Carbon pyrolyzate adsorbent having utility for CO2 capture and methods of making and using the same

Patent metadata

Field	Value
Publication number	US-9156020-B2
Application number	US-201514672127-A
Country	US
Kind code	B2
Filing date	Mar 28, 2015
Priority date	Jan 31, 2011
Publication date	Oct 13, 2015
Grant date	Oct 13, 2015

Abstract

A particulate form carbon pyrolyzate adsorbent, having the following characteristics: (a) CO 2 capacity greater than 105 cc/gram at one bar pressure and temperature of 273° Kelvin; (b) CO 2 Working Capacity greater than 7.0 weight percent; (c) CO 2 heats of adsorption and desorption each of which is in a range of from 10 to 50 kJ/mole; and (d) a CO 2 /N 2 Henry's Law Separation Factor greater than 5. The carbon pyrolyzate material can be formed from a polyvinylidene chloride-based polymer or copolymer, or other suitable resin material, to provide an adsorbent that is useful for carbon dioxide capture applications, e.g., in treatment of flue gases from coal-fired power generation plants.

First claim

What is claimed is:

1. A carbon pyrolyzate adsorbent, comprising a pyrolyzate of a PVDC copolymer, wherein the PVDC copolymer comprises a copolymer of an acrylic acid ester, said adsorbent having the following characteristics:
(a) CO 2 capacity greater than 105 cc/gram at one bar pressure and temperature of 273° Kelvin;
(b) CO 2 Working Capacity greater than 7.0 weight percent;
(c) CO 2 heats of adsorption and desorption each of which is in a range of from 10 to 50 kJ/mole; and
(d) a CO 2 /N 2 Henry's Law Separation Factor greater than 5.

2. The adsorbent of claim 1 , wherein the acrylic acid ester comprises methyl acrylate.

3. The adsorbent of claim 1 , comprising particles of diameter in a range of from 10 to 500 μm.

4. The adsorbent of claim 1 , comprising particles having a median particle diameter in a range of from 200 to 350 μm.

5. The adsorbent of claim 1 , having a water sorptive capacity of less than 5% by weight, based on weight of the adsorbent, at 303° Kelvin and 40% relative humidity.

6. The adsorbent of claim 1 , having porosity at least 50% of the pore volume of which is constituted by pores in a pore size range of from 0.35 to 0.7 nm.

7. The adsorbent of claim 1 , having porosity characterized by a median pore width below 1 nm.

8. The adsorbent of claim 1 , having a nitrogen BET surface area of at least 800 m 2 per gram.

9. The adsorbent of claim 1 , having a nitrogen micropore volume of at least 0.2 mL per gram.

10. The adsorbent of claim 1 , characterized by CO 2 capture recovery of at least 90% and CO 2 capture purity of at least 90%, when contacted with a simulated flue gas composition comprising air containing 15% CO 2 and saturated with water vapor, at 383° Kelvin and volumetric flow rate of 100 L/minute of simulated flue gas composition per liter of bed of the adsorbent.

11. The adsorbent of claim 1 , wherein the adsorbent has at least one additional compatible characteristic selected from the group consisting of:
(e) being a pyrolyzate of homopolymer PVDC, PVDC-MA copolymer, PVDC-polyvinyl chloride (PVDC-PVC) copolymers, polyfurfuryl alcohol, polyacrylonitrile, and polymers containing heteroatoms that upon carbonization are left as dispersed species throughout the carbon material;
(f) an average particle diameter greater than 50 μm;
(g) particle diameter in a range of from 10 to 500 μm;
(h) particle diameter in a range of 150 to 500 μm;
(i) median particle diameter in a range of from 200 to 350 μm;
(j) bulk density greater than 0.55 g/mL;
(k) CO 2 heats of adsorption and desorption each of which is in a range of from 20 to 30 kJ/mole;
(l) water adsorptive capacity of less than 5% by weight, based on weight of the adsorbent, at 303° Kelvin and 40% relative humidity;
(m) average pore size below 1 nm;
(n) porosity at least 50% of the pore volume of which is constituted by pores in a pore size range of from 0.35 to 0.7 nm;
(o) porosity characterized by a median pore width below 1 nm;
(p) an attrition rate index less than 1 wt %/hr as measured by the procedure of ASTM D 5757;
(q) N 2 BET surface area of at least 800 m 2 per gram;
(r) N 2 BET surface area of at least 900 m 2 per gram;
(s) N 2 BET surface area of at least 1000 m 2 per gram;
(t) N 2 micropore volume of at least 0.2 mL per gram;
(u) N 2 micropore volume in a range of from 0.3 to 0.6 mL per gram;
(v) CO 2 capture recovery of at least 90% and CO 2 capture purity of at least 90%, when contacted with a simulated flue gas composition comprising air containing 15% CO 2 and saturated with water vapor, at 383° Kelvin and volumetric flow rate of 100 L/minute of simulated flue gas composition per liter of a bed of the adsorbent;
(w) being a pyrolyzate of homopolymer PVDC, PVDC-MA copolymer having a weight average molecular weight in a range of from 80,000 to 100,000;
(x) bulk density greater than 0.55 grams per cubic centimeter;
(y) bulk density greater than 0.9 grams per cubic centimeter;
(z) bulk density in a range of from about 1.0 to about 2.2 grams per cubic centimeter;
(aa) being in a form of granules;
(ab) being in a bead form;
(ac) being in a form of a monolith;
(ad) being in a cylindrical form;
(ae) being in a disc form;
(af) being of porous, non-graphitized carbon;
(ag) N 2 BET surface area being in a range of from tw m 2 per gram;
(ah) having porosity, substantially all of which is in pores <2 nm in diameter;
(ai) CO 2 capacity greater than 120 volumes of CO 2 /volume of carbon pyrolyzate adsorbent as measured at 273° Kelvin and 1 atmosphere pressure;
(aj) CO 2 capacity greater than 130 volumes of CO 2 /volume of carbon pyrolyzate adsorbent as measured at 273° Kelvin and 1 atmosphere pressure;
(ak) CO 2 capacity of at least 20 wt % at 1 atm CO 2 , based on weight of the adsorbent;
(al) CO 2 adsorption activation energy less than 5 kJ/mole;
(am) CO 2 heats of adsorption and desorption each of which is in a range of from 25 to 28 kJ/mole;
(an) CO 2 being desorbable from the adsorbent with steam;
(ao) adsorbent lifetime of at least 50,000 adsorption/desorption cycles for adsorption and desorption of CO 2 ;
(ap) being in a form of spherical adsorbent granules;
(aq) being in a form of spherical adsorbent granules 100 to 300 μm in diameter;
(ar) non-agglomerable or sinterable at 100° C.;
(as) being of hydrophobic character;
(at) CO 2 capacity of at least 100 volumes of CO 2 /volume of carbon material, as measured at 273° Kelvin and 1 atmosphere pressure;
(au) being >40% by volume micropores;
(av) having at least 50% of pore volume in pores <0.7 nm;
(aw) a separation factor greater than 6 for CO 2 over N 2 ;
(ax) a separation factor in a range of from 6.2 to 7.5 for CO 2 over N 2 ;
(ay) a permeability for CO 2 greater than 900 cc/psi/cm 2 /min;
(az) a permeability for CO 2 in a range of from 910 to 1250 cc/psi/cm 2 /min; and
(ba) an attrition rate index <0.01 wt % per hour in a downflow reactor.

12. A method of making an adsorbent for carbon capture, said method comprising pyrolyzing a PVDC copolymer, wherein the PVDC copolymer comprises a copolymer of an acrylic acid ester, under conditions that are effective to yield a carbon pyrolyzate material having the following characteristics:
(a) CO 2 capacity greater than 105 cc/gram at one bar pressure and temperature of 273° Kelvin;
(b) CO 2 Working Capacity greater than 7.0 weight percent;
(c) CO 2 heats of adsorption and desorption each of which is in a range of from 10 to 50 kJ/mole; and
(d) a CO 2 /N 2 Henry's Law Separation Factor greater than 5.

13. The method of claim 12 , wherein the acrylic acid ester comprises methyl acrylate.

14. The method of claim 12 , wherein the PVDC copolymer comprises a PVDC-MA copolymer having a weight average molecular weight in a range of from 80,000 to 100,000.

15. The method of claim 12 , wherein said pyrolyzing is conducted at temperature in a range of from 600° C. 2 900° C. under inert atmosphere.

16. The method of claim 15 , followed by exposing the carbon pyrolyzate material to an oxidizing atmosphere at temperature above 250° C.

17. A CO2 capture apparatus, comprising the carbon pyrolyzate adsorbent of claim 1 in a reactor configured for contacting of the carbon pyrolyzate adsorbent with CO2-containing gas.

18. The CO2 capture apparatus of claim 17 , configured for regeneration of the carbon pyrolyzate adsorbent after it has been loaded to a predetermined extent with CO2 in said contacting.

19. The CO2 capture apparatus of claim 17 , comprising a m

Assignees

• Entegris Inc

Inventors

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

Classifications

• B01D53/04

  with stationary adsorbents {(B01D53/025 takes precedence)} · CPC title

• B01J20/28011

  Other properties, e.g. density, crush strength · CPC title

• B01J20/3078

  Thermal treatment, e.g. calcining or pyrolizing · CPC title

• B01D2258/0283

  Flue gases · CPC title

• B01D2257/504

  Carbon dioxide · CPC title