Metal-organic frameworks based on on 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid

Abstract

The present invention relates to porous metallic frameworks comprising at least one at least bidentate organic compound coordinated to at least one metal ion, wherein the at least one at least bidentate organic compound is derived from 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid. The present invention further relates to shaped bodies comprising these frameworks, processes for producing them and their use, in particular for the storage and separation of gases.

Claims

1. A method of separating gaseous water from a gas mixture, the method comprising exposing the gas mixture to a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion that includes aluminum ion, wherein the at least one at least bidentate organic compound is derived from 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid, wherein the porous metal-organic framework has a Langmuir surface area of from 1153 m.sup.2/g to 1375 m.sup.2/g, or a BET surface area of 850 m.sup.2/g to 1021 m.sup.2/g, follow preactivation at 130C.

2. The method according to claim 1, wherein the porous metal-organic framework is comprised in a shaped body.

3. The method according to claim 1, wherein the porous metal-organic framework is prepared by a process, the process comprising: (a) reaction of a reaction mixture comprising a metal salt corresponding to the at least one metal ion and 2,5-furandicarboxylic acid or 2,5- thiophenedicarboxylic acid and also a solvent at a temperature in the range from 100 C. to 150 C. for at least 3 hours and (b) isolation of the precipitated solid.

4. The method according to claim 3, wherein the initial concentration of the metal salt in the reaction mixture is in the range from 0.05 mol/L to 0.8 mol/L .

5. The method according to claim 3, wherein the ratio of the initial molar amount of 2,5-furandicarboxylic acid or 2,5-thiophenedicarboxylic acid used to the initial molar amount of metal salt used, based on the metal, is in the range from 0.5:1 to 2:1.

6. The method according to claim 5, wherein the gaseous mixture is natural gas that includes the gaseous water.

7. The method according to claim 3, wherein the solvent comprises N,N-dimethylformarmide.

8. The method according to claim 1, wherein the at least one at least bidentate organic compound is derived from unsubstituted 2,5-furandicarboxylic acid or unsubstituted 2,5- thiophenedicarboxylic acid.

9. The method according to claim 1, wherein the at least one at least bidentate organic compound is derived from 2,5-furandicarboxylic acid.

10. The method according to claim 1, wherein the at least one at least bidentate organic compound is derived from 2,5-thiophenedicarboxylic acid.

11. The method according to claim 1, wherein the gaseous mixture is natural gas that includes the gaseous water.

12. A method of separating gaseous water from a gas mixture, the method comprising exposing the gas mixture to a porous metal-organic framework comprising at least one at least bidentate organic compound coordinated to at least one metal ion that includes aluminum ion, wherein the at least one at least bidentate organic compound is derived from 2,5-thiophenedicarboxylic acid.

Description

(1) The present invention is illustrated with the aid of the figures and the examples below.

(2) FIG. 1 shows the adsorption and desorption at 40 C. for a metal-organic framework according to the invention (Al-2,5-furandicarboxylic acid MOF). Here, the amount of adsorbed gas (N) in mg per gram of framework is shown as a function of the absolute pressure p in mbar.

(3) As can be seen from FIG. 1, it is possible to separate off CO.sub.2 due to the different adsorption isotherms.

(4) FIG. 2 shows the hydrogen adsorption at 77 K for the framework (Al-2,5-furandicarboxylic acid) as per Example 1, with preactivation being carried out at 130 C. for 4 hours (P.sub.0 H.sub.2 at 77 K =94 632.4 torr). FIG. 2 shows the amount of hydrogen absorbed (in cm.sup.3/gSTP) (left-hand scale) and the proportion by weight of hydrogen (% by weight) (right-hand scale) as a function of the relative pressure p divided by p0.

(5) FIG. 3 shows the absorption of gaseous water by Al-2,5-thiophenedicarboxylic acid MOF at various relative humidities (RH). Here, the amount W in % by weight is shown as a function of RH in %.

EXAMPLES

Example 1

Al-2,5-Furandicarboxylic acid MOF

(6) Experimental Method:

(7) TABLE-US-00001 Starting material Molar Calculated Experimental 1) Aluminum chloride * 6 water 48.75 mmol 11.8 g 11.8 g 2) 2,5-Furandicarboxylic acid 82.87 mmol 12.9 g 12.9 g 3) DMF 6.8 mol 500.0 g 500.0 g

(8) In a 2 l four-neck flask, the furandicarboxylic acid and the aluminum chloride are suspended in the DMF. The solution with a proportion of solids is boiled at 130 C. for 24 hours, resulting in formation of a white suspension. After cooling, the white precipitate is filtered off and washed 1 ml with 200 ml of DMF and 4 times with 200 ml of methanol. The filter cake is dried at RT for 16 hours in a vacuum.

(9) Weight obtained: 10.3 g

(10) Color: white

(11) Solids concentration: 2.0%

(12) Space-time yield: 19.6 kg/m.sup.2/d

(13) Yield based on Al: 91%

(14) Analyses:

(15) Langmuir surface area (preactivation at 130 C.): 1153 m.sup.2/g (BET: 850 m.sup.2/g)

(16) Chemical Analysis:

(17) TABLE-US-00002 Chloride ion 0.47 g/100 g Carbon 34.7 g/100 g Oxygen 51 g/100 g Nitrogen 0.9 g/100 g Hydrogen 2.4 g/100 g Al 11.7 g/100 g

(18) H.sub.2O adsorption, RT, 75% relative humidity: 35 wt %

Example 2

Mg-2,5-Furandicarboxylic acid MOF

(19) Experimental Method:

(20) TABLE-US-00003 Starting material Molar Calculated Experimental 1) Magnesium nitrate * 6 water 73.1 mmol 18.7 g 18.7 g 2) 2,5-Furandicarboxylic acid 82.87 mmol 12.9 g 12.9 g 3) DMF 6.8 mol 500.0 g 500.0 g

(21) In a 1 l four-neck flask, the furandicarboxylic acid and the magnesium nitrate are suspended in the DMF. The solution with a proportion of solids is boiled at 130 C. for 24 hours, resulting in formation of a white suspension. After cooling, the white precipitate is filtered off and washed once with 200 ml of DMF and four times with 200 ml of methanol. The filter cake is dried at RT for 16 hours in a high vacuum.

(22) Weight obtained: 15.3 g

(23) Color: white

(24) Solids concentration: 2.9%

(25) Space-time yield: 29.3 kg/m.sup.2/d

(26) Yield based on Mg: 79.5%

(27) Analyses:

(28) Langmuir surface area (preactivation at 130 C.): 10 m.sup.2/g (BET: 7 m.sup.2/g)

(29) Chemical Analysis:

(30) TABLE-US-00004 Carbon 43.2 g/100 g Oxygen 38.7 g/100 g Nitrogen 5.8 g/100 g Hydrogen 4.1 g/100 g Mg 8.1 g/100 g

(31) H.sub.2O adsorption, RT, 75% relative humidity: 41 wt %

Example 3

Fe-2,5-Furandicarboxylic acid MOF

(32) Experimental Method:

(33) TABLE-US-00005 Starting material Molar Calculated Experimental 1) Iron nitrate * 9 water 48.7 mmol 19.6 g 19.6 g 2) 2,5-Furandicarboxylic acid 82.87 mmol 12.9 g 12.9 g 3) DMF 6.8 mol 500.0 g 500.0 g

(34) In a 1 l four-necked flask, the furandicarboxylic acid and the iron nitrate are suspended in the DMF. During heating to 130 C., the solution thickens to form a dark brown viscose gel. After the stirrer speed has been increased, the gel liquefies slightly. The gel is boiled at 130 C. for 24 hours. After cooling, the dark brown precipitate is filtered off and washed once with 200 ml of DMF and 4 times with 200 ml of methanol. The filter cake is dried at RT for 16 hours in a high vacuum.

(35) Weight obtained: 17.5 g

(36) Color: rust-brown

(37) Solids concentration: 3.2%

(38) Space-time yield: 32.3 kg/m.sup.2/d

(39) Yield based on Fe: 69.1%

(40) Analyses:

(41) Langmuir surface area (preactivation at 130 C.): 419 m.sup.2/g (BET: 303 m.sup.2/g)

(42) Chemical Analysis:

(43) TABLE-US-00006 Carbon 37.9 g/100 g Oxygen 33.9 g/100 g Nitrogen 7.1 g/100 g Fe 15.0 g/100 g

Example 4

Zn-2,5-Furandicarboxylic acid MOF

(44) Experimental Method:

(45) TABLE-US-00007 Starting material Molar Calculated Experimental 1) Zinc nitrate * 4 water 73.1 mmol 19.5 g 19.5 g 2) 2,5-Furandicarboxylic acid 82.87 mmol 12.9 g 12.9 g 3) DMF 6.8 mol 500.0 g 500.0 g

(46) In a 1 l four-neck flask, the furandicarboxylic acid and the zinc nitrate are suspended in the DMF. The solution with a proportion of solids is boiled at 130 C. for 24 hours, resulting in formation of a white suspension. After cooling, the white precipitate is filtered off under a nitrogen atmosphere and washed once with 200 ml of DMF and 4 times with 200 ml of chloroform. The filter cake is dried at RT for 16 hours in a high vacuum.

(47) Weight obtained: 15.6 g

(48) Color: white

(49) Solids concentration: 2.9%

(50) Space-time yield: 29.3 kg/m.sup.2/d

(51) Yield based on Zn: 54.1%

(52) Analyses:

(53) Langmuir surface area (preactivation at 130 C.): 3 m.sup.2/g (BET: 2 m.sup.2/g)

(54) Chemical Analysis:

(55) TABLE-US-00008 Carbon 39.2 g/100 g Oxygen 33.9 g/100 g Nitrogen 5.7 g/100 g Hydrogen 3.9 g/100 g Zn 17.1 g/100 g

Example 5

Cu-2,5-Furandicarboxylic acid MOF

(56) Experimental Method:

(57) TABLE-US-00009 Starting material Molar Calculated Experimental 1) Copper chloride * 2 water 73.1 mmol 12.5 g 12.5 g 2) 2,5-Furandicarboxylic acid 82.87 mmol 12.9 g 12.9 g 3) DMF 6.8 mol 500.0 g 500.0 g

(58) In a 1 l four-neck flask, the furandicarboxylic acid and the copper chloride are suspended in the DMF. The solution with a proportion of solids is boiled at 130 C. for 24 hours, resulting in formation of a blue suspension. After cooling, the blue precipitate is filtered off and washed once with 200 ml of DMF and 4 times with 200 ml of methanol. The filter cake is dried at RT for 16 hours in a high vacuum.

(59) Weight obtained: 2.5 g

(60) Color: blue

(61) Solids concentration: 0.5%

(62) Space-time yield: 7.6 kg/m.sup.2/d

(63) Yield based on Cu: 9.6%

(64) Analyses:

(65) Langmuir surface area (preactivation at 130 C.): 307 m.sup.2/g (BET: 227 m2/g)

(66) Chemical Analysis:

(67) TABLE-US-00010 Carbon 36.2 g/100 g Oxygen 32.7 g/100 g Nitrogen 5.6 g/100 g Cu 17.9 g/100 g

Example 6

Al-2,5-Thiophenedicarboxylic acid MOF

(68) Apparatus:

(69) 500 ml four-neck flask

(70) Low-temperature cooler

(71) Oil bath

(72) Stirrer, PTFE coated

(73) Thermometer

(74) Nitrogen blanketing

(75) Batch:

(76) TABLE-US-00011 Molar Mass Batch Comment 2,5-Thiophene- 172.16 23.20 mmol 3.99 g dicarboxylic acid g/mol Aluminum 241.43 13.65 mmol 3.33 g w = 99% chloride 6 water g/mol DMF 73.0 1904 mmol 138.99 g 146 ml D = 0.95 g/cm.sup.3 Temperature: 130 C./reflux Duration: 24 hours
Procedure:

(77) Place 146 ml of N,N-dimethylformamide in a four-neck flask and introduce 3.99 g of thiophenedicarboxylic acid (1) and 3.33 g of aluminum chloride6 water (2) at room temperature while stirring. A colorless solution is formed. The reaction mixture is subsequently heated to 130 C. (reflux). The reaction mixture is maintained at 130 C. for 24 hours and then cooled to RT.

(78) The white suspension/precipitate is separated off on a glass filter frit No. 3, and can be filtered readily.

(79) DMF Washing:

(80) The filter cake is slurried with 100 ml of N,N-DMF, left in contact for 15 minutes, subsequently filtered off with suction. The procedure is repeated twice using 100 ml of DMF each time.

(81) Methanol Washing:

(82) The filter cake is subsequently slurried with 100 ml of AR methanol, left in contact for 15 minutes, subsequently filtered off with suction. The procedure is repeated 4 times using 100 ml of AR methanol each time.

(83) Drying:

(84) The filter cake is dried at 130 C. for 24 hours in a vacuum drying oven at <20 mbar.

(85) Color: colorless

(86) Weight obtained: 3.1 g

(87) Analysis:

(88) BET/LM: 1021 /1375 m.sup.2/g

(89) General Data:

(90) Yield (linker): 62.5%

(91) Yield (metal salt): 105.8%

(92) Solids content (product): 2.2% by weight

(93) Space-time yield: 21.2 kg/m.sup.3/d