Polyamine-appended metal-organic frameworks for carbon dioxide separations

Patent metadata

Field	Value
Publication number	US-11014067-B2
Application number	US-201816175708-A
Country	US
Kind code	B2
Filing date	Oct 30, 2018
Priority date	Oct 31, 2017
Publication date	May 25, 2021
Grant date	May 25, 2021

Abstract

Polyamines with lengths carefully tailored to the framework dimensions are appended to metal-organic frameworks such as Mg2(dobpdc) (dobpdc4-=4,4′-dioxidobiphenyl-3,3′-dicarboxylate) with the desired loading of one polyamine per two metal sites. The polyamine-appended materials show step-shaped adsorption and desorption profiles due to a cooperative CO2 adsorption/desorption mechanism. Several disclosed polyamine-appended materials exhibit strong ability to capture CO2 from various compositions. Increased stability of amines in the framework has been achieved using high molecular weight polyamine molecules that coordinate multiple metal sites in the framework. The preparation of these adsorbents as well as their characterization are provided.

First claim

We claim:

1. An activated adsorption material, comprising:
a metal-organic framework comprising a plurality of metal cations and a plurality of polytopic organic linkers; and
a plurality of polyamine ligands, wherein
each respective polyamine ligand in the plurality of polyamine ligands comprises:

X 1 and X 2 are respective first and second metal cations in the plurality of metal cations,
Y is:

Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Q 1 and Q 2 are each independently carbon, silicon, germanium, sulfur, or selenium,
i, j, k, x, y, and z are each independently 0, 1, or 2,
m is 2, 3, or 4, and
each instance of each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 is independently H, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted arlyoxy, or substituted or unsubstituted heteroaryloxy, wherein at least twenty percent of the polyamine ligands in the plurality of polyamine ligands are (i) amine appended by a first amine to a first metal cation in the plurality of metal cations and (ii) amine appended by a second amine to a second cation in the plurality of metal cations of the metal-organic framework.

2. The activated adsorption material of claim 1 , wherein at least eighty percent of the polyamine ligands in the plurality of polyamine ligands are (i) amine appended by a first amine to a first metal cation in the plurality of metal cations and (ii) amine appended by a second amine to a second metal cation in the plurality of metal cations of the metal-organic framework.

3. The activated adsorption material of claim 1 , wherein each metal cation in the plurality of metal cations is Mg, Ca, Cr, Mn, Fe, Co, Ni, Cu, or Zn.

4. The activated adsorption material of claim 1 , wherein
Y is:

and
wherein,
i and j are each zero,
i is 1 and j is zero,
i is 1 and j is 1, or
i is 1 and j is 2.

5. The activated adsorption material of claim 1 , wherein
Y is:

k and x are zero, and
m is 2.

6. The activated adsorption material of claim 1 , wherein
Y is:

k and x are each 1, and
m is 3 or 4.

7. The activated adsorption material of claim 1 , wherein
Y is:

and
y and z are each two.

8. The activated adsorption material of claim 1 , wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Q 1 and Q 2 are each independently carbon.

9. The activated adsorption material of claim 1 , wherein each instance of each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 is independently H, halogen, substituted or unsubstituted n-alkyl or a substituted or unsubstituted branched-chain alkyl.

10. The activated adsorption material of claim 9 , wherein each instance of each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 is H.

11. The activated adsorption material of claim 1 , wherein each metal ion (X) in the plurality of metal ions is Mg.

12. The activated adsorption material of claim 1 , wherein the polytopic organic linker is
4,4′-dioxidobiphenyl-3,3′-dicarboxylate (dobpdc 4− ),
4,4″-dioxido-[1,1′:4′,1″-terphenyl]-3,3″-dicarboxylate (dotpdc 4− ),
2,5-dioxidobenzene-1,4-dicarboxylate (dobdc 4− ), or
3,3′ dioxide-biphenyl-4,4′-dicarboxylate (para-carboxylate-dobpdc 4− ).

13. The activated adsorption material of claim 1 , wherein each polyamine ligand in the plurality of polyamine ligands is:
diethylenetriamine,
N-(2-aminoethyl)-1,3-propanediamine,
bis(3-aminopropyl)amine,
N-(3-Aminopropyl)-1,4-diaminobutane,
triethylenetetramine,
N,N′-bis(2-aminoethyl)-1,3-propanediamine,
1,2-bis(3-aminopropylamino)ethane,
N,N′-bis(3-aminopropyl)-1,3-propanediamine,
N,N′-bis(3-aminopropyl)-1,4-diaminobutane, or
tetraethylenepentamine.

14. The activated adsorption material of claim 1 , wherein the loading of the plurality of polyamine ligands to the metal-organic framework is between 80 percent and 120 percent.

15. The activated adsorption material of claim 1 , wherein the adsorption material exhibits a step-shaped CO 2 adsorption profile or desorption profile.

16. The activated adsorption material of claim 1 , wherein the adsorption material exhibits a single or multiple-step-shaped CO 2 adsorption or desorption profile.

17. The activated adsorption material of claim 1 , wherein the adsorption material exhibits a CO 2 adsorption profile that includes a CO 2 adsorption step above 140° C.

18. The activated adsorption material of claim 1 , wherein the polytopic organic linker has the formula:

wherein,
R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.

19. The activated adsorption material of claim 1 , wherein the polytopic organic linker has the formula:

wherein R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.

20. The activated adsorption material of claim 1 , wherein the polytopic organic linker has the formula:

wherein,
R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl.

21. The activated adsorption material of claim 1 , wherein the polytopic organic linker has the formula:

wherein,
R 19 , R 20 , R 21 , R 23 , R 24 , and R 25 , are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl, and
R 22 is selected from substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

22. The activated adsorption material of claim 1 , wherein the polytopic organic linker has the formula:

wherein,
R 19 , R 20 , R 21 , R 23 , R 24 , and R 25 are each independently selected from H, halogen, hydroxyl, methyl, and halogen substituted methyl, and
R 22 is selected from substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

23. The activated ads

Assignees

• Univ California
• Exxonmobil Res & Eng Co

Inventors

• Weston Simon C
• Falkowski Joseph M
• Long Jeffrey R
• Kim Eugene J
• Martell Jeffrey D
• Milner Phillip J
• Siegelman Rebecca L

Classifications

• B01J20/3491

  by pressure treatment · CPC title

• B01J20/3483

  by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling · CPC title

• B01J20/3433

  of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425 · CPC title

• B01J20/3248

  the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such · CPC title

• B01J20/3206

  Organic carriers, supports or substrates · CPC title