CN115193425B - Preparation and application of ion imprinting modified porous sodium alginate microsphere material - Google Patents
Preparation and application of ion imprinting modified porous sodium alginate microsphere material Download PDFInfo
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- CN115193425B CN115193425B CN202210835878.1A CN202210835878A CN115193425B CN 115193425 B CN115193425 B CN 115193425B CN 202210835878 A CN202210835878 A CN 202210835878A CN 115193425 B CN115193425 B CN 115193425B
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 57
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 55
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 55
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000004005 microsphere Substances 0.000 title claims abstract description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000004098 Tetracycline Substances 0.000 claims abstract description 50
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 50
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 50
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229960002180 tetracycline Drugs 0.000 claims abstract description 49
- 229930101283 tetracycline Natural products 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 8
- 244000144972 livestock Species 0.000 claims abstract description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 244000144977 poultry Species 0.000 claims abstract description 6
- 230000001360 synchronised effect Effects 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 56
- 229910052802 copper Inorganic materials 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003463 adsorbent Substances 0.000 abstract description 10
- -1 calcium chloride modified sodium alginate Chemical class 0.000 abstract description 9
- 239000001110 calcium chloride Substances 0.000 abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009395 breeding Methods 0.000 abstract description 2
- 230000001488 breeding effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 5
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 4
- 229940072056 alginate Drugs 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 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
- 238000009304 pastoral farming Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000009374 poultry farming Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses preparation and application of an ion imprinting modified porous sodium alginate microsphere material, and belongs to the technical field of environmental functional materials. The preparation method comprises the following steps: firstly, reacting epichlorohydrin with thiourea at 70 ℃, then adding sodium alginate for reaction, then adding a calcium chloride pore-forming agent for pore-forming after reacting for a period of time, then adding copper sulfate pentahydrate for ion imprinting adhesion, and eluting to obtain the thiourea and calcium chloride modified sodium alginate material. The synthetic material disclosed by the invention is simple in preparation process and low in raw material cost, overcomes the defects of poor adsorption performance, low utilization rate and poor mechanical property of sodium alginate serving as an adsorbent, remarkably improves the synchronous selective removal effect of tetracycline and copper ions in water, and has a wide application prospect in treatment of livestock and poultry breeding wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental functional materials, and in particular relates to a method for synchronously removing tetracycline and copper ions (Cu 2+ ) The preparation and application of the ion imprinting modified porous sodium alginate microsphere material are mainly applied to the treatment of livestock and poultry breeding wastewater.
Background
In the course of livestock and poultry farming, animal feeds rich in chemical additives are widely used. Antibiotics and heavy metals are used as main components of the additive, and healthy growth of animals can be effectively promoted through an antibacterial activity mechanism. The related report shows that 3-9 times of copper required by animal growth is usually added into livestock feed, and the medicines put into use are rich in tetracycline, most of the additives cannot be absorbed by animals, and finally discharged along with excrement and urine, so that serious threat is caused to animal and human health. Due to tetracycline and Cu 2+ Complex with higher toxicity is easy to form in water body, and is enriched in human body through food chain, so that human body is acutely poisoned, therefore, the design can effectively and synchronously remove tetracycline and Cu in water body 2+ Has important practical significance.
At present, the treatment of heavy metals and antibiotics in water mainly comprises a chemical precipitation method, a photocatalysis method, an adsorption method and a membrane separation technology. Adsorption has been widely used for removing organic matter and heavy metals as a highly efficient, green and economical water pollution treatment technology. The biological adsorbent is mainly prepared from dead or inactive biological materials, can effectively adsorb water pollutants through physical and chemical processes, and has the advantages of low cost, economy, environmental protection and the like. Sodium alginate is a water-soluble polysaccharide biopolymer material, the annual output is about 3 ten thousand tons, and because of a large number of hydroxyl and carboxyl groups on the surface of the sodium alginate, the sodium alginate can perform flocculation reaction with divalent and trivalent cations and has strong adsorptivity. Therefore, the sodium alginate is utilized to synchronously remove the tetracycline and Cu in the water body 2+ Has certain theoretical feasibility. However, sodium alginate alone as an adsorbent has a series of problems of poor adsorption performance, low utilization rate, poor mechanical properties and the like, and limits the application thereof in practical engineering, so that proper modification of sodium alginate is necessary.
Researches show that the calcium chloride is taken as a good pore-forming agent, so that the specific surface area of the material can be increased, and the adsorption performance of the material is improved. Thiourea is a sulfur-containing organic compound that itself contains a c=s functional group that selectively complexes with a portion of the metal ions. Metal ion imprinting technologyIn the method, template molecules and functional monomers can be combined through chelation between metal and ligand atoms, and the coordination of the template molecules and the functional monomers has better stability relative to non-covalent bonds, so that the selective removal performance of heavy metal ions can be remarkably improved. Therefore, the thiourea and calcium chloride modified sodium alginate microsphere material is researched and developed by applying the ion imprinting technology to synchronously remove the tetracycline and Cu in the water body 2+ Not only enriches the application ways of biomass adsorbent alginate, but also improves tetracycline and Cu in livestock and poultry raising wastewater 2+ Has important significance in the efficient and selective removal of the waste water.
In the prior art, sodium alginate is used for preparing related adsorbing materials, and the related adsorbing materials have partial achievements, such as Chinese patent application number: 202111484023.0, application publication No. 2021, no. 03 and No. 08, disclose a patent document entitled "preparation method, product and application of sodium alginate/polyvinyl alcohol/polyacrylamide/kaolin adsorption material"; chinese patent application No.: 202111190093.5, application publication day 2021, 10 and 13, discloses a patent document named "a polyamide-amine modified sodium alginate gel ball for removing heavy metal ions in water" and a preparation method thereof; chinese patent application No.: 201811410014.5, publication date 2019, month 03 and 15, discloses a patent document named "a preparation method of sodium alginate gel spheres"; the three adsorption materials have better removal effect on single heavy metals or antibiotics, but the material selectivity is not high, and the adsorption materials are used for tetracycline and Cu 2+ The removal effect of the formed complex is unknown; chinese patent application No.: 202010908342.9 and 12-04 in the publication of the application, disclose a patent document named as a preparation method of amino-terminated hyperbranched magnetic sodium alginate gel microsphere, and the patent sequentially prepares magnetic nanoparticles, magnetic sodium alginate and amino-terminated hyperbranched polysilane, and wraps the amino-terminated hyperbranched polysilane on the surface of the magnetic sodium alginate through amidation reaction, so that the preparation of the amino-terminated hyperbranched magnetic sodium alginate gel microsphere is completed, however, the preparation method in the patent has more steps and complex process.
There have been some efforts in water body tetracycline and copper ion removal studies. For example, chinese patent application No.: CN202010950939.X, application publication date 2020, 12 months and 11 days, discloses a patent document named as "Cu-containing biochar adsorption synergistic catalytic oxidation for removing tetracycline in water body"; chinese patent application No.: 202111624683.4, published application 2022, 04/08, discloses a patent document named "copper oxide-iron oxide/foam nickel composite material for degrading tetracycline and preparation method"; chinese patent application No.: 202210010958.3, published application 2022, 01 and 06, discloses a patent document named "preparation and application of quartz sand @ hollow CuS nano cubic composite material", wherein although the three materials can effectively remove tetracycline in water, the synthesis process and the removal way of the adsorption material are complex, the treatment cost is high, and synchronous removal of copper and tetracycline is not realized. Chinese patent application No.: 202110544277.0, published application 2021, 05-19, discloses a patent document named "a degradation treatment method of copper complexing reinforced tetracycline pollutants", and the adsorption material has good tetracycline removal effect, is easy to oxidize and is relatively complex to store. Chinese patent application No.: CN108911008A, publication date 2018, month 07 and 19, discloses a patent document named "method for removing copper and tetracycline from water body"; chinese patent application No.: CN202010349463.4, publication date 2020, 04 and 28, discloses a patent document named "a composite adsorbent for efficiently removing mixed pollutants in wastewater and a preparation method thereof". The two materials have certain removal effects on copper and tetracycline, but the influence of other coexisting ions of the solution is not considered, the selection performance is unknown, the material synthesis process is complex, and the treatment cost is high.
Disclosure of Invention
Synchronous removal of tetracycline and Cu in water body aiming at the prior art 2+ The invention aims to provide a method for synchronously removing tetracycline and Cu in water body 2+ The preparation method of thiourea and calcium chloride modified sodium alginate and ion imprinting technology material is used for improving biological adsorptionThe selectivity, the utilization rate and the mechanical property of the material are also the actual tetracycline and Cu in the water body 2+ Provides a technical reference for the synchronization removal of (a).
In order to solve the problems, the invention adopts the following technical scheme.
The invention provides a preparation method of a modified sodium alginate material for removing tetracycline and copper in a water body, which specifically comprises the following steps:
(1) Firstly preparing 5% sodium hydroxide solution, then adding 2g of thiourea and 4ml of epichlorohydrin, placing the mixture in a wide-mouth bottle, sealing the wide-mouth bottle in a constant-temperature shaking box pot, and shaking the mixture for 4 hours under the condition of 70 ℃ and 200 rmp; then adding 2-4 g of sodium alginate solution, and continuing to react for 7h under the above conditions; the gel obtained is oscillated for 15-20 minutes in a frozen ultrasonic instrument, then 2% calcium chloride solution is added, and the reaction is continued for 12 hours.
(2) Preparation of 2.0-4.0 mmol/L Cu 2+ The pH of the ionic solution is adjusted to be 1-1.5 by a pH meter, 20ml of the solution prepared in the step (1) is taken out and added, and the reaction is continued for 12 hours under the reaction condition of the step (1); the obtained material is subjected to static layering, redundant solution is filtered, then ethanol solution containing 4-6% of urea is added, and the material is soaked for 12 hours at 70 ℃.
(3) Filtering the solution obtained in the step (2), and then adding 0.1-0.3 mmol/L HCl (20 ml) and standing at 70 ℃ for 6 hours; filtering the solution after standing, repeatedly cleaning for at least three times by using distilled water, and then drying at room temperature to obtain the ion imprinting porous alginate microsphere material.
The ion imprinting porous sodium alginate microsphere material obtained by the preparation method can be applied to the efficient and selective removal of tetracycline and copper ions in livestock and poultry raising wastewater.
Further, at an initial concentration of tetracycline of 0.1mmol/L, an initial concentration of copper of 0.05mmol/L and an initial solution pH of 5.0, adsorption amounts of the thiourea modified sodium alginate material to tetracycline and copper are 3.672mmol/g and 4.569mmol/g, respectively.
The specific principle of the invention is presumed as follows:
the modified sodium alginate can form porous material to increase specific surface areaAnd its active site: under acidic conditions, TC and Cu (II) complex to form a significant amount of CuHTC + And CuH 2 TC 2+ When the pH value of the modified sodium alginate is more than 4.52, the surface of the modified sodium alginate is negatively charged, and the modified sodium alginate has good electrostatic effect on the formed complex; thiourea is a compound formed by replacing oxygen in urea with sulfur, and has rich amino groups. After the thiourea is used for modifying the sodium alginate, TC and Cu (II) can be directly adsorbed through amino groups on the surface of the thiourea, and C=S contained in the thiourea has a good complexing effect on the TC and the Cu (II).
The removal mechanism of the thiourea modified sodium alginate material for tetracycline and copper is mainly ion exchange and complexation.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method has the advantages of simple preparation flow, low raw material cost, high removal efficiency and strong selectivity. In the preparation process, the problems of poor adsorption performance, low utilization rate, poor mechanical performance and the like of sodium alginate are solved by optimizing the conditions of temperature, stirring speed and the like, and the adsorption rate of the sodium alginate is improved.
(2) The material can effectively remove tetracycline and copper in water, the initial concentration of the tetracycline is 0.1mmol/L, the initial concentration of the copper is 0.05mmol/L, the pH value of an initial solution is 5.0, the adsorption capacity (3.672 mmol TC/g and 4.569mmol Cu (II)/g) of the thiourea modified sodium alginate material on the tetracycline and the copper is far higher than that of the sodium alginate (1.651 mmol TC/g and 2.104mmol Cu (II)/g), and the reaction process can reach balance within 240 min.
(3) The modified adsorbing material disclosed by the invention has the advantages that the specific surface area is increased, and more surface reaction sites are provided, so that the modified adsorbing material has higher adsorption capacity and faster reaction rate on tetracycline and copper. The material remarkably enhances the removal effect of the tetracycline and the copper in the water body, and the removal of the tetracycline and the copper in the water body is little influenced by other coexisting ions in the water body.
Drawings
FIG. 1 is a scanning electron microscope image of a thiourea modified porous sodium alginate material obtained in example 1 of the present invention;
the graph shows that the modified material belongs to a porous structure, the porosity is increased, and the adsorption of TC and Cu (II) is facilitated.
FIG. 2 is a graph showing the adsorption effect of tetracyclines on thiourea modified porous sodium alginate material obtained in example 1 of the present invention at different pH values;
as can be seen from the graph, when the pH is increased from 3 to 5, the adsorption amount of TC is increased, and then when the pH is increased from 5 to 9, the adsorption amount of TC is decreased, and when the ph=5, the adsorption amount is the highest, and the adsorption effect is the best.
FIG. 3 is a graph showing the adsorption effect of copper at different pH values of the thiourea modified porous sodium alginate material obtained in example 1 of the present invention;
as can be seen from the graph, the adsorption amount of Cu (II) showed an upward trend when the pH increased from 3 to 5, and then showed a downward trend when the pH increased from 5 to 9, and the adsorption amount reached the highest at ph=5, with the best adsorption effect.
FIG. 4 is a plot of the presence of tetracycline and its relative amounts at various pH values, as derived from MINTEQ software;
from the figure, at ph=5, TC is mainly H in TC and Cu (II) complexes 2 TC and CuHTC + And the adsorbent has a negative surface charge at ph=5, indicating the presence of electrostatic adsorption.
FIG. 5 shows the presence of copper and its relative amounts at different pH values, as derived from MINTEQ software;
from the figure, at ph=5, cu (II) in the TC and Cu (II) complexes is mainly found as CuHTC + And the adsorbent has a negative surface charge at ph=5, indicating the presence of electrostatic adsorption.
Detailed Description
The technical scheme of the present invention is described in further detail below with reference to specific examples, but is not limited thereto.
Example 1
The embodiment provides a preparation method of thiourea modified porous sodium alginate microspheres (the modification ratio of thiourea is 0.5, namely the mass ratio of thiourea to sodium alginate is 1:2), which comprises the following steps:
(1) Firstly preparing 30ml of 5% sodium hydroxide solution, then adding 2g of thiourea and 4ml of epichlorohydrin, placing the mixture in a wide-mouth bottle, sealing the wide-mouth bottle in a constant-temperature shaking box pot, and shaking the mixture for 4 hours under the condition of 70 ℃ and 200 rmp; then adding 4g of sodium alginate solution, and continuing to react for 7 hours under the above conditions; oscillating the obtained gel in a frozen ultrasonic instrument for 15 minutes, then adding 2% calcium chloride solution, and continuing to react for 12 hours;
(2) Preparation of 2.0mmol/L Cu 2+ The solution is adjusted to pH=1 for standby by a pH meter, 20ml of the solution prepared in the step (1) is taken out and added, and the reaction is continued for 12 hours under the reaction condition of the step (1); standing and layering the obtained material, filtering redundant solution, adding ethanol solution containing 4% urea, and soaking for 12h at 70 ℃;
(3) Filtering the solution in the step (2), and then adding 20ml of 0.1mmol/L HCl and standing at 70 ℃ for 6 hours; filtering the solution after standing, repeatedly cleaning for at least three times by using distilled water, and then drying at room temperature to obtain the ion imprinting porous alginate microsphere material.
Example 2
The embodiment provides a preparation method of thiourea modified porous sodium alginate microspheres (the modification ratio of thiourea is 1, namely the mass ratio of thiourea to sodium alginate is 1:1), which comprises the following steps:
(1) The pretreatment of sodium alginate was as described in step (1) of example 1. Except that 2g of sodium alginate was weighed and dissolved in 30mL of 5% ethanol solution.
(2) The preparation of the ion-imprinted sodium alginate was as described in step (2) of example 1.
(3) The rinsing process was as described in step (3) of example 1.
Example 3
The embodiment provides a preparation method of thiourea modified porous sodium alginate microspheres (the modification ratio of thiourea is 1, namely the mass of thiourea and sodium alginate is 1:2), wherein the copper ion concentration is 4.0mmol/L in the ion imprinting process, and the method comprises the following steps:
(1) The pretreatment of sodium alginate was as described in step (1) of example 1. Preparation of the separatorThe sub-blotting sodium alginate procedure is as described in step (2) of example 1. Except that 4.0mmol/L Cu was prepared 2+ For use in ion imprinting processes.
(2) The rinsing process was as described in step (3) of example 1.
Example 4
The embodiment provides a research on removal efficiency of tetracycline and copper by thiourea modified porous sodium alginate microspheres under different coexisting ions. That is, under the same experimental conditions, 0.04mmol/L of competing cation Mg was added to the reaction solution 2+ 。
Comparative example 1
The comparative example provides a preparation method of a nonionic imprinting thiourea modified porous sodium alginate microsphere, which comprises the following steps:
(1) Firstly preparing 30ml of 5% sodium hydroxide solution, then adding 2g of thiourea and 4ml of epichlorohydrin, placing the mixture in a wide-mouth bottle, sealing the wide-mouth bottle in a constant-temperature shaking box pot, and shaking the mixture for 4 hours under the condition of 70 ℃ and 200 rmp; then adding 4g of sodium alginate solution, and continuing to react for 7 hours under the above conditions; oscillating the obtained gel in a frozen ultrasonic instrument for 15 minutes, then adding 2% calcium chloride solution, and continuing to react for 12 hours;
(2) Filtering the solution in the step (1), and then adding 20ml of 0.1mmol/L HCl and standing at 70 ℃ for 6 hours; filtering the solution after standing, repeatedly cleaning for at least three times by using distilled water, and then drying at room temperature to obtain the ion imprinting porous alginate microsphere material.
Comparative example 2
The comparative example provides a preparation method of ion imprinting thiourea modified sodium alginate microspheres, which comprises the following steps:
(1) Firstly preparing 30ml of 5% sodium hydroxide solution, then adding 2g of thiourea and 4ml of epichlorohydrin, placing the mixture in a wide-mouth bottle, sealing the wide-mouth bottle in a constant-temperature shaking box pot, and shaking the mixture for 4 hours under the condition of 70 ℃ and 200 rmp; then adding 4g of sodium alginate solution, and continuing to react for 7 hours under the above conditions; oscillating the obtained gel in a frozen ultrasonic instrument for 15 minutes;
(2) Preparation of 2.0mmol/L Cu 2+ Solution, ph=1 adjusted by pH meterTaking out 20ml of the solution prepared in the step (1) for standby, and continuing to react for 12 hours under the reaction condition of the step (1); standing and layering the obtained material, filtering redundant solution, adding ethanol solution containing 4% urea, and soaking for 12h at 70 ℃;
the whole experiment was carried out at a tetracycline concentration of 0.1mmol/L, a copper ion concentration of 0.05mmol/L, pH =5.0, t=298K and a reaction time of 4 h.
The thiourea modified porous sodium alginate materials prepared in examples 1-2 (the ratio of thiourea to sodium alginate is 0.5 and 1 respectively) were used as adsorbents to treat laboratory-simulated tetracycline and copper-containing wastewater, respectively. As shown in Table 1, the adsorption amount of tetracycline and copper was high when the ratio of thiourea to sodium alginate was 0.5.
The thiourea modified sodium alginate material prepared in example 1, the nonionic imprinting thiourea modified porous sodium alginate material in comparative example 1 and the ion imprinting thiourea modified sodium alginate material in comparative example 2 are respectively used as adsorbents to respectively treat tetracycline and copper wastewater simulated in a laboratory. The experimental results are shown in Table 1, and it can be seen that both ion imprinting and porous structure are beneficial to adsorption of tetracycline and copper.
Thiourea modified porous sodium alginate materials prepared in example 1 and example 3 (Cu added in ion blotting) 2+ Concentrations of 2 and 4mmol/L, respectively) were used as adsorbents to treat laboratory simulated tetracycline and copper containing wastewater. As a result of the experiment, it is shown in Table 1 that example 3 has a lower removal effect than example 1, and that 2.0mmol/LCu is observed 2+ Is more favorable for adsorbing tetracycline and copper.
Comparing the adsorption amounts of examples 1 and 4, it can be seen that the adsorption amounts of tetracycline and copper in examples 1 and 4 do not change much, and the experimental results are shown in table one, so that the modified sodium alginate has a certain selectivity and anti-interference capability to heavy metals.
The test data shows that the adsorption materials obtained in examples 1-4 of the present invention have very significant removal efficiency for tetracycline and copper in wastewater (as shown in table 1). The adsorption capacity of the adsorption materials 1-4 for tetracycline and copper is obviously higher than that of the comparison material.
TABLE 1 removal of Tetracycline and copper Complex pollutants by different materials
Claims (2)
1. The application of the ion imprinting modified porous sodium alginate microsphere material in the synchronous removal of tetracycline and copper ions in livestock and poultry raising wastewater is characterized in that the preparation of the ion imprinting modified porous sodium alginate microsphere material comprises the following steps:
(1) Firstly preparing 5% sodium hydroxide solution, then adding 2g of thiourea and 4ml of epichlorohydrin, placing the mixture in a wide-mouth bottle, sealing the wide-mouth bottle in a constant-temperature shaking box pot, and shaking the mixture under the condition of 70 ℃ and 200rmp for 4h; then adding 2-4 g of sodium alginate solution, and continuing to react under the conditions to obtain 7-h; oscillating the obtained gel in a frozen ultrasonic instrument for 15-20 minutes, then adding 2% calcium chloride solution, and continuing to react for 12-h;
(2) Preparation of 2.0-4.0 mmol/L Cu 2+ The pH of the ionic solution is adjusted to be 1-1.5 through a pH meter, 20ml of the solution prepared in the step (1) is taken out and added, and the reaction is continued under the reaction condition of the step (1) for 12h; standing and layering the obtained material, filtering redundant solution, adding an ethanol solution containing 4-6% of urea, and soaking 12-h at 70 ℃;
(3) Filtering the solution obtained in the step (2), and then adding 0.1-0.3 mmol/L HCl (20 ml) and standing at 70 ℃ for 6h; filtering the solution after standing, repeatedly cleaning for at least three times by using distilled water, and then drying at room temperature to obtain the ion imprinting modified porous sodium alginate microsphere material.
2. The application of the ion imprinting modified porous sodium alginate microsphere material in synchronous removal of tetracycline and copper ions in livestock and poultry raising wastewater, as claimed in claim 1, wherein the ion imprinting modified porous sodium alginate microsphere material has the adsorption capacity of 3.672mmol/g and 4.569mmol/g on tetracycline and copper respectively when the initial concentration of tetracycline is 0.1mmol/L, the initial concentration of copper is 0.05mmol/L and the pH of initial solution is 5.0.
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| CN108339526A (en) * | 2018-02-26 | 2018-07-31 | 西南科技大学 | Modified sodium alginate sorbing material and preparation method thereof for tetracycline antibiotics absorption |
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| CN108212114A (en) * | 2018-02-08 | 2018-06-29 | 福州大学 | A kind of copper ion trace composite adsorbing material and preparation method thereof |
| CN108339526A (en) * | 2018-02-26 | 2018-07-31 | 西南科技大学 | Modified sodium alginate sorbing material and preparation method thereof for tetracycline antibiotics absorption |
| CN110975821A (en) * | 2019-12-09 | 2020-04-10 | 安徽工业大学 | Silicon dioxide and calcium alginate composite metal ion adsorbent, preparation method and application |
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