar groups and a similar molecular imprinting specific structure, can realize selective adsorption of heavy metals, has good water and fertilizer retention performance, and is particularly suitable for a heavy metal polluted soil repairing material.
The second purpose of the invention is to provide a preparation method of the carbon aerogel material, which has simple process and lower cost and is beneficial to large-scale production.
The third purpose of the invention is to provide an application of the carbon aerogel material in repairing heavy metal contaminated soil, the carbon aerogel material can realize the conversion of the occurrence form of heavy metal with higher content in the heavy metal contaminated soil from a weak acid extractable state with high biological effectiveness to a residue state with low biological effectiveness, the soil particle structure is improved, the water and fertilizer holding performance is improved, and the soil matrix can be obviously improved when the carbon aerogel material is added into the heavy metal contaminated soil.
In order to achieve the technical purpose, the invention provides a preparation method of a carbon aerogel material, which comprises a scheme A or a scheme B:
scheme A: adding metal chloride and polyamine compounds into the linear phenolic resin solution to perform a crosslinking reaction to obtain wet gel; drying the wet gel to remove the solvent to obtain dry gel; carbonizing the xerogel, and performing acid washing and activating treatment on the obtained carbonized product to obtain a carbon aerogel material;
scheme B: adding polyamine compounds into the linear phenolic resin solution to perform crosslinking reaction to obtain wet gel; drying the wet gel to remove the solvent to obtain dry gel; and mixing the xerogel and metal chloride, sequentially performing carbonization treatment and high-temperature activation treatment, and performing acid pickling activation treatment on a high-temperature activated product to obtain the carbon aerogel material.
The linear phenolic resin is thermoplastic resin, can be well dissolved in a conventional organic solvent, and can be cross-linked with a polyamine compound under the condition of full dissolution to form a three-dimensional network structure with certain strength, the linear phenolic resin is converted into solid gel, and the skeleton structure of the cross-linked phenolic resin can be maintained after high-temperature carbonization, so that the three-dimensional carbon aerogel is obtained.
The key point of the technical scheme is that metal chloride is adopted as a template agent in the process of preparing the carbon aerogel by utilizing the phenolic resin, the carbon aerogel is synthesized by a molecular imprinting technology and a template method, metal ions are doped in a carbon aerogel precursor space structure, and the metal chloride template agent is removed by adopting modes of acid washing and the like after carbonization, so that the carbon aerogel has a specific structure similar to molecular imprinting, the selective adsorption of certain heavy metal ions can be realized, meanwhile, the metal chloride also has the function of high-temperature pore forming, the pore structure of the carbon aerogel material can be improved, and the carbon aerogel with developed pores and higher specific surface can be obtained. In the scheme A, metal chloride is mainly doped in the cross-linking process of the linear phenolic resin, enters the interior of the cross-linked phenolic resin gel, and is removed by acid washing after high-temperature carbonization treatment, so that the space occupied by the metal chloride is left in the carbon aerogel, and a special specific structure similar to molecular imprinting is formed. In the scheme B, the solid-phase reaction between the cross-linked phenolic resin gel and the metal chloride is mainly adopted, the metal chloride is gasified at high temperature and uniformly permeates into the cross-linked phenolic resin gel, the uniformity is better, the metal chloride is volatilized by a high-temperature activator, and the metal chloride is removed by acid washing, so that a space occupied by the metal chloride is left in the carbon aerogel, and a special specific structure similar to the molecular imprinting is formed.
In a preferred embodiment, in the embodiment a or B, the polyamine compound is at least one of diethylenetriamine, triethylenetetramine, and hexamethylenetetramine. These amine compounds also act as catalysts for the self-crosslinking reaction themselves.
In a preferable embodiment, in the embodiment a or the embodiment B, the mass ratio of the polyamine-based compound to the phenolic resin is 1:10 to 2: 1.
As a preferable scheme, in the scheme A or the scheme B, the crosslinking reaction is carried out in a closed environment, the reaction temperature is 40-120 ℃, and the reaction time is 1 d-10 d. The preferable reaction time is 4-6 d.
As a preferred scheme, in the scheme A, the metal chloride salt is NaCl or ZnCl2、AlCl3At least one of them. In scheme B, the metal chloride salt is ZnCl2、AlCl3At least one of them. The metal chloride can be used as a pore-forming agent, a molecular imprinting material and a stabilizing agent in the preparation process of the carbon aerogel, and has a remarkable effect of improving the pore structure of the material. NaCl, ZnCl2And AlCl3The three metal salts are respectively common compounds of monovalent, divalent and trivalent metal chlorides, different metal salts are selected as template agents to effectively regulate and control molecular imprinting inside the carbon aerogel, for example, zinc ions and aluminum ions are used as representatives of divalent and trivalent metal cations, different reaction sites formed in the carbon material through the template can correspondingly adsorb heavy metal cations such as lead, trivalent chromium and the like in heavy metal pollution remediation, and therefore, different metal chlorides can be selected as template agents to prepare the carbon aerogel aiming at main heavy metal pollution sources in heavy metal polluted soil to be remedied. In the scheme A, NaCl and ZnCl are generated in the process of the crosslinking reaction of the linear phenolic resin and the polyamine compound2And AlCl3Are doped into the cross-linked phenolic resin as molecular imprinting substances, and ZnCl2、AlCl3Is a special property ofIs ZnCl2、AlCl3And also can be used as a catalyst for the cross-linking reaction of the linear phenolic resin and polyamine compound, and ZnCl is generated in the carbonization process2、AlCl3The effect of corroding carbon is strong, the volatilization temperature is low, and the carbon aerogel exists in a gaseous state, so that the uniform corrosion pore-forming effect of the carbon aerogel can be realized. The particularity of sodium chloride is that the sodium chloride has higher volatilization temperature, presents a liquid phase in the high-temperature carbonization process and mainly plays a role in inducing the pore-forming of the carbon growth template. In the scheme B, zinc chloride and aluminum chloride are mainly used as template agents, and when high-temperature nitrogen atmosphere heating carbonization is carried out, the two salts have lower boiling points and can permeate into the cross-linked phenolic resin in a heating sublimation mode to play a role of molecular imprinting, and meanwhile, carbonized products are corroded to form pores, so that the pores are more abundant. In addition, in the case of the scheme A, these metal chloride salts can act as a stabilizer during the crosslinking reaction, can control the reaction rate, maintain the chemical equilibrium, and prevent the thermal decomposition and oxidation reaction in the reaction system from occurring.
As a preferable scheme, in the scheme A or the scheme B, the temperature of the carbonization treatment is 300-1000 ℃ and the time is 1-24 hours. The carbonization treatment is performed in an inert atmosphere, and an inert atmosphere such as nitrogen or argon can be selected. The reaction temperature is preferably 500-800 ℃, and the reaction time is preferably 3-6 h.
In a preferable embodiment, in the embodiment a, the amount of the metal chloride is 0.1 to 10% by mass of the novolac resin solution.
As a preferable scheme, in the scheme B, the dosage of the metal chloride is 0.1-10 times of the mass of the xerogel; more preferably 1/3-3 times.
As a preferable scheme, in the scheme A, the carbonized product is 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.
As a preferable scheme, in the scheme B, after the carbonized product is subjected to high-temperature activation treatment at 600-1000 ℃ for 1-12 hours, the high-temperature activated product is placed in inorganic dilute acid to oscillate for 1-48 hours. The mixing mode is preferably ball milling mixing, and the ball milling time is 10-180 min. The high temperature activation is carried out in an inert atmosphere, including an argon and/or nitrogen atmosphere. The high-temperature activation treatment time is preferably 1 to 10 hours, and more preferably 1 to 3 hours.
As a preferable scheme, the novolac resin solution uses an alcohol solvent, and the alcohol solvent generally uses one or more short-chain alcohols, such as methanol, ethanol, isopropanol, and the like. These solvents can sufficiently dissolve the novolac resin.
As a preferable scheme, the total mass percentage concentration of the linear phenolic resin and the polyamine compound in the linear phenolic resin dissolving solution is 20-40%. Even gel formation is difficult at either too low or too high a concentration.
As a preferable scheme, the wet gel drying mode can adopt vacuum drying, supercritical drying and freeze drying.
The invention also provides a carbon aerogel material, which is obtained by the preparation method. The specific surface area of the carbon aerogel material is 600-1000 m2Per g, pore volume of 2.6cm3/g～3.2cm3And/g, contains polar groups and has special molecular imprinting-like specific structures.
The invention also provides an application of the carbon aerogel material, which is characterized in that: the material is applied as a heavy metal contaminated soil remediation material. Not only can realize the stabilization of heavy metal ions, but also has better water and fertilizer retention effects and improves the soil structure.
As a preferable scheme, the doping proportion of the carbon aerogel material 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 material provided by the invention has the advantages of simple process, no generation of harmful wastes and mild reaction conditions, and is suitable for large-scale production of the carbon aerogel functional material.
2. The carbon aerogel material provided by the invention has selectivity on target metal restoration, can be subjected to targeted design, synthesis and adjustment aiming at the heavy metal pollution characteristic, and can be used for synthesizing carbon aerogels with different molecular imprinting by adopting different metal chloride template agents so as to achieve the optimal restoration effect.
3. The carbon aerogel material provided by the invention has ultralow density and larger specific surface area, has a similar molecular imprinting specific structure, has a selective and specific remediation effect on heavy metal pollution, has long-term effectiveness and stability on remediation of soil heavy metal pollutants and improvement of soil matrix, and provides a basis and reference for realizing remediation of heavy metal polluted soil.
4. The carbon aerogel material provided by the invention is simple in use method, small in addition amount in heavy metal contaminated soil, small in soil capacity increase and has the potential of recycling.
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
In a 250mL beaker, 25g of phenolic novolac resin, 5g of diethylenetriamine, 0.6g of solid anhydrous aluminum trichloride and 100mL of ethanol are added, stirred vigorously and poured into a hydrothermal reaction kettle to start heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 4 days. After the reaction was complete, a yellow solid appeared, which was taken out and dried in vacuo for 24 h. Heating the mixture for 4 hours at 800 ℃ in a tube furnace under the nitrogen atmosphere, cooling the mixture, taking out black solid, grinding the black solid, sieving the black solid by a 60-mesh sieve, washing the finely sieved solid by dilute hydrochloric acid to remove metal salt, and then washing the solid by pure water until the pH value of washing liquor is constant, thus obtaining the carbon aerogel material with aluminum trichloride print. The carbonization yield of the carbon aerogel is as follows: 53.5% and the specific surface area is 660m2Per g, average pore diameter: 1532nm, pore volume: 3.2cm3/g。
Example 2
Adding 25g of linear phenolic resin, 5g of hexamethylenetetramine, 0.61g of solid zinc chloride and 100mL of ethanol into a 250mL beaker, stirring vigorously, pouring into a hydrothermal reaction kettle,heating was started. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 6 days. After the reaction was completed, a yellow solid appeared, and the yellow solid was taken out and freeze-dried. Heating for 6 hours at 600 ℃ in a tube furnace under the atmosphere of nitrogen, cooling, taking out black solids, grinding, sieving by a 60-mesh sieve, washing the finely sieved solids by dilute hydrochloric acid and dilute nitric acid to remove metal salts, and washing by pure water until the pH value of washing liquor is constant, thus obtaining the carbon aerogel material with zinc chloride marks. The carbonization yield of the carbon aerogel is as follows: 55.24% and the specific surface area is 968m2Per g, average pore diameter: 786nm, pore volume: 2.71cm3/g。
Example 3 (control example without addition of Metal chloride salt)
In a 250mL beaker, 25g of phenol novolac resin, 5g of hexamethylenetetramine and 100mL of ethanol were added, stirred vigorously, poured into a hydrothermal reaction vessel, and heated. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 6 days. After the reaction was completed, a yellow solid appeared, and the yellow solid was taken out and freeze-dried. And heating for 6h at 600 ℃ in a tubular furnace under the nitrogen atmosphere, cooling, and taking out black solids to obtain the carbon aerogel material. The carbonization yield of the carbon aerogel is as follows: 51.57% and the specific surface area is 413m2Per g, average pore diameter: 452nm, pore volume: 2.11cm3(ii) in terms of/g. This example illustrates that, without the use of a metal chloride salt as a templating agent, a carbon aerogel is obtained having a low specific surface area and an undeveloped pore structure.
Example 4 (comparative example with too low a concentration of novolak resin solution)
5g of phenol novolac resin, 1g of triethylene tetramine and 100mL of methanol are added into a 250mL beaker, stirred vigorously and poured into a hydrothermal reaction kettle to start heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 70 ℃ for 5 days. After the reaction was completed, a yellow liquid was formed, and no gel was formed. Since the concentration of the reactant is too low, it is difficult to form a network structure, and a gel cannot be formed.
Example 5
In a 250mL beaker, 15g of phenol novolac resin and 5g of hexamethylene were addedStirring tetramine and 100ml ethanol vigorously, pouring into a hydrothermal reaction kettle, and heating. And starting timing when the reaction reaches the set temperature. The reaction was carried out at a reaction temperature of 80 ℃ for 7 days. And after the reaction is finished, taking out the yellow solid, drying the yellow solid at normal temperature for 24h, then drying the yellow solid in vacuum for 8h, mixing and ball-milling the obtained dry gel and 10g of zinc chloride solid for 30min, grinding the dry gel, then sieving the ground dry gel through a 60-mesh sieve, heating the dry gel in a tube furnace at 700 ℃ for 3h under the argon atmosphere, cooling the dry gel, and reacting the black solid in the tube furnace at 800 ℃ for 2h under the argon atmosphere to obtain the carbon aerogel material with zinc chloride imprinting. The carbonization yield of the carbon aerogel is as follows: 52.17% and the specific surface area is 798m2Per g, average pore diameter: 865nm, pore volume: 2.62cm3/g。
Example 6:
the carbon aerogel materials prepared in example 2 were mixed 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 90 days are shown in table 1.
TABLE 9 basic physicochemical Properties of the different formulations
The table shows that the carbon aerogel material 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 porosity and the water retention performance are improved.
Example 7:
3g of the carbon aerogel materials prepared in examples 2 and 3 were added to 200ml of 1mol/L CuSO4、PbSO4And ZnSO4The solution is stirred and mixed for a certain time, the removal rate of Cu, Pb and Zn heavy metal ions in the carbon aerogel material of the embodiment 2 is more than 95 percent, and the removal rate of the carbon aerogel material of the embodiment 3 is about 70 percent; the same amount of carbon aerogel material prepared in example 2 was added while containing CuSO4、PbSO4And ZnSO4All the concentrations of (1) are mixed inIn the mixed solution, the removal rate of Zn ions is higher than 95 percent and is obviously higher than that of Cu and Pb (40 percent of Cu and 65 percent of Pb).
Claims (7)
1. A preparation method of a carbon aerogel material is characterized by comprising the following steps: adding polyamine compounds into the linear phenolic resin solution to perform crosslinking reaction to obtain wet gel; drying the wet gel to remove the solvent to obtain dry gel; mixing the xerogel and metal chloride, sequentially performing carbonization treatment and high-temperature activation treatment, and performing acid pickling activation treatment on a high-temperature activated product to obtain a carbon aerogel material; the mass ratio of the polyamine compound to the linear phenolic resin is 1: 10-2: 1; the metal chloride is ZnCl2、AlCl3At least one of (1); the dosage of the metal chloride is 0.1-10 times of the mass of the xerogel; the total mass percentage concentration of the linear phenolic resin and the polyamine compound in the linear phenolic resin solution is 20-40%.
2. The method of claim 1, wherein the step of preparing the carbon aerogel material comprises: the polyamine compound is at least one of diethylenetriamine, triethylene tetramine and hexamethylene tetramine.
3. The method of producing a carbon aerogel material according to claim 1 or 2, characterized in that: the crosslinking reaction is carried out in a closed environment, the reaction temperature is 40-120 ℃, and the reaction time is 1-10 d.
4. The method of claim 1, wherein the step of preparing the carbon aerogel material comprises: the temperature of the carbonization treatment is 300-1000 ℃, and the time is 1-24 hours.
5. The method of claim 1, wherein the step of preparing the carbon aerogel material comprises: and after the carbonized product is subjected to high-temperature activation treatment at 600-1000 ℃ for 1-12 hours, the high-temperature activated product is placed in an inorganic dilute acid and oscillated for 1-48 hours.
6. A carbon aerogel material, characterized by: the preparation method of any one of claims 1 to 5.
7. Use of a carbon aerogel material according to claim 6, wherein: the material is applied as a heavy metal contaminated soil remediation material.
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