CN111362774A - Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound - Google Patents
Application of ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compound Download PDFInfo
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Abstract
The invention discloses an ethoxy column [6]]Use of aromatic hydrocarbon crystal material in selective adsorption of heterocyclic compounds, heterocyclesThe compound is at least one of pyridine, 2-methylthiophene and 3-methylthiophene, and ethoxy column [6]]The structural formula of the aromatic hydrocarbon crystal material is as follows:
the invention also discloses a method for separating toluene and a heterocyclic compound, which utilizes the ethoxy column [6]]The aromatic hydrocarbon crystal material adsorbs and separates the mixture of toluene and the heterocyclic compound. 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 field of adsorption separation, in particular to application of an ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compounds.
Background
Toluene is used as a very important chemical raw material in the petrochemical industry, is widely used in the fields of medicines, dyes, daily chemical industry and the like, and has wide market prospect. In recent years, as the toluene market application field is expanding, the purity requirement is also increasing, so that the toluene market is widely regarded as important.
Currently, commercial toluene is obtained mainly from petroleum and coal, and includes catalytic reforming, hydrocarbon cracking, and coking. However, in the production of toluene, a small amount of heterocyclic compounds including pyridine, 2-methylthiophene and 3-methylthiophene always remain. The presence of these heterocyclic compounds not only severely affects the toluene odor and acid wash color, but also limits its further processing utilization. Toluene (110.6 ℃ C.) had a poor purity because of the close boiling points of pyridine (115.2 ℃ C.), 2-methylthiophene (113.0 ℃ C.) and 3-methylthiophene (114.0 ℃ C.), making it difficult to remove these heterocyclic compounds. Therefore, how to separate toluene from heterocyclic compounds becomes a key link for toluene purification.
Chinese patent publication No. CN 102964200 a discloses a purification method of coking toluene. The patent firstly uses a 5A molecular sieve and acidic alumina as adsorbents to replace original fillers in a rectifying tower, and then coked toluene enters a tower kettle of the rectifying tower in a liquid phase form to carry out normal pressure continuous rectification. Wherein the temperature of the bottom of the rectifying tower is 115-130 ℃, the temperature of the top of the rectifying tower is 105-112 ℃, and the reflux ratio is 2.0-6.0. The method can well remove most harmful impurities and improve the purity of the toluene.
However, the temperature required in the rectification process of the method is high, huge energy consumption is required, and the method is not beneficial to the development of green energy in China; and the maintenance cost of the rectification 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 that can effectively separate toluene and heterocyclic compounds and requires less energy consumption becomes the key of toluene purification in the industry at present.
Disclosure of Invention
Aiming at the defects in the field, the invention provides the application of the ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compounds, and trace heterocyclic compounds can be adsorbed at high selectivity at normal temperature.
The application of the ethoxy column [6] arene crystal material in selective adsorption of a heterocyclic compound, wherein the heterocyclic compound is at least one of pyridine, 2-methylthiophene and 3-methylthiophene, and the structural formula of the ethoxy column [6] arene crystal material is as follows:
the invention also provides a separation method of toluene and a heterocyclic compound, wherein the mixture of toluene and the heterocyclic compound is adsorbed and separated by using the ethoxy column [6] arene crystal material, and the heterocyclic compound is at least one of pyridine, 2-methylthiophene and 3-methylthiophene.
The separation method adopts a non-porous self-adaptive ethoxy column [6] arene crystal material to purify toluene. The crystal material can effectively adsorb the heterocyclic compound in high selectivity from a mixture of toluene and the heterocyclic compound, has low energy consumption, short equilibrium time and simple operation, and solves the problems of high energy consumption, complex equipment, high operation risk coefficient and the like in the toluene purification process in the industry.
Due to the difference of the molecular structures of the toluene and the heterocyclic compound, the ethoxy column [6] arene crystal material can form a host-guest complex with different stoichiometric ratios with the toluene and the heterocyclic compound. Due to the difference of the stability of the host-guest complex, the ethoxy column [6] arene crystal material can selectively adsorb heterocyclic compounds. The ethoxy column [6] arene crystal material is stable at the desorption temperature, can be repeatedly used after the desorption is completed, and the selectivity effect cannot be reduced.
The preparation method of the ethoxy column [6] arene crystal material comprises the following steps: adding p-phenyl diethyl ether into a trichloromethane 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 ethoxy column [6] arene crystal material.
The ethyoxyl column [6] arene crystal material subjected to column chromatography separation can be activated by removing solvent molecules through vacuum reduced pressure drying and overnight mode at 100-140 ℃. The activated ethoxy column [6] arene crystal material can be directly used for the adsorption separation of toluene and heterocyclic compounds.
The separation method of the toluene and the heterocyclic compound comprises the following specific steps: placing the ethoxy column [6] aromatic hydrocarbon crystal material in a mixed steam atmosphere of toluene and a heterocyclic compound, wherein the temperature is 20-30 ℃, and the adsorption time is determined according to the time for the heterocyclic compound to reach adsorption saturation.
In the adsorption process, the cavity of the ethoxy column [6] arene crystal material is opened to accommodate gas molecules, so that the crystal form is changed. Due to multiple weak interactions of hydrogen bonds, CH-pi and pi-pi stacking, the heterocyclic compound in the mixed vapor and the ethoxypillared [6] arene form a host-guest complex with the stoichiometric ratio of 2:1 or 3: 1.
The volume ratio of the toluene to the heterocyclic compound in the mixed vapor is 1: 99-99: 1. The ethoxy column [6] arene crystal material is suitable for adsorption and separation of trace heterocyclic compounds.
In the process of adsorbing and separating the mixture of the toluene and the heterocyclic compound by the ethoxy column [6] aromatic hydrocarbon crystal material, the surface of the ethoxy column [6] aromatic hydrocarbon crystal material can adsorb to form the mixture of the toluene and the heterocyclic compound. The mixture of toluene and heterocyclic compound adsorbed on the surface of the ethoxy column [6] aromatic hydrocarbon crystal material can be removed by heating under normal pressure or reduced pressure.
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 vacuum heating mode can be adopted to desorb the heterocyclic compound adsorbed and complexed by the ethoxy column [6] arene crystal material.
Preferably, the temperature of the vacuum heating is 100-140 ℃. The heating time may be specifically determined.
The temperature condition destroys the complexing force of the host and the guest, the adsorbed heterocyclic compound molecules can be gradually released, and the ethyoxyl column [6] arene crystal material is stable and only changes the crystal form in the desorption process. And the desorbed ethoxy column [6] arene crystal material is restored to the initial activated state and can be continuously used for adsorbing and separating toluene and heterocyclic compounds for the next cycle. The selectivity of the ethoxy column [6] arene crystal material to heterocyclic compounds is not obviously changed after five times of adsorption and desorption cycles.
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) pattern of an ethoxyquin [6] arene crystalline material of examples 1 and 2 after adsorption of toluene and a heterocyclic compound, respectively;
FIG. 2 is a diagram showing the results of gas chromatography characterization of a binary mixture composed of toluene and three heterocyclic compounds by adsorption separation of an ethoxybased column [6] aromatic hydrocarbon crystal material of examples 3 to 5;
FIG. 3 is a graph showing selectivity of adsorption separation effect of the ethoxy column [6] arene crystal materials of examples 6 and 7 when recycled;
FIG. 4 is a graph showing the effect of adsorption separation of a four-component mixture of p-toluene, pyridine, 2-methylthiophene and 3-methylthiophene in the ethoxyphenyl [6] arene crystal material of example 8.
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 an ethoxy column [6] arene crystal material: preparing ethoxy column [6] arene by utilizing p-phenyl diethyl ether.
To 300mL of chloroform was added p-phenylethyther (6.00g, 36mmol), and BF was added3·O(C2H5)2(36-37 mmol), stirring the mixed solution at 25 ℃ for 20-30 minutes, quenching the mixed solution by using a saturated sodium bicarbonate solution to finish the reaction, washing the mixed solution twice by using deionized water, concentrating an organic phase under reduced pressure to obtain a crude product, and purifying the crude product by using flash column chromatography (the volume ratio of petroleum ether to dichloromethane is 1:4) to obtain the ethoxy column [6]]Aromatic hydrocarbons (1.20g, 15% yield) were white solids. The white solid was placed in a vacuum oven at 140 ℃ overnight to give activated ethoxypillars [6]]Aromatic hydrocarbon crystalline material, white powder, noted EtP 6.
The product prepared in this example has the following characterization data:
EtP6，1H NMR(400MHz,CDCl3，298K，ppm)δ6.69(s,12H),3.83(q,J＝6.4Hz,24H),3.79(s,12H),1.28(t,J＝6.4Hz,36H)。
PXRD detection results are shown in figure 1, and the obtained ethyoxyl column [6] arene crystal material has good crystallinity.
Example 2
Adsorption of an ethoxy column [6] aromatic hydrocarbon crystal material on single toluene or a heterocyclic compound: taking four 20mL strain bottles, respectively adding 2mL toluene, pyridine, 2-methylthiophene and 3-methylthiophene which are named as EtP6@ Tol, EtP6@ Py, EtP6@2-MTP and EtP6@3-MTP, respectively placing 30mg1 prepared ethyoxyl column [6] aromatic hydrocarbon crystal material in the four 5mL strain bottles, respectively placing the four open 5mL strain bottles in the four 20mL strain bottles, sealing the 20mL strain bottles, placing the strain bottles at the normal temperature of 25 ℃ for 12 hours, and placing the obtained powder in an oven at the temperature of 30 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
EtP6@Tol,1H NMR(400MHz,CDCl3,298K,ppm)δ7.18(d,J＝6.4Hz,3H),6.70(s,12H),3.82(dd,J＝13.9,6.9Hz,36H),2.36(s,3H),1.29(t,J＝7.0Hz,36H)。
EtP6@Py,1H NMR(400MHz,CDCl3,298K,ppm)δ8.65(s,4H),7.77(s,2H),7.37(d,J＝5.6Hz,4H),6.69(s,12H),3.81(dd,J＝13.9,6.9Hz,36H),1.28(t,J＝7.0Hz,36H)。
EtP6@2-MTP,1H NMR(400MHz,CDCl3,298K,ppm)δ7.08(dd,J＝5.2,1.1Hz,2H),6.90(dd,J＝5.1,3.4Hz,2H),6.76(dd,J＝2.2,1.1Hz,2H),6.70(s,12H),3.82(dd,J＝13.9,6.9Hz,36H),2.51(d,J＝0.9Hz,6H),1.28(t,J＝7.0Hz,36H)。
EtP6@3-MTP,1H NMR(400MHz,CDCl3,298K,ppm)δ7.24-7.22(m,2H),6.93-6.89(m,4H),6.69(s,12H),3.82(dd,J＝13.9,6.9Hz,36H),2.29(s,6H),1.28(t,J＝7.0Hz,36H)。
1h NMR results showed ethoxy column [6]]The aromatic hydrocarbon crystal material can adsorb toluene and heterocyclic compounds in a stoichiometric ratio mode.
The PXRD detection result is shown in fig. 1, and relative to the PXRD pattern of the initially activated ethoxy column [6] arene crystal material, the PXRD pattern of the ethoxy column [6] arene crystal material after being placed in toluene or heterocyclic compound vapor for a period of time all changes, which indicates that the unit cell parameters of the material change, i.e. toluene or heterocyclic compound can be adsorbed into the ethoxy column [6] arene crystal material; but PXRD spectrogram of the ethyoxyl column [6] aromatic hydrocarbon crystal material adsorbing the toluene or the heterocyclic compound is different, which shows that the material presents different microcosmic crystalline arrangement modes after adsorbing different components; in addition, the similarity of PXRD spectra of the ethyoxyl column [6] arene crystal material adsorbing the 2-methylthiophene and the 3-methylthiophene is higher, which shows that the material shows a similar microcosmic crystal arrangement mode after adsorbing the two components.
Example 3
Adsorption of an ethoxy column [6] arene crystal material to a toluene and pyridine mixture with a volume ratio of 1: a20 mL seed bottle was charged with 1mL toluene and 1mL pyridine, designated as EtP6@ (Tol/Py), 30mg of the ethoxyquin [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 12 hours, and the resulting powder was placed in an oven at 30 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
EtP6@(Tol/Py),1H NMR(400MHz,CDCl3,298K,ppm)δ8.62(d,J＝4.2Hz,4H),7.68(t,J＝7.6Hz,2H),7.31-7.28(m,23H),6.69(s,12H),3.81(dd,J＝13.9,6.9Hz,36H),1.28(t,J＝6.9Hz,36H)。
in that1The H NMR spectrum showed a strong signal for the hydrogen atom corresponding to pyridine and a weak signal for the hydrogen atom corresponding to toluene, indicating an ethoxy column [6]]The aromatic hydrocarbon crystal material can selectively adsorb pyridine.
The result of the headspace gas chromatography is shown in fig. 2a, and the result shows that the ethoxy column [6] arene crystal material can selectively adsorb pyridine, and the selectivity is 97.7%.
Example 4
Adsorption of an ethoxy column [6] arene crystal material to a mixture of toluene and 2-methylthiophene in a volume ratio of 1: a20 mL strain bottle was taken, 1mL of toluene and 1mL of 2-methylthiophene, which was named EtP6@ (Tol/2-MTP) were added thereto, 30mg of the ethoxycolumn [6] arene crystal material prepared in example 1 was placed in the 5mL strain bottle, the 5mL strain bottle was placed in the above 20mL strain bottle, the 20mL strain bottle was sealed, placed at room temperature of 25 ℃ for 12 hours, and the resulting powder was placed in an oven at 30 ℃ for 30 minutes.
The product characterization data obtained in this example are as follows:
EtP6@(Tol/2-MTP),1H NMR(400MHz,CDCl3,298K,ppm)δ7.08(dd,J＝5.2,1.1Hz,2H),6.90(dd,J＝5.1,3.4Hz,2H),6.78-6.74(m,2H),6.70(s,12H),3.82(dd,J＝13.9,6.9Hz,36H),2.51(d,J＝0.9Hz,6H),1.29(t,J＝7.0Hz,36H)。
in that1The H NMR spectrum only shows the signal of the hydrogen atom corresponding to 2-methylthiophene, while the signal of the hydrogen atom corresponding to toluene is very weak, which indicates that the ethoxy column [6]]The aromatic hydrocarbon crystal material can selectively adsorb 2-methylthiophene.
The result of the headspace gas chromatography is shown in fig. 2b, and the result shows that the ethoxy column [6] arene crystal material can selectively adsorb 2-methylthiophene, and the selectivity is 92.8%.
Example 5
Adsorption of an ethoxy column [6] arene crystal material to a mixture of toluene and 3-methylthiophene in a volume ratio of 1: a20 mL strain bottle was taken, 1mL of toluene and 1mL of 3-methylthiophene, which was named EtP6@ (Tol/3-MTP) were added thereto, 30mg of the ethoxycolumn [6] arene crystal material prepared in example 1 was placed in the 5mL strain bottle, the 5mL strain bottle was placed in the above 20mL strain bottle, the 20mL strain bottle was sealed, placed at room temperature of 25 ℃ for 12 hours, and the resulting powder was placed in an oven at 30 ℃ for 30 minutes.
The product prepared in this example has the following characterization data:
EtP6@(Tol/3-MTP),1H NMR(400MHz,CDCl3,298K,ppm)δ7.24-7.22(m,2H),6.91(dd,J＝3.6,0.9Hz,4H),6.69(s,12H),3.82(dd,J＝13.9,6.9Hz,36H),2.29(s,6H),1.28(t,J＝7.0Hz,36H)。
in that1The H NMR spectrum only shows the signal of the hydrogen atom corresponding to 3-methylthiophene, while the signal of the hydrogen atom corresponding to toluene is very weak, which indicates that the ethoxy column [6]]The aromatic hydrocarbon crystal material can selectively adsorb 3-methylthiophene.
The result of the headspace gas chromatography is shown in fig. 2c, and the result shows that the ethoxy column [6] arene crystal material can selectively adsorb 3-methylthiophene, and the selectivity is 89.9%.
Example 6
Regeneration of an ethoxy column [6] arene crystal material: 30mg of ethoxy column [6] arene crystal material saturated with adsorbed heterocyclic compounds is heated in a vacuum oven at 100 ℃ for 12 hours and is marked as EtP 6-D.
The product characterization data obtained in this example are as follows:
EtP6-D,1H NMR(400MHz,CDCl3,298K,ppm)δ6.69(s,12H),3.83(q,J＝6.4Hz,24H),3.79(s,12H),1.28(t,J＝6.4Hz,36H)。
in that1The signal of the hydrogen atom corresponding to the heterocyclic compound was found to have disappeared in the H NMR spectrum, indicating that the ethoxy column [6]The aromatic hydrocarbon crystal material has completed desorption regeneration, and the heterocyclic compound molecules have been completely released.
Example 7
Recycling of an ethoxy column [6] arene crystal material: example 3, 4 and 5 were repeated using 30mg of the regenerated ethoxypillared [6] arene crystalline material of example 6, respectively.
The result of headspace gas chromatography shows that, as shown in FIG. 3, the ethoxy column [6] arene crystal material can selectively adsorb heterocyclic compounds, and the selectivity of the material is not obviously reduced in 5-cycle adsorption experiments.
Example 8
Adsorption of an ethoxy column [6] arene crystal material to a mixture of four components of toluene, pyridine, 2-methylthiophene and 3-methylthiophene with a volume ratio of 96.5:1.5:1: two 20mL strain bottles are taken and named as A and B respectively, 0.2mL four-component mixed solution prepared in advance according to the proportion is added into the A, 400mg of the ethyoxyl column [6] arene crystal material prepared in example 1 is placed into the 5mL strain bottle, the 5mL strain bottle with an opening is placed into the 20mL strain bottle A, the two 20mL strain bottles of the A and the B are sealed, the mixture is placed for 12 hours at the normal temperature of 25 ℃, and the concentration of each component in the two strain bottles of the A and the B is measured.
The results of gas chromatography-mass spectrometry show that, as shown in FIG. 4, the ethoxy column [6] arene crystal material can selectively adsorb trace heterocyclic compounds, further improve the purity of toluene from 96.78% to 99.00%, further obtain high-purity toluene, and has great industrial application prospects.
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 (9)
1. The application of the ethoxy column [6] arene crystal material in selective adsorption of heterocyclic compounds is characterized in that the heterocyclic compounds are at least one of pyridine, 2-methylthiophene and 3-methylthiophene, and the structural formula of the ethoxy column [6] arene crystal material is as follows:
2. the method for separating the toluene and the heterocyclic compound is characterized in that a mixture of the toluene and the heterocyclic compound is adsorbed and separated by using an ethoxy column [6] arene crystal material, wherein the heterocyclic compound is at least one of pyridine, 2-methylthiophene and 3-methylthiophene, and the structural formula of the ethoxy column [6] arene crystal material is as follows:
3. the method for separating toluene and a heterocyclic compound according to claim 2, characterized in that the method for preparing the ethoxypillared [6] arene crystalline material comprises: adding p-phenyl diethyl ether into a trichloromethane 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 ethoxy column [6] arene crystal material.
4. The method for separating toluene and a heterocyclic compound according to claim 2, wherein the method for separating toluene and a heterocyclic compound specifically comprises: placing the ethoxy column [6] aromatic hydrocarbon crystal material in a mixed steam atmosphere of toluene and a heterocyclic compound, wherein the temperature is 20-30 ℃, and the adsorption time is determined according to the time for the heterocyclic compound to reach adsorption saturation.
5. The method according to claim 4, wherein the volume ratio of toluene to the heterocyclic compound in the mixed vapor is 1:99 to 99: 1.
6. The method for separating toluene from heterocyclic compounds according to claim 2, wherein the mixture of toluene and heterocyclic compounds adsorbed on the surface of the ethoxycolumn [6] aromatic hydrocarbon crystal material is removed by heating under normal pressure or under reduced pressure.
7. The method according to claim 6, wherein the temperature of the atmospheric heating or the reduced-pressure heating is 30 to 50 ℃.
8. The method for separating toluene from heterocyclic compounds according to claim 2, wherein the adsorbing and complexing heterocyclic compounds are desorbed by the crystal material of ethoxy column [6] arene by means of vacuum heating.
9. The method for separating toluene from a heterocyclic compound according to claim 8, wherein the temperature of the vacuum heating is 100 to 140 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142545A (en) * | 2020-09-29 | 2020-12-29 | 浙江大学 | Method for separating isopropyl benzene and alpha-methyl styrene |
| CN113061088A (en) * | 2021-04-09 | 2021-07-02 | 南通大学 | Asymmetric column [5] arene and preparation method and application thereof |
| CN114522668A (en) * | 2022-01-13 | 2022-05-24 | 浙江大学杭州国际科创中心 | Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole |
| CN114773258A (en) * | 2022-05-10 | 2022-07-22 | 浙江大学杭州国际科创中心 | Separation and purification method of 2, 6-dimethylpyridine |
| CN115536486A (en) * | 2022-09-05 | 2022-12-30 | 北京理工大学 | High-selectivity separation method of benzene and cyclohexane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964200A (en) * | 2012-11-26 | 2013-03-13 | 北京旭阳化工技术研究院有限公司 | Purifying method of coking toluene |
| CN107586554A (en) * | 2017-09-20 | 2018-01-16 | 中国石油大学(华东) | It is a kind of to be used to remove the refining agent of organic nitrogen compound and thiophene-type sulfide in fuel oil |
| CN110372580A (en) * | 2019-06-20 | 2019-10-25 | 浙江大学 | A kind of separation method of 2- chloropyridine and 3- chloropyridine |
-
2020
- 2020-03-03 CN CN202010138825.5A patent/CN111362774B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964200A (en) * | 2012-11-26 | 2013-03-13 | 北京旭阳化工技术研究院有限公司 | Purifying method of coking toluene |
| CN107586554A (en) * | 2017-09-20 | 2018-01-16 | 中国石油大学(华东) | It is a kind of to be used to remove the refining agent of organic nitrogen compound and thiophene-type sulfide in fuel oil |
| CN110372580A (en) * | 2019-06-20 | 2019-10-25 | 浙江大学 | A kind of separation method of 2- chloropyridine and 3- chloropyridine |
Non-Patent Citations (2)
| Title |
|---|
| QING LI 等: "Highly Selective Separation of Minimum-Boiling Azeotrope Toluene/Pyridine by Nonporous Adaptive Crystals of Cucurbit[6]uril", 《ANGEW. CHEM. INT. ED.》 * |
| WEIWEI YANG 等: "Tiara[5]arenes: Synthesis, Solid-State Conformational Studies, Host–Guest Properties, and Application as Nonporous Adaptive Crystals", 《ANGEW. CHEM. INT. ED.》 * |
Cited By (9)
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|---|---|---|---|---|
| CN112142545A (en) * | 2020-09-29 | 2020-12-29 | 浙江大学 | Method for separating isopropyl benzene and alpha-methyl styrene |
| CN112142545B (en) * | 2020-09-29 | 2021-08-31 | 浙江大学 | Method for separating isopropyl benzene and alpha-methyl styrene |
| CN113061088A (en) * | 2021-04-09 | 2021-07-02 | 南通大学 | Asymmetric column [5] arene and preparation method and application thereof |
| CN113061088B (en) * | 2021-04-09 | 2023-05-02 | 南通大学 | Asymmetric column [5] arene and preparation method and application thereof |
| CN114522668A (en) * | 2022-01-13 | 2022-05-24 | 浙江大学杭州国际科创中心 | Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole |
| CN114522668B (en) * | 2022-01-13 | 2023-10-13 | 浙江大学杭州国际科创中心 | Application of ethoxy column [6] arene crystal material in selective adsorption of tetrahydropyrrole |
| CN114773258A (en) * | 2022-05-10 | 2022-07-22 | 浙江大学杭州国际科创中心 | Separation and purification method of 2, 6-dimethylpyridine |
| CN114773258B (en) * | 2022-05-10 | 2023-08-11 | 浙江大学杭州国际科创中心 | Separation and purification method of 2, 6-lutidine |
| CN115536486A (en) * | 2022-09-05 | 2022-12-30 | 北京理工大学 | High-selectivity separation method of benzene and cyclohexane |
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