CN115487785A - Resin-based lanthanum-cerium bimetallic nano-oxide composite material, preparation method thereof and application thereof in removing fluorinion in water - Google Patents
Resin-based lanthanum-cerium bimetallic nano-oxide composite material, preparation method thereof and application thereof in removing fluorinion in water Download PDFInfo
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- CN115487785A CN115487785A CN202211154672.9A CN202211154672A CN115487785A CN 115487785 A CN115487785 A CN 115487785A CN 202211154672 A CN202211154672 A CN 202211154672A CN 115487785 A CN115487785 A CN 115487785A
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- composite material
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- cerium
- lanthanum
- fluorine
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 44
- 229920005989 resin Polymers 0.000 title claims abstract description 44
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 67
- 239000011737 fluorine Substances 0.000 claims abstract description 67
- -1 fluorine ions Chemical class 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 27
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000004793 Polystyrene Substances 0.000 claims abstract description 17
- 229920002223 polystyrene Polymers 0.000 claims abstract description 17
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 239000002114 nanocomposite Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000011159 matrix material Substances 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003795 desorption Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 230000035515 penetration Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006115 defluorination reaction Methods 0.000 description 3
- 208000004042 dental fluorosis Diseases 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 206010016818 Fluorosis Diseases 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 208000021959 Abnormal metabolism Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 208000030172 endocrine system disease Diseases 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006371 metabolic abnormality Effects 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing 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
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a resin-based lanthanum-cerium bimetal nano oxide composite material, a preparation method thereof and application thereof in removing fluorine ions in water, belonging to the technical field of wastewater treatment. The matrix of the bimetal nano composite material is polystyrene anion exchange resin, and hydrated lanthanum oxide and cerium oxide nano particles are loaded in carrier pores. The steps of the invention for treating wastewater are as follows: (1) adjusting the pH value of the fluorine-containing wastewater and filtering; (2) The filtrate passes through an adsorption tower filled with the bimetallic nano composite material; (3) Stopping adsorption when the concentration of fluorine in the effluent of the adsorption tower reaches a breakthrough point, and desorbing and regenerating the composite material by using a saline-alkali (NaCl and NaOH) mixed solution; (4) And cleaning the composite material to be neutral for recycling. The water body fluorine removal technology can reduce the concentration of fluorine ions in water from 0.5-50 mg/L to below 0.01 mg/L; the composite material has the advantages of high reaction activity and millimeter size, and the adsorption capacity, stability and selectivity of the composite material to fluorine ions are effectively improved.
Description
Technical Field
The invention relates to the technical field of sewage treatment and harmlessness, in particular to a resin-based lanthanum-cerium bimetallic nano-oxide composite material, a preparation method thereof and application thereof in removing fluorinion in water.
Background
Fluorine is a necessary micronutrient element for human bodies, however, excessive fluorine taken for a long time can cause abnormal metabolism of calcium and phosphorus by the human bodies and inhibit the activity of enzymes, thereby causing disorder of endocrine systems, finally causing diseases such as dental fluorosis and fluorosis, and seriously affecting the health of the human bodies. With the increasing importance of people on life health and public health, the local fluorosis is generally concerned. The largest source of fluorine intake by human body is drinking water, when the fluorine content in the water is more than 1.0 mg/L, the drinking water is called fluorine-containing water and is also called high fluorine water. China is a country with relatively short water resources, but fluorine pollution causes certain damage to the water resources, so that the research on fluorine-containing water treatment methods and materials is particularly important.
Fluorine is usually the anion F in the free form - Is present in water due to the low concentration of fluorine-containing water in the pathological limit (below 1.0 mg/L), and F - The ionic solution has unique hydration chemical property and is difficult to react with other substances, so that the deep removal of trace fluorine from fluorine-containing water is extremely difficult. Therefore, fluorine-containing water treatment methods and processes have been important research subjects. In recent years, many studies have been made on the treatment of fluorine-containing water at home and abroad, including a coagulation precipitation method, a chemical precipitation method, an adsorption method and the like. For example, removal of fluoride ions in industrial waste water is commonTwo natural coagulants, namely ferric silicate and sodium aluminosilicate are used, but the former has low fluorine removal effect and harsh operating conditions. The latter can remove fluorinion in wastewater by ligand exchange, rolling, physical and chemical adsorption and the like under the conditions of neutral low temperature or alkali resistance high temperature. In addition, the industrial wastewater containing a small amount of fluoride ions can also adopt a chemical precipitation method, and the fluoride ions are removed by utilizing calcium ions in lime and mineral calcium sulfate to react with the fluoride ions to generate calcium fluoride precipitate. Although the reagents are low in price and low in solubility, the dosage of the reagents needs to be increased when the reagents are used for removing a large amount of fluorine, and the slag yield is large, so that the complex subsequent treatment is caused. The adsorption method is mainly used for removing fluorine ions in water through various physical and chemical actions, electrostatic adsorption and ligand exchange actions. The whole process is simple to operate, does not need to add other medicines, does not need secondary treatment, does not need to treat solid waste, but has the problems of high cost, secondary precipitation and secondary pollution in the traditional treatment of fluoride ions. Therefore, the preparation of the novel defluorination material and the defluorination process which have simple operation, low cost, stable performance and higher efficiency and can be applied to practical production can be realized, and the research on the current deep defluorination problem is considered
Has great significance.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a resin-based lanthanum-cerium bimetal nano oxide composite material, a preparation method thereof and application thereof in removing fluorine ions in water. Particularly, the invention provides a method for rapidly trapping fluorine ions in a composite material by utilizing a lanthanum-cerium bimetal nano oxide composite material through electrostatic adsorption and kernel coordination, and solves the problems of complex process, secondary precipitation and secondary pollution in the prior art; meanwhile, the composite material can be regenerated after desorption of the saline-alkali mixed solution and recycled.
The resin-based lanthanum-cerium bimetallic nano-oxide composite material is characterized in that lanthanum-cerium bimetallic nano-oxide particles are loaded in polystyrene anion exchange resin pore channels with quaternary ammonium groups, and the nano hydrated lanthanum oxide and cerium oxide loading rates of the resin-based nano-composite material are respectively4-8% and 4-9%. The composite material adopted by the invention is that the polystyrene-divinylbenzene skeleton is provided with quaternary ammonium group [ -N ] + (CH 3 ) 3 OH]The group resin, and amorphous nanometer hydrated lanthanum oxide and hydrated cerium oxide are loaded in the pore canal. The rare earth elements lanthanum and cerium have higher adsorption capacity to fluorine, and lanthanum hard acid and fluorine hard alkali have stronger binding capacity, so that the fluorine in water can be quickly removed. Firstly, the quaternary ammonium group with positive charge in the resin captures the fluorinion through electrostatic attraction, and then the exchange and complex reaction of the bimetallic oxide in the nano composite material and the fluorinion ligand promote the fluorinion to be removed from the water.
Furthermore, the particle size distribution of the polystyrene anion exchange resin is between 0.3 and 1.0 mm, and the pore size distribution is between 5.0 and 80.0 nm.
The invention discloses a resin-based lanthanum-cerium bimetallic nano-oxide composite material which is obtained by taking polystyrene anion exchange resin as a carrier and loading lanthanum-cerium bimetallic nano-oxide particles in a carrier pore channel by an ion exchange-in-situ deposition method, and the specific preparation method comprises the following steps:
1) Adding polystyrene anion exchange resin with quaternary ammonium groups into an aqueous solution containing lanthanum chloride, cerium chloride and lower alcohol in different solid-to-liquid ratios, and soaking for 18 to 24 hours under the condition of constant-temperature water bath;
2) Adding the resin preloaded with lanthanum-cerium in the step 1) into a sodium hydroxide solution with the weight percentage of 10-15%, and stirring for 10-12 h at room temperature;
3) Rinsing the composite material obtained in the step 2) with deionized water until the pH value is neutral, then rinsing with 5-8 wt% NaCl solution to convert the functional group of the carrier from hydroxide type to chloride type, finally washing with deionized water and ethanol, and drying to obtain the lanthanum-cerium bimetal nano oxide composite material.
Further, the resin base in the step 1) is polystyrene anion exchange resin with quaternary ammonium groups, the ion exchange capacity of the resin is 2-3 meq/g, and the crosslinking degree is 6-10%.
Further, the solid-to-liquid ratio in the step 1) is 1 g (5 to 12) mL, and the lanthanum-cerium metal molar ratio is 1 to 4 (1). Further, the temperature of the impregnation in the step 1) is 60 to 70 ℃.
Further, the lower alcohol in the step 1) is ethanol, and the volume of the lower alcohol in the aqueous solution accounts for 20 to 30 percent of the total volume.
The resin-based lanthanum-cerium bimetal nano oxide composite material has good application in the aspect of removing fluorinion in water, and the application method comprises the following steps:
(1) Filling the resin-based nano composite material into an adsorption tower;
(2) Adjusting the pH value of the fluorine-containing wastewater to 2-14, and filtering to remove suspended particles;
(3) Enabling the fluorine-containing wastewater filtrate obtained in the step (2) to pass through an adsorption tower filled with a resin-based lanthanum-cerium bimetallic nano-oxide composite material, so that the fluorine-containing ion water body is fully contacted with the composite material to obtain a treated water body;
(4) Stopping adsorption after the treated water body reaches a penetration point, and performing desorption regeneration on the nano composite material;
(5) And (5) cleaning the composite material in the step (4) with clear water until the effluent of the adsorption tower is nearly neutral, and entering the step (3) for recycling.
Further, in the step (2), fluoride ion (F) - ) And the mass concentration of the fluorine ions in the water body is less than 50mg/L, and the mass concentration of other coexisting anions in the water body is less than 50 times of the mass concentration of the fluorine ions.
Further, in the step (3), the temperature of the filtrate passing through the adsorption tower is 10-40 ℃, and the flow rate of the filtrate is not more than 10 resin bed volumes per hour.
Further, in the step (4), the penetration point is that the mass concentration of the fluorine ions in the effluent is more than 0.01 mg/L.
Further, in the step (4), desorption liquid for desorption regeneration is saline alkali solution formed by mixing sodium chloride and sodium hydroxide, the mass concentration of the sodium chloride and the mass concentration of the sodium hydroxide are both 4-6%, the saline alkali mixed liquid passes through the resin-based lanthanum-cerium bimetallic nano-oxide composite material, desorption is carried out at the temperature of 10-40 ℃ and at the flow rate of 2-5 resin bed volumes (BV/h) per hour, and when the mass concentration of fluorine ions in desorption effluent liquid is less than 0.5 mg/L, the desorption is finished.
Further, the operation mode adopted in the steps (2), (3) and (4) is single-tower adsorption-single-tower desorption or multi-tower series adsorption-single-tower desorption.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, the lanthanum-cerium bimetallic nano-oxide resin composite material is adopted to capture fluorine ions in water, and on the basis that polystyrene anion resin quickly adsorbs the fluorine ions, the composite material quickly captures the fluorine ions by utilizing ligand exchange and complexation of hydrated lanthanum oxide and hydrated cerium oxide, and a satisfactory and stable fluorine adsorption effect can be obtained under near-neutral conditions; experiments show that the adsorption of fluorine ions in water can be realized when the pH value of the water body is 2.0-14.0.
(2) The lanthanum-cerium bimetal nano oxide resin composite material adopted by the method loads the nano-scale hydrated lanthanum oxide/cerium on the resin carrier, so that the speed and the adsorption capacity for capturing fluorine ions in water are improved; in the presence of other anions, the composite material still has high adsorption capacity.
(3) The lanthanum-cerium bimetal nano oxide resin composite material adopted by the method can be regenerated by saline-alkali mixed liquor after reaction, and can be recycled, so that the treatment cost is reduced.
(4) The lanthanum-cerium bimetallic nano-oxide resin composite material adopted by the method disclosed by the invention adopts an ion exchange-in-situ deposition method in the preparation method, so that the defect of agglomeration and inactivation of nano particles is avoided, meanwhile, the loaded nano-scale hydrated lanthanum oxide/cerium has an indefinite shape, and has a high surface area-volume ratio and reaction activity, and the composite resin can stably maintain the activity and stability of the hydrated lanthanum oxide/cerium.
The invention loads the lanthanum-cerium bimetal nano oxide particles into the resin with quaternary amine groups, and can obtain the millimeter-scale bimetal lanthanum-cerium oxide resin composite material with both nano effect (high surface area-volume ratio and high reaction activity) and millimeter size advantage (simple operation and agglomeration resistance). Hydroxyl in the hydrated lanthanum oxide/cerium oxide in the nano composite material improves the adsorption and adsorption selectivity of fluorine; the fluorine ions and the composite material are subjected to complexation to generate a new complex, so that the stability of the composite material is improved.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Blank example 1:
the resin-based lanthanum-cerium bimetallic nano-oxide composite material is prepared by the following specific steps:
i) The polystyrene anion exchange resin with quaternary ammonium groups is purchased from Hangzhou optical resin Limited, the pore size distribution of the polystyrene anion exchange resin is basically 10 to 50 nm, the ion exchange capacity of the polystyrene anion exchange resin is about 2.5 meq/g, and the crosslinking degree of the polystyrene anion exchange resin is about 8 percent. Sieving the polystyrene anion exchange resin, and selecting the resin with the particle size of 0.6-0.7 mm. The resin was mixed at a ratio of 5 g:50 Adding the mixed solution containing 0.5 mol/L lanthanum chloride, 0.25 mol/L cerium chloride and ethanol in a solid-liquid ratio of mL (the molar ratio of lanthanum to cerium metal is = 2, the volume of ethanol in the mixed solution accounts for 25% of the total solution volume, and water is used as a solvent), stirring the mixed solution in a water bath kettle at the temperature of 60 ℃ for 12 hours, then stirring the mixed solution in a water bath kettle at the temperature of 70 ℃ for 6 hours, and filtering the mixed solution to obtain the polystyrene anion exchange resin preloaded with lanthanum and cerium;
ii) adding the polystyrene anion exchange resin pre-loaded with the lanthanum-cerium obtained in the step i) into a sodium hydroxide solution with the mass concentration of 15 wt%, continuously stirring for 12 hours at 25 ℃, and filtering the solution after the reaction is finished to obtain the hybrid polymer resin;
iii) Rinsing the hybrid polymer resin obtained in the step ii) with a large amount of deionized water until the pH value is neutral, and then rinsing with a sodium chloride solution with the mass concentration of 5% to convert the functional groups of the carrier from hydroxide type to chloride type. Finally, the material was washed with deionized water and ethanol and the solid particles were filtered. And drying in a 50 ℃ oven for 12 h to obtain the resin-based lanthanum-cerium bimetallic nano-oxide composite material. The loading rates of the nanometer hydrated lanthanum oxide and the cerium oxide of the final resin-based nanometer composite material are respectively 7.95 percent and 4.07 percent.
The composite adsorbents used in examples 1 to 15 were composite adsorbents prepared by the method of blank example 1.
Example 1
The treatment method for capturing the fluorine ions in water by using the resin-based lanthanum-cerium bimetallic nano-oxide composite material comprises the following specific steps:
(1) Filtering the solution containing fluoride ions, adjusting the pH to be = 6.7 +/-0.2, and adding 0.05 g of the lanthanum-cerium loaded bimetallic nano-oxide composite material into the solution; wherein the concentration of the fluorinion is 9.5 mg/L, the volume of the solution is 100 mL, and the solution is put into a constant temperature shaking table at 25 ℃ to be shaken for 24 h.
(2) After the reaction is finished, taking the supernatant of the solution to measure the fluorinion, and measuring that the removal rate of the fluorinion in the supernatant after the reaction is more than 65 percent and the adsorption capacity of the composite material to the fluorinion is 12.3 mg/g.
(3) And (3) performing solid-liquid separation on the composite material saturated in adsorption and the solution, washing with deionized water for 6-8 times, adding a mixed solution of sodium chloride and sodium hydroxide (the mass concentration of the sodium chloride and the sodium hydroxide is 5%) for regeneration, washing with deionized water for 6-8 times after regeneration until the material is neutral, and performing an adsorption reaction test again.
Repeating the adsorption saturation-desorption regeneration process of the steps (1) - (3) on the composite material, wherein the experimental result is as follows: after 5 times of cycles, the adsorbent still keeps good fluoride ion adsorption performance, the removal rate of the supernatant after the reaction is more than 50 percent when the adsorption process of the steps (1) to (2) is repeated, the adsorption capacity is 9.5 mg/g, and fluoride ions trapped by the resin composite material are completely trapped inside the composite material. Therefore, the loaded lanthanum-cerium bimetal nano oxide composite material is determined to be better regenerated, and the regenerated loaded lanthanum-cerium bimetal nano oxide composite material can be recycled.
Example 2
The same method as that of example 1 is adopted to treat the fluorinion in the water body, and the difference is that: the pH of the filtrate was controlled at 3.0. + -. 0.2. The experimental results are as follows: after the reaction, the removal rate of the fluorine ions in the supernatant is 50.1%, and the adsorption capacity of the composite material is 9.5 mg/g.
Example 3
The same method as in example 1 is adopted to treat the fluorine ions in the water body, and the difference is that: adding 5 mmol/L SO into the solution obtained in the step (1) 4 2— (the cation bonded to the anion is Na + As in the other embodiments). The experimental results are as follows: after the reaction, the removal rate of fluorine ions in the supernatant is 57.91%, and the adsorption capacity of the composite material is 11.0 mg/g.
Example 4
The same method as that of example 1 is adopted to treat the fluorinion in the water body, and the difference is that: adding 5 mmol/L Cl into the solution obtained in the step (1) — . The experimental results are as follows: the removal rate of the fluorine ions in the supernatant after the reaction is still 49.04 percent, and the adsorption capacity of the composite material is 9.3 mg/g.
Example 5
The same method as in example 1 is adopted to treat the fluorine ions in the water body, and the difference is that: controlling the temperature of the constant-temperature water bath shaking table in the step (1) to be 10 +/-2 ℃. The experimental results are as follows: the removal rate of the fluorine ions in the supernatant after the reaction is 30.5 percent, and the adsorption capacity of the composite material is 5.8 mg/g.
Example 6
A treatment method for capturing fluorinion in water by using a resin-based lanthanum-cerium bimetal nano oxide composite material comprises the following specific steps:
(1) Adjusting the water body containing fluorine ions (F) - The concentration of (1) is 0.5 mmol/L) is adjusted to 6.7 +/-0.2, and the filtrate is obtained after filtration;
(2) 5 mL (about 3 g) of nano-scale bimetal lanthanum cerium oxide resin composite material is filled into a glass adsorption column (phi 32 multiplied by 360 mm) with a jacket, the filtrate obtained in the step (1) passes through the adsorption column containing the lanthanum-cerium bimetal lanthanum cerium oxide resin composite material bed layer from bottom to top at the temperature of 25 +/-5 ℃ and the flow rate of 1 BV/h, and effluent F - The concentration of (A) is reduced to below 0.01 mg/L, and the treatment amount reaching the penetration point is about 820 BV;
(3) When the breakthrough point is reached (F of the effluent) - Concentration more than 0.01 mg/L), stopping operation, mixing with 1L of saline and alkalineThe resultant solution (the mixed solution of sodium chloride and sodium hydroxide with the mass concentration of 5 percent respectively) passes through the resin bed layer from bottom to top at the temperature of 25 +/-5 ℃ and the flow rate of 1 BV/h to be desorbed and removed of fluorine ions, and when the concentration of the outflowing fluorine ions is less than 0.5 mg/L, the desorption is finished.
And (3) repeating the adsorption saturation-desorption regeneration processes of the steps (2) to (3) on the composite material, wherein after 5 times of cycles, the adsorbent still keeps good fluoride ion adsorption performance, and the treatment capacity of the composite material reaching a penetration point is more than 600 BV when the adsorption process of the step (2) is repeated.
Example 7
The same method as in example 6 is used to treat the fluoride ions in the water body, with the following differences: in the step (1), the pH value of the fluorine-containing ions is adjusted to 3.0 +/-0.2. The experimental results are as follows: the throughput to reach the breakthrough point is about 570 BV.
Example 8
The same method as in example 6 is used to treat the fluoride ions in the water body, with the following differences: in the step (1), the pH value of the fluorine-containing ions is adjusted to 10.0 +/-0.2. The experimental results are as follows: the throughput to reach the breakthrough point is about 510 BV or so.
Example 9
The same method as in example 6 was used to treat fluoride ions in water, except that: controlling the temperature of the constant-temperature water bath shaking table in the step (1) to be 10 +/-2 ℃. The experimental results are as follows: the throughput to reach the breakthrough point is about 348 BV.
Example 10
The same method as in example 6 was used to treat fluoride ions in water, except that: controlling the temperature of the constant temperature water bath shaking table in the step (1) to be 40 +/-2 ℃. The experimental results are as follows: the throughput to reach the breakthrough point is about 850 BV.
Example 11
The same method as in example 6 was used to treat fluoride ions in water, except that: in the step (1), 5 mmol/L SO is added into fluorine-containing plasma 4 2- . The experimental results are as follows: the throughput to reach the breakthrough point is about 660 BV.
Example 12
The same method as in example 6 was used to treat fluoride ions in water, except that: in the step (1), 5 mmol/L NO is added into fluorine-containing plasma 3 - . The experimental results are as follows: the throughput to reach the breakthrough point was about 612 BV.
Example 13
The same method as in example 6 was used to treat fluoride ions in water, except that: in the step (1), 5 mmol/L Cl is added into fluorine-containing plasma - . The experimental results are as follows: the throughput to reach the breakthrough point was about 558 BV.
Example 14
The same method as in example 6 was used to treat fluoride ions in water, except that: in the step (1), 5 mmol/L PO is added into the fluorine-containing plasma 4 3- . The experimental results are as follows: the throughput to reach the breakthrough point was about 600 BV.
Example 15
The same method as in example 6 was used to treat fluoride ions in water, except that: in step (2), the flow rate was changed to 2 BV/h. The experimental results are as follows: the throughput to reach the breakthrough point was about 500 BV.
Claims (10)
1. A resin-based lanthanum-cerium bimetallic nano-oxide composite material is characterized in that a matrix of the nano-composite material is polystyrene anion exchange resin with quaternary ammonium groups; holes are uniformly distributed in the matrix, hydrated lanthanum oxide and cerium oxide nanoparticles are loaded in the holes, and the nano hydrated lanthanum oxide and cerium oxide loading rates of the resin matrix nano composite material are respectively 4-8% and 4-9%.
2. The resin-based lanthanum-cerium bimetal nano oxide composite material as claimed in claim 1, wherein the particle size distribution of the polystyrene anion exchange resin is between 0.3 and 1.0 mm, and the pore size distribution is between 5.0 and 80.0 nm.
3. The preparation method of the resin-based lanthanum-cerium bimetal nano oxide composite material according to claim 1 or 2, characterized by comprising the following preparation steps:
1) Adding polystyrene anion exchange resin with quaternary ammonium groups into an aqueous solution containing lanthanum chloride, cerium chloride and lower alcohol in different solid-to-liquid ratios, and soaking for 18 to 24 hours under the condition of constant-temperature water bath;
2) Adding the resin pre-loaded with lanthanum-cerium obtained in the step 1) into a sodium hydroxide solution with the weight percentage of 10-15%, and stirring for 10-12 h at room temperature;
3) Rinsing the composite material obtained in the step 2) by using deionized water until the pH value is neutral, then rinsing by using 5-8 wt% NaCl solution, converting the functional group of the carrier from an hydroxyl type to a chloride type, finally washing by using deionized water and ethanol, and drying to obtain the lanthanum-cerium bimetal nano oxide composite material.
4. The method for preparing the resin-based lanthanum-cerium bimetal nano-oxide composite material according to claim 3, wherein the method comprises the following steps: the purchased ion exchange capacity of the resin in the step 1) is 2-3 meq/g, and the crosslinking degree is 6-10%.
5. The method for preparing the resin-based lanthanum-cerium bimetal nano-oxide composite material according to claim 3, wherein the method comprises the following steps: the solid-liquid ratio in the step 1) is 1 g [5 to 12] mL, the lanthanum-cerium metal molar ratio [1 to 4] is 1, the volume of lower alcohol in the aqueous solution accounts for 20 to 30 percent of the total solution volume, and the lower alcohol is ethanol; the temperature for dipping in the step 1) is 60 to 70 ℃.
6. The use of the resin-based lanthanum-cerium bimetallic nano-oxide composite material in the removal of fluoride ions in water according to claim 1, characterized in that the application method comprises the following steps:
(1) Filling the resin-based lanthanum-cerium bimetallic nano-oxide composite material as defined in claim 1 or 2 into an adsorption column;
(2) Adjusting the pH value of the fluorine-containing wastewater to 2 to 14, and filtering to remove suspended particles;
(3) Enabling the fluorine-containing wastewater filtrate obtained in the step (2) to pass through an adsorption tower filled with a resin-based lanthanum-cerium bimetallic nano-oxide composite material, so that the fluorine-containing ion water body is fully contacted with the composite material to obtain a treated water body;
(4) Stopping adsorption after the treated water body reaches a penetration point, and performing desorption regeneration on the composite material;
(5) And (4) cleaning the composite material in the step (4) by using clean water until the effluent of the adsorption tower is nearly neutral, and entering the step (3) for recycling.
7. Use according to claim 6, characterized in that in step (3), fluoride ions (F) are used - ) The mass concentration of the fluorine ions in the fluorine-containing wastewater is less than 50mg/L, and the mass concentration of other coexisting anions in the water body is less than 50 times of the mass concentration of the fluorine ions;
in the step (3), the temperature of the filtrate passing through the adsorption tower is 10-40 ℃, and the flow of the filtrate is not more than 10 resin bed volumes per hour.
8. The use of claim 6, wherein in step (4), the breakthrough point is a mass concentration of fluoride ions in the effluent of more than 0.01 mg/L.
9. The application of claim 6, wherein in the step (4), the desorption solution for desorption regeneration is a saline alkali solution formed by mixing sodium chloride and sodium hydroxide, the mass concentration of the sodium chloride and the mass concentration of the sodium hydroxide are both within a range of 4-6%, the saline alkali mixed solution passes through the bimetallic nanocomposite material, desorption is carried out at a temperature of 10-40 ℃ and a flow rate of 2-5 resin bed volumes (BV/h) per hour, and when the mass concentration of fluorine ions in the desorption effluent is less than 0.5 mg/L, the desorption is finished.
10. The use according to claim 6, characterized in that the mode of operation employed in steps (2), (3) and (4) is single-column adsorption-single-column desorption or multi-column series adsorption-single-column desorption.
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| CN85105637A (en) * | 1985-02-21 | 1986-09-17 | 旭化成工业株式会社 | The adsorption treatment method of dissolving fluorine |
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