CN116651397B - Waste suaeda salsa biochar, preparation method and application thereof - Google Patents
Waste suaeda salsa biochar, preparation method and application thereof Download PDFInfo
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- CN116651397B CN116651397B CN202310630672.XA CN202310630672A CN116651397B CN 116651397 B CN116651397 B CN 116651397B CN 202310630672 A CN202310630672 A CN 202310630672A CN 116651397 B CN116651397 B CN 116651397B
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- suaeda salsa
- biochar
- benzoyl urea
- waste
- environmental water
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- 241000586290 Suaeda salsa Species 0.000 title claims abstract description 309
- 239000002699 waste material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 163
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 claims abstract description 159
- 239000000575 pesticide Substances 0.000 claims abstract description 159
- 230000007613 environmental effect Effects 0.000 claims abstract description 123
- 238000003763 carbonization Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 81
- 238000005406 washing Methods 0.000 claims abstract description 36
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 31
- 239000012498 ultrapure water Substances 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 238000007873 sieving Methods 0.000 claims abstract description 20
- 239000006228 supernatant Substances 0.000 claims abstract description 19
- 238000000703 high-speed centrifugation Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 230000010355 oscillation Effects 0.000 claims description 37
- 238000000967 suction filtration Methods 0.000 claims description 33
- UISUNVFOGSJSKD-UHFFFAOYSA-N chlorfluazuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC(C=C1Cl)=CC(Cl)=C1OC1=NC=C(C(F)(F)F)C=C1Cl UISUNVFOGSJSKD-UHFFFAOYSA-N 0.000 claims description 30
- 239000005912 Lufenuron Substances 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 25
- PWPJGUXAGUPAHP-UHFFFAOYSA-N lufenuron Chemical compound C1=C(Cl)C(OC(F)(F)C(C(F)(F)F)F)=CC(Cl)=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F PWPJGUXAGUPAHP-UHFFFAOYSA-N 0.000 claims description 25
- 229960000521 lufenuron Drugs 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 25
- 238000012986 modification Methods 0.000 claims description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims description 25
- 239000005979 Forchlorfenuron Substances 0.000 claims description 24
- GPXLRLUVLMHHIK-UHFFFAOYSA-N forchlorfenuron Chemical compound C1=NC(Cl)=CC(NC(=O)NC=2C=CC=CC=2)=C1 GPXLRLUVLMHHIK-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- RGNPBRKPHBKNKX-UHFFFAOYSA-N hexaflumuron Chemical compound C1=C(Cl)C(OC(F)(F)C(F)F)=C(Cl)C=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F RGNPBRKPHBKNKX-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- 239000005893 Diflubenzuron Substances 0.000 claims description 16
- QQQYTWIFVNKMRW-UHFFFAOYSA-N diflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C=C1 QQQYTWIFVNKMRW-UHFFFAOYSA-N 0.000 claims description 16
- 229940019503 diflubenzuron Drugs 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 14
- YOWNVPAUWYHLQX-UHFFFAOYSA-N fluazuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C(OC=2C(=CC(=CN=2)C(F)(F)F)Cl)=C1 YOWNVPAUWYHLQX-UHFFFAOYSA-N 0.000 claims description 13
- 229950006719 fluazuron Drugs 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 24
- 239000003463 adsorbent Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- -1 transition metal carbides Chemical class 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000002917 insecticide Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000005944 Chlorpyrifos Substances 0.000 description 3
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 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
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RYLHNOVXKPXDIP-UHFFFAOYSA-N flufenoxuron Chemical group C=1C=C(NC(=O)NC(=O)C=2C(=CC=CC=2F)F)C(F)=CC=1OC1=CC=C(C(F)(F)F)C=C1Cl RYLHNOVXKPXDIP-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion
Abstract
The invention provides waste suaeda salsa biochar, a preparation method and application thereof, wherein the application comprises a method for removing benzoyl urea pesticides from environmental water by using the waste suaeda salsa biochar, and the method comprises the following steps: washing waste suaeda salsa with ultrapure water, drying in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a shielding gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; dispersing the suaeda salsa biochar in environmental water, sufficiently vortex oscillating to remove the benzoyl urea pesticides, and separating the biochar from the solution by high-speed centrifugation, wherein the obtained supernatant is the environmental water after the benzoyl urea pesticides are removed. The suaeda salsa biochar constructed by the invention is used for removing benzoyl urea pesticides from environmental water, and has the advantages of low cost, rapidness and high removal efficiency.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to waste suaeda salsa biochar, a preparation method and application thereof.
Background
The benzoyl urea pesticide (BUs) is a high-efficiency pesticide with the characteristics of wide insecticidal spectrum, high insecticidal rate, low price and the like, and has been widely used for pest control of fruits, vegetables and crops. However, the widespread use of BUs causes pollution of farmland soil and irrigation water, and is transferred to groundwater, lake water, aquatic organisms, etc. by migration, affecting human health and ecological environment. At present, the common pesticide removal technology mainly comprises an adsorption method, a photochemical degradation method, a microbial degradation method and the like. The adsorption method is widely used because the operation is simple, the adsorbent can be reused and byproducts are not generated, and the adsorption method mainly utilizes the large specific surface area of the adsorbent or functional groups and pollutants to accumulate and concentrate the pollutants through the actions of static electricity, chelation, chemical bonds and the like so as to realize removal.
Conventional solid phase adsorbent materials include natural adsorbent materials (zeolite and clay mineral materials, etc.), nano-oxides (TiO 2 And SiO 2 Etc.), nano zero-valent iron, biochar, etc. Along with the development of material science, novel adsorbent materials such as graphene oxide, metal-organic frameworks, covalent organic frameworks, two-dimensional transition metal carbides and the like are continuously emerging, but the problems of high cost, long adsorption and removal time, complex preparation method, poor removal effect and the like exist in both traditional adsorbents and novel adsorbents. In addition, there are few reports on studies on removal of BUs from environmental water, and the types and extent of pesticides that can be removed are very limited.
Therefore, how to provide a method for removing BUs from environmental water by using a novel adsorbent, which reduces BUs removal cost and improves the removal efficiency of benzoyl urea pesticides is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The technical problems to be solved by the invention are that the adsorbent used for removing pesticides in the prior art has the problems of high cost, long time consumption, complex preparation method, poor removing effect and the like, and the technical problems of researches and reports on removing benzoyl urea pesticides in environmental water are rare at present.
In order to solve the above problems, a first aspect of the present invention provides a method for removing a benzoylurea pesticide from ambient water, the method comprising: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method is 400-800 ℃ and the carbonization time is 2-8h; dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water, carrying out high-speed centrifugation on the environment water after vortex oscillation, and obtaining supernatant after centrifugation, wherein the supernatant is the environmental water after removal of the benzoyl urea pesticides.
In a first aspect, the high temperature carbonization process has a carbonization temperature of 600 ℃ and a carbonization time of 2 hours; after the suaeda salsa biochar is dispersed in the environmental water containing the benzoyl urea pesticides, the vortex oscillation of the environmental water comprises the following steps: dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, and then carrying out vortex oscillation on the environmental water for 2min; the concentration of the benzoyl urea pesticides in the environmental water is 5 mug/mL; the benzoyl urea pesticide at least comprises one of the following components: chlorfluazuron, lufenuron, forchlorfenuron, chlorpyrifos, chlorfluazuron or hexaflumuron; and when the environment water subjected to vortex oscillation is subjected to high-speed centrifugation, the centrifugation speed is 10000rmp, and the centrifugation time is 5min.
In the first aspect, after preparing the suaeda salsa biochar by adopting the high-temperature carbonization method, before dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, performing nitric acid modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after nitric acid modification comprises: adding 1g of suaeda salsa biochar into 30mL of 5mol/L nitric acid solution, uniformly mixing to obtain a mixture, placing the mixture into a 100mL round-bottom flask, heating the mixture until the mixture is boiled for 6h, refluxing and condensing, cooling the mixture to room temperature after the reaction is completed, carrying out suction filtration, repeatedly washing the mixture after suction filtration with distilled water, and carrying out vacuum drying at 60 ℃ to obtain the suaeda salsa biochar modified by nitric acid.
In the first aspect, after preparing the suaeda salsa biochar by adopting the high-temperature carbonization method, before dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, performing acid-alkali modification on the suaeda salsa biochar to obtain the acid-alkali modified suaeda salsa biochar, and performing acid-alkali modification on the suaeda salsa biochar to obtain the acid-alkali modified suaeda salsa biochar comprises: adding 4mg of suaeda salsa biochar into 30mL of sodium hydroxide solution with the concentration of 2mol/L, stirring in a water bath at 90 ℃ for 2h, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into nitric acid solution with the concentration of 14mol/L, carrying out mechanical stirring, carrying out suction filtration after stirring, repeatedly washing precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid.
In a second aspect, the present invention provides a method for removing a benzoylurea pesticide from ambient water, the method comprising: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, dispersing 3g of sieved suaeda salsa biochar in a 50% phosphoric acid aqueous solution, magnetically stirring for 1 hour to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, reacting for 4 hours at 200 ℃, collecting a black product after the reaction, washing the black product with ultrapure water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar after phosphoric acid activation; dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water, carrying out high-speed centrifugation on the environment water after vortex oscillation, and obtaining supernatant after centrifugation, wherein the supernatant is the environmental water after removal of the benzoyl urea pesticides.
In a third aspect, the invention provides a method for preparing waste suaeda salsa biochar, which comprises the following steps: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in a baking oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing the waste suaeda salsa in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method is 400-800 ℃ and the carbonization time is 2-8h.
In a third aspect, further comprising, after preparing the suaeda salsa biochar by high-temperature carbonization, performing nitric acid modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after nitric acid modification comprises: adding 1g of suaeda salsa biochar into 30mL of 5mol/L nitric acid solution, uniformly mixing to obtain a mixture, placing the mixture into a 100mL round-bottom flask, heating the mixture until the mixture is boiled for 6h, refluxing and condensing, cooling the mixture to room temperature after the reaction is completed, carrying out suction filtration, repeatedly washing the mixture after suction filtration with distilled water, and carrying out vacuum drying at 60 ℃ to obtain the suaeda salsa biochar modified by nitric acid.
In a third aspect, the method further includes, after preparing the suaeda salsa biochar by high-temperature carbonization, performing acid-alkali modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after acid-alkali modification, and performing acid-alkali modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after acid-alkali modification includes: adding 4mg of suaeda salsa biochar into 30mL of sodium hydroxide solution with the concentration of 2mol/L, stirring in a water bath at 90 ℃ for 2h, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into nitric acid solution with the concentration of 14mol/L, carrying out mechanical stirring, carrying out suction filtration after stirring, repeatedly washing precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid.
In a fourth aspect, the invention provides a method for preparing waste suaeda salsa biochar, which comprises the following steps: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, dispersing 3g of sieved suaeda salsa biochar in a 50% phosphoric acid aqueous solution, magnetically stirring for 1 hour to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, reacting for 4 hours at 200 ℃, collecting a black product after the reaction, washing the black product with ultrapure water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar after phosphoric acid activation.
In a fifth aspect, the invention provides waste suaeda salsa biochar prepared by the preparation method, wherein the waste suaeda salsa biochar has the following purposes: the method is used for removing the benzoyl urea pesticides in the environmental water, and the benzoyl urea pesticides at least comprise one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
The beneficial effects are that: the invention provides a method for removing benzoyl urea pesticides from environmental water, which comprises the steps of preparing waste suaeda salsa into suaeda salsa biochar by a high-temperature carbonization method, so that the suaeda salsa biochar can be used as an adsorbent to remove the benzoyl urea pesticides in the environmental water through electrostatic adsorption, and the prepared suaeda salsa biochar has a good hole structure and a large specific surface area so as to provide a large adsorption capacity, thereby improving the removal efficiency of the benzoyl urea pesticides; the waste suaeda salsa is used as the raw material of the adsorbent for adsorbing the benzoyl urea pesticides, so that the cost is low, the waste suaeda salsa can be recycled, and the waste of resources is reduced; in addition, the suaeda salsa biochar prepared by the waste suaeda salsa has good solvent stability and environmental protection, can be repeatedly used for a plurality of times, and can save the cost to the greatest extent. The method for removing the benzoyl urea pesticides from the environmental water has the advantages of low cost, high benzoyl urea pesticide removing efficiency and environmental friendliness, expands the application range of waste suaeda salsa, enriches the application of the suaeda salsa biochar in the field of pretreatment of organic pesticides, and provides important technical support and reference for removing the benzoyl urea pesticides from the environmental water.
Drawings
In order to more clearly illustrate the embodiments of the present description or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for removing benzoylurea insecticides from ambient water in an embodiment of the present invention;
FIG. 2 is a graph showing the adsorption capacity of Suaeda salsa biochar prepared at different carbonization temperatures to 6 benzoylurea insecticides in the examples of the present invention;
FIG. 3 is a graph showing the adsorption capacity of Suaeda salsa biochar prepared at different carbonization times for 6 benzoylurea insecticides in the examples of the present invention;
FIG. 4 is a graph showing the adsorption capacity of suaeda salsa biochar in an example of the present invention for 6 benzoylurea insecticides in environmental waters of different pH;
FIG. 5 is a graph showing the adsorption capacity of suaeda salsa biochar in the example of the present invention for 6 benzoylurea insecticides in ambient water of varying ionic strength;
FIG. 6 is a scanning electron micrograph (magnification 10000 times) of suaeda salsa biochar produced in the examples of the present invention;
FIG. 7 is an X-ray diffraction analysis chart of suaeda salsa biochar prepared in the examples of the present invention;
wherein CHLO in the attached drawings is chlorfluazuron; LUFE is lufenuron; the FORC is forchlorfenuron; DIFL is diflubenzuron; PFLR is flufenoxuron; HEXA is hexaflumuron.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Meanwhile, throughout the specification, unless otherwise specifically indicated, the terms used herein should be construed as meaning as commonly used in the art. Accordingly, 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. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
As shown in fig. 1-2, a first embodiment of the present invention provides a method for removing benzoylurea insecticides from ambient water, the method comprising: s101, fully washing waste suaeda salsa by using ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing the waste suaeda salsa in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method is 400-800 ℃ and the carbonization time is 2-8h; s102, dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water, carrying out high-speed centrifugation on the environment water after vortex oscillation, and obtaining supernatant after centrifugation, wherein the environmental water after removal of the benzoyl urea pesticides is obtained.
Specifically, the invention provides a method for removing benzoyl urea pesticides from environmental water, which comprises the steps of preparing waste suaeda salsa into suaeda salsa biochar by a high-temperature carbonization method, so that the suaeda salsa biochar can be used as an adsorbent to remove the benzoyl urea pesticides in the environmental water through electrostatic adsorption, and the prepared suaeda salsa biochar has a good pore structure and a large specific surface area so as to provide a large adsorption capacity, thereby improving the removal efficiency of the benzoyl urea pesticides; the waste suaeda salsa is used as the raw material of the adsorbent for removing the benzoyl urea pesticides, so that the cost is low, the waste suaeda salsa can be recycled, and the waste of resources is reduced; in addition, the suaeda salsa biochar prepared by the waste suaeda salsa has good solvent stability and green environmental protection, can be repeatedly used for a plurality of times, and can save the cost to the greatest extent. The method for removing the benzoyl urea pesticides from the environmental water has the advantages of low cost, high benzoyl urea pesticide removing efficiency and environmental friendliness, expands the application range of waste suaeda salsa, enriches the application of the suaeda salsa biochar in the field of pretreatment of organic pesticides, and provides important technical support and reference for removing the benzoyl urea pesticides from the environmental water.
In some possible embodiments, the high temperature carbonization process has a carbonization temperature of 600 ℃ and a carbonization time of 2 hours; after the suaeda salsa biochar is dispersed in the environmental water containing the benzoyl urea pesticides, the vortex oscillation of the environmental water comprises the following steps: dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, and then carrying out vortex oscillation on the environmental water for 2min; the concentration of the benzoyl urea pesticides in the environmental water is 5 mug/mL; the benzoyl urea pesticide at least comprises one of the following components: chlorfluazuron, lufenuron, forchlorfenuron, chlorpyrifos, chlorfluazuron or hexaflumuron; and when the environment water subjected to vortex oscillation is subjected to high-speed centrifugation, the centrifugation speed is 10000rmp, and the centrifugation time is 5min.
The method is characterized in that the carbonization temperature is 600 ℃ and the carbonization time is 2h as the optimal condition, so that the cost is lower, and the prepared suaeda salsa biochar has a good pore structure, a larger specific surface area and a higher adsorption capacity; after 3mg of suaeda salsa biochar is dispersed in 20mL of environmental water containing benzoyl urea pesticides, the environmental water is subjected to vortex oscillation for 2min, the concentration of the benzoyl urea pesticides is 5ug/mL, the environmental water after vortex oscillation is subjected to high-speed centrifugation, the centrifugation speed is 10000rmp, and the centrifugation time is 5min, so that the removal effect of the benzoyl urea pesticides in the environmental water is optimal; the benzoyl urea pesticide at least comprises one of the following components: the chlorfluazuron, lufenuron, forchlorfenuron, chlorpyriuron, chlorfluazuron or hexaflumuron can effectively remove one or more of chlorfluazuron, lufenuron, forchlorfenuron, chlorpyriuron, chlorfluazuron or hexaflumuron in the environmental water through the suaeda salsa biochar, so that the variety and breadth of the pesticide target object adsorbed by the adsorbent are widened.
In some possible embodiments, after preparing suaeda salsa biochar by high temperature carbonization, before dispersing the suaeda salsa biochar in the environmental water containing benzoyl urea pesticides, performing nitric acid modification on the suaeda salsa biochar to obtain nitric acid-modified suaeda salsa biochar, wherein the steps of: adding 1g of suaeda salsa biochar into 30mL of 5mol/L nitric acid solution, uniformly mixing to obtain a mixture, placing the mixture into a 100mL round-bottom flask, heating the mixture until the mixture is boiled for 6h, refluxing and condensing, cooling the mixture to room temperature after the reaction is completed, carrying out suction filtration, repeatedly washing the mixture after suction filtration with distilled water, and carrying out vacuum drying at 60 ℃ to obtain the suaeda salsa biochar modified by nitric acid.
This is because the specific surface area of the suaeda salsa biochar can be increased by the nitric acid-modified suaeda salsa biochar, and the adsorption capacity can be further improved.
In some possible embodiments, further comprising, after preparing the suaeda salsa biochar by high temperature carbonization, performing acid-base modification on the suaeda salsa biochar before dispersing the suaeda salsa biochar in environmental water containing benzoylurea pesticide to obtain the acid-base modified suaeda salsa biochar, the performing acid-base modification on the suaeda salsa biochar to obtain the acid-base modified suaeda salsa biochar comprising: adding 4mg of suaeda salsa biochar into 30mL of sodium hydroxide solution with the concentration of 2mol/L, stirring in a water bath at 90 ℃ for 2h, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into nitric acid solution with the concentration of 14mol/L, carrying out mechanical stirring, carrying out suction filtration after stirring, repeatedly washing precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid.
This is because the alkali-acid modified suaeda salsa biochar can increase the specific surface area of the suaeda salsa biochar and thereby increase the adsorption capacity.
Example 2
The second embodiment of the invention provides a method for removing benzoyl urea pesticides from environmental water, which comprises the following steps: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, dispersing 3g of sieved suaeda salsa biochar in a 50% phosphoric acid aqueous solution, magnetically stirring for 1 hour to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, reacting for 4 hours at 200 ℃, collecting a black product after the reaction, washing the black product with ultrapure water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar after phosphoric acid activation; dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water, carrying out high-speed centrifugation on the environment water after vortex oscillation, and obtaining supernatant after centrifugation, wherein the supernatant is the environmental water after removal of the benzoyl urea pesticides.
This is because phosphoric acid is modified by a hydrothermal method to synthesize suaeda salsa biochar, which can increase the specific surface area of the suaeda salsa biochar and further increase the adsorption capacity.
Example 3
The third embodiment of the invention provides a preparation method of waste suaeda salsa biochar, which comprises the following steps: fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method is 400-800 ℃ and the carbonization time is 2-8h.
Specifically, the invention provides a preparation method of waste suaeda salsa biochar, which comprises the steps of washing waste suaeda salsa with ultrapure water, drying in a 60 ℃ oven for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a shielding gas, and preparing the waste suaeda salsa biochar by adopting a high-temperature carbonization method. Wherein the benzoyl urea pesticide at least comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
In some possible embodiments, further comprising, after preparing the suaeda salsa biochar by high temperature carbonization, performing nitric acid modification on the suaeda salsa biochar to obtain the nitric acid-modified suaeda salsa biochar comprises: adding 1g of suaeda salsa biochar into 30mL of 5mol/L nitric acid solution, uniformly mixing to obtain a mixture, placing the mixture into a 100mL round-bottom flask, heating the mixture until the mixture is boiled for 6h, refluxing and condensing, cooling the mixture to room temperature after the reaction is completed, carrying out suction filtration, repeatedly washing the mixture after suction filtration with distilled water, and carrying out vacuum drying at 60 ℃ to obtain the suaeda salsa biochar modified by nitric acid.
In some possible embodiments, further comprising, after preparing suaeda salsa biochar by high temperature carbonization, performing acid-base modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after acid-base modification, and performing acid-base modification on the suaeda salsa biochar to obtain the suaeda salsa biochar after acid-base modification comprises: adding 4mg of suaeda salsa biochar into 30mL of sodium hydroxide solution with the concentration of 2mol/L, stirring in a water bath at 90 ℃ for 2h, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into nitric acid solution with the concentration of 14mol/L, carrying out mechanical stirring, carrying out suction filtration after stirring, repeatedly washing precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid.
It should be noted that, in the preparation method of waste suaeda salsa biochar provided in this embodiment 3, the prepared suaeda salsa biochar is the suaeda salsa biochar described in embodiment 1, and the implementation principle and technical concept are exactly the same as those of embodiment 1, so that a part, which is not described in detail in this embodiment 3, only needs to be referred to embodiment 1, and details are not repeated here.
Example 4
The fourth embodiment of the invention provides a preparation method of waste suaeda salsa biochar, which comprises the following steps: washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, dispersing 3g of sieved suaeda salsa biochar in a 50% phosphoric acid aqueous solution, magnetically stirring for 1 hour to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, reacting for 4 hours at 200 ℃, collecting a black product after the reaction, washing the black product with ultrapure water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar after phosphoric acid activation.
It should be noted that, in the preparation method of waste suaeda salsa biochar provided in embodiment 4, the prepared suaeda salsa biochar is the suaeda salsa biochar described in embodiment 2, and the implementation principle and technical concept are exactly the same as those of embodiment 2, so that a part, which is not described in detail in embodiment 4, only needs to be referred to embodiment 2, and details thereof are not repeated here.
In order to further describe the technical scheme of the present application in detail to support the technical problems to be solved by the present application, a method for removing benzoylurea insecticides from environmental water and a method for preparing waste suaeda salsa biochar are specifically exemplified as in examples 5-13.
Example 5
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the application is the waste suaeda salsa grown in Cao Feidian area, the environmental water containing the benzoyl urea pesticides is a solution prepared from the benzoyl urea pesticides and pure water, and the concentration of the benzoyl urea pesticides is 5 mug/mL:
fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method comprises one of the following steps: 400 ℃, 500 ℃, 600 ℃, 700 ℃ or 800 ℃ and 2 hours of carbonization time;
dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: in this example 5, the influence of the suaeda salsa biochar prepared at different carbonization temperatures (400 ℃, 500 ℃, 600 ℃, 700 ℃, or 800 ℃) on the adsorption capacity of one of six benzoylurea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, chlorpyriuron, fluarouron) was examined by a controlled variable method, and as a result, as shown in fig. 2, it was found that the adsorption capacity of the suaeda salsa biochar prepared at the carbonization temperature of 400 ℃ to 600 ℃ on 6 benzoylurea pesticides increased with the increase of the carbonization temperature, but the influence of the suaeda salsa biochar prepared at the carbonization temperature of 600 ℃ to 800 ℃ on the adsorption capacity of 6 benzoylurea pesticides was small. Therefore, in combination with yield and cost problems, a carbonization temperature of 600 ℃ was chosen as the optimal condition.
Example 6
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa grown in Cao Feidian area, the environmental water containing the benzoyl urea pesticides is a solution prepared from the benzoyl urea pesticides and pure water, and the concentration of the benzoyl urea pesticides is 5 mug/mL:
fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method comprises one of the following steps: 2h, 4h, 6h or 8h, the carbonization temperature is 600 ℃;
Dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: in this example 6, the influence of the suaeda salsa biochar prepared at different carbonization times (2 h, 4h, 6h or 8 h) on the adsorption capacity of one of six benzoyl urea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, diflubenzuron, fluvaluron or hexaflumuron) was investigated by a controlled variable method, and the result is shown in fig. 3, and it is known that the carbonization time has no obvious change on the adsorption capacity of the suaeda salsa biochar. Therefore, in combination with the productivity and cost problems, 2h of carbonization time was selected as the optimal condition.
Example 7
The benzoyl urea pesticide is removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa growing in Cao Feidian areas, the environmental water containing the benzoyl urea pesticide is a solution with the benzoyl urea pesticide concentration of 5 mug/mL, which is prepared by the benzoyl urea pesticide, pure water and a pH regulator, and the pH value of the environmental water comprises one of the following components: 3. 4, 5, 6, 7, 8 or 9; the pH regulator comprises hydrochloric acid or sodium hydroxide:
fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃;
dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: in this example 7, the influence of the suaeda salsa biochar on the adsorption capacity of one of six benzoyl urea pesticides (fluazuron, lufenuron, forchlorfenuron, diflubenzuron, fluvaluron or hexaflumuron) in environmental water with different pH values (3, 4, 5, 6, 7, 8 or 9) is studied by a controlled variable method, and the result is shown in fig. 4, and it is known that the adsorption capacities of the six benzoyl urea pesticides are not obviously changed under different pH values, and the benzoyl urea pesticides can be effectively removed under both acidic conditions and alkaline conditions by the suaeda salsa biochar prepared by the invention, so that the application range is wider.
Example 8
The benzoyl urea pesticide is removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is waste suaeda salsa growing in Cao Feidian areas, and the environmental water containing the benzoyl urea pesticide is a solution with the benzoyl urea pesticide concentration of 5 mug/mL prepared from the benzoyl urea pesticide, pure water and sodium chloride; the concentration of sodium chloride in the ambient water comprises one of the following: 0. 20, 40, 60 or 80mmol/L:
fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃;
Dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: in this example 8, the influence of the suaeda salsa biochar on the adsorption capacity of one of six benzoyl urea pesticides (fluazuron, lufenuron, forchlorfenuron, chlorfenuron or hexaflumuron) in the environmental water with different ionic strengths (namely, 0, 20, 40, 60 or 80mmol/L and NaCl) is explored by adding NaCl with different concentrations into the environmental water to change the ionic strength of the environmental water, and as a result, as shown in fig. 5, the adsorption capacity of the six benzoyl urea pesticides is not obviously changed under the different ionic strengths, and the benzoyl urea pesticides can be effectively removed under the condition of high ionic strength by the suaeda salsa biochar prepared by the invention, and the application range is wider.
Example 9
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa growing in Cao Feidian areas, the environmental water containing the benzoyl urea pesticides is the benzoyl urea pesticides, and the benzoyl urea pesticides are prepared from pure water to obtain a solution with the concentration of 5 mug/mL:
fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃;
adding 1g of suaeda salsa biochar into 30mL of 5mol/L nitric acid solution, uniformly mixing to obtain a mixture, heating the mixture in a 100mL round-bottom flask until the mixture boils for 6 hours, refluxing and condensing, cooling the mixture to room temperature after the reaction is completed, performing suction filtration, repeatedly washing the suction-filtered mixture with distilled water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar modified by nitric acid;
Dispersing 3mg of the suaeda salsa biochar modified by nitric acid in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water subjected to vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar adsorbed with the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: the maximum adsorption capacity and RSD of each of six benzoyl urea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, chlorpyriuron, chlorfluazuron or hexaflumuron) in the environmental water are studied by the suaeda salsa biochar modified by nitric acid, and the results are shown in the following table 1, and it is known that the specific surface area of the suaeda salsa biochar can be increased by the suaeda salsa biochar modified by nitric acid, so that the adsorption capacity can be further improved.
TABLE 1
Example 10
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa growing in Cao Feidian areas, the environmental water containing the benzoyl urea pesticides is the benzoyl urea pesticides, and the benzoyl urea pesticides are prepared from pure water to obtain a solution with the concentration of 5 mug/mL:
Fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃;
adding 4mg of suaeda salsa biochar into 30mL of sodium hydroxide solution with the concentration of 2mol/L, stirring for 2h in a water bath at 90 ℃, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into nitric acid solution with the concentration of 14mol/L, carrying out mechanical stirring, carrying out suction filtration after stirring, repeatedly washing a precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid;
dispersing 3mg of the suaeda salsa biochar subjected to alkali-acid modification in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water subjected to vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar adsorbed with the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: the results of exploring the maximum adsorption capacity and RSD of the alkali-acid modified suaeda salsa biochar to one of six benzoylurea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, diflubenzuron or hexaflumuron) in the environmental water respectively are shown in table 2 below, and it is known that the specific surface area of the suaeda salsa biochar can be increased by the alkali-acid modified suaeda salsa biochar, thereby improving the adsorption capacity.
TABLE 2
Example 11
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa growing in Cao Feidian areas, the environmental water containing the benzoyl urea pesticides is the benzoyl urea pesticides, and the benzoyl urea pesticides are prepared from pure water to obtain a solution with the concentration of 5 mug/mL:
washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, dispersing 3g of sieved suaeda salsa biochar in a 50% phosphoric acid aqueous solution, magnetically stirring for 1 hour to obtain a mixed solution, transferring the mixed solution into a 100mL polytetrafluoroethylene reaction kettle, reacting for 4 hours at 200 ℃, collecting a black product after the reaction, washing the black product with ultrapure water, and vacuum drying at 60 ℃ to obtain the suaeda salsa biochar after phosphoric acid activation;
Dispersing 3mg of the suaeda salsa biochar after phosphoric acid activation in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
Experimental results: the maximum adsorption capacity and RSD of each of six benzoylurea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, diflubenzuron, fluvaluron or hexaflumuron) in the environmental water were investigated, and the results are shown in table 3 below, and it is known that the specific surface area of the suaeda salsa biochar can be increased and the adsorption capacity can be further improved by the suaeda salsa biochar after phosphoric acid activation.
TABLE 3 Table 3
Example 12
The waste suaeda salsa biochar is prepared by the following steps:
Fully washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃.
The suaeda salsa biochar is characterized by adopting a Scanning Electron Microscope (SEM), and the result is shown in fig. 6, wherein the suaeda salsa biochar prepared by the embodiment has a porous structure, the pores are uniformly distributed, most of the suaeda salsa biochar has a macroporous structure, and the pore diameter is about 10nm; as shown in FIG. 7, the suaeda salsa biochar has characteristic diffraction peaks of graphite at 24.0 degrees (002), 31.4 degrees (110) and 42.6 degrees (103), which indicates that the suaeda salsa biochar prepared by the method has good graphitization degree.
Example 13
The benzoyl urea pesticides are removed from the environmental water by the following steps, wherein the waste suaeda salsa adopted by the invention is the waste suaeda salsa grown in Cao Feidian area, the environmental water containing the benzoyl urea pesticides is a solution prepared from the benzoyl urea pesticides and pure water, and the concentration of the benzoyl urea pesticides is 5 mug/mL:
S1, fully washing waste suaeda salsa by using ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 hours, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing the waste suaeda salsa in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization time of the high-temperature carbonization method is 2 hours, and the carbonization temperature is 600 ℃;
s2 adsorption: dispersing 3mg of suaeda salsa biochar in 20mL of environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water for 2min, adsorbing the benzoyl urea pesticides in the environmental water by the suaeda salsa biochar, and then carrying out high-speed centrifugation on the environment water after vortex oscillation at 10000rmp for 5min to separate the suaeda salsa biochar after adsorbing the benzoyl urea pesticides, wherein the obtained supernatant is the environmental water after removing the benzoyl urea pesticides; the benzoyl urea pesticide comprises one of the following components: chlorfluazuron, lufenuron, forchlorfenuron, chlorpyrifos, chlorfluazuron or hexaflumuron;
s3, desorption: acetonitrile is added into the suaeda salsa biochar after the benzoyl urea pesticides are adsorbed for desorption, so that the regenerated suaeda salsa biochar after the benzoyl urea pesticides are removed is obtained;
S4, repeatedly performing an S2 adsorption-S3 desorption experiment, calculating the recovery rate and the Relative Standard Deviation (RSD) of the suaeda salsa biochar after each regeneration on six benzoyl urea pesticides (chlorfluazuron, lufenuron, forchlorfenuron, chlorfluazuron or hexaflumuron) respectively, and evaluating the repeated use times of the suaeda salsa biochar.
Experimental results: after the suaeda salsa biochar is repeatedly used for 10 times, the adsorption capacity of the suaeda salsa biochar on lufenuron, diflubenzuron, chlorfluazuron and fluazuron still can reach 29.9mg/g, and the RSD is less than or equal to 11.3 percent.
In summary, the invention prepares the suaeda salsa biochar by a high-temperature carbonization method, perfects the conditions for preparing the suaeda salsa biochar by a high-temperature pyrolysis method, provides a foundation for the preparation and performance research of the suaeda salsa biochar in the future, and uses the prepared suaeda salsa biochar in the field of removal, so as to quickly and efficiently remove benzoyl urea pesticides in environmental water, thereby establishing a novel method for low-cost, high-efficiency and quick benzoyl urea pesticides in environmental water; the suaeda salsa biochar serving as an adsorbent has good solvent stability and larger adsorption capacity (8-32 mg/g) in acid or alkaline solution and high ionic strength, and when the loading volume is 20mL, the adsorption can be completed within 2min by using 3mg of the suaeda salsa biochar, so that the purpose of high-efficiency and rapid removal is achieved; in addition, the raw material of the adsorbent adopted by the invention is waste suaeda salsa, the cost is lower, and the suaeda salsa biochar prepared by the invention has good solvent stability and environmental protection, can be reused for at least 10 times, and compared with the traditional adsorbent in the removing method, the cost is saved to the greatest extent. The method expands the application value of the waste suaeda salsa, enriches the application of the suaeda salsa biochar in the field of pretreatment of organic pesticides, and provides important technical support and reference for removing benzoyl urea in environmental water.
The adsorption capacity measured in the embodiment of the invention is that the concentration of the benzoylurea pesticide in the environmental water (supernatant after centrifugation) after removing the benzoylurea pesticide is detected by adopting a high performance liquid chromatograph (Agilent 1200 high performance liquid chromatograph), and the maximum adsorption capacity of the suaeda salsa biochar under a certain time (t) is q t The representation is calculated by equation (1):
wherein:
C 0 initial concentration of BUs, μg/mL;
C t residual mass concentration of BUs, μg/mL at-t time;
adding the mass of the biochar in the m-adsorption process, and mg;
V-BUs standard volume of ambient water, mL.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (2)
1. A method of removing a benzoylurea pesticide from ambient water, the method comprising:
washing waste suaeda salsa with ultrapure water, drying the washed waste suaeda salsa in an oven at 60 ℃ for 2 h, grinding the dried waste suaeda salsa, sieving with a 100-mesh sieve, placing in a tubular furnace, taking nitrogen as a protective gas, and preparing suaeda salsa biochar by adopting a high-temperature carbonization method; the carbonization temperature of the high-temperature carbonization method is 400-800 ℃ and the carbonization time is 2-8 h;
after preparing suaeda salsa biochar by adopting a high-temperature carbonization method, before dispersing the suaeda salsa biochar in environmental water containing benzoyl urea pesticides, performing alkali-acid modification on the suaeda salsa biochar to obtain alkali-acid modified suaeda salsa biochar, and performing alkali-acid modification on the suaeda salsa biochar to obtain alkali-acid modified suaeda salsa biochar, wherein the preparation method comprises the following steps of:
Adding 4 mg of suaeda salsa biochar into a sodium hydroxide solution with the concentration of 2 mol/L of 30 mL, stirring 2 h in a water bath at 90 ℃, cooling the suaeda salsa biochar to room temperature after stirring, carrying out suction filtration, adding the suaeda salsa biochar obtained after suction filtration into a nitric acid solution with the concentration of 14 mol/L, mechanically stirring, carrying out suction filtration after stirring, repeatedly washing a precipitate obtained after suction filtration with ultrapure water, and carrying out vacuum drying on the washed precipitate at 60 ℃ to obtain the suaeda salsa biochar modified by alkali-acid;
dispersing the suaeda salsa biochar modified by alkali-acid in environmental water containing benzoyl urea pesticides, carrying out vortex oscillation on the environmental water, carrying out high-speed centrifugation on the environmental water subjected to vortex oscillation, and obtaining supernatant after centrifugation, wherein the supernatant is the environmental water after the benzoyl urea pesticides are removed;
the benzoylurea pesticide comprises at least one of the following components: fluazuron, lufenuron, forchlorfenuron, diflubenzuron, chlorfluazuron or hexaflumuron.
2. The method according to claim 1, characterized in that:
the carbonization temperature of the high-temperature carbonization method is 600 ℃, and the carbonization time is 2 h;
after the suaeda salsa biochar modified by alkali-acid is dispersed in the environmental water containing the benzoyl urea pesticides, the vortex oscillation of the environmental water comprises the following steps: dispersing the suaeda salsa biochar modified by the alkali-acid in the environment water containing benzoyl urea pesticides in the amount of 3 mg in 20 mL, and then carrying out vortex oscillation on the environment water for 2 min; the concentration of the benzoyl urea pesticides in the environmental water is 5 mug/mL;
And when the environment water subjected to vortex oscillation is subjected to high-speed centrifugation, the centrifugation speed is 10000 rpm, and the centrifugation time is 5 min.
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| CN110681350A (en) * | 2019-09-19 | 2020-01-14 | 天津大学 | Preparation method of phosphoric acid modified enteromorpha biological carbon and application of phosphoric acid modified enteromorpha biological carbon in removal of heavy metal cadmium |
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| CN108264044A (en) * | 2018-04-26 | 2018-07-10 | 济南大学 | A kind of fluffy base Ultramicro-powder agglomerated activated carbon of alkali and preparation method thereof |
| CN114272942A (en) * | 2021-11-12 | 2022-04-05 | 南昌航空大学 | Phosphoric acid modified hydrothermal carbon and preparation method and application thereof |
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