CN114160096B - Adsorbent for separating ethylbenzene from carbon octa-aromatic hydrocarbons and preparation method thereof - Google Patents
Adsorbent for separating ethylbenzene from carbon octa-aromatic hydrocarbons and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an adsorbent for separating ethylbenzene from carbon eight aromatic hydrocarbon and a preparation method thereof2/Al2O3) 2.0-2.3, and the grain size is 0.5-5 μm, and the adsorbent is prepared by treating X zeolite by a combined treatment process of alkali metal ion exchange and surface silicon ester modification. The adsorbent can separate the ethylbenzene from the mixed carbon octa-arene, and the ethylbenzene product has higher purity and yield.
Description
Technical Field
The invention belongs to the technical field of zeolite type adsorbent preparation, and particularly relates to an adsorbent for separating ethylbenzene from mixed carbon octaarene through adsorption and a preparation method thereof.
Background
Ethylbenzene is an important basic chemical raw material, and more than 99 percent of ethylbenzene is used for producing styrene. In 2020, the demand of styrene in China is higher than 1100 ten thousand tons per year, the import quantity is kept above 250 ten thousand tons per year, and the market gap is obvious. In the face of the current complex international environment, the ethylbenzene production technology in China is further developed, and the method has obvious economic and strategic significance for making up the market gap of the downstream product styrene. The current ethylbenzene production technology is mainly benzene and ethylene alkylation. Due to the occurrence of excessive alkylation reaction, the alkylation technology is difficult to obtain good results on the conversion rate and the selectivity of raw materials at the same time, and has the disadvantages of high material consumption, high energy consumption, high investment cost and the like.
The adsorption separation method is a method for separating ethylbenzene by utilizing different adsorption capacities of an adsorbent to ethylbenzene and other carbon octaarene, and the main process is to selectively adsorb the ethylbenzene on the adsorbent, desorb the ethylbenzene by using a solvent under a certain condition, and obtain a high-purity ethylbenzene product through subsequent simple separation. Compared with alkylation method, the adsorption separation technology has the advantages of low material consumption, low energy consumption, high product yield, high purity and good application prospect. The ethylbenzene adsorption separation technology is mainly different from the technology, and the yield of ethylbenzene is increased mainly by separating ethylbenzene in catalytic reforming oil or ethylene pyrolysis gasoline by using a high-efficiency adsorbent. The development of the ethylbenzene adsorption separation technology can effectively relieve the waste of ethylbenzene resources contained in the conventional reformate and ethylene pyrolysis gasoline, effectively expand the ethylbenzene productivity in China, optimize the conventional aromatic hydrocarbon production process flow, and realize energy conservation and emission reduction.
At present, the technology for realizing industrial application in the field of adsorption separation is mainly separation of Paraxylene (PX) in carbon octaarene, and the large-scale popularization technology is a Parex process of American UOP company and an Eluxyl process of France Axens. The main components of the adsorbent used are barium ion-exchanged X-type zeolite. The following patents disclose the preparation of an adsorbent for adsorptive separation of ethylbenzene component from carbon octaaromatic hydrocarbons:
patent CN112573987A discloses a method for preparing ethylbenzene adsorbent, which uses rolling ball shaped X-type zeolite adsorbent as carrier, and adopts column type exchange method to exchange Cs ions to the surface of spherical carrier, and the exchange rate is higher than 60 mol%. The prepared adsorbent has excellent ethylbenzene separation performance. Mixed carbon octa-arene is used as a raw material, and after adsorption separation, the purity of the product ethylbenzene reaches 99.85wt%, and the yield reaches 95%.
Patent CN110871053A discloses a method for preparing adsorbent for separating ethylbenzene from carbon octaaromatic hydrocarbons. The adsorbent has a BEA/MFI core-shell structure, the cation position of the adsorbent is occupied by alkali metal ions, and the highest purity of ethylbenzene separated by adsorption is 99.9 wt%.
Patent US4079094 discloses the technical details of the EBex process developed by UOP for the separation of ethylbenzene in mixed carbon octaaromatics. The adsorbent is Sr and K exchanged faujasite (X or Y zeolite), and the technological form is simulated moving bed. Under certain separation conditions, the ethylbenzene component in the mixed carbon octaaromatic hydrocarbon can be separated, but the ethylbenzene component is separated from the raw material in the form of raffinate. The yield of the ethylbenzene product is more than 95 percent, and the purity of the ethylbenzene is more than 98 weight percent.
Patent US4584424 discloses a process for the preparation of an ethylbenzene adsorbent. The main component of the adsorbent is Beta zeolite, which can realize the separation of ethylbenzene from mixed carbon-eight aromatic hydrocarbons, and comparison shows that the Beta zeolite subjected to Cs ion exchange has a higher separation coefficient and performance superior to that of the adsorbent prepared by taking X zeolite as a matrix under the same condition. The adsorbent used is an alkylbenzene or heteroatom-substituted alkylbenzene, preferably p-diethylbenzene.
Patent US4613725 discloses a process for the preparation of an ethylbenzene adsorbent. The main component of the adsorbent is X zeolite, which can realize the separation of ethylbenzene from mixed carbon eight aromatic hydrocarbons. The ethylbenzene adsorbent is prepared by exchanging the zeolite X with Rb ions, and alkylbenzene substances are used as the adsorbent. It is also disclosed in the patent that doping the zeolite with a small amount of Al or Ga atoms does not have a major effect on the separation performance of the adsorbent.
The USP3724170 uses ZSM-5 zeolite and ZSM-8 zeolite or their mixture as adsorbent to adsorb and separate ethylbenzene and p-xylene from C-eight aromatic hydrocarbon, and uses silane as modified zeolite.
In addition, there are patents relating to the preparation of adsorbents based on zeolite molecular sieves for separating the ethylbenzene component of the C-octaaromatic hydrocarbons. For example, patents US104513124, US3997619, US4021499, US4107224, US4108915, US4175099, US4497972, US6177604, etc. all relate to the study of the preparation of ethylbenzene adsorbents or ethylbenzene separation processes.
In the operation process of the PX adsorption separation device, the water content of the adsorbent is controlled in a water injection mode so that the adsorbent can keep the optimal separation capacity, and the adsorbent has obvious water absorption in the operation process. However, for adsorptive separation of ethylbenzene from the carbon octaaromatics, it is desirable that the adsorbent be maintained at as low a water content as possible. The problem that is difficult to solve is that in the actual operation process of industrial devices, raw materials or desorbents inevitably contain trace moisture, and along with the extension of operation time, water molecules can be continuously accumulated on the adsorbent, so that the separation capacity of the adsorbent is reduced. However, none of the above patents relates to a method for improving the hydrophobic performance of an ethylbenzene adsorbent as much as possible on the premise of maintaining high ethylbenzene separation selectivity, so as to avoid the reduction of the separation performance due to water absorption in the use process. From this point, it is of obvious research significance to prepare an ethylbenzene adsorbent with certain hydrophobicity, so that the ethylbenzene adsorbent is not easy to lose separation performance due to water accumulation in the using process.
Disclosure of Invention
In order to separate high-yield and high-purity ethylbenzene products from mixed carbon octaarene and realize high-value utilization of an ethylbenzene component, the invention provides an adsorbent which takes X zeolite as a matrix, adds a proper amount of kaolin as a binder, forms a rolling ball to obtain X zeolite balls, and then separates the ethylbenzene component from the mixed carbon octaarene through a combined treatment mode of alkali metal ion exchange and surface silicon ester modification.
The invention provides a preparation method of an adsorbent for separating ethylbenzene in carbon octaarene, which comprises the following steps:
1) preparing the X zeolite into X zeolite balls with 20-50 meshes,
2) adding the X zeolite spheres into an alkali metal salt solution for alkali metal ion exchange, washing with deionized water, and drying to obtain alkali metal ion exchange X zeolite spheres;
3) then the alkali metal ion exchange X zeolite spheres are modified by surface organic silicon ester to improve the water-resistant stability of the alkali metal ion exchange X zeolite spheres, and the alkali metal ion exchange X zeolite spheres are dried and then roasted in inert atmosphere to obtain a finished adsorbent;
wherein the silica-alumina molar ratio of the X zeolite is 2.0-2.3 calculated by oxide; the grain size of the X zeolite is 0.5-5 mu m;
the organic silicon ester is one or more of ethyl orthosilicate, n-octyl trichlorosilane, vinyl trichlorosilane and methyl vinyl dichlorosilane.
In the technical scheme of the preparation method of the adsorbent for separating ethylbenzene from carbon octa-arene, the surface organic silicon ester modification preferably comprises the following steps: dissolving organosilicone into a cyclohexane solution to prepare a surface silicon modified organic solution, wherein the mass ratio of cyclohexane to organosilicone is 1-10: 1; and (3) placing the alkali metal ion exchange X zeolite balls into the surface silicon modified organic solution, and soaking for 12-24 hours at 15-50 ℃.
In the technical scheme of the preparation method of the adsorbent for separating ethylbenzene from carbon octaarene, the preparation method preferably comprises the following steps:
a) fully mixing the X zeolite powder and kaolin powder, wherein the kaolin accounts for 5-10% of the total material; putting the obtained mixed material into a rotary table of a sugar-coating machine, rolling and spraying water simultaneously to promote the powder to roll into balls, wherein the mass ratio of the total amount of the added water to the mixed material in the rolling process is 30-50 wt%; sieving the small balls with the particle size of 20-50 meshes, and drying the small balls for more than 10 hours at the temperature of 100-140 ℃ to obtain X zeolite small balls;
b) taking an alkali metal salt aqueous solution with the mass concentration of 5-15% as an alkali metal ion exchange solution;
c) putting the X zeolite spheres into an exchange kettle, adding the alkali metal ion exchange solution prepared in the step (b), carrying out ion exchange at the temperature of 70-95 ℃, wherein the exchange time is 1-10 h, washing the exchanged X zeolite spheres with deionized water after the exchange is finished, and then drying the washed and exchanged X zeolite spheres for more than 10 hours at the temperature of 180-250 ℃ to obtain the alkali metal ion exchange X zeolite spheres;
d) dissolving a certain amount of organic silicon ester in a cyclohexane solution to prepare a surface silicon modified organic solution, wherein the mass ratio of cyclohexane to organic silicon ester is 1-10: 1;
e) and (c) placing the alkali metal ion exchange X zeolite spheres obtained in the step (c) in the surface silicon modified organic solution obtained in the step (d), soaking at 15-50 ℃ for 12-24 hours, drying at 90-110 ℃ for more than 10 hours after soaking, and roasting at 400-600 ℃ for 4-10 hours in an inert gas atmosphere after drying to obtain the adsorbent for separating ethylbenzene in the carbon octaarene.
In the technical scheme of the preparation method of the adsorbent for separating ethylbenzene from carbon octaarene, the alkali metal salt preferably comprises one or more of cesium chloride, cesium nitrate, rubidium chloride, rubidium nitrate, potassium chloride and potassium nitrate.
Preferably, the ion exchange temperature is 85-95 ℃, and further, the temperature is controlled to be 90-95 ℃.
Preferably, the drying temperature of the washed and exchanged X zeolite balls is 220-230 ℃.
Preferably, the inert gas atmosphere comprises nitrogen, helium, argon or a mixture of the above gases.
The ethylbenzene adsorbent prepared by the invention can be applied to a simulated moving bed device, mixed carbon-octaarene is used as a raw material, and an ethylbenzene product with the purity of 99.7wt% is obtained through separation, wherein the ethylbenzene yield is higher than 95 wt%. In the adsorption separation process, a raw material inlet point, a desorbent inlet point, an extract liquid extraction point and a raffinate extraction point divide the whole adsorption tower into four areas: the area between the desorbent and the extract is a desorption area; the area between the extract and the adsorption feed is a refining area; the region between the adsorption feed and the raffinate is the adsorption zone; the region between the raffinate and desorbent is the separation zone. The whole adsorption tower is divided into 24 beds, the number of beds in an adsorption zone, a refining zone, a desorption zone and an isolation zone is respectively 8, 9, 5 and 2, the adsorption and separation temperature is 60-80 ℃, and the pressure is 0.6-1.0 MPa.
The method has the beneficial effects that the high-efficiency adsorbent for adsorbing and separating ethylbenzene in the mixed carbon-octaarene can be prepared by adopting X zeolite which is easy to synthesize and low in cost as a matrix and combining treatment methods such as alkali metal ion exchange, surface silicon ester modification and the like in a simple balling mode. The adsorbent provided by the invention is matched with a simulated moving bed adsorption separation process, so that a complete ethylbenzene adsorption separation process technology can be formed. The ethylbenzene adsorption separation device can also be grafted to the front of a PX adsorption separation unit in the aromatic hydrocarbon combined device, so that a high-purity ethylbenzene product can be obtained, the operation severity of the subsequent PX and isomerization units can be reduced, and the economic benefit of the aromatic hydrocarbon combined device is fully improved.
Detailed Description
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1:
(1) 5 kg of zeolite X was thoroughly mixed with 0.48 kg of kaolin to form a powder mixture. The powder is put into a rotary table of the sugar coating machine and sprayed with a proper amount of water while rolling, so that the powder is promoted to roll into balls. The total amount of water added during the whole rolling process is about 30wt% of the total mass of the powder. And screening the small balls with the particle size of 20-50 meshes, and drying for 10 hours at the temperature of 140 ℃.
(2) A solution for ion-exchanging the X zeolite beads was prepared by dissolving 3.4 kg of cesium chloride in 40L of deionized water.
(3) And (3) putting 4kg of the dried formed small balls in the step (1) into an exchange kettle, adding the small balls into the CsCl solution prepared in the step (2), and carrying out ion exchange at the temperature of 95 ℃ for 4 hours. After the exchange is finished, a large amount of deionized water is used for washing the exchanged pellets. Then, the washed pellets were dried at 200 ℃ for 10 hours.
(4) 1.49 kg of ethyl orthosilicate was dissolved in 15 kg of cyclohexane solution to prepare a solution for further surface silicon modification of the beads after ion exchange in (3).
(5) And (3) placing the dried pellets subjected to Cs ion exchange in (3) into the tetraethoxysilane solution prepared in (4), soaking for 12 hours at 25 ℃, and drying for 12 hours at 110 ℃ after soaking. After drying, the mixture is roasted for 4 hours at 550 ℃ in a muffle furnace under the nitrogen atmosphere.
(6) Evaluation of ethylbenzene adsorbent: mixed carbon octa-arene is used as an adsorption raw material, wherein the mass fraction of ethylbenzene is 17.1% (the specific composition is shown in table 1). The adsorbent is loaded into a small simulated moving bed, a countercurrent simulated moving bed adsorption separation process is adopted, the number of layers of the adsorption bed is 24, the adsorption separation temperature is 80 ℃, and the desorbent is toluene. Two materials are extracted from the simulated moving bed, one material is rich in ethylbenzene component (extract liquid), the other material is poor in ethylbenzene component (raffinate), and the ethylbenzene content in the two materials is analyzed. The results of the evaluation are shown in Table 2, experiment I.
(7) Ethylbenzene adsorbent evaluation under aqueous conditions: water is added into the mixed carbon eight aromatic hydrocarbon raw material to ensure that the water content in the mixed carbon eight aromatic hydrocarbon is 1000 mu g/g, other conditions are consistent with the step (6), and the evaluation results are shown in an experiment II in the table 2.
Example 2:
the total amount of water added in the ball rolling process in the step (1) is about 40wt% of the total mass of the powder, and other conditions are consistent with those of the example 1;
the alkali metal salt adopted in the step (2) is rubidium chloride, the adding amount is 2.42 kg, and other conditions are consistent with those of the example 1;
step (3) was the same as in example 1;
the organic silicon ester in the step (4) is vinyl trichlorosilane, the using amount is 3.86kg, and other conditions are the same as those in the example 1;
the roasting atmosphere in the step (5) is helium atmosphere, and other conditions are consistent with those in the example 1;
step (6) was the same as in example 1;
step (7) corresponds to example 1.
Example 3:
the total amount of water added in the rolling process in the step (1) is about 50wt% of the total mass of the powder, and other conditions are consistent with those of the example 1;
the alkali metal salt adopted in the step (2) is potassium chloride, the adding amount is 1.5 kg, and other conditions are consistent with those of the example 1;
step (3) was the same as in example 1;
the organic silicon ester adopted in the step (4) is methyl vinyl dichlorosilane, the using amount is 5.04kg, and other conditions are consistent with those of the embodiment 1;
the roasting atmosphere in the step (5) is argon atmosphere, and other conditions are consistent with those in the example 1;
step (6) was the same as in example 1;
step (7) corresponds to example 1.
Example 4:
step (1) was the same as in example 1;
step (2) was the same as in example 1;
the drying temperature of the pellets after the ion exchange in the step (3) is changed to 230 ℃, and other conditions are consistent with those in the embodiment 1;
step (4) was the same as in example 1;
step (5) was the same as in example 1;
step (6) was the same as in example 1;
step (7) corresponds to example 1.
Example 5:
step (1) was the same as in example 1;
step (2) was the same as in example 1;
step (3) was the same as in example 1;
the organosilicon ester adopted in the step (4) is n-octyl trichlorosilane, the dosage is 1.77 kg, and other conditions are consistent with those of the example 1;
step (5) was the same as in example 1;
step (6) was the same as in example 1;
step (7) corresponds to example 1.
Example 6:
example 1 was repeated, and the firing atmosphere in step (5) was changed to a helium atmosphere, and the other operation steps were not changed.
Comparative example 1:
(1) 5 kg of NaX zeolite was thoroughly mixed with 0.48 kg of kaolin to form a mixed powder. The powder is put into a rotary table of the sugar coating machine and sprayed with a proper amount of water while rolling, so that the powder is promoted to roll into balls. The total amount of water added in the whole rolling process is about 30 percent of the total mass of the powder. And screening the small balls with the particle size of 20-50 meshes, and drying for 10 hours at the temperature of 140 ℃.
(2) A solution for ion-exchanging the X zeolite beads was prepared by dissolving 3.4 kg of cesium chloride in 40L of deionized water.
(3) And (3) putting 4kg of the dried formed small balls in the step (1) into an exchange kettle, adding the small balls into the CsCl solution prepared in the step (2), and carrying out ion exchange at the temperature of 95 ℃ for 4 hours. After the exchange is finished, a large amount of deionized water is used for washing the exchanged pellets. Then, the washed pellets were dried at 200 ℃ for 10 hours. After drying, the mixture is roasted for 4 hours at 550 ℃ in a muffle furnace under the nitrogen atmosphere.
Comparative example 2:
comparative example 1 was repeated except that cesium chloride used in step (2) was changed to rubidium chloride, and the amount added was 2.42 kg, and the other operation steps were not changed.
TABLE 1 ethylbenzene adsorption separation of mixed C-octa-aromatic feedstock composition
| Components | Content wt. -%) |
| Ethylbenzene production | 17.10 |
| Para-xylene | 18.24 |
| Meta-xylene | 40.86 |
| Ortho-xylene | 23.29 |
| Toluene | 0.09 |
| Non-aromatic hydrocarbons | 0.37 |
| C9+ | 0.05 |
| Is totaled | 100 |
Table 2 composition of ethylbenzene extract from the adsorbent obtained by the methods described in example 1 and comparative example 1
Claims (9)
1. A preparation method of an adsorbent for separating ethylbenzene in carbon octaarene is characterized by comprising the following steps:
1) fully mixing the X zeolite powder and kaolin powder, wherein the kaolin accounts for 5-10% of the total material; putting the obtained mixed material into a rotary table of a sugar-coating machine, rolling and spraying water simultaneously to promote the powder to roll into balls, wherein the mass ratio of the total amount of the added water to the mixed material in the rolling process is 30-50 wt%; sieving the small balls with the particle size of 20-50 meshes, and drying the small balls for more than 10 hours at the temperature of 100-140 ℃ to obtain X zeolite small balls;
2) adding the X zeolite spheres into an alkali metal salt solution for alkali metal ion exchange, washing with deionized water, and drying to obtain alkali metal ion exchange X zeolite spheres;
3) modifying the alkali metal ion exchange X zeolite spheres by surface organic silicon ester to improve the water-resistant stability of the alkali metal ion exchange X zeolite spheres, drying the alkali metal ion exchange X zeolite spheres, and roasting the dried alkali metal ion exchange X zeolite spheres in an inert gas atmosphere to obtain a finished adsorbent;
wherein the silica-alumina molar ratio of the X zeolite is 2.0-2.3 calculated by oxide; the grain size of the X zeolite is 0.5-5 mu m;
the surface organic silicon ester modification comprises the following steps: dissolving organosilicone into a cyclohexane solution to prepare a surface silicon modified organic solution, wherein the mass ratio of cyclohexane to organosilicone is 1-10: 1; placing the alkali metal ion exchange X zeolite balls in the surface silicon modified organic solution, and soaking for 12-24 hours at 15-50 ℃;
the organic silicon ester is one or more of ethyl orthosilicate, n-octyl trichlorosilane, vinyl trichlorosilane and methyl vinyl dichlorosilane.
2. The method of claim 1, comprising the steps of:
a) fully mixing the X zeolite powder and kaolin powder, wherein the kaolin accounts for 5-10% of the total material; putting the obtained mixed material into a rotary table of a sugar coating machine, rolling and spraying water simultaneously to promote the powder to roll into balls, wherein the mass ratio of the total amount of the added water to the mixed material in the process of rolling the balls is 30-50 wt%; sieving the small balls with the particle size of 20-50 meshes, and drying the small balls for more than 10 hours at the temperature of 100-140 ℃ to obtain X zeolite small balls;
b) taking an alkali metal salt aqueous solution with the mass concentration of 5-15% as an alkali metal ion exchange solution;
c) putting the X zeolite spheres into an exchange kettle, adding the alkali metal ion exchange solution prepared in the step b), carrying out ion exchange at the temperature of 70-95 ℃, wherein the exchange time is 1-10 h, washing the exchanged X zeolite spheres with deionized water after the exchange is finished, and then drying the washed and exchanged X zeolite spheres for more than 10 hours at the temperature of 180-250 ℃ to obtain the alkali metal ion exchange X zeolite spheres;
d) dissolving a certain amount of organic silicon ester in a cyclohexane solution to prepare a surface silicon modified organic solution, wherein the mass ratio of cyclohexane to organic silicon ester is 1-10: 1;
e) placing the alkali metal ion exchange X zeolite balls obtained in the step c) in the surface silicon modified organic solution obtained in the step d), dipping for 12-24 hours at 15-50 ℃, drying for more than 10 hours at 90-110 ℃ after finishing dipping, and roasting for 4-10 hours at 400-600 ℃ in an inert gas atmosphere after finishing drying to obtain the adsorbent for separating ethylbenzene in the carbon octaarene.
3. The preparation method according to claim 1, wherein the alkali metal salt is one or more of cesium chloride, cesium nitrate, rubidium chloride, rubidium nitrate, potassium chloride and potassium nitrate.
4. The method according to claim 1, wherein the inert gas atmosphere is one or more of nitrogen, helium and argon.
5. The method according to claim 1, wherein the X zeolite has a grain size of 0.8 to 1 μm.
6. The method according to claim 2, wherein the temperature of the alkali metal ion exchange is 85 to 95 ℃.
7. The preparation method of claim 2, wherein the drying temperature of the X zeolite balls after washing and exchanging in the step c) is 220-230 ℃.
8. An adsorbent for separating ethylbenzene from carbon octa-aromatic hydrocarbons, prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the adsorbent of claim 8 in separation of ethylbenzene from C-eight aromatic hydrocarbons by simulated moving bed adsorptive separation process, wherein mixed C-eight aromatic hydrocarbons are used as adsorption raw materials, and ethylbenzene product with purity of 99.7wt% is obtained by separation, wherein the ethylbenzene yield is higher than 95 wt%.
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| CN112573985B (en) * | 2019-09-29 | 2023-04-07 | 中国石油化工股份有限公司 | From C 8 Method for producing paraxylene and ethylbenzene by aromatic hydrocarbon |
| CN113087585B (en) * | 2020-01-08 | 2023-01-06 | 中国石化工程建设有限公司 | Method for producing paraxylene and ethylbenzene from mixed C8 aromatic hydrocarbons |
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2022
- 2022-02-08 CN CN202210117567.1A patent/CN114160096B/en active Active
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- 2023-02-07 WO PCT/CN2023/074837 patent/WO2023151561A1/en unknown
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| CN101045671A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Method for adsorbing-crystal separation of paraxylene and ethylbenzene from C8 aromatic |
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| WO2023151561A1 (en) | 2023-08-17 |
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