Method for separating 2-pentanone and 2-pentanol by using symmetric conjugated column [5] arene derivative crystalline non-porous material
Through the crystalline non-porous material of aromatic derivatives, 2-pentanone is selectively adsorbed by a crystalline non-porous material of symmetric conjugated column [5], forming a host-guest complex with a stoichiometric ratio of 1:1, solving the problems of high cost and high energy consumption of the 2-pentanone and 2-pentanol separation equipment in the prior art, and achieving an efficient and environmentally friendly separation effect.
Patent Information
- Application Number
- CN202510473691.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-16
- Publication Date
- 2025-07-04
AI Technical Summary
The prior art has problems such as high equipment cost, large energy consumption and complex operation when separating 2-pentanone and 2-pentanol. The traditional methods are inefficient and cost-effective, making it difficult to achieve efficient and environmentally friendly separation.
The crystalline non-porous material of aromatic derivatives is selectively adsorbed 2-pentanone by non-covalent force to form a host-guest complex with a stoichiometric ratio of 1:1, and decomplexing under heating conditions to achieve separation of 2-pentanone and 2-pentanol.
Efficient and accurate separation of 2-pentanone and 2-pentanol is achieved, reducing separation costs, simplifying the operation process, improving separation purity, and reusable materials.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of chemical separation, and particularly relates to a method for adsorptive separation of 2-pentanone and 2-pentanol by a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative. Background Art
[0002] As an important organic solvent and chemical intermediate, 2-pentanone plays a very important role in industry. It is often used to dissolve nitrocellulose, acrylic resin, and epoxy resin, as a solvent for printing ink and glue, can remove grease, lubricating oil and processing residues on the metal surface, and is also an intermediate for synthesizing drugs, pesticides, and spices. 2-Pentanol is also an important organic solvent, chemical raw material and intermediate, often used to dissolve alkyd resin, nitro paint, etc., for synthesizing phthalate plasticizers, manufacturing emulsifiers, and can also improve the combustion performance of gasoline or biodiesel. The two are complementary in the fields of fine chemicals, coatings, cleaning agents, etc., and are important industrial solvents and intermediates. Therefore, they must be used separately.
[0003] There are many methods for separating 2-pentanone and 2-pentanol, such as distillation method, chemical separation method, extraction method, membrane separation method, etc. The distillation method separates by using the difference in boiling points. This method requires a precision shunting device and has a high cost in industry; the chemical separation method separates by using the difference in functional groups, and some ketones may remain in the mother liquor, resulting in a reduced yield; the extraction method separates by using the difference in polarity, and some will be slightly extracted, and the yield will also be reduced; the membrane separation method separates by using pervaporation or organic solvent nanofiltration. This method has expensive membrane materials and low separation efficiency. Therefore, it is of great significance to develop a simpler, more efficient and more energy-saving method to separate the azeotrope of 2-pentanone and 2-pentanol.
[0004] Crystalline non-porous materials (CNMs) have shown great potential in the field of adsorptive separation of volatile organic compounds (VOCs) in recent years due to their structural designability, high stability and unique adsorption properties. Compared with traditional materials, CNMs achieve adsorptive separation through weak intermolecular interactions (such as π-π stacking, hydrogen bonding and van der Waals forces), and have higher selectivity and controllability. As a new type of macrocyclic host molecule, pillar[5]arene provides an ideal platform for designing high-performance CNMs with its unique cavity structure and easy functionalization.
[0005] The triphenylamine group has excellent hole - transporting ability and a rigid planar structure. Introducing it into the pillar[5]arene skeleton can not only enhance the adsorption performance of the material but also achieve highly selective recognition of chiral molecules or specific VOCs through intermolecular interactions. Based on this, this study designed and synthesized a crystalline non - porous material of triphenylamine - modified bilateral functionalized pillar[5]arene, aiming to utilize its unique structural characteristics to achieve efficient adsorption and separation of 2 - pentanone and 2 - pentanol. By systematically studying its adsorption performance and separation mechanism, it provides new ideas for the development of new VOCs separation materials. Summary of the Invention
[0006] The purpose of the present invention is to provide an adsorption and separation method for a crystalline non - porous material of symmetric conjugated pillar[5]arene derivatives. It can separate the mixture of 2 - pentanone and 2 - pentanol in an efficient, precise, and environmentally friendly manner, overcoming the defects such as high equipment cost, large process energy consumption, and complex operation process during the separation of 2 - pentanone and 2 - pentanol, improving the separation purity, and realizing the reusable adsorption material.
[0007] The technical solution of the present invention is as follows: A method for separating 2 - pentanone and 2 - pentanol using a crystalline non - porous material of symmetric conjugated pillar[5]arene derivatives, which selectively adsorbs and complexes 2 - pentanone from the mixed solvent of 2 - pentanone and 2 - pentanol by using the crystalline non - porous material of symmetric conjugated pillar[5]arene derivatives, thereby realizing the separation of 2 - pentanone and 2 - pentanol.
[0008] The structural formula of the crystalline non - porous material of the symmetric conjugated pillar[5]arene derivatives is as follows: 。
[0009] This study of the present invention found that in view of the inherent surface charges and structural differences of 2 - pentanone and 2 - pentanol themselves, the cavity of the crystalline non - porous material of symmetric conjugated pillar[5]arene derivatives can selectively adsorb and complex 2 - pentanone to form a host - guest complex with a stoichiometric ratio of 1:1. This host - guest complex dissociates during heating, releasing the adsorbed and complexed 2 - pentanone again. The crystalline non - porous material of the symmetric conjugated pillar[5]arene derivatives is chemically stable under the desorption temperature conditions set in the present invention and can be recycled.
[0010] The crystalline non - porous material of the symmetric conjugated pillar[5]arene derivatives is obtained by evaporation crystallization in acetone solvent. The obtained crystalline porous material needs to be heated to remove solvent molecules for activation treatment. The activation temperature is 70 °C and the activation time is not less than 2 hours. The activated crystalline non - porous material of the symmetric conjugated pillar[5]arene derivatives can be directly used for the adsorption and separation of 2 - pentanone and 2 - pentanol.
[0011] Specific steps for separating 2-pentanone and 2-pentanol using a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative: Place the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative in an atmosphere of a mixed vapor of 2-pentanone and 2-pentanol. At room temperature, selectively adsorb 2-pentanone through non-covalent interactions to form a host-guest complex with a stoichiometric ratio of 1:1. After standing at room temperature for a period of time, remove the mixture of 2-pentanone and 2-pentanol adsorbed on the surface of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative, and then desorb and separate the 2-pentanone adsorbed and complexed inside the cavity of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative by vacuum heating to achieve the activation and regeneration of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative, and reuse it for the adsorption and separation of 2-pentanone and 2-pentanol.
[0012] Remove the mixture adsorbed on the surface at room temperature. The desorption time is not less than 2 hours, and the desorption time is optimized and adjusted according to the sample weight.
[0013] The operating temperature for vacuum heating desorption and separation of 2-pentanone is 70 °C. The desorption time is not less than 2 hours and is optimized and adjusted according to the sample weight.
[0014] Compared with the existing separation technologies, the excellent effects of the present invention are as follows: The separation process has simple operation and low equipment requirements; the separation process does not require rectification operation, and the process energy consumption is low; the separation cost of catalytic hydrogenation of 2-pentanone to produce 2-pentanol is reduced; the crystalline non-porous material is simple to prepare, chemically stable, has high selectivity and high-capacity adsorption for 2-pentanone, and the separation effect is stable. Description of the Drawings
[0015] Figure 1 It is a flow chart for the adsorption and separation of 2-pentanone and 2-pentanol using a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative; Figure 2 It is a single crystal structure diagram of a symmetric conjugated pillar[5]arene derivative obtained by slow evaporation in an acetone solution; Figure 3 It is a single crystal X-ray diffraction diagram of a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative; Figure 4 It is an N2 adsorption-desorption isotherm diagram of a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative; Figure 5 It is a thermogravimetric analysis characterization diagram of a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative; Figure 6 It is a curve diagram of a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative adsorbing a single-component vapor; Figure 7 It is a thermogravimetric analysis characterization diagram of a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative adsorbing a single-component vapor; Figure 8 Single crystal X-ray diffraction pattern of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative for the adsorption of single-component vapor; Figure 9 Single crystal structure diagram of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative obtained by slow evaporation in 2-pentanone solution; Figure 10 Curve graph and NMR titration graph of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative for the adsorption of mixed vapor; Figure 11 PXRD pattern of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative for the adsorption of single-component vapor and mixed vapor; Figure 12 Recycling curve graph of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative for the adsorption and desorption of mixed vapor; Figure 13 For the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative 1 1H NMR spectrum; Figure 14 For the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative 13 13C NMR spectrum; Figure 15 Mass spectrum of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative. Specific implementation manners
[0016] The following further illustrates the specific implementation manners of the present invention in conjunction with the accompanying drawings and examples. The following examples are only used to illustrate the present invention and are not used to limit the scope of the present invention.
[0017] The following specific separation operation methods described in conjunction with the examples, those without special instructions are conventional conditions or the conditions recommended by the equipment reagent manufacturers.
[0018] Example 1 Preparation of the crystalline non-porous material of symmetric conjugated pillar[5]arene derivative: Weigh 2 g of the symmetric conjugated pillar[5]arene derivative solid and dissolve it in 10 mL of acetone. Slowly volatilize the solvent in a normal temperature and pressure environment for 2 - 3 days, collect the precipitated crystals, and activate the crystals at 70 °C for no less than 2 hours to obtain white crystals, denoted as P5NNα.
[0019] The product characterization data of the crystalline non-porous material P5NNα of symmetric conjugated pillar[5]arene derivative are as follows: P5NNα, 11H NMR (400 MHz, CDCl3) δ 7.31–7.26 (m, 8H), 7.19 (s,2H), 7.15(d, J J = 7.8 Hz, 8H), 7.06–6.99 (m, 12H), 6.76 (s, 2H), 6.59 (s,2H), 6.52 (s,2H), 5.97 (s, 2H), 3.97 (d, J J = 13.7 Hz, 2H), 3.86–3.81 (m, 6H), 3.78–3.71 (m,6H), 3.69–3.63 (m, 8H), 3.56 (d, J J = 7.0 Hz, 4H), 1.21 (t, J J = 6.9 Hz, 6H), 1.15(t, J J = 6.9 Hz, 6H), 0.99 (t, J J = 6.8 Hz, 6H), 0.90 (t, J J = 6.8 Hz, 6H). 13C NMR(151 MHz, CDCl3) δ 150.03, 149.98, 149.73, 149.54, 149.45, 148.63, 147.83,146.85, 146.23, 142.05, 139.73, 139.03,136.74, 136.59, 134.31, 132.61,131.84, 130.30, 129.68, 129.29, 128.94, 128.80, 128.70, 128.52, 124.34,122.96, 122.85, 115.64, 115.14, 114.98, 114.84, 64.16,63.82, 63.80, 63.60,32.87, 30.07, 30.03, 15.05, 15.00, 14.59, 14.39. ESI-HRMS (m / z): calcd. forC 87 H 88 N2O8[M+H] + 1289.6613, found 1289.6613. As Figure 3 shown: Single crystal X-ray diffraction (PXRD) was performed on P5NNα, and the results proved that P5NNα still maintained a crystalline state, but it was different from the PXRD simulated by the single crystal, indicating that a new unknown crystal phase was generated.
[0020] As Figure 4 shown: The N2 adsorption - desorption isotherm experiment was carried out on P5NNα, and it was found that P5NNα is a non - porous material.
[0021] As Figure 5 shown: The thermogravimetric detection was carried out on P5NNα, and it was found that the solvent molecules were completely removed from the host, and there was no weight loss below 340 °C, which supports its high stability.
[0022] Single - crystal X - ray diffraction detection, N2 adsorption - desorption isotherm experiment detection, and thermogravimetric detection prove that the P5NNα material is a crystalline non - porous material with high stability.
[0023] Example 2 Adsorption of single - component vapors of 2 - pentanone or 2 - pentanol by the crystalline non - porous P5NNα material: Take two 20 - mL glass bottles and fill them with 1 mL of 2 - pentanone and 2 - pentanol respectively. Take 5 mg of the crystalline non - porous P5NNα material prepared in Example 1 and put it in two 2 - mL glass bottles. Place the two open 2 - mL glass bottles in the two 20 - mL glass bottles, seal the bottle caps, and adsorb 2 - pentanone and 2 - pentanol for 6 h under normal temperature and pressure conditions, denoted as one@P5NNα and ol@P5NNα respectively.
[0024] As Figure 6 shown: The time - dependent solid - vapor adsorption experiment was carried out on single - component 2 - pentanone and 2 - pentanol, and it was found that the adsorption of 2 - pentanone by P5NNα reached saturation within 1 h. After saturation, 5 mg of P5NNα could adsorb 0.5 mg of 2 - pentanone, but only 0.1 mg of 2 - pentanol. This shows that P5NNα has a high adsorption selectivity for 2 - pentanone.
[0025] As Figure 7 shown, the thermogravimetric detection was carried out on P5NNα adsorbed with 2 - pentanone and 2 - pentanol respectively. It was found that at 360 °C, after P5NNα adsorbed 2 - pentanone for 6 h, the weight loss was 13.6%, which proved that one molecule of P5NNα could adsorb one molecule of 2 - pentanone. However, after P5NNα adsorbed 2 - pentanol for 6 h, the weight loss was only 3.3%. The results showed that P5NNα only adsorbed 2 - pentanone and hardly adsorbed 2 - pentanol.
[0026] As Figure 8 shown, the PXRD detection was carried out on the crystal adsorbed with 2 - pentanone, and it was found that the PXRD showed the same PXRD pattern as that simulated by the single crystal grown in 2 - pentanone, but was different from the PXRD of P5NNα. This proved that the crystal structure of P5NNα changed during the adsorption of 2 - pentanone.
[0027] AsFigure 9 As shown, 20 mg of P5NN solid was dissolved in 2-pentanone and 2-pentanol respectively and slowly evaporated to obtain single crystals of one@P5NNα and ol@P5NNα. From the single crystal structure, it can be seen that 2-pentanone entered the cavity of the P5NN solid, and the host-guest complexation ratio was 1:1. However, it was found that 2-pentanol did not enter the cavity of the P5NN solid, which also indicates that P5NNα can adsorb and separate 2-pentanone and 2-pentanol.
[0028] Single-component adsorption experiments, thermogravimetric analysis, PXRD detection, and single crystal results proved that the crystalline non-porous material P5NNα rapidly adsorbed 2-pentanone in a stoichiometric ratio of 1:1, and the adsorption of 2-pentanol was almost negligible.
[0029] Example 3 Adsorption of P5NNα crystalline non-porous material on a 1:1 mixed vapor of 2-pentanone and 2-pentanol: Take 1 20 mL glass bottle and fill it with 0.5 mL of 2-pentanone and 0.5 mL of 2-pentanol respectively. Take 5 mg of the P5NNα crystalline non-porous material prepared in Example 1 and place it in 1 2 mL glass bottle. Place the open 2 mL glass bottle in the 20 mL glass bottle and seal the bottle cap. Adsorb for 6 h under normal temperature and pressure conditions, denoted as one and ol@P5NNα.
[0030] As Figure 10 shown, a time-dependent solid-gas adsorption separation experiment was carried out on an equimolar mixture of 2-pentanone and 2-pentanol. It was found that the adsorption of 2-pentanone by P5NNα reached saturation within only 2 h as time increased. This adsorption rate was faster than that of most non-porous adaptive crystal materials based on pillar[5]arenes reported in the literature. Moreover, after adsorption saturation, P5NNα had a high adsorption selectivity for 2-pentanone, but there was also a small amount of adsorption of 2-pentanol, which was caused by surface adsorption and could thus be almost ignored, which was consistent with the above single-component adsorption. This experimental result indicates that P5NNα can adsorb and separate 2-pentanone and 2-pentanol. NMR detection also confirmed that P5NNα mainly adsorbed 2-pentanone and hardly adsorbed 2-pentanol.
[0031] As Figure 11 shown: PXRD detection was carried out and it was found that P5NNα adsorbed with a 1:1 mixed vapor showed the same PXRD pattern as the crystal adsorbed with 2-pentanone, but the PXRD of the single-component and 1:1 mixed vapor adsorbed P5NNα showed different patterns from that of P5NNα, which indicates that the adsorption changed the structure of P5NNα. The results show that P5NNα shows a high adsorption selectivity for 2-pentanone.
[0032] The mixed vapor adsorption experiment, NMR detection, and PXRD detection prove that the P5NNα crystalline non-porous material rapidly adsorbs 2-pentanone in a stoichiometric ratio of 1:1, and the adsorption of 2-pentanol is almost negligible.
[0033] Example 4 As Figure 12 shown: The P5NNα crystalline non-porous material after adsorption in Example 3 was vacuum heated at 70 °C for desorption to separate the 2-pentanone adsorbed and complexed inside the material cavity, realizing the activation and regeneration of the P5NNα crystalline non-porous material, and it was used again for the adsorption and separation of 2-pentanone and 2-pentanol, and the adsorption performance did not decrease.
[0034] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art can make various adjustments or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.
Claims
1. A method for separating 2-pentanone and 2-pentanol by using a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative, characterized in that, Use a crystalline non-porous material of a symmetric conjugated pillar[5]arene derivative to adsorb and separate a mixture of 2-pentanone and 2-pentanol. The crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative selectively and rapidly adsorbs 2-pentanone in the mixture to achieve the separation of 2-pentanone and 2-pentanol; The structural formula of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative is: 。 2. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative as claimed in claim 1, characterized in that, Expose the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative to a mixed vapor of 2-pentanone and 2-pentanol, and selectively adsorb 2-pentanone at room temperature to form a host-guest complex with a stoichiometric ratio of 1:
1.
3. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative according to claim 2, characterized in that, The molar ratio of 2-pentanone to 2-pentanol in the mixed vapor is 1:
1.
4. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative as claimed in claim 1, wherein, The crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative is obtained by crystal cultivation of the symmetric conjugated pillar[5]arene derivative followed by activation treatment.
5. The method for separating 2-pentanone and 2-pentanol by the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative according to claim 4, characterized in that, The solvent for crystal cultivation is acetone; activation treatment is carried out by removing solvent molecules through vacuum heating. The activation temperature is 70 °C, and the activation time is not less than 2 hours.
6. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative as claimed in claim 1, wherein, Vacuum heating desorption is used to separate the 2-pentanone adsorbed and complexed inside the cavity of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative, realizing the regeneration of the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative.
7. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative according to claim 6, characterized in that, The operating temperature of the vacuum heating desorption is 70 °C, and the desorption time is not less than 2 hours.
8. The method for separating 2-pentanone and 2-pentanol by using the crystalline non-porous material of the symmetric conjugated pillar[5]arene derivative according to claim 1, characterized in that, The material can be recycled at least 5 times with no significant decrease in adsorption performance.