CN117902669A - Low-concentration coupling defluorinating agent and preparation method thereof - Google Patents
Low-concentration coupling defluorinating agent and preparation method thereof Download PDFInfo
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- 230000008878 coupling Effects 0.000 title claims abstract description 32
- 238000010168 coupling process Methods 0.000 title claims abstract description 32
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 68
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- -1 cerium oxide-modified carbon nanotube compound Chemical class 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 11
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 11
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001110 calcium chloride Substances 0.000 claims abstract description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 27
- 239000002041 carbon nanotube Substances 0.000 claims description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002048 multi walled nanotube Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
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- 230000007935 neutral effect Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 13
- 239000010802 sludge Substances 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910000420 cerium oxide Inorganic materials 0.000 description 11
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006115 defluorination reaction Methods 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 238000007306 functionalization reaction Methods 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- OLYKTICNIVCGSY-UHFFFAOYSA-N [O-2].[Ce+3].[C+4] Chemical compound [O-2].[Ce+3].[C+4] OLYKTICNIVCGSY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
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- 230000009257 reactivity Effects 0.000 description 3
- 238000009270 solid waste treatment Methods 0.000 description 3
- NUXZAAJDCYMILL-UHFFFAOYSA-K trichlorolanthanum;hydrate Chemical compound O.Cl[La](Cl)Cl NUXZAAJDCYMILL-UHFFFAOYSA-K 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000012695 Ce precursor Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 208000020084 Bone disease Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000001185 bone marrow Anatomy 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- Water Treatment By Sorption (AREA)
Abstract
The invention relates to the technical field of treatment of water, wastewater, sewage or sludge, and particularly discloses a low-concentration coupling defluorinating agent and a preparation method thereof. The fluorine removing agent comprises the following components in percentage by mass: 3-5% of polymeric aluminum ferric sulfate, 2-4% of magnesium oxide, 1-2% of lanthanum nitrate, 0.5-1.5% of cerium oxide-modified carbon nanotube compound, 0.2-1% of polyacrylamide, 0.5-1.5% of calcium chloride, 0.1-0.3% of hydrochloric acid and the balance of water. The invention also provides a preparation method of the composite. Compared with the prior art, the fluorine removing agent prepared by the invention has the advantages of good fluorine removing effect, high utilization rate, low cost and the like.
Description
Technical Field
The invention relates to the technical field of treatment of water, wastewater, sewage or sludge, in particular to a low-concentration coupling fluorine removing agent and a preparation method thereof.
Background
Fluorine is one of elements widely distributed in nature, the stock of the fluorine in the crust is 0.065%, the order number of the stock is 13, and the fluorine is also an important trace vital element of a human body and is mainly distributed in bones and teeth. Fluorine required by a human body is mainly from drinking water, fluorine is widely existed in water bodies in nature, excessive fluorine uptake can cause fluorine poisoning, if the fluorine content in the water is less than 0.5ppm, the occurrence rate of decayed teeth can reach 70-90%, but if the fluorine content in the drinking water exceeds 1ppm, spots can be generated gradually and become crisp, and when the fluorine content in the drinking water exceeds 4ppm, people are prone to suffering from fluorine bone diseases and cause bone marrow malformation, so that the fluorine content in drinking water regulated in China is 0.5-1.0 mg/L, and the fluorine content of discharged water is very necessary to be strictly controlled.
At present, high-content fluorine-containing wastewater is basically subjected to coagulating sedimentation by adopting calcium salt, aluminum salt and ferric salt, so that the fluorine content in the wastewater can be effectively controlled to be about 30mg/L, the fluorine content is difficult to be controlled to be below 8mg/L, a large amount of medicaments are hydrolyzed or insoluble by themselves, the product utilization rate is low, the sludge amount is large, and the fluorine removal effect is not obvious. And the conventional defluorinating agent in the market has higher price, and the cost of the defluorinating unit of the enterprise wastewater is more than 3 yuan/m under the condition that the 15mg/L of inflow water is reduced to 8mg/L, thereby bringing trouble to the operation and development of the enterprise. At present, the industries of crystal processing and manufacturing, photovoltaics and the like are urgent to further reduce fluoride emission indexes and treatment cost.
Chinese patent 202111246694.3 discloses an aluminum-based compound defluorinating agent and a preparation method thereof, wherein the aluminum-based compound defluorinating agent mainly comprises an aluminum dry base, special hydroxyapatite powder and an improved base, and the aluminum dry base comprises polyaluminum chloride, aluminum sulfate, magnesium oxide and other components; the modified material comprises one or two components of rare earth element oxide (lanthanum oxide and cerium oxide); hydroxyapatite powder is prepared by the process steps described in the present invention. The aluminum-based compound defluorination agent belongs to the synergistic principles of flocculation, complexation, coprecipitation, ion exchange and the like, has stronger selectivity and anti-interference performance, and is suitable for defluorination by a chemical addition method of large water quantity and low concentration fluorine ions. The agent has low adding treatment cost, the defluorination effect reaches more than 76.25%, the fluorine content of the effluent is less than 1.0mg/L, and the III class limit value requirement in the surface water environment quality standard is met.
Chinese patent 202110467118.5 provides a synthesis method of a lanthanum-doped graphene oxide nano-composite fluorine removing agent, belonging to a production method of fluorine removing agents. (1) Graphene oxide, lanthanum chloride hydrate and ammonia water are used as raw materials; (2) Weighing graphene oxide, lanthanum chloride hydrate and water according to the mass ratio of 1:30:1000; (3) Uniformly mixing weighed graphene oxide with water, performing ultrasonic dispersion for 2 hours, and centrifuging at a speed of 3000rpm, wherein the centrifuged upper liquid is graphene oxide colloid; (4) Adding weighed lanthanum chloride hydrate into the colloid, uniformly mixing, and performing ultrasonic dispersion for 30min; (5) Then 8mol L -1 of ammonia water is dripped into the system until the pH value is 8-10; (6) Then placing the system in a water bath at 60 ℃ for continuous stirring for 1h, and aging for 24h at normal temperature; (7) filtering, washing with water until the filtrate is neutral; (8) Drying the filter residue at 60 ℃ for 24 hours, and crushing to obtain the lanthanum hydroxide/graphene oxide carbon-based nano composite fluorine removing agent. The advantages are that: the process is simple, easy to operate and suitable for large-scale production and application.
The defluorination medicament in the prior art has the defects of poor defluorination effect, low utilization rate and high cost on the fluorine-containing wastewater, so that the defluorination medicament has high defluorination efficiency and high utilization rate, is suitable for being added in large-scale wastewater treatment and has relatively low cost by combining the advantages of conventional metal salts and coagulating sedimentation, and has practical significance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide a low-concentration coupling defluorinating agent and a preparation method thereof.
Rare earth elements such as oxides or hydroxides of lanthanum and cerium have strong selectivity on fluoride ions, and rare earth adsorbents have small pollution and large adsorption capacity and can overcome the defects of other adsorbents. According to the theory of soft and hard acid and alkali: rare earth ions such as lanthanum and cerium ions have the characteristics of small volume, high oxidation valence state and weak polarization, belong to stearic acid, are extremely easy to combine with hard alkali such as fluorine ions, and the adsorption mechanism is mainly that the rare earth ions are combined with the fluorine ions to form stable complexes, and the rare earth adsorbent can be desorbed and regenerated by sodium hydroxide solution after adsorption. Owing to the small size and high specific surface area of cerium oxide, more adsorption sites can be provided to improve adsorption performance during material adsorption, but the larger surface energy enables the particles to be easily mutually agglomerated, and finally the actual treatment effect is affected. Therefore, in the invention, cerium oxide is combined with the adsorption carrier, and uniformly distributed and grown on the carrier material in a loading mode, so that the composite material of the nano material and the adsorption carrier is prepared, the agglomeration behavior of nano particles is effectively avoided, and the separation difficulty of the adsorbent after adsorption is reduced. The carbon nano tube has larger specific surface area, so that the carbon nano tube can be used as an excellent carrier and is also a common adsorbent. But is poorly dispersible in aqueous solutions due to its own drawbacks. The inventor carries out functional modification on the carbon nano tube and then carries with cerium oxide, so that the defects of poor dispersibility and easy agglomeration of the carbon nano tube and the cerium oxide can be overcome, the carbon nano tube can also serve as an electronic medium, the concentration of rare earth ions can be maintained, and the aim of effective adsorption is achieved.
According to the invention, the carbon nano tube is modified, so that the water solubility of the carbon nano tube is improved, a certain steric hindrance is formed through grafted long alkyl chain, the defects of easy agglomeration and poor dispersibility are overcome, when the modified carbon nano tube is mixed with a cerium precursor, the precursor is physically adsorbed on a carbon nano tube layer, ammonia water is added and then the precursor reacts with the cerium precursor, cerium oxide nano particles are formed in a hydrothermal process, the nano particles are loaded on the carbon nano tube, the formed composite not only performs embedded functionalization but also performs covalent functionalization, the dispersibility and the reactivity of the carbon nano tube are improved through functionalization, the agglomeration of the carbon nano tube and the cerium oxide nano particles is reduced, the specific surface area of the material is increased, the adsorption activity point of the surface of the material is increased, and the fluorine adsorption capacity of the material is remarkably improved. The cerium oxide-modified carbon nanotube compound not only can form a stable complex by combining rare earth ions with fluoride ions, but also can adsorb negatively charged fluoride ions through electrostatic action, and the polymeric aluminum ferric sulfate, magnesium oxide, lanthanum nitrate, polyacrylamide, calcium chloride and the like are coupled to form strong cohesive force and strong charge adsorption capacity to polymerize calcium, aluminum and iron, so that the formed fluorine removing agent improves the adsorption capacity and charge net capturing capacity of calcium, aluminum and iron to fluorine, the fluorine content can be effectively controlled to be 2-6 mg/L, the inorganic sludge amount generated by the product is small, the solid waste treatment cost is reduced, the fluorine removing effect is relatively good, and the utilization rate is relatively high.
In order to achieve the purpose, the invention provides a low-concentration coupling defluorinating agent which comprises the following components in percentage by mass: 3-5% of polymeric aluminum ferric sulfate, 2-4% of magnesium oxide, 1-2% of lanthanum nitrate, 0.5-1.5% of cerium oxide-modified carbon nanotube compound, 0.2-1% of polyacrylamide, 0.5-1.5% of calcium chloride, 0.1-0.3% of hydrochloric acid and the balance of water.
The preparation method of the cerium oxide-modified carbon nano tube compound comprises the following steps:
x1: adding the multiwall carbon nanotubes into concentrated nitric acid, uniformly dispersing by ultrasonic, heating and stirring for 16-24 hours, cooling to room temperature, filtering, washing the filtrate to be neutral, and drying residues for the next step;
X2: adding the product of the last step into N, N-dimethylformamide, adding 1, 10-diaminodecane after ultrasonic dispersion is uniform, heating and stirring for 16-24 h, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
X3: adding the product of the last step into water, uniformly dispersing by ultrasonic, adding cerium nitrate hexahydrate, uniformly stirring, adding ammonia water to adjust pH to be alkaline, performing hydrothermal reaction for 2-5 hours, cooling to room temperature, filtering, washing to be neutral, and drying the residue to obtain the cerium oxide-modified carbon nano tube compound.
Further, the temperature range of heating and stirring in the step X1 is 110-130 ℃.
Further, the temperature range of heating and stirring in the step X2 is 70-100 ℃.
Further, in the step X3, the pH is adjusted to 9-10.
Further, the temperature range of the hydrothermal reaction in the step X3 is 130-150 ℃.
Preferably, the preparation method of the cerium oxide-modified carbon nanotube composite comprises the following steps:
x1: adding 2-5 parts by weight of multiwall carbon nanotubes into 400-1000 parts by weight of concentrated nitric acid, uniformly dispersing by ultrasonic, heating to 110-130 ℃, stirring for 16-24 hours, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
x2: adding 1-3 parts by weight of the product of the previous step into 100-3000 parts by weight of N, N-dimethylformamide, uniformly dispersing by ultrasonic waves, adding 50-100 parts by weight of 1, 10-diaminodecane, heating to 70-100 ℃, stirring for 16-24 hours, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
X3: adding 1-3 parts by weight of the product of the last step into 500-3000 parts by weight of water, adding 0.5-2 parts by weight of cerium nitrate hexahydrate after uniform ultrasonic dispersion, adding ammonia water to adjust pH to alkalinity after uniform stirring, carrying out hydrothermal reaction at 130-150 ℃ for 2-5 hours, cooling to room temperature, filtering, washing to neutrality, and drying residues to obtain the cerium oxide-modified carbon nanotube compound.
A preparation method of a low-concentration coupling defluorinating agent comprises the following steps:
S1: according to the formula amount, measuring polymeric aluminum ferric sulfate, magnesium oxide, lanthanum nitrate, cerium oxide-modified carbon nanotube compound and polyacrylamide, and mechanically stirring the materials for 1-3 hours to obtain a coupling primary product;
S2: adding water into the primary product to prepare mother liquor with the solid content of 50% by mass, and continuously stirring and curing for 1-2 h;
S3: and adding the formula amount of calcium chloride and hydrochloric acid into the mother solution, regulating the pH value of the solution to be acidic, continuously stirring for 1-2 hours, and adding the balance of water for dilution to obtain the low-concentration coupling defluorinating agent.
Further, in the step S1, the stirring speed is 8-12 rpm.
Further, in the step S2, the stirring speed is 50 to 70rpm.
Further, in the step S3, the pH range of the solution is 3-5.
The invention has the beneficial effects that:
1. Compared with the prior art, the fluorine removing agent has the three functions of adsorption, ion exchange and complex sedimentation, and the colloidal particles formed by the compound salt in water have large specific surface area, positive charge and high zeta potential. The radius of the fluoride ion is small, the electronegativity is strong, so that the fluoride ion is strongly adsorbed; part of the aluminum exists in the form of polyhydroxy cation [ Al 13O4(OH)24]7+ ] and has higher charge density and polymerization degree. Because of the close ionic radii and charges of F - and OH -, [ some OH - in Al 13O4(OH)24]7+ can be exchanged separated from F -; the strong polar electron cloud hybridization orbit of the effective component of the high-efficiency fluorine removing agent is utilized to form the strong bond of the polydentate ligand with fluorine element in the wastewater, so that the generated fluoride is more stable than a common complex, and the fluoride can be effectively separated from the wastewater. The fluorine content of the effluent can be controlled to be 2-6 mg/L according to the regional management requirement.
2. Compared with the prior art, the cerium oxide-modified carbon nano tube compound formed by the invention not only has embedded functionalization of the carbon nano tube, but also has covalent functionalization, and the dispersibility and the reactivity of the cerium oxide-modified carbon nano tube compound are improved by the functionalization, so that the agglomeration of the carbon nano tube and cerium oxide nano particles is reduced, the specific surface area of the material is increased, the surface adsorption active sites of the material are increased, and the fluorine adsorption capacity of the material is obviously improved.
3. According to the invention, calcium, aluminum and iron are polymerized through the strong cohesive force and the strong charge adsorption capacity of the coupling primary product prepared from each basic raw material, the formed fluorine removing agent improves the adsorption capacity and charge net capturing capacity of calcium, aluminum and iron to fluorine, the fluorine content can be effectively controlled to be 2-6 mg/L, the inorganic sludge amount generated by the product is small, the solid waste treatment cost is reduced, the fluorine removing effect is relatively good, and the utilization rate is relatively high.
Detailed Description
Polymeric aluminum ferric sulfate, 60 mesh, model: SPFCS Zhengzhou Yiliter chemical industry.
Polyacrylamide, cat No.: JZY-XA-089, gong yi.
Hydrochloric acid, 30wt%.
The outer diameter of the multiwall carbon nanotube is 20-30 nm, and the length is 5-20 mm.
Ammonia, 2mol/L.
Example 1,
A preparation method of a low-concentration coupling defluorinating agent comprises the following steps:
S1: taking 4g of polymeric aluminum ferric sulfate, 3g of magnesium oxide, 1.5g of lanthanum nitrate, 1g of cerium oxide-modified carbon nanotube compound and 0.5g of polyacrylamide, and mechanically stirring the materials for 2 hours at 10rpm to obtain a coupling primary product;
s2: adding water into the primary product to prepare mother liquor with the solid content of 50 percent by mass, and continuously stirring and curing for 2 hours at 60 rpm;
s3: adding 0.8g of calcium chloride and 0.2g of hydrochloric acid into the mother solution, regulating the pH value of the solution to 4, continuously stirring for 2 hours, and adding the balance of water for dilution to obtain the low-concentration coupling defluorinating agent.
The preparation method of the cerium oxide-modified carbon nano tube compound comprises the following steps:
X1: adding 4g of multi-wall carbon nano tube into 800mL of concentrated nitric acid, uniformly dispersing by ultrasonic at 45kHz and 400W, heating to 120 ℃, stirring for 18 hours, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
X2: adding 3g of the product obtained in the last step into 1.5L of N, N-dimethylformamide, uniformly dispersing by ultrasonic at 45kHz and 400W, adding 85g of 1, 10-diaminodecane, heating to 80 ℃, stirring for 20h, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
X3: adding 2g of the product of the last step into 2L of water, uniformly dispersing by ultrasonic at 45kHz and 400W, adding 1g of cerium nitrate hexahydrate, uniformly stirring, adding ammonia water to adjust the pH value to 10, carrying out hydrothermal reaction at 140 ℃ for 4 hours, cooling to room temperature, filtering, washing to neutrality, and drying the residue to obtain the cerium oxide-modified carbon nano tube compound.
EXAMPLE 2,
The only difference was that the amount of the cerium oxide-modified carbon nanotube complex was 0.5g as in example 1.
EXAMPLE 3,
The only difference was that the amount of the cerium oxide-modified carbon nanotube complex was 0.8g as in example 1.
EXAMPLE 4,
The only difference was that the amount of the cerium oxide-modified carbon nanotube complex was 1.5g as in example 1.
Comparative example 1,
A preparation method of a low-concentration coupling defluorinating agent comprises the following steps:
S1: taking 4g of polymeric aluminum ferric sulfate, 3g of magnesium oxide, 1.5g of lanthanum nitrate, 1g of multi-wall carbon nano tube and 0.5g of polyacrylamide, and mechanically stirring the materials for 2 hours at 10rpm to obtain a coupling primary product;
s2: adding water into the primary product to prepare mother liquor with the solid content of 50 percent by mass, and continuously stirring and curing for 2 hours at 60 rpm;
s3: adding 0.8g of calcium chloride and 0.2g of hydrochloric acid into the mother solution, regulating the pH value of the solution to 4, continuously stirring for 2 hours, and adding the balance of water for dilution to obtain the low-concentration coupling defluorinating agent.
Comparative example 2,
A preparation method of a low-concentration coupling defluorinating agent comprises the following steps:
S1: taking 4g of polymeric aluminum ferric sulfate, 3g of magnesium oxide, 1.5g of lanthanum nitrate, 1g of cerium oxide-carbon nano tube compound and 0.5g of polyacrylamide, and mechanically stirring the materials for 2 hours at 10rpm to obtain a coupling primary product;
s2: adding water into the primary product to prepare mother liquor with the solid content of 50 percent by mass, and continuously stirring and curing for 2 hours at 60 rpm;
s3: adding 0.8g of calcium chloride and 0.2g of hydrochloric acid into the mother solution, regulating the pH value of the solution to 4, continuously stirring for 2 hours, and adding the balance of water for dilution to obtain the low-concentration coupling defluorinating agent.
The preparation method of the cerium oxide-carbon nano tube compound comprises the following steps:
Adding 2g of multi-wall carbon nano tube into 2L of water, adding 1g of cerium nitrate hexahydrate after ultrasonic dispersion is uniform, adding ammonia water to adjust pH to 10 after stirring uniformly, carrying out hydrothermal reaction at 140 ℃ for 4 hours, cooling to room temperature, filtering, washing filtrate to neutrality, and drying residues to obtain the cerium oxide-carbon nano tube compound.
Comparative example 3,
A preparation method of a low-concentration coupling defluorinating agent comprises the following steps:
S1: taking 4g of polymeric aluminum ferric sulfate, 3g of magnesium oxide, 1.5g of lanthanum nitrate, 1g of cerium oxide and 0.5g of polyacrylamide, and mechanically stirring the materials for 2 hours at 10rpm to obtain a coupling primary product;
s2: adding water into the primary product to prepare mother liquor with the solid content of 50 percent by mass, and continuously stirring and curing for 2 hours at 60 rpm;
S3: adding 0.8g of calcium chloride and 0.2g of hydrochloric acid into the mother solution, regulating the pH value of the solution to 4, continuously stirring for 2 hours, and adding the rest of water to dilute to obtain the low-concentration coupling defluorinating agent.
Test example 1,
Preparing a fluorine-containing aqueous solution with the mass fraction of fluorine ions of 5mg/L, adding 0.2g of the fluorine removing agent of the example and the fluorine removing agent of the comparative example into 1L of the fluorine-containing aqueous solution respectively, adsorbing for 2 hours at 20 ℃, measuring the concentration of fluorine ions in the fluorine-containing aqueous solution by using a spectrophotometer, and calculating the removal rate R (%) of fluorine ions, wherein the calculation formula is R=1-C/C 0, and C is the concentration of fluorine ions in adsorption balance; c 0 is the initial concentration of fluoride ion and the specific test results are shown in Table 1.
As can be seen from comparison of comparative examples 1 to 2 with example 1, the fluorine removal effect of the examples was better, probably due to the cerium oxide-modified carbon nanotube composite used in example 1. In contrast, the carbon nanotubes added in comparative example 1, the cerium oxide-carbon nanotube composite in comparative example 2, the cerium oxide in comparative example 3, the rare earth ions can form stable complexes by combining fluoride ions to achieve the effect of removing fluorine, and the carbon nanotubes can adsorb negatively charged fluoride ions by electrostatic action, but both have the defects of easy agglomeration and poor dispersibility, and the effect is inferior to that of example 1 when used alone, which may be that not only the defect of poor dispersibility of the carbon nanotubes is improved after modification, but also the electrostatic attraction is improved by a large amount of amino groups on the surface after modification, so that the effect of removing fluorine of example 1 is better than that of comparative example 2.
Test example 2,
Industrial wastewater defluorination tests were performed by sampling wastewater from crystal deep processing in a certain park, and the content of fluorine ions in wastewater before and after defluorination was tested respectively, and the specific results are shown in table 2.
From the treatment effect of wastewater, the fluorine removing agent prepared by the invention has good adsorptivity to fluorine ions, and the fluorine content can be effectively controlled to be 2-6 mg/L, because the fluorine removing agent prepared by the invention has three functions of adsorption, ion exchange and complex sedimentation, the compound salt forms colloidal particles in water, and the specific surface area is large, the positive charge is carried out, and the zeta potential is high. The radius of the fluoride ion is small, the electronegativity is strong, so that the fluoride ion is strongly adsorbed; part of the aluminum exists in the form of polyhydroxy cation [ Al 13O4(OH)24]7+ ] and has higher charge density and polymerization degree. Because of the close ionic radii and charges of F - and OH-, [ some OH - in Al 13O4(OH)24]7+ can exchange separate with F -; the strong polar electron cloud hybridization orbit of the effective component of the high-efficiency fluorine removing agent is utilized to form the strong bond of the polydentate ligand with fluorine element in the wastewater, so that the generated fluoride is more stable than a common complex, and the fluoride can be effectively separated from the wastewater. The cerium oxide-modified carbon nanotube compound added in the embodiment 1 not only performs embedded functionalization on the carbon nanotubes, but also performs covalent functionalization, improves the dispersibility and the reactivity of the carbon nanotubes, reduces the agglomeration of the carbon nanotubes and cerium oxide nanoparticles, increases the specific surface area of the material, increases the adsorption activity point on the surface of the material, and obviously improves the adsorption capacity of the material to fluorine, so that the adsorption performance of the material to fluorine ions is optimal. The fluorine removing agent formed by the coupling primary product prepared by the basic raw materials has the advantages that the strong cohesive force and the strong charge adsorption capacity of the coupling primary product are used for polymerizing calcium, aluminum and iron, the adsorption capacity of the calcium, aluminum and iron on fluorine and the charge net capturing capacity are improved, the inorganic sludge amount generated by the coupling primary product is small, the solid waste treatment cost is reduced, the fluorine removing effect is good, and the utilization rate is high.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The low-concentration coupling defluorinating agent is characterized by comprising the following components in percentage by mass: 3-5% of polymeric aluminum ferric sulfate, 2-4% of magnesium oxide, 1-2% of lanthanum nitrate, 0.5-1.5% of cerium oxide-modified carbon nanotube compound, 0.2-1% of polyacrylamide, 0.5-1.5% of calcium chloride, 0.1-0.3% of hydrochloric acid and the balance of water; the cerium oxide-modified carbon nanotube compound is prepared by modifying a carbon nanotube and then carrying out hydrothermal reaction with cerium nitrate hexahydrate.
2. The low concentration coupled defluorinating agent according to claim 1, wherein the preparation method of the cerium oxide-modified carbon nanotube composite comprises the steps of:
x1: adding the multiwall carbon nanotubes into concentrated nitric acid, uniformly dispersing by ultrasonic, heating and stirring for 16-24 hours, cooling to room temperature, filtering, washing the filtrate to be neutral, and drying residues for the next step;
X2: adding the product of the last step into N, N-dimethylformamide, adding 1, 10-diaminodecane after ultrasonic dispersion is uniform, heating and stirring for 16-24 h, cooling to room temperature, filtering, washing to neutrality, and drying residues for the next step;
X3: adding the product of the last step into water, uniformly dispersing by ultrasonic, adding cerium nitrate hexahydrate, uniformly stirring, adding ammonia water to adjust pH to be alkaline, performing hydrothermal reaction for 2-5 hours, cooling to room temperature, filtering, washing to be neutral, and drying the residue to obtain the cerium oxide-modified carbon nano tube compound.
3. The low-concentration coupled defluorinating agent according to claim 2, wherein the temperature of the heating and stirring in the step X1 is 110-130 ℃.
4. The low-concentration coupled defluorinating agent according to claim 2, wherein the temperature range of the heating and stirring in the step X2 is 70-100 ℃.
5. The low concentration coupled defluorinating agent according to claim 2, wherein the pH is adjusted in the range of 9 to 10 in the step X3.
6. The low concentration coupled defluorinating agent according to claim 2, wherein the hydrothermal reaction in step X3 is performed at a temperature ranging from 130 ℃ to 150 ℃.
7. The method for preparing the low-concentration coupling fluorine removal agent according to any one of claims 1 to 6, comprising the steps of:
S1: according to the formula amount, measuring polymeric aluminum ferric sulfate, magnesium oxide, lanthanum nitrate, cerium oxide-modified carbon nanotube compound and polyacrylamide, and mechanically stirring the materials for 1-3 hours to obtain a coupling primary product;
S2: adding water into the primary product to prepare mother liquor with the solid content of 50% by mass, and continuously stirring and curing for 1-2 h;
S3: and adding the formula amount of calcium chloride and hydrochloric acid into the mother solution, regulating the pH value of the solution to be acidic, continuously stirring for 1-2 hours, and adding the balance of water for dilution to obtain the low-concentration coupling defluorinating agent.
8. The method for preparing a low concentration coupling defluorinating agent according to claim 7, wherein the stirring speed in the step S1 is 8-12 rpm.
9. The method for preparing a low-concentration coupling defluorinating agent according to claim 7, wherein the stirring speed in the step S2 is 50-70 rpm.
10. The method for preparing a low concentration coupling defluorinating agent according to claim 7, wherein the pH of the solution in the step S3 is 3-5.
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