CN113117644A - Preparation method and application of modified toona sinensis seed hydrothermal carbon - Google Patents
Preparation method and application of modified toona sinensis seed hydrothermal carbon Download PDFInfo
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- CN113117644A CN113117644A CN202110316780.0A CN202110316780A CN113117644A CN 113117644 A CN113117644 A CN 113117644A CN 202110316780 A CN202110316780 A CN 202110316780A CN 113117644 A CN113117644 A CN 113117644A
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- 241000425037 Toona sinensis Species 0.000 title claims abstract description 139
- 235000011783 Cedrela sinensis Nutrition 0.000 title claims abstract description 119
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000012043 crude product Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 44
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000003610 charcoal Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000356 contaminant Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000011160 research Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 49
- 230000000694 effects Effects 0.000 description 25
- 238000002474 experimental method Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 12
- 238000005303 weighing Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- -1 ether compound Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of materials, and particularly relates to a preparation method and application of modified toona sinensis seed hydrothermal carbon. The method comprises the steps of carrying out hydrothermal carbonization treatment on the toona sinensis seed powder, and then cleaning until filtrate is colorless and the pH value of the filtrate is 6.0-8.0 to obtain a toona sinensis seed hydrothermal carbon crude product; soaking the toona sinensis seed hydrothermal carbon crude product with a modifier, then modifying the toona sinensis seed hydrothermal carbon crude product in a water bath environment at 50-70 ℃ for 0.5-1.5 h, and then respectively washing with hydrochloric acid and distilled water and drying to obtain modified toona sinensis seed hydrothermal carbon; the modifier is selected from phosphoric acid, potassium hydroxide, sodium hydroxide and sodium chloride. The method expands the raw material range of the hydrothermal carbon, the used raw materials are low in price, the adsorption efficiency of the toona sinensis seed hydrothermal carbon is further improved after specific treatment, and the method has important significance for the removal research and application of organic matters by using the biomass hydrothermal carbon.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method and application of modified toona sinensis seed hydrothermal carbon.
Background
The removal of organic pollutants from wastewater is often carried out by: distillation, extraction and adsorption processes. However, the distillation method and the extraction method are not suitable for removing low-concentration organic pollutants, the adsorption method is a good choice, and common adsorbents comprise: biochar, clay, zeolite, synthetic apatite, polymer resin and metal organic framework, and the removal of organic pollutants in wastewater by biochar is a popular field which is being researched in recent years.
The hydrothermal carbon is a black solid product which takes biomass or components thereof as raw materials, takes water as a solvent and a reaction medium, and is obtained by hydrothermal reaction, takes carbon as a main body and is rich in oxygen-containing functional groups. The hydrothermal carbon has the characteristics of small surface energy, excellent flow property, good biocompatibility, good chemical stability and the like, and is widely applied to catalyst carriers, adsorbent materials, electrode materials and the like. Particularly, the hydrothermal carbon prepared by the biomass hydrothermal carbonization method has the advantages of low production cost, wide raw material source, simple operation process and the like.
Therefore, how to develop more varieties of hydrothermal carbons with better adsorption effect has important significance for increasing the raw material sources of the hydrothermal carbons and reducing the production cost.
Disclosure of Invention
The invention provides a new hydrothermal carbon raw material aiming at the technical problems in the prior art, namely the hydrothermal carbon is prepared by adopting Chinese toon seeds, and the prepared hydrothermal carbon has good organic matter adsorption effect through modification treatment.
The invention realizes the purpose through the following technical scheme: the invention provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: carrying out hydrothermal carbonization treatment on the cedrela sinensis seed powder, and then cleaning until the filtrate is colorless and the pH value of the filtrate is 6.0-8.0 to obtain a cedrela sinensis seed hydrothermal carbon crude product; soaking the toona sinensis seed hydrothermal carbon crude product with a modifier, then modifying the toona sinensis seed hydrothermal carbon crude product in a water bath environment at 50-70 ℃ for 0.5-1.5 h, and then respectively washing with hydrochloric acid and distilled water and drying to obtain modified toona sinensis seed hydrothermal carbon; the modifier is selected from phosphoric acid, potassium hydroxide, sodium hydroxide and sodium chloride.
As a preferred embodiment, when the modifier is phosphoric acid, the crude cedrela sinensis seed hydrothermal carbon is directly soaked by 20% phosphoric acid.
As a preferred embodiment, when the modifier is one of potassium hydroxide, sodium hydroxide and sodium chloride, the wetting step is as follows: mixing the cedrela sinensis seed hydrothermal carbon crude product and a modifier according to the mass ratio of (2-4) to 1, and then soaking the mixture in distilled water.
As a preferred embodiment, the preparation of the crude cedrela sinensis seed hydrothermal charcoal comprises the following steps: crushing the Chinese toon seeds, sieving the crushed Chinese toon seeds by a screen of 60-100 meshes, soaking the sieved Chinese toon seed powder in deionized water, carbonizing the powder at the constant temperature of 180-250 ℃ for 6-10 hours, naturally cooling the carbonized powder to the room temperature, respectively carrying out suction filtration by using ethanol and water until the filtrate is colorless and the pH value is close to 7, and drying the filtrate to obtain the crude Chinese toon seed hydrothermal carbon product.
As a preferred embodiment, the preparation method is as follows: soaking the cedrela sinensis seed powder sieved by a 80-mesh screen in deionized water, carbonizing at the constant temperature of 220 ℃ for 8h, naturally cooling to room temperature, respectively carrying out suction filtration by using ethanol and water until the filtrate is colorless and the pH value is close to 7, and drying to obtain a cedrela sinensis seed hydrothermal carbon crude product; uniformly mixing the crude toona sinensis seed hydrothermal carbon product and potassium hydroxide according to the mass ratio of 3:1, soaking the mixture in distilled water, modifying the mixture in a water bath environment at 60 ℃ for 1 hour, and then respectively washing the modified toona sinensis seed hydrothermal carbon product with hydrochloric acid and distilled water and then drying the product to obtain the modified toona sinensis seed hydrothermal carbon.
In a preferred embodiment, the temperature raising procedure during carbonization is as follows: raising the temperature from room temperature to 180-250 ℃ at the speed of 0.5-1.5 ℃/min, and then keeping the temperature.
The invention also aims to provide the hydrothermal carbon prepared by the preparation method.
The invention also aims to provide application of the prepared hydrothermal carbon in removing organic pollutants in wastewater.
As a preferred embodiment, the organic contaminant is pyridine.
In a preferred embodiment, the pyridine concentration in the wastewater is 0-100mg/L, the adding amount of the hydrothermal carbon in 50ml of wastewater is 0.1-0.25 g, the pH value is 4-12, and the adsorption time is 90-120 min.
According to the invention, the toona sinensis seeds are adopted to prepare the hydrothermal carbon, the hydrothermal carbon is subjected to modification treatment, 0.15g of the modified toona sinensis seeds is added into 50mg/L pyridine solution, the adsorption reaction is carried out for 90min under the condition that the pH value is 7, and the adsorption rate can reach 20-40%.
Drawings
FIG. 1 is an infrared spectrum of a Chinese toon seed hydrothermal charcoal;
FIG. 2 is an XRD (X-ray diffraction) spectrum of the Chinese toon seed hydrothermal carbon;
FIG. 3 is an SEM picture of cedrela sinensis seeds, wherein A is an SEM picture of cedrela sinensis seed powder, B is an SEM picture of a cedrela sinensis seed hydrothermal carbon crude product, and C is an SEM picture of cedrela sinensis seed hydrothermal carbon modified by potassium hydroxide;
FIG. 4 is a graph showing the effect of the amount of addition on the adsorption effect;
FIG. 5 is a graph showing the effect of initial concentration on adsorption effect;
FIG. 6 is a graph showing the effect of pH on adsorption effect;
FIG. 7 is a graph showing the effect of adsorption time on adsorption effect;
FIG. 8 is a graph showing the effect of different modifiers on adsorption performance;
FIG. 9 is a kinetic fitting result of cedrela sinensis seed adsorbing pyridine, wherein A is a primary kinetic model fitting result, B is a secondary kinetic model fitting result, C is a bi-constant kinetic model fitting result, D is an intra-particle diffusion kinetic model fitting result, and E is an Elocich kinetic model fitting result;
fig. 10 shows the isotherm fitting results of the modified cedrela sinensis seed hydrothermal carbon adsorption pyridine, wherein a is the Freundlich adsorption isotherm model fitting result, and B is the Langmuir adsorption isotherm model fitting result.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, the examples given are intended to illustrate the invention and are not intended to limit the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The inventor firstly carries out infrared spectrum experimental analysis on the toona sinensis seed powder to obtain an infrared absorption spectrum as shown in figure 1, wherein an absorption peak at 2928cm & lt-1 & gt in the figure is stretching vibration of C-H on an aromatic ring; the temperature range of 1000-1450cm < -1 > is mainly initiated by a C-O bond and an O-H bond in a hydroxyl group, an ester group or an ether compound; one peak at 620cm-1 is the out-of-plane bending vibration of ═ C-H on the aromatic ring; a broad peak at 3729-3015cm-1 is the expansion shock absorption peak of the O-H bond; 1604cm-1 shows a stretching vibration absorption peak of C ═ O bond. Therefore, the toona sinensis seed hydrothermal carbon contains rich oxygen-containing functional groups, and the functional groups can increase the coulomb force between the adsorbent and the adsorbate, so that the aim of removing organic pollutants is fulfilled.
XRD powder diffraction experiments were performed on cedrela sinensis seed powder to obtain a powder diffraction pattern shown in fig. 2, from which we know that two broad and relatively strong diffraction peaks in the range of 2 θ 10-30 ° are characteristic peaks of cellulose and hemicellulose and are classified as poorly ordered amorphous carbon.
Based on the above research results, the inventors tried to prepare hydrothermal charcoal using toona sinensis seeds and to use it for the removal of organic contaminants.
Example 1
The embodiment provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: cleaning Toona sinensis seed, oven drying at 105 deg.C, pulverizing with high-speed multifunctional pulverizer, and sieving with 80 mesh sieve. Weighing 25g of sieved Chinese toon seed powder, adding 100mL of deionized water, stirring to fully dip-dye the raw materials and the water, transferring the raw materials and the water into a reaction kettle, screwing the reaction kettle, putting the reaction kettle into a reaction sleeve, heating the reaction kettle to 220 ℃ from room temperature at a speed of 1 ℃/min, and keeping the temperature for 8 hours. Opening the reaction kettle after the reaction kettle is naturally cooled to room temperature, taking out a product, respectively washing with ethanol and deionized water, performing suction filtration until the filtrate is colorless and the pH value is close to 7, drying at 105 ℃ to constant weight, and storing to obtain a toona sinensis seed hydrothermal carbon crude product;
weighing 3g of toona sinensis seed hydrothermal carbon crude product and 1g of potassium hydroxide respectively, uniformly mixing the toona sinensis seed hydrothermal carbon crude product and the potassium hydroxide, soaking the mixture in 12-15 mL of distilled water, modifying the mixture in a water bath environment at the temperature of 60 ℃ for 1h, washing the mixture with 1mol/L hydrochloric acid and distilled water respectively after the reaction is finished, and drying the mixture at the temperature of 105 ℃ to obtain the modified toona sinensis seed hydrothermal carbon.
Example 2
The embodiment provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: cleaning Toona sinensis seed, oven drying at 105 deg.C, pulverizing with high-speed multifunctional pulverizer, and sieving with 80 mesh sieve. Weighing 25g of sieved Chinese toon seed powder, adding 100mL of deionized water, stirring to fully dip-dye the raw materials and the water, transferring the raw materials and the water into a reaction kettle, screwing the reaction kettle, putting the reaction kettle into a reaction sleeve, heating the reaction kettle to 220 ℃ from room temperature at a speed of 1 ℃/min, and keeping the temperature for 8 hours. Opening the reaction kettle after the reaction kettle is naturally cooled to room temperature, taking out a product, respectively washing with ethanol and deionized water, performing suction filtration until the filtrate is colorless and the pH value is close to 7, drying at 105 ℃ to constant weight, and storing to obtain a toona sinensis seed hydrothermal carbon crude product;
weighing 3g of toona sinensis seed hydrothermal carbon crude product and 1g of sodium hydroxide respectively, uniformly mixing the toona sinensis seed hydrothermal carbon crude product and the sodium hydroxide, soaking the mixture in 12-15 mL of distilled water, modifying the mixture in a water bath environment at the temperature of 60 ℃ for 1h, washing the mixture with 1mol/L hydrochloric acid and distilled water respectively after the reaction is finished, and drying the mixture at the temperature of 105 ℃ to obtain the modified toona sinensis seed hydrothermal carbon.
Example 3
The embodiment provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: cleaning Toona sinensis seed, oven drying at 105 deg.C, pulverizing with high-speed multifunctional pulverizer, and sieving with 80 mesh sieve. Weighing 25g of sieved Chinese toon seed powder, adding 100mL of deionized water, stirring to fully dip-dye the raw materials and the water, transferring the raw materials and the water into a reaction kettle, screwing the reaction kettle, putting the reaction kettle into a reaction sleeve, heating the reaction kettle to 220 ℃ from room temperature at a speed of 1 ℃/min, and keeping the temperature for 8 hours. Opening the reaction kettle after the reaction kettle is naturally cooled to room temperature, taking out a product, respectively washing with ethanol and deionized water, performing suction filtration until the filtrate is colorless and the pH value is close to 7, drying at 105 ℃ to constant weight, and storing to obtain a toona sinensis seed hydrothermal carbon crude product;
weighing 3g of toona sinensis seed hydrothermal carbon crude product and 1g of sodium chloride respectively, uniformly mixing the toona sinensis seed hydrothermal carbon crude product and the sodium chloride, soaking the mixture in 12-15 mL of distilled water, modifying the mixture in a water bath environment at the temperature of 60 ℃ for 1h, washing the mixture with 1mol/L hydrochloric acid and distilled water respectively after the reaction is finished, and drying the mixture at the temperature of 105 ℃ to obtain the modified toona sinensis seed hydrothermal carbon.
Example 4
The embodiment provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: cleaning Toona sinensis seed, oven drying at 105 deg.C, pulverizing with high-speed multifunctional pulverizer, and sieving with 80 mesh sieve. Weighing 25g of sieved Chinese toon seed powder, adding 100mL of deionized water, stirring to fully dip-dye the raw materials and the water, transferring the raw materials and the water into a reaction kettle, screwing the reaction kettle, putting the reaction kettle into a reaction sleeve, heating the reaction kettle to 220 ℃ from room temperature at a speed of 1 ℃/min, and keeping the temperature for 8 hours. Opening the reaction kettle after the reaction kettle is naturally cooled to room temperature, taking out a product, respectively washing with ethanol and deionized water, performing suction filtration until the filtrate is colorless and the pH value is close to 7, drying at 105 ℃ to constant weight, and storing to obtain a toona sinensis seed hydrothermal carbon crude product;
weighing 3g of a toona sinensis seed hydrothermal carbon crude product, soaking the toona sinensis seed hydrothermal carbon crude product with 12-15 mL of 20% phosphoric acid, then modifying the toona sinensis seed hydrothermal carbon crude product in a water bath environment at the temperature of 60 ℃ for 1h, after the reaction is finished, washing the toona sinensis seed hydrothermal carbon crude product with 1mol/L hydrochloric acid and distilled water respectively, and then drying the toona sinensis seed hydrothermal carbon crude product at the temperature of 105 ℃ to obtain the modified toona sinensis seed hydrothermal carbon.
Comparative example 1
The embodiment provides a preparation method of modified toona sinensis seed hydrothermal carbon, which comprises the following steps: cleaning Toona sinensis seed, oven drying at 105 deg.C, pulverizing with high-speed multifunctional pulverizer, and sieving with 80 mesh sieve. Weighing 25g of sieved Chinese toon seed powder, adding 100mL of deionized water, stirring to fully dip-dye the raw materials and the water, transferring the raw materials and the water into a reaction kettle, screwing the reaction kettle, putting the reaction kettle into a reaction sleeve, heating the reaction kettle to 220 ℃ from room temperature at a speed of 1 ℃/min, and keeping the temperature for 8 hours. Opening the reaction kettle after the reaction kettle is naturally cooled to room temperature, taking out a product, respectively washing with ethanol and deionized water, performing suction filtration until the filtrate is colorless and the pH value is close to 7, drying at 105 ℃ to constant weight, and storing to obtain a toona sinensis seed hydrothermal carbon crude product;
weighing 3g of toona sinensis seed hydrothermal carbon crude product and 1g of potassium ferrate respectively, uniformly mixing the toona sinensis seed hydrothermal carbon crude product and the potassium ferrate, soaking the toona sinensis seed hydrothermal carbon crude product and the potassium ferrate in 12-15 mL of distilled water, modifying the mixture in a water bath environment at the temperature of 60 ℃ for 1h, washing the mixture with 1mol/L hydrochloric acid and distilled water respectively after the reaction is finished, and drying the mixture at the temperature of 105 ℃ to obtain the modified toona sinensis seed hydrothermal carbon.
Adsorption applications
Respectively scanning pyridine with full wavelength to obtain the maximum absorption wavelength of the pyridine at 257nm, and performing a standard curve experiment under the corresponding wavelength, wherein the method comprises the following specific steps: 6 concentration gradients of 10, 13, 16, 19, 22 and 25mg/L were prepared, the absorbance of pyridine was measured at 257nm of absorption wavelength, and the standard curve fitted to the pyridine solution was calculated as y-0.0319 +0.002(R is 0.0319+ 0.002)2＝0.9993)。
And (3) detecting the adsorbed wastewater solution by an ultraviolet spectrophotometer, and then performing correlation calculation according to the following formula to obtain the adsorption quantity and the removal rate of the adsorbent.
Amount of adsorption
Wherein, C0Initial concentration of organic solution (mg/L); ctConcentration (mg/L) of the waste aqueous solution after the adsorption is finished; qt is the mass (mg/g) of the organic pollutant adsorbed by each gram of adsorbent after the adsorption reaction is finished; v is the solution volume (L); and m is the dosage (g) of the adsorbent.
In the adsorption process, the main factors influencing the adsorption effect are as follows: the adding amount, the pH value, the adsorption time, the initial concentration of the organic wastewater, the reaction temperature and the like all have certain influence on the adsorption effect, but the influence degree of each factor on the adsorption effect is inconsistent, and the sequence of each influence factor experiment needs to be determined through an orthogonal experiment while a single-factor experiment is carried out. The toona sinensis seed hydrothermal carbon prepared in example 1 is used, and the influence of reaction time, pH value, initial concentration and dosage on adsorption effect is determined by using an orthogonal experiment, wherein the orthogonal experiment adopts the design of four-factor five level of L25, the scheme of the four-factor five level of the orthogonal experiment is shown in the following table 1, and range analysis is shown in the following table 2:
TABLE 1 levels and factors of orthogonal experiments
TABLE 2 range analysis of orthogonal experiments
From the analysis of the results in orthogonal table 2 we can see that the worst value is 18.78% of the dosed amount, then 10.04% of the initial concentration, and that pH and time have the least effect on the adsorption effect, 4.29% and 2.20% respectively. Therefore, the influence sequence on the adsorption effect is as follows: the adding amount is more than the initial concentration, the pH value is more than the reaction time, and the optimal adsorption condition is as follows: the amount of pyridine added was 7g/L, the initial concentration of pyridine was 0.05mL/L, the pH was 7, and the reaction time was 120 minutes. And (3) discussing each influence factor one by one according to the strength sequence obtained by the orthogonal experiment, wherein the influence factors are as follows:
(1) influence of dosage on adsorption effect
Putting the cedrela sinensis seed hydrothermal charcoal with the dosage of 0.05, 0.075, 0.1, 0.15, 0.2, 0.25 and 0.35g into a pyridine solution with the initial concentration of 40mg/L and the volume of 50mL, and carrying out constant-temperature water bath for 120min under the conditions of room temperature and pH value of 7 to complete the dosage experiment. The adsorption results are shown in FIG. 4: as can be seen from the figure, the removal rate is increased from 9.4 percent to 20.1 percent along with the increase of the adding amount, and the adsorption amount is gradually reduced from 3.76mg/g to 1.15 mg/g; as can be seen from the trend line of the adsorption amount, when the addition amount is increased from 0.05 to 0.15g, the unit adsorption amount is reduced from 3.76mg/g to 1.78mg/g, the reduction trend is obvious, and the trend becomes slow after the addition amount is 0.15g, so that 0.15g is selected as the addition amount of the cedrela sinensis seeds for adsorbing pyridine.
(2) Effect of initial concentration on adsorption Effect
From the conclusion (1), we chose 0.15g as the addition amount of the adsorption experiment, the initial concentrations of pyridine were 20, 30, 40, 50, 60, 80, 100mg/L, the volume was 50mL, the pH value was 7, the adsorption was performed for 120min under the constant temperature condition by shaking the water bath, and the results after the adsorption are shown in FIG. 5: from fig. 5 we can see that the removal rate gradually decreases with increasing initial concentration. However, the adsorption amount is gradually increased because the concentration is continuously increased, the adsorption sites are limited, the removal rate is continuously reduced, and the two curves of the adsorption amount and the removal rate are intersected at the concentration of 50mg/L, so that the initial concentration point is selected to be 50 mg/L.
(3) Influence of pH value on adsorption Effect
The addition amount of the hydrothermal charcoal is 0.15g, the initial concentration of the pyridine is 50mg/L, the volume is 50mL, and the pH values are 2, 4, 6, 7, 8, 10 and 12 respectively. Shaking in water bath at room temperature for 120 min. The adsorption results are shown in fig. 6: the adsorption of pyridine by the toona sinensis seeds is not facilitated under acidic and alkaline conditions, and the best adsorption effect of the toona sinensis seeds is 4.54mg/L when the pH value is 7, namely under neutral conditions.
(4) Influence of adsorption time on adsorption Effect
The adding amount of the hydrothermal charcoal is 0.15g, the initial concentration of the pyridine is 50mg/L, the volume is 50mL, the pH value is 7, the adsorption time is 20, 30, 40, 60, 90, 120 and 180min respectively, and the adsorption is carried out by water bath oscillation at room temperature. The adsorption results are shown in 7: from the figure, we can see that the unit adsorption amount and the removal rate are gradually increased along with the increase of time, and at 90 minutes, adsorption and desorption basically reach dynamic equilibrium, so that we select 90 minutes as the time condition of the adsorption reaction.
An adsorption experiment was performed on the toona sinensis seed hydrothermal carbons obtained in examples 1 to 4 and comparative example 1 according to the determined optimal adsorption conditions, and an adsorption effect is shown in fig. 8, where the adsorption rate of the toona sinensis seed hydrothermal carbon obtained in example 1 is 36.17%, the adsorption rate of the toona sinensis seed hydrothermal carbon obtained in example 2 is 28.83%, the adsorption rate of the toona sinensis seed hydrothermal carbon obtained in example 3 is 33.83%, the adsorption rate of the toona sinensis seed hydrothermal carbon obtained in example 4 is 29.17%, and the adsorption rate of the toona sinensis seed hydrothermal carbon obtained in comparative example 1 is 25%.
Respectively carrying out morphology characterization on the toona sinensis seed powder, the obtained toona sinensis seed hydrothermal carbon crude product after hydrothermal carbonization and the obtained hydrothermal carbon after modification by means of SEM (scanning electron microscope), and obtaining a graph 3, wherein (A) is the toona sinensis seed powder; (B) is a hydrothermal carbon crude product obtained by carrying out hydrothermal carbonization on the toona sinensis seeds; (C) is hydrothermal carbon modified by potassium hydroxide. As can be seen from the figure, the cedrela sinensis seed powder has a loose sheet structure and obvious pore structures, wherein the surfaces of the cedrela sinensis seed powder in the step A are smooth and glossy, a layer of floccule is attached to the surface of a hydrothermal carbon crude product obtained after hydrothermal carbonization in the step B and is relatively rough, and more hydrothermal carbon floccules are formed after modification by potassium hydroxide in the step C and are piled up to form a net structure near the pores.
According to the determined optimal adsorption conditions, the adsorption experiment is carried out on the crude cedrela sinensis seeds subjected to hydrothermal carbonization in example 1 and the modified cedrela sinensis seeds hydrothermal carbon in example 1, the measured adsorption rate is 26.7%, and the adsorption rate of the modified cedrela sinensis seeds hydrothermal carbon is 36.17%.
Through a large amount of researches, the inventor discovers that the adsorption rate of the prepared toona sinensis hydrothermal carbon can be kept between 20 and 40 percent by detecting according to the determined optimal adsorption conditions after the toona sinensis is crushed and sieved by a sieve of 60 to 100 meshes, the carbonization temperature is controlled between 180 and 250 ℃, the carbonization time is controlled between 6 and 10 hours, the modification temperature is controlled between 50 and 70 ℃, and the modification time is controlled between 0.5 and 1.5 hours.
Adsorption kinetics experiment
The study on the adsorption kinetics of the toona sinensis seed hydrothermal carbon prepared in example 1 was performed. The kinetic process generally has four processes: (1) carrying out integral transportation; (2) diffusion around the particle surface (membrane diffusion or external mass transfer) by the liquid film (or boundary layer); (3) diffusion of ions or molecules through the particles (intraparticle diffusion); (4) chemical reaction with a functional group attached to the group. Adsorption kinetics are important to provide a valuable insight into the adsorption mechanism.
Within the time range of 20-180min, other reaction conditions are consistent (the initial concentration is 50mg/g, the adding amount is 0.15g, and the pH value is 7), an adsorption experiment is completed, and the adsorption result is subjected to kinetic fitting.
Fig. 9 is the kinetic data of cedrela sinensis seed hydrothermal charcoal adsorption pyridine: panel (A) is first order kinetics, R2＝0.992；qe＝4.755mg/g；k10.02303; panel (B) is secondary kinetics: r2＝0.981；k20.00408; graph (C) is a bi-constant kinetic model: r20.897; graph (D) is an intra-particle diffusion kinetic model: r20.847; panel (E) is an Elovich kinetic model: r20.944. The five dynamics models are used for fitting correlation coefficient results, and the Chinese toon seed adsorption can be knownPyridine conforms to first order kinetics, R2＝0.992。
Adsorption isotherm
Completing an adsorption experiment under the condition that other reaction conditions are consistent (the reaction time is 120min, the adding amount is 0.15g, and the pH value is 7) within the concentration gradient range of 20-100mg/L, and carrying out adsorption isotherm fitting on obtained data.
FIG. 10 is an isotherm of pyridine adsorption by Cedrela sinensis seed activated carbon, wherein (A) is Freundlich model; taking LnCe as an abscissa; lnqe is the ordinate. Fitted R20.98011; n is 0.643; lnkf 5.091. FIG. 2 is a Langmuir adsorption isotherm model with 1/ce as abscissa; fitting by taking 1/qe as a vertical coordinate to obtain related data as follows: qmax 2.581; kL ═ 0.0097; r20.95347. In conclusion, the adsorption process of the cedrela sinensis seeds for adsorbing pyridine conforms to the Freundlich adsorption isotherm model.
Thermodynamics of adsorption
Performing thermodynamic experiments on the toona sinensis seed hydrothermal carbon obtained in the example 1, namely completing the experiments of adsorption isotherms at the temperatures of 293, 308 and 323K to obtain three groups of LnkfAccording to R x lnkfThe relation to 1/T can result in the equation y-419.31 x + 43.757. Other thermodynamic parameters calculated from this equation are shown in table 3: delta G is less than 0, which shows that the process of adsorbing pyridine by the toona sinensis seeds through hydrothermal carbon is performed spontaneously; Δ H > 0 indicates that the adsorption process is an endothermic reaction process.
TABLE 3 thermodynamic parameters of hydrothermal carbon adsorption reaction of Toona sinensis seeds
The Chinese toon seed characterization experiment shows that the Chinese toon seed has a developed porous structure and rich oxygen-containing functional groups on the surface, the adsorption capacity of the Chinese toon seed hydrothermal carbon in the adsorption process can reach 5-6 mg/g, the production cost is low, the operation process is simple, the removal rate can reach 34.6% at most, the kinetic fitting follows the quasi-first-order kinetics, and the correlation coefficient R20.992, the adsorption process is a spontaneous endothermic process, conforming to the Freundlich isotherm model, R2＝0.98011。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of modified toona sinensis seed hydrothermal carbon is characterized by comprising the following steps:
carrying out hydrothermal carbonization treatment on the cedrela sinensis seed powder, and then cleaning until the filtrate is colorless and the pH value of the filtrate is 6.0-8.0 to obtain a cedrela sinensis seed hydrothermal carbon crude product;
soaking the toona sinensis seed hydrothermal carbon crude product with a modifier, then modifying the toona sinensis seed hydrothermal carbon crude product in a water bath environment at 50-70 ℃ for 0.5-1.5 h, and then respectively washing with hydrochloric acid and distilled water and drying to obtain modified toona sinensis seed hydrothermal carbon;
the modifier is selected from phosphoric acid, potassium hydroxide, sodium hydroxide and sodium chloride.
2. The preparation method of the modified toona sinensis fruit hydrothermal charcoal according to claim 1, wherein when the modifier is phosphoric acid, the crude toona sinensis fruit hydrothermal charcoal is directly soaked with 20% phosphoric acid.
3. The preparation method of the modified toona sinensis seed hydrothermal carbon according to claim 1, wherein when the modifier is one of potassium hydroxide, sodium hydroxide and sodium chloride, the soaking step is as follows: mixing the cedrela sinensis seed hydrothermal carbon crude product and a modifier according to the mass ratio of (2-4) to 1, and then soaking the mixture in distilled water.
4. The preparation method of the modified toona sinensis seed hydrothermal charcoal according to any one of claims 1 to 3, wherein the preparation of the crude toona sinensis seed hydrothermal charcoal comprises the following steps: crushing the Chinese toon seeds, sieving the crushed Chinese toon seeds by a screen of 60-100 meshes, soaking the sieved Chinese toon seed powder in deionized water, carbonizing the powder at the constant temperature of 180-250 ℃ for 6-10 hours, naturally cooling the carbonized powder to the room temperature, respectively carrying out suction filtration by using ethanol and water until the filtrate is colorless and the pH value is close to 7, and drying the filtrate to obtain the crude Chinese toon seed hydrothermal carbon product.
5. The preparation method of the modified toona sinensis seed hydrothermal carbon according to claim 4, characterized by comprising the following steps:
soaking the cedrela sinensis seed powder sieved by a 80-mesh screen in deionized water, carbonizing at the constant temperature of 220 ℃ for 8h, naturally cooling to room temperature, respectively carrying out suction filtration by using ethanol and water until the filtrate is colorless and the pH value is close to 7, and drying to obtain a cedrela sinensis seed hydrothermal carbon crude product;
uniformly mixing the crude toona sinensis seed hydrothermal carbon product and potassium hydroxide according to the mass ratio of 3:1, soaking the mixture in distilled water, modifying the mixture in a water bath environment at 60 ℃ for 1 hour, and then respectively washing the modified toona sinensis seed hydrothermal carbon product with hydrochloric acid and distilled water and then drying the product to obtain the modified toona sinensis seed hydrothermal carbon.
6. The preparation method of the modified toona sinensis seed hydrothermal carbon according to claim 4, wherein the temperature rise procedure during carbonization is as follows: raising the temperature from room temperature to 180-250 ℃ at the speed of 0.5-1.5 ℃/min, and then keeping the temperature.
7. The hydrothermal carbon prepared by the preparation method of the modified toona sinensis seed hydrothermal carbon as claimed in any one of claims 1 to 6.
8. Use of the hydrothermal charcoal of claim 7 for removing organic contaminants from wastewater.
9. Use of the hydrothermal charcoal according to claim 8 for removing organic contaminants from wastewater, wherein the organic contaminants are pyridine.
10. The application of the hydrothermal carbon in removing organic pollutants in wastewater according to claim 9, wherein the concentration of pyridine in the wastewater is 0-100mg/L, the adding amount of the hydrothermal carbon in 50ml of wastewater is 0.1-0.25 g, the pH is 4-12, and the adsorption time is 90-120 min.
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