CN113499756B - Defluorinating agent based on metal organic framework material - Google Patents
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Abstract
The invention relates to a fluorine removal agent based on a metal organic framework material, which contains the metal organic framework material, wherein the metal element in a metal compound for synthesizing the metal organic framework material comprises an Al element and at least one of K, na, ca, mg, ti, zr, hf, V and Fe. Compared with the prior art, the metal organic framework material in the defluorinating agent does not need to be additionally added with alkali to deprotonate the organic carboxylic acid ligand; furthermore, toxic organic solvents such as N, N-dimethylformamide and the like which are used in the traditional solvothermal method are not involved; the raw materials are cheap and easy to obtain; green and environment-friendly, short reaction time, simple process, high product purity, simple activation, contribution to realizing industrial production and fluorine removal efficiency of more than 99 percent.
Description
Technical Field
The invention belongs to the field of Metal Organic Framework (MOFs) materials, and particularly relates to a defluorinating agent based on a MOFs material.
Background
The metal organic framework material is a novel crystalline porous material with a periodic network structure formed by self-assembly of metal ions and organic carboxylic acid ligands. Compared with the traditional inorganic porous material, the metal organic framework material has extremely high specific surface area, a special topological structure, adjustable pore channel size and easy functionalization of the structure, thereby showing great mining potential in the fields of gas storage and separation, heterogeneous catalysis, drug loading, molecular recognition, environmental remediation and the like.
The aluminum fumarate metal organic framework is a porous metal organic framework material with a one-dimensional channel structure formed by the coordination of aluminum ions and fumarate ions. Wherein a linear chain of aluminium ions and hydroxyl groups (Al-OH-Al) is bridged by a fumarate to giveWith [ Al (OH) (O) ] 2 C-CH＝CH-CO 2 )]Is a three-dimensional orthogonal structure of structural units. The aluminum fumarate metal organic framework material has a high specific surface area, shows high water stability, and has a great application prospect in the fields of gas storage and separation, adsorption and removal of water pollutants and the like.
Common water body defluorination technologies include chemical agent method, ion exchange method, membrane method, adsorption method and the like. The chemical method is to form precipitate by using a precipitant and fluorine ions, and then remove the precipitate by solid-liquid separation. The commonly used chemical precipitating agents comprise lime milk, calcium chloride, carbide slag and the like, and are suitable for treating high-concentration fluorine-containing wastewater, but when the low-concentration fluorine-containing wastewater is treated, the dosage of the chemical agent is large, the sludge yield is high, the fluoride ion removal rate is low, and the deep purification effect is difficult to achieve. The ion exchange method is suitable for wastewater with small water volume and low concentration, and has no advantages in the aspects of treatment cost and operation efficiency when treating wastewater with large water volume and high concentration containing fluorine; although the treatment effect is good, the cost is high, high operation management experience is required, problems may frequently occur in operation, and the biggest problem is that the generated concentrated water also needs to be treated; the adsorption method is mainly used for adsorbing fluorine ions on the inner surface and the outer surface of a material through the actions of surface adsorption, complexation, ion exchange mass transfer and the like, so that the aim of reducing the concentration of the fluorine ions in the water body is fulfilled, and the method is particularly suitable for deep purification of low-concentration fluorine-containing wastewater. The traditional adsorbing materials comprise activated alumina (magnesium), zeolite, hydroxyapatite, activated carbon and the like, but have the defects of low adsorption capacity, large adding amount, poor regeneration capability and the like. The novel porous material used for removing fluorine from water is a hot point of fluorine removal research at present, and the development of a high-efficiency fluorine removal agent with high activity, high capacity, low cost and simple use has important environmental protection significance and commercial value.
The following patents and publications report synthetic studies of aluminum fumarate metal organic framework materials:
patent CN101448568A discloses an aluminum fumarate metal organic framework material and a preparation method thereof, wherein a reaction mixture of aluminum compounds (aluminum chloride, aluminum sulfate, aluminum nitrate, etc.) and fumaric acid or a salt thereof is dissolved in N, N-Dimethylformamide (DMF) organic solvent, stirred at 100-200 ℃, and filtered. Washing the filtered solid with acetone and methanol for 5-6 times, and vacuum drying at 100 deg.C to obtain white pre-product.
Patent CN103140495A discloses a process for preparing a porous metal organic framework based on aluminum fumarate. The reaction is carried out in an aqueous solvent with an alkaline reaction using an alkali metal hydroxide or a mixture of a plurality of different alkali metal hydroxides as the base. Specifically, fumaric acid and alkali are dissolved in water solution, the mixture is gradually added into water solution of aluminum compound (aluminum chloride, aluminum sulfate, aluminum nitrate, etc.), and stirred at 20-100 deg.C for 0.2-4 hr to form white suspension. The suspension was filtered and washed several times with water and dried at 100 ℃.
The publication International Journal of Heat and Mass Transfer,2017,14, 621-627, mentions a method for synthesizing an aluminum fumarate metal organic framework material. Specifically, aluminum chloride salt and fumaric acid were dissolved in DMF solvent together, stirred at 130 ℃ for 4 days, and centrifuged. The obtained white product is washed twice by acetone and methanol, dried at 80 ℃ and activated for 3h at 150 ℃.
A green synthesis method of an aluminum fumarate metal organic framework material is reported in published Materials Letters,2018 and 221. Specifically, fumaric acid and sodium hydroxide solution are dissolved in the aqueous solution together and are stirred and mixed uniformly, and then the mixed solution is added into the aqueous solution of aluminum sulfate salt drop by drop to obtain a clear solution. Stirring and heating the clear solution at 90 ℃ for 60min, centrifugally separating the obtained white precipitate, washing with deionized water for three times, vacuum-drying at 80 ℃ to obtain a white powdery aluminum fumarate metal organic framework material, and vacuum-activating at 150 ℃ for 6h.
Disclosure of Invention
The applicant of the present invention finds out after deep analysis of the prior art that:
the method of patent CN101448568A enables the synthesis of aluminum fumarate metal organic framework materials, but must be synthesized in high boiling point toxic organic solvents such as N, N-Dimethylformamide (DMF).
The method of patent CN103140495A can synthesize the aluminum fumarate metal organic framework material, but an additional alkali metal hydroxide is required to be added in the synthesis system.
The method of the publication International Journal of Heat and Mass Transfer,2017,14, 621-627, enables the synthesis of aluminum fumarate metal organic framework materials, but must be synthesized in a toxic organic solvent DMF, and is time-consuming and time-costly.
The method disclosed in the publications Materials Letters,2018,221 can synthesize the aluminum fumarate metal organic framework material, is short in time consumption and mild in condition, but needs additional alkali metal hydroxide in a synthesis system.
At present, most of aluminum fumarate metal organic framework materials are synthesized by using a large amount of toxic organic solvents such as N, N-Dimethylformamide (DMF) and the like, and the synthesis is long, and when water is used as the solvent, alkali metal hydroxide is additionally added for deprotonation of fumaric acid. In order to avoid the use of toxic organic solvents and reduce the cost of raw materials, the research on green synthesis of the aluminum fumarate metal organic framework material in a non-DMF system is a necessary way for realizing the industrial production and application of the novel material.
The invention aims to provide a method for synthesizing a metal organic framework material, which has at least one of the advantages of simple process, greenness and economy.
It is another object of the present invention to provide a metal-organic framework material obtained by said synthesis method.
The invention also aims to provide application of the metal organic framework material.
Another object of the present invention is to provide a fluorine removing agent comprising the metal-organic framework material.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a synthesis method of a metal organic framework material, which comprises the following steps: adding a metal compound and an organic carboxylic acid ligand into a solvent, uniformly mixing, and heating for reaction; carrying out phase separation on the reacted system to obtain a non-liquid phase product, namely the metal organic framework material;
the solvent is organic solvent or water; when the solvent is organic solvent, the metal compound is metal salt or polymeric hydroxyl metal salt, and when the solvent is water, the metal compound is polymeric hydroxyl metal salt.
The synthesis of the metal organic framework material in the invention does not need to add alkali (hydroxide of alkali metal), and is simpler than the synthesis process in the prior art.
In the present invention, the organic solvent may be an organic solvent such as an alcohol, an organic amine (e.g., N-Dimethylformamide (DMF), N-Diethylformamide (DEF), dimethylacetamide (DMAC), or the like), or Dimethylsulfoxide (DMSO). Preferably, the organic solvent is an alcohol or DMF. More preferably, the organic solvent is an alcohol.
In the present invention, the alcohol may be methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, etc. Preferably the alcohol is methanol, ethanol or isopropanol. More preferably, the alcohol is ethanol, and has moderate polarity and low toxicity.
The invention preferably uses green and environment-friendly alcohols (such as ethanol) and water as solvents, overcomes the environmental pollution and/or the harm to organisms caused by using toxic organic solvents such as N, N-Dimethylformamide (DMF) and the like in the traditional organic metal framework material, and simultaneously does not need to additionally add alkali.
In the case of using water as a solvent in the present invention, in the conventional method, the conventional metal salt as a metal source is reacted with the organic carboxylic acid ligand to remove protons by adding an alkali metal hydroxide additionally. In the invention, when water is used as a solvent, the polymeric hydroxyl metal salt is innovatively used as a metal source, and the metal-organic framework material can be synthesized with the organic carboxylic acid ligand without adding extra alkali. When water is used as the solvent, the resulting product is usually a powdered metal organic framework material.
When water is used as a solvent, the pH of the solution is weakly acidic after the polymeric hydroxy metal salt is dissolved.When organic carboxylic acid ligand is added into the system, the metal hydroxyl (M-OH) in the polymeric hydroxyl metal salt can promote the deprotonation of the carboxyl (-COOH) in the ligand to form carboxylate ion (-COO-), and the carboxylate ion (-COO-), is converted into metal ion M n+ (n is the number of charges of the metal ion). The deprotonated organic carboxylic acid ligand is further assembled with the metal ion in the polymeric hydroxy metal salt through a coordination bond to form a metal organic framework material. Compared with the difference that the water is used as the solvent to synthesize the metal-organic framework material in other published documents, the method needs to additionally add the alkali metal hydroxide, and when the polymeric hydroxyl metal salt is used as the metal compound, the water is used as the solvent to successfully synthesize the metal-organic framework material without additionally adding the alkali metal hydroxide.
The invention can also use alcohols (particularly preferably ethanol) as a solvent, so that the polymeric hydroxyl metal salt and the conventional metal salt can react with the organic carboxylic acid ligand to synthesize the metal-organic framework material without adding alkali metal hydroxide additionally. The conventional method does not report the synthesis of metal organic framework materials by adopting polymeric hydroxy metal salts and using alcohols as solvents.
Dissolving inorganic salt containing crystal water in alcohol, and performing hydrolysis or alcoholysis reaction on the inorganic salt, and then performing polycondensation to form nano-scale particles to form sol. Generally, the transition metal inorganic salt is hydrolyzed rapidly, and when small molecular alcohols are used as solvents, metal ions and alcoholic hydroxyl groups can form chelate complexes, so that reactants are not easy to hydrolyze, and the hydrolysis rate is controlled. Therefore, when alcohols are used as solvents, the resulting product is usually a metal organogel.
The present invention can also use conventional DMF and the like as a solvent. Organic amines such as DMF (dimethyl formamide) are used as a common metal organic framework material synthesis solvent, the organic amines are decomposed into small molecular amines (alkalescence) such as dimethylamine under the heating condition, a carboxylic acid organic carboxylic acid ligand solvent and deprotonation are promoted, and the deprotonated organic carboxylic acid ligand is further assembled with metal ions through coordination bonds to form the metal organic framework material.
The organic carboxylic acid ligand of the present invention may be any organic carboxylic acid ligand suitable for reaction to form a metal organic framework material. The organic carboxylic acid ligand comprises at least one at least bidentate organic compound. The at least bidentate organic compound may be fumaric acid, isophthalic acid, terephthalic acid, succinic acid, itaconic acid, epoxysuccinic acid, trimesic acid, and the like; or a salt thereof. When an at least bidentate salt of an organic compound is used, the solubility in a general solvent (e.g., water) is higher, and the reaction proceeds more easily. However, in the present invention, even in the case of a bidentate organic compound (e.g., fumaric acid) having poor solubility in water at room temperature, the reaction can be smoothly carried out under heating.
The organic carboxylic acid ligand of the present invention is preferably fumaric acid, isophthalic acid or terephthalic acid.
The organic carboxylic acid ligand in the present invention is more preferably fumaric acid.
The metal element in the metal compound of the present invention may be any metal element suitable for reacting to form a metal-organic framework material. For example, it may be at least one of K, na, ca, mg, ti, zr, hf, V, fe, al, etc.
The metal element in the metal compound of the present invention is preferably at least one element selected from Ca, ti, zr, al, fe, and the like. The high-valence metal element can form polymorphic polymeric hydroxyl metal ions with hydroxide radicals in water, and the higher the valence state is, the more abundant the forms of the corresponding polymeric hydroxyl metal ions are formed, and the higher the hydroxyl content in the obtained polymeric hydroxyl metal salt is.
The metal element in the metal compound of the present invention is more preferably Al. The valence of the metal ion is moderate, and the stability of polymorphous polymeric hydroxyl metal ion formed by the metal ion and hydroxide radical in water is best.
In the present invention, the metal salt is a metal normal salt. The acid radical ion of the normal salt may be Sulfate (SO) 4 2- ) Hydrochloric acid (Cl) - ) Nitrate radical (NO) 3 - ) Inorganic acid radical ion, and optionally formate (HCOO) - ) Acetate (CH) 3 COO - ) Oxalic acid radical (C) 2 O 4 2- ) And organic acid radical ions.
In the present invention, the acid ion of the metal salt is preferably an inorganic acid ion.
In the present invention, the polymeric hydroxy metal salt means: the inorganic polymer formed by metal ions, hydroxyl and water molecules through coordination bonds and covalent bonds is a general name of a hydrolysate after metal ions in a metal ion aqueous solution reach hydrolysis equilibrium.
In the present invention, the polymeric hydroxy metal salt is a polymeric hydroxy sulfate of a metal, a polymeric hydroxy chloride salt of a metal, or the like.
In the present invention, the polymeric hydroxy metal salt is preferably a metal polychloride.
In the invention, the salinity of the polymeric hydroxyl metal salt is 8-95 percent, and the content of the metal oxide is 10-50 percent. Within a certain range, the higher the basicity, the greater the hydrophilicity (the greater the water vapor adsorption capacity); the lower the metal oxide content, the higher the basicity, and the metal oxide content also represents the raw material usage, so the higher the basicity, the lower the synthesis cost. Therefore, the salt size of the present invention is preferably 15% to 65%.
In the present invention, the molar ratio of the metal compound to the organic carboxylic acid ligand may be 1 (1 to 20), preferably 1.
The concentration of the organic carboxylic acid ligand in the solvent can be 0.05 mol/L-2.0 mol/L. The concentration of the organic carboxylic acid ligand in the solvent is preferably 0.1mol/L to 1.0mol/L. More preferably, the concentration of the organic carboxylic acid ligand in the solvent is 0.25mol/L to 0.5mol/L.
The temperature of the heating reaction in the invention can be 40-150 ℃; the heating reaction time is 5min-2.0h. The temperature of the heating reaction is preferably 80-120 ℃; the heating reaction time is 10min-2h. When the heating temperature is low, the metal compound and the organic carboxylic acid ligand do not react in the solvent, or even if the reaction occurs, the reaction may be incomplete, the crystallinity of the product is low, and the yield is low. The heating temperature is too high, the energy consumption is large, the synthesis cost is increased, and the requirement on synthesis conditions is high. More preferably, the temperature is between 90 and 100 ℃, the system reaction is stable, the yield is high, the crystallinity is strong, and the aluminum fumarate metal organic framework material is easier to synthesize. According to the experimental results, the reaction has synthesized the metal organic framework material with strong crystallinity within ten minutes from the start of heating, the yield gradually increases with the time, the sign of complete reaction is that the yield does not change with the time of reaction, and the heating reaction time is more preferably 30min-1h.
In the present invention, the heating reaction can be performed under the condition of microwave heating, or under the condition of air, water bath or steam heating, or under other feasible heating reaction conditions. Generally, microwave heating can accelerate the reaction.
In the present invention, the heating reaction may be carried out under normal pressure or slightly more than 1 atmosphere depending on the reaction temperature.
The method further comprises the step of post-treating the non-liquid phase product, wherein the post-treating step comprises at least one of washing, solid-liquid separation and drying. The primary product formed by the metal compound and the organic carboxylic acid ligand is directly obtained after the heating reaction, and the metal compound or the organic carboxylic acid ligand which is not reacted is usually contained, and the metal organic framework material with high purity and good crystallinity can be obtained by simple washing and drying. The washing can be performed by using water or alcohols, the metal organic framework material has strong crystallinity, high purity and high yield, and the metal organic framework material can be simply washed once by using water or alcohols. The drying can be realized by adopting a drying mode, and other feasible drying (vacuum drying and the like) modes can also be adopted. When the drying mode is adopted, the drying temperature and time can be reasonably selected according to actual conditions. Usually 80-120 deg.C and drying time of 0.5-8 hr.
The invention also provides a metal organic framework material based on the synthesis method, which is obtained by heating and reacting a metal compound and an organic carboxylic acid ligand in water or an organic solvent serving as a solvent; when the solvent is organic solvent, the metal compound is metal salt or polymeric hydroxyl metal salt, and when the solvent is water, the metal compound is polymeric hydroxyl metal salt.
In the invention, when the solvent is water, the metal organic framework material is in a nano tablet structure.
In the present invention, when the solvent is water, the metal-organic framework material preferably has a circular nano-sheet structure, a square nano-sheet structure, or a morphological structure between the circular nano-sheet structure and the square nano-sheet structure.
In the invention, when the solvent is water, the plane size of the single nano flaky metal organic framework material is 50-400nm, and the thickness is 1-5nm.
In the invention, the organic metal framework material is a porous material, and the porous structure is composed of mesopores and micropores.
In the present invention, the mesopores preferably have a pore volume of 0.05 to 1.0cm 3 Per g, pore volume of the micropores is 0.2-0.5cm 3 /g。
The invention also provides application of the metal organic framework material in the aspects of gas storage and separation, heterogeneous catalysis, drug loading, molecular recognition, environmental remediation and the like.
The invention also provides a fluorine removing agent containing the metal organic framework material, wherein the metal element in the metal compound for synthesizing the metal organic framework material comprises Al element and at least one of K, na, ca, mg, ti, zr, hf, V and Fe.
In the present invention, in the metal compound used for synthesizing the metal-organic framework material, the metal element other than Al element is preferably Na, K, ca, mg, fe, zr, or Ti.
In the invention, when the fluorine removing agent is used for removing fluorine, the removal rate of fluorine ions in the water body is up to more than 99%.
The fluorine removing agent in the present invention may be in the form of a solid or a dispersion (aqueous solution).
The specific method for testing the defluorination performance comprises the following steps: 50mL of a 40mg/L fluorine-containing solution was prepared, the initial pH of the solution was adjusted to =6, 37.5mg of a sample (0.75 g/L of the amount added) was added, the reaction was stirred at room temperature for 24 hours, and then the sample was filtered and the concentration of the remaining fluorine ions in the solution was measured by an ion selective electrode method.
Compared with the prior art, the invention has the following beneficial effects:
1 except metal salt and organic carboxylic acid ligand, the invention does not need to add extra alkali, reduces the synthesis cost, simplifies the synthesis process and improves the product purity.
2. When water or alcohols (especially ethanol) are adopted as solvents, the invention only relates to environment-friendly solvents such as water and alcohols in the synthesis and activation processes, avoids the use of toxic organic solvents such as DMF, and has the advantages of low cost, less pollution, greenness and economy.
3. When water is used as the solvent, the solvent is completely nontoxic, and the synthesis method is more environment-friendly.
4. The invention adopts the polymeric hydroxyl metal salt as the metal compound, and compared with the conventional metal salt (such as sulfate, nitrate, hydrochloride and the like), the raw material is cheap and easy to obtain.
5. The metal organic framework material synthesized by the method has the advantages of strong crystallinity, high purity, high yield, simple washing once by using water or alcohol and simple activation.
6. The metal organic framework material has the advantages of large specific surface area, high water stability, strong adsorption capacity and no toxic and harmful heavy metal ions.
7. The metal organic framework material is applied to the aspect of removing fluorinions in water, and compared with the conventional fluorine removal products (such as activated alumina and the like), the metal organic framework material has large adsorption capacity and stable removal efficiency.
Drawings
FIG. 1 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 1;
FIG. 2 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 1;
FIG. 3 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 1 (left: SEM; right: TEM);
FIG. 4 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 2;
FIG. 5 is a nitrogen isothermal adsorption and desorption curve of the synthesized aluminum fumarate metal organic framework material of example 2;
FIG. 6 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 2 (left: SEM; right: TEM);
FIG. 7 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 3;
FIG. 8 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 3;
FIG. 9 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 3 (left: SEM; right: TEM);
FIG. 10 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 4;
FIG. 11 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 4;
FIG. 12 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 4 (left: SEM; right: TEM);
FIG. 13 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 5;
FIG. 14 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 5;
FIG. 15 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 5 (left: SEM; right: TEM);
FIG. 16 is an XRD pattern for the synthetic aluminum fumarate metal organic framework material of example 6;
FIG. 17 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 6;
FIG. 18 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 6 (left: SEM; right: TEM);
FIG. 19 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 7;
FIG. 20 is a nitrogen isothermal sorption desorption curve for the synthetic aluminum fumarate metal organic framework material of example 7;
FIG. 21 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 7 (left: SEM; right: TEM);
FIG. 22 is an XRD pattern of the as-synthesized product of example 8;
FIG. 23 is an XRD pattern of the synthetic product of example 9;
FIG. 24 is an XRD pattern for the synthetic aluminum fumarate metal organic framework material of example 11;
FIG. 25 is a nitrogen isothermal sorption/desorption curve for the synthetic aluminum fumarate metal organic framework material of example 11;
FIG. 26 is an SEM and TEM image of a synthetic aluminum fumarate metal organic framework material of example 11 (left: SEM; right: TEM);
FIG. 27 is an XRD pattern for the synthetic aluminum fumarate metal organic framework material of example 12;
FIG. 28 is a nitrogen isothermal sorption-desorption curve for the synthetic aluminum fumarate metal organic framework material of example 12;
FIG. 29 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 12 (left: SEM; right: TEM);
FIG. 30 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 13;
FIG. 31 is a nitrogen isotherm desorption curve of the synthetic aluminum fumarate metal organic framework material of example 13;
FIG. 32 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 13 (left: SEM; right: TEM);
FIG. 33 is an XRD pattern for the synthetic aluminum fumarate metal organic framework material of example 14;
FIG. 34 is a nitrogen isotherm desorption curve of the synthesized aluminum fumarate metal organic framework material of example 14;
FIG. 35 is an SEM and TEM image of a synthetic aluminum fumarate metal organic framework material of example 14 (left: SEM; right: TEM);
FIG. 36 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 15;
FIG. 37 is a nitrogen isothermal sorption-desorption curve for the synthetic aluminum fumarate metal organic framework material of example 15;
FIG. 38 is an SEM and TEM image of the synthetic aluminum fumarate metal organic framework material of example 15 (left: SEM; right: TEM);
FIG. 39 is an XRD pattern of the synthetic aluminum fumarate metal organic framework material of example 16;
FIG. 40 is a nitrogen isotherm desorption curve of the synthetic aluminum fumarate metal organic framework material of example 16;
FIG. 41 is a TEM image of a synthetic aluminum fumarate metal organic framework material of example 16;
FIG. 42 is an XRD pattern for the synthetic aluminum fumarate metal organic framework material of example 17.
Detailed Description
A method for synthesizing a metal organic framework material, the method comprising the steps of: adding a metal compound and an organic carboxylic acid ligand into a solvent, uniformly mixing, and heating for reaction; carrying out phase separation on the reacted system to obtain a non-liquid phase product, namely the metal organic framework material; the solvent is organic solvent or water; when the solvent is organic solvent, the metal compound is metal salt or polymeric hydroxyl metal salt, and when the solvent is water, the metal compound is polymeric hydroxyl metal salt.
The organic solvent may be an alcohol, an organic amine (N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), dimethylacetamide (DMAC), or the like), or an organic solvent such as Dimethylsulfoxide (DMSO). Preferably, the organic solvent is an alcohol or DMF. More preferably, the organic solvent is an alcohol. The alcohol can be methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, etc. Preferably the alcohol is methanol, ethanol or isopropanol. More preferably, the alcohol is ethanol, which has moderate polarity and low toxicity. The invention preferably uses green and environment-friendly alcohols (such as ethanol) and water as solvents, overcomes the environmental pollution and/or the harm to organisms caused by using toxic organic solvents such as N, N-Dimethylformamide (DMF) and the like in the traditional organic metal framework material, and does not need to add extra alkali.
The organic carboxylic acid ligand may be any organic carboxylic acid ligand suitable for reaction to form a metal organic framework material. The organic carboxylic acid ligand comprises at least one at least bidentate organic compound. The at least bidentate organic compound may be fumaric acid, isophthalic acid, terephthalic acid, succinic acid, itaconic acid, epoxysuccinic acid, trimesic acid, and the like; or a salt thereof. When an at least bidentate organic compound salt is used, the solubility in a general solvent (e.g., water) is higher, and the reaction proceeds more easily. However, in the present invention, the reaction can be smoothly carried out under heating conditions even in the case of a bidentate organic compound (e.g., fumaric acid) having poor solubility in water at ordinary temperature. The organic carboxylic acid ligand is preferably fumaric acid, isophthalic acid or terephthalic acid. More preferably, the organic carboxylic acid ligand is fumaric acid.
The metal element in the metal compound may be any metal element suitable for reacting to form a metal-organic framework material. For example, it may be at least one of K, na, ca, mg, ti, zr, hf, V, fe, al, etc. The metal element in the metal compound is preferably at least one element selected from Ca, ti, zr, al, fe, and the like. The high valence metal element can form polymorphic polymeric hydroxyl metal ions with hydroxide radicals in water, and the higher the valence state is, the more abundant the forms of the corresponding polymeric hydroxyl metal ions are formed, and the higher the hydroxyl content in the obtained polymeric hydroxyl metal salt is. The metal element in the metal compound is more preferably Al. The metal ion has moderate valence, and the stability of polymorphous polymeric hydroxyl metal ion formed by the metal ion and hydroxide radical in water is the best.
The metal salt is preferably a normal salt of a metal. The acid radical ion of the normal salt may be Sulfate (SO) 4 2- ) Hydrochloric acid radical (Cl) - ) Nitrate radical (NO) 3 - ) Inorganic acid radical ion, and optionally formate (HCOO) - ) Acetate (CH) 3 COO - ) Oxalic acid radical (C) 2 O 4 2- ) And organic acid radical ions. The acid ion of the metal salt is preferably an inorganic acid ion.
Polymeric hydroxy metal salts refer to: the inorganic polymer formed by metal ions, hydroxyl and water molecules through coordination bonds and covalent bonds is a general name of a hydrolysate after metal ions in a metal ion aqueous solution reach hydrolysis balance. The polymeric hydroxy metal salt is preferably a polymeric hydroxy sulfate of a metal, a polymeric hydroxy chloride salt of a metal, or the like. The polymeric hydroxy metal salt is more preferably a polymeric chloride salt of a metal. The salinity of the polymeric hydroxyl metal salt is preferably 8-95%, and the content of the metal oxide is 10-50%. Within a certain range, the higher the basicity, the greater the hydrophilicity (the greater the water vapor adsorption capacity); the lower the metal oxide content, the higher the basicity, and the metal oxide content also represents the raw material usage, so the higher the basicity, the lower the synthesis cost. Therefore, the salt size of the present invention is preferably 15% to 65%.
The molar ratio of the metal compound to the organic carboxylic acid ligand may be 1 (1 to 20), preferably 1.
The concentration of the organic carboxylic acid ligand in the solvent may be 0.05mol/L to 2.0mol/L. The concentration of the organic carboxylic acid ligand in the solvent is preferably 0.1mol/L to 1.0mol/L. More preferably, the concentration of the organic carboxylic acid ligand in the solvent is 0.25mol/L to 0.5mol/L.
The heating reaction temperature can be 40-150 ℃; the heating reaction time is 5min-2.0h. The temperature for heating reaction is preferably 80-120 ℃; the heating reaction time is 10min-2h. When the heating temperature is low, the metal compound and the organic carboxylic acid ligand do not react in the solvent, or even if the reaction occurs, the reaction may be incomplete, the crystallinity of the product is low, and the yield is low. The heating temperature is too high, the energy consumption is large, the synthesis cost is increased, and the requirements on synthesis conditions are high. More preferably, the temperature is between 90 and 100 ℃, the system reaction is stable, the yield is high, the crystallinity is strong, and the aluminum fumarate metal organic framework material is easier to synthesize. According to the experimental results, the reaction has synthesized a metal organic framework material with strong crystallinity at ten minutes from the start of heating, the yield gradually increases with time, the sign of complete reaction is that the yield does not change with the time of reaction, and the heating reaction time is more preferably 30min-1h.
The heating reaction can be carried out under the condition of microwave heating, also can be carried out under the condition of air, water bath or steam heating, and also can be other feasible heating reaction conditions. Generally, microwave heating can accelerate the reaction.
The heating reaction may be carried out at normal pressure or slightly more than 1 atmosphere depending on the reaction temperature.
The method further comprises the step of post-treating the non-liquid phase product, wherein the post-treating step comprises at least one of washing, solid-liquid separation and drying. The primary product formed by the metal compound and the organic carboxylic acid ligand is directly obtained after the heating reaction, and the metal compound or the organic carboxylic acid ligand which is not reacted is usually contained, and the metal organic framework material with high purity and good crystallinity can be obtained by simply washing and drying. The washing can use water or alcohol, the metal organic framework material has strong crystallinity, high purity and high yield, and the metal organic framework material can be simply washed once by using water or alcohol. The drying can be realized by adopting a drying mode, and other feasible drying (vacuum drying and the like) modes can also be adopted. When the drying mode is adopted, the drying temperature and time can be reasonably selected according to the actual situation. Generally, the temperature can be 80-120 ℃, and the drying time can be 0.5-8h.
A metal organic framework material based on the synthesis method, which is obtained by heating and reacting a metal compound and an organic carboxylic acid ligand in water or an organic solvent as a solvent; when the solvent is organic solvent, the metal compound is metal salt or polymeric hydroxyl metal salt, and when the solvent is water, the metal compound is polymeric hydroxyl metal salt.
When the solvent is water, the metal organic framework material is in a nano-sheet (nano-sheet) structure. When the solvent is water, the metal organic framework material is preferably in a round nano sheet structure, a square nano sheet structure or a morphological structure between the round nano sheet structure and the square nano sheet structure. When the solvent is water, the plane size of the single nano flaky metal organic framework material is 50-400nm, and the thickness is 1-5nm.
The organic metal framework material is a porous material, and the porous structure is composed of mesopores and micropores. The preferred mesoporous volume is 0.05-1.0cm 3 Per g, the pore volume of the micropores is 0.2-0.5cm 3 /g。
The metal can be applied to the aspects of gas storage and separation, heterogeneous catalysis, drug loading, molecular recognition, environmental remediation and the like of organic framework materials.
In the fluorine removing agent, the metal element in the metal compound for synthesizing the metal organic framework material comprises Al element and at least one of K, na, ca, mg, ti, zr, hf, V and Fe. In the metal compound used for synthesizing the metal-organic framework material, the metal element other than Al element is preferably Na, K, ca, mg, fe, zr, or Ti. When the fluorine removing agent is used for removing fluorine, the removal rate of fluorine ions in a water body is up to more than 99%. The fluorine removing agent in the invention can be in a solid form or in a dispersing agent (water agent) form. The specific method for testing the defluorination performance comprises the following steps: 50mL of a 40mg/L fluorine-containing solution was prepared, the initial pH of the solution was adjusted to =6, 37.5mg of a sample (0.75 g/L of the amount added) was added, the reaction was stirred at room temperature for 24 hours, and then the sample was filtered and the concentration of the remaining fluorine ions in the solution was measured by an ion selective electrode method.
The invention is described in detail below with reference to the figures and the specific embodiments.
In the following examples:
the specific surface area is measured by a static capacity method in GB/T19587-2004 'determination of solid matter specific surface area by gas adsorption BET method', and the micropore specific surface area and the mesopore specific surface area are calculated by a T-Plot method according to the nitrogen adsorption test result. Taking P/P from the total pore volume according to the nitrogen adsorption test result 0 And (3) calculating single-point adsorption data when the adsorption time is not less than 0.99, calculating the micropore volume according to the nitrogen adsorption test result by adopting a t-Plot method, and calculating the mesopore volume according to the nitrogen adsorption test result by adopting a BJH method. The sample was degassed under vacuum for not less than 6 hours prior to the nitrogen adsorption test.
When the obtained product is used for removing fluorine, the specific method for testing the fluorine removal performance comprises the following steps: 50mL of a 40mg/L fluorine-containing solution was prepared, the initial pH of the solution was adjusted to =6, 37.5mg of a sample (0.75 g/L of the amount added) was added, the reaction was stirred at room temperature for 24 hours, and then the sample was filtered and the concentration of the remaining fluorine ions in the solution was measured by an ion selective electrode method.
Example 1
1.67g of aluminum sulfate octadecahydrate and 0.58g of fumaric acid were weighed out separately and placed in a reaction flask and added10mL of water (the molar ratio of aluminum to fumaric acid is 1, and the concentration of fumaric acid in water is 0.5 mol/L), 0.6g of sodium hydroxide is added after uniform stirring and dispersion, and the mixture is heated for 1 hour at 100 ℃ by microwave (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 1, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 2 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 1, and fig. 3 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 2341 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 98.0%.
TABLE 1 pore structure parameters for the product of example 1
Example 2
0.91g of polyaluminum hydroxychloride and 0.58g of fumaric acid are weighed respectively and placed in a reaction flask, 10mL of water (molar ratio of aluminum to fumaric acid is 1, and concentration of fumaric acid in water is 0.5 mol/L) is added, and after uniform stirring and dispersion, microwave heating is carried out for 1h at 80 ℃ (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization is shown in figure 4, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 5 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 2, and fig. 6 is an SEM and TEM image of the product. The space-time yield under the conditions of this example was 2780 kg/(m) 3 D). The results of the fluorine removal performance tests show that under the experimental conditions, the removal efficiency of the material on fluorine ions in water is 97.5%.
Table 2 pore structure parameters of the product of example 2
Example 3
0.91g of polyaluminum hydroxychloride and 0.58g of fumaric acid were weighed out and placed in a reaction flask, 10mL of water was added (molar ratio of aluminum to fumaric acid: 1, concentration of fumaric acid in water: 0.5 mol/L), and after uniform dispersion by stirring, microwave heating was carried out at 100 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 7, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 8 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 3, and fig. 9 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 2773 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 98.7%.
Table 3 pore structure parameters for the product of example 3
Example 4
0.91g of polyaluminum hydroxychloride and 0.58g of fumaric acid were weighed out separately and placed in a reaction flask and 10mL of water (molar ratio of aluminum to fumaric acid 1, concentration of fumaric acid in water 0.5 mol/L) was added, followed by microwave heating at 120 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization is shown in figure 10, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 11 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 4, and fig. 12 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 3054 kg/(m) 3 D). The result of the defluorination performance test shows that under the experimental condition, the material can be used for treating the fluorine ions in waterThe removal efficiency of (2) was 98.4%.
Table 4 pore structure parameters of the product of example 4
Example 5
0.46g of polyaluminum hydroxychloride and 0.29g of fumaric acid were weighed out separately and placed in a reaction flask and 10mL of water (molar ratio of aluminum to fumaric acid 1, concentration of fumaric acid in water 0.25 mol/L) was added, followed by microwave heating at 100 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 13, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 14 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 5, and fig. 15 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 1439 kg/(m) 3 D). The results of the fluorine removal performance tests show that under the experimental conditions, the removal efficiency of the material on fluorine ions in water is 97.2%.
Table 5 pore structure parameters of the product of example 5
Example 6
1.82g of polyaluminum hydroxychloride and 1.16g of fumaric acid were weighed respectively and placed in a reaction flask, and 10mL of water (molar ratio of aluminum to fumaric acid 1, 1.0mol/L concentration of fumaric acid in water) was added, followed by microwave heating at 100 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and performing 80 ℃ treatmentDrying for 6h to obtain white powder product. The XRD characterization of the material is shown in figure 16, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 17 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 6, and fig. 18 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 5674 kg/(m) 3 D). The results of the fluorine removal performance tests show that under the experimental conditions, the removal efficiency of the material on fluorine ions in water is 98.8%.
Table 6 pore structure parameters of the product of example 6
Example 7
0.91g of polyaluminum hydroxychloride and 2.32g of fumaric acid were weighed out separately and placed in a reaction flask and 10mL of water (molar ratio of aluminum to fumaric acid: 1, 2mol/L concentration of fumaric acid in water) was added, and the mixture was heated by microwave at 100 ℃ for 1 hour (power: 250W, stirring condition). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 19, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 20 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 7, and fig. 21 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 2199 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 97.6%.
Table 7 pore structure parameters for the product of example 7
Example 8
1.67g of aluminum sulfate octadecahydrate and 0.58g of fumaric acid were weighed out into a reaction flask, and 10mL of water (molar ratio of aluminum to fumaric acid 1, 0.5mol/L concentration of fumaric acid in water) was added thereto, followed by microwave reaction at 120 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. Its XRD characterization is shown in fig. 22, which shows that the product synthesized by this example is not a typical aluminum fumarate metal organic framework material.
Example 9
1.86g of aluminum nitrate nonahydrate and 0.58g of fumaric acid were weighed out separately and placed in a reaction flask, and 10mL of water (molar ratio of aluminum to fumaric acid 1, concentration of fumaric acid in water 0.5 mol/L) was added thereto, and microwave reaction was carried out at 120 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. Its XRD characterization is shown in fig. 23, which shows that the product synthesized by this example is not a typical aluminum fumarate metal organic framework material.
Example 10
1.21g of aluminum chloride hexahydrate and 0.58g of fumaric acid were weighed out and placed in a reaction flask, and 10mL of water (molar ratio of aluminum to fumaric acid: 1, concentration of fumaric acid in water: 0.5 mol/L) was added, and microwave reaction was carried out at 120 ℃ for 1 hour (power: 250W, stirring condition). After the reaction, the solution was found to be clear and transparent, and no product was formed.
Example 11
291g of polyaluminum hydroxychloride and 185g of fumaric acid are weighed respectively and placed in a reaction kettle, 1.6L of water (the molar ratio of the aluminum to the fumaric acid is 1. After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. Its XRD characterizationAs shown in fig. 24, is a typical aluminum fumarate metal organic framework material. Fig. 25 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 8, and fig. 26 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 5652 kg/(m) 3 D). The results of the fluorine removal performance tests show that under the experimental conditions, the removal efficiency of the material on fluorine ions in water is 98.8%.
Table 8 pore structure parameters for the product of example 11
Example 12
1.02g of polymeric aluminum hydroxysulfate and 1.16g of fumaric acid were weighed out and placed in a reaction flask, 10mL of water was added (molar ratio of aluminum to fumaric acid is 1, concentration of fumaric acid in water is 1.0 mol/L), and after uniform stirring and dispersion, the mixture was heated by microwave at 100 ℃ for 1 hour (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 27, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 28 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 9, and fig. 29 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 3858 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 98.1%.
TABLE 9 pore structure parameters for the product of example 12
Example 13
1.82g of polyaluminum hydroxychloride, 1.16g of fumaric acid, and 0.007g of calcium chloride dihydrate were weighed out and placed in a reaction flask, and 10mL of water (molar ratio of aluminum to fumaric acid is 1, concentration of fumaric acid in water is 1.0 mol/L) was added, and stirred to disperseAfter being homogenized, the mixture is heated for 1 hour by microwave under the condition of 100 ℃ (power: 250W, stirring condition). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization is shown in figure 30, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 31 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 10, and fig. 32 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 5525 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 99.1%.
TABLE 10 pore structure parameters for the product of example 13
Example 14
1.82g of polyaluminum hydroxychloride, 1.16g of fumaric acid and 0.009g of ferric chloride hexahydrate are weighed out and placed in a reaction flask, 10mL of water (the molar ratio of aluminum to fumaric acid is 1, and the concentration of fumaric acid in water is 1.0 mol/L) is added, and after uniform stirring and dispersion, the mixture is heated by microwave at 100 ℃ for 1h (power: 250W, stirring conditions). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 33, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 34 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of the product are listed in table 11, and fig. 35 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 5633 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 99.0%.
TABLE 11 pore structure parameters for the product of example 14
Example 15
1.82g of polyaluminum hydroxychloride, 1.16g of fumaric acid, 0.007g of calcium chloride dihydrate and 0.009g of ferric chloride hexahydrate are weighed respectively and placed in a reaction flask, 10mL of water (the molar ratio of aluminum to fumaric acid is 1, and the concentration of fumaric acid in water is 1.0 mol/L) is added, and after uniform stirring and dispersion, microwave heating is carried out for 1h under the condition of 100 ℃ (power: 250W, stirring condition). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 36, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 37 is a nitrogen sorption and desorption curve of the product, the pore structure parameters of which are listed in table 12, and fig. 38 is SEM and TEM images of the product. The space-time yield under the conditions of this example was 5350 kg/(m) 3 D). The result of the fluorine removal performance test shows that under the experimental condition, the removal efficiency of the material to the fluorine ions in the water is 98.6%.
TABLE 12 pore structure parameters for the product of example 15
Example 16
0.91g of polyaluminum hydroxychloride and 0.58g of fumaric acid were weighed respectively in a reaction flask and added with 10mL of ethanol (molar ratio of aluminum to fumaric acid: 1, concentration of fumaric acid in water: 0.5 mol/L), and heated by microwave at 100 ℃ for 10min (power: 250W, stirring condition). After the reaction is finished, obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol once respectively, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a white powdery product. The XRD characterization of the material is shown in figure 39, and the material is a typical aluminum fumaric acid metal organic framework material. Fig. 40 is a nitrogen desorption curve of the product, the pore structure parameters of the product are listed in table 13, and fig. 41 is a TEM image of the product. The space-time yield under the conditions of this example was 478 kg/(m) 3 D). The result of the defluorination performance test shows that the defluorination efficiency of the material to the fluorinion in water is 98.9 percent under the experimental condition。
TABLE 13 pore structure parameters for the product of example 16
Example 17
1.86g of aluminum nitrate nonahydrate and 0.58g of fumaric acid were weighed and placed in a reaction flask, and 10mL of ethanol (molar ratio of aluminum to fumaric acid is 1, concentration of fumaric acid in ethanol is 0.5 mol/L) was added, and microwave reaction was carried out at 120 ℃ for 30min. After the reaction was complete, the product was found to be in the gel state in the microwave vial. And (3) obtaining a white precipitate product through centrifugal separation, washing the white precipitate product with water and ethanol respectively once, transferring the white precipitate product into an oven, and drying the white precipitate product for 6 hours at the temperature of 80 ℃ to obtain a crystal granular product. The XRD characterization is shown in fig. 42, which indicates that the product synthesized by this example is a typical aluminum fumarate metal organic framework material.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A fluorine removing agent based on a metal organic framework material is characterized in that the fluorine removing agent contains the metal organic framework material, and metal elements in a metal compound for synthesizing the metal organic framework material comprise Al elements, wherein the Al elements are derived from polyaluminium hydroxychloride or polyaluminium hydroxysulfate; the metal elements also comprise at least one of K, na, ca, mg, ti, zr, hf, V and Fe;
the metal organic framework material is obtained by heating and reacting a metal compound and an organic carboxylic acid ligand in water as a solvent,
the organic carboxylic acid ligand is fumaric acid;
the molar ratio of the metal to the organic carboxylic acid ligand in the metal compound is 1-20;
the concentration of the organic carboxylic acid ligand in the solvent is 0.05 mol/L-2.0 mol/L;
the heating reaction temperature is 40-150 ℃, and the heating reaction time is 5min-2.0 h;
the preparation process of the metal organic framework material also comprises a step of post-treating the non-liquid phase product, wherein the post-treating step comprises at least one of washing, solid-liquid separation and drying.
2. The fluorine removing agent for metal organic framework material according to claim 1, wherein the metal compound for synthesizing the metal organic framework material comprises Na, K, ca, mg, fe, zr or Ti.
3. The fluorine removal agent based on metal organic framework material of claim 1, wherein the metal organic framework material has a nano-sheet structure.
4. The fluorine removing agent based on metal organic framework material as claimed in claim 3, wherein the metal organic framework material is in a round nano sheet structure, a square nano sheet structure or a morphological structure between the round nano sheet structure and the square nano sheet structure.
5. The fluorine removing agent based on metal organic framework material according to claim 3, wherein the single nano-flake metal organic framework material has a planar size of 50-400nm and a thickness of 1-5nm.
6. The fluorine removing agent based on metal organic framework material as claimed in claim 1, wherein the metal organic framework material is porous material, and the porous structure is composed of mesopores and micropores; in the porous structure, the pore volume of the mesopores is 0.05-1.0cm and the pore volume of the micropores is 0.2-0.5 cm.
7. The fluorine removing agent based on metal organic framework material as claimed in claim 1, wherein the fluorine removing efficiency of the fluorine removing agent is up to 99% or more.
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| WO2014114948A1 (en) * | 2013-01-24 | 2014-07-31 | Johnson Matthey Public Limited Company | Method of manufacture |
| CN103301813B (en) * | 2013-06-19 | 2016-08-10 | 中国科学院合肥物质科学研究院 | A kind of defluorinating agent based on metallo-organic framework and preparation method thereof |
| CN103626655B (en) * | 2013-11-27 | 2017-01-04 | 安徽大学 | Preparation method of metal organic framework material with controllable exposed crystal face |
| CN105289506A (en) * | 2015-11-13 | 2016-02-03 | 兰州交通大学 | Multielement modified bentonite adsorption material and preparation method thereof |
| CN110078406B (en) * | 2019-05-15 | 2021-09-03 | 陕西天福盛源新材料有限公司 | Liquid alkali-free accelerator and preparation method thereof |
| CN111547804B (en) * | 2020-05-15 | 2022-06-28 | 苏州清控环保科技有限公司 | Composite defluorinating agent for industrial wastewater, preparation method and method for defluorinating industrial wastewater |
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