CN114618441A - Controllable preparation method of MIL material and application of MIL material in separation and enrichment of polyhydric alcohol - Google Patents
Controllable preparation method of MIL material and application of MIL material in separation and enrichment of polyhydric alcohol Download PDFInfo
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Abstract
The invention discloses a controllable preparation method of an MIL material and application of the MIL material in separation and enrichment of polyhydric alcohol. The MIL material has the structural characteristics of designable pore channel micro-chemical environment, one-dimensional pore channel structure and good respiration effect, and based on the advantages of the material body, the MIL material preparation method disclosed by the invention has the advantages of low energy consumption, simplicity and convenience in operation and simple process. In view of the wide industrial application of polyols, the use of MIL materials for separation and enrichment of polyols is of far-reaching importance for the large-scale industrial production of biomass-based industrial products and energy structure optimization.
Description
Technical Field
The invention belongs to the field of material chemical separation, and particularly relates to controllable preparation of an MIL material and separation and enrichment application of polyhydric alcohol.
Background
MIL (materials of Institute Lavoiser) materials are MOFs materials composed of a carboxylic acid ligand and a trivalent metal SBU (Secondary Building units). The micro-porous membrane has a designable pore channel micro-chemical environment and a unique one-dimensional pore channel structure, and has a good breathing effect. The MIL material effects separation of the mixture by modulating its own pore size in response to stress. Therefore, under controllable external conditions (such as mixture concentration, temperature, illumination, presence or absence of an electric field or no magnetic field, etc.), the separation of mixtures by using MIL materials is certainly a breakthrough in the field of separation. The current MIL material preparation process is developed at a high speed, but a liquid phase solvent is inevitably introduced into a pore channel in a preparation process of a classical liquid phase synthesis method (a hydrothermal/solvothermal method, a layer-by-layer self-assembly method, an interface microfluid method and the like), so that a pore channel activation process is inevitably needed, waste is caused, energy consumption is increased, and the environment is polluted. Therefore, the MIL material preparation process which simplifies the process flow and reduces the preparation cost is necessary.
Polyols (such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol and the like) are biomass-based chemicals and are important intermediates for producing varnishes, adhesives, plasticizers, surfactants and the like, and therefore, the polyols have high industrial application values. However, the polyhydric alcohols have high boiling points and are very close to each other, and are generated in an aqueous system, and the concentration is low, so that the separation is difficult. Therefore, the traditional rectification method has high energy consumption and high cost. The adsorption method is a separation and enrichment method based on an adsorbent at normal temperature and takes the adsorbent as a core, and has the advantages of low energy consumption, simple and convenient process and low cost. Currently, MIL materials are used mostly for gas separation and rarely for liquid separation, especially biomass-based chemical separation.
Therefore, the method has the advantages of developing an MIL material with low energy consumption, easy operation and simple process flow, constructing an efficient separation method suitable for the polyhydric alcohol, and having great significance for realizing industrial scale production of biomass industrial chemicals and energy structure optimization.
Disclosure of Invention
The invention aims to provide a controllable preparation method of an MIL material and application of the MIL material in separation and enrichment of polyhydric alcohols.
The invention firstly provides a controllable preparation method of an MIL material, which comprises the following steps:
(1) preparing a precursor solution: at room temperature, dissolving a carboxylic acid ligand in a nitrogen-containing organic solvent to form a solution A, and dissolving a trivalent metal salt in water or an oxygen-containing organic solvent to form a solution B;
(2) precursor solution contact reaction: slowly adding the solution A into the solution B drop by drop at room temperature to form a solid-liquid mixture;
(3) and (3) refluxing reaction: heating the solid-liquid mixture obtained in the step (2) to the reflux temperature TcAnd a reflux time period tcCentrifugally enriched and at a drying temperature TdryTime period of down drying tdryObtaining a crude product;
(4) and (3) purifying a crude product: wrapping the crude product obtained in the step (3) by using filter paper, fixing the crude product by using cotton threads, putting the crude product into a Soxhlet extractor, and carrying out Soxhlet extraction by using an oxygen-containing organic solvent at an extraction temperature TpTime of next extraction tpThen dynamically drying the sample in the filter paper bag in vacuum at a drying temperature TdryTime period of down drying tdryThen obtaining an MIL material;
wherein the molar ratio of the carboxylic acid ligand to the trivalent metal salt is 0.01 to 100: 1.
based on the above technical scheme, preferably, the carboxylic acid ligand comprises benzoic acid, 2-methylbenzoic acid, 2-aminobenzoic acid, 2-fluorobenzoic acid, 2-hydroxybenzoic acid, 3- (trifluoromethyl) benzoic acid, 2, 4-dimethylbenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 4-diaminobenzoic acid, 2, 4-difluorobenzoic acid, 2,4, 6-trimethylbenzoic acid, terephthalic acid, 2- (trifluoromethyl) terephthalic acid, 2-aminoterephthalic acid, 2-methylterephthalic acid, 2-fluoroterephthalic acid, 2-hydroxyterephthalic acid, (2, 5-dicarboxyphenyl) boronic acid, 2, 5-dimethylterephthalic acid, 2, 5-difluoroterephthalic acid, 2-fluorobenzoic acid, 2-aminobenzoic acid, 2-fluorobenzoic acid, 2-aminobenzoic acid, 2-fluorobenzoic acid, 4-fluorobenzoic acid, 2-dihydroxybenzoic acid, 2-carboxylic acid, 2-dihydroxybenzoic acid, and/or the like, One or more of 2, 5-diamino terephthalic acid, 2, 5-dihydroxy terephthalic acid, tetrafluoro terephthalic acid and trimesic acid;
the trivalent metal salt is one or more of scandium trichloride, scandium trichloride hydrate, scandium nitrate hydrate, scandium oxalate hydrate, chromium nitrate hydrate, chromium sulfate hydrate, chromium trifluoride hydrate, chromium chloride hydrate, ferric nitrate hydrate, ferric sulfate hydrate, ferric phosphate hydrate, ferric oxalate hydrate, ferric fluoride hydrate, ferric chloride hydrate, ferric bromide, aluminum nitrate hydrate, aluminum sulfate hydrate, aluminum phosphate, aluminum trichloride hydrate, aluminum fluoride hydrate, aluminum bromide, aluminum iodide, gallium nitrate hydrate, gallium sulfate hydrate, gallium trichloride, gallium tribromide, gallium triiodide, indium nitrate hydrate, indium sulfate, indium trichloride hydrate, indium fluoride hydrate, indium bromide;
the nitrogen-containing organic solvent is one or more of N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and acetonitrile, and the oxygen-containing organic solvent is one or more of methanol, ethanol, phenol, diethyl ether and acetone.
Based on the above technical solution, it is preferable that the drying temperature T in the step (3) and the step (4)dryDrying at 20-300 ℃ for a period of time tdry＝0.5～240h。
Based on the above technical solution, preferably, the reflux temperature T in the step (3)c20-220 ℃, and the refluxing time is tc＝0.5～360h。
Based on the above technical solution, preferably, the extraction temperature T in the step (4)p20-350 ℃, and the extraction time tp＝0.5～360h。
In another aspect of the present invention, there is provided an MIL material prepared by the above method.
The invention also provides a method for separating, enriching, desorbing and recycling the polyalcohol by using the MIL material, which comprises the following steps:
(1) adsorption separation: adding MIL material with mass m into volume V and concentration C0In the polyol aqueous solution, keeping for a certain time t under the continuous mixing states；
Wherein m is 0-5000 g, V is 0.001-10000 ml, C00.001-1000 g/L, and the mixing speed is highThe degree is 0-2500 rpm, tsThe detection zero point of the MIL material is not added or blank comparison is performed when m is 0-240 h;
(2) solid-liquid separation: centrifuging the solution obtained in step (1), wherein the solid substance is MIL material adsorbed with polyalcohol, and the upper liquid is CeAn aqueous polyol solution of (a); analyzing the composition, determining C by liquid chromatography or gas chromatographyeThe theoretical enrichment Q of the polyhydric alcohol is further determined;
Q＝V·(C0–Ce)·m-1
wherein V is the volume of the aqueous polyol solution used (mL), C0Is the concentration of polyol in the aqueous solution before adsorption (g L)-1)，CeIs the concentration of polyol in the aqueous solution after adsorption (g L)-1) M is the mass (g) of the MIL material used;
(3) desorption and recycling: desorbing and recovering the polyol from the MIL material adsorbed with the polyol in the step (2) in three ways, and simultaneously realizing regeneration of the MIL material for repeated use;
a) vacuum purging thermal desorption: and (3) placing the MIL material adsorbed with the polyhydric alcohol in a vacuum environment, desorbing at 50-200 ℃ for 0.5-100 h, and collecting the polyhydric alcohol by using cold hydrazine. The vacuum is a low-pressure environment of 0-100 mbar and can be provided by an oil pump, a diaphragm pump or a turbo molecular pump. The temperature of the cold hydrazine is-200 to 5 ℃; the vacuum purging thermal desorption recovery device is shown in fig. 3;
b) and (3) airflow purging thermal desorption: placing the MIL material adsorbed with the polyol in a certain atmosphere, desorbing for 0.5-100 h in a purging environment at 50-200 ℃, and collecting the polyol by using cold hydrazine. The atmosphere is one of air, nitrogen, argon, helium and carbon dioxide, and the gas flow rate is 1-500 ml/min. The temperature of the cold hydrazine is-200 to 5 ℃; the gas flow purging thermal desorption recovery device is shown in figure 4;
c) low boiling point solvent elution: putting the MIL material adsorbed with the polyhydric alcohol into a low-boiling solvent, stirring and washing at 40-90 ℃ for 0.5-240 h, then filtering or centrifuging to obtain a solid substance which is a recovered MIL material, and removing the low-boiling solvent from the obtained liquid through rotary distillation to recover the polyhydric alcohol. The low boiling point solvent refers to volatile organic solvent with boiling point lower than 80 ℃ at normal pressure, and includes but is not limited to methanol, n-hexane and dichloromethane. The low boiling point solvent elution recovery apparatus is shown in FIG. 5.
The invention aims to provide a preparation method of MIL series materials and a method for adsorbing, separating, enriching, desorbing and recycling polyhydric alcohols (such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol and the like).
Advantageous effects
The preparation method of the MIL material provided by the invention has the advantages of low energy consumption, simple process and easy operation, the prepared MIL material has designable pore channel chemical characteristics and a unique one-dimensional pore channel structure, and the MIL material is widely applied in the industry in view of the fact that the polyalcohol is a biomass-based chemical, and the MIL material is used for separating and enriching the polyalcohol and has profound significance for large-scale industrial production of biomass-based industrial products and energy structure optimization.
Drawings
FIG. 1 is an X-ray diffraction pattern of OH-MIL-53(Al) prepared in example 1.
FIG. 2 is a schematic diagram of an adsorption apparatus for polyols by MIL materials; wherein, the material I is MIL material and polyhydric alcohol; ② an absorber; and the third step is a blending device.
FIG. 3 is a schematic view of a vacuum purge thermal desorption recovery unit; wherein, I is an MIL material absorbed with polyalcohol; secondly, a recoverer is used; thirdly, a heating device; fourthly, a collector is obtained; fifthly, cold hydrazine is adopted; and sixthly, a vacuum pump.
FIG. 4 is a schematic view of a gas flow purge thermal desorption recovery unit; wherein, the material is MIL material absorbed with polyalcohol; secondly, a recoverer is used; thirdly, a heating device; fourthly, a collector is obtained; fifthly, cold hydrazine is adopted; sixthly, the vacuum pump is adopted; and a tail gas collector.
FIG. 5 is a schematic view of a low boiling point solvent elution recovery unit; wherein, I is an MIL material absorbed with polyalcohol; ② a low-boiling solvent; thirdly, a recoverer; fourthly, a heating device is used; a reflux device; and cooling water.
Detailed Description
The following specific examples further illustrate the invention and should not be construed as limiting it in any way.
EXAMPLE 1 controlled preparation of OH-MIL-53(Al)
Dissolving 1.87g of 2-hydroxy terephthalic acid in 30mL of N, N-dimethylformamide to form a precursor solution A, dissolving 7.81g of aluminum nitrate nonahydrate in 30mL of ultrapure water to form a precursor solution B, dropwise and slowly adding the solution A into the solution B to form a solid-liquid mixture, and then refluxing at 90 ℃ for 36 h. Naturally cooling, centrifuging to obtain crude product, and completely drying in air at 80 deg.C. Wrapping the crude product with filter paper, fixing with cotton thread, placing into Soxhlet extractor, and extracting with ethanol at 100 deg.C for 48 hr. And then dynamically drying the sample in the filter paper bag in vacuum at the drying temperature of 120 ℃ for 24 hours to obtain the OH-MIL-53(Al) material. FIG. 1 shows the X-ray diffraction pattern of OH-MIL-53(Al), indicating that OH-MIL-53(Al) was successfully prepared by the method provided by the present invention.
Example 2 OH-MIL-53(Al) for separation and enrichment of polyol, ethylene glycol
The adsorption performance of ethylene glycol on OH-MIL-53(Al) prepared in example 1 was tested by the attrition method. At room temperature, 0.050g of OH-MIL-53(Al) is uniformly dispersed in 0.50mL of ethylene glycol aqueous solution (the initial concentration is 200g/L), and the mixture is adsorbed for 0-20 min under a continuous and uniform state, wherein the device is shown in figure 2. And centrifuging to obtain supernatant after adsorption equilibrium, and analyzing the concentration of ethylene glycol in the supernatant by liquid chromatography. To correct the adsorption data, a blank comparative experiment without the OH-MIL-53(Al) material was performed under the same conditions. Equilibrium adsorption quantity Q (mg g)-1) Can be calculated by the following formula:
Q＝V·(C0–Ce)·m-1
wherein V is the volume (mL) of the ethylene glycol aqueous solution used, C0The concentration of ethylene glycol in the aqueous solution before adsorption (g L)-1)，CeThe concentration of ethylene glycol in the aqueous solution after adsorption (g L)-1) And m is the mass (g) of OH-MIL-53(Al) used.
EXAMPLE 3 ethylene glycol Desorption recovery (Low boiling solvent elution method)
OH-MIL-53 adsorbed with glycol obtained in example 2 and named as OH-MIL-53@ EG (EG: ethylene glycol, English abbreviation) was placed in a methanol solvent, the apparatus was stirred at 70 ℃ for 120 hours as shown in FIG. 5, and then centrifuged to obtain OH-MIL-53 as a solid substance, and the obtained supernatant was subjected to rotary distillation to remove methanol to obtain high-purity ethylene glycol.
Example 4B (OH)2Controlled preparation of-MIL-53 (Al)
2.14g of (2, 5-dicarboxyphenyl) boric acid is dissolved in 30mL of N, N-dimethylformamide to form a precursor solution A, 7.81g of aluminum nitrate nonahydrate is dissolved in 30mL of ultrapure water to form a precursor solution B, the solution A is slowly added dropwise into the solution B to form a solid-liquid mixture, and then the mixture is refluxed at the temperature of 90 ℃ for 36 hours. Naturally cooling, centrifuging to obtain crude product, and completely drying in air at 80 deg.C. Wrapping the crude product with filter paper, fixing with cotton thread, placing into Soxhlet extractor, and extracting with ethanol at 100 deg.C for 48 hr. Then dynamically drying the sample in the filter paper bag in vacuum at the drying temperature of 120 ℃ for 24 hours to obtain B (OH)2-MIL-53(Al) material.
Example 5 CH3Controlled preparation of-MIL-101 (Cr)
Dissolving 1.86g of 2-methyl terephthalic acid in 30mL of N, N-dimethylformamide to form a precursor solution A, dissolving 8.33g of chromium nitrate nonahydrate in 50mL of ultrapure water to form a precursor solution B, dropwise and slowly adding the solution A into the solution B to form a solid-liquid mixture, and then refluxing at the temperature of 95 ℃ for 24 hours. Naturally cooling, centrifuging to obtain crude product, and completely drying in 85 deg.C air. Wrapping the crude product with filter paper, fixing with cotton thread, placing into Soxhlet extractor, and extracting with methanol at 85 deg.C for 36 h. Then dynamically drying the sample in the filter paper bag in vacuum at the drying temperature of 120 ℃ for 24 hours to obtain CH3-MIL-101(Cr) material.
Example 6 CH3Controlled preparation of MIL-53(Fe)
Dissolving 1.86g of 2-methyl terephthalic acid in 60mL of N, N-dimethylacetamide to form a precursor solution A, dissolving 8.41g of nitric acid-gallium in 80mL of absolute ethanol to form a precursor solution B, slowly adding the solution A dropwise into the solution B to form a solid-liquid mixture, and refluxing for 48 hours at 120 ℃. FromThen the crude product is obtained by cooling and centrifugation and is dried completely in air at 85 ℃. Wrapping the crude product with filter paper, fixing with cotton thread, placing into Soxhlet extractor, and extracting with methanol at 90 deg.C for 50 hr. Then dynamically drying the sample in the filter paper bag in vacuum at the drying temperature of 150 ℃ for 24 hours to obtain CH3-MIL-53(Fe) material.
Claims (10)
1. A method for preparing an MIL material, which is characterized by comprising the following steps:
(1) preparing a precursor solution: dissolving a carboxylic acid ligand in a nitrogen-containing organic solvent to form a solution A at room temperature, and dissolving a trivalent metal salt in water or an oxygen-containing organic solvent to form a solution B;
(2) precursor solution contact reaction: dropwise adding the solution A into the solution B at room temperature to form a solid-liquid mixture;
(3) and (3) refluxing reaction: refluxing the solid-liquid mixture obtained in the step (2) at 20-220 ℃ for 0.5-360 h, centrifuging and drying to obtain a crude product;
(4) and (3) purifying a crude product: wrapping the crude product obtained in the step (3) by using filter paper, fixing the crude product by using cotton threads, then putting the crude product into a Soxhlet extractor, carrying out Soxhlet extraction by using an oxygen-containing organic solvent, and after the Soxhlet extraction is finished, carrying out dynamic vacuum drying on a sample to obtain an MIL material;
wherein the molar ratio of the carboxylic acid ligand to the trivalent metal salt is 0.01 to 100: 1.
2. the method according to claim 1, wherein the carboxylic acid ligand is benzoic acid, 2-methylbenzoic acid, 2-aminobenzoic acid, 2-fluorobenzoic acid, 2-hydroxybenzoic acid, 3- (trifluoromethyl) benzoic acid, 2, 4-dimethylbenzoic acid, 2, 4-dihydroxybenzoic acid, 2, 4-diaminobenzoic acid, 2, 4-difluorobenzoic acid, 2,4, 6-trimethylbenzoic acid, terephthalic acid, 2- (trifluoromethyl) terephthalic acid, 2-aminoterephthalic acid, 2-methylterephthalic acid, 2-fluoroterephthalic acid, 2-hydroxyterephthalic acid, (2, 5-dicarboxyphenyl) boronic acid, 2, 5-dimethylterephthalic acid, 2, 5-difluoroterephthalic acid, 2, 4-dihydroxybenzoic acid, 2, 4-diaminobenzoic acid, 2-dihydroxybenzoic acid, dibenzoic acid, dihydroxybenzoic acid, dibenzoic acid, and benzoic acid, dibenzoic acid, and benzoic acid, One or more of 2, 5-diamino terephthalic acid, 2, 5-dihydroxy terephthalic acid, tetrafluoro terephthalic acid and trimesic acid;
the trivalent metal salt is one or more of scandium trichloride, scandium trichloride hydrate, scandium nitrate hydrate, scandium oxalate hydrate, chromium nitrate hydrate, chromium sulfate hydrate, chromium trifluoride hydrate, chromium chloride hydrate, ferric nitrate hydrate, ferric sulfate hydrate, ferric phosphate hydrate, ferric oxalate hydrate, ferric fluoride hydrate, ferric chloride hydrate, ferric bromide, aluminum nitrate hydrate, aluminum sulfate hydrate, aluminum phosphate, aluminum trichloride hydrate, aluminum fluoride hydrate, aluminum bromide, aluminum iodide, gallium nitrate hydrate, gallium sulfate hydrate, gallium trichloride, gallium tribromide, gallium triiodide, indium nitrate hydrate, indium sulfate, indium trichloride hydrate, indium fluoride hydrate, indium bromide;
the nitrogen-containing organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and acetonitrile, and the oxygen-containing organic solvent is one or more of methanol, ethanol, phenol, diethyl ether and acetone.
3. The preparation method according to claim 1, wherein the extraction temperature in the step (4) is 20 to 350 ℃, and the extraction time is 0.5 to 360 h; the drying temperature in the step (3) and the drying time in the step (4) is 20-300 ℃, and the drying time is 0.5-240 hours.
4. A MIL material prepared by the preparation method of any one of claims 1-3.
5. A method for separating and enriching polyol, which is characterized by using the MIL material of claim 5, and comprises the following steps:
(1) adsorption separation: adding the MIL material with the mass m into the mixture with the volume V and the concentration C0In the polyol aqueous solution, the mixture is kept in a continuously uniform stateFor a certain time ts(ii) a Wherein m is 0-5000 g, and V is 0.001-10000 ml; c0＝0.001～1000g/L；ts＝0～240h；
(2) Solid-liquid separation: centrifuging the solution obtained in step (1), wherein the solid substance is MIL material adsorbed with polyalcohol, and the supernatant is CeAn aqueous polyol solution of (a); determining C of the supernatant by liquid chromatography or gas chromatographyeThe theoretical enrichment Q of the polyol is further determined.
6. The separation and enrichment method of claim 5, wherein the theoretical enrichment Q is calculated by the formula
Q＝V·(C0–Ce)·m-1
Wherein V is the volume of the aqueous polyol solution used (mL), C0Is the concentration of polyol in the aqueous solution before adsorption (g L)-1)，CeIs the concentration of polyol in the aqueous solution after adsorption (g L)-1) And m is the mass (g) of the MIL material used.
7. The separation and enrichment method according to claim 5, further comprising (3) desorption and recovery: recovering the polyol from the MIL material adsorbed with the polyol in the step (2) in a desorption manner, and realizing regeneration of the MIL material; the desorption mode is vacuum purging thermal desorption, airflow purging thermal desorption or low-boiling solvent elution.
8. The separation and enrichment method according to claim 7, wherein the vacuum purge thermal desorption is: placing the MIL material adsorbed with the polyhydric alcohol in a vacuum environment, desorbing at 50-200 ℃ for 0.5-100 h, and collecting the polyhydric alcohol by using cold hydrazine; the vacuum is a low-pressure environment of 0-100 mbar and can be provided by an oil pump, a diaphragm pump or a turbo molecular pump; the temperature of the cold hydrazine is-200-5 ℃.
9. The separation and enrichment method according to claim 7, wherein the gas stream purge thermal desorption is: placing the MIL material adsorbed with the polyhydric alcohol in a certain atmosphere, desorbing for 0.5-100 h in a purging environment at 50-200 ℃, and collecting the polyhydric alcohol by using cold hydrazine; the atmosphere is one of air, nitrogen, argon, helium and carbon dioxide, and the gas flow rate is 1-500 ml/min; the temperature of the cold hydrazine is-200 to 5 ℃.
10. The separation and enrichment method according to claim 7, wherein the low boiling solvent is eluted as: putting the MIL material adsorbed with the polyhydric alcohol into a low-boiling solvent, stirring and washing at 40-90 ℃ for 0.5-72 h, then filtering or centrifuging to obtain a solid substance which is a recovered MIL material, and removing the low-boiling solvent from the obtained liquid through rotary distillation to recover the polyhydric alcohol; the low boiling point solvent refers to a volatile organic solvent with the boiling point lower than 80 ℃ at normal pressure, and the low boiling point solvent is preferably methanol, n-hexane or dichloromethane.
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| CN104667876A (en) * | 2013-11-29 | 2015-06-03 | 北京思达安新材料科技有限公司 | Series MOF (Metal-Organic Framework) type hierarchical porous materials IPD-mesoMOF-1-8 and preparation method thereof as well as method for regulating mesoporous size |
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