CN112973628B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 125000000524 functional group Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 244000298697 Actinidia deliciosa Species 0.000 claims abstract description 45
- 235000009436 Actinidia deliciosa Nutrition 0.000 claims abstract description 45
- 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 24
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000013138 pruning Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 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 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000009434 Actinidia chinensis Nutrition 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 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 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000000227 grinding 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
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 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
- 239000000975 dye Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 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
- 230000003213 activating effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000005389 magnetism Effects 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
- 239000003795 chemical substances by application Substances 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
- 229910052742 iron 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
- 238000005245 sintering Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000012190 activator Substances 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
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 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
- 238000006243 chemical reaction 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
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000012299 nitrogen atmosphere 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
- 238000005979 thermal decomposition reaction 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
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- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 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
- 238000004519 manufacturing process Methods 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
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- 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
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- 230000008961 swelling 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
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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Abstract
A kind of rich basic officerThe preparation method of energetic active carbon takes kiwi fruit pruning as raw material and adopts [ BMIM ]]And (2) Cl is soaked at normal temperature for pretreatment to obtain kiwi fruit pruning branch powder, then the kiwi fruit pruning branch powder, potassium oxalate, ferric nitrate and deionized water form a mixture, the mixture is stirred vigorously, filtered and dried, the temperature is raised to 500 to 600 ℃ in the atmosphere with the volume ratio of nitrogen to hydrogen being 20. 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 1600m 2 More than g, the basic functional groups on the surface of the activated carbon are increased, the catalytic performance of the activated carbon is improved, meanwhile, the activated carbon has excellent adsorption performance on anionic organic dyes, the adsorption quantity of the activated carbon on acid red 18 with the concentration of 200mg/L is 406.6mg/g or more, the activated carbon is repeatedly utilized for 10 times, and the removal rate of the acid red 18 is still maintained to be more than 92%.
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 variety and 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 form into a high-yield and stable-yield tree form 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 a large amount of 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 repeated utilization rate of activated carbon, the magnetic activated carbon is prepared by adopting a two-step method mostly at present, an activated carbon finished 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 activated carbon finished product, or the finished product of activated carbon is immersed in Fe (NO) 3 In solution, in N 2 The negative magnetic cost is increased by high-temperature treatment in the atmosphere and secondary high-temperature sintering, 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, a large number of adsorption sites and functional groups of the finished product of the activated carbon are occupied and covered, the adsorption performance of the magnetic activated carbon is reduced, the steps are complicated, the labor and time cost are high, 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 by comprising the following steps: using 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 of a volume ratio of nitrogen to hydrogen of 20, 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 pruned branch powder to the potassium oxalate to the ferric nitrate to the deionized water is 1g.
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 effect 2 O 2 Ability to acquire electrons at the surface of activated carbon and thus for catalyzing H 2 O 2 The 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 improved 2 O 2 It is easier to pick up electrons from its surface, thus contributing to H 2 O 2 Decomposing to produce OH.
In the system of the invention, fe is present at 500-600 DEG C 3+ 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 K 2 C 2 O 4 (Potassium oxalate) does not decompose, and when the reaction temperature rises to 700 ℃ or higher, K as an activator is magnetized 2 C 2 O 4 Thermal decomposition occurs to generate K 2 CO 3 And CO, at which temperature K 2 CO 3 Further decomposing as a main activating agent, and simultaneously activating and forming pores in multiple paths.
The above multipath pore-forming is (1) K 2 C 2 O 4 Decomposition to K above 700 deg.C 2 CO 3 And CO, K 2 CO 3 Directly used as an activator to react with CForming a hole; (2) K 2 CO 3 Thermal decomposition to form K 2 O and CO 2 Respectively taking the decomposition products as an activating agent to react with C to form pores; (3) K 2 And 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 vigorous stirring is 600 to 800rpm, and the stirring is carried out for 1 to 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 promoted 2 C 2 O 4 And 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 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 ℃.
Further, the pretreatment is to cut the kiwi pruned branches into small sections of 2-3 cm, soak the small sections in ionic liquid [ BMIM ] Cl for 1 hour, dry the small sections at 80 ℃ after filtering, then crush the small sections, and screen the small sections through a sieve of 60-80 meshes to obtain the kiwi 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 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;
and step 3: putting the kiwi pruned branch powder treated in the step 2 in N 2 And H 2 Heating 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 ℃.
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 1600m 2 More 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 characteristics, 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 406.6mg/g or more, the activated carbon is repeatedly used for 10 times, the removal rate of the acid red 18 is still maintained to be 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 the powder of pruning branches of fructus Actinidiae chinensis with K 2 C 2 O 4 Mixing ferric nitrate and deionized water according to the mass volume ratio of 1g;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N 2 And H 2 Heating to 500 ℃ at a speed of 5 ℃/min in a mixed gas atmosphere with a volume ratio of 20.
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 408.9mg/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 K 2 C 2 O 4 Mixing ferric nitrate and deionized water according to a mass volume ratio of 1g;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N 2 And H 2 Heating to 600 ℃ at the speed of 8 ℃/min in the mixed gas atmosphere with the volume ratio of 20.
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 406.6mg/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% 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 K 2 C 2 O 4 Mixing ferric nitrate and deionized water according to a mass volume ratio of 1g;
and step 3: placing the kiwi pruned branch powder treated in the step 2 in N 2 And H 2 Heating to 550 ℃ at the speed of 6 ℃/min in the mixed gas atmosphere with the volume ratio of 20.
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 2 hours, the concentration of organic matters in the solution to be detected is detected, and then the absorption capacity is obtained to be 413.2mg/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 by a 70-mesh sieve to obtain kiwi pruned branch powder;
and 2, step: mixing the powder of pruning branches of fructus Actinidiae chinensis with K 2 CO 3 Mixing ferric nitrate and deionized water according to a mass volume ratio of 1 g;
and step 3: placing the kiwi fruit pruned branches processed in the step 2 in N 2 And H 2 Heating to 550 ℃ at the speed of 6 ℃/min in the mixed gas atmosphere with the volume ratio of 20.
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 277.4mg/g.
According to the IUPAC regulations, micropores are pores with a diameter of 0 to 2nm, mesopores are pores with a diameter of 2 to 50nm, and macropores are pores with a diameter of more than 50 nm.
The pore size structure and distribution were analyzed and the results are shown in table 1.
Table 1: 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 carbon pzc (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 | pH pzc |
| 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 process 2 CO 3 As the main activator, and K 2 CO 3 Decomposition starts at a temperature above 300 ℃ to form K 2 O and CO, the reductive CO reduces the iron catalyst converted from ferric nitrate, so that the iron catalyst can not participate in the ammonia synthesis reaction at 500-600 ℃, thereby preventing a large amount of basic functional groups from being generated on the surface of the activated carbon. 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, and the recovery and utilization of the kiwi pruning branch-based magnetic activated carbon are promoted, after the kiwi pruning branch-based magnetic activated carbon adsorbs acid red 18 and Congo red for 5 times, the removal rate of the kiwi pruning branch-based magnetic activated carbon on the acid red 18 and the Congo red is still over 95%, and after the adsorption is repeated for 10 times, the removal rate is still over 92%.
Claims (6)
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, soaking and pretreating the kiwi pruned branches by using 1-butyl-3-methylimidazole chloride at normal temperature to obtain kiwi pruned branch powder, then forming a mixture with potassium oxalate, ferric nitrate and deionized water, violently stirring, filtering, drying, heating to 500 to 600 ℃ in an atmosphere with a volume ratio of nitrogen to hydrogen being 20, keeping the temperature for 1 to 2h, stopping introducing hydrogen, heating to 760 to 850 ℃ in the atmosphere of nitrogen, keeping the temperature for 0.5 to 1.5h, 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.
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 760-850 ℃.
4. The method for preparing an activated carbon rich in basic functional groups according to claim 3, wherein: the pretreatment comprises the steps of cutting the kiwi pruned branches into small sections of 2-3 cm, soaking in ionic liquid 1-butyl-3-methylimidazole chloride for 1h, filtering, drying at 80 ℃, then crushing, and sieving with a sieve of 60-80 meshes to obtain the kiwi pruned branch powder.
5. The method for preparing an activated carbon rich in basic functional groups according to claim 1, wherein: the violent stirring time is 1 to 2h.
6. The method for preparing an activated carbon rich in basic functional groups according to claim 1, wherein: the washing and drying after cooling are specifically grinding and crushing after cooling, centrifugal washing with distilled water and ethanol, and drying at 60 ℃.
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