CN117358202A - Metal doped eutectic solvent-based hydrothermal carbon and preparation method and application thereof - Google Patents
Metal doped eutectic solvent-based hydrothermal carbon and preparation method and application thereof Download PDFInfo
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- CN117358202A CN117358202A CN202311674454.2A CN202311674454A CN117358202A CN 117358202 A CN117358202 A CN 117358202A CN 202311674454 A CN202311674454 A CN 202311674454A CN 117358202 A CN117358202 A CN 117358202A
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- eutectic solvent
- straw
- hydrothermal
- hydrothermal carbon
- metal
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- 230000005496 eutectics Effects 0.000 title claims abstract description 118
- 239000002904 solvent Substances 0.000 title claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010902 straw Substances 0.000 claims abstract description 76
- 238000001179 sorption measurement Methods 0.000 claims abstract description 59
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000004202 carbamide Substances 0.000 claims abstract description 50
- 238000001035 drying Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000003763 carbonization Methods 0.000 claims abstract description 26
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 22
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000011282 treatment Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 45
- 239000011701 zinc Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 7
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 9
- 239000011574 phosphorus Substances 0.000 abstract description 9
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000003795 desorption Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 239000010452 phosphate Substances 0.000 description 12
- 239000011550 stock solution Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 238000007865 diluting Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000196252 Ulva Species 0.000 description 2
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000028389 Nerve injury Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 230000008764 nerve damage Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[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 XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of adsorption materials, and discloses a metal doped eutectic solvent-based hydrothermal carbon, and a preparation method and application thereof, wherein the preparation method comprises the following steps: cleaning, drying and crushing the straw to obtain high straw powder; adding the obtained straw powder into a urea-based eutectic solvent-water mixed solvent, performing hydrothermal carbonization treatment, and cleaning and drying the obtained solid to obtain a eutectic solvent modified straw-based hydrothermal carbon material; and mixing the eutectic solvent modified straw-based hydrothermal carbon material with metal inorganic salt for mechanical modification, washing and drying to obtain the metal doped eutectic solvent-based hydrothermal carbon. The adsorption and desorption of the material are reversible reactions, can be recycled, and have great economic value and environmental protection value. The result shows that the material of the invention is used as an adsorbent, the accumulated removal rate of Cd and Zn in the wastewater is close to 100%, and the accumulated removal rate of phosphorus is as high as 100%.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a metal doped eutectic solvent-based hydrothermal carbon, and a preparation method and application thereof.
Background
Heavy metal pollution of water is a serious environmental problem, and excessive accumulation of the heavy metal pollution poses serious threat to human health and environment, and has received extensive attention from the international society. Water pollution is a complex phenomenon, and mixed heavy metal pollution frequently occurs. Cadmium (Cd) and zinc (Zn) have similar geochemical properties, often combined as water pollutants. Cd is one of the most toxic elements and is also classified as a class i carcinogen. Continuous exposure to cadmium can cause deleterious and irreversible damage to the human body, including metabolic disorders, nerve damage, renal failure, osteoporosis, and cancer. Zn is a homolog of Cd, and excessive Zn has various adverse effects on human health, including skin irritation, stomach cramps, nausea, anemia, and the like. Therefore, it is important to develop a technique for removing Cd and Zn to reduce damage to organisms.
At present, the technical methods for removing Cd and Zn in water mainly comprise a chemical precipitation method, an adsorption method, an ion exchange method, a membrane separation method and the like. Among them, adsorption technology is receiving extensive attention internationally because of its advantages of high efficiency, ease of use, economic feasibility, environmental safety, etc. Biochar is a sustainable and environmentally friendly black carbon that has been used to remove various contaminants from aqueous media due to its strong adsorption capacity. Biochar is a carbon-rich solid and has shown great potential in environmental remediation. Biochar can be classified into pyrolytic carbon and hydrothermal carbon according to the preparation conditions.
Hydrothermal carbonization (HTC, hydrothermal carbonization) is a process of synthesizing a carbon-rich product in a closed container with biomass material as a raw material and water as a medium in the reaction process at 150-375 ℃ accompanied by a certain autogenous pressure. Different from the huge energy consumption of the traditional pyrolysis method for preparing the carbon, the reaction temperature of the hydrothermal method for preparing the carbon is low, the reaction process is not limited by the moisture content and the carbon content in the raw materials, the energy consumption of the reaction process is low, and the method is an efficient, sustainable, economic and innovative biomass oxidation treatment technology. However, research on the use of the catalyst as a novel adsorption material for simultaneously adsorbing heavy metals Cd and Zn has not been reported yet. Meanwhile, the adsorption capacity and the application in the field of environmental remediation are hindered due to the low arene structure and poor development porosity. For example, chinese patent CN111389350A discloses a method for adsorbing Cd by using enteromorpha hydrothermal carbon (serving as an adsorbent) by removing heavy metal cadmium in water, adding the enteromorpha hydrothermal carbon into wastewater with an initial Cd concentration of 5-100 mg/L, oscillating at normal temperature, adsorbing for 24 h, and filtering; wherein the amount of the adsorbent is 0.8-6.4 g/L. The adsorbent only utilizes adsorption to remove Cd, and has poor Cd removal effect.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a metal doped eutectic solvent-based hydrothermal carbon, and a preparation method and application thereof.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
(1) Cleaning, drying and crushing the straw to obtain straw powder;
(2) Adding the obtained straw powder into a urea-based eutectic solvent-water mixed solvent, performing hydrothermal carbonization treatment, and cleaning and drying the obtained solid to obtain a eutectic solvent modified straw-based hydrothermal carbon material;
wherein the temperature during the hydrothermal carbonization treatment is 170-220 ℃, and the carbonization time is 12-36 h; the drying temperature is 50-90 ℃;
(3) Mixing the eutectic solvent modified straw-based hydrothermal carbon material with metal inorganic salt for mechanical modification, washing and drying to obtain metal doped eutectic solvent-based hydrothermal carbon;
wherein the mechanical modification is mechanical ball milling modification, the rotation speed of mechanical ball milling is 500-1500 rpm, and the drying temperature is 50-90 ℃.
Further, in the hydrothermal carbonization treatment process, the urea-based eutectic solvent-water mixed solvent is a mixture of urea-based eutectic solvent and water, the mass ratio of the eutectic solvent to the straw is 1:1-1:4, more preferably 1:2, and the water addition amount is 5-9 mL/g, more preferably 5-6g/mL.
Further, the metal inorganic salt comprises one or more of lanthanum inorganic salt, iron inorganic salt, magnesium inorganic substance, zinc inorganic salt and calcium inorganic salt.
Further, the mass ratio of the eutectic solvent modified straw-based hydrothermal carbon material to the metal inorganic salt is 1:2-6.
Further, the ball milling rotation speed is 550 rmp, the mechanical ball milling time is 0.5-8 h, preferably, the ball milling time is 0.5-4 h, and more preferably, 4 h.
Further, the number of washing with water is 2 to 4, more preferably 3 to 4.
Further, the drying temperature is 50-90 ℃, the heat preservation time is 8-24 h, and the preferable temperature is 12-24 h.
The metal-doped eutectic solvent-based hydrothermal carbon prepared by the method is prepared.
Further, the hydro-carbon material comprises straw hydro-carbon, eutectic solvent modified straw-based hydro-carbon and metal doped eutectic solvent modified straw-based hydro-carbon material.
The use of the metal-doped eutectic solvent-based hydrothermal char as described above for the preparation and/or as an adsorbent for the simultaneous removal of Cd and Zn in wastewater.
The invention has the advantages and positive effects that:
1. the metal and the phosphate radical introduced by the method generate hydroxyapatite sediment, the ion exchange effect and the coordination complexing effect to adsorb ammonia nitrogen, the adsorption capacity is large, the adsorption speed is high, and the removal rate of harmful substances is high; meanwhile, the adsorption and desorption of the metal doped eutectic solvent-based hydrothermal carbon are reversible reactions, can be recycled, and have great economic value and environmental protection value. The result shows that the metal doped eutectic solvent-based hydrothermal carbon prepared by the method is used as an adsorbent, the accumulated removal rate of Cd and Zn in wastewater is close to 100%, and the accumulated removal rate of phosphorus is as high as 100%.
2. According to the method, the urea-based eutectic solvent is added in the straw hydrothermal carbonization process, so that nitrogen-based functional groups are doped in situ in the hydrothermal carbonization process, and the content of the functional groups of the hydrothermal carbon is increased. The addition of the eutectic solvent can improve the solubility of the straw in the water solvent and the yield of the straw-based solid carbon, and the obtained metal doped eutectic solvent-based hydrothermal carbon has large adsorption capacity.
3. The method takes metal inorganic matters as active components, introduces lanthanum metal by a mechanical ball milling method for modification, and obtains the target adsorption material. The method for introducing urea-based eutectic solvent in the carbonization process can increase the solubility of straw biomass and the yield of the hydrothermal carbon, and can increase the functional groups (oxygen-containing functional groups) of the straw-based hydrothermal carbon, and can realize in-situ incorporation of nitrogen-containing functional groups. The loss of the original functional group of the straw-based hydrothermal carbon can be avoided by a mechanical ball milling modification method, the agglomeration of metals can be reduced, and the dispersity of the active metals can be increased.
Drawings
FIG. 1 is an XPS chart of the invention after adsorption of Cd by a urea-based eutectic solvent-based hydrothermal carbon in example 1;
FIG. 2 is an XPS plot of the invention after adsorption of Zn by a urea-based eutectic solvent-based hydrothermal carbon in example 1;
FIG. 3 is an XPS plot of example 3 of the present invention after lanthanum doped eutectic solvent based hydrothermal carbon adsorption P;
FIG. 4 is an SEM image of a lanthanum doped eutectic solvent-based hydrothermal carbon of example 3 of the present invention;
FIG. 5 is a graph of the adsorption kinetics model of the urea-based eutectic solvent-based hydrothermal carbon of example 1 of the present invention against Cd and Zn;
FIG. 6 is a graph showing adsorption kinetics of the lanthanum doped eutectic solvent-based hydrothermal carbon to P in accordance with example 3 of the present invention;
FIG. 7 is a graph of an adsorption kinetics model of the straw-based hydrothermal carbon material of comparative example 1 on Cd and Zn;
FIG. 8 is a graph of the adsorption kinetics of the straw-based hydrothermal carbon material versus P for comparative application example 3 of the present invention;
FIG. 9 is a graph showing the effect of urea-based eutectic solvent-based hydrothermal carbon on multiple adsorption of Cd and Zn in actual wastewater in example 1 of the present invention;
fig. 10 is a graph showing the effect of the urea-based eutectic solvent-based hydrothermal carbon of example 3 on multiple adsorption of P in actual wastewater.
Among them, the dynamic model fitting uses pseudo-first-order model (PFO) and pseudo second-order model (PSO).
Detailed Description
The invention will now be further illustrated by reference to the following examples, which are intended to be illustrative, not limiting, and are not intended to limit the scope of the invention.
The various experimental operations involved in the specific embodiments are conventional in the art, and are not specifically noted herein, and may be implemented by those skilled in the art with reference to various general specifications, technical literature or related specifications, manuals, etc. before the filing date of the present invention.
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
(1) Cleaning, drying and crushing the straw to obtain straw powder;
(2) Adding the obtained straw powder into a urea-based eutectic solvent-water mixed solvent, performing hydrothermal carbonization treatment, and cleaning and drying the obtained solid to obtain a eutectic solvent modified straw-based hydrothermal carbon material;
wherein the temperature during the hydrothermal carbonization treatment is 170-220 ℃, and the carbonization time is 12-36 h; the drying temperature is 50-90 ℃;
(3) Mixing the eutectic solvent modified straw-based hydrothermal carbon material with metal inorganic salt for mechanical modification, washing and drying to obtain metal doped eutectic solvent-based hydrothermal carbon;
wherein the mechanical modification is mechanical ball milling modification, the rotation speed of mechanical ball milling is 500-1500 rpm, and the drying temperature is 50-90 ℃.
Preferably, in the hydrothermal carbonization treatment process, the urea-based eutectic solvent-water mixed solvent is a mixture of urea-based eutectic solvent and water, the mass ratio of the eutectic solvent to the straw is 1:1-1:4, more preferably 1:2, and the water addition amount is 5-9 mL/g, more preferably 5-6g/mL.
Preferably, the metal inorganic salt comprises one or more of lanthanum inorganic salt, iron inorganic salt, magnesium inorganic substance, zinc inorganic salt and calcium inorganic salt.
Preferably, the mass ratio of the eutectic solvent modified straw-based hydrothermal carbon material to the metal inorganic salt is 1:2-6.
Preferably, the ball milling speed is 550 rmp, the mechanical ball milling time is 0.5-8 h, preferably, the ball milling time is 0.5-4 h, and more preferably, 4 h.
Preferably, the number of washing with water is 2 to 4, more preferably 3 to 4.
Preferably, the drying temperature is 50-90 ℃, the heat preservation time is 8-24 h, and more preferably 12-24 h.
The metal-doped eutectic solvent-based hydrothermal carbon prepared by the method is prepared.
Preferably, the hydro-carbon material comprises straw hydro-carbon, eutectic solvent modified straw-based hydro-carbon and metal doped eutectic solvent modified straw-based hydro-carbon material.
The use of the metal-doped eutectic solvent-based hydrothermal char as described above for the preparation and/or as an adsorbent for the simultaneous removal of Cd and Zn in wastewater.
Specifically, the related preparation and detection are as follows:
example 1
A method for preparing urea-based eutectic solvent-based hydrothermal carbon, comprising the following steps:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 3mL of urea-based eutectic solvent and 27mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon.
Example 2
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 3mL of urea-based eutectic solvent and 27mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon material.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with lanthanum chloride according to a mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at a rotating speed of 550 r/min for 4 h, mixing the ball-milled product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at a temperature of 70 ℃ for 12 h to obtain the lanthanum-doped eutectic solvent-based hydrothermal carbon.
Example 3
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 6mL of urea-based eutectic solvent and 24mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon material.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with lanthanum chloride according to a mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at a rotating speed of 550 r/min for 4 h, mixing the ball-milled product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at a temperature of 70 ℃ for 12 h to obtain the lanthanum-doped eutectic solvent-based hydrothermal carbon.
Example 4
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; adding 1.5mL of urea-based eutectic solvent and 28.5mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with lanthanum chloride according to a mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at a rotating speed of 550 r/min for 4 h, mixing the ball-milled product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at a temperature of 70 ℃ for 12 h to obtain the lanthanum-doped eutectic solvent-based hydrothermal carbon.
Example 5
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 3mL of urea-based eutectic solvent and 27mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with ferric chloride according to the mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at the rotating speed of 550 r/min for 4 h, mixing the ball milling product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at the temperature of 70 ℃ for 12 h to obtain the iron-doped eutectic solvent-based hydrothermal carbon.
Example 6
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 6mL of urea-based eutectic solvent and 24mL of distilled water into 6g of the ball-milled straw powder, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with calcium chloride according to a mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at a rotating speed of 550 r/min for 4 h, mixing the ball-milled product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at a temperature of 70 ℃ for 12 h to obtain the calcium-doped eutectic solvent-based hydrothermal carbon.
Example 7
The preparation method of the metal doped eutectic solvent-based hydrothermal carbon comprises the following steps of:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; and adding 6mL of urea-based eutectic solvent and 24mL of distilled water into 6g of the ball-milled straw powder, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the urea-based eutectic solvent-based hydrothermal carbon.
Mixing the obtained urea-based eutectic solvent-based hydrothermal carbon with magnesium chloride according to a mass ratio of 1:1, placing the mixture in a ball milling tank, ball milling the mixture at a rotating speed of 550 r/min for 4 h, mixing the ball-milled product with ultrapure water, sequentially stirring and centrifuging the mixture, and drying the product at a temperature of 70 ℃ for 12 h to obtain the magnesium-doped eutectic solvent-based hydrothermal carbon.
Comparative example 1
A preparation method of a straw-based hydrothermal carbon material comprises the following steps:
cutting the straws into pieces by scissors, putting the broken straw powder into a ball milling tank, and ball milling for 10 min at the rotating speed of 500 r/min; adding 30mL of distilled water into the ball-milled straw powder 6g, mixing and transferring the mixture into a reaction kettle, carrying out hydrothermal carbonization at 180 ℃ for 18 h, and drying and dehydrating the product to obtain the straw-based hydrothermal carbon material.
Application example 1
Cd 2+ Preparing a stock solution: dissolving high-grade pure cadmium nitrate tetrahydrate 2.7439 g in water, transferring into 1000mL volumetric flask, diluting to marked line, and adding 1000 mg Cd per liter 2+ Obtaining Cd 2+ A stock solution;
cd is processed 2+ Diluting stock solution by corresponding times to prepare the Cd with the initial concentration of 50 mg/L 2+ Solution, then 0.01g urea-based eutectic solvent-based hydrothermal charcoal of example 1 was added to 50 mg/L Cd 2+ In the solution, 24. 24 h was shaken to adsorption equilibrium, the solution was taken out, filtered through a 0.45 μm filter, and the residual Cd in the filtrate was determined by ICP-MS 2+ Concentration, calculated to obtain p-Cd 2+ The adsorption capacity is 19.9 mg/g, cd 2+ About 100% and has a high solid char yield (63.6%).
Application example 2
Zn 2+ Preparing a stock solution: dissolving high-grade pure zinc nitrate hexahydrate 4.5489 g in water, transferring into 1000mL volumetric flask, diluting to marked line, and adding 1000 mg Zn per liter 2+ Obtaining Zn 2+ A stock solution;
zn is added 2+ Diluting stock solution by corresponding times to prepare Zn with initial concentration of 50 mg/L 2+ Solution, then 0.01g urea-based eutectic solvent-based hydrothermal charcoal of example 1 was dosed to 50 mg/L Zn 2+ In the solution, 24. 24 h was shaken to adsorption equilibrium, the solution was taken out, filtered through a 0.45 μm filter membrane, and the filtrate was assayed for residual Zn by ICP-MS 2+ Concentration, calculated to obtain Zn 2+ Adsorption capacity is 17.3 mg/g, zn 2+ About 100% and has a high solid char yield (63.6%).
Application example 3
Phosphate stock solution preparation: drying 2 h of high-grade pure potassium dihydrogen phosphate at 110 ℃, cooling, weighing 0.2197 g, dissolving in water, transferring into a 1000mL volumetric flask, adding 5mL of sulfuric acid, diluting to mark line, and obtaining phosphate stock solution containing 50.0 micrograms of phosphorus per milliliter;
the phosphate stock solution was diluted by a corresponding factor to prepare a phosphate solution with an initial concentration of 50 mg/L, then 0.01g lanthanum doped eutectic solvent-based hydrothermal carbon of example 3 was added to the 50 mg/L phosphate solution, the pH of the solution was controlled to 5.35, the solution was shaken for 24. 24 h to adsorption equilibrium, the solution was taken out and passed through a 0.45 μm filter membrane, and the residual phosphorus concentration of the filtrate was measured by atomic absorption spectrophotometry, and the phosphate adsorption capacity was 48.2 mg/g, the 4-time cumulative removal rate of phosphorus was 98.8%, and the solid carbon yield was 61.5%.
Comparative application example 1
Cd is processed 2+ Diluting stock solution by corresponding times to prepare the Cd with the initial concentration of 50 mg/L 2+ Solution, then 0.01. 0.01g of the straw-based hydrothermal carbon material of comparative example 1 was added to 50 mg/LCd 2+ In the solution, 24. 24 h was shaken to adsorption equilibrium, the solution was taken out, filtered through a 0.45 μm filter, and the residual Cd in the filtrate was determined by ICP-MS 2+ Concentration, calculated to obtain p-Cd 2+ The adsorption amount was 13.1. 13.1 mg/g.
Comparative application example 2
Zn is added 2+ Diluting stock solution by corresponding times to prepare Zn with initial concentration of 50 mg/L 2+ Solution, then 0.01g of the straw-based hydrothermal charcoal material of comparative example 1 was added to 50 mg/L of Zn 2+ In the solution, 24. 24 h was shaken to adsorption equilibrium, the solution was taken out, filtered through a 0.45 μm filter membrane, and the filtrate was assayed for residual Zn by ICP-MS 2+ Concentration, calculated to obtain Zn 2+ The adsorption amount was 11.6. 11.6 mg/g.
Comparative application example 3
The phosphate stock solution is diluted by corresponding times to prepare a phosphate solution with the initial concentration of 50 mg/L, then 0.01g of the straw-based hydrothermal carbon material of comparative example 1 is added into the phosphate solution with the concentration of 50 mg/L, the pH of the solution is controlled to be 5.35, the solution is oscillated for 24 h to the adsorption balance, the solution is taken out to pass through a 0.45-micrometer filter membrane, the residual phosphorus concentration of the filtrate is measured by utilizing an atomic absorption spectrophotometry, and the phosphate adsorption amount is calculated to be 4.3 mg/g.
Application example 1 of the invention is carried out on XPS spectrum test after heavy metal is adsorbed by urea-based eutectic solvent-based hydrothermal carbon, and the result is shown in figure 1. As can be seen from FIG. 1, the XPS spectrum of the urea-based eutectic solvent-based hydrothermal carbon of example 1 of the present invention appears to belong to Cd at 411.78 ev and 405.08ev 3d The new peak of the (2) shows that the urea-based eutectic solvent-based hydrothermal carbon of the invention successfully adsorbs heavy metal Cd.
Application example 2 XPS spectrum test is carried out after heavy metal is adsorbed by urea-based eutectic solvent-based hydrothermal carbon, and the result is shown in figure 2. As can be seen from FIG. 2, the XPS spectrum of the urea-based eutectic solvent-based hydrothermal carbon of example 1 of the present invention appears to belong to Zn at 1044.98 ev and 1021.98ev 2p The new peak of the (2) shows that the urea-based eutectic solvent-based hydrothermal carbon of the invention successfully adsorbs heavy metal Zn.
Application example 3 XPS spectrum test is carried out after lanthanum doped eutectic solvent based hydrothermal carbon adsorbs phosphorus, and the result is shown in figure 3. Root of Chinese characterAs can be seen from FIG. 3, the XPS spectrum of the lanthanum doped eutectic solvent based hydrothermal carbon of example 3 of the present invention shows a spectrum belonging to P at 133.28 and 133.28 ev 2p The new peak of the present invention shows that the lanthanum doped eutectic solvent-based hydrothermal carbon of the present invention successfully adsorbs phosphorus.
The lanthanum doped eutectic solvent based hydrothermal carbon of example 3 of the present invention was tested using a scanning electron microscope and the results are shown in fig. 4. As can be seen from fig. 4, the lanthanum-doped eutectic solvent-based hydrothermal carbon prepared by the method has uniform distribution of components and no obvious structural defects.
The kinetic model was fitted to the adsorption of Cd and Zn by the urea-based eutectic solvent-based hydrothermal carbons of application example 1 and application example 2, and the results are shown in fig. 5. As can be seen from FIG. 5, the adsorption of the urea-based eutectic solvent-based hydrothermal carbon prepared by the invention to Cd reaches equilibrium within 360 minutes, and the equilibrium adsorption quantity reaches 19.9 mg/g; the adsorption of Zn reaches equilibrium within 360 minutes, and the equilibrium adsorption quantity reaches 17.3 mg/g;
the kinetic model fit application example 3 lanthanum doped eutectic solvent based hydrothermal carbon adsorption to P and the results are shown in figure 6. As can be seen from fig. 6, the adsorption of the lanthanum-doped eutectic solvent-based hydrothermal carbon prepared by the invention to P reaches equilibrium within about 120 minutes, and the equilibrium adsorption quantity reaches 48.2 mg/g;
the kinetic model fits the adsorption of Cd and Zn by the straw-based hydrothermal carbon materials of comparative application example 1 and comparative application example 2, and the results are shown in FIG. 7. As can be seen from fig. 7, the adsorption of the comparative straw-based hydrothermal carbon material to Cd reaches equilibrium in about 240 minutes, and the equilibrium adsorption amount reaches 13.1 mg/g; the adsorption of Zn reaches equilibrium within 240 minutes, and the equilibrium adsorption quantity reaches 11.6 mg/g;
the kinetic model was fitted to the adsorption of the comparative application example 3 straw-based hydrothermal carbon material to P, and the result is shown in fig. 8. As can be seen from fig. 8, the adsorption of the comparative straw-based hydrothermal carbon material to P reaches equilibrium in about 240 minutes, and the equilibrium adsorption amount reaches 4.3 mg/g;
the repeated adsorption effect of urea-based eutectic solvent-based hydrothermal carbon of application example 1 and application example 2 on Cd and Zn in actual sewage is shown in FIG. 9. As can be seen from FIG. 9, after 6 times of cumulative adsorption, sewage waterMiddle CdThe removal rate of (2) is about 100%; after 6 times of accumulated adsorption, zn in the sewageThe removal rate of (2) is about 100%;
application example 3 lanthanum doped eutectic solvent-based hydrothermal carbon has multiple adsorption effects on P in actual sewage, and the result is shown in FIG. 10. As can be seen from FIG. 10, P in the sewage is subjected to 5 times of cumulative adsorptionThe removal rate of (2) is about 100%. Meanwhile, as can be seen from application example 3 and comparative application example 3, the invention has a synergistic effect between 3mL urea-based eutectic solvent and 27mL distilled water, and the adsorption capacity of lanthanum-doped eutectic solvent-based hydrothermal carbon prepared by the method of the invention to phosphate can be synergistically improved.
According to the embodiment, the metal doped eutectic solvent-based hydrothermal carbon provided by the invention has the advantages of large adsorption capacity, high adsorption rate, high solid carbon yield and good economic benefit, and can be used for efficiently removing harmful substances such as harmful heavy metals, phosphorus and the like in water, so that the problem of water pollution is solved.
Although embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments.
Claims (10)
1. A preparation method of metal doped eutectic solvent-based hydrothermal carbon is characterized by comprising the following steps of: the method comprises the following steps:
(1) Cleaning, drying and crushing the straw to obtain straw powder;
(2) Adding the obtained straw powder into a urea-based eutectic solvent-water mixed solvent, performing hydrothermal carbonization treatment, and cleaning and drying the obtained solid to obtain a eutectic solvent modified straw-based hydrothermal carbon material;
wherein the temperature during the hydrothermal carbonization treatment is 170-220 ℃, and the carbonization time is 12-36 h; the drying temperature is 50-90 ℃;
(3) Mixing the eutectic solvent modified straw-based hydrothermal carbon material with metal inorganic salt for mechanical modification, washing and drying to obtain metal doped eutectic solvent-based hydrothermal carbon;
wherein the mechanical modification is mechanical ball milling modification, the rotation speed of mechanical ball milling is 500-1500 rpm, and the drying temperature is 50-90 ℃.
2. The method of manufacturing according to claim 1, characterized in that: in the hydrothermal carbonization treatment process, the urea-based eutectic solvent-water mixed solvent is a mixture of urea-based eutectic solvent and water, the mass ratio of the eutectic solvent to the straw is 1:1-1:4, and the water adding amount is 5-9 mL/g.
3. The method of manufacturing according to claim 1, characterized in that: the metal inorganic salt comprises one or more of lanthanum inorganic salt, iron inorganic salt, magnesium inorganic substance, zinc inorganic salt and calcium inorganic salt.
4. The method of manufacturing according to claim 1, characterized in that: the mass ratio of the eutectic solvent modified straw-based hydrothermal carbon material to the metal inorganic salt is 1:2-6.
5. The method of manufacturing according to claim 1, characterized in that: the ball milling rotating speed is 550 rmp, and the mechanical ball milling time is 0.5-8 h.
6. The method of manufacturing according to claim 1, characterized in that: the washing times of the water washing are 2-4 times.
7. The method of manufacturing according to claim 1, characterized in that: the drying temperature is 50-90 ℃, and the heat preservation time is 8-24 h.
8. A metal-doped eutectic solvent-based hydrothermal char produced by the production method of any one of claims 1 to 7.
9. The hydrothermal carbon material of claim 8, wherein: the hydro-carbon material comprises straw hydro-carbon, eutectic solvent modified straw-based hydro-carbon and metal doped eutectic solvent modified straw-based hydro-carbon.
10. Use of a metal-doped eutectic solvent-based hydrothermal char according to claim 8 or 9 for the preparation and/or as an adsorption material for simultaneous removal of Cd and Zn in wastewater.
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