Method for separating aromatic hydrocarbon using extractive distillation

Abstract

A method for separating aromatic hydrocarbons by an extractive distillation, comprising introducing a hydrocarbon mixture containing aromatic hydrocarbons into the middle of an extractive distillation column (8); introducing an extraction solvent into the upper part of the extractive distillation column; after an extractive distillation, a raffinate containing benzene is discharged from the top of the column, wherein the benzene content is 3-40% by mass, and sent to the lower part of the extraction column (10); the extraction solvent is introduced to the upper part of the extraction column for a liquid-liquid extraction; a raffinate liquid free of aromatic hydrocarbons is discharged from the top of the extraction column; a rich solvent containing benzene is discharged from the bottom of the column and enters the upper-middle part of the extractive distillation column; the rich solvent obtained at the bottom of the extractive distillation column is sent to the solvent recovery column to separate the aromatic hydrocarbons and the solvent. By combining an extractive distillation with a liquid-liquid extraction ingeniously, the method can achieve the separation of aromatic hydrocarbons with a high purity and a high recovery rate, and a significant decrease of the energy consumption in the extraction and separation process.

Claims

1. A method for separating aromatic hydrocarbons by an extractive distillation, comprising following operations: (1) introducing a hydrocarbon mixture containing aromatic hydrocarbons into middle part of an extractive distillation column; introducing an extraction solvent into upper part of the extractive distillation column; after an extractive distillation, discharging a raffinate containing benzene from the top of the extractive distillation column, wherein the benzene content in the raffinate is 3-40% by mass; and a rich solvent rich in aromatic hydrocarbons is obtained at the bottom of the extractive distillation column, (2) sending the raffinate discharged from the top of the extractive distillation column to lower part of an extraction column; introducing the extraction solvent into upper part of the extraction column; after a liquid-liquid extraction, discharging a raffinate liquid free of aromatic hydrocarbons from the top of the extraction column; discharging a rich solvent containing benzene from the bottom of the extraction column and introducing the rich solvent containing benzene into upper-middle part of the extractive distillation column, which lies between the positions at which the extraction solvent and the hydrocarbon mixture are introduced, wherein the rich solvent containing benzene is introduced to the 2.sup.nd-9.sup.th theoretical plates downstream of the position at which the extraction solvent is introduced in the extractive distillation column, and (3) sending the rich solvent rich in aromatic hydrocarbons obtained from the bottom of the extractive distillation column to middle part of a solvent recovery column; after a vacuum distillation, discharging a streaming comprising aromatic hydrocarbons from the top of the solvent recovery column, and discharging a lean solvent from the bottom of the solvent recovery column.

2. The method according to claim 1, characterized in that a mass ratio of the raffinate containing benzene discharged from the top of the extractive distillation column to the hydrocarbon mixture entering the extractive distillation column is 5-45%, wherein the benzene content in the raffinate containing benzene is 10-30% by mass.

3. The method according to claim 1, characterized in that the extraction solvent is selected from sulfolane, triethylene glycol, tetraethylene glycol, pentaethylene glycol and triethylene glycol monomethyl ether.

4. The method according to claim 1, characterized in that the extraction solvent comprises 0.1-1.0% by mass of water.

5. The method according to claim 1, characterized in that the extraction solvent comprises 0.4-0.8% by mass of water.

6. The method according to claim 1, characterized in that in operation (1), the raffinate containing benzene discharged from the top of the extractive distillation column is condensed and thereafter subjected to an oil-water separation to obtain a dehydrated raffinate; then the dehydrated raffinate containing benzene is sent to the bottom of the extraction column.

7. The method according to claim 1, characterized in that in operation (1), the upper part of the extractive distillation column is not provided with a raffinate reflux.

8. The method according to claim 1, characterized in that the raffinate liquid discharged from the top of the extraction column in operation (2) is washed with water.

9. The method according to claim 1, characterized in that the lean solvent obtained in operation (3) is respectively returned to the upper parts of the extractive distillation column and the extraction column for reuse.

10. The method according to claim 1, characterized in that a theoretical plate number of the extractive distillation column in operation (1) is 25-60; a temperature at the bottom of the extractive distillation column is 140-185° C.; and an overhead pressure of the extractive distillation column is 0.1-0.4 MPa.

11. The method according to claim 10, characterized in that a temperature of the extraction solvent introduced into the extractive distillation column is controlled at 80-130° C., and a volume ratio of the extraction solvent introduced into the extractive distillation column to the hydrocarbon mixture is 2.0-5.5.

12. The method according to claim 1, characterized in that a theoretical plate number of the extraction column in operation (2) is 3-30; a temperature of the extraction solvent introduced into the extraction column is 40-90° C.; and a volume ratio of the extraction solvent introduced into the upper part of the extraction column to the raffinate containing benzene discharged from top of the extractive distillation column is 1-3.

13. The method according to claim 1, characterized in that a theoretical plate number of the solvent recovery column in operation (3) is 8-28; an overhead pressure of the of the solvent recovery column is 0.02-0.1 MPa; an overhead reflux ratio of the of the solvent recovery column is 0.3-1.0; an overhead temperature of the of the solvent recovery column is 50-80° C.; and a temperature at the bottom of the solvent recovery column is 150-185° C.

14. The method according to claim 1, characterized in that a content of the aromatic hydrocarbons in the hydrocarbon mixture is 60-98% by mass.

Description

DESCRIPTION OF DRAWINGS

(1) FIGURE is a flow diagram for separating aromatic hydrocarbons by an extractive distillation in the present invention.

SPECIFIC EMBODIMENTS

(2) The present invention is mainly based on the operation of an extractive distillation, controls the range of the benzene evaporation amount at the top of the extractive distillation column, and carries out the liquid-liquid extraction on the raffinate containing benzene to further recover benzene; the resulting rich solvent containing benzene from the liquid-liquid extraction is recycled to the upper-middle part of the extractive distillation column; then the aromatic hydrocarbons in the rich solvent obtained from the bottom of extractive distillation column are separated from the solvent. The method can obtain mixed aromatic hydrocarbons of high purity and allow the C.sub.8 cycloalkanes in the raw material to enter the raffinate liquid, thereby recovering benzene in the raw material completely. Moreover, the energy consumption in the whole process is relatively low.

(3) Step (1) of the method of the present invention is the extractive distillation of the raw material. In the distillation process, a suitable amount of benzene is charged into the overhead effluents, i.e., obtaining a raffinate containing benzene, so that the C.sub.8 cycloalkanes in the raw material substantively enter the raffinate. Preferably, the mass ratio of the raffinate containing benzene discharged from the top of the extractive distillation column to the raw material entering the column is 5-45%, preferably 5-30%, and the benzene content in the raffinate containing benzene is 10-30% by mass.

(4) Preferably, the raffinate containing benzene discharged from the top of the extractive distillation column is condensed and thereafter subjected to an oil-water separation. Then the dehydrated raffinate containing benzene is sent to the lower part of the extraction column.

(5) In Step (1), it is preferred that the upper part of the extractive distillation column is not provided with a raffinate reflux. Instead, the raffinate containing benzene discharged from the top of the extractive distillation column is wholly sent to the extraction column for a liquid-liquid extraction.

(6) The extraction solvent of the present invention is selected from sulfolane, triethylene glycol, tetraethylene glycol, pentaethylene glycol or triethylene glycol monomethyl ether, preferably sulfolane.

(7) The extraction solvent according to the present invention may comprise 0.1-1.0% by mass of water, preferably 0.4-0.8% by mass of water, so as to increase the selectivity of the solvent.

(8) Step (2) of the method of the present invention is the liquid-liquid extraction on the raffinate containing benzene discharged from the top of the extractive distillation column for recovering the benzene therein. A raffinate liquid substantively free of aromatic hydrocarbons is discharged from the top of the extraction column. The content of the aromatic hydrocarbons in the raffinate liquid is preferably no more than 0.5% by mass, more preferably no more than 0.3% by mass. The rich solvent containing benzene at the bottom returns to the upper-middle part of the extractive distillation column, and the position at which the rich solvent enters the extractive distillation column is between the positions at which the extraction solvent and the raw material enter the column. The upper-middle part of the extractive distillation column refers to the region between the positions at which the extraction solvent and the raw material enter the column, where the region close to the position at which the extraction solvent is introduced is the upper part and the rest portion is the middle part. Preferably, the rich solvent containing benzene is introduced to the 1.sup.st-20.sup.th, preferably the 2.sup.nd-9.sup.th theoretical plates, downstream of the position at which the extraction solvent is introduced in the extractive distillation column.

(9) Preferably, the raffinate liquid discharged from the top of the extraction column is washed with water; the water washing is carried out in a water washing column; the raffinate liquid after the water washing is discharged out of the system; the water after the washing is stripped to remove the trace non-aromatic hydrocarbons therein and then used as a stripping medium. The water washing temperature is preferably 35-45° C.

(10) Step (3) of the method of the present invention is sending the rich solvent rich in aromatic hydrocarbons discharged from the bottom of the extractive distillation column into the solvent recovery column to separate the aromatic hydrocarbons and the solvent. Preferably, the lean solvent obtained in Step (3) is respectively returned to the upper parts of the extractive distillation column and the extraction column for reuse.

(11) The theoretical plate number of the extractive distillation column according to Step (1) of the present invention is preferably 25-60; the temperature at the bottom of the column is preferably 140-185° C.; the overhead pressure is preferably 0.1-0.4 MPa; the overhead temperature is preferably 110-135° C. Preferably, the temperature of the extraction solvent entering the extractive distillation column is controlled at 80-130° C., and the volume ratio(solvent ratio) of the extraction solvent entering the extractive distillation column to the raw material for the extractive distillation is 2.0-5.5.

(12) The theoretical plate number of the extraction column according to Step (2) is preferably 3-30; the temperature of the extraction solvent entering the column is preferably 40-90° C.; the volume ratio(solvent ratio) of the extraction solvent to the raw material to be extracted is preferably 1-3.

(13) The theoretical plate number of the solvent recovery column according to Step (3) is preferably 8-28; the overhead pressure is preferably 0.02-0.1 MPa, more preferably 0.02-0.08 MPa; the overhead reflux ratio, i.e., the mass ratio of the refluxed material to the material discharged from the top of the column is preferably 0.3-1.0; the overhead temperature is preferably 50-80° C., and the temperature at the bottom of the column is preferably 150-185° C.

(14) The pressures of the present invention are all absolute pressures.

(15) The content of the aromatic hydrocarbons in the hydrocarbon mixture of the present invention may be 60-98% by mass, preferably 70-98% by mass. The hydrocarbon mixture may be C.sub.6-C.sub.8 fractions of a catalytic reformate, ethylene cracking hydrogenated gasoline or tar-crude benzene.

(16) The present invention also provides a device for separating aromatic hydrocarbons by an extractive distillation, comprising an extractive distillation column, an extraction column and a solvent recovery column; the upper parts of the extractive distillation column and the extraction column are both provided with lines for injection of the extraction solvent; the middle of the extractive distillation column is provided with a line for feeding a hydrocarbon mixture containing aromatic hydrocarbons; the top is provided with a line for discharging the raffinate containing benzene; the line for discharging the raffinate is connected with the lower part of the extraction column; the top of the extraction column is provided with a line for discharging a raffinate liquid; the bottom of the column is provided with a line in connection with the upper-middle part of the extractive distillation column for returning the rich solvent containing benzene; the bottom of the extractive distillation column is provided with a line for discharging the rich solvent in connection with the middle of the solvent recovery column; the top of the solvent recovery column is provided with a line for discharging the aromatic hydrocarbons; the line for discharging a lean solvent at the bottom of the solvent recovery column is respectively connected with the lines for injecting the extraction solvent in the upper parts of the extractive distillation column and the extraction column.

(17) Preferably, the device is further provided with a water washing column for the raffinate liquid, the top of which is provided with a line for discharging the raffinate liquid after water washing, the bottom of which is provided with a line for discharging the water after water washing, and the upper part of which is provided with a line for injecting the water for water washing.

(18) Preferably, the top line of the extractive distillation column is connected with a separator for separating water; the separator is provided with a line for discharging the water and a line for discharging the dehydrated raffinate; the line for discharging the dehydrated raffinate is connected with the lower part of the extraction column.

(19) Preferably, the overhead line of the solvent recovery column is connected with a reflux tank which is provided with a line for discharging the water and a line for discharging the dehydrated aromatic hydrocarbons; the line for discharging the dehydrated aromatic hydrocarbons is provided with a reflux line.

(20) The present invention is illustrated in details in combination with the figures.

(21) In the FIGURE, the hydrocarbon mixture containing aromatic hydrocarbons enters the middle of the extractive distillation column 8 via line 1; the extraction solvent enters the upper part of the extractive distillation column via line 2. After the extractive distillation, the raffinate containing benzene is discharged from the overhead line 3 of the extractive distillation column and then enters the condenser 4. The condensed and cooled stream enters the separator 5. After an oil-water separation, water containing a small amount of solvent is discharged via line 6, and the raffinate containing benzene is sent to the lower part of the extraction column 10 via line 7; the extraction solvent enters the upper part of the extraction column 10 via line 12; an extraction and separation is carried out by a countercurrent liquid phase contact in the extraction column. The raffinate liquid substantively free of aromatic hydrocarbons is introduced to the lower part of the water washing column 13 for the raffinate via line 11; water from line 23 is introduced into the water washing column from the upper part; the raffinate liquid product obtained after water washing is discharged out of the device via line 14; the water after the washing is discharged via line 15. The rich solvent containing benzene discharged from the bottom of the extraction column 10 returns to the upper part, or the middle, of the extractive distillation column via line 9.

(22) The rich solvent containing aromatic hydrocarbons at the bottom of the extractive distillation column is sent to the middle of the solvent recovery column 17 via line 24; the stripping water or the steam is introduced to the lower part of the solvent recovery column 17 via line 16; after vacuum stripping, the aromatic hydrocarbons and the steam are discharged from the top of the column and enter condenser 19 via line 18, and after condensation and cooling, enter the reflux tank 20; after an oil-water separation, a part of the oil phase flows back to the upper part of the solvent recovery column via line 21 and the rest of the oil phase is discharged as the mixed aromatic hydrocarbons via line 22; the lean solvent obtained after the separation of the aromatic hydrocarbons is discharged from the bottom of the solvent recovery column; after heat exchange and temperature controlling by cooling, most of the lean solvent is recycled to the upper part of the extractive distillation column, and a small part acts as the extraction solvent of the extraction column.

(23) The present invention is further explained with the examples. However, the present invention is not limited by these examples.

Example 1

(24) According to the process of the FIGURE, a pure BTX was recovered by an extractive distillation from the raw material of C.sub.6-C.sub.8 fractions of the hydrogenated pyrolysis gasoline, with the water-containing sulfolane as the extraction solvent. See Table 1 for the composition of the employed raw material. The benzene content in the raffinate discharged from the top of the column during the extractive distillation process was controlled at 15% by mass. See Table 2 for the main operation conditions and the water content of the lean solvent. See Table 3 for the extractive distillation and the results after the BTX separation by the distillation. The rich solvent containing benzene after the liquid-liquid extraction returned to the 3.sup.rd theoretical plate in the upper part of the extractive distillation column. The position at which the lean solvent entered the column was the 1.sup.st theoretical plate; the position at which the raw material entered the column was the 13.sup.th theoretical plate. The temperature for the water washing of the raffinate liquid discharged from the top of the extraction column was 40° C.

Example 2

(25) C.sub.6-C.sub.8 fractions of the tar-crude benzene were used as the raw material. See Table 1 for the composition BTX was recovered by the extractive distillation according to the method of Example 1, except that the benzene content in the raffinate discharged from the top of the column during the extractive distillation process was controlled at 23.8% by mass. The rich solvent containing benzene after the liquid-liquid extraction returned to the 5.sup.th theoretical plate in the upper part of the extractive distillation column. See Table 2 for the main operation conditions and the water content of the lean solvent. See Table 3 for the results of the extractive distillation and the BTX separation by the distillation.

Example 3

(26) BTX was recovered by the extractive distillation according to the method of Example 1, except that the top of the extractive distillation column was provided with a raffinate reflux. The raffinate flew back to the 1.sup.st theoretical plate in the upper part of the column with a reflux ratio (the mass ratio of the refluxed material to the material discharged from the top of the column) of 0.20. See Table 2 for the main operation conditions. See Table 3 for the results of the extractive distillation and the separation by the distillation.

Comparative Example 1

(27) BTX was recovered by an extractive distillation of the raw material according to Example 1 in a conventional extractive distillation method. The device was not provided with an extraction column and a water washing column. The rest was substantively the same as the FIGURE, except that after an oil-water separation, a part of the overhead effluents of the extractive distillation column was sent to the 1.sup.st theoretical plate in the upper part of the column as a reflux. The rest was discharged out of the system as a raffinate oil. See Table 2 for the main operation conditions. See Table 3 for the results of the extractive distillation and the BTX separation by the distillation.

Comparative Example 2

(28) BTX was recovered by an extractive distillation according to the method of Example 1, except that the rich solvent containing benzene after the extraction returned to the 27.sup.th theoretical plate in the lower part of the extractive distillation column. See Table 2 for the main operation conditions. See Table 3 for the results of the extractive distillation and the separation by the distillation.

Comparative Example 3

(29) The raw material and the solvent of Example 1 were used. According to the method of CN103232317A, the overhead gas phase of the extractive distillation column and the gas phase discharged from the side line of the 3.sup.rd theoretical plate were mixed and then condensed, and after that, were sent to the extraction column for recovering benzene by a liquid phase extraction. Moreover, the rich solvent containing benzene at the bottom of the extraction column was returned to the top of the extractive distillation column. See Table 2 for the main operation conditions. See Table 3 for the results of the extractive distillation and the separation by the distillation.

(30) It can be seen from the data in Table 3 that, in the mixed aromatic hydrocarbons obtained by the method of the present invention, the content of C.sub.8 cycloalkanes is as low as 0.019-0.054% by mass, the content of C.sub.8 and C.sub.9+ cycloalkanes is ≯0.16% by mass; the benzene content in the raffinate liquid is as low as about 0.1% by mass; the content of the aromatic hydrocarbons is as low as 0.3% by mass or lower. It shows that the recovery of benzene was full and the recovery of toluene and xylene was also relatively full. After the distillation, the purities of the B, T and X products reached 99.99% by mass, 99.90-99.93% by mass and 99.0% by mass, respectively. All of the above meet or are superior to the requirements on the highest product specifications of the market. The purities are greatly improved compared to the purities of BTX separated in Comparative Examples 1-3.

(31) TABLE-US-00001 TABLE 1 C.sub.6-C.sub.8 fractions C.sub.6-C.sub.8 fractions of hydrogenated of tarcrude composition pyrolysis gasoline benzene alkane, % by mass C.sub.5 0.00 0.19 C.sub.6 1.19 0.11 C.sub.7 1.47 0.11 C.sub.8.sup.+ 0.48 0.21 cycloalkanes, % by mass C.sub.5 0.30 0.87 C.sub.6 5.00 0.62 C.sub.7 1.54 0.16 C.sub.8 0.80 0.15 C.sub.9.sup.+ 0.10 0.02 aromatic hydrocarbons, % by mass C.sub.6 51.67 75.65 C.sub.7 26.21 16.36 C.sub.8 11.24 5.55 C.sub.9.sup.+ 0.000 0.00

(32) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Example Example Example Example Example Example items 1 2 3 1 2 3 extractive distillation column theoretical plate number 30 30 35 35 30 30 ordinal number of the 13 13 18 18 13 13 theoretical plate which the raw material entered* solvent ratio (to the raw 3.8 4.6 3.8 3.9 3.8 3.8 material, by volume) reflux ratio (to the — — 0.2 0.3 0.25 — material discharged from the top of the column, by mass) overhead pressure, MPa 0.16 0.20 0.16 0.16 0.16 0.16 temperature of the 110 102 110 110 110 110 solvent entering the column, ° C. ordinal number of the 1 1 6 6 1 1 theoretical plate which the solvent entered mass ratio of the 16.1 5.2 16.9 16.0 16.6 16.1 raffinate discharged from the top of the column/raw material entering the column, % benzene content in the 15.0 23.8 13.0 5.8 12.0 15.0 raffinate discharged at the top of the column, % by mass ordinal number of the 3 5 8 — 27 1 theoretical plate to which the rich solvent containing benzene returns overhead temperature of 124 126 123 102 123 124 the column, ° C. temperature at the 170 169 170 171 170 170 bottom of the column, ° C. extraction column theoretical plate number 8 8 8 — 8 8 solvent ratio (to the raw 1.3 1.4 1.3 — 1.3 1.3 material, by volume) temperature of the 65 65 65 — 65 65 solvent entering the column, ° C. solvent recovery column theoretical plate number 12 12 12 12 12 12 overhead pressure, MPa 0.04 0.04 0.04 0.04 0.04 0.04 reflux ratio (to the 0.6 0.6 0.6 0.6 0.6 0.6 material discharged from the top of the column, by mass) overhead temperature of 72 66 72 73 72 72 the column, ° C. temperature at the 173 171 173 173 173 173 bottom of the column, ° C. water content of the lean 0.6 0.7 0.6 0.6 0.6 0.6 solvent, % by mass

(33) The theoretical plate ordinal number of the extractive distillation column refers to the sequence number from the top to the bottom

(34) TABLE-US-00003 TABLE 3 Comparatative Comparative Comparative Example Example Example Example Example Example items 1 2 3 1 2 3 content of C.sub.8 cycloalkanes 0.035 0.019 0.054 0.290 0.122 0.117 in the mixed aromatic hydrocarbons, % by mass content of C.sub.9.sup.+ 0.093 0.021 0.101 0.112 0.106 0.099 cycloalkanes in the mixed aromatic hydrocarbons, % by mass benzene content in the 0.087 0.120 0.087 5.80 0.082 0.087 raffinate liquid, % by mass content of aromatic 0.237 0.280 0.200 6.28 0.210 0.240 hydrocarbons in the raffinate liquid, % by mass purity of benzene after the 99.99 99.99 99.99 99.97 99.99 99.99 distillation, % by mass purity of toluene after the 99.93 99.96 99.90 99.70 99.78 99.81 distillation, % by mass purity of xylene after the 99.04 99.61 99.00 97.65 98.57 98.71 distillation, % by mass heat load in the extractive 1.150 1.180 1.156 1.151 1.160 1.150 distillation, 10.sup.9 J/ton of feedstock