CN112142545B - Method for separating isopropyl benzene and alpha-methyl styrene - Google Patents
Method for separating isopropyl benzene and alpha-methyl styrene Download PDFInfo
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 146
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000013078 crystal Substances 0.000 claims abstract description 61
- -1 perbromoethoxy Chemical group 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 description 17
- 239000002178 crystalline material Substances 0.000 description 14
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 238000003795 desorption Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001144 powder X-ray diffraction data Methods 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000510672 Cuminum Species 0.000 description 3
- 235000007129 Cuminum cyminum Nutrition 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 102100037279 Secretoglobin family 1D member 2 Human genes 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000006014 bromoethoxy group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000003988 headspace gas chromatography Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
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- 238000011069 regeneration method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/92—Systems containing at least three condensed rings with a condensed ring system consisting of at least two mutually uncondensed aromatic ring systems, linked by an annular structure formed by carbon chains on non-adjacent positions of the aromatic system, e.g. cyclophanes
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Abstract
The invention discloses a separation method of isopropyl benzene and alpha-methyl styrene, which utilizes perbromoethoxy column [6]]Aromatic hydrocarbon crystal material adsorbs and separates the mixture of isopropyl benzene and alpha-methyl styrene, and the perbromoethoxy column [6]]The structural formula of the aromatic hydrocarbon crystal material is as follows:
the separation process is simple to operate, complex equipment is not needed, and the operation safety is good; the separation does not need rectification operation, thereby saving energy and reducing production cost; the used crystal material has high stability, can be recycled, and the separation effect cannot be reduced.
Description
Technical Field
The invention relates to the technical field of adsorption separation, in particular to a method for separating isopropyl benzene and alpha-methyl styrene.
Background
Alpha-methyl styrene is used as a very important raw material in the petrochemical industry, is widely used in the fields of synthetic spices, resin, coatings and the like, and has wide market prospect. In recent years, as the field of application of α -methylstyrene is expanded, the purity requirement is also increased, and thus, it is widely regarded.
Currently, there are two major methods used in the industry for the synthesis of α -methylstyrene: by-product processes and dehydrogenation processes. The by-product method is a method in which alpha-methylstyrene is recovered as a by-product in the synthesis of acetone and phenol from propylene and benzene. However, this process generates a large amount of impurities, which greatly increases the cost required for purifying α -methylstyrene. The dehydrogenation method takes cumene as a raw material and directly generates alpha-methyl styrene through catalytic dehydrogenation under mild conditions. However, since the reaction conversion rate cannot reach 100%, a small amount of cumene impurity is always contained in the production process of alpha-methylstyrene, and the presence of such impurity adversely affects the further polymerization of alpha-methylstyrene. Therefore, how to separate cumene from alpha-methylstyrene becomes a key link for purifying alpha-methylstyrene.
Patent document CN 103052611 a discloses a method for producing α -methylstyrene from cumene. According to the selective hydrogenation process of cumene hydroperoxide obtained by oxidizing cumene, the explosion danger of cumene hydroperoxide generated along with the increase of concentration during the hydrogenation reaction is reduced, the selectivity of the cumene hydroperoxide is improved to more than 90 percent, and then the obtained hydrogenation product is separated by a distillation device to obtain high-purity alpha-methyl styrene.
However, the method requires high temperature in the distillation process, requires huge energy consumption and is not beneficial to the development of green energy in China; and the maintenance cost of the distillation equipment is high, the production cost of an enterprise is improved, and the economic benefit of the enterprise is reduced.
In conclusion, finding a novel method which can effectively separate cumene and alpha-methylstyrene and requires less energy consumption becomes the key of the purification of alpha-methylstyrene in the industry at present.
Disclosure of Invention
Aiming at the problems of high energy consumption, complex equipment, high operation risk coefficient and the like in the process of purifying alpha-methylstyrene in the industry and the defects in the field, the invention provides a method for separating isopropylbenzene and alpha-methylstyrene, which adopts a non-porous self-adaptive perbromoethoxy column [6] arene crystal material to purify the alpha-methylstyrene. The material can effectively absorb the cumene in high selectivity from the mixture of the cumene and the alpha-methylstyrene, and leave the high-purity alpha-methylstyrene, and the process has the advantages of low energy consumption, short balance time and simple operation.
Due to the difference of molecular structures of cumene and alpha-methylstyrene, the perbromoethoxyphenyl [6] arene crystalline material is capable of forming a host-guest complex with them in a stoichiometric ratio of 1: 1. Due to the difference of the stability of the host-guest complex and the difference of the molecular structures of the cumene and the alpha-methylstyrene, the perbromoethoxyphenyl column [6] arene crystal material can selectively adsorb the cumene in the mixture of the cumene and the alpha-methylstyrene. The all-bromine ethoxy column [6] arene crystal material is stable at the desorption temperature, can be repeatedly used after the desorption is finished, and the selectivity effect cannot be reduced.
A method for separating isopropyl benzene and alpha-methyl styrene is characterized in that a mixture of isopropyl benzene and alpha-methyl styrene is adsorbed and separated by utilizing a perbromoethoxy column [6] arene crystal material, wherein the perbromoethoxy column [6] arene crystal material has the following structural formula:
the preparation method of the perbromoethoxy column [6] arene crystal material comprises the following steps: adding 1, 1-dibromo-p-phenyl diethyl ether into a 1, 2-dichloroethane solvent, adding Lewis acid, reacting for 20-30 minutes at 25-30 ℃, quenching with a saturated solution of sodium bicarbonate after the reaction is finished, washing with water, separating liquid, concentrating to obtain a crude product, and performing column chromatography separation, drying and activation on the crude product to obtain the all-bromo ethoxy column [6] arene crystal material.
The drying and activating mode can be vacuum decompression drying and overnight removing solvent molecules at 100-150 ℃, so that the perbromoethoxy column [6] arene crystal material is activated. The activated perbromoethoxy column [6] arene crystal material can be directly used for the adsorption separation of isopropyl benzene and alpha-methyl styrene.
The method for separating the isopropylbenzene and the alpha-methyl styrene specifically comprises the following steps: putting the perbromoethoxy column [6] arene crystal material in a mixed steam atmosphere or a liquid mixture of isopropyl benzene and alpha-methyl styrene, wherein the temperature is 20-30 ℃.
The adsorption time can be determined according to the time for cumene to reach adsorption saturation.
Preferably, the volume ratio of cumene to alpha-methylstyrene in the mixed vapor or liquid mixture is 0.5 to 1.5: 1.
In the adsorption process, the cavity of the perbromoethoxy column [6] arene crystal material is opened to accommodate target molecules, so that the crystal form is changed. Cumene in a mixed vapor or liquid mixture will form a host-guest complex with perbromoethoxyphenyl [6] arene, due to multiple weak interactions of hydrogen bonds, CH-pi, in a stoichiometric ratio of 1: 1.
In the process of adsorbing and separating the mixture of the cumin and the alpha-methylstyrene by the perbromoethoxy column [6] arene crystal material, the surface of the perbromoethoxy column [6] arene crystal material can be adsorbed to form the mixture of the cumin and the alpha-methylstyrene. The mixture of cumene and alpha-methyl styrene absorbed on the surface of the perbromoethoxyprop [6] arene crystal material can be removed by adopting a normal pressure heating or reduced pressure heating mode.
Preferably, the temperature of the normal pressure heating or the reduced pressure heating is 30-50 ℃, and the complexing force of the host and the guest is not damaged under the condition, so that the host and guest complex still exist stably, and the mixture adsorbed on the surface can be removed gradually. The heating time may be specifically determined.
After the adsorption is finished, the perbromoethoxy column [6] arene crystal material can be desorbed by adopting a vacuum heating mode to adsorb the complexed cumene.
Preferably, the temperature of the vacuum heating is 100-150 ℃. The heating time may be specifically determined.
The temperature condition destroys the complexing action force of the host and the guest, absorbed cumene molecules can be gradually released, and the perbromoethoxy column [6] arene crystal material is stable and only changes the crystal form in the desorption process. The fully bromoethoxy column [6] arene crystal material after the desorption is restored to the initial activated state and can be continuously used for adsorbing and separating the isopropylbenzene and the alpha-methyl styrene for the next circulation. The selectivity of the perbromoethoxy column [6] arene crystal material to the cumin is not obviously changed after five times of absorption and desorption cycles.
The invention also provides application of the perbromoethoxy column [6] arene crystal material in selectively adsorbing cumene in a mixture of the cumene and alpha-methyl styrene.
Compared with the prior art, the invention has the main advantages that: the separation process is simple to operate, complex equipment is not needed, and the operation safety is good; the separation does not need rectification operation, thereby saving energy and reducing production cost; the used crystal material has high stability, can be recycled, and the separation effect cannot be reduced.
Drawings
FIG. 1 is a powder X-ray diffraction (PXRD) diagram of a perbromoethoxyphenyl column [6] arene crystal material and its adsorbed cumene and/or alpha-methylstyrene of examples 1-5;
FIG. 2 is a graph showing the effect of the single adsorption separation selectivity of the perbromoethoxyphenyl column [6] arene crystalline material of examples 4 and 5 on cumene and alpha-methylstyrene;
FIG. 3 is a graph showing the selectivity of the adsorption separation effect of the perbromoethoxyphenyl column [6] arene crystalline material of examples 7 and 8 on cumene and alpha-methylstyrene when recycled.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Preparing a crystal material of perbromoethoxy column [6] arene: preparing the perbromoethoxy column [6] arene by using 1, 1-dibromo-p-phenyl diethyl ether.
1, 1-dibromo-p-phenylenethylether (6.74g, 23.0mmol) was added to 100mL of 1, 2-dichloroethane, and BF was added3·O(C2H5)2(23.0-23.5 mmol), stirring the mixed solution at 25 ℃ for 20-30 minutes, quenching the mixed solution with a saturated sodium bicarbonate solution to finish the reaction, washing the mixed solution with deionized water twice, concentrating the organic phase under reduced pressure to obtain a crude product, and purifying the crude product by flash column chromatography (the volume ratio of petroleum ether to dichloromethane is 1:2) to obtain a perbromoethoxy column [6]]Aromatic hydrocarbon (1.20g, yield 16.9%) as white solid. Subjecting the white solid to a vacuum at 120 deg.CThe mixture is left in an air oven overnight to obtain activated perbromoethoxy column [6]]Aromatic hydrocarbon crystalline material, white powder, noted BrP 6.
The product prepared in this example has the following characterization data:
BrP6，1H NMR(400MHz,CDCl3，298K，ppm)δ6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H)。
PXRD detection results are shown in figure 1, and the obtained perbromoethoxy column [6] arene crystal material has good crystallinity.
Example 2
Adsorption of pure bromine ethoxy column [6] arene crystal material to single cumene or alpha-methyl styrene steam: taking two 20mL strain bottles, respectively adding 1mL cumene and alpha-methyl styrene which are named as BrP6@ IPB and BrP6@ AMS, respectively placing 20mg total bromoethoxy column [6] aromatic hydrocarbon crystal material into the two 5mL strain bottles, placing the two open 5mL strain bottles into the two 20mL strain bottles, sealing the 20mL strain bottles, placing the strain bottles at the normal temperature of 25 ℃ for 24 hours, and placing the obtained powder in an oven at the temperature of 40 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
BrP6@IPB,1H NMR(400MHz,CDCl3,298K,ppm)δ7.31–7.15(m,5H),6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.93–2.88(m,1H),1.26(d,J＝6.9Hz,6H)。
BrP6@AMS,1H NMR(400MHz,CDCl3,298K,ppm)δ7.49–7.46(m,2H),7.33(dd,J＝8.2,6.6Hz,2H),6.78(s,12H),5.37(s,1H),5.09–5.08(m,1H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.16(s,3H)。
1h NMR results showed ethoxy column [6]]Aromatic hydrocarbon crystalline materials are capable of adsorbing cumene and alpha-methylstyrene vapors in a stoichiometric ratio of 1: 1.
The PXRD detection result is shown in fig. 1a, and relative to the PXRD pattern of the initially activated perbromoethoxylbenzyl [6] arene crystalline material, the PXRD pattern of the perbromoethoxylbenzyl [6] arene crystalline material after being placed in steam of cumene and alpha-methylstyrene for a period of time is changed, which indicates that the unit cell parameters of the material are changed, i.e. both cumene and alpha-methylstyrene can be adsorbed into the perbromoethoxylbenzyl [6] arene crystalline material; but the PXRD spectrogram of the perbromoethoxyphenyl column [6] arene crystal material adsorbing the isopropyl benzene or the alpha-methyl styrene is different, which shows that the material shows different microcosmic crystal arrangement modes after adsorbing different components.
Example 3
The adsorption of the perbromoethoxy column [6] arene crystal material on single cumene or alpha-methyl styrene liquid: two 5mL strain bottles are taken, 1mL of cumene and alpha-methyl styrene which are named as BrP6@ LIPB and BrP6@ LAMS are respectively added into the two 5mL strain bottles, 20mg of perbromoethoxy column [6] aromatic hydrocarbon crystal material is respectively placed into the two 5mL strain bottles, the two 5mL strain bottles are sealed, the two 5mL strain bottles are placed at the normal temperature of 25 ℃ for 24 hours, liquid in the bottles is removed through filtration, and the obtained powder is placed in an oven at the temperature of 40 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
BrP6@LIPB,1H NMR(400MHz,CDCl3,298K,ppm)δ7.31–7.15(m,5H)，6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.93–2.88(m,1H),1.27–1.24(m,6H)。
BrP6@LAMS,1H NMR(400MHz,CDCl3,298K,ppm)δ7.49–7.46(m,2H),7.33(t,J＝7.4Hz,2H),6.78(s,12H),5.37(s,1H),5.09–5.07(m,1H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.16(s,3H)。
1h NMR results showed ethoxy column [6]]The aromatic hydrocarbon crystal material can adsorb cumene and alpha-methyl styrene liquid in a stoichiometric ratio of 1: 1.
The PXRD detection result is shown in fig. 1b, and relative to the PXRD pattern of the initially activated perbromoethoxylbenzyl [6] arene crystalline material, the PXRD pattern of the perbromoethoxylbenzyl [6] arene crystalline material after being placed in a liquid of cumene and alpha-methylstyrene for a period of time is changed, which indicates that the unit cell parameters of the material are changed, i.e. both cumene and alpha-methylstyrene can be adsorbed into the perbromoethoxylbenzyl [6] arene crystalline material; but the PXRD spectrogram of the perbromoethoxyphenyl column [6] arene crystal material adsorbing the isopropyl benzene or the alpha-methyl styrene is different, which shows that the material shows different microcosmic crystal arrangement modes after adsorbing different components.
Example 4
The adsorption of a perbromoethoxyphenyl column [6] arene crystal material to the steam of a mixture of cumene and alpha-methylstyrene in a volume ratio of 1: a20 mL seed bottle was taken, 1mL cumene and 1mL alpha-methylstyrene, designated as BrP6@ (IPB/AMS), 20mg of the perbromoethoxylyl [6] arene crystal material prepared in example 1 was placed in the 5mL seed bottle, the open 5mL seed bottle was placed in the 20mL seed bottle, the 20mL seed bottle was sealed, placed at room temperature of 25 ℃ for 24 hours, and the resulting powder was placed in an oven at 40 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
BrP6@(IPB/AMS),1H NMR(400MHz,CDCl3,298K,ppm)δ7.32–7.15(m,5H)，6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.90(dd,J＝13.7,6.8Hz 1H),1.26(d,J＝6.9Hz,6H)。
in that1Only the signal of the hydrogen atom corresponding to cumene was found in the H NMR spectrum, indicating that the perbromoethoxylene [6]]The aromatic hydrocarbon crystal material can selectively adsorb the cumene.
The PXRD detection result is shown in figure 1a, the adsorption separation selectivity effect is shown in figure 2a, and the result shows that the perbromoethoxyphenyl column [6] arene crystal material can selectively adsorb cumene, and the selectivity is 95.43%.
Example 5
The method comprises the following steps of (1) adsorbing a perbromoethoxyprop [6] arene crystal material to a cumene and alpha-methyl styrene mixture liquid with a volume ratio of 1: a5 mL seed bottle was taken, 1mL cumene and 1mL alpha-methylstyrene, designated BrP6@ L (IPB/AMS) were added, 20mg of the perbromoethoxyprop [6] arene crystal material prepared in example 1 was placed in the 5mL seed bottle, the 5mL seed bottle was sealed, placed at room temperature of 25 ℃ for 24 hours, the liquid in the bottle was removed by filtration, and the resulting powder was placed in an oven at 40 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
BrP6@L(IPB/AMS),1H NMR(400MHz,CDCl3,298K,ppm)δ7.34–7.15(m,5H)，6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.8Hz,24H),2.93–2.88(m,1H),1.25(d,J＝6.9Hz,6H)。
in that1Only the signal of the hydrogen atom corresponding to cumene was found in the H NMR spectrum, indicating that the perbromoethoxylene [6]]The aromatic hydrocarbon crystal material can selectively adsorb the cumene.
PXRD detection results are shown in figure 1b, adsorption separation selectivity effects are shown in figure 2b, and results show that the perbromoethoxylyl column [6] arene crystal material can selectively adsorb cumene, and the selectivity of the perbromoethoxylyl column [6] arene crystal material is 94.62 percent
Example 6
Regeneration of a perbromoethoxy column [6] aromatic hydrocarbon crystal material: 20mg of a crystalline material of perbromoethoxyphenyl column [6] arene saturated to adsorb cumene was heated in a vacuum oven at 120 ℃ for 12 hours and recorded as BrP 6-D.
The product characterization data obtained in this example are as follows:
BrP6-D,1H NMR(400MHz,CDCl3,298K,ppm)δ6.78(s,12H),4.16(t,J＝5.8Hz,24H),3.87(s,12H),3.55(t,J＝5.9Hz,24H)。
in that1The signal of the hydrogen atom corresponding to cumene was found to have disappeared in the H NMR spectrum, indicating that the perbromoethoxyphenyl column [6]The aromatic hydrocarbon crystal material has completed desorption regeneration, and the cumene molecule has been completely released.
Example 7
Cycle adsorption experiment of perbromoethoxyphenyl column [6] arene crystal material on cumene and alpha-methyl styrene mixture vapor: examples 4 and 6 were repeated in sequence using 20mg cycles of the regenerated perbromoethoxyphenyl column [6] aromatic hydrocarbon crystalline material of example 6.
The results of the headspace gas chromatography show that, as shown in fig. 3a, the perbromoethoxy column [6] arene crystal material can selectively adsorb cumene, and the selectivity of the perbromoethoxy column [6] arene crystal material is not obviously reduced in 5 times of cyclic adsorption experiments.
Example 8
Cycle adsorption experiment of perbromoethoxy column [6] arene crystal material on cumene and alpha-methyl styrene mixture liquid: examples 5 and 6 were repeated in sequence using 20mg cycles of the regenerated perbromoethoxyphenyl column [6] aromatic hydrocarbon crystalline material of example 6.
The results of the headspace gas chromatography show that, as shown in fig. 3b, the perbromoethoxy column [6] arene crystal material can selectively adsorb cumene, and the selectivity of the perbromoethoxy column [6] arene crystal material is not obviously reduced in 5 times of cyclic adsorption experiments.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A method for separating cumene and alpha-methyl styrene is characterized in that a mixture of the cumene and the alpha-methyl styrene is absorbed and separated by using a perbromoethoxy column [6] arene crystal material, wherein the perbromoethoxy column [6] arene crystal material has the following structural formula:
2. the separation method according to claim 1, wherein the separation method of cumene and alpha-methylstyrene is specifically: putting the perbromoethoxy column [6] arene crystal material in a mixed steam atmosphere or a liquid mixture of isopropyl benzene and alpha-methyl styrene, wherein the temperature is 20-30 ℃.
3. The separation process according to claim 2, wherein the volume ratio of cumene to alpha-methylstyrene in the mixed vapor or liquid mixture is 0.5 to 1.5: 1.
4. The separation method according to claim 1, wherein the mixture of cumene and alpha-methyl styrene adsorbed on the surface of the perbromoethoxyprop [6] arene crystal material is removed by heating under normal pressure or reduced pressure.
5. The separation method according to claim 4, wherein the temperature of the atmospheric heating or the reduced-pressure heating is 30 to 50 ℃.
6. The separation method according to claim 1, wherein the perbromoethoxylene [6] arene crystal material is desorbed by vacuum heating to adsorb the complexed cumene.
7. The separation method according to claim 6, wherein the temperature of the vacuum heating is 100 to 150 ℃.
8. The application of the perbromoethoxy column [6] arene crystal material in selectively adsorbing cumene in a mixture of the cumene and alpha-methyl styrene is characterized in that the perbromoethoxy column [6] arene crystal material has the following structural formula:
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