Method for the separation of C4 olefin mixtures

Abstract

A method for the separation of C4 olefin mixtures using anion-pillared hybrid porous materials as physical adsorbents is provided. The anion-pillared hybrid porous material was constructed by metal ions (M), organic ligand (L), and inorganic anion (A), forming a three-dimensional structure (A-L-M). C4 olefin mixtures contact with hybrid porous materials in certain ways, then each single C4 olefin monomer can be obtained. The pore size of anion-pillared hybrid porous materials and the spatial configurations of the anions within the pores can be fine-tuned and pre-designed. C4 olefins with different size and shape can be efficiently separated by the anion-pillared hybrid porous materials through shape recognition and size-sieving mechanism.

Claims

1. A method of separating C4 olefins by using anion-pillared hybrid porous materials as a separation material, comprising a step of contacting the separation material with C4 olefins to achieve separation, wherein the C4 olefins are any two or more of 1-butene, iso-butene, 1,3-butadiene, cis-2-butene, and trans-2-butene; the hybrid porous materials are constructed by metal ions, inorganic anions, and organic ligands, in which the metal ions, the inorganic anions, and the organic ligands link together through coordination bonds forming a three-dimensional framework with formula of A-L-M; wherein the metal ions, M, are one or more of Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+; wherein the inorganic anions, A, are one or more of SiF.sub.6.sup.2−, TiF.sub.6.sup.2−, SnF.sub.6.sup.2−, GeF.sub.6.sup.2−, or NbF.sub.6.sup.−, and NbOF.sub.5.sup.2−; wherein the organic ligand L is selected from the group consisting of 2,6-Diaminopurine, 2-Amino-6-chloropurine, and Guanine.

2. A method of separating C4 olefins by using anion-pillared hybrid porous materials as a separation material, comprising a step of contacting the separation material with C4 olefins to achieve separation, wherein the C4 olefins are any two or more of 1-butene, iso-butene, 1,3-butadiene, cis-2-butene, and trans-2-butene; the hybrid porous materials are constructed by metal ions, inorganic anions, and organic ligands, in which the metal ions, the inorganic anions, and the organic ligands link together through coordination bonds forming a three-dimensional framework with formula of A-L-M; wherein the metal ions, M, are one or more of Fe.sup.2+, Co.sup.2+, Ni.sup.2+, Cu.sup.2+; wherein the inorganic anions, A, are one or more of SiF.sub.6.sup.2−, TiF.sub.6.sup.2−, SnF.sub.6.sup.2−, GeF.sub.6.sup.2−, or NbF.sub.6.sup.−, and NbOF.sub.5.sup.2−; wherein the organic ligand L is 2,6-Diaminopurine; wherein the resulted hybrid porous materials A-L-M can separate 1-butene and 1,3-butadiene mixtures with polymer-grade of iso-butene and high purity 1,3-butadiene obtained; or can separate the mixtures of 1,3-butadiene, 1-butene, trans-2-butene, iso-butene and cis-2-butene; or can separate 1,3-butadiene and iso-butene mixtures with polymer-grade of iso-butene obtained; or can separate 1-butene and iso-butene mixtures with polymer-grade of iso-butene obtained; or can separate trans-2-butene and cis-2-butene mixtures with polymer-grade of cis-2-butene and high purity trans-butene obtained.

3. The method of separating C4 olefins according to claim 1, wherein the contacting between the gas mixture with a hybrid porous material is selected from the group consisting of fixed bed adsorption separation, fluidized bed adsorption separation, moving bed adsorption separation, simulated moving bed adsorption separation, and membrane separation.

4. The method of separating C4 olefins according to claim 1, wherein the contacting is in fixed bed adsorption, and the steps are as following: (1) C4 olefin mixtures passing through a column packed with the anion-pillared hybrid porous materials under a pre-determined temperature and pressure with a pre-determined flow rate, wherein C4 olefins which interact with hybrid porous materials are retained in the column while other C4 compounds are not retained in the column; (2) after breakthrough of the retained C4 olefins, stopping the adsorption process in step (1), desorbing the C4 olefins retained in the column by means of decompressing desorption, temperature increasing desorption, inert gas scavenging, or pure gas scavenging, then obtaining the C4 olefins.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the adsorption isotherms of cis-2-butene, trans-2-butene at 298 K on anion-pillared hybrid porous materials synthesized in example 1.

(2) FIG. 2 shows the adsorption isotherms of 1, 3-dutadiene, 1-butene, iso-butene, cis-2-butene, trans-2-butene at 298 K on anion-pillared hybrid porous materials synthesized in example 12.

(3) FIG. 3 shows the breakthrough curves of example 13.

(4) FIG. 4 shows the breakthrough curves of example 14.

(5) FIG. 5 shows the adsorption isotherms of N.sub.2 (77 K) and CO.sub.2 (196 K) on anion-pillared hybrid porous materials synthesized in example 16.

(6) FIG. 6 shows the adsorption isotherms of 1, 3-dutadiene, 1-butene, iso-butene, cis-2-butene, trans-2-butene at 298 K on anion-pillared hybrid porous materials synthesized in example 16.

(7) FIG. 7 shows the breakthrough curves of example 17.

(8) FIG. 8 shows the breakthrough curves of example 18.

(9) FIG. 9 shows the adsorption isotherms of 1, 3-dutadiene, 1-butene, iso-butene, cis-2-butene, trans-2-butene at 298 K on anion-pillared hybrid porous materials synthesized in example 24.

(10) FIG. 10 shows the adsorption isotherms of N.sub.2 (77 K) and CO.sub.2 (196 K) on anion-pillared hybrid porous materials synthesized in example 27.

(11) FIG. 11 shows the adsorption isotherms of 1, 3-dutadiene, 1-butene, iso-butene, cis-2-butene, trans-2-butene at 298 K on anion-pillared hybrid porous materials synthesized in example 27.

(12) FIG. 12 shows the crystal structure of anion-pillared hybrid porous materials synthesized in example 27.

(13) FIG. 13. shows the breakthrough curves of example 28.

SPECIFIC EMBODIMENTS

Example 1

(14) An acetonitrile and water (1:1 in volume) mixture solution (3 mL) was carefully dropped onto an aqueous solution (6 mL) containing 25.5 mg Cu(BF.sub.4).sub.2˜H.sub.2O and 19.7 mg (NH.sub.4).sub.2TiF.sub.6. Then a solution (4 mL, acetonitrile:water=1:1) containing 30.0 mg 2,6-Diaminopurine was dropped on the top of the solution. After 7 days, the obtained materials were filtrated and washed by methanol, then activated under vacuum conditions and 50° C. The resulted materials were MPM-2-TIFSIX.

(15) FIG. 1 presents the adsorption isotherms of cis-2-butenes and trans-2-butenes onto MPM-2-TIFSIX materials at 298 K.

Example 2

(16) The obtained MPM-2-TIFSIX was packed into the column with length of 15 cm. Then the 1,3-butadiene and 1-butene (50:50 in volume) mixtures was flowed through the column with flow rate of 1.0 ml/min under 0.2 MPa. The high purity iso-butene (>99.999%) can be obtained. After 1,3-butadiene broke through the column, the separation process was done. The column was then degassed under vacuum conditions, leading to high purity 1,3-butadiene (>90%). The column then can be reused.

Example 3

(17) The acetonitrile and water (1:1 in volume) mixture solution (3 mL) was carefully dropped onto the top of aqueous solution (6 mL) containing 27.7 mg ZnSiF.sub.6. Then a solution (4 mL, acetonitrile:water=1:1 in volume) containing 50.0 mg 2-Amino-6-chloropurine was dropped onto the solution. After 4 days, the obtained materials were filtrated and washed by methanol, then activated under vacuum conditions and 70° C. The resulted materials were MPM-3-SIFSIX.

Example 4

(18) An acetonitrile and water (1:1 in volume) mixture solution (3 mL) was carefully dropped onto the aqueous solution (6 mL) containing 32.8 mg Cu(NO.sub.3).sub.2.3H.sub.2O and 17.7 mg (NH.sub.4).sub.2SiF.sub.6. Then a solution (4 mL, acetonitrile:water=1:1 in volume) containing 30.0 mg adenine was dropped on the top of the solution. After 5 days, the obtained materials were filtrated and washed by acetonitrile, then activated under vacuum conditions at room temperature for 2 days. The resulted materials were MPM-4-TIFSIX.

Example 5

(19) The obtained MPM-4-TIFSIX was packed into the column with length of 5 cm. Then trans-2-butene and cis-2-butene (50:50 in volume) mixtures was flowed through the column with flow rate of 1.0 ml/min under 0.1 MPa. The high purity cis-butene (>99.999%) can be obtained. When trans-2-butene broke through the column, the separation process was done. The column was then degassed under vacuum conditions, leading to high purity trans-2-butene (>95%). The column then can be reused.

Example 6

(20) 1,3-butadiene and iso-butene (95:5 in volume) mixtures was flowed through the column with flow rate of 1.0 mL/min under 0.2 MPa. The high purity iso-butene (>99.99%) can be obtained. When 1,3-butadiene broke out, the separation process was done. The column was then degassed under vacuum conditions at 60° C., leading to high purity 1,3-butadiene (>90%). The column then can be reused.

Example 7

(21) 125.0 mg Fe(BF.sub.4).sub.2.H.sub.2O and 90.0 mg (NH.sub.4).sub.2SiF.sub.6 were dissolved into 10 mL water in a bottle, then mixed with methanol solution containing 190.0 mg 2-fluoro-4,4′-dipyridylacetylene under stirring. Then the capped bottle was heated at 85° C. for 12 hours. The resulted products were then filtered and washed by methanol, then activated under vacuum conditions for 24 hours. The resulted materials were SIFSIX-2F-Fe-i.

Example 8

(22) 125.0 mg Co(BF.sub.4).sub.2.H.sub.2O and 100.0 mg (NH.sub.4).sub.2GeF.sub.6 were dissolved into 10 mL water in a bottle, then mixed with methanol solution containing 205.0 mg 3-fluoro-4,4′-dipyridylacetylene under stirring. Then the capped bottle was heated at 60° C. for 12 hours. The resulted products were then filtered and washed by methanol, then activated under vacuum conditions for 24 hours. The resulted materials were GeFSIX-2-OH-Co-i.

Example 9

(23) The activated GeFSIX-2-OH-Co-i of Example 8 was packed into the column (inner diameter 4.6 mm, length 50 mm). iso-butene and 1-butene (70:30 in volume) was introduced into the column with flow rate of 1.5 mL/min under 0.1 MPa and 25° C. The polymer-grade of iso-butene (>99.999%) can be obtained. When 1-butene broke through the column, the separation process was over. The column was then purged by He for 15 hours. The column then can be reused.

Example 10

(24) An aqueous solution dissolved 270.0 mg Co(BF.sub.4).sub.2.xH.sub.2O and 200.0 mg (NH.sub.4).sub.2SiF.sub.6 dropped into the glycol solution containing 4,4′-bipyridine under stirring. Then the resulted solution was heated at 60° C. for 3 hours. The resulted products were filtered and washed by methanol, then immersed into methanol for 3 days. After filtered, SIFSIX-1-Cu was obtained.

(25) The activated SIFSIX-1-Cu was loaded into the column (inner diameter 4.6 mm, length 250 mm). iso-butene and 1-butene (50:50 in volume) was introduced into the column with flow rate of 1.0 mL/min under 0.2 MPa at room temperature. The polymer-grade of iso-butene (>99.9%) can be obtained. When 1-butene broke through the column, the separation process was over. The column was then degassed under vacuum condition at 40° C., leading to the high purity 1-butene (>95%). The column then can be reused.

Example 11

(26) 1,3-butadiene and ethane (60:40 in volume) mixture was introduced into the column of SIFSIX-1-Cu, the high purity ethane (99.99%) can be obtained. When 1,3-butadiene broke through the column, the adsorption was stopped. The column with adsorbed 1,3-butadiene was desorbed under vacuum conditions for 24 hours, and then could be reused.

Example 12

(27) 125.0 mg Cu(BF.sub.4).sub.2.H.sub.2O and 90.0 mg (NH.sub.4).sub.2SiF.sub.6 were dissolved into 10 mL water in a bottle, then mixed with methanol solution containing 182.0 mg 4,4′-dipyridylacetylene under stirring, and then stirring for 24 hours at room temperature. The resulted products were then filtered and washed by methanol, then activated under vacuum 50° C. for 24 hours. The resulted materials were SIFSIX-2-Cu-i.

(28) FIG. 2 presents the adsorption isotherms of 1,3-butadiene, 1-butene, iso-butene, cis-butene, and trans-butene on SIFSIX-2-Cu-i at 25° C.

Example 13

(29) The activated SIFSIX-2-Cu-i was loaded into the column (inner diameter 4.6 mm, length 100 mm). The iso-butene, 1-butene, 1,3-butadiene and He (30:15:50:5 om volume) was introduced into the column with flow rate of 1.5 mL/min under 0.1 MPa at 30° C. The polymer-grade of iso-butene (>99.999%) can be obtained. When 1-butene broke through the column, the adsorption was stopped. The column was purged with He for 15 hours, the column could be reused. FIG. 3 shows the breakthrough curves of iso-butene, 1-butene, 1,3-butadien and He (30:15:50:5) on SIFSIX-2-Cu-i.

Example 14

(30) The mixture comprising of iso-butene, 1-butene, 1,3-butadiene, cis-2-butene and trans-2-butene (20:20:20:20:20 in volume) was introduced into the column of SIFSIX-2-Cu-i. When 1,3-butadiene broke through the column, the adsorption was stopped. The column was then purged with He for 12 h, the column could be reused. FIG. 4 show the breakthrough curves of iso-butene, 1-butene, 1,3-butadiene, cis-butene and trans-butene (20:20:20:20:20) mixtures on SIFSIX-2-Cu-i, indicating the separation ability of SIFSIX-2-Cu-i for C4 olefins.

Example 15

(31) The mixture comprising of iso-butene and 1,3-butadiene (50:50 in volume) was introduced into the column of SIFSIX-2-Cu-i with flow rate of 0.5 mL/min at 40° C. When iso-butene broke out the column with high purity (>99.99%). When 1,3-butadiene broke through the column, the adsorption was stopped. The column was then degassed under vacuum conditions, resulting in 1,3-butadiene with purity higher than 90%, and then the column could be reused.

Example 16

(32) A methanol solution (10 mL) containing 182.0 mg 4,4′-dipyridylacetylene was carefully dropped on the top of glycol and methanol solution (20 mL, 1:1 in volume) containing 125.0 mg Cu(BF.sub.4).sub.2.H.sub.2O and 122.0 mg NH.sub.4NbF.sub.6. After 3 days, the resulted products were then filtered and washed with methanol, and then activated by purging N2 flow at 45° C. for 24 hours. The resulted materials were NbFSIX-2-Cu-i. FIG. 5 shows the adsorption isotherms of N2 (77.2 K) and CO2 (196 K) on NbFSIX-2-Cu-i; FIG. 6 shows the adsorption isotherms of 1,3-butadiene, 1-butene, and iso-butene on NbFSIX-2-Cu-i at 25° C. (298K).

Example 17

(33) The activated NbFSIX-2-Cu-i obtained in Example 16 was packed into the 5 cm column. The 1,3-butadiene, 1-butene, iso-2-butene, and He (50:15:25:10 in volume) was introduced into the column with flow rate of 2.0 mL/min under 0.1 MPa at 15° C. The iso-butene and 1-butene mixtures broke out the column firstly, when the second component broke through, the adsorption was stopped. The column was purged with N.sub.2 for 15 hours at 50° C., the column could be reused. FIG. 7 shows the breakthrough curves of 1,3-butadiene:1-butene:iso-butene:He (50:15:25:10) mixtures on NbFSIX-2-Cu-i.

Example 18

(34) The 1-butene and iso-butene (50:50 in volume) was introduced into the column of Example 17 with a flow rate of 0.5 mL/min under 0.2 MPa at 10° C. The iso-butene (>99.99%) broke out the column. When 1-butene breaks out the column, the adsorption was stopped. The column was purged with He for 12 hours at room temperature, the column could be reused. FIG. 8 presents the breakthrough curves of 1-butene:iso-butene (50:50) mixtures on NbFSIX-2-Cu-i.

Example 19

(35) The 1,3-butadiene:1-butene:iso-butene:iso-butane (50:15:35:5 in volume) was introduced into the column of NbFSIX-2-Cu-i as in Example 17 with flow rate of 1.0 mL/min under 1 MPa at 10° C. The iso-butene and iso-butane mixtures can be firstly obtained. When 1-butene broke out the column, the adsorption was stopped. The column was purged with He for 12 hours at room temperature, the column could be reused.

Example 20

(36) The 1-butene:cis-2-butene (50:50 in volume) mixture was introduced into the column of NbFSIX-2-Cu-i as in Example 17 with flow rate of 0.5 mL/min under 0.2 MPa at 30° C. The cis-2-butene with purity higher than 99.99% can be firstly obtained. When 1-butene broke out the column, the adsorption was stopped. The column was degassed under vacuum conditions, the column could be reused.

Example 21

(37) A methanol solution (10 mL) containing 196.0 mg 4,4′-Dipyridyl disulphide was mixed with the glycol and methanol solution (15 mL, 1:1 in volume) containing 125.0 mg Co(BF.sub.4).sub.2.H.sub.2O and 90.0 mg (NH.sub.4)2NSiF.sub.6. The resulted solution was heated to 60° C. for 24 hours, the products were then filtered and washed with methanol, and then activated under vacuum conditions at 40° C. The resulted materials were SIFSIX-S-Co-i.

Example 22

(38) The 1,3-butadiene:cis-2-butene:methane:propane (2:1:1:1 in volume) mixture was introduced into the column (inner diameter 4.6 mm, length 100 mm) packed with SIFSIX-S-Co-i with flow rate of 1.0 mL/min. When 1,3-butadiene broke out the column, the adsorption was stopped. The column was degassed under vacuum condition, which resulted in 1,3-butadiene with high purity (>90%), then the column could be reused.

Example 23

(39) The cis-2-butene:trans-2-butene (50:50 in volume) mixture was introduced into the SIFSIX-S-Co-i column with flow rate of 1.0 mL/min at 10° C. High purity cis-2-butene (99.99%) can be obtained, when trans-2-butene broke out the column, the adsorption was stopped. The column was purged with He for 12 hours, then the column could be reused.

Example 24

(40) A methanol solution (25 mL) of 138.0 mg CuSiF.sub.6 was mixed with another methanol solution containing 98.0 mg 4,4′-azopyridine, the mixture was then stirred for 24 hours at room temperature. The resulted products were then filtered and washed with methanol, and then activated by under vacuum condition at 40° C. for 24 hours. The resulted materials were SIFSIX-14-Cu-i.

(41) FIG. 9 exhibits the adsorption isotherms of 1,3-butadiene, 1-butene, iso-butene, trans-2-butene and cis-2-butene on SIFSIX-14-Cu-I under 298K.

Example 25

(42) The SIFSIX-14-Cu-i material was packed into the column (inner diameter 4.6 mm, length 150 mm), and then the mixture of 1,3-butadiene:iso-butene:ethylene:methane (50:50:5:5 in volume) was introduced into the column with flow rate of 2.5 mL/min. The outflow gas is iso-butene, ethylene and methane mixtures. when 1,3-butadiene broke through the column, the adsorption was stopped. The column was purged with 1,3-butadiene, and then degassed under vacuum condition, leading to high purity 1,3-butadiene (>99%), the column could be reused.

Example 26

(43) The mixture of trans-2- and cis-2-butenes (50:50 in volume, 0.1 MPa) was introduced into the SIFSIX-14-Cu-i column with flow rate of 1.0 mL/min at 25° C. High purity cis-butene (higher than 99.99%) firstly broke through the column, when trans-2-butene broke out, the adsorption was stopped. The column was purged with He to desorb trans-2-butene, then the column could be reused.

Example 27

(44) A methanol solution (20 mL) containing 244.0 mg Cu(BF.sub.4).sub.2.3H.sub.2O and 272.0 mg (NH.sub.4).sub.2GeF.sub.6 was mixed with 360.0 mg 4,4′-azopyridine in methanol solution (20 mL). The mixture was stirred at room temperature for 12 hours, then filtered and washed methanol. The resulted products were then purged with N2 for 24 hours at 45° C., leading to GEFSIX-14-Cu-i. FIG. 10 presents the N.sub.2 (77 K) and CO.sub.2 (196 K) adsorption isotherms on GEFSIX-14-Cu-i; FIG. 11 presents the adsorption isotherms of 1,3-butadiene, 1-butene, iso-butene, cis-butene and trans-butene on GEFSIX-14-Cu-i at 298 K. FIG. 12 illustrates the crystal structures of GEFSIX-14-Cu-i.

Example 28

(45) The obtained GEFSIX-14-Cu-i was packed into the column of 10 cm (inner diameter 4.6 mm, length 150 mm), into which then introduced the mixtures of 1,3-butadiene:iso-butene:1-butene:trans-2-butene:cis-2-butene (20:20:20:20:20) with flow rate of 1.0 mL/min at 20° C. When 1,3-butadiene broke out the column, the adsorption process was stopped. The column was purged with 1,3-butadiene to remove the adsorbed trans-butene, then 1,3-butadiene was desorbed from the column under vacuum with high purity 1,3-butadiene (>99%) obtained, then the column could be reused. FIG. 13 shows the corresponding breakthrough curves.

Example 29

(46) The mixtures of 1,3-butadiene, iso-butene, and iso-butane (80:15:5 in volume) was introduced into the GEFSIX-14-Cu-i column of Example 28 with flow rate of 1.0 mL/min at 35° C. The iso-butene and iso-butane mixture with 1,3-butadiene less than 10 ppm was obtained. When 1,3-butadiene broke through the column, the adsorption process was stopped. Then 1,3-butadiene was used to remove the adsorbed iso-butene and iso-butane onto GEFSIX-14-Cu-i column, after that, high purity 1,3-butadiene (more than 97%) could be obtained by degassing the column under vacuum, and the column could be reused.

Example 30

(47) The mixtures of 1,3-butadiene, 1-butene, iso-butene, cis-2-butene, trans-2-butene, and iso-butane (50:10:25:5:5 in volume) was introduced into the GEFSIX-14-Cu-i column of Example 28 with flow rate of 2.0 ml/min at 20° C. Then the NbFSIX-2-Cu-i column under 10° C. was connected back with GEFSIX-14-Cu-i column. When 1-butene broke through the column, the adsorption was stopped. GEFSIX-14-Cu-i column was then purged with 1,3-butadiene to remove trans-2-butene, then this column was degassed under vacuum, resulting high purity 1,3-butadien (higher than 97%), then the column could be reused. The NbFSIX-2-Cu-i column was degassed under vacuum, resulting in high purity 1-butene (95%), the column could be reused.

Example 31

(48) A methanol solution (10 mL) containing 185.0 mg 4,4′-azopyridine was carefully dropped onto 20 mL glycol and methanol solution (1:1 in volume) containing 125.0 mg CuCl.sub.2.H.sub.2O and 117.0 mg NH.sub.4NbF.sub.6. After one week, the obtained products were filtered and washed with methanol, the resulted samples were activated under vacuum for 24 hours, leading to NbFSIX-14-Cu-i.

Example 32

(49) The obtained NbFSIX-14-Cu-i was packed into the column of 10 cm, then the mixture of 1-butene:iso-butene:propane (40:40:20 in volume) with flow rate of 1.0 mL/min. The mixture of iso-butene and propane firstly broke out the column, when 1-butene broke through the column, the adsorption was stopped. Then high purity 1-butene (97%) was desorbed from the column under vacuum, then the column could be reused.

(50) Furthermore, the foregoing descriptions of the embodiments according to the present invention are provided for illustration only, not for the purpose of limiting the invention as defined by the appended claims and their equivalents. Although only the selected embodiments have been chosen to illustrate the present invention, the all involved change or modification without departing from the scope of the invention as defined in the appended claims are covered in this invention.