Adsorbent having utility for CO2 capture from gas mixtures

Patent metadata

Field	Value
Publication number	US-9283512-B2
Application number	US-201514833225-A
Country	US
Kind code	B2
Filing date	Aug 24, 2015
Priority date	Apr 5, 2013
Publication date	Mar 15, 2016
Grant date	Mar 15, 2016

Abstract

A carbon pyrolyzate adsorbent is described that is selective for carbon dioxide in contact with gas mixtures including carbon dioxide and methane. The adsorbent has a carbon dioxide adsorbent capacity at 1 bar pressure of greater than 50 cm 3 carbon dioxide per gram of adsorbent at 273K, a methane adsorption capacity at 1 bar pressure of less than 35 cm 3 methane per gram of adsorbent at 21° C., and a bulk density of greater than 0.55 gram per cubic centimeter of volume. Such adsorbent can be utilized, for example, for biogas upgrading, natural gas purification, coal bed methane purification, and refining operations.

First claim

What is claimed is:

1. A method of removing carbon dioxide from a gas mixture including carbon dioxide and methane, said method comprising contacting said gas mixture with a carbon pyrolyzate adsorbent having a carbon dioxide adsorbent capacity at 1 bar pressure of greater than 50 cm 3 carbon dioxide per gram of adsorbent at 273K, a methane adsorption capacity at 1 bar pressure of less than 35 cm 3 methane per gram of adsorbent at 21° C., and a bulk density of greater than 0.55 gram per cubic centimeter of volume, wherein said gas mixture comprises gas selected from the group consisting of biogas, natural gas, coal bed methane, refining operations gas, methane fuel gas, and steam-methane reforming gas.

2. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has the following characteristics: (i) total ash content of less than 1% as measured by ASTM D2866; (ii) bulk density, as measured by ASTM D2854, of greater than 0.55 g/cc and less than 1.25 g/cc; (iii) carbon dioxide adsorption capacity measured at 1 bar pressure and a temperature of 273 Kelvin of greater than 50 cm3 carbon dioxide per gram of adsorbent; (iv) methane adsorption capacity measured at 1 bar pressure and a temperature of 21° C. of less than 35 cm 3 methane per gram of adsorbent; (v) CO 2 heats of adsorption and desorption each of which is in the range of 5 to 50 kJ/mole; (vi) single pellet radial crush strength for a nominal 3 mm pellet of greater than 7 kilopound (kP), as measured by ASTM D4179.

3. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has a monolith, block, brick, bar, disc, columnar, honeycomb, channeled block, fibrous wool, felt, fabric, sponge, mat, particulate, tablet, pellet, extrudate, or bead form.

4. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has a monolithic form.

5. The method of claim 2 , wherein said carbon pyrolyzate adsorbent has a monolithic form.

6. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has a particulate, tablet, pellet, bead, or extrudate form.

7. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has a particulate form.

8. The method of claim 2 , wherein said carbon pyrolyzate adsorbent has a particulate form.

9. The method of claim 1 , wherein said carbon pyrolyzate adsorbent has a particulate form and comprises carbon pyrolyzate adsorbent particles of particle size in a range of 0.1 to 7.0 mm.

10. The method of claim 1 , wherein the carbon pyrolyzate adsorbent comprises a pyrolyzate of a polymer or copolymer, selected from the group consisting of polyvinylidene fluoride, polyvinylidene chloride, and copolymers of polyvinylidene fluoride or polyvinylidene chloride with any of acrylonitrile, styrene, methyl acrylate, vinyl fluoride, vinyl chloride, and methyl methacrylate.

11. The method of claim 1 , wherein the carbon pyrolyzate adsorbent comprises a polymer or copolymer of polyvinylidene fluoride.

12. The method of claim 1 , wherein the carbon pyrolyzate adsorbent comprises a polymer or copolymer of polyvinylidene chloride.

13. The method of claim 1 , wherein the carbon pyrolyzate adsorbent comprises a copolymer of (i) polyvinylidene chloride and (ii) methyl acrylate or methyl methacrylate.

14. The method of claim 2 , wherein the carbon pyrolyzate adsorbent comprises a polymer or copolymer of polyvinylidene fluoride.

15. The method of claim 2 , wherein the carbon pyrolyzate adsorbent comprises a polymer or copolymer of polyvinylidene chloride.

16. The method of claim 2 , wherein the carbon pyrolyzate adsorbent comprises a copolymer of (i) polyvinylidene chloride and (ii) methyl acrylate or methyl methacrylate.

17. The method of claim 10 , wherein the polymer or copolymer has a density in a range of from 0.75 to 1.75 g/cc, and a melting point in a range of from 125 to 265° C.

18. A method of making a carbon pyrolyzate adsorbent that is selective for carbon dioxide in contact with gas mixtures including carbon dioxide and methane, said method comprising pyrolyzing a polymer or copolymer of polyvinylidene fluoride or polyvinylidene chloride to form a pyrolyzate, and activating the pyrolyzate under sufficient conditions of environment, pressure, temperature, and time to yield said carbon pyrolyzate adsorbent, having a carbon dioxide adsorption capacity at 1 bar pressure of greater than 50 cm 3 carbon dioxide per gram of adsorbent at 273° K, a methane adsorption capacity at 1 bar pressure of less than 35 cm 3 methane per gram of adsorbent at 21° C., and a bulk density of greater than 0.55 gram per cubic centimeter of volume.

19. The method of claim 18 , wherein the polymer or copolymer has a bulk density in a range of from 0.75 to 1.75 g/cc, and a melting point in a range of from 125 to 265° C., said polymer or copolymer optionally also having up to 15% by weight other additives or processing aids.

20. A method of enhancing removal of carbon dioxide from a gas mixture including carbon dioxide and methane in a process for such removal, said method comprising supplying for use in said process a carbon pyrolyzate adsorbent having a carbon dioxide adsorbent capacity at 1 bar pressure of greater than 50 cm 3 carbon dioxide per gram of adsorbent at 273K, a methane adsorption capacity at 1 bar pressure of less than 35 cm 3 methane per gram of adsorbent at 21° C., and a bulk density of greater than 0.55 gram per cubic centimeter of volume, as an adsorbent medium for contacting the gas mixture in said process.

21. The method of claim 1 , wherein the carbon pyrolyzate adsorbent includes porosity comprising pores having pore size in a range of from 0.30 nm to 0.40 nm.

22. The method of claim 1 , wherein the gas mixture comprises natural gas.

23. The method of claim 1 , wherein the gas mixture comprises refining operations gas.

24. The method of claim 18 , wherein the carbon pyrolyzate adsorbent includes porosity comprising pores having pore size in a range of from 0.30 nm to 0.40 nm.

25. An adsorbent that is selective for carbon dioxide in contact with gas mixtures including carbon dioxide and methane, said adsorbent having a carbon dioxide adsorption capacity at 1 bar pressure of greater than 50 cm 3 carbon dioxide per gram of adsorbent at 273K, a methane adsorption capacity at 1 bar pressure of less than 35 cm 3 methane per gram of adsorbent at 21° C., a bulk density of greater than 0.55 gram per cubic centimeter of volume, and porosity comprising pores having pore size in a range of from 0.30 nm to 0.40 nm.

26. The adsorbent of claim 25 , having the following characteristics: (i) total ash content of less than 1% as measured by ASTM D2866; (ii) bulk density, as measured by ASTM D2854, of greater than 0.55 g/cc and less than 1.25 g/cc; (iii) carbon dioxide adsorption capacity measured at 1 bar pressure and a temperature of 273 Kelvin of greater than 50 cm3 carbon dioxide per gram of adsorbent; (iv) methane adsorption capacity measured at 1 bar pressure and a temperature of 21° C. of less than 35 cm 3 methane per gram of adsorbent; (v) CO 2 heats of adsorption and desorption each of which is in the range of 5 to 50 kJ/mole; (vi) single pellet radial crush strength for a nominal 3 mm pellet of greater than 7 kilopound (kP), as measured by ASTM D4179.

27. The adsorbent of claim 25 , wherein said adsorbent has a monolithic form.

28. The adsorbent of claim 25 , wherein said adsorbent has a particula

Assignees

• Entegris Inc

Inventors

• Carruthers J Donald
• Petruska Melissa A
• Wilson Shaun M
• Sturm Edward A

Classifications

• B01J20/20

  comprising free carbon; comprising carbon obtained by carbonising processes · CPC title

• B01D2253/202

  Polymeric adsorbents · CPC title

• B01D2253/311

  Porosity, e.g. pore volume · CPC title

• B01D2258/05

  Biogas · CPC title

• B01J20/28016

  Particle form · CPC title