CN115044050B - Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof - Google Patents
Metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and a preparation method thereof. The metal organic framework-organic molecular chain covalent modification material prepared by the invention has high selectivity and high propane selectivity with adsorption capacity, the adsorption capacity and alkane selectivity to alkane are superior to most of reported MOFs adsorbents at normal temperature and normal pressure, theoretical experience is provided for the design and preparation of the propane selective adsorbent, and the method has important guiding significance for obtaining high-purity alkene in one step.
Description
Technical Field
In particular to a metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane and a preparation method thereof.
Background
Propylene is an important chemical raw material for synthesizing bulk products, and mainly comes from naphtha steam cracking, catalytic cracking (FCC) and the like. The production process is often accompanied by the production of small amounts of propane. In order to obtain high-purity propylene, the traditional separation process adopts an energy-intensive high-pressure low-temperature distillation technology, and has high energy consumption and strict requirements on equipment.
The adsorption separation technology can realize the separation and purification of chemical products at normal temperature and normal pressure, is clean and efficient, is expected to become a substitute technology of high-pressure low-temperature distillation technology, and is characterized in that the invention provides a high-performance adsorption material. In recent years, metal Organic Frameworks (MOFs) have a strong development potential in the field of gas separation due to the advantages of large specific surface area, adjustable pore diameter and the like.
Traditional thinking research on propane/propylene separation has focused on the selective adsorption of propylene by utilizing pi-bond interaction between unsaturated metal vacancies in MOFs and olefins. However, in the actual industrial separation process, the content of propylene is far more than that of propane impurities, the traditional thought not only increases the using amount of the propylene selective adsorbent, but also the adsorbed propylene still needs to be desorbed to obtain a propylene product with higher purity, and the problem of carbon deposition is easily caused. To avoid these problems, propane selective adsorbents are gaining wide attention. The adsorbent can preferentially adsorb propane, and can obtain polymerization-grade propylene at an outlet in one step, so that the adsorbent has extremely high industrial value. However, since propylene and propane have similar sizes and propane lacks a strong adsorption mechanism, the design and construction of propane selective adsorbents face a great challenge. Only a few propane selective adsorbents are reported at present, and poor selectivity and low adsorption capacity always restrict the industrial application of propane selective adsorbents. Therefore, the development of a propane selective adsorbent with high selectivity and high adsorption capacity and the elucidation of the mechanism of enhancing propane selectivity are the key to obtaining polymerization grade propylene with low energy consumption.
Disclosure of Invention
Aiming at the problems of low adsorption capacity, low selectivity and the like of a propane selective adsorbent, the invention provides a preparation method of a covalent modification material of a metal organic framework-organic molecular chain for preferentially adsorbing alkane, the method covalently couples the organic molecular chain with propane selectivity on an MOFs framework through a ring opening reaction, on one hand, the pore diameter is cut and adjusted by utilizing the space limited domain of the organic molecular chain, on the other hand, C is formed by alkaline sites on the molecular chain and propane δ- -H δ+ ···N δ- 、C δ- -H δ+ ···O δ- Multiple hydrogen bonds, thereby obtaining the metal organic framework-organic molecular chain covalent modification material with high propane adsorption capacity and enhanced propane/propylene separation performance.
The invention also aims to provide a metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing alkane, which is prepared by the method and has high selectivity and high propane selectivity of adsorption capacity.
The invention is realized by the following technical scheme:
a preparation method of a metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane comprises the following steps:
(1) Preparation of Zr-BPDC-NH 2 The adsorbent solid specifically comprises: weighing metal zirconium salt and 4,4' -biphenyldicarboxylic acid (H) 2 BPDC), 2-amino-4, 4' -biphenyldicarboxylic acid (H) 2 ABPDC) and organic acid are added into an organic solvent A to be uniform, and then the mixture is put into a reaction kettle to react for 24 to 30 hours at the temperature of between 115 and 125 ℃ to obtain crude Zr-BPDC-NH 2 Cooling the solid adsorbent, performing suction filtration and washing by using DMF (dimethyl formamide), soaking and activating by using an organic solvent B, and drying to obtain Zr-BPDC-NH 2 A solid adsorbent;
(2) Preparing Zr-BPDC-organic molecular chain adsorbent solid, which specifically comprises the following steps: weighing the Zr-BPDC-NH obtained in the step (1) 2 Adding Tetrahydrofuran (THF) and inorganic acid into a solid adsorbent, uniformly dispersing by ultrasonic, adding organic molecular chains, uniformly stirring, heating for reaction, cooling, and washing by tetrahydrofuran in a suction filtration manner to obtain a crude Zr-BPDC-organic molecular chain material.
(3) Activating the solid obtained in the step (2), specifically: and (3) soaking and activating the crude Zr-BPDC-organic molecular chain material prepared in the step (2) by using an organic solvent, filtering, and drying to obtain the metal organic framework-organic molecular chain covalent modification material.
The metal zirconium salt in the step (1) is zirconium chloride (ZrCl) 4 ) Zirconium oxychloride (ZrOCl) 2 ·8H 2 O), at least one of zirconium acetate, zirconium carbonate, zirconium oxalate, zirconium citrate, and the like; the organic acid refers to at least one of glacial acetic acid, formic acid, benzoic acid and the like;
the organic solvent A in the step (1) refers to DMF, absolute ethyl alcohol and the like;
the metal zirconium salt and H in the step (1) 2 BPDC and H 2 The mass ratio of the ABPDC is 1 (0.5-0.7) to 0.5-0.7;
the dosage ratio of the metal zirconium salt and the organic acid in the step (1) is 1mol (0.95-2.86) L;
the volume ratio of the organic acid to the organic solvent A in the step (1) is 1ml (19-21) ml;
the step (1) of homogenizing refers to homogenizing through stirring and ultrasonic treatment;
the drying in the step (1) refers to vacuum drying at 120-150 ℃ for 8-12h; the organic solvent B is absolute ethyl alcohol or methanol;
the inorganic acid in the step (2) refers to HCl and HNO 3 、H 3 PO 4 At least one of HF, etc.;
the dosage ratio of the adsorbent, THF, inorganic acid and organic molecular chain in the step (2) meets 1g: (75-85) mL: (0-1.7) mL: (0.3-6.9) ml; the concentration of the inorganic acid is 0.01-0.05mol/L;
the organic molecular chain in the step (2) is one of Glycidyl Methacrylate (GMA), triglycidyl triacrylate and divinyl glycidyl ether;
the ultrasonic dispersion in the step (2) is ultrasonic for 10-60min;
the heating in the step (2) is to put the mixture into an oven with the temperature of 50-75 ℃ for 25-40h;
the organic solvent in the step (3) is one of chloroform, absolute ethyl alcohol, cyclohexane, dichloromethane or acetonitrile;
the suction filtration in the step (3) refers to filtration by using an organic filter membrane with the average pore diameter of 0.45 um; the drying refers to vacuum drying at 50-120 ℃ for 8-24h;
the metal organic framework-organic molecular chain covalent modification material preferentially adsorbs alkane, which is prepared by the method.
Compared with the prior art, the invention has the following advantages and beneficial effects:
compared with the prior art, the method utilizes ring-opening reaction on Zr-BPDC-NH 2 The alkaline molecular chain with stronger covalent coupling steric effect in the framework is utilized to segment the space limited domain of the alkaline molecular chain and rich alkaline sites to successfully prepare the propane selective adsorbent Zr-BPDC-organic molecular chain with enhanced propane/propylene selectivity. The material is first reported internationally and is propane selectivityThe design and preparation of the adsorbent provide theoretical experience and have important guiding significance for obtaining high-purity olefin in one step.
Drawings
FIG. 1 is a graph of the adsorbent materials prepared in examples 1,2,3 and N of a comparative example 2 An adsorption isotherm diagram (77K);
FIG. 2 is a XRD characterization of the adsorbent materials prepared in examples 1,2,3 and a comparative example;
FIG. 3 is a graph (298K) showing the adsorption isotherms for propylene and propane of the adsorbent prepared in accordance with the present invention, wherein (a) is the adsorbent prepared in example 1, (b) is the adsorbent prepared in example 2, and (c) is the adsorbent prepared in example 3;
FIG. 4 is an adsorption isotherm (298K) for propylene and propane for a comparative example prepared according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Preparation of Zr-BPDC-NH 2 Adsorbent solids, in particular: 0.245g of zirconium chloride (ZrCl) 4 ) And 0.13 g of 4,4' -biphenyldicarboxylic acid (H) 2 BPDC), 0.14g2-amino-4, 4' -biphenyldicarboxylic acid (H) 2 ABPDC) and 2ml of glacial acetic acid are dissolved in 40ml of DMF, added into a reaction kettle and stirred for 1h at normal temperature, and then heated for 24h at 120 ℃ to obtain crude Zr-BPDC-NH 2 Cooling the solid adsorbent, performing suction filtration to collect the solid, washing the solid with DMF (dimethyl formamide), soaking and activating the solid for 2 days by using absolute ethyl alcohol, and performing vacuum drying for 8 hours at the temperature of 150 ℃;
weighing Zr-BPDC-NH 2 (120 mg) was added to THF (10 mL) and sonicated for 20min, followed by GMA 396uL, mixed well, held at 55 ℃ for 36 hours, then washed with tetrahydrofuran by suction filtration, soaked with chloroform for 1 day for activation, and finally the material was suction filtered, dried at 50 ℃ for 24 hours under vacuum to give pure product Zr-BPDC-GMA, andlabeled as example 1.
Example 2
Preparation of Zr-BPDC-NH 2 Adsorbent solids, in particular: 0.3388g of zirconium oxychloride (ZrOCl) 2 ·8H 2 O) and 0.14g4,4' -biphenyldicarboxylic acid (H) 2 BPDC), 0.14g 2-amino-4, 4' -biphenyldicarboxylic acid (H) 2 ABPDC) and 1ml formic acid are dissolved in 40ml absolute ethyl alcohol and added into a reaction kettle for ultrasonic treatment for 1 hour, and then the mixture is heated for 30 hours at 115 ℃ to obtain crude Zr-BPDC-NH 2 Cooling the solid adsorbent, performing suction filtration to collect the solid, washing the solid with DMF, soaking and activating the solid for 2 days by using methanol, and performing vacuum drying at 120 ℃ for 12 hours;
weighing Zr-BPDC-NH 2 (120 mg) was added to THF (10.2 mL) and sonicated for 30min followed by 36uL of triglycidyl ether and 0.01mol/L HNO 3 204uL were mixed well, kept at 75 ℃ for 25 hours, then washed with tetrahydrofuran by suction filtration, and activated by immersion in acetonitrile for 1 day, and finally the material was suction filtered and dried in vacuo at 110 ℃ for 12h to give the pure product Zr-BPDC-triacrylate glycidyl ether, labeled as example 2.
Example 3
Preparation of Zr-BPDC-NH 2 The adsorbent solid specifically comprises: 0.245g of zirconium chloride (ZrCl) 4 ) And 0.15 g of 4,4' -biphenyldicarboxylic acid (H) 2 BPDC), 0.17g 2-amino-4, 4' -biphenyldicarboxylic acid (H) 2 ABPDC) and 2.5ml of glacial acetic acid are dissolved in 50ml of DMF, added into a reaction kettle for ultrasonic treatment for 1h, and then heated at 125 ℃ for 24h to obtain crude Zr-BPDC-NH 2 Cooling the solid adsorbent, performing suction filtration to collect the solid, washing the solid with DMF, soaking and activating the solid by using absolute ethyl alcohol for 2 days, and performing vacuum drying at 140 ℃ for 10 hours;
weighing Zr-BPDC-NH 2 (120 mg) was added to THF (9 mL) and sonicated for 60min, followed by addition of 828uL of diethylene glycidyl ether and 100uL of 0.05mol/L HF, mixed well, held at 50 ℃ for 40 hours, then washed with tetrahydrofuran and filtered, and then activated by soaking in dichloromethane for 1 day, and finally the material was filtered and dried under vacuum at 120 ℃ for 8 hours to give the pure product Zr-BPDC-diethylene glycidyl ether and labeled as example 3.
Comparative example
Preparing a Zr-BPDC adsorbent solid, which specifically comprises the following steps: 0.245g of zirconium chloride (ZrCl) 4 ) And 0.26g of 4,4' -Biphenyldicarboxylic acid (H) 2 BPDC), 2ml glacial acetic acid was dissolved in 40ml DMF and added to the reaction kettle for 1h of sonication, followed by heating at 120 ℃ for 24h to give crude Zr-BPDC solid adsorbent, which was then cooled to room temperature. The solid is collected by suction filtration and washed by DMF, and then is soaked in absolute ethyl alcohol for 2 days and dried in vacuum at 120 ℃ for 10 hours, and the mark is a comparative example;
characterization and performance determination of composite adsorption material adsorbent
Table 1 the covalently modified materials prepared in examples 1,2,3 and comparative examples were tested for specific surface area and pore structure characterization parameters using an ASAP2460 specific surface area and pore distribution structure tester, and the results are shown in table 1.
TABLE 1
(Note: a S BET is BET specific surface area; b V t in order to obtain a total pore volume, c V micro the pore volume of the micropores is the pore volume of the micropores, d V meso is mesoporous volume. )
Table 1 shows that the specific surface area of the covalent modification material prepared by the invention is 1885-2198m 2 Per g, pore volume is 0.80-0.82cm 3 Compared with the raw materials, the total pore volume of the covalent modification material prepared by the invention is slightly reduced, micropores are increased, and mesopores are reduced. This is because the introduction of organic molecular chains occupies some channels, which reduces the pore volume. In addition, the molecular chain in the pore channel divides the mesopores into smaller cavities, so that the mesopores are reduced, the micropores are increased, the strategy can increase the micropores, the electrostatic interaction between the propane and the adsorbent is favorably enhanced, and the selectivity is improved.
FIG. 1 shows the adsorption materials prepared in examples 1,2,3 and N of comparative example 2 Adsorption isotherm diagram (77K), from which it can be seen that the adsorbent materials prepared in examples 1,2,3 and the comparative example both exhibit type I isotherms at low pressures, indicating that they both have developed micro-scalePore structure. N of example 1 2 The high adsorption amount compared to the comparative example shows that the specific surface area compared to the comparative example is high, because the GMA in example 1 is a flexible chain, can exist in the pore channels and can also exist on the surface, so that the roughness of the surface can be increased, and the specific surface is improved. N of examples 2 and 3 2 The adsorption amount is slightly lower than that of the comparative example, which shows that the specific surface area of the organic chains of example 2 and example 3 is lower than that of the comparative example because both ends of the organic chains can be covalently bonded with the ligand and exist in the channels to block part of the channels, thereby reducing the surface area.
Fig. 2 is XRD spectra of the covalently modified materials prepared in examples 1,2,3 and the comparative example, and as shown in fig. 2, the characteristic peak results of the covalently modified materials prepared in examples 1,2,3 in the range of 2 θ =5 ° -30 ° indicate that the covalently modified materials do not affect the growth of the crystal structure of the raw materials.
FIGS. 3 (a), (b), and (c) are the adsorption isotherms of the covalently modified materials prepared in examples 1,2, and 3 for propane and propylene under 298K conditions, respectively. As can be seen from the figure, the material preferentially adsorbs propane, and the adsorption capacity of propane of example 1 is as high as 10.08mmol/g, which is in the front of the world. Specifically, the adsorbents obtained in examples 1 to 3 were found to have an adsorption capacity of 10.08mmol/g, 7.99mmol/g and 8.28mmol/g for propane at 298K, and the adsorbents obtained in examples 1 to 3 had an adsorption capacity of 9.09mmol/g, 8.37mmol/g and 8.06mmol/g for propylene at 298K, respectively. Comparative examples the adsorbed amounts of propane and propylene under 298K were 8.49mmol/g and 8.95mmol/g, respectively. It can be seen that the covalent modification material prepared by the invention can realize preferential adsorption of propane at normal temperature and normal pressure, and obtain polymerization-grade propylene at an outlet in one step.
Table 4 shows C at 298K for examples 1,2,3 and comparative example 3 H 8 /C 3 H 6 The Henry coefficient of (1).
TABLE 4
| Example 1 | Example 2 | Example 3 | Comparative example |
| 1.73 | 1.38 | 1.32 | 0.97 |
Table 4 shows that the propane selectivity of the material can be improved by covalently modifying an organic molecular chain, and the technical means of the invention can provide a reference idea for the preparation of propane selective materials.
The present invention is not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and equivalents thereof, which are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane is characterized by comprising the following steps:
(1) Preparation of Zr-BPDC-NH 2 The adsorbent solid specifically comprises: weighing metal zirconium salt, 4 '-biphenyldicarboxylic acid, 2-amino-4, 4' -biphenyldicarboxylic acid and organic acid into an organic solvent A, uniformly mixing the metal zirconium salt, the 4,4 '-biphenyldicarboxylic acid, the 2-amino-4, 4' -biphenyldicarboxylic acid and the organic acid, then putting the mixture into a reaction kettle, and reacting for 24-30h at 115-125 ℃ to obtain crude Zr-BPDC-NH 2 Cooling the solid adsorbent, then carrying out suction filtration and washing by using DMF (dimethyl formamide), and then soaking, activating and drying by using an organic solvent B to obtain Zr-BPDC-NH 2 A solid adsorbent;
(2) Preparation of Zr-BPDC-organic molecular chain adsorbent solidComprises the following steps: weighing the Zr-BPDC-NH obtained in the step (1) 2 Adding tetrahydrofuran and inorganic acid into a solid adsorbent, uniformly dispersing by ultrasonic, adding an organic molecular chain, uniformly stirring, carrying out heating reaction, cooling, and carrying out suction filtration and washing by using tetrahydrofuran to obtain a crude Zr-BPDC-organic molecular chain material;
(3) Activating the solid obtained in the step (2), specifically: soaking and activating the crude Zr-BPDC-organic molecular chain material prepared in the step (2) by using an organic solvent, filtering, and drying to obtain a metal organic framework-organic molecular chain covalent modification material;
the organic molecular chain in the step (2) is glycidyl methacrylate.
2. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps: the metal zirconium salt in the step (1) refers to at least one of zirconium chloride, zirconium oxychloride, zirconium acetate, zirconium carbonate, zirconium oxalate and zirconium citrate;
the organic solvent A in the step (1) refers to DMF and absolute ethyl alcohol;
the organic acid in the step (1) refers to at least one of glacial acetic acid, formic acid and benzoic acid.
3. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps: the mass ratio of the metal zirconium salt, the 4,4 '-biphenyldicarboxylic acid and the 2-amino-4, 4' -biphenyldicarboxylic acid in the step (1) is 1 (0.5-0.7) to (0.5-0.7).
4. The method for preparing the covalent modification material with metal organic framework-organic molecular chain for preferentially adsorbing propane according to claim 1, wherein the covalent modification material comprises the following steps:
the dosage ratio of the metal zirconium salt to the organic acid in the step (1) is 1mol (0.95-2.86) L;
the volume ratio of the organic acid to the organic solvent A in the step (1) is 1ml (19-21) ml.
5. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps:
the drying in the step (1) refers to vacuum drying at 120-150 ℃ for 8-12h; the organic solvent B is absolute ethyl alcohol or methanol.
6. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps: the inorganic acid in the step (2) refers to HCl and HNO 3 、H 3 PO 4 And at least one of HF.
7. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps: the dosage ratio of the adsorbent, tetrahydrofuran, inorganic acid and organic molecular chains in the step (2) meets 1g: (75-85) mL: (0-1.7) mL: (0.3-6.9) ml; the concentration of the inorganic acid is 0.01-0.05 mol/L.
8. The method for preparing the metal organic framework-organic molecular chain covalent modification material for preferentially adsorbing propane according to claim 1, wherein the metal organic framework-organic molecular chain covalent modification material comprises the following steps:
the ultrasonic dispersion in the step (2) is ultrasonic for 10-60min;
the heating in the step (2) is to put the mixture into an oven with the temperature of 50-75 ℃ for 25-40 h.
9. The method for preparing a metal organic framework-organic molecular chain covalent modification material preferentially adsorbing propane according to claim 1, wherein the organic solvent in the step (3) is one of chloroform, absolute ethanol, cyclohexane, dichloromethane or acetonitrile;
the suction filtration in the step (3) refers to filtration by using an organic filter membrane with the average pore diameter of 0.45 um; the drying refers to vacuum drying at 50-120 ℃ for 8-24 h.
10. A metal organic framework-organic molecular chain covalent modification material preferentially adsorbing alkane prepared by the method of any one of claims 1 to 9.
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