CN112086298B - Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof - Google Patents
Modified activated carbon/ferroferric oxide composite material and preparation method and application thereof Download PDFInfo
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- CN112086298B CN112086298B CN202010979373.3A CN202010979373A CN112086298B CN 112086298 B CN112086298 B CN 112086298B CN 202010979373 A CN202010979373 A CN 202010979373A CN 112086298 B CN112086298 B CN 112086298B
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- activated carbon
- ferroferric oxide
- drying
- composite material
- iron
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 547
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 156
- 229910052742 iron Inorganic materials 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 71
- 238000005554 pickling Methods 0.000 claims abstract description 70
- 239000007787 solid Substances 0.000 claims abstract description 56
- 150000007524 organic acids Chemical class 0.000 claims abstract description 40
- -1 iron ions Chemical class 0.000 claims abstract description 38
- 238000005470 impregnation Methods 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 150000002505 iron Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 53
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000003828 vacuum filtration Methods 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims 3
- 238000007605 air drying Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 33
- 238000005406 washing Methods 0.000 description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 13
- 235000015165 citric acid Nutrition 0.000 description 12
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 11
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 11
- 239000001630 malic acid Substances 0.000 description 11
- 235000011090 malic acid Nutrition 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 9
- 239000011668 ascorbic acid Substances 0.000 description 8
- 235000010323 ascorbic acid Nutrition 0.000 description 8
- 229960005070 ascorbic acid Drugs 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 7
- 229960000907 methylthioninium chloride Drugs 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 244000062748 Eupatorium adenophorum Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract
The invention provides a modified activated carbon/ferroferric oxide composite material as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Performing first impregnation treatment on the activated carbon by using an organic acid solution, and performing solid-liquid separation after the activated carbon is adsorbed and saturated, wherein the obtained solid is acid-impregnated activated carbon; (2) Performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is the iron-loaded pickling activated carbon; (3) Roasting the iron-loaded pickling activated carbon obtained in the step (2) to obtain a modified activated carbon/ferroferric oxide composite material; wherein the ferric salt solution in the step (2)The iron ions in the liquid include Fe 2+ And/or Fe 3+ . The modified activated carbon/ferroferric oxide composite material can be used as an adsorption material, a superparamagnetic material, a Fenton-like catalyst or a supercapacitor electrode material.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a modified activated carbon composite material, in particular to a modified activated carbon/ferroferric oxide composite material as well as a preparation method and application thereof.
Background
In recent years, the preparation and application of the activated carbon/ferroferric oxide composite material are receiving more and more attention. Ferroferric oxide particles are loaded on the surface of the active carbon, so that the agglomeration phenomenon of the particles can be effectively avoided.
The conventional preparation method of the active carbon/ferroferric oxide composite material based on the finished active carbon is a dipping-roasting method. The typical method comprises the steps of soaking activated carbon by using ferrous salt or ferric salt solution, then directly drying the solvent or carrying out solid-liquid separation by suction filtration, and then roasting the mixture of the ferrous salt or ferric salt and the activated carbon in an inert gas atmosphere (the roasting temperature is usually higher than 700 ℃), so that the activated carbon/ferroferric oxide composite material can be finally obtained.
The method has the disadvantages of harsh preparation conditions and high energy consumption. In addition, if the solution is completely dried, the surface of the activated carbon is easily covered by iron-containing compounds generated by ferrous salt or ferric salt hydrolysis, and pores can be blocked after roasting; ferrous ion (Fe) bonded with activated carbon if solid-liquid separation is performed by vacuum filtration 2+ ) Or iron ions (Fe) 3+ ) Mainly based on the chemical adsorption of surface functional groups to the surface of the activated carbon. Activated carbon is usually prepared by high temperature activation, and has fewer surface functional groups, so that Fe 2+ And Fe 3+ Is suckedThe amount of the additive is less, so that the content of ferroferric oxide in the final compound is also lower.
Some documents adopt concentrated nitric acid to perform oxidation modification on commercial activated carbon under a heating condition, so that the content of oxygen-containing functional groups on the surface of the activated carbon is increased, and the adsorption capacity of the activated carbon on ferrous ions or ferric ions is further improved. However, concentrated nitric acid is used as an oxidizing agent with extremely strong corrosivity, the oxidation condition is not easy to control, if the oxidation degree is too high, a large number of carbon atoms in an activated carbon matrix are etched, and finally, the mechanical strength of the oxidized activated carbon is deteriorated, so that the use of the material is influenced; in addition, concentrated nitric acid is easy to escape acid mist and nitrogen dioxide in the heating process, thereby causing environmental pollution.
CN 104190360A provides an oxidation-loaded iron modified activated carbon water treatment adsorbent and a preparation method thereof, the method comprises the steps of firstly adding nitric acid or phosphoric acid into activated carbon, and effectively increasing the number of acidic functional groups on the surface of the activated carbon by utilizing the strong oxidizing property of the nitric acid or phosphoric acid, thereby increasing the adsorption sites of metal ions; then adding ferric chloride or ferric sulfate and the like to introduce metal (hydroxide), can increase the adsorption force on metal ions, and is combined with the properties of developed porosity, specific surface area and the like of the active carbon, thereby finally realizing the removal of various metal ions in water. However, the strong oxidizing acid used in the method is easy to corrode the pore structure of the activated carbon and weaken the mechanical strength of the activated carbon, thereby affecting the adsorption performance of the modified activated carbon and reducing the service life.
CN 106268719A provides a preparation method of modified activated carbon loaded with ferroferric oxide particles, which comprises the step of firstly preparing FeCl 2 、FeCl 3 Uniformly mixing the solid NaOH and the mixture, roasting and melting the mixture by microwave heating in a nitrogen atmosphere, and cooling the mixture after the melting is finished to obtain molten liquid; and sequentially adding sodium dodecyl benzene sulfonate and activated carbon prepared from the eupatorium adenophorum raw material into the molten liquid, uniformly mixing, carrying out loading under the ultrasonic-assisted condition, adding distilled water for cleaning after loading is finished, carrying out solid-liquid separation and drying to obtain the modified activated carbon loaded with the ferroferric oxide particles. However, the method cannot well avoid the agglomeration phenomenon of the ferroferric oxide particles in the drying process,the loading under ultrasonic-assisted conditions is also not suitable for large-scale production applications.
CN 105597682A provides a room-temperature formaldehyde-removing modified activated carbon and a preparation method thereof, wherein the modified activated carbon takes granular, columnar, spherical or honeycomb-shaped coconut shell activated carbon with high specific surface area as a carrier and CuCl 2 And FeCl 3 The mixed metal salt is used as a modified component and is prepared by adopting the processes of dipping, drying and calcining. The modified activated carbon has the characteristics of rapid capture, high-efficiency adsorption, long working period and the like on gaseous formaldehyde, and can meet the requirement of effectively removing formaldehyde for a long time in an indoor environment. However, the pores of the modified activated carbon are easily blocked by metal salts in the calcining process, and the surface metal adsorption amount of the modified activated carbon is not high due to the fact that the surface functional groups of the activated carbon are few, so that the formaldehyde adsorption performance is affected.
CN 109502583A provides a preparation method of modified activated carbon, wherein the method is characterized in that through a two-step modification method of organic acid and transition metal ions, carboxyl groups on the surface of the prepared activated carbon are increased, the bonding force between the transition metal ions and the surface of the activated carbon is enhanced, and the dispersibility of the metal ions is effectively improved; meanwhile, due to the reducibility of the carboxyl, the metal ions can be reduced into metal simple substances or low-valence metal ions, and the adsorption performance of the metal ions on low-concentration methylbenzene is obviously improved. The method has simple operation flow and low cost, and can be used for protective products such as activated carbon filter elements and the like. However, stable ferroferric oxide magnetic particles are not formed in the modified activated carbon prepared by the method, and the modified activated carbon can only be applied to the treatment of organic waste gas and cannot be applied to a liquid phase environment.
Therefore, how to provide a modified activated carbon/ferroferric oxide composite material and a preparation method and application thereof, wherein the preparation method is used for improving Fe on the surface of activated carbon 2+ And/or Fe 3+ The adsorption capacity is avoided, the damage of the activated carbon structure in the preparation process is avoided, the requirements of energy conservation and environmental protection are also required to be met, and the problem which needs to be solved urgently at present is solved.
Disclosure of Invention
The invention aims to provide a modified active carbon/ferroferric oxide composite material and a preparation method thereofThe method and the application thereof, and the preparation method improves the Fe on the surface of the activated carbon 2+ And/or Fe 3+ The adsorption capacity, and simultaneously, the damage of the activated carbon structure in the preparation process is avoided, and the requirements of energy conservation and environmental protection are also met.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Performing first impregnation treatment on the activated carbon by using an organic acid solution, and performing solid-liquid separation after the activated carbon is adsorbed and saturated, wherein the obtained solid is acid-impregnated activated carbon;
(2) Performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) Roasting the iron-loaded pickling activated carbon obtained in the step (2) to obtain a modified activated carbon/ferroferric oxide composite material;
wherein, the iron ions in the iron salt solution in the step (2) comprise Fe 2+ And/or Fe 3+ 。
In the invention, the organic acid solution is used in the step (1) to modify the surface of the activated carbon, so that the damage of the conventional concentrated nitric acid modification to the structure of the activated carbon is avoided; meanwhile, the organic acid is selected for modification, so that the adsorption capacity of the activated carbon on iron ions can be remarkably improved, and finally, more ferroferric oxide is contained in the composite material. In addition, the organic acid molecules on the surface of the acid-leaching activated carbon can realize selective complexing adsorption of iron ions, so that the iron ions are fixed on the adsorption active site of the activated carbon, the agglomeration of the iron ions in the subsequent drying and roasting processes is inhibited, and the blockage of active carbon pore channels is avoided, thereby being beneficial to maintaining the original pore structure of the activated carbon.
In the invention, the roasting in the step (3) can not only convert the iron ions in the iron-carrying pickling activated carbon into stable metal oxides, namely ferroferric oxide magnetic particles, but also enable organic acid molecules to escape through thermal cracking, reduce the residue of the organic acid molecules in the activated carbon and effectively avoid the release of the organic acid molecules in the practical application process; in addition, iron ions are firmly combined with the activated carbon through roasting, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment.
Preferably, the first impregnation treatment of step (1) is an excess impregnation.
Preferably, the time of the first impregnation treatment is 4 to 24 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the activated carbon can be any one commercial activated carbon, the maximum adsorption capacity of the activated carbon is calculated by using a static adsorption method before the organic acid solution is impregnated, and then the activated carbon is ensured to reach a state of saturated adsorption on the organic acid solution by using an excess impregnation method, namely, organic acid molecules occupy all active sites of the activated carbon which can be adsorbed.
Preferably, the solute of the organic acid solution in step (1) comprises any one or a combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid or ethylenediaminetetraacetic acid, and typical but non-limiting combinations include a combination of tartaric acid and oxalic acid, a combination of oxalic acid and citric acid, a combination of citric acid and malic acid, a combination of malic acid and ascorbic acid, a combination of ascorbic acid and ethylenediaminetetraacetic acid, a combination of tartaric acid, oxalic acid and citric acid, a combination of oxalic acid, citric acid and malic acid, a combination of citric acid, malic acid and ascorbic acid, or a combination of malic acid, ascorbic acid and ethylenediaminetetraacetic acid.
Preferably, the solvent of the organic acid solution in the step (1) is deionized water.
Preferably, the solid-liquid separation mode in the step (1) comprises vacuum filtration and/or centrifugal dehydration.
Preferably, the solid-liquid separation in step (1) is followed by a drying treatment.
Preferably, the drying treatment is drying and/or airing, and further preferably drying.
Preferably, the temperature of the drying is 30 to 150 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the drying is used for removing moisture in the pickling activated carbon; the end point of the drying is that the quality of the acid leaching activated carbon is not changed any more.
Preferably, the second impregnation treatment of step (2) is an excess impregnation.
Preferably, the time of the second dipping treatment is 4 to 24 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, before the ferric salt solution is impregnated, the maximum adsorption capacity of the dried pickling activated carbon is calculated by using a static adsorption method, and then an excessive impregnation method is used for ensuring that the pickling activated carbon reaches a state of saturated adsorption on the ferric salt solution, namely, iron ions occupy all active sites available for adsorption of the pickling activated carbon.
Preferably, the solute of the iron salt solution of step (2) comprises FeSO 4 、FeCl 2 、Fe(NO 3 ) 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 Any one or a combination of at least two of the above, typical but not limiting combinations include FeSO 4 With FeCl 2 Combinations of FeCl 2 With Fe (NO) 3 ) 2 Combination of (1), fe (NO) 3 ) 2 With Fe 2 (SO 4 ) 3 Combination of (1), fe 2 (SO 4 ) 3 With Fe (NO) 3 ) 3 Combination of (2), fe (NO) 3 ) 3 With FeCl 3 Combination of (1), feSO 4 、FeCl 2 With Fe (NO) 3 ) 2 Combinations of FeCl 2 、Fe(NO 3 ) 2 With Fe 2 (SO 4 ) 3 In combination with (1)，Fe(NO 3 ) 2 、Fe 2 (SO 4 ) 3 With Fe (NO) 3 ) 3 A combination of (1), or Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 With FeCl 3 A combination of (a) and (b).
Preferably, the solvent of the iron salt solution in the step (2) is deionized water.
Preferably, the solid-liquid separation mode in the step (2) comprises vacuum filtration and/or centrifugal dehydration.
Preferably, the solid-liquid separation in step (2) is followed by a drying treatment.
Preferably, the drying treatment is drying and/or airing, and more preferably drying.
Preferably, the temperature of the drying is 30 to 150 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In the invention, the drying is used for removing moisture in the iron-carrying pickling activated carbon; the end point of the drying is that the quality of the iron-loaded pickling activated carbon is not changed any more.
Preferably, the calcination of step (3) is carried out under a protective atmosphere.
Preferably, the protective gas used in the protective atmosphere comprises nitrogen and/or argon.
Preferably, the temperature of the calcination in step (3) is 300-750 ℃, and may be, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃ or 750 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the calcination time in step (3) is 0.5-6h, such as 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
In the invention, organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and the decomposition products can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature. In the temperature range of 350-750 ℃, carbon particles derived from organic acid molecules can serve as a reducing agent in the process of continuously increasing the temperature, and the intermediate product of the ferric oxide is promoted to be continuously converted into the ferroferric oxide. When the roasting temperature is lower than 250 ℃, iron ions cannot be fully converted into ferroferric oxide particles; when the roasting temperature is higher than 750 ℃, ferroferric oxide is continuously reduced by carbon in the activated carbon matrix, namely, carbothermic reduction reaction occurs, so that the ferroferric oxide is converted into elementary substance iron.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Carrying out first excess impregnation treatment on the activated carbon for 4-24h by using an organic acid solution, carrying out vacuum filtration and/or centrifugal dehydration after the activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is the acid-impregnated activated carbon; the solute of the organic acid solution comprises one or the combination of at least two of tartaric acid, oxalic acid, citric acid, malic acid, ascorbic acid and ethylenediamine tetraacetic acid, and the solvent is deionized water;
(2) Carrying out secondary excessive impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution for 4-24h, carrying out vacuum filtration and/or centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is iron-loaded pickling activated carbon; the solute of the iron salt solution comprises FeSO 4 、FeCl 2 、Fe(NO 3 ) 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 Any one or a combination of at least two of the above, wherein the solvent is deionized water;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 300-750 ℃ in an atmosphere with nitrogen and/or argon as a protective gas for 0.5-6h to obtain the modified activated carbon/ferroferric oxide composite material.
In a second aspect, the invention provides a modified activated carbon/ferroferric oxide composite material prepared by the preparation method in the first aspect.
Compared with unmodified activated carbon, the modified activated carbon/ferroferric oxide composite material has many advantages, which are mainly reflected in the following aspects:
(1) The modified active carbon/ferroferric oxide composite material can adsorb certain pollutants which cannot be adsorbed by the active carbon;
(2) Based on superparamagnetism of ferroferric oxide, the modified activated carbon/ferroferric oxide composite material can be quickly separated from a liquid-phase medium through an external magnetic field;
(3) Ferroferric oxide is used as a Fenton-like catalyst, the modified activated carbon/ferroferric oxide composite material can be used for catalytic oxidation decomposition of refractory organic matters, and an oxidizing agent can also be used for catalytic oxidation regeneration of the modified activated carbon/ferroferric oxide composite material saturated with organic matters;
(4) The ferroferric oxide can obviously improve the specific capacitance of the original activated carbon.
In a third aspect, the invention provides an application of the modified activated carbon/ferroferric oxide composite material as described in the second aspect in an adsorption material, a superparamagnetic material, a fenton-like catalyst or a supercapacitor electrode material.
In the invention, when the modified activated carbon/ferroferric oxide composite material is used as the Fenton-like catalyst, the modified activated carbon/ferroferric oxide composite material is matched with an oxidant to degrade the methylene blue which is an organic pollutant in water, and the degradation rate is up to 90-99%.
Preferably, the oxidant is hydrogen peroxide.
Preferably, the mass fraction of the hydrogen peroxide is 10-50%, and the dosage is 0.1-1 mL/(g of catalyst).
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the organic acid solution is used for carrying out surface modification on the activated carbon, so that the damage of the conventionally selected concentrated nitric acid modification to the structure of the activated carbon is avoided, the adsorption quantity of the activated carbon to iron ions is increased, and finally, the composite material contains more ferroferric oxide;
(2) According to the invention, the organic acid molecules on the surface of the acid-leaching activated carbon realize selective complexing adsorption of iron ions, so that the iron ions are fixed at the adsorption active site of the activated carbon, and the agglomeration phenomenon of the iron ions in the subsequent drying and roasting processes is inhibited, thereby being beneficial to maintaining the original pore structure of the activated carbon;
(3) Organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and decomposition products of the organic acid molecules can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature;
(4) According to the invention, iron ions and activated carbon can be firmly combined through the later roasting process, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment;
(5) The preparation method of the invention avoids introducing impurities into the organic acid solution and the ferric salt solution, and only needs to change the concentrations of the impurities, so the impurities can be recycled by replenishing materials.
Drawings
FIG. 1 is XRD spectra of a modified activated carbon/ferroferric oxide composite material provided in example 1 and a modified activated carbon material and commercial activated carbon provided in comparative example 1;
FIG. 2 is an XRD spectrum of the modified activated carbon/ferroferric oxide composite material provided in example 2 and the modified activated carbon material provided in comparative example 2;
FIG. 3 is a nitrogen adsorption and desorption curve of the modified activated carbon/ferroferric oxide composite material provided in example 2;
FIG. 4 is a nitrogen adsorption and desorption curve of commercial activated carbon;
FIG. 5 is a graph showing the change in iron ion content before and after the modified activated carbon/ferroferric oxide composite material provided in example 3 and the modified activated carbon material provided in comparative example 3 are used in a liquid phase environment;
fig. 6 is XRD spectra of the modified activated carbon/ferroferric oxide composite material provided in example 4 and the modified activated carbon material provided in comparative example 4.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL citric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the citric acid solution, carrying out first excess impregnation treatment for 14h, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was made up with deionized water 3 ) 2 Solution, reuse of said Fe (NO) 3 ) 2 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 14 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at the temperature of 300 ℃ in the atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 1.
Example 2
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL oxalic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the oxalic acid solution, carrying out first excessive impregnation treatment for 9 hours, carrying out centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL FeCl was prepared with deionized water 2 Solution, reuse of said FeCl 2 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 9 hours, carrying out centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 5 hours at 750 ℃ in an atmosphere taking argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 2, and the nitrogen adsorption and desorption curve is shown in figure 3.
As can be seen from FIG. 3, the specific surface area and the total pore volume of the product of example 2 were 1085m, respectively 2 G and 0.539cm 3 (ii)/g; as can be seen from FIG. 4, the specific surface area and the total pore volume of the commercial activated carbon were 1197m 2 G and 0.585cm 3 (ii) in terms of/g. The results show that the introduction of the ferroferric oxide particles can cause slight blockage of the original pores of the activated carbon, and the specific surface area and the total pore volume of the activated carbon are still kept above 90 percent of the original level.
Example 3
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL malic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the malic acid solution, performing first excessive impregnation treatment for 19 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe was made up with deionized water 2 (SO 4 ) 3 Solution, reuse of said Fe 2 (SO 4 ) 3 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 19 hours, carrying out centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 2 hours at 700 ℃ in an atmosphere taking argon as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
0.5g of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is placed in a 50mL conical flask, 20mL deionized water is added, and the conical flask is placed in a shaking table to oscillate at the rotating speed of 180rpm after being sealed. Sampling and detecting the concentration of iron ions in the deionized water after 0h, 8h, 16h and 24h after the beginning of oscillation respectively.
The content of iron ions of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is changed before and after the modified activated carbon/ferroferric oxide composite material is used in a liquid phase environment as shown in figure 5.
Example 4
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL tartaric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the tartaric acid solution, performing first excessive impregnation treatment for 4 hours, performing vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, drying at 30 ℃ until the activated carbon is completely dehydrated, and obtaining the solid which is the acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL FeSO was prepared with deionized water 4 Solution, reuse of said FeSO 4 The solution is used for pickling the pickling obtained in the step (1)Oscillating the activated carbon in an oscillator at the rotating speed of 180rpm at room temperature, carrying out second excessive impregnation treatment for 4 hours, carrying out vacuum filtration after the impregnated activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-carrying impregnated activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 6 hours at 550 ℃ in an atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The XRD spectrum of the modified activated carbon/ferroferric oxide composite material obtained in the embodiment is shown in figure 6.
Example 5
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL ascorbic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the ascorbic acid solution, carrying out first excessive impregnation treatment for 24 hours, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, drying at 150 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water 3 ) 3 Solution, reuse of said Fe (NO) 3 ) 3 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 24 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 150 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 400 ℃ in an atmosphere taking nitrogen as protective gas for 0.5h to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Example 6
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 50mL of 0.1g/mL ethylenediaminetetraacetic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at a rotating speed of 180rpm at room temperature by using the ethylenediaminetetraacetic acid solution, performing first excessive impregnation treatment for 14 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is pickling activated carbon;
(2) 50mL of 0.1g/mL FeCl was prepared with deionized water 3 Solution, reuse of said FeCl 3 Oscillating the pickling activated carbon obtained in the step (1) at a rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 14 hours, carrying out centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying the solid at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 550 ℃ in an atmosphere taking argon as a protective gas for 3.25 hours to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Example 7
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 15mL of 0.05g/mL citric acid solution and 15mL of 0.05g/mL oxalic acid solution by using deionized water, and mixing the two organic acid solutions to obtain a mixed organic acid solution; oscillating 15g of commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the mixed organic acid solution, carrying out first excessive impregnation treatment for 14h, carrying out vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL Fe (NO) was made up with deionized water 3 ) 2 Solution, reuse of said Fe (NO) 3 ) 2 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 14 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) for 3.25 hours at the temperature of 300 ℃ in the atmosphere taking nitrogen as protective gas to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted here.
Example 8
The embodiment provides a preparation method of a modified activated carbon/ferroferric oxide composite material, which comprises the following steps:
(1) Preparing 60mL of 0.1g/mL citric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the citric acid solution, performing first excessive impregnation treatment for 14 hours, performing vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is acid-impregnated activated carbon;
(2) 25mL of 0.05g/mL Fe (NO) was prepared with deionized water 3 ) 2 Solution and 25mL of 0.05g/mL Fe (NO) 3 ) 3 Mixing the two ferric salt solutions to obtain a mixed ferric salt solution; then the mixed iron salt solution is utilized to carry out 180rp treatment on the pickling activated carbon obtained in the step (1) in an oscillator at room temperatureOscillating the rotation speed of m, carrying out second excessive dipping treatment for 14h, carrying out vacuum filtration after the absorption saturation of the pickling activated carbon, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-carrying pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 300 ℃ in an atmosphere taking nitrogen as protective gas for 3.25 hours to obtain the modified activated carbon/ferroferric oxide composite material.
The crystal phase structure and the pore structure of the modified activated carbon/ferroferric oxide composite material obtained in this embodiment are similar to those of the modified activated carbon/ferroferric oxide composite material obtained in example 2, and therefore, the description thereof is omitted.
Comparative example 1
The present comparative example provides a method for preparing a modified activated carbon material, comprising the steps of:
(1) 50mL of 0.1g/mL Fe (NO) was prepared with deionized water 3 ) 2 Solution, reuse of said Fe (NO) 3 ) 2 Oscillating commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the solution, carrying out excessive impregnation treatment for 14 hours, carrying out vacuum filtration after the impregnated activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 90 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded activated carbon;
(2) And (2) roasting the iron-loaded activated carbon obtained in the step (1) at 300 ℃ in an atmosphere with nitrogen as a protective gas for 3.25 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 1.
As can be seen from FIG. 1, the XRD pattern of the commercial activated carbon has two wider diffraction peaks at 23 degrees and 46 degrees, which indicates the existence of amorphous carbon in the commercial activated carbon; the XRD pattern of the product of example 1, in addition to having diffraction peaks for amorphous carbon, also has sharp diffraction peaks at 30 °, 35 °, 56 °, 62 °, indicating the presence of a crystalline phase of ferriferrous oxide in the product of example 1; the XRD pattern of the product of comparative example 1 was similar to that of commercial activated carbon, indicating that the product of comparative example 1 did not contain the ferriferrous oxide crystalline phase. From this, it was found that the surface modification of activated carbon with an organic acid solution in advance enabled successful preparation of a modified activated carbon/ferroferric oxide composite material even at a calcination temperature of 300 ℃.
Comparative example 2
The present comparative example provides a method for preparing a modified activated carbon material, comprising the steps of:
(1) 50mL of 0.1g/mL FeCl was prepared with deionized water 2 Solution, reuse of said FeCl 2 Oscillating commercial activated carbon in an oscillator at the rotating speed of 180rpm at room temperature by using the solution, carrying out excessive impregnation treatment for 9 hours, carrying out centrifugal dehydration after the impregnated activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 60 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is iron-loaded activated carbon;
(2) And (2) roasting the iron-loaded activated carbon obtained in the step (1) at 750 ℃ in an atmosphere taking argon as a protective gas for 5 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 2.
As can be seen from fig. 2, the XRD pattern of the product of example 2 shows diffraction peaks with distinct intensities at 30 °, 35 °, 53 °, 56 °, 62 °, whereas the XRD pattern of the product of comparative example 2 shows diffraction peaks only at 30 ° and 35 °, which are weaker in intensity. The method comprises the following steps of (1) in example 2, performing surface modification on activated carbon in advance by using organic acid, and successfully preparing a modified activated carbon/ferroferric oxide composite material loaded with a large amount of ferroferric oxide crystals under the condition that the roasting temperature is 850 ℃; since the surface of the activated carbon is not modified in advance by using the organic acid in the comparative example 2, only a small amount of ferroferric oxide crystals are formed even if the roasting temperature reaches 750 ℃, and the qualified modified activated carbon/ferroferric oxide composite material cannot be successfully prepared. Therefore, the organic acid is used for carrying out surface modification on the active carbon in advance, and the content of ferroferric oxide crystals in the final composite material can be greatly improved.
Comparative example 3
The present comparative example provides a method for preparing a modified activated carbon material, comprising the steps of:
(1) Preparing 50mL of 0.1g/mL malic acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotation speed of 180rpm by using the malic acid solution, performing first excessive impregnation treatment for 19 hours, performing centrifugal dehydration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is pickling activated carbon;
(2) 50mL of 0.1g/mL Fe was prepared with deionized water 2 (SO 4 ) 3 Solution, reuse of said Fe 2 (SO 4 ) 3 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 19 hours, carrying out centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at 120 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon.
The change of the iron ion content of the modified activated carbon material obtained in the comparative example before and after the use in a liquid phase environment is shown in FIG. 5.
As can be seen from FIG. 5, the sample prepared in example 3 did not release iron ions at all times during the shaking process; in the sample prepared by the comparative example, the phenomenon of continuous and obvious release of iron ions exists in the liquid phase oscillation process. In addition, after 24 hours of shaking, the immersion liquid of example 3 was still colorless, while the color of the immersion liquid of the sample prepared in this comparative example changed from colorless to yellow. The results show that the roasting process can firmly combine iron ions with the activated carbon, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment.
Comparative example 4
The present comparative example provides a method of preparing a modified activated carbon material, the method comprising the steps of:
(1) Preparing 50mL of 0.1g/mL nitric acid solution by using deionized water, oscillating 15g of commercial activated carbon in an oscillator at room temperature at a rotating speed of 180rpm by using the nitric acid solution, performing first excessive impregnation treatment for 4 hours, performing vacuum filtration after the activated carbon is adsorbed and saturated, washing the obtained solid to be neutral, drying at 30 ℃ until the activated carbon is completely dehydrated, and obtaining the solid which is the acid-impregnated activated carbon;
(2) 50mL of 0.1g/mL FeSO was prepared with deionized water 4 Solution, reuse of the FeSO 4 Oscillating the pickling activated carbon obtained in the step (1) at the rotation speed of 180rpm in an oscillator at room temperature by using the solution, carrying out second excessive dipping treatment for 4 hours, carrying out vacuum filtration after the pickling activated carbon is adsorbed and saturated, washing the obtained solid until the washing liquid is colorless and transparent, and drying at the temperature of 30 ℃ until the activated carbon is completely dehydrated, wherein the obtained solid is the iron-loaded pickling activated carbon;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 550 ℃ in an atmosphere taking nitrogen as protective gas for 6 hours to obtain the modified activated carbon material.
The XRD pattern of the modified activated carbon material obtained in the comparative example is shown in figure 6.
As can be seen from fig. 6, both the XRD patterns of the sample obtained in this comparative example and the sample obtained in example 4 have the diffraction peak of ferroferric oxide, but the intensity of the diffraction peak of the ferroferric oxide is weak, which indicates that the ferroferric oxide has a small amount of crystalline phase, which indicates that the content of ferroferric oxide crystals in the modified activated carbon material cannot be increased by performing surface modification on the activated carbon with an inorganic acid at room temperature.
Application example 1
In the application example, the modified activated carbon/ferroferric oxide composite material provided in embodiment 1 is used as a fenton-like catalyst, and is used in combination with hydrogen peroxide to degrade methylene blue, which is an organic pollutant in water, and the specific operation is as follows:
preparing a methylene blue solution with the concentration of 500mg/L, putting 60mL of the methylene blue solution into a 250mL conical flask, adding 0.1g of the modified activated carbon/ferroferric oxide composite material prepared in the embodiment 1, then adding 50 mu L of hydrogen peroxide solution with the mass fraction of 30%, sealing, putting into a shaking table, oscillating at 180rpm for 4h, measuring the content of methylene blue in the solution by a spectrophotometry method, and further calculating the removal rate. In a comparative experiment, only the modified activated carbon/ferroferric oxide composite material and hydrogen peroxide are respectively added, the other conditions are kept unchanged, and the removal rate of a single element on methylene blue is investigated.
The results of the relevant experiments are shown in table 1.
TABLE 1
| Materials and reagents | Removal pathway | Removal Rate (%) |
| Modified active carbon/ferroferric oxide composite material and hydrogen peroxide | Catalytic oxidative decomposition | 95.3％ |
| Modified active carbon/ferroferric oxide composite material | Adsorption | 63.6％ |
| Hydrogen peroxide solution | Oxidation by oxygen | 5.2％ |
The results in table 1 show that the removal rate of methylene blue in the solution by the single modified activated carbon/ferroferric oxide composite material and hydrogen peroxide is relatively limited, and when the single modified activated carbon/ferroferric oxide composite material and the hydrogen peroxide are used in combination, the removal rate is obviously increased, which shows that a synergistic effect exists between the two materials, namely, the modified activated carbon/ferroferric oxide composite material is used as a fenton-like catalyst to catalyze the decomposition of hydrogen peroxide in hydrogen peroxide to generate hydroxyl radicals with strong oxidizability, and the purpose of advanced oxidation is achieved.
Therefore, the organic acid solution is used for carrying out surface modification on the activated carbon, so that the damage of the conventionally selected concentrated nitric acid modification to the structure of the activated carbon is avoided, the adsorption quantity of the activated carbon to iron ions is improved, and finally more ferroferric oxide is contained in the composite material; according to the invention, the organic acid molecules on the surface of the acid-leaching activated carbon realize selective complexing adsorption of iron ions, so that the iron ions are fixed at the adsorption active site of the activated carbon, and the agglomeration phenomenon of the iron ions in the subsequent drying and roasting processes is inhibited, thereby being beneficial to maintaining the original pore structure of the activated carbon; organic acid molecules adsorbed on the surface of the iron-carrying pickling activated carbon can be decomposed within the temperature range of 300-350 ℃, and decomposition products of the organic acid molecules can participate in the conversion process of iron ions, so that the formation of ferroferric oxide particles in an activated carbon matrix can be promoted even at a mild roasting temperature; according to the invention, iron ions and activated carbon can be firmly combined through a later roasting process, and the iron ions are not easy to fall off due to hydraulic impact under the application condition of a liquid phase environment; the preparation method of the invention avoids introducing impurities into the organic acid solution and the ferric salt solution, and only needs to change the concentrations of the impurities, so the impurities can be recycled by replenishing materials.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein fall within the scope and disclosure of the present invention.
Claims (24)
1. A preparation method of a modified activated carbon/ferroferric oxide composite material is characterized by comprising the following steps:
(1) Carrying out first impregnation treatment on the activated carbon by using an organic acid solution, carrying out solid-liquid separation after the activated carbon is adsorbed and saturated, and obtaining solid which is the acid-impregnated activated carbon; the solute of the organic acid solution comprises citric acid;
(2) Performing secondary impregnation treatment on the pickling activated carbon obtained in the step (1) by using an iron salt solution, and performing solid-liquid separation after the pickling activated carbon is adsorbed and saturated, wherein the obtained solid is iron-loaded pickling activated carbon;
(3) Roasting the iron-loaded pickling activated carbon obtained in the step (2) at 300-350 ℃ to obtain a modified activated carbon/ferroferric oxide composite material;
wherein, the iron ions in the iron salt solution in the step (2) comprise Fe 2+ And/or Fe 3+ 。
2. The method of claim 1, wherein the first impregnation treatment of step (1) is excess impregnation.
3. The method of claim 1, wherein the first impregnation treatment of step (1) is carried out for a period of 4 to 24 hours.
4. The method according to claim 1, wherein the solvent of the organic acid solution in step (1) is deionized water.
5. The preparation method according to claim 1, wherein the solid-liquid separation in step (1) comprises vacuum filtration and/or centrifugal dehydration.
6. The method according to claim 1, wherein the solid-liquid separation in step (1) is followed by a drying treatment.
7. The method according to claim 6, wherein the drying treatment is drying and/or airing.
8. The method of claim 7, wherein the drying process is oven drying.
9. The method of claim 7, wherein the temperature of the drying is 30 to 150 ℃.
10. The production method according to claim 1, wherein the second impregnation treatment of step (2) is excess impregnation.
11. The method according to claim 1, wherein the time of the second impregnation treatment in step (2) is 4 to 24 hours.
12. The method according to claim 1, wherein the solute of the iron salt solution of step (2) comprises FeSO 4 、FeCl 2 、Fe(NO 3 ) 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 Any one or a combination of at least two of them.
13. The method according to claim 1, wherein the solvent of the iron salt solution in step (2) is deionized water.
14. The preparation method according to claim 1, wherein the solid-liquid separation in step (2) comprises vacuum filtration and/or centrifugal dehydration.
15. The method according to claim 1, wherein the solid-liquid separation in step (2) is followed by a drying treatment.
16. The method of claim 15, wherein the drying process is oven drying and/or air drying.
17. The method of claim 16, wherein the drying process is oven drying.
18. The method of claim 16, wherein the temperature of the drying is 30-150 ℃.
19. The method according to claim 1, wherein the firing in step (3) is performed under a protective atmosphere.
20. The method of claim 19, wherein the protective atmosphere comprises nitrogen and/or argon.
21. The method according to claim 1, wherein the roasting time in step (3) is 0.5-6h.
22. The method of any one of claims 1-21, comprising the steps of:
(1) Carrying out first excess impregnation treatment on the activated carbon for 4-24h by using an organic acid solution, carrying out vacuum filtration and/or centrifugal dehydration after the activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is the acid-impregnated activated carbon; the solute of the organic acid solution comprises citric acid, and the solvent is deionized water;
(2) Carrying out secondary excessive impregnation treatment on the pickling activated carbon obtained in the step (1) by using a ferric salt solution for 4-24h, carrying out vacuum filtration and/or centrifugal dehydration after the pickling activated carbon is adsorbed and saturated, and drying at 30-150 ℃, wherein the obtained solid is iron-loaded pickling activated carbon; the solute of the iron salt solution comprises FeSO 4 、FeCl 2 、Fe(NO 3 ) 2 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Or FeCl 3 Any one or a combination of at least two of the above, wherein the solvent is deionized water;
(3) And (3) roasting the iron-loaded pickling activated carbon obtained in the step (2) at 300-350 ℃ in an atmosphere with nitrogen and/or argon as a protective gas for 0.5-6h to obtain the modified activated carbon/ferroferric oxide composite material.
23. A modified activated carbon/ferroferric oxide composite material prepared by the preparation method according to any one of claims 1 to 22.
24. The use of the modified activated carbon/ferroferric oxide composite material according to claim 23 in an adsorbent material, a superparamagnetic material, a fenton-like catalyst or a supercapacitor electrode material.
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