A hypercrosslinked polymer adsorbent for separating olefins and paraffins, and a preparation method and application thereof

Abstract

The present invention provides a hypercrosslinked polymer adsorbent for separating olefins and alkanes, and a preparation method and application thereof, belonging to the technical field of separating olefins and alkanes. The method comprises the following steps: mixing a monomer, an acidic catalyst and a solvent to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer; sulfonating the hypercrosslinked polymer to obtain a sulfonation product; carrying out a hydrolysis reaction on the sulfonation product under an alkaline condition to obtain a hydrolysis product; and carrying out ion exchange on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for separating olefins and alkanes. The adsorbent prepared by the present invention can be applied to the separation of liquid-phase olefins and alkanes (C6, C7 and C8), and the preparation process and the post-treatment method are simple. The monomer, the acidic catalyst and the solvent used are all cheap and easily available, and the preparation process is easy to realize industrial scale-up.

Description

Technical Field

[0001] The present invention relates to the technical field of olefin and paraffin separation, and particularly relates to a hypercrosslinked polymer adsorbent for olefin and paraffin separation, a preparation method thereof, and an application thereof. Background Art

[0002] With the accelerating trend of the transformation of petroleum to chemical industry, the increase in chemical raw materials through oil refining has attracted wide attention. This transformation process requires relevant catalytic and separation technologies as support. In the existing oil refining process, components are mainly separated according to the boiling range, and it is difficult to effectively separate components with close boiling points. Olefins are important raw materials for producing products such as plastics, polyolefins, surfactants, and rubbers. However, in the petrochemical industry, olefins and paraffins coexist in many process flows, including steam cracking reactions, Fischer-Tropsch synthesis, etc. If efficient application is to be achieved, the two must be separated accordingly before use. Since paraffins and olefins with the same number of carbon atoms usually have similar boiling points and kinetic diameters, it is very difficult to separate them.

[0003] Cryogenic distillation, as a traditional separation process, is commonly used for the separation of gas-phase components such as ethylene and ethane. Although the technology is mature, it has problems such as high energy consumption and complex processes, and it is necessary to seek a more economical alternative method. Existing research mainly focuses on the separation of gas-phase olefins and paraffins (C2 and C3), while relatively few studies have been conducted on the separation of liquid-phase olefins and paraffins. In recent years, new liquid-liquid extraction, membrane separation, and adsorption separation technologies have attracted much attention and have gradually become the best choice to replace cryogenic distillation. Among them, adsorption separation is regarded as a separation technology with application prospects due to its high selectivity, mild operating conditions, and low separation cost. The difficulties in separating liquid-phase olefins and paraffins are as follows: 1. The molecular weights and molecular volumes of liquid-phase components are relatively large, and molecular sieves and the like have low adsorption capacities due to too small pore volumes; 2. Olefins and paraffins with long carbon chains only have a difference in one C-C bond. For example, the structures of 1-hexene and n-hexane are very close, and there is only one difference among the five C-C bonds. Their difference is relatively smaller compared to gas-phase molecules, and the separation difficulty is greater. Separating olefins and paraffins in gasoline fractions can, on the one hand, reduce the olefin content in gasoline, and on the other hand, the olefins in gasoline can be used as raw materials for cracking to produce olefins or be functionalized to achieve high-value utilization. Currently, metal-organic framework materials (MOFs) and molecular sieves are mainly used as adsorbents to achieve the separation of liquid-phase olefins and paraffins. The pore volume of molecular sieves is too small, while MOFs have disadvantages such as expensive monomers, harsh preparation conditions, and poor stability, which limit their large-scale application. Therefore, it is necessary to find new materials with high adsorption capacity and high selectivity as adsorbents for liquid-phase olefin and paraffin separation. Summary of the Invention

[0004] In view of this, the object of the present invention is to provide a hypercrosslinked polymer adsorbent for separating olefins and alkanes, and its preparation method and application. The hypercrosslinked polymer adsorbent prepared by the present invention can achieve efficient separation of liquid-phase olefins and alkanes, and has the advantages of high specific surface area, high adsorption capacity and adsorption selectivity.

[0005] In order to achieve the above object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a preparation method of a hypercrosslinked polymer adsorbent for separating olefins and alkanes, comprising the following steps:

[0007] Mixing a monomer, an acidic catalyst and a solvent to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer, wherein the monomer contains a benzene ring and the solvent contains a methylene group;

[0008] Sulfonating the hypercrosslinked polymer to obtain a sulfonation product;

[0009] Carrying out a hydrolysis reaction on the sulfonation product under alkaline conditions to obtain a hydrolysis product;

[0010] Carrying out ion exchange on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for separating olefins and alkanes, and the metal ions used in the ion exchange include Ag + , Cu 2+ , Ni 2+ and Co 2+ or one or more of them.

[0011] Preferably, the monomer includes one or more of 4,4'-biphenyldimethyldimethylether, 1,3,5-triphenylbenzene and 4,4'-dichloromethylbiphenyl.

[0012] Preferably, the acidic catalyst includes one or more of ferric chloride, aluminum chloride and chlorosulfonic acid.

[0013] Preferably, the solvent includes 1,2-dichloroethane and / or dichloromethane.

[0014] Preferably, the molar ratio of the acidic catalyst to the monomer is 0.5-8.0:1.

[0015] Preferably, the temperature of the Friedel-Crafts alkylation reaction is 60-80 °C and the time is 18-48 h.

[0016] Preferably, the sulfonation reagent used for sulfonation includes chlorosulfonic acid or fuming sulfuric acid.

[0017] Preferably, the dosage ratio of the hypercrosslinked polymer to the metal ions is 1 g:0.015-0.050 mol.

[0018] The present invention also provides a hypercrosslinked polymer adsorbent for olefin and paraffin separation prepared by the preparation method described in the above technical solution.

[0019] The present invention also provides an application of the hypercrosslinked polymer adsorbent for olefin and paraffin separation described in the above technical solution in the field of olefin and paraffin separation.

[0020] The present invention provides a preparation method of a hypercrosslinked polymer adsorbent for olefin and paraffin separation, comprising the following steps: mixing a monomer, an acidic catalyst and a solvent to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer, wherein the monomer contains a benzene ring and the solvent contains a methylene group; sulfonating the hypercrosslinked polymer to obtain a sulfonation product; carrying out a hydrolysis reaction on the sulfonation product under alkaline conditions to obtain a hydrolysis product; carrying out ion exchange on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for olefin and paraffin separation, and the metal ions used in the ion exchange include Ag + , Cu 2+ , Ni 2+ and Co 2+ one or more of them.

[0021] The present invention selects a monomer to carry out a Friedel-Crafts alkylation reaction under the action of an acidic catalyst to form a hypercrosslinked polymer, anchors sulfonic acid groups in the benzene ring structure through a sulfonation reaction, and then removes incompletely crosslinked terminal C-Cl bonds through a hydrolysis reaction under alkaline conditions. Subsequently, through ion exchange, a hypercrosslinked polymer adsorbent with olefin adsorption metal sites is formed and applied to the selective separation of liquid-phase olefins and paraffins.

[0022] Moreover, the monomer, acidic catalyst and solvent selected in the present invention are all cheap and easily available, the preparation conditions are mild and simple, and it is easy to realize industrial scale-up production.

[0023] The present invention also provides an application of the hypercrosslinked polymer adsorbent for olefin and paraffin separation described in the above technical solution in the selective adsorption separation of liquid-phase olefin / paraffin. The data of the examples show that all four adsorbents prepared have good olefin adsorption capacity. At 30 °C, a static adsorption test is carried out, and the composition of a 1-hexene / n-hexane mixed oil product with different mole fractions is tested before and after adsorption by gas chromatography (GC). Analysis is carried out in combination with a liquid-phase adsorption model established based on the Langmuir adsorption model, and the corresponding model equation is shown in Equation (1):

[0024]

[0025] Wherein, and are respectively the mole fractions of olefin and paraffin in the oil product at adsorption equilibrium; n σ / m (mmol / g) is the molar amount of molecules adsorbed by the adsorbent per unit mass; K is the average adsorption equilibrium constant; is the apparent adsorption amount.

[0026] Nonlinear fitting of the test results according to Equation (1) can obtain the composite adsorption isotherm of the above hypercrosslinked polymer. In addition, by performing linear fitting and parameter calculation on the test results according to Equation (1), the average adsorption equilibrium constants K of HCP-BMMBP-SO3-Ag + , HCP-TPB-SO3-Ag + , HCP-BCMBP-SO3-Ag + , HCP-BCMBP-SO3-Cu 2+ , HCP-BCMBP-SO3-Ni 2+ and HCP-BCMBP-SO3-Co 2+ are 14, 9, 20, 7, 18 and 16 respectively, and the saturated adsorption amounts of 1-hexene are 185.99, 166.64, 196.93, 177.58, 184.31 and 173.37 mg / g (calculated per gram of adsorbent). BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 is the synthesis route diagram of the synthesized sample in the embodiment;

[0028] Figure 2 is the solid-state nuclear magnetic resonance carbon spectrum of the synthesized sample in the embodiment;

[0029] Figure 3 is the scanning electron micrograph of the synthesized sample in the embodiment;

[0030] Figure 4 is the composite adsorption isotherm diagram of the synthesized samples a, b, c and d in the embodiment for 1-hexene / n-hexane;

[0031] Figure 5 is the schematic diagram of the linear fitting results of the synthesized samples a, b, c and d in the embodiment for 1-hexene / n-hexane;

[0032] Figure 6 is the composite adsorption isotherm diagram of the synthesized samples e and f in the embodiment for 1-hexene / n-hexane;

[0033] Figure 7 is the schematic diagram of the linear fitting results of the synthesized samples e and f in the embodiment for 1-hexene / n-hexane. DETAILED DESCRIPTION OF THE INVENTION

[0034] The present invention provides a method for preparing a hypercrosslinked polymer adsorbent for olefin and alkane separation, comprising the following steps:

[0035] Mixing a monomer, an acidic catalyst and a solvent to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer, wherein the monomer contains a benzene ring and the solvent contains a methylene group;

[0036] Sulfonating the hypercrosslinked polymer to obtain a sulfonation product;

[0037] Carrying out a hydrolysis reaction on the sulfonation product under alkaline conditions to obtain a hydrolysis product;

[0038] Carrying out ion exchange on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for olefin and alkane separation, and the metal ions used in the ion exchange include Ag + , Cu 2+ , Ni 2+ and Co 2+ or one or more of them.

[0039] In the present invention, unless otherwise specified, the raw materials used are all commercially available products in the art.

[0040] In the present invention, a monomer, an acidic catalyst and a solvent are mixed to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer, wherein the monomer contains a benzene ring and the solvent contains a methylene group.

[0041] In the present invention, the monomer preferably includes one or more of 4,4'-biphenyldimethyldimethylether (BMMBP), 1,3,5-triphenylbenzene (TPB) and 4,4'-dichloromethylbiphenyl (BCMBP).

[0042] In the present invention, the acidic catalyst preferably includes one or more of ferric chloride, aluminum chloride and chlorosulfonic acid.

[0043] In the present invention, the mechanism of the Friedel-Crafts alkylation reaction preferably includes: for BMMBP, methanol is removed under the catalysis of ferric chloride, and a hypercrosslinked polymer structure in which new methylene groups are formed between monomers for connection; for TPB, under the action of the catalyst aluminum chloride, the benzene rings form a hypercrosslinked polymer with new methylene groups connected between benzene rings by means of the solvent, and hydrogen chloride will be removed; for BCMBP, BCMBP removes hydrogen chloride under the catalysis of chlorosulfonic acid to form a hypercrosslinked polymer with new methylene groups connected between benzene rings.

[0044] In the present invention, the solvent preferably includes 1,2-dichloroethane and / or dichloromethane, and the functions of the solvent are: one is to dissolve the monomer to form a synthesis environment; the other is to act as a reaction reagent to form methylene groups connecting the monomers.

[0045] In the present invention, the molar ratio of the acidic catalyst to the monomer is preferably 0.5 to 8.0:1, more preferably 1 to 5:1.

[0046] In the present invention, the temperature of the Friedel-Crafts alkylation reaction is preferably 60 to 80 °C, more preferably 65 to 75 °C, and the time is preferably 18 to 48 h, more preferably 24 to 36 h.

[0047] In the present invention, the Friedel-Crafts alkylation reaction is preferably carried out in a nitrogen atmosphere.

[0048] In the present invention, it is preferred to first stir the monomer and the solvent evenly at room temperature, evacuate the air, introduce nitrogen protection, and then add the acidic catalyst to carry out the Friedel-Crafts alkylation reaction.

[0049] After the Friedel-Crafts alkylation reaction is completed, in the present invention, it is preferred to wash the obtained Friedel-Crafts alkylation reaction product with an organic solvent, and then carry out filtration and drying in sequence to obtain the hypercrosslinked polymer. The present invention has no special limitation on the type of the organic solvent. The present invention has no special limitation on the specific methods of the washing and filtration, and the methods well-known to those skilled in the art can be adopted. In the present invention, the drying is preferably rotary evaporation, and the present invention has no special limitation on the specific parameters of the rotary evaporation, as long as the organic solvent can be completely removed.

[0050] In the present invention, the hypercrosslinked polymer is a porous material, and the basic structure of the hypercrosslinked polymer is that benzene rings are connected by methylene groups.

[0051] After obtaining the hypercrosslinked polymer, in the present invention, the hypercrosslinked polymer is sulfonated to obtain a sulfonation product.

[0052] In the present invention, the sulfonating reagent used for sulfonation preferably includes chlorosulfonic acid or fuming sulfuric acid.

[0053] In the present invention, when the acidic catalyst preferably includes chlorosulfonic acid, the Friedel-Crafts alkylation reaction and sulfonation occur simultaneously. During the reaction process, it is preferred to react at 0 °C for 15 min first, and then react at 80 °C for 22 h.

[0054] In the present invention, the sulfonation is preferably carried out at room temperature, and the time is preferably 24 h. The sulfonation is carried out by reacting the sulfonic acid group with the benzene ring, and the hydrogen on the surface of the benzene ring will be replaced by the sulfonic acid group.

[0055] In the present invention, it is preferred to add the hypercrosslinked polymer to the sulfonating reagent and the organic solvent, stir to form a homogeneous system, and carry out the sulfonation. The present invention has no special limitation on the type of the organic solvent, and the types well-known to those skilled in the art can be adopted, such as dichloromethane specifically.

[0056] In the present invention, the dosage ratio of the hypercrosslinked polymer to the sulfonation reagent is preferably 0.8 - 1.0 g: 1.00 mL.

[0057] After the sulfonation is completed, in the present invention, the obtained solid is preferably washed successively with dichloromethane, anhydrous methanol and deionized water, filtered, rotary evaporated and dried to obtain the sulfonation product.

[0058] After obtaining the sulfonation product, the present invention carries out a hydrolysis reaction on the sulfonation product under alkaline conditions to obtain a hydrolysis product.

[0059] In the present invention, the alkaline condition is preferably provided by sodium hydroxide.

[0060] In the present invention, the temperature of the hydrolysis reaction is preferably 100 °C, and the time is preferably 2 - 4 h. The function of the hydrolysis reaction is to remove the C-Cl bonds formed on the benzene ring surface due to incomplete crosslinking reaction, preventing it from reacting with metals (such as Ag + ) to form precipitates or insoluble substances (such as AgCl), which may affect the adsorption performance.

[0061] In the present invention, the hydrolysis reaction is preferably carried out in an organic solvent - water environment, and the organic solvent is preferably N,N'-dimethylformamide.

[0062] After the hydrolysis reaction is completed, in the present invention, deionized water is preferably added to the obtained product for washing, then centrifuged, and hydrochloric acid is added to adjust the pH value of the obtained aqueous mixture to 4 - 5 to obtain the hydrolysis product.

[0063] After obtaining the hydrolysis product, the present invention carries out ion exchange on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for separating olefins and alkanes. The metal ions used in the ion exchange include Ag + , Cu 2+ , Ni 2+ and Co 2+ or one or more of them.

[0064] In the present invention, the dosage ratio of the hypercrosslinked polymer to the metal ions is preferably 1 g: 0.015 - 0.050 mol, more preferably 1 g: 0.0250 mol.

[0065] In the present invention, the temperature of the ion exchange is preferably room temperature, and the time is preferably 24 h. During the ion exchange process, the hydrogen ions in the sulfonic acid groups of the hydrolysis product are exchanged with the metal ions, and the sulfonic acid groups also have the function of anchoring the metal ions.

[0066] In the present invention, the metal ions are preferably added in the form of metal nitrates. The present invention preferably dissolves the metal nitrates in water to obtain a metal nitrate solution, and then disperses the hydrolysis product into the metal nitrate solution.

[0067] After the ion exchange is completed, the present invention preferably subjects the obtained product to centrifugal separation, washing, and rotary evaporation drying in sequence to obtain the hypercrosslinked polymer adsorbent for separating olefins and alkanes. The present invention has no special limitation on the specific parameters of the centrifugal separation, washing, and rotary evaporation drying.

[0068] The present invention also provides a hypercrosslinked polymer adsorbent for separating olefins and alkanes prepared by the preparation method described in the above technical solution.

[0069] The present invention also provides the application of the hypercrosslinked polymer adsorbent for separating olefins and alkanes described in the above technical solution in the field of separating olefins and alkanes.

[0070] In the present invention, the separation of olefins and alkanes is preferably the separation of liquid-phase olefins and alkanes.

[0071] In the present invention, the number of carbon atoms in the liquid-phase olefins and alkanes is preferably 6, 7, or 8.

[0072] To further illustrate the present invention, the hypercrosslinked polymer adsorbent for separating olefins and alkanes provided by the present invention, its preparation method, and application will be described in detail below with reference to examples, but they should not be construed as limiting the protection scope of the present invention.

[0073] Example 1

[0074] Preparation of Ag-containing + Hypercrosslinked polymer HCP-BMMBP-SO3-Ag +. Weigh 3.73 g of 4,4'-biphenyldimethyldimethylether (BMMBP) and add 50.00 mL of anhydrous 1,2-dichloroethane to a 250 mL four-necked flask. After purging with nitrogen and stirring for 30 min, add 4.98 g of anhydrous ferric chloride under the protection of nitrogen. The above mixture is heated to 80 °C and reacted for 48 h, then cooled to room temperature. The obtained solid product is collected by filtration through a Buchner funnel, washed with anhydrous methanol until the filtrate is colorless, and then 100.00 mL of anhydrous methanol is added to the obtained solid and stirred and washed for 24 h. After filtration, it is dried by rotary evaporation to obtain HCP-BMMBP. Weigh 2.40 g of HCP-BMMBP and 100.00 mL of anhydrous 1,2-dichloroethane, add them to a 250 mL four-necked flask, stir at room temperature for 5 min, and then add 3.00 mL of ClSO3H. After the mixture is stirred at room temperature for 18 h, it is filtered through a Buchner funnel, and then washed three times with 100.00 mL of dichloromethane, anhydrous methanol, and deionized water in sequence. After rotary evaporation and drying, HCP-BMMBP-SO3H-1 is obtained. Weigh 2.00 g of HCP-BMMBP-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide, and 8.00 mL of deionized water and add them together to a 100 mL single-necked flask. Heat to 100 °C and react for 4 h, then cool to room temperature. The obtained solid is centrifuged, washed, and the pH value of the filtrate is adjusted to 4 - 5 with dilute hydrochloric acid. After rotary evaporation and drying, HCP-BMMBP-SO3H is obtained. Weigh 1.00 g of HCP-BMMBP-SO3H and 25.00 mL of 1.00 M AgNO3 aqueous solution, exchange them under dark conditions at room temperature for 24 h. The obtained solid is centrifuged, washed, and dried by rotary evaporation to obtain product a. The corresponding synthetic route is shown in Figure 1 a in 13 By solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 C MAS NMR) analysis, the synthesized hypercrosslinked polymer HCP-BMMBP has the corresponding polymer structure, as shown in Figure 3 a in Figure 4 The composite adsorption isotherm obtained by fitting according to the liquid-phase adsorption model equation for the adsorption separation determination of product a for 1-hexene / n-hexane simulated oil is shown in Figure 5 a in

[0075] Example 2

[0076] Preparation of Ag + hypercrosslinked polymer HCP-TPB-SO3-Ag +. Weigh 3.06 g of 1,3,5-triphenylbenzene (TPB) and 120.00 mL of anhydrous dichloromethane, add them to a 250 mL four-necked flask, and stir evenly. Under the protection of nitrogen, weigh 9.96 g of anhydrous aluminum trichloride and quickly add it. Heat the above mixture to 60 °C and react for 36 h. Cool it to room temperature. Wash the obtained solid successively with deionized water and anhydrous ethanol, then add 100.00 mL of anhydrous ethanol, tetrahydrofuran, acetone, and anhydrous methanol respectively and stir and wash for 6 h. After rotary evaporation and drying, HCP-TPB is obtained. Weigh 2.40 g of HCP-TPB and 100.00 mL of anhydrous 1,2-dichloroethane and add them to a 250 mL four-necked flask. Stir at room temperature for 5 min, then add 3.00 mL of ClSO3H. Stir the above mixture at room temperature for 18 h, filter it using a Buchner funnel, and wash it three times successively with 100.00 mL of dichloromethane, anhydrous methanol, and deionized water. After rotary evaporation and drying, HCP-TPB-SO3H-1 is obtained. Weigh 2.00 g of HCP-TPB-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide, and 8.00 mL of deionized water and add them to a 100 mL single-necked flask. Heat to 100 °C and react for 4 h. Cool it to room temperature. Centrifuge, wash the obtained solid, and adjust the pH value of the filtrate to 4 - 5 using dilute hydrochloric acid. After rotary evaporation and drying, HCP-TPB-SO3H is obtained. Weigh 1.00 g of HCP-TPB-SO3H and then add 25.00 mL of 1.00 M AgNO3 aqueous solution. Exchange at room temperature in the dark for 24 h. Centrifuge, wash, and rotary evaporate and dry the obtained solid to get product b. The corresponding synthetic route is shown in Figure 1 b in 13 By solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 C MAS NMR) analysis, the polymer structure corresponding to the synthesized hypercrosslinked polymer HCP-TPB is shown in Figure 3 b in Figure 4 The composite adsorption isotherm obtained by fitting according to the liquid-phase adsorption model equation for the adsorption separation determination of product b for 1-hexene / n-hexane simulated oil is shown in Figure 5 b in

[0077] Example 3

[0078] Preparation of Ag + -containing hypercrosslinked polymer HCP-BCMBP-SO3-Ag +. Weigh 3.08 g of 4,4'-bis(chloromethyl)biphenyl (BCMBP) and add 30.00 mL of anhydrous 1,2-dichloroethane to a 100 mL four-necked flask. Cool the mixture to 0 °C and stir for 10 min. Under the protection of a nitrogen atmosphere and at 0 °C, a mixture of 1.22 mL of ClSO3H and 6.00 mL of anhydrous 1,2-dichloroethane is added dropwise. After stirring and reacting at 0 °C for 15 min, the reaction is continued at 80 °C for 22 h. Add 200.00 mL of anhydrous methanol to the reaction product, stir and wash at room temperature for 24 h, and then obtain HCP-BCMBP-SO3H-1 by rotary evaporation and drying. Weigh 2.00 g of HCP-BCMBP-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide and 8.00 mL of deionized water and add them to a 100 mL single-necked flask. React at 100 °C for 4 h, cool to room temperature, centrifuge, wash the obtained solid, and adjust the pH value of the filtrate to 4 - 5 with dilute hydrochloric acid, and then obtain HCP-BCMBP-SO3H by rotary evaporation and drying. Weigh 1.00 g of HCP-BCMBP-SO3H and 25.00 mL of 1.00 M aqueous AgNO3 solution, exchange them under dark conditions at room temperature for 24 h, centrifuge, wash and rotary evaporate and dry the obtained solid to get product c. The corresponding synthetic route is shown in Figure 1 c in 13 Solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 C MAS NMR) analysis shows that the synthesized hypercrosslinked polymer HCP-BCMBP has the corresponding polymer structure, as shown in Figure 3 c in Figure 4 The composite adsorption isotherm obtained by fitting according to the liquid-phase adsorption model equation is shown in Figure 5 c in

[0079] Example 4

[0080] Preparation of Cu-containing 2+ hypercrosslinked polymer HCP-BCMBP-SO3-Cu 2+. Weigh 3.08 g of 4,4'-bis(chloromethyl)biphenyl (BCMBP) and add 30.00 mL of anhydrous 1,2-dichloroethane to a 100 mL four-necked flask. Cool the mixture to 0 °C and stir for 10 min. Under the protection of a nitrogen atmosphere and at 0 °C, a mixture of 1.22 mL of ClSO3H and 6.00 mL of anhydrous 1,2-dichloroethane is added dropwise. After stirring and reacting at 0 °C for 15 min, the reaction is continued at 80 °C for 22 h. Add 200.00 mL of anhydrous methanol to the reaction product, stir and wash at room temperature for 24 h, and then obtain HCP-BCMBP-SO3H-1 by rotary evaporation and drying. Weigh 2.00 g of HCP-BCMBP-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide and 8.00 mL of deionized water and add them to a 100 mL single-necked flask. React at 100 °C for 4 h, cool to room temperature, centrifuge, wash the obtained solid, and adjust the pH value of the filtrate to 4 - 5 with dilute hydrochloric acid, and then obtain HCP-BCMBP-SO3H by rotary evaporation and drying. Weigh 1.00 g of HCP-BCMBP-SO3H and 25.00 mL of 1.00 M Cu(NO3)2 aqueous solution, exchange at room temperature in the dark for 24 h, centrifuge, wash and rotary evaporate and dry the obtained solid to get product d. The corresponding synthetic route is shown in Figure 1 d in 13 . Analyzed by solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 CMAS NMR), the synthesized hypercrosslinked polymer HCP-BCMBP is the corresponding polymer structure, as shown in Figure 3 c in Figure 4 . The composite adsorption isotherm obtained by fitting according to the liquid-phase adsorption model equation for product d is shown in Figure 5 d in

[0081] Example 5

[0082] Preparation of Ni 2+ -containing hypercrosslinked polymer HCP-BCMBP-SO3-Ni 2+. Weigh 3.08 g of 4,4'-bis(chloromethyl)biphenyl (BCMBP) and add 30.00 mL of anhydrous 1,2-dichloroethane to a 100 mL four-necked flask. Cool the mixture to 0 °C and stir for 10 min. Under the protection of a nitrogen atmosphere and at 0 °C, a mixture of 1.22 mL of ClSO3H and 6.00 mL of anhydrous 1,2-dichloroethane is added dropwise. After stirring and reacting at 0 °C for 15 min, the reaction is continued at 80 °C for 22 h. Add 200.00 mL of anhydrous methanol to the reaction product, stir and wash at room temperature for 24 h, and then obtain HCP-BCMBP-SO3H-1 by rotary evaporation and drying. Weigh 2.00 g of HCP-BCMBP-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide and 8.00 mL of deionized water and add them to a 100 mL single-necked flask. React at 100 °C for 4 h, cool to room temperature, centrifuge, wash the obtained solid, and adjust the pH value of the filtrate to 4 - 5 with dilute hydrochloric acid, and then obtain HCP-BCMBP-SO3H by rotary evaporation and drying. Weigh 1.00 g of HCP-BCMBP-SO3H and 25.00 mL of 1.00 M Ni(NO3)2 aqueous solution, exchange at room temperature in the dark for 24 h, centrifuge, wash and rotary evaporate and dry the obtained solid to get product e. The corresponding synthetic route is shown in Figure 1 e in 13 Solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 CMAS NMR) analysis shows that the synthesized hypercrosslinked polymer HCP-BCMBP has the corresponding polymer structure, as shown in Figure 3 c in Figure 6 The electron scanning microscope photograph (SEM) of product d is shown in Figure 7 e in

[0083] Example 6

[0084] Prepare Co 2+ -containing hypercrosslinked polymer HCP-BCMBP-SO3-Co 2+Weigh 3.08 g of 4,4'-bis(chloromethyl)biphenyl (BCMBP) and add 30.00 mL of anhydrous 1,2-dichloroethane to a 100 mL four-necked flask. Cool the mixture to 0 °C and stir for 10 min. Under the protection of a nitrogen atmosphere and at 0 °C, a mixture of 1.22 mL of ClSO3H and 6.00 mL of anhydrous 1,2-dichloroethane is added dropwise. After stirring and reacting at 0 °C for 15 min, the reaction is continued at 80 °C for 22 h. Add 200.00 mL of anhydrous methanol to the reaction product, stir and wash at room temperature for 24 h, and then obtain HCP-BCMBP-SO3H-1 by rotary evaporation and drying. Weigh 2.00 g of HCP-BCMBP-SO3H-1, 4.00 g of sodium hydroxide, 28.00 mL of N,N'-dimethylformamide, and 8.00 mL of deionized water and add them to a 100 mL single-necked flask. React at 100 °C for 4 h, cool to room temperature, centrifuge, wash the obtained solid, and adjust the pH value of the filtrate to 4 - 5 with dilute hydrochloric acid, and then obtain HCP-BCMBP-SO3H by rotary evaporation and drying. Weigh 1.00 g of HCP-BCMBP-SO3H and 25.00 mL of 1.00 M Co(NO3)2 aqueous solution, exchange at room temperature in the dark for 24 h, centrifuge, wash, and rotary evaporate and dry the obtained solid to get product f. The corresponding synthetic route is shown in Figure 1 f in 13 By solid-state nuclear magnetic resonance carbon spectrum ( Figure 2 CMAS NMR) analysis, the synthesized hypercrosslinked polymer HCP-BCMBP has the corresponding polymer structure, as shown in Figure 3 c in Figure 6 The composite adsorption isotherm obtained by fitting according to the liquid-phase adsorption model equation for product f is shown in Figure 7 f in

[0085] Table 1 shows the pore characteristics of the synthesized samples determined by nitrogen adsorption in the examples. It can be seen from Table 1 that the adsorbent prepared in the present invention has the advantages of high specific surface area, high adsorption capacity, and adsorption selectivity, and can achieve efficient separation of liquid-phase olefins and alkanes.

[0086] Table 1 Pore characteristics of the synthesized samples determined by nitrogen adsorption in the examples

[0087]

[0088] Note: a Obtained by the BET multipoint method; b Pore volume calculated from the nitrogen adsorption isotherm at P / P0 = 0.99; c Obtained by the t-plot method.

[0089] The hypercrosslinked polymer adsorbents for olefin and paraffin separation prepared in Examples 1 to 6 were applied to the selective adsorption separation of liquid-phase olefin / paraffin. Static adsorption tests were carried out at 30 °C. The composition of 1-hexene / n-hexane mixed oil products with different mole fractions before and after adsorption was tested by gas chromatography (GC), and analysis was carried out in combination with the liquid-phase adsorption model established based on the Langmuir adsorption model. The corresponding model equation is shown in Equation (1):

[0090]

[0091] where and are the mole fractions of olefin and paraffin in the oil product at adsorption equilibrium, respectively; n σ / m (mmol / g) is the molar amount of adsorbed molecules per unit mass of adsorbent; K is the average adsorption equilibrium constant; is the apparent adsorption amount.

[0092] Nonlinear fitting of the test results according to Equation (1) can obtain the composite adsorption isotherm of the above hypercrosslinked polymer. By linear fitting and parameter calculation of the test results according to Equation (1), the average adsorption equilibrium constants K of HCP-BMMBP-SO3-Ag + , HCP-TPB-SO3-Ag + , HCP-BCMBP-SO3-Ag + , HCP-BCMBP-SO3-Cu 2+ , HCP-BCMBP-SO3-Ni 2+ and HCP-BCMBP-SO3-Co 2+ are 14, 9, 20, 7, 18 and 16 respectively, and the saturated adsorption amounts of 1-hexene are 185.99, 166.64, 196.93, 177.58, 184.31 and 173.37 mg / g (calculated per gram of adsorbent), respectively.

[0093] The above is only the preferred embodiment of the present invention and does not impose any form of limitation on the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a hypercrosslinked polymer adsorbent for olefin and alkane separation, characterized in that, It includes the following steps: Mix a monomer, an acidic catalyst and a solvent to carry out a Friedel-Crafts alkylation reaction to obtain a hypercrosslinked polymer, wherein the monomer contains a benzene ring and the solvent contains a methylene group; Sulfonate the hypercrosslinked polymer to obtain a sulfonation product; Carry out a hydrolysis reaction on the sulfonation product under alkaline conditions to obtain a hydrolysis product; Ion exchange is performed on the hydrolysis product to obtain the hypercrosslinked polymer adsorbent for olefin and alkane separation, and the metal ions used in the ion exchange include Ag + , Cu 2+ , Ni 2+ and Co 2+ or one or more of them; The monomer includes one or more of 4,4'-biphenyldimethyldimethylether, 1,3,5-triphenylbenzene and 4,4'-dichloromethylbiphenyl.

2. The preparation method according to claim 1, wherein The acidic catalyst includes one or more of ferric chloride, aluminum chloride and chlorosulfonic acid.

3. The preparation method according to claim 1, characterized in that The solvent includes 1,2-dichloroethane and / or dichloromethane.

4. The preparation method according to claim 1 or 2, characterized in that, The molar ratio of the acidic catalyst to the monomer is 0.5-8.0:

1.

5. The preparation method according to claim 1, characterized in that, The temperature of the Friedel-Crafts alkylation reaction is 60-80°C and the time is 18-48 h.

6. The preparation method according to claim 1, characterized in that, The sulfonation reagent used for sulfonation includes chlorosulfonic acid or fuming sulfuric acid.

7. The preparation method according to claim 1, characterized in that, The dosage ratio of the hypercrosslinked polymer to the metal ion is 1 g: 0.015-0.050 mol.

8. A hypercrosslinked polymer adsorbent for separating olefins and alkanes prepared by the preparation method according to any one of claims 1-7.

9. Application of the hypercrosslinked polymer adsorbent for separating olefins and alkanes according to claim 8 in the field of separating olefins and alkanes.

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