Composite adsorbent for separation of ethylbenzene by adsorption distillation and application thereof

Abstract

A composite adsorbent for separating ethylbenzene from C8 arene by an adsorption distillation contains 1-50 mass % of a xylene adsorbent and 50-99 mass % of a carrier liquid. The carrier liquid is selected from one or two of alkane, aryl-substituted alkane, decalin and alkyl-substituted decalin. The alkane is C10-C26 alkane, and the aryl-substituted alkane is C13-C16 aryl-substituted alkane. The composite adsorbent can increase the volatility of ethylbenzene relative to other C8 arenes and thus can separate a high-purity ethylbenzene from C8 arene by the adsorption distillation.

Claims

1. A composite adsorbent for separating ethylbenzene from C.sub.8 arene by an adsorption distillation, including 1-50 mass % of a xylene adsorbent and 50-99 mass % of a carrier liquid, wherein the carrier liquid is selected from one or two of alkane, aryl-substituted alkane, decalin and alkyl-substituted decalin, the alkane is C.sub.10-C.sub.26 alkane, and the aryl-substituted alkane is C.sub.13-C.sub.16 aryl-substituted alkane.

2. The composite adsorbent according to claim 1, characterized in that the composite adsorbent includes 5-35 mass % of the xylene adsorbent and 65-95 mass % of the carrier liquid.

3. The composite adsorbent according to claim 1, characterized in that the xylene adsorbent is a Y molecular sieve with Group IA and/or Group IIA metal ions occupying cation sites.

4. The composite adsorbent according to claim 3, characterized in that the xylene adsorbent is a NaY molecular sieve.

5. The composite adsorbent according to claim 3, characterized in that a grain size of the Y molecular sieve is 0.1-2 microns.

6. The composite adsorbent according to claim 1, characterized in that the alkane is C.sub.10-C.sub.24 n-alkane; the aryl-substituted alkane is C.sub.13-C.sub.16 diphenyl alkane; the alkyl of the alkyl-substituted decalin is C.sub.1-C.sub.12 alkyl and the number of the substituting alkyl is 1-4.

7. The composite adsorbent according to claim 6, characterized in that the alkane is C.sub.1-C.sub.20 n-alkane; and the alkyl of the alkyl-substituted decalin is C.sub.3-C.sub.10 alkyl.

8. A method for separating ethylbenzene by an adsorption distillation, comprising: introducing a C.sub.8 arene mixture into a middle part of an adsorption distillation column (3), introducing the composite adsorbent of claim 1 into an upper part of the adsorption distillation column (3), after the adsorption distillation, withdrawing ethylbenzene from the top of the adsorption distillation column, withdrawing the composite adsorbent enriched with xylene from the bottom of the column and subjecting it to a middle part of a distillation desorption column (4), after a distillation desorption, withdrawing a mixed xylene from the top of the column, obtaining a regenerated composite adsorbent at the bottom of the column and returning it to the upper part of the adsorption distillation column for reuse.

9. The method according to claim 8, characterized in that an overhead pressure of the adsorption distillation column is 0.01-0.2 MPa; a theoretical plate number is 30-100; the composite adsorbent enters the column at a temperature of 90-130° C.; and a column bottom temperature is 140-250° C.

10. The method according to claim 9, characterized in that a mass ratio of the xylene adsorbent in the composite adsorbent entering the adsorption distillation column to the C.sub.8 arene mixture is 1.5 to 6; a mass ratio of the carrier liquid to the xylene adsorbent is 1.5 to 20; a reflux ratio is 1 to 15.

11. The method according to claim 8, characterized in that an overhead pressure of the distillation desorption column is 0.01-0.15 MPa; a theoretical plate number is 20-50; and a bottom temperature is 160-280° C.

12. The method according to claim 11, characterized in that a reflux ratio of the distillation desorption column is 0.3-3.

13. The method according to claim 8, characterized in that the content of ethylbenzene in the C.sub.8 arene mixture is 10-85 mass %.

Description

DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is a flowchart of the method provided in the present invention for separating ethylbenzene from C.sub.8 arene by the adsorption distillation.

MODE OF CARRYING OUT THE INVENTION

[0013] The composite adsorbent provided in the present invention comprises a xylene adsorbent and a carrier liquid. The said xylene adsorbent adsorbs xylene during the adsorption distillation, making it easy to separate ethylbenzene from xylene in C.sub.8 arene. The said carrier liquid is used to carry the xylene adsorbent to flow. It does not react with C.sub.8 arene, and its boiling point is preferably above 180° C. In this way, it is possible that the carrier liquid does not volatilize to the top of the adsorption distillation column during the adsorption distillation, and carries the adsorbent that adsorbs xylene into the distillation desorption column. The xylene in the adsorbent is desorbed in the distillation desorption column. The carrier liquid carries the regenerated xylene adsorbent and returns to the adsorption distillation column for reuse. The composite adsorbent can significantly increase the relative volatility of ethylbenzene relative to the respective isomers of xylene, and thus can separate a high-purity ethylbenzene from C.sub.8 arene by the adsorption distillation.

[0014] The xylene adsorbent in the composite adsorbent of the present invention is used to increase the relative volatility of ethylbenzene relative to the respective isomers of xylene, and the carrier liquid is used to carry the xylene adsorbent to flow. The composite adsorbent preferably includes 5-35 mass % of the xylene adsorbent and 65-95 mass % of the carrier liquid.

[0015] The xylene adsorbent is preferably a Y molecular sieve with Group IA and/or Group IIA metal ions occupying cation sites, wherein the Group IA metal ions are preferably Li.sup.+ or Na.sup.+, the Group IIA metal ions are preferably Sr.sup.2+ or Ba.sup.2+, more preferably a NaY molecular sieve.

[0016] The grain size of the Y molecular sieve is preferably 0.1˜2 microns, more preferably 0.2-1.5 microns.

[0017] The carrier liquid is selected from one or arbitrary two of alkane, aryl-substituted alkane, decalin and alkyl-substituted decalin, wherein the said alkane may be n-alkane or isoalkane, preferably C.sub.10-C.sub.24 n-alkane, more preferably C.sub.11-C.sub.20 n-alkane.

[0018] The said aryl-substituted alkane is preferably C.sub.13-C.sub.16 diphenyl alkane.

[0019] The alkyl of the said alkyl-substituted decalin may be C.sub.1-C.sub.12 alkyl, preferably C.sub.3-C.sub.10 alkyl, more preferably C.sub.2-C.sub.6 alkyl. The number of the substituting alkyl can be 1-4, preferably 1-2.

[0020] The method for separating ethylbenzene by the adsorption distillation provided in the present invention comprises introducing the C.sub.8 arene mixture into the middle part of the adsorption distillation column and introducing the composite adsorbent of the present invention into the upper part of the adsorption distillation column. After the adsorption distillation, ethylbenzene is withdrawn from the top of the adsorption distillation column, and the composite adsorbent enriched with xylene is withdrawn from the bottom of the column and enters the middle part of the distillation desorption column. After the distillation desorption, a mixed xylene is withdrawn from the top of the column, and the regenerated composite adsorbent is obtained at the bottom of the column and is returned to the upper part of the adsorption distillation column for reuse.

[0021] In the above method, the overhead pressure of the adsorption distillation column is preferably 0.01-0.2 MPa. The theoretical plate number is preferably 30-100, more preferably 30-80. The composite adsorbent enters the column at a temperature of preferably 90-130° C., the column bottom temperature is preferably 140-250° C., and the overheard temperature is preferably 70-100° C.

[0022] The mass ratio of the composite adsorbent entering the adsorption distillation column to the C.sub.8 arene mixture is preferably 5 to 30, more preferably 8 to 23; the mass ratio of the xylene adsorbent in the composite adsorbent to the C.sub.8 arene mixture is preferably 1.5 to 6, more preferably 2 to 5; the mass ratio of the carrier liquid to the xylene adsorbent is preferably 1.5 to 20, more preferably 2 to 10. The reflux ratio at the upper part of the column is preferably 1 to 15, and more preferably 1 to 8.

[0023] The overhead pressure of the distillation desorption column is preferably 0.01-0.15 MPa, more preferably 0.01-0.06 MPa; the theoretical plate number is preferably 20-50, more preferably 25-45; the bottom temperature is preferably 160-280° C., and the overhead temperature is preferably 60-90° C. The reflux ratio at the upper part of the distillation desorption column is preferably 0.3-3, more preferably 0.5-2.

[0024] In the above method, the reflux ratio is the mass ratio of the materials returning to the upper part of the column to the materials discharged from the top of the column.

[0025] The said adsorption distillation column and the said distillation desorption column may be a packed column or a plate column.

[0026] In the method of the invention, the content of ethylbenzene in the C.sub.8 arene mixture is preferably 10-85 mass %, more preferably 15-60 mass %.

[0027] In the adsorption distillation, the relative volatility is used to measure the separation effect of the solvents. The relative volatility (a) refers to the ratio of the volatility of the easily volatile component i to the volatility of the difficultly involatile component j in the solution to be separated, which can reflect the difficulty degree of separating the two components during the distillation process. The relative volatility of the two components i and j to be separated when reaching the gas-liquid equilibrium is calculated according to formula (1):

[00001]$\begin{array}{cc}{\alpha }_{i/j}=\frac{y_i/x_i}{y_j/x_j}& \left(1\right)\end{array}$

[0028] In formula (1), x is the liquid phase mole fraction of the component under the equilibrium state, and y is the gas phase mole fraction of the component under the equilibrium state. When a is 1, the volatilities of the two components are equal, indicating that the two components cannot be separated by an adsorption distillation; when a is greater than 1, the higher the value of a is, the easier it is to separate the two components by the adsorption distillation.

[0029] The invention is further described below through the drawing.

[0030] In FIG. 1, a C.sub.8 arene mixture from pipeline 1 is introduced into the middle part of the adsorption distillation column 3. The composite adsorbent is introduced from pipeline 2 into the upper part of the adsorption distillation column. The C.sub.8 arene is in countercurrent contact with the composite adsorbent in the column for the adsorption and the distillation. The xylene in the C.sub.8 arene is adsorbed by the xylene adsorbent. The ethylbenzene is distilled to the overhead and withdrawn from the overhead pipeline 7, and an ethylbenzene product is obtained after condensation. The composite adsorbent that adsorbed xylene is withdrawn from the bottom of the adsorption distillation column and enters the middle part of the distillation desorption column 4 through pipeline 5. The xylene is desorbed from the composite adsorbent through distillation to realize the desorption and the regeneration of the xylene adsorbent. The desorbed xylene is withdrawn from the overhead pipeline 8 of the distillation desorption column and condensed to obtain xylene. The regenerated composite adsorbent is withdrawn from the bottom of the distillation desorption column, and returned via pipeline 6 and pipeline 2 to the adsorption distillation column for reuse. The said xylene basically contains no ethylbenzene and can be used as an isomerization raw material to produce p-xylene.

[0031] The present invention is further illustrated by the following examples, but the present invention is not limited thereto.

[0032] In the examples and the comparative examples, the method for determining the relative volatility of the respective components of the C.sub.8 arene is: adding the sample to be tested into the Agilent 7694 headspace sampler, letting it stand for certain time, determining the gas and liquid phase compositions in the sampler using Agilent 7890 chromatography when the gas-liquid equilibrium is reached, and calculating the relative volatility of the components according to Formula (1).

Example 1

[0033] Ethylbenzene, p-xylene, o-xylene, m-xylene were mixed according to the same mass ratio to formulate a C.sub.8 arene mixture as the feedstock oil. The content of ethylbenzene in the feedstock oil is 25 mass %. A NaY molecular sieve powder with a grain size of 0.2-1 m was used as the xylene adsorbent, and n-tetradecane was used as the carrier liquid. The xylene adsorbent was mixed with the carrier liquid to produce a composite adsorbent having a xylene adsorbent content of 20 mass % and a carrier liquid content of 80 mass %.

[0034] The composite adsorbent and the feedstock oil were added to the headspace sampler, wherein the mass ratio of the carrier liquid/the xylene adsorbent/the feedstock oil was 8:2:1, and the mass ratio of the composite adsorbent to the feedstock oil was 10:1, and was let stand at 80° C. for 45 minutes to achieve the gas-liquid equilibrium. The gas and liquid phases were respectively taken for a composition analysis. The determined relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent are shown in Table 1.

Example 2

[0035] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of the carrier liquid/the xylene adsorbent/the feedstock oil as used was 8:3:1 and the mass ratio of the composite adsorbent to the feedstock oil was 11:1. The result is shown in Table 1.

Example 3

[0036] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of the carrier liquid/the xylene adsorbent/the feedstock oil as used was 8:4:1 and the mass ratio of the composite adsorbent to feedstock oil was 12:1. The result is shown in Table 1.

Example 4

[0037] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of the carrier liquid/the xylene adsorbent/the feedstock oil as used was 13:2:1 and the mass ratio of the composite adsorbent to the feedstock oil was 15:1. The result is shown in Table 1.

Example 5

[0038] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of the carrier liquid/the xylene adsorbent/the feedstock oil as used was 18:2:1 and the mass ratio of the composite adsorbent to the feedstock oil was 20:1. The result is shown in Table 1.

Example 6

[0039] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the used carrier liquid was n-undecane. The result is shown in Table 1.

Example 7

[0040] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the used carrier liquid was n-hexadecane. The result is shown in Table 1.

Example 8

[0041] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the used carrier liquid was diphenylmethane. The result is shown in Table 1.

Examples 9-10

[0042] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the used carrier liquids were respectively butyldecalin and decalin. The result is shown in Table 1.

Example 11

[0043] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of ethylbenzene/p-xylene/o-xylene/m-xylene in the used feedstock oil was 1:2:1:1 and the ethylbenzene content in the feedstock oil was 20 mass %. The result is shown in Table 1.

Example 12

[0044] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil after addition of the composite adsorbent were determined according to the method of Example 1, except that the mass ratio of ethylbenzene/p-xylene/o-xylene/m-xylene in the used feedstock oil was 2:1:1:1 and the ethylbenzene content in the feedstock oil was 40 mass %. The result is shown in Table 1.

TABLE-US-00001 TABLE 1 mass ratio of ethylbenzene carrier content in liquid/xylene Example feedstock adsorbent/feedstock relative volatility No. oil, mass % carrier liquid oil α.sub.EB/PX α.sub.EB/OX α.sub.EB/MX 1 25 n-tetradecane 8:2:1 1.50 1.54 3.07 2 25 n-tetradecane 8:3:1 1.74 1.80 3.55 3 25 n-tetradecane 8:4:1 2.15 2.21 4.39 4 25 n-tetradecane 13:2:1 1.48 1.52 3.05 5 25 n-tetradecane 18:2:1 1.47 1.51 3.00 6 25 n-undecane 8:2:1 1.50 1.53 3.06 7 25 n-hexadecane 8:2:1 1.49 1.54 3.06 8 25 diphenylmethane 8:2:1 1.45 1.49 2.97 9 25 butyldecalin 8:2:1 1.47 1.51 3.01 10 25 decalin 8:2:1 1.47 1.50 2.99 11 20 n-tetradecane 8:2:1 1.34 1.38 2.84 12 40 n-tetradecane 8:2:1 1.57 1.68 3.35 Comparative 25 — 0:0:1 1.06 1.22 1.08 Example 1 Comparative 20 — 0:0:1 1.06 1.23 1.08 Example 2 Comparative 40 — 0:0:1 1.07 1.24 1.09 Example 3 Comparative 25 n-tetradecane 8:0:1 1.08 1.24 1.09 Example 4

Comparative Example 1

[0045] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil were determined according to the method of Example 1, except that no composite adsorbent was used. The result is shown in Table 1.

Comparative Example 2

[0046] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil were determined according to the method of Example 1, except that no composite adsorbent was used, and the mass ratio of ethylbenzene/p-xylene/o-xylene/m-xylene in the used feedstock oil was 1:2:1:1. The result is shown in Table 1.

Comparative Example 3

[0047] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil were determined according to the method of Example 1, except that no composite adsorbent was used, and the mass ratio of ethylbenzene/p-xylene/o-xylene/m-xylene in the used feedstock oil was 2:1:1:1. The result is shown in Table 1.

Comparative Example 4

[0048] The relative volatilities of ethylbenzene relative to the respective xylene isomers in the feedstock oil were determined according to the method of Example 1, except that only n-tetradecane was added in the feedstock oil and the mass ratio of n-tetradecane to the feedstock oil was 8:1. The result is shown in Table 1.

[0049] As can be seen from Table 1, the use of the composite adsorbent in the present invention, compared with the method of using no composite adsorbent or only using a carrier liquid, can significantly increase the relative volatilities of ethylbenzene relative to the respective xylene isomers, indicating that the use of the composite adsorbent in the present invention can separate ethylbenzene from C.sub.8 arene.

Example 13

[0050] Ethylbenzene and xylene in C.sub.8 arene were separated according to the process shown in FIG. 1, using the composite adsorbent and the feed oil as in Example 1. The operating conditions of the adsorption distillation column and the distillation desorption column and the purity of the obtained product are shown in Table 2.

Comparative Example 5

[0051] A common distillation column was used to separate ethylbenzene and xylene in the feedstock oil of Example 1. The operating conditions of the distillation column and the purity of the obtained product are shown in Table 2.

Comparative Example 6

[0052] Ethylbenzene was separated from C.sub.8 arene by the extractive distillation method. The C.sub.8 arene was introduced into the middle part of the extractive distillation column, and the extraction solvent was introduced into the upper part of the column. After the extractive distillation, ethylbenzene was withdrawn from the overhead. The rich solvent rich in xylene was withdrawn from the bottom of the column, and entered the solvent recovery column. After distillation, the xylene was withdrawn from the overhead, and the lean solvent was withdrawn from the bottom of the column and returned to the extractive distillation column. 1,2,4-trichlorobenzene was used as the extraction solvent. The C.sub.8 arene feedstock oil was formulated according to the method of Example 1. The operating conditions of the extractive distillation column and the solvent recovery column and the purity of the obtained product are shown in Table 2.

TABLE-US-00002 TABLE 2 Comparative Comparative Items Example 13 Example 5 Example 6 adsorption theoretical plate number 40 240 80 distillation overhead pressure, MPa 0.02 0.02    0.02 column/ composite adsorbent/extraction 120 — 120  common solvent entry temperature, ° C. distillation overhead temperature, ° C. 85 85 85 column/ column bottom temperature, ° C. 200 151 165  extractive mass ratio of composite 10 —  10* distillation adsorbent/feedstock oil column reflux ratio 3 80 50 distillation theoretical plate number 40 — 40 desorption overhead pressure, MPa 0.01 —    0.01 column/solvent overhead temperature, ° C. 72 — 72 recovery column bottom temperature, ° C. 242 — 172  column reflux ratio 1 —  3 ethylbenzene product purity, mass % 99.8 99.8   99.8 ethylbenzene product yield, mass % 99.5 99.5   99.5 xylene product purity, mass % 99.8 99.8   99.8 xylene product yield, mass % 99.5 99.5   99.5 relative energy consumption 40 100 78 *mass ratio of extraction solvent/feedstock oil

Example 14

[0053] The composite adsorbent of Example 1 was used and the feedstock oil was a reformate C.sub.8 fraction, wherein the mass ratio of ethylbenzene/p-xylene/m-xylene/o-xylene was 18:19:39:24. The ethylbenzene and the xylene in the C.sub.8 fraction were separated according to the process shown in FIG. 1. The operating conditions of the adsorption distillation column and the distillation desorption column and the purity of the obtained product are shown in Table 3.

Comparative Example 7

[0054] The ethylbenzene and the xylene in the feedstock oil of Example 14 were separated using a common distillation column. The operating conditions of the distillation column and the purity of the obtained product are shown in Table 3.

TABLE-US-00003 TABLE 3 Comparative Items Example 14 Example 7 adsorption theoretical plate number 40 240 distillation overhead pressure, MPa 0.02 0.02 column/ overhead temperature, ° C. 85 85 common column bottom temperature, ° C. 200 153 distillation composite adsorbent entry 120 — column temperature, ° C. mass ratio of composite 10 — adsorbent/feedstock oil reflux ratio 3 100 distillation theoretical plate number 40 — desorption overhead pressure, MPa 0.01 — column overhead temperature, ° C. 72 column bottom temperature, ° C. 242 — reflux ratio 1 — ethylbenzene product purity, mass % 99.8 99.8 ethylbenzene product yield, mass % 99.5 99.5 xylene product purity, mass % 99.8 99.8 xylene product yield, mass % 99.5 99.5 relative energy consumption 42 100

Example 15

[0055] The composite adsorbent of Example 1 was used and the feedstock oil was an ethylene cracking gasoline C.sub.8 fraction, wherein the mass ratio of ethylbenzene/p-xylene/m-xylene/o-xylene was 52:10:23:15. The ethylbenzene and xylene in the C.sub.8 fraction were separated according to the process shown in FIG. 1. The operating conditions of the adsorption distillation column and the distillation desorption column and the purity of the obtained product are shown in Table 4.

Comparative Example 8

[0056] The ethylbenzene and the xylene in the feedstock oil of Example 15 were separated using a common distillation column. The operating conditions of the distillation column and the purity of the obtained product are shown in Table 4.

TABLE-US-00004 TABLE 4 Comparative Items Example 15 Example 8 adsorption theoretical plate number 40 240 distillation overhead pressure, MPa 0.02 0.02 column/ composite adsorbent 120 — common entry temperature, ° C. distillation overhead temperature, ° C. 85 85 column column bottom temperature, ° C. 210 153 mass ratio of composite 10 — adsorbent/feedstock oil reflux ratio 2 35 distillation theoretical plate number 40 — desorption overhead pressure, MPa 0.01 — column overhead temperature, ° C. 72 column bottom temperature, ° C. 242 — reflux ratio 1.5 — ethylbenzene product purity, mass % 99.8 99.8 ethylbenzene product yield, mass % 99.5 99.5 xylene product purity, mass % 99.8 99.8 xylene product yield, mass % 99.5 99.5 relative energy consumption 44 100

[0057] As can be seen from Tables 2-4, separating ethylbenzene from the C.sub.8 arene mixture by the adsorption distillation of the present invention, compared with the separation of ethylbenzene using a common distillation column or an extractive distillation alone, can significantly reduce the energy consumption and improve the separation efficiency of ethylbenzene and xylene.