CN114950358B - Manganese-titanium oxide-biomass charcoal composite material and preparation method and application thereof - Google Patents
Manganese-titanium oxide-biomass charcoal composite material and preparation method and application thereof Download PDFInfo
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- CN114950358B CN114950358B CN202210429193.7A CN202210429193A CN114950358B CN 114950358 B CN114950358 B CN 114950358B CN 202210429193 A CN202210429193 A CN 202210429193A CN 114950358 B CN114950358 B CN 114950358B
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- biomass charcoal
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- titanium oxide
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- 239000002028 Biomass Substances 0.000 title claims abstract description 77
- 239000003610 charcoal Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 33
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 241000234295 Musa Species 0.000 claims description 5
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 44
- 239000000463 material Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 206010048610 Cardiotoxicity Diseases 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 231100000259 cardiotoxicity Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- VQHHOXOLUXRQFQ-UHFFFAOYSA-L dipotassium;4,5,6,7-tetrachloro-2',4',5',7'-tetraiodo-3-oxospiro[2-benzofuran-1,9'-xanthene]-3',6'-diolate Chemical compound [K+].[K+].O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C([O-])C(I)=C1OC1=C(I)C([O-])=C(I)C=C21 VQHHOXOLUXRQFQ-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- IXZOTKANSDQAHZ-UHFFFAOYSA-N manganese(ii) titanate Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Mn+2] IXZOTKANSDQAHZ-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229940073450 sudan red Drugs 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/06—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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a manganese titanium oxide-biomass charcoal composite material which is composed of biomass charcoal, manganese dioxide particles and titanium dioxide particles, wherein the manganese dioxide particles are uniformly distributed on the biomass charcoal, and the titanium dioxide particles are uniformly distributed on the biomass charcoal and the manganese dioxide particles. The invention also discloses a preparation method of the manganese titanium oxide-biomass charcoal composite material and application of the manganese titanium oxide-biomass charcoal composite material serving as an adsorbent to adsorption removal of dye rhodamine B in water. The manganese titanium oxide-biomass charcoal composite material has the advantages of low cost, quick adsorption and good stability, is an excellent adsorption material, and has a good application prospect.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a manganese titanium oxide-biomass charcoal composite material, and a preparation method and application thereof.
Background
With the rapid development of population growth, global warming and industrial production, serious pollution of water resources is directly caused, and the problem of human drinking water is caused. The organic dye has complete color spectrum, bright color and good firmness, is widely applied to large-scale industrial production of textiles, printing and dyeing, cosmetics and the like, and if the dye wastewater is discharged into water without treatment, the photosynthesis of plants is reduced to influence the growth of the plants, and simultaneously, the water organisms and crops can be absorbed to cause cancer to human bodies. Wherein rhodamine B (Rhodamine B), also known as rhodamine B, rose bengal B and alkaline rose bengal, has a molecular formula of C28H31ClN2O3, and is an artificially synthesized dye with a bright pink color. Is easily dissolved in water and ethanol, and is slightly dissolved in acetone, chloroform, hydrochloric acid and sodium hydroxide solution. The aqueous solution is blue-red, and has strong fluorescence after dilution, and the alcoholic solution has red fluorescence. The fluorescent dye is commonly used as a cell fluorescent dye in a laboratory and is widely applied to industries such as colored glass, special fireworks and crackers and the like. It also directly harms human health as sudan red, with potential carcinogenesis, mutagenicity, and cardiotoxicity.
The adsorption method has the characteristics of simple operation, environmental protection, low price, good removal effect and the like, and is one of the effective methods for removing the dye in the wastewater at present. However, most activated carbon has a general adsorption performance for dye in wastewater and is expensive. Therefore, the preparation of an adsorbent which has excellent adsorptivity and is inexpensive is of great significance for the treatment of dye-containing wastewater.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a manganese titanium oxide-biomass charcoal composite material, and a preparation method and application thereof.
The manganese titanium oxide-biomass charcoal composite material provided by the invention is composed of biomass charcoal, manganese dioxide particles and titanium dioxide particles, wherein the manganese dioxide particles are uniformly distributed on the biomass charcoal, and the titanium dioxide particles are uniformly distributed on the biomass charcoal and the manganese dioxide particles;
the manganese dioxide particles are of porous spherical or hemispherical structures, and the particle size is 3-8 mu m; the particle diameter of the titanium dioxide particles is 1-2 mu m.
Preferably, in the composite material, the molar ratio of carbon, manganese dioxide and titanium dioxide is 1: (1-3): (1-2).
Preferably, the biomass charcoal is prepared by taking banana peels as raw materials and carbonizing the raw materials at a high temperature; preferably, the high-temperature carbonization temperature is 300-400 ℃ and the time is 2-4h.
Preferably, cleaning banana peel, drying, acidifying, activating, carbonizing at 300-400 deg.C for 2-4 hr, grinding to powder, neutralizing, acidifying, filtering, washing to neutrality, and drying.
Preferably, the specific method for acidification and activation is as follows: adding hydrochloric acid solution for soaking treatment, wherein the concentration of the hydrochloric acid is 4-8mol/L, and the soaking treatment time is 10-20h; the specific method for neutralizing and acidifying comprises the following steps: adding sodium hydroxide solution, stirring and reacting, wherein the concentration of the sodium hydroxide solution is 4-8mol/L, and the stirring and reacting time is 2-4h.
The preparation method of the manganese titanium oxide-biomass charcoal composite material comprises the following steps:
s1, weighing biomass charcoal, titanium dioxide and manganese dioxide, adding hydrochloric acid solution to dissolve the titanium dioxide and the manganese dioxide completely, then adding sodium hydroxide solution to stir and react to adjust the pH to be neutral, and obtaining reaction liquid;
s2, carrying out hydrothermal reaction on the reaction liquid to obtain the catalyst.
Preferably, in S1, the concentration of the hydrochloric acid solution is 1-5mol/L.
Preferably, in S1, sodium hydroxide solution with the concentration of 1-5mol/L is added, and the mixture is stirred for 2-4 hours to adjust the pH to be neutral.
Preferably, in S2, the hydrothermal reaction conditions are: the temperature is 120-180 ℃ and the time is 24-72h.
The manganese-titanium oxide-biomass charcoal composite material is used as an adsorbent for adsorbing and removing dye rhodamine B in water.
The beneficial effects of the invention are as follows:
the invention uses MnO 2 Is manganese source, biomass charcoal and TiO 2 The ternary composite material has excellent adsorption performance on dye rhodamine B, can be used as an adsorbent for adsorbing and removing the dye rhodamine B in water, has excellent adsorption and low price, and is beneficial to industrialization of dye wastewater adsorbent application.
Drawings
Fig. 1 is an SEM image of biomass charcoal and manganese titanium oxide-biomass charcoal composite material prepared in the example of the present invention.
FIG. 2 is a graph showing BET adsorption and desorption curves of the manganese titanium oxide-biomass charcoal composite material prepared in the example of the present invention.
FIG. 3 is an XRD pattern of a manganese titanium oxide-biomass charcoal composite material prepared in an example of the present invention.
Fig. 4 is an adsorption curve of the biomass charcoal and the manganese titanium oxide-biomass charcoal composite material prepared in the embodiment of the invention to dye rhodamine B in a water body.
Fig. 5 is a fitted curve of the quasi-first-order kinetic equation of dye rhodamine B in a water body by using the biomass charcoal and manganese-titanium oxide-biomass charcoal composite material prepared in the embodiment of the invention.
Fig. 6 is a fitted curve of a quasi-second-order kinetic equation of dye rhodamine B in a water body by using the biomass charcoal and manganese-titanium oxide-biomass charcoal composite material prepared in the embodiment of the invention.
Fig. 7 is a mechanism diagram of rhodamine B adsorption by the manganese titanium oxide-biomass charcoal composite material of the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparing biomass charcoal:
washing a certain amount of banana peel with deionized water, cutting into pieces, drying in an oven at 105 ℃ for 8 hours, soaking in 100mL of hydrochloric acid solution with the concentration of 6mol/L for 12 hours, taking out, placing in a crucible, calcining at 360 ℃ for 3 hours in a muffle furnace, naturally cooling to room temperature, grinding uniformly, placing the obtained powder in 100mL of sodium hydroxide solution with the concentration of 6mol/L, stirring for reacting for 3 hours, filtering, washing to neutrality, and finally drying in the oven at 105 ℃ for 12 hours to obtain biomass charcoal.
Preparing a manganese titanium oxide-biomass charcoal composite material:
weighing a certain amount of the prepared biomass charcoal and a certain amount of TiO 2 、MnO 2 Soaking in 25mL of hydrochloric acid solution with the concentration of 3mol/L for 6 hours to dissolve completely, adding 30mL of sodium hydroxide solution with the concentration of 3mol/L, stirring to react for 3 hours, placing in a reaction kettle, performing hydrothermal reaction in an oven at 160 ℃ for 48 hours, cooling to room temperature, performing suction filtration, washing to neutrality, and drying at 105 ℃ for 6 hours to obtain the manganese titanium oxide-biomass charcoal composite material; the manganese titanium oxide-biomass charcoal composite material obtained by the preparation method comprises biomass charcoal, manganese dioxide particles and titanium dioxide particles, wherein the manganese dioxide particles are uniformly distributed on the biomass charcoal, and the titanium dioxide particles are uniformly distributed on the biomass charcoal and the manganese dioxide particles; wherein the manganese dioxide particles are porous spheresA shape or hemispherical structure with a particle size of 3-8 μm; the particle diameter of the titanium dioxide particles is 1-2 mu m.
In the manganese titanium oxide-biomass charcoal composite material prepared by the preparation method, the mole ratio of charcoal, manganese dioxide and titanium dioxide is 1:1:1 is recorded as 1:1:1 (Mn-Ti-C), the molar ratio of carbon, manganese dioxide to titanium dioxide being 1:2:1 is recorded as 1:2:1 (Mn-Ti-C), the molar ratio of carbon, manganese dioxide to titanium dioxide being 1:3:1 is recorded as 1:3:1 (Mn-Ti-C). The activated carbon sample obtained is designated as C.
Fig. 1 is an SEM image of biomass charcoal and manganese titanium oxide-biomass charcoal composite material prepared in the example of the present invention. Wherein FIG. 1a is biomass charcoal, FIG. 1b is 1:3:1 (Mn-Ti-C), FIG. 1C is 1:2:1 (Mn-Ti-C), and FIG. 1d is 1:1:1 (Mn-Ti-C). As can be seen from fig. 1, SEM fig. 1 and a, b, c, d show that manganese oxide with a composite proportion gradually becomes a spherical or hemispherical structure, and some areas have the morphology of a spherical core-shell structure, are uniformly distributed on biomass charcoal, have a porous structure and have a relatively large specific surface area. And the surface has white granular substances which are very uniformly distributed on the surface of the manganese oxide, which illustrates TiO 2 Successful loading on the surface of the manganese oxide is beneficial to the adsorption of pollutants. The active sites are provided for the manganese oxide, and when the addition amount of the manganese oxide is too large, the activity of the composite material is reduced, so that the adsorption efficiency is reduced.
FIG. 2 is a graph showing BET adsorption and desorption curves of the manganese titanium oxide-biomass charcoal composite material prepared in the example of the present invention. The specific surface area of the manganese titanium oxide-biomass charcoal composite material sample 1:1:1 (Mn-Ti-C) is 27.627m through BET detection 2 Per g, pore diameter 2.403nm, pore volume 0.110cm 3 And/g. The BET data shows that the specific surface area of the manganese titanium oxide-biomass charcoal composite material prepared by the invention has larger aperture, can effectively provide adsorption sites, and is beneficial to the removal of rhodamine B. From the adsorption curve of fig. 2, it can be seen that the curve shows a tape phenomenon and the pore size distribution is very uniform. Mainly comprises mesopores.
FIG. 3 is a schematic diagram of a manganese titanium oxide-raw material prepared in an embodiment of the present inventionXRD pattern of the mass carbon composite. As can be seen from FIG. 3, the biomass charcoal has a significant diffraction peak in the (111) crystal plane, tiO 2 The (211) crystal face and the (301) crystal face have obvious diffraction peaks, which indicates that the composite material has TiO 2 A crystalline component. MnO (MnO) 2 The crystal face (220) has obvious diffraction peak, and has higher intensity and better crystallinity, thereby being beneficial to the expression of the activity of the substance. TiO (titanium dioxide) 2 -MnO 2 The bond of (C) has obvious diffraction peak at the (521) crystal face, which indicates that the surface of the composite material has the bond of manganese-titanium oxide. The Ti-C has an obvious diffraction peak at the (311) crystal face, the Mn-C has an obvious diffraction peak at the (200) crystal face, and the three are effectively compounded and have obvious diffraction peaks, so that the crystallinity is better, and the catalytic adsorption activity of the substance is better reflected.
The samples 1:1:1 (Mn-Ti-C), 1:2:1 (Mn-Ti-C), 1:3:1 (Mn-Ti-C) and biomass charcoal prepared by the invention are respectively used as adsorbents for carrying out adsorption tests on rhodamine B, and the specific steps are as follows: 100mL of rhodamine B solution with the concentration of 100mg/L is measured in a 250mL conical flask, 0.5g of adsorbent is added, the mixture is taken out after ultrasonic treatment is carried out for 15min in ultrasonic waves, adsorption is carried out for 6h in a fume hood which is prevented from being irradiated by light at 25 ℃, sampling and centrifugation are carried out, the concentration of rhodamine B supernatant after centrifugal separation at 554nm is represented, and the experiment is repeated for 3 times. The adsorption rate was calculated and the result is shown in fig. 4.
Fig. 4 is an adsorption curve of the biomass charcoal and the manganese titanium oxide-biomass charcoal composite material prepared in the embodiment of the invention to dye rhodamine B in a water body. As shown in fig. 4, after adsorption for 1h, the biomass charcoal composite material and the biochar with different proportions basically reach adsorption balance respectively, the adsorption removal rate of the manganese titanium oxide-biomass charcoal composite material sample 1:1:1 (Mn-Ti-C) is highest, and the time to reach balance is also shortest. Therefore, when dye wastewater is removed, if the dosage proportion is uniform, the balance time can be effectively shortened, so that the removal rate of the composite material to rhodamine B is improved. With the change of the adsorption time, when the adsorption time was 1h, the adsorption removal rate of the biomass charcoal was 90.46%, the removal rate of the manganese titanium oxide-biomass charcoal composite material sample 1:1:1 (Mn-Ti-C) was 98.27%, the removal rate of the sample 1:2:1 (Mn-Ti-C) was 91.48%, and the removal rate of the sample 1:3:1 (Mn-Ti-C) was 96.74%. The longer the time, the adsorption removal rate is slowly increased until the adsorption equilibrium is reached. Therefore, the adsorption removal rate of rhodamine B as a whole is increased. It can be seen that the adsorption effect of the composite material prepared by the invention for adsorbing rhodamine B is obviously higher than that of the independent biomass charcoal.
Quasi-first order kinetic equationIntegrate the above formula and substitute t=0, q t ＝0；t＝t，q t ＝q t The method can obtain: ln (q) e -q t )＝-k 1 t+lnq e The method comprises the steps of carrying out a first treatment on the surface of the Q in the formula e Representative is the equilibrium adsorption amount (mg.g) of rhodamine B by the adsorbent -1 )；q t Represents the adsorption amount (mg.g) of rhodamine B by the adsorbent at the time t -1 )；k 1 (min -1 ) Is the adsorption rate constant of the quasi-first order kinetics.
Quasi-second-order kinetic equationIntegrate the above and substitute: t=0, q t ＝0；t＝t，q t ＝q t The method can obtain: />K in 2 [g/(mg·min)]Adsorption rate constant for pseudo-second order kinetic model, < ->In linear relation to t, k 2 、q e Can be obtained from the slope and intercept of the straight line.
FIG. 5 is a fitted curve of a quasi-first-order kinetic equation of dye rhodamine B in a water body by using the biomass charcoal and manganese titanium oxide-biomass charcoal composite material prepared in the embodiment of the invention, and FIG. 6 is a fitted curve of a quasi-second-order kinetic equation of dye rhodamine B in a water body by using the biomass charcoal and manganese titanium oxide-biomass charcoal composite material prepared in the embodiment of the inventionA curve. From the linear correlation coefficients of fig. 5 and 6, the best fit of quasi-second order dynamics to the equilibrium data (R 2 =0.9945), which illustrates that the adsorption process of rhodamine B on adsorbents is mainly controlled by chemisorption. The quasi-second-level kinetic model comprises liquid film diffusion, surface adsorption process, particle internal diffusion process and the like, and can reflect the adsorption mechanism of rhodamine B on the adsorbent more truly.
The mechanism diagram of the adsorption of rhodamine B by the manganese titanium oxide-biomass charcoal composite material is shown in figure 7. On one hand, the surface of biomass carbon in the manganese titanium oxide-biomass carbon composite material contains more hydroxyl and carboxyl, and rhodamine B is adsorbed through electrostatic action and hydrogen bonding action. Because rhodamine B is a cyclic aromatic molecule, coupling reaction can occur to form pi-pi conjugated bond interaction and other interactions so as to promote the adsorption of rhodamine B but have a secondary effect on the adsorption of rhodamine B. On the other hand, the adsorbed rhodamine B molecules are decomposed and oxidized by manganese dioxide and titanium dioxide to carbon dioxide and other molecules. Therefore, the manganese titanium oxide-biomass charcoal composite material has both oxidative decomposition and electrostatic adsorption on rhodamine B in the adsorption process. In addition, the whole adsorption process is accompanied by the process of intermolecular van der Waals force. Therefore, the preparation of the low-cost and high-efficiency composite adsorbent by utilizing the waste biomass and the metal oxide is one of important ways for effectively removing environmental pollutants in wastewater.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (5)
1. The manganese titanium oxide-biomass charcoal composite material is characterized by comprising biomass charcoal, manganese dioxide particles and titanium dioxide particles, wherein the manganese dioxide particles are uniformly distributed on the biomass charcoal, and the titanium dioxide particles are uniformly distributed on the biomass charcoal and the manganese dioxide particles;
the manganese dioxide particles are of porous spherical or hemispherical structures, and the particle size is 3-8 mu m; the particle size of the titanium dioxide particles is 1-2 mu m;
in the composite material, the molar ratio of carbon to manganese dioxide to titanium dioxide is 1:3:1 or 1:1:1;
the preparation method of the biomass charcoal comprises the following steps: washing banana peel, drying, acidifying and activating, carbonizing at 300-400 ℃ for 2-4h, grinding into powder, neutralizing and acidifying, filtering, washing to neutrality, and drying to obtain the banana peel;
the preparation method of the manganese titanium oxide-biomass charcoal composite material comprises the following steps:
s1, weighing biomass charcoal, titanium dioxide and manganese dioxide, adding hydrochloric acid solution to dissolve the titanium dioxide and the manganese dioxide completely, then adding sodium hydroxide solution to stir and react to adjust the pH to be neutral, and obtaining reaction liquid;
s2, carrying out hydrothermal reaction on the reaction liquid to obtain the catalyst; the hydrothermal reaction conditions are as follows: the temperature is 120-180 ℃ and the time is 24-72h.
2. The manganese titanium oxide-biomass charcoal composite material according to claim 1, wherein the specific method for acidification and activation is as follows: adding hydrochloric acid solution for soaking treatment, wherein the concentration of the hydrochloric acid is 4-8mol/L, and the soaking treatment time is 10-20h; the specific method for neutralizing and acidifying comprises the following steps: adding sodium hydroxide solution, stirring and reacting, wherein the concentration of the sodium hydroxide solution is 4-8mol/L, and the stirring and reacting time is 2-4h.
3. The manganese titanium oxide-biomass charcoal composite material according to claim 1, wherein in S1, the concentration of the hydrochloric acid solution is 1-5mol/L.
4. The manganese titanium oxide-biomass charcoal composite material according to claim 1, wherein in S1, sodium hydroxide solution with the concentration of 1-5mol/L is added, and stirring reaction is carried out for 2-4 hours to adjust the pH to be neutral.
5. The use of the manganese-titanium oxide-biomass charcoal composite material according to any one of claims 1-4 as an adsorbent for adsorbing and removing dye rhodamine B in water.
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