CN112973628A - Preparation method of activated carbon rich in basic functional groups - Google Patents
Preparation method of activated carbon rich in basic functional groups Download PDFInfo
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- CN112973628A CN112973628A CN202110173698.7A CN202110173698A CN112973628A CN 112973628 A CN112973628 A CN 112973628A CN 202110173698 A CN202110173698 A CN 202110173698A CN 112973628 A CN112973628 A CN 112973628A
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- activated carbon
- kiwi
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 125000000524 functional group Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 14
- 244000298697 Actinidia deliciosa Species 0.000 claims abstract description 46
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims abstract description 46
- 238000001035 drying Methods 0.000 claims abstract description 26
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- 238000013138 pruning Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 235000009434 Actinidia chinensis Nutrition 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002608 ionic liquid Substances 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 5
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 2
- 239000011148 porous material Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005389 magnetism Effects 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 240000006063 Averrhoa carambola Species 0.000 description 1
- 235000010082 Averrhoa carambola Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241001631271 Prunus fasciculata Species 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A method for preparing activated carbon rich in basic functional groups from pruning kiwi fruit by using [ BMIM ]]And (2) carrying out soaking pretreatment on Cl at normal temperature to obtain kiwi fruit pruned branch powder, then forming a mixture with potassium oxalate, ferric nitrate and deionized water, violently stirring, filtering, drying, heating to 500-600 ℃ in an atmosphere with a volume ratio of nitrogen to hydrogen being 20:1, carrying out heat preservation for 1-2 h, stopping introducing hydrogen, heating to 760-850 ℃ in a nitrogen atmosphere, carrying out heat preservation for 0.5-1.5 h, cooling, washing and drying. The invention adopts a one-step method to prepare the alkaline energy-hanging group-rich activated carbon material, and the BET specific surface area reaches 1600m2More than g, basic functional groups on the surface of the activated carbon are increased, the catalytic performance of the activated carbon is improved, the activated carbon has excellent adsorption performance on anionic organic dye, and the adsorption quantity of the activated carbon on acid red 18 with the concentration of 200mg/L is406.6mg/g, the removal rate of the acid red 18 is still kept above 92% after 10 times of repeated use.
Description
Technical Field
The invention relates to the technical field of activated carbon preparation, in particular to a preparation method of activated carbon rich in basic functional groups.
Background
With the increasing concern of people on environmental protection, the demand of various industries on activated carbon is increasing. At present, the raw materials for preparing the activated carbon mainly comprise coal, wood and fruit shells, but the supply price of the activated carbon is high due to the limitation of the raw material sources. Therefore, it is more and more important to develop a cheap and easily available raw material of activated carbon and reduce the production cost of activated carbon. However, the source and composition of the activated carbon raw material are very different, and the types and the number of the surface functional groups are limited, so that the application of the biochar in the aspect of polluted environment remediation is greatly limited.
Kiwi fruit is also called kiwi fruit, carambola, wild peach, etc. The kiwi fruit is rich in nutrition, has higher health care value, is the name of the king of the fruit and the crown of VC, and is popular with consumers. In order to cultivate the kiwi fruit tree into a high-yield and stable-yield tree structure, branches such as over-dense branches, cross branches, overlapped branches, weak branches and the like of the kiwi fruit tree need to be frequently trimmed, so that branches at all levels are continuously rejuvenated, and the mass growth of growing bearing branches is promoted. If the kiwi fruit branches generated by pruning cannot be effectively utilized, precious biological resources are wasted. The kiwi branches are high-quality raw materials of the activated carbon.
At present, the magnetic activated carbon nano composite material synthesized by using biomass can improve the recycling rate of activated carbon, at present, a two-step method is mostly adopted for preparing the magnetic activated carbon, a finished activated carbon product is synthesized firstly, then a modified magnetic nano material is adopted on the activated carbon, a coprecipitation method is generally adopted for modifying the magnetic nano material on the finished activated carbon product, or the finished activated carbon product is immersed in Fe (NO)3In solution, in N2The negative magnetic cost is increased by high-temperature treatment in the atmosphere and secondary high-temperature sintering, and the adsorption performance of the finished product of the activated carbon in the impregnation process promotes the penetration of metal ions, so that the metal content is too high, and a large number of adsorption sites of the finished product of the activated carbon are occupied and coveredThe adsorption performance of the magnetic activated carbon is reduced by the point and the functional group, and the steps are complicated, the working time and the energy are wasted, and the material performance is poor.
Disclosure of Invention
The invention aims to provide a preparation method of activated carbon rich in basic functional groups, which is simple in process, and the prepared activated carbon has high magnetism, does not need secondary high-temperature sintering, reduces negative magnetism cost and has excellent cation exchange characteristics.
The purpose of the invention is realized by the following technical scheme:
a preparation method of activated carbon rich in basic functional groups is characterized in that: using trimming branches of kiwi fruits as a raw material, adopting [ BMIM ] Cl (1-butyl-3-methylimidazole chloride) to soak and pretreat at normal temperature to obtain trimming branch powder of kiwi fruits, then forming a mixture with potassium oxalate, ferric nitrate and deionized water, violently stirring, filtering and drying, heating to 500-600 ℃ in an atmosphere with a volume ratio of nitrogen to hydrogen of 20:1, preserving heat for 1-2 h, stopping introducing hydrogen, heating to 760-850 ℃ in a nitrogen atmosphere, preserving heat for 0.5-1.5 h, cooling, washing and drying.
Further, the mass volume ratio of the kiwi fruit pruning branch powder, potassium oxalate, ferric nitrate and deionized water is 1g: 0.5-1 g: 0.1-0.15 g: 20-50 mL.
It is known in the art that the difference in surface properties of activated carbon results in different adsorption and catalytic properties. The active carbon with acidic surface groups has cation exchange property, the active carbon with basic surface groups has anion exchange property, and the acidic oxygen-containing functional groups (hydroxyl, carboxyl and ester oxygen-containing functional groups) on the surface of the active carbon reduce the electron cloud density and weaken H due to electron-withdrawing effect2O2Ability to acquire electrons at the surface of activated carbon and thus for catalyzing H2O2The decomposition of (A) has an inhibiting effect on OH, and the basic functional group can conjugate unpaired electrons to a pi electron system on the surface of the activated carbon, so that the electron cloud density, H, of the surface of the activated carbon is improved2O2It is easier to pick up electrons from its surface, thus contributing to H2O2Decomposing to produce OH.
In the system of the invention, Fe is present at 500-600 DEG C3+The catalyst is effectively converted into a high-activity iron catalyst, ammonia synthesis reaction is carried out in the atmosphere of nitrogen and hydrogen, ammonia gas reacts with functional groups such as acidic oxygen-containing functional group hydroxyl and carboxyl on the surface of carbon at high temperature to generate amino and amide functional groups, basic functional groups on the surface of the activated carbon are increased, the alkalinity of the activated carbon is enhanced, and the catalyst has more excellent anion exchange property; under a temperature environment K2C2O4(Potassium oxalate) does not decompose, and when the reaction temperature rises to 700 ℃ or higher, K as an activator is magnetized2C2O4Thermal decomposition occurs to generate K2CO3And CO, at which temperature K2CO3Further decomposing as a main activating agent, and simultaneously activating and forming pores in multiple paths.
The above multipath pore-forming is (1) K2C2O4Decomposition to K above 700 deg.C2CO3And CO, K2CO3Directly taking the mixture as an activating agent to react with C to form pores; (2) k2CO3Thermal decomposition to form K2O and CO2Respectively taking the decomposition products as an activating agent to react with C to form pores; (3) k2And reacting the O with the C to generate simple substance potassium, gasifying the potassium into potassium steam at high temperature to shuttle in the carbon, embedding the potassium steam into the carbon layer, and causing the carbon layer to bend and deform to form pores.
Further, the violent stirring is 600-800 rpm and is carried out for 1-2 hours.
Further, the [ BMIM ] Cl has a mass volume concentration of 0.6 to 1%.
The invention adopts one-step negative magnetism, completes the negative magnetism while preparing the activated carbon, and does not need secondary high-temperature sintering. However, the kiwi pruned branches have high and rich lignin, hemicellulose and cellulose, are compact in structure and difficult to activate, and when negative magnetism is generated in one step, potassium oxalate is taken as an activating agent and is difficult to permeate into wood fibers, magnetic nano ions generated by the reaction are mainly attached to the surface of activated carbon, so that shuttling and pore-forming from the surface to the interior of the activating agent in the high-temperature activation process are hindered, and the pore-forming efficiency is reduced.
The invention adopts ionic liquid BMIM]Soaking Cl at normal temperature, wherein the Cl-Hydrogen bonds are formed with hydrogen on hydroxyl groups in the molecular chain of the kiwi fruit pruned branch lignocellulose, and cations in the ionic liquid are combined with oxygen in hydroxyl groups of the kiwi fruit pruned branch cellulose molecules, so that the effect of swelling lignocellulose is achieved, the original compact structures of lignin, hemicellulose and cellulose are destroyed, the effect of hydrogen bonds in and among lignocellulose molecules is reduced, and the subsequent K is promoted2C2O4And ferric nitrate quickly permeates into the lignocellulose, and under a high-temperature environment, ferric salt generates an iron catalyst in situ and is finally converted into magnetic nanoparticles.
Further, the temperature rise rate is 5 to 8 ℃/min when the temperature rises to 500 to 600 ℃, and the temperature rise rate is 2 to 3 ℃/min when the temperature rises to 750 to 900 ℃.
Further, the pretreatment comprises the steps of cutting the kiwi fruit pruned branches into small sections of 2-3 cm, soaking in ionic liquid [ BMIM ] Cl for 1 hour, filtering, drying at 80 ℃, crushing, and sieving with a 60-80-mesh sieve to obtain the kiwi fruit pruned branch powder.
Most particularly, the preparation method of the activated carbon rich in the basic functional group is characterized by comprising the following steps:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in 0.6-1% of ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a sieve of 60-80 meshes to obtain kiwi pruned branch powder;
step 2: mixing the kiwi fruit pruned branch powder with potassium oxalate, ferric nitrate and deionized water according to the mass-volume ratio of 1g to 0.5-1 g to 0.1-0.15 g to 20-50 mL, violently stirring at 600-800 rpm for 1-2 h, filtering, and drying at 60-80 ℃;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N2And H2Heating to 500-600 ℃ at a speed of 5-8 ℃/min in a mixed gas atmosphere with a volume ratio of 20:1, preserving heat for 1-2 h, stopping introducing hydrogen, and then taking the temperature of 2-3 ℃ for based on the pressure of the nitrogenAnd continuously heating to 760-850 ℃ at the min rate, preserving heat for 0.5-1.5 h, cooling, grinding, crushing, centrifugally washing with distilled water and ethanol, and drying at 60 ℃.
The invention has the following technical effects:
the magnetic activated carbon material rich in basic functional groups is prepared by adopting a one-step method, the synthesis process is simple, secondary high-temperature sintering is not needed, the negative magnetic cost is reduced, the magnetic activated carbon material has excellent specific surface area and rich pore size structure, and the BET specific surface area reaches 1600m2More than g, basic functional groups on the surface of the activated carbon are increased, the catalytic performance of the activated carbon is improved, the activated carbon has excellent anion exchange property, the activated carbon has excellent adsorption performance on the anionic organic dye acid red 18, the adsorption quantity of the activated carbon on the acid red with the concentration of 200mg/L is more than 406.6mg/g, the activated carbon is repeatedly used for 10 times, the removal rate of the acid red 18 is still more than 92%, and the activated carbon has excellent repeated use stability.
Drawings
FIG. 1: the change curve of the adsorption capacity of the magnetic activated carbon prepared by the invention in acid red 18 solutions with different concentrations.
FIG. 2: the magnetic activated carbon prepared by the method has the removal rate of acid red 18 after being repeatedly used for 10 times.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A preparation method of magnetic activated carbon rich in basic functional groups comprises the following steps:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in 0.6% of ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a 60-mesh sieve to obtain kiwi pruned branch powder;
step 2: mixing macaquePeach prune branch powder and K2C2O4Mixing ferric nitrate and deionized water according to the mass volume ratio of 1g:0.5g:0.1g:20mL, violently stirring for 2h at 600rpm, filtering, and drying at 60 ℃;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N2And H2Heating to 500 ℃ at a speed of 5 ℃/min in a mixed gas atmosphere with a volume ratio of 20:1, preserving heat for 2h, stopping introducing hydrogen, continuously heating to 760 ℃ at a speed of 2 ℃/min in a nitrogen atmosphere, preserving heat for 1.5h, cooling, grinding, crushing, centrifugally washing with distilled water and ethanol, and drying at 60 ℃.
0.01g of the magnetic activated carbon prepared in the embodiment is weighed and respectively added into 200mL of acid red 18 solution to be detected with the concentration of 200mg/L, the solution is adsorbed for 2 hours, the concentration of organic matters in the solution to be detected is detected, and then the adsorption capacity is 408.9 mg/g. By recycling the magnetic activated carbon prepared in this example, the removal rate of acid red 18 after 10 times was 92.4%.
Example 2
A preparation method of magnetic activated carbon rich in basic functional groups comprises the following steps:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in 1% mass volume ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a 60-80-mesh sieve to obtain kiwi pruned branch powder;
step 2: mixing the powder of pruning branches of fructus Actinidiae chinensis with K2C2O4Mixing ferric nitrate and deionized water according to the mass volume ratio of 1g:1g:0.15g:50mL, violently stirring for 1h at 800rpm, filtering, and drying at 80 ℃;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N2And H2Heating to 600 ℃ at the speed of 8 ℃/min in a mixed gas atmosphere with the volume ratio of 20:1, preserving heat for 1h, stopping introducing hydrogen, continuously heating to 850 ℃ at the speed of 3 ℃/min in a nitrogen atmosphere, preserving heat for 0.5h, cooling, grinding, crushing, centrifugally washing with distilled water and ethanol, and drying at the temperature of 60 ℃.
0.01g of the magnetic activated carbon prepared in the embodiment is weighed and respectively added into 200mL of acid red 18 solution to be detected with the concentration of 200mg/L, the adsorption is carried out for 2 hours, the concentration of organic matters in the solution to be detected is detected, and then the adsorption capacity is 406.6 mg/g. By recycling the magnetic activated carbon prepared in this example, the removal rate of acid red 18 after 10 times was 92.1%.
Example 3
A preparation method of magnetic activated carbon rich in basic functional groups comprises the following steps:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in 0.8% mass volume concentration of ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a 70-mesh sieve to obtain kiwi pruned branch powder;
step 2: mixing the powder of pruning branches of fructus Actinidiae chinensis with K2C2O4Mixing ferric nitrate and deionized water according to the mass volume ratio of 1g:0.6g:0.1g:40mL, violently stirring at 700rpm for 1.5h, filtering, and drying at 70 ℃;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N2And H2Heating to 550 ℃ at the speed of 6 ℃/min in a mixed gas atmosphere with the volume ratio of 20:1, preserving heat for 1.5h, stopping introducing hydrogen, continuously heating to 800 ℃ at the speed of 3 ℃/min in a nitrogen atmosphere, preserving heat for 1h, grinding and crushing after cooling, centrifugally washing with distilled water and ethanol, and drying at the temperature of 60 ℃.
0.01g of the magnetic activated carbon prepared in the example is weighed and respectively added into 200mL of acid red 18 solution to be detected with the concentration of 200mg/L, the absorption is carried out for 2h, the concentration of organic matters in the solution to be detected is detected, and then the absorption capacity is obtained to be 413.2 mg/g. By recycling the magnetic activated carbon prepared in this example, the removal rate of acid red 18 after 10 times was 92.9%.
Comparative example 1
Preparing magnetic activated carbon by using kiwi pruned branches as raw materials:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, drying at 80 ℃, then crushing, and sieving with a 70-mesh sieve to obtain kiwi pruned branch powder;
step 2: mixing the powder of pruning branches of fructus Actinidiae chinensis with K2CO3Mixing ferric nitrate and deionized water according to the mass volume ratio of 1g:0.6g:0.1g:40mL, violently stirring at 700rpm for 1.5h, filtering, and drying at 70 ℃;
and step 3: placing the kiwi fruit pruned branches processed in the step 2 in N2And H2Heating to 550 ℃ at the speed of 6 ℃/min in a mixed gas atmosphere with the volume ratio of 20:1, preserving heat for 1.5h, stopping introducing hydrogen, continuously heating to 800 ℃ at the speed of 3 ℃/min in a nitrogen atmosphere, preserving heat for 1h, grinding and crushing after cooling, centrifugally washing with distilled water and ethanol, and drying at the temperature of 60 ℃.
0.01g of the magnetic activated carbon of the comparative example 1 is weighed and respectively added into 200mL of the acid red 18 solution to be detected with the concentration of 200mg/L, the solution is adsorbed for 2 hours, the concentration of organic matters in the solution to be detected is detected, and then the adsorption capacity is 277.4 mg/g.
According to IUPAC regulations, micropores are pores with the diameter of 0-2 nm, mesopores are pores with the diameter of 2-50 nm, and macropores are pores with the diameter of more than 50 nm.
The pore size structure and distribution were analyzed and the results are shown in table 2.
Table 2: physical properties of the magnetic activated carbon were analyzed.
The invention adopts acid-base titration method to test the surface group content of the prepared magnetic activated carbon, and adopts inert electrolyte titration method to test the pH value of the prepared activated carbonpzc(pH value at potential zero) as shown in Table 2.
Table 2: magnetic activated carbon surface functional group content.
| Preparation scheme | Carboxyl group | Lactone group | Phenolic hydroxyl group | Amino group | Amide group | Total alkalinity | pHpzc |
| Comparative example 1 | 2.378 | 0.229 | 2.534 | 0.0467 | 0.004 | 0.221 | 4.9 |
| Example 3 | 1.327 | 0.294 | 1.102 | 0.3042 | 0.126 | 0.774 | 10.1 |
Comparative example 1 since K is used in the preparation process2CO3As the main activator, and K2CO3Decomposition starts at a temperature above 300 ℃ to form K2O and CO, the reductive CO reduces the iron catalyst converted from ferric nitrate to 500-600 deg.CCan not participate in the reaction of synthesizing ammonia at the temperature of DEG C, thereby preventing the surface of the activated carbon from generating a large amount of basic functional groups. In the invention, N is introduced, so that the types and the number of basic functional groups on the surface of the activated carbon are increased, the alkalinity is enhanced, the surface chemical property of the activated carbon is converted into alkalinity, the promotion effect on the generation of OH by hydrogen peroxide oxidation is realized, and the magnetic activated carbon has excellent anion exchange property and high adsorption property on anionic dyes due to the abundant basic functional groups.
When the magnetic activated carbon composite material prepared by the invention is used for adsorbing acid red 18, the adsorption capacity of the magnetic activated carbon gradually increases with the increase of the concentration of the acid red 18 solution, as shown in figure 1.
The magnetic particles are compounded in the kiwi pruning branch-based magnetic activated carbon prepared by the invention, the recovery and separation efficiency of the activated carbon is enhanced, the recovery and utilization of the kiwi pruning branch-based magnetic activated carbon are promoted, the removal rate of the kiwi pruning branch-based magnetic activated carbon on acid red 18 and congo red is still more than 95% after the adsorption of the acid red 18 and congo red for 5 times, and the removal rate is still more than 92% after the adsorption for 10 times.
Claims (5)
1. A preparation method of activated carbon rich in basic functional groups is characterized in that: the method comprises the steps of taking kiwi pruned branches as raw materials, adopting [ BMIM ] Cl (1-butyl-3-methylimidazole chloride) to soak and pretreat at normal temperature to obtain kiwi pruned branch powder, then forming a mixture with potassium oxalate, ferric nitrate and deionized water, violently stirring, filtering and drying, heating to 500-600 ℃ in an atmosphere with a volume ratio of nitrogen to hydrogen being 20:1, preserving heat for 1-2 h, stopping introducing hydrogen, heating to 760-850 ℃ in a nitrogen atmosphere, preserving heat for 0.5-1.5 h, cooling, washing and drying.
2. The method for preparing an activated carbon rich in basic functional groups according to claim 1, wherein: the mass-volume ratio of the kiwi fruit pruning branch powder to the potassium oxalate to the ferric nitrate to the deionized water is 1g: 0.5-1 g: 0.1-0.15 g: 20-50 mL.
3. The method for preparing an activated carbon rich in basic functional groups according to claim 1 or 2, wherein: the heating rate is 5-8 ℃/min when the temperature is raised to 500-600 ℃, and the heating rate is 2-3 ℃/min when the temperature is raised to 750-900 ℃.
4. A process for preparing an activated carbon rich in basic functional groups according to any one of claims 1 to 3, wherein: the pretreatment comprises the steps of cutting the kiwi fruit pruned branches into small sections of 2-3 cm, soaking in ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a sieve of 60-80 meshes to obtain the kiwi fruit pruned branch powder.
5. A preparation method of activated carbon rich in basic functional groups is characterized by comprising the following steps:
step 1: cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in ionic liquid [ BMIM ] Cl for 1h, filtering, drying at 80 ℃, crushing, and sieving with a 60-80-mesh sieve to obtain kiwi pruned branch powder;
step 2: mixing the kiwi fruit pruned branch powder with potassium oxalate, ferric nitrate and deionized water according to the mass-volume ratio of 1g to 0.5-1 g to 0.1-0.15 g to 20-50 mL, violently stirring for 1-2 h, filtering, and drying at 60-80 ℃;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N2And H2Heating to 500-600 ℃ at a speed of 5-8 ℃/min in a mixed gas atmosphere with a volume ratio of 20:1, preserving heat for 1-2 h, stopping introducing hydrogen, continuously heating to 760-850 ℃ at a speed of 2-3 ℃/min in a nitrogen atmosphere, preserving heat for 0.5-1.5 h, cooling, grinding, crushing, centrifugally washing with distilled water and ethanol, and drying at 60 ℃.
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