Preparation of sorbent pellets with high integrity for sorption of CO;from gas streams

• US 9,333,485 B1
• Filed: 04/24/2015
• Issued: 05/10/2016
• Est. Priority Date: 04/22/2013
• Status: Active Grant

• Current Assignee: US Department of Energy (Government of the United States of America)
• Original Assignee: US Department of Energy (Government of the United States of America)
• Inventors: Siriwardane, Ranjani V.
• Primary Examiner(s): Anthony, Joseph D
• Application Number:
  US14/695,069
• Time in Patent Office: 382 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/20 Organic adsorbents
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/62 Carbon oxides
• CPC Class Codes: B01J 20/041 Oxides or hydroxides
• CPC Class Codes: B01J 20/043 Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
• CPC Class Codes: B01J 20/045 containing sulfur, e.g. sulfates, thiosulfates, gypsum
• CPC Class Codes: B01J 20/048 containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/10 comprising silica or silicate
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/223 containing metals, e.g. organo-metallic compounds, coordination complexes
• CPC Class Codes: B01J 20/26 Synthetic macromolecular compounds
• CPC Class Codes: B01J 20/2805 Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
• CPC Class Codes: B01J 20/30 Processes for preparing, regenerating, or reactivating
• CPC Class Codes: B01J 20/3042 Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• CPC Class Codes: B01J 20/3287 Layers in the form of a liquid
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3458 : in the gas phase
• CPC Class Codes: Y02A 50/20 : Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 : of CO2

Abstract

Method for the production of a CO₂ sorbent prepared by integrating a clay substrate, basic alkali salt, amine liquid, hydraulic binder, and a liquid binder. The basic alkali salt is present relative to the clay substrate in a weight ratio of from about 1 part to about 50 parts per 100 parts of the clay substrate. The amine liquid is present relative to a clay-alkali combination in a weight ratio of from about 1 part to about 10 parts per 10 parts of the clay-alkali combination. The clay substrate and basic alkali salt may be combined in a solid-solid heterogeneous mixture and followed by introduction of the amine liquid. Alternatively, an alkaline solution may be blended with the amine solution prior to contacting the clay substrate. The clay-alkali-amine CO₂ sorbent is particularly advantageous for low temperature CO₂ removal cycles in a gas stream having a CO₂ concentration less than around 2000 ppm and an oxygen concentration around 21%, such as air.

Claims

1. A method of making a CO₂ sorbent comprising:

supplying a clay substrate;

supplying a basic alkali salt, where the basic alkali salt is supplied at from about 1 part to about 50 parts per 100 parts of the clay substrate by weight;

supplying an amine liquid comprised of an amine, where the amine liquid is supplied at from about 1 part to about 10 parts per 10 parts of a clay-alkali combination by weight, where the clay-alkali combination is a combined proportion of the clay substrate and the basic alkali salt;

integrating the clay substrate, the basic alkali salt, and the amine liquid, thereby producing a clay-alkali-amine powder;

supplying a hydraulic binder, where the hydraulic binder is supplied at from about 0.5 parts to about 25 parts per 62 parts of the clay-alkali-amine powder;

mixing the clay-alkali-amine powder and the hydraulic binder, thereby producing a powder-binder mixture;

supplying a liquid binder where the liquid binder has a melting temperature of at least 50°

C. and where the liquid binder has a temperature of at least 50°

C., where the liquid binder is supplied at from about 0.5 part to about 3 parts per 1 part of the hydraulic binder;

blending the liquid binder and the powder-binder mixture, thereby producing CO₂ sorbent pellets; and

cooling the CO₂ sorbent pellets to a temperature of less than 25°

C., thereby generating the CO₂ sorbent.

2. The method of claim 1 where the liquid binder comprises an amino or hydroxy group.

3. The method of claim 2 where the liquid binder comprises ethylene glycol, diethylene glycol, propylene glycol, 1,3-propane diol, glycerol monoacetate, ethyl glycolate, mono- and di-ethanol amines, or combinations thereof.

4. The method of claim 1 where the hydraulic binder comprises calcium sulfate, calcium aluminate, calcium silicate, or mixtures thereof.

5. The method of claim 1 where the clay substrate is a plurality of clay substrate granules and where the basic alkali salt is a plurality of basic alkali salt granules, and where the integrating step comprises:

mixing the plurality of basic alkali salt granules and the plurality of clay substrate granules, thereby generating a solid-solid heterogeneous mixture; and

combining the solid-solid heterogeneous mixture and the amine liquid, thereby producing the clay-alkali-amine powder.

6. The method of claim 5 where the plurality of clay substrate granules and the plurality of basic alkali salt granules has a mean diameter of less than 500 micron.

7. The method of claim 1 further comprised of adding an alkaline solution to the amine liquid, where the alkaline solution is comprised of a second basic alkali salt.

8. The method of claim 1 where the basic alkali salt is comprised of a metallic cation and an anion, where the metallic cation is Na, K, Li, Rb, Cs, Ca, Ba, or Sr and where the anion is hydroxide ion, a carbonate ion, a acetate ion, a phosphate ion, or an oxide.

9. The method of claim 8 where the metallic cation is Na and the anion is the carbonate ion, and further comprised of adding an alkaline solution to the amine liquid, where the alkaline solution is comprised of a second basic alkali salt, where the second basic alkali salt is comprised of Na, and where a mass of the second basic alkali salt comprising the alkaline solution is less than about 30% of the mass of the amine comprising the amine liquid.

10. The method of claim 1 where the clay substrate is a plurality of porous clay particles, and where the basic alkali salt is an alkali solution comprised of the basic alkali salt, and where a mass of the basic alkali salt comprising the alkali solution is less than about 30% of the mass of the amine comprising the amine liquid, and where the integrating step is comprised of:

blending the liquid amine, the alkali solution, and a solvent, where the basic alkali salt is soluble in the solvent, and where the solvent is soluble in the amine, thereby generating an amine-alkali liquid;

contacting the plurality of porous clay particles and the amine-alkali liquid and allowing at least a portion of the amine alkali liquid to impregnate at least a portion of the plurality of porous clay particles, thereby producing the clay-alkali-amine powder.

11. The method of claim 10 where the basic alkali salt is comprised of a metallic cation and an anion, where the metallic cation is Na, K, Li, Rb, Cs, Ca, Ba, or Sr and where the anion is hydroxide ion, a carbonate ion, a acetate ion, a phosphate ion, or an oxide ion.

12. The method of claim 11 where the metallic cation is Na and the anion is the carbonate ion.

13. The method of claim 11 where the plurality of porous clay particles has a mean diameter of less than 500 micron.