WO2014110395A1 - Articles of manufacture formed of amine-support particles, and methods of making and using same - Google Patents
Articles of manufacture formed of amine-support particles, and methods of making and using same Download PDFInfo
- Publication number
- WO2014110395A1 WO2014110395A1 PCT/US2014/011078 US2014011078W WO2014110395A1 WO 2014110395 A1 WO2014110395 A1 WO 2014110395A1 US 2014011078 W US2014011078 W US 2014011078W WO 2014110395 A1 WO2014110395 A1 WO 2014110395A1
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- WO
- WIPO (PCT)
- Prior art keywords
- amine
- paste
- mixture
- sorbent
- carbon dioxide
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 71
- 238000005201 scrubbing Methods 0.000 claims abstract description 45
- 239000008188 pellet Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 229920002873 Polyethylenimine Polymers 0.000 claims description 28
- 239000002594 sorbent Substances 0.000 claims description 27
- 239000012190 activator Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 122
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 64
- 239000001569 carbon dioxide Substances 0.000 abstract description 58
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 abstract description 2
- -1 sheets Substances 0.000 abstract 1
- 239000003463 adsorbent Substances 0.000 description 38
- 239000007789 gas Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910021485 fumed silica Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3021—Milling, crushing or grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/304—Linear dimensions, e.g. particle shape, diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4566—Gas separation or purification devices adapted for specific applications for use in transportation means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- the embodiments of the invention encompass compositions and articles of manufacture capable of capturing carbon dioxide and made from organic amine materials and high surface area particles.
- the adsorbent for scrubbing carbon dioxide can be formed into shapes either as individual particles in a fixed bed or as a single monolithic shape as necessary for a particular use.
- the method encompassed by the invention includes the combination of at least one organic amine, at least one type of high surface area particle, and water to form a surface coated particle that is dried and formed into a desired shape.
- Solid sorbents have been used to scrub or remove carbon dioxide from gases emitted from combustion processes and the atmosphere, as well as air in closed quarters, such as in submarines and spacecraft.
- One particular class of solid sorbents for scrubbing carbon dioxide is solid-supported amines. These sorbents are often made using either expensive solvents or water soluble alcohols such as ethanol or methanol. However, such solvents have made the process of making these solid sorbents either too expensive for large scale commercial development or too dangerous as some solvents are flammable. Further complications arise because typically the solid sorbents comprise very small functionalized particles which can be carried off in the movement of gases or are difficult to handle due to their limited size and shape.
- the invention encompasses a solid supported amine sorbent for scrubbing carbon dioxide, formaldehyde, or other gases from indoor air comprising at least one support particle and at least one organic amine, wherein the organic amine and support particles are aggregated to form a larger pellets, clusters, or shaped form to be used as a fixed bed for flow-through adsorption.
- the organic amine is a primary, secondary amine, or a compound having both primary and secondary amines.
- the amines include, but are not limited to polyethylenimine (PEI), aziridine, ethanolamine, diethanolamine, triethylenetetramine,
- the support particle has a composition of carbon, silica alumina, or a combination thereof. Typically, the support particle is fumed, pyrolytic or precipitated.
- the solid sorbent for scrubbing carbon dioxide further comprises a chemical activator, such a polyethylene glycol.
- the solid sorbent for scrubbing carbon dioxide is shaped in the form of a pellet, filament, sheet, or globules.
- the shaped is in the form of a cylinder, sphere, spheroid, ellipsoid, cube, rectangle, triangle, ring, or disc.
- the particle or shaped form has at least one dimension greater than about 0.1 mm. Alternatively, the dimension is greater than about 10 mm. Large shaped forms are referred to as monoliths.
- Another embodiment of the invention encompasses a method of making a paste or solid sorbent for scrubbing carbon dioxide comprising adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture; and forming a paste.
- the method may include a drying step to remove water from the mixture and form a paste.
- the method may further comprise extruding or molding the paste to form a shaped solid adsorbent for scrubbing carbon dioxide.
- a solid sorbent in another embodiment of the invention encompasses a method of making a solid sorbent comprising adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture, extruding or molding the mixture to form a shaped product, and drying the shaped product to remove the water and forming a solid adsorbent for scrubbing carbon dioxide or other gases.
- the organic amine is present in an amount of about 10% to 60% by weight.
- the mixture is about 20% to 50% by weight organic amine and 80% to 50% support particle.
- the ratio of organic amine and support particle to water is about 1:2-11 by weight.
- the ratio of organic amine and support particle to water is about 1:7 by weight.
- the drying step is performed by drying during the extrusion process, heat drying, air drying, or vacuum processing.
- the drying step is a heat drying step and is performed at a temperature of about 70 °C to about 120 °C and for a time of about 1 to about 24 hours.
- the extruding step extrudes to form of pellets, filaments, sheets, globules, or shapes the solid sorbent for scrubbing carbon dioxide into cylinders, spheres, spheroids, ellipsoids, cubes, rectangles, triangles, rings, or discs.
- Figure 1 illustrates a pellet of the invention wherein the size of the pellet is greater than that of the individual support particle.
- Figure 2 illustrates a photograph of an adsorbent for scrubbing carbon dioxide of the invention, wherein the product is extruded into the shape of a small cylinder, where the support particles bonded to each other to form one or more clusters.
- Figure 3 illustrates the capacity of an adsorbent for scrubbing carbon dioxide to adsorbed carbon dioxide over time, wherein the adsorbed carbon is measured in mg of CO 2 per gram of product over 75 minutes;
- Figure 4 illustrates a graph of a thermogravimetric analysis (TGA) of the material of Example 1.
- TGA thermogravimetric analysis
- the adsorbent encompassed by the invention are capable of adsorbing carbon dioxide and other chemical species over a period of time. Not to be limited by theory, but it is believed that the organic amine covering the support particle performs two functions. Firstly, the organic amine captures or bonds to carbon dioxide in a manner that can remove carbon dioxide from gasses. This capturing may be reversible or irreversible depending on the conditions. Secondly, the organic amine serves as a binding agent to help form clusters of support particles that can be shaped into a variety of forms depending upon end use.
- the adsorbent of the invention features solid sorbents which can be readily handled, formed into shapes or articles and not subject to movement due to the flow of gases through or about the solid sorbent at flow rates suitable for applications such as indoor ventilation and air purification.
- These adsorbent for scrubbing carbon dioxide can be used as articles used to scrub, capture, or remove carbon dioxide, formaldehyde, and/or other contaminants from indoor air in buildings and vehicles, or gases produced in combustion processes, such as exhaust, atmospheric gases, or gases containing large amounts of carbon dioxide due to industrial output or biological sources.
- gases having carbon dioxide includes, but is not limited to, gases comprising carbon dioxide in whole or in part. The term does not suggest or imply that the gas comprises only carbon dioxide.
- One embodiment of the present invention is directed to an article of manufacture comprising a paste of the reaction product of an organic amine and support particles.
- the term "paste” refers to a smooth or semi-smooth thick flowable or malleable material having a large solids content held in suspension in a liquid.
- the paste is a thick fluid of viscosity in the range of about 10,000 to about 10,000,000 centipoise (cP); and preferably the viscosity is about 100,000 to about 2,000,000 cP.
- the paste can be extruded through orifices or screens to form pellets, filaments, sheets, globules, and other shapes as desired for the end use.
- paste can be molded or poured into forms including, but not limited to, filaments, sheets, cylinders, spheres, cubes, rectangles, triangles, rings, discs, or forms designed to snugly fit in a specialized shaped container or receptacle.
- the paste may be allowed to take any shape, such as that necessary to fill a void in machinery, and if desired the product can be separated into parts to form clusters of particles.
- the adsorbent for scrubbing carbon dioxide or other gases may be shaped into a pellet or cluster of particles necessary to fill a compartment wherein the scrubbing is desired to take place.
- the adsorbent may also assume an amorphous shape, separated into pieces or clusters of particles of a desired size to achieve the design objectives of the scrubbing system including contact area, air flow resistance, and holding the adsorbent in place.
- the adsorbent may also include a porous cluster or shape wherein gas may flow through the porous cluster or shape.
- the sorbent may be formed into a monolith that is perforated with holes or channels for gas to flow through.
- One or more monoliths may replace a bed of sorbent particles where during scrubbing the gas is forced through or along the monolith.
- the adsorbent for scrubbing carbon dioxide may also form one or more clusters, globules, shaped forms, pellets or extrudates.
- shaped form refers to a three dimensional design or shape which is preconceived as in a molded or sculpted article.
- the adsorbent for scrubbing carbon dioxide may be shaped into a cluster, form, pellet or extrudate having at least one dimension greater than about 0.1 mm. Alternatively, the dimensions may be in the range of about 0.25 mm to about 1 mm. Thus, the adsorbent for scrubbing carbon dioxide can be grouped or packed into a bed and resist movement with the flow of fluids within and about the adsorbent.
- pellet 11 comprises an organic amine and support particles.
- pellet 11 has a height, width or depth, depending on the orientation of the pellet and the designation of top and bottom, front or back, which can be arbitrary, that is greater than 0.1 mm.
- Other embodiments feature at least one dimension up to or exceeding 10 mm, 20 mm, or 50 mm.
- the dimensions are about 0.3 mm to about 1 mm, and alternatively the range may have an upper limit of 3 mm.
- the diameter is about 0.5 mm to about 1 mm and/or the extrudate may have a length of a few mm, but no more than about 10 mm.
- a packed bed of pellets (11) can support movement of gases around the individual pellets (11) or through the pellets (11) due to the porous nature of the grouping of individual support particles.
- Each pellet (11) has a plurality of support particles which are bonded or affixed to each other wherein the organic amine, by itself or with additional binders covers and bonds the support particles. Without being bound to a method of formation, it is presently contemplated that the organic amine forms bonds with a plurality of particles to bind the particles.
- the adsorbent for scrubbing carbon dioxide of the invention comprises at least one organic amine combined with a support particle to form a cluster product capable of capturing or removing carbon dioxide.
- the adsorbent for scrubbing carbon dioxide may also contain additional ingredients such as binders or chemical activators.
- the binders and chemical activators may facilitate binding the support particles, drying, alter pH levels, and hinder amine oxidation, among other properties.
- organic amine refers to an organic molecule having at least one amine functional group.
- the organic amine has at least one alkane, alkene, alkyne, alkyl, or aryl group.
- the organic amine may have multiple alkanes, alkenes, alkynes, alkyl, aryl groups, or combinations thereof.
- the amine can be a primary, secondary or tertiary amine, preferably the amine is a primary or secondary amine and more preferable a secondary amine.
- the invention encompasses molecules having a mixture of primary, secondary, and/or tertiary amines.
- Typical amines used in the invention include, but are not limited to, polyethylenimine (PEI), aziridine, ethanolamine, diethanolamine (DEA),
- PEI polyethylenimine
- DEA diethanolamine
- the amines include polyethylenimine (PEI), diethanolamine (DEA), triethylenetetramine, tetraethylenepentamine (TEPA), or pentaethylenehexamine. More preferably the amines include polyethylenimine (PEI), diethanolamine (DEA), or
- Organic amines of the invention may be purchased through commercial vendors such as Sigma Aldrich (Milwaukee, Wisconsin) or BASF (Florham Park, New Jersey).
- the support particle includes, but is not limited to, a generally inert particle capable of binding with the organic amine and forming a cluster or shaped form upon extrusion or drying.
- support particles may have a composition of carbon, silica, alumina, aluminosilicates, or combinations thereof.
- silica the support particle is preferably of a fumed, pyrolytic, or precipitated type.
- alumina the support particle is preferably of a fumed, pyrolytic, or precipitated type.
- the support particle is preferably carbon black, porous carbon, or carbon nanoparticles.
- a mixture of fumed silica and fumed alumina may be combined in a weight ratio of about 5: 1, preferably about 4:1, and more preferably about 3: 1.
- the support particles can be either manufactured or purchased through commercial vendors.
- Examples of commercially available silica include Cab-O-Sil ⁇ sold by Cabot Corporation (Boston, Massachusetts) or Aerosil ⁇ or Sipernat ⁇ sold by Evonik Industries (Parsippany, New Jersey).
- Examples of commercially available carbon is Carbon Pearls sold by Cabot Corporation.
- Examples of commercially available alumina include the CP product line by BASF Corporation.
- the adsorbent for scrubbing carbon dioxide may include one or more chemical activators to the organic amine, support particles or paste. These chemical activators may facilitate wetting or bonding of individual support particles and/or drying of the products. Examples of activator or modifier include, but are not limited to, polyethylene glycol or polyvinyl alcohol. Other examples of chemical activators include, but are not limited to, organic binders, polymerization catalysts and agents, cellulose, and alkaline salts.
- the invention also encompasses methods of making an adsorbent for scrubbing carbon dioxide or formaldehyde.
- the method for making the adsorbent comprises adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture, if needed, partially drying the mixture to remove some of the water and form a product in the form of a paste, and extruding or molding the paste to form a shaped solid adsorbent. After shaping, the shaped forms are dried as described herein.
- the method includes an additional step of adding at least one chemical activator to the mixture. The order of mixing may be altered such as combing the organic amine with the water prior to adding the support particle.
- an alternative embodiment of the method for making the solid adsorbent for scrubbing carbon dioxide comprises adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture, extruding the mixture to form a shaped product, and drying the shaped product to remove the water and forming a solid adsorbent for scrubbing carbon dioxide.
- the ratio of organic amine to support particle should be sufficient to coat and bind the support particle in a manner sufficient to impart carbon dioxide adsorbing properties to the material.
- the ratio of materials will depend on a number of considerations including, but not limited to, surface area, stability, or cost benefit. Increasing the amount of amine is generally expected to increase CO 2 capture or removal; however, too much amine can lead to reduced active surface area, thereby undermining the performance. Also, too much amine content may lead to weaker binding of the amines and instability of the material.
- the mixture is about 10% to 60% by weight organic amine and 90% to 40% by weight support particle.
- the mixture is about 20% to 50% by weight organic amine and 80% to 50% by weight support particle.
- the mixture is about 30% to 50% by weight organic amine and 70% to 50% by weight support particle.
- one of ordinary skill in the art with little or no experimentation can vary the amounts depending upon the amine and support particle used.
- the amount of water used in the process will depend on the desired properties of the adsorbent for scrubbing carbon dioxide. For instance, the greater amount of water used the easier it is to mix the ingredients; however, large amounts of water need to be removed after mixing and before a stable paste is obtained and require longer drying times or harsher drying conditions. In contrast, small amounts of water can create a very dense paste that is difficult to mix.
- the ratio of dry ingredients to water is about 1 :2-11 by weight.
- the ratio of dry ingredients to water is about 1:5-9 by weight.
- the ratio of dry ingredients to water is about 1 :7 by weight.
- the solid adsorbent for scrubbing carbon dioxide is substantially free of organic solvents.
- the term “substantially free of organic solvents” refers to a solid adsorbent for scrubbing carbon dioxide having less than 1% by weight of organic solvents.
- solid adsorbent for scrubbing carbon dioxide having less than 0.5% by weight organic solvents and more preferably, less than 0.1% by weight of organic solvents.
- organic solvents it is meant solvents used during the mixing step and not the organic amine.
- the drying step may be conducted by any method known in the art as long as the drying process does not damage the adsorbent for scrubbing carbon dioxide.
- drying methods are described in Catalyst Manufacture by Alvin b. Stiles (2d edition, CRC Press, 1995).
- the known drying methods include, but are not limited to, drying during the extrusion process, heat drying, air drying, drying under a vacuum (vacuum processing), and the like. Drying may be carried out at elevated temperatures relative to water until water removal is complete.
- drying conditions will depend upon a variety of factors such as the temperature, the amount of water present, whether a vacuum is used, the amount of time for drying, and the amount of acceptable residual water.
- the temperature may be about 70 °C to about 120 °C, preferably about 80 °C to about 110 °C, and more preferably the temperature during drying is about 90 °C to about 100 °C.
- the time for drying may be about 1 to about 24 hours, preferably about 2 to about 12 hours, and more preferably about 3 to about 6 hours.
- a vacuum if a vacuum is used, then a skilled artisan may use lower temperatures and shorter drying times.
- the drying step under vacuum may be carried out for about 1 hour at about 70°C.
- the duration and temperature of the drying may determine the brittleness of the solid adsorbent for scrubbing dioxide, such as the pellets (11) of Figure 1 or Figure 2.
- the amount of residual water may affect the adsorption kinetics with water hindering access of gas molecules to the active amine sites, as well as the production costs associated with drying times and energy usage.
- the apparatus for drying includes, but is not limited to, a fixed oven, a sealed chamber for vacuum or ambient control, or a moving belt oven.
- the extrusion step typically consists of extruding the paste-like mixture from an apparatus to shape the adsorbent.
- the extrusion step may be carried out using techniques commonly known to the skilled artisan such as those found in Catalyst Manufacture (see above).
- the mixture may be extruded into the form of pellets, filaments, sheets, globules, and other shapes as desired for the end use.
- the mixture can be extruded into molds or poured into forms including, but not limited to, filaments, sheets, cylinders, spheres, spheroids, ellipsoids, cubes, rectangles, triangles, rings, or discs.
- the dimensions of the extruded adsorbent for scrubbing carbon dioxide are discussed above.
- the optional step of adding at least one chemical activator or inhibitor to the mixture can be performed at any time prior to extrusion.
- the chemical activators may facilitate wetting or bonding of individual support particles and/or drying of the products, a skilled artisan readily knows when to add the chemical activator to achieve the desired purpose.
- a chemical activator such as polyethylene glycol or polyvinyl alcohol can be added to the mixture, water, organic amine, or support particle during the mixing step.
- Other examples of chemical activators include, but are not limited to, organic binders, polymerization catalysts and agents, cellulose, and alkaline salts.
- the invention also encompasses a method of scrubbing gas to remove carbon dioxide comprising the step of placing a gas comprising carbon dioxide in contact with the solid adsorbent for scrubbing carbon dioxide material in a shaped form, pellet, cluster or extrudate having a reaction product of an organic amine and a support particle wherein said shaped form, pellet, cluster and extrudate has at least one dimension greater than about 0.1 mm.
- the method also includes a shaped form, pellet, cluster or extrudate constructed and arranged as a fixed bed through which said gas is compelled through.
- Example 1 Pellets The pellets, such as those of Figure 1 (11), are made without the use of organic solvents.
- Dilute polyethylenimine (PEI) is mixed with deionized water in a weight ratio of 1:7 ⁇ :]3 ⁇ 40.
- the PEI and water are combined in an industrial mixer, such as those described in Catalyst Manufacture.
- fumed silica (Cab-O-Sil ⁇ from Cabot Corporation) is gradually added to the mixture in a 10:4 weight ratio of fumed silica:PEI.
- This paste is extruded using a simple lab syringe or 1-2 mm mesh screens.
- the extruded paste forms pellets with 1 mm and 2 mm diameter.
- the pellets formed from such extrusions have at least one dimension which is greater than 1 mm.
- the pellets were dried on a tray in a lab oven.
- Solid forms of amine-bound fumed silica are made without the use of organic solvents.
- a thick paste of water, PEI, and fumed silica was made. Thereafter, the paste is placed in molds shaped as discs. The discs are approximately 50 mm in diameter and 20 mm in height. The drying step was performed on a hot plate.
- the pellets or molded shapes of examples 1 and 2 are dried at elevated temperatures for several hours to form a solid adsorbent for scrubbing carbon dioxide.
- the solid adsorbent for scrubbing carbon dioxide is a brittle, rigid, and highly porous solid that is easy to manipulate and distribute.
- the discs and pellets were dried at 90 °C for over 4 hours.
- Figure 2 illustrates the solid adsorbent for scrubbing carbon dioxide of the invention in the form of pellets.
- the solid adsorbent for scrubbing carbon dioxide in the shape of pellets was tested to determine the carbon dioxide absorbing properties.
- the product of example 1 was test under the following conditions: adsorption and desorption repetitive cycles of 30 minutes each. Desorption was carried out at 50 °C under dry compressed air and adsorption was carried out at 30 °C under dry and compressed air containing 1000 ppm carbon dioxide.
- Figure 4 illustrates a TGA graph of this process, where the change percent in weight of material (X axis) changes as carbon dioxide is adsorbed over time (Y axis).
- Figure 3 depicts the results of thermogravimetric analysis (TGA) of the CO 2 adsorption properties of the solid sorbent for scrubbing carbon dioxide of the present invention.
- the material has performance comparable to solvent-formed FS-PEI with CO 2 adsorption capacity over 3% weight per weight, and has the mechanical form that is conducive to fixed bed flow adsorption.
- Example 1 the order of mixing the reactants of Example 1 is altered. Following the amounts used in Example 1, fumed silica is first mixed with deionized water, and the amine is added to the fumed silica-water mixture to form a paste. This paste is then used to form an extrudate or solid form.
- This example illustrates the substitution of other organic amines for PEI or as additional organic amines to PEI.
- Such other organic amines include but are not limited to ethanolamines, ethyleneamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) or pentaethylenehexamine (PEHA), linear-chain polyethylenimine, and sterically hindered amines such as 2-amino-2-methyl-l- propanol (AMP).
- TETA triethylenetetramine
- TEPA tetraethylenepentamine
- PEHA pentaethylenehexamine
- AMP 2-amino-2-methyl-l- propanol
- Such organic amines are used singularly in place of PEI, or in combination with PEI or in combination with each other.
- pellets such as those of Figure 1 (11) are made without the use of organic solvents and using a combination of fumed silica and alumina. Dilute
- polyethylenimine PEI
- deionized water in a weight ratio of 1 :7 PEI:H 2 0.
- the PEI and water are combined in an industrial mixer.
- fumed silica and fumed alumina in a weight ratio of 3: 1 is gradually added to the mixture in a 10:4 weight ratio of fumed silica and fumed alumina to PEI.
- the mixture forms a thick paste, which is extruded using a lab syringe of 1-2 mm mesh screen.
- the extruded paste forms elongated rods with 1 mm and 2 mm diameter and varying lengths.
- the elongated rods formed from such extrusions have at least one dimension which is greater than 1 mm.
- the elongated rods were dried on a tray inside a conventional lab oven at 90°C.
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Abstract
Embodiments of the present invention feature article of manufacture, methods of making and methods of using a paste of the reaction product of an organic amine and support particles, shaped as pellets, sheets, films, rings discs or other forms useful for scrubbing carbon dioxide from emissions and the atmosphere.
Description
ARTICLES OF MANUFACTURE FORMED OF AMINE-SUPPORT PARTICLES, AND METHODS OF MAKING AND USING SAME
Cross Reference to Related Applications
This application claims the benefit of U.S. Provisional Application No.
61/751,070, filed on January 10, 2013, hereby incorporated by reference.
Field of the Invention
The embodiments of the invention encompass compositions and articles of manufacture capable of capturing carbon dioxide and made from organic amine materials and high surface area particles. The adsorbent for scrubbing carbon dioxide can be formed into shapes either as individual particles in a fixed bed or as a single monolithic shape as necessary for a particular use. The method encompassed by the invention includes the combination of at least one organic amine, at least one type of high surface area particle, and water to form a surface coated particle that is dried and formed into a desired shape.
Background of the Invention
Solid sorbents have been used to scrub or remove carbon dioxide from gases emitted from combustion processes and the atmosphere, as well as air in closed quarters, such as in submarines and spacecraft. One particular class of solid sorbents for scrubbing carbon dioxide is solid-supported amines. These sorbents are often made using either expensive solvents or water soluble alcohols such as ethanol or methanol. However, such solvents have made the process of making these solid sorbents either too expensive for large scale commercial development or too dangerous as some solvents are flammable. Further complications arise because typically the solid sorbents comprise very small functionalized particles which can be carried off in the movement of gases or are difficult to handle due to their limited size and shape.
Thus, a need in the art arose for solid sorbents which can be more readily handled, formed into desired shapes and articles, and not subject to movement due to the flow of air through or about the particles at flow rates suitable for applications, such as indoor ventilation.
Summary of the Invention
The invention encompasses a solid supported amine sorbent for scrubbing carbon dioxide, formaldehyde, or other gases from indoor air comprising at least one support particle and at least one organic amine, wherein the organic amine and support particles are aggregated to form a larger pellets, clusters, or shaped form to be used as a fixed bed for flow-through adsorption. In one embodiment, the organic amine is a primary, secondary amine, or a compound having both primary and secondary amines. The amines include, but are not limited to polyethylenimine (PEI), aziridine, ethanolamine, diethanolamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, or mixtures thereof. In another embodiment, the support particle has a composition of carbon, silica alumina, or a combination thereof. Typically, the support particle is fumed, pyrolytic or precipitated. In another embodiment, the solid sorbent for scrubbing carbon dioxide further comprises a chemical activator, such a polyethylene glycol.
In another embodiment, the solid sorbent for scrubbing carbon dioxide is shaped in the form of a pellet, filament, sheet, or globules. Alternatively, the shaped is in the form of a cylinder, sphere, spheroid, ellipsoid, cube, rectangle, triangle, ring, or disc. In another embodiment, the particle or shaped form has at least one dimension greater than about 0.1 mm. Alternatively, the dimension is greater than about 10 mm. Large shaped forms are referred to as monoliths.
Another embodiment of the invention encompasses a method of making a paste or solid sorbent for scrubbing carbon dioxide comprising adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture; and forming a paste. Optionally, the method may include a drying step to remove water from the mixture and form a paste. The method may further comprise extruding or molding the paste to form a shaped solid adsorbent for scrubbing carbon dioxide.
In another embodiment of the invention encompasses a method of making a solid sorbent comprising adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture, extruding or molding the mixture to form a shaped product, and drying the shaped product to remove the water and forming a solid adsorbent for scrubbing carbon dioxide or other gases.
In one embodiment of the method, the organic amine is present in an amount of about 10% to 60% by weight. In another embodiment, the mixture is about 20% to 50% by weight organic amine and 80% to 50% support particle. In yet another embodiment, the ratio of organic amine and support particle to water is about 1:2-11 by weight. Alternatively, in another embodiment, the ratio of organic amine and support particle to water is about 1:7 by weight.
In the method of making a solid sorbent for scrubbing carbon dioxide, the drying step is performed by drying during the extrusion process, heat drying, air drying, or vacuum processing. In one embodiment, the drying step is a heat drying step and is performed at a temperature of about 70 °C to about 120 °C and for a time of about 1 to about 24 hours.
In one embodiment of the method of making a solid sorbent for scrubbing carbon dioxide, the extruding step extrudes to form of pellets, filaments, sheets, globules, or shapes the solid sorbent for scrubbing carbon dioxide into cylinders, spheres, spheroids, ellipsoids, cubes, rectangles, triangles, rings, or discs.
Brief Description of the Drawings
Figure 1 illustrates a pellet of the invention wherein the size of the pellet is greater than that of the individual support particle.
Figure 2 illustrates a photograph of an adsorbent for scrubbing carbon dioxide of the invention, wherein the product is extruded into the shape of a small cylinder, where the support particles bonded to each other to form one or more clusters.
Figure 3 illustrates the capacity of an adsorbent for scrubbing carbon dioxide to adsorbed carbon dioxide over time, wherein the adsorbed carbon is measured in mg of CO2 per gram of product over 75 minutes; and
Figure 4 illustrates a graph of a thermogravimetric analysis (TGA) of the material of Example 1. The vertical axis shows the change in sample weight over time under exposure to a flow of air with controlled concentration of carbon dioxide and controlled temperature. Each measurement exhibits adsorption and desorption repetitive cycles of 30 minutes each. In this example desorption was carried out at 50 °C under dry compressed air and adsorption at 30 °C under dry and compressed air containing 1000 ppm CO2.
Detailed Description of the Invention
The adsorbent encompassed by the invention are capable of adsorbing carbon dioxide and other chemical species over a period of time. Not to be limited by theory, but it is believed that the organic amine covering the support particle performs two functions. Firstly, the organic amine captures or bonds to carbon dioxide in a manner that can remove carbon dioxide from gasses. This capturing may be reversible or irreversible depending on the conditions. Secondly, the organic amine serves as a binding agent to help form clusters of support particles that can be shaped into a variety of forms depending upon end use.
The adsorbent of the invention features solid sorbents which can be readily handled, formed into shapes or articles and not subject to movement due to the flow of gases through or about the solid sorbent at flow rates suitable for applications such as indoor ventilation and air purification. These adsorbent for scrubbing carbon dioxide can be used as articles used to scrub, capture, or remove carbon dioxide, formaldehyde, and/or other contaminants from indoor air in buildings and vehicles, or gases produced in combustion processes, such as exhaust, atmospheric gases, or gases containing large amounts of carbon dioxide due to industrial output or biological sources. As used herein, gases having carbon dioxide includes, but is not limited to, gases comprising carbon dioxide in whole or in part. The term does not suggest or imply that the gas comprises only carbon dioxide.
One embodiment of the present invention is directed to an article of manufacture comprising a paste of the reaction product of an organic amine and support particles. As used herein, the term "paste" refers to a smooth or semi-smooth thick flowable or malleable material having a large solids content held in suspension in a liquid. Typically, the paste is a thick fluid of viscosity in the range of about 10,000 to about 10,000,000 centipoise (cP); and preferably the viscosity is about 100,000 to about 2,000,000 cP.
In another embodiment, the paste can be extruded through orifices or screens to form pellets, filaments, sheets, globules, and other shapes as desired for the end use. Further, paste can be molded or poured into forms including, but not limited to, filaments, sheets, cylinders, spheres, cubes, rectangles, triangles, rings, discs, or forms designed to snugly fit in a specialized shaped container or receptacle. In fact, the paste may be allowed to take any shape, such as that necessary to fill a void in
machinery, and if desired the product can be separated into parts to form clusters of particles. In other words, the adsorbent for scrubbing carbon dioxide or other gases may be shaped into a pellet or cluster of particles necessary to fill a compartment wherein the scrubbing is desired to take place. The adsorbent may also assume an amorphous shape, separated into pieces or clusters of particles of a desired size to achieve the design objectives of the scrubbing system including contact area, air flow resistance, and holding the adsorbent in place. The adsorbent may also include a porous cluster or shape wherein gas may flow through the porous cluster or shape. The sorbent may be formed into a monolith that is perforated with holes or channels for gas to flow through. One or more monoliths may replace a bed of sorbent particles where during scrubbing the gas is forced through or along the monolith. The adsorbent for scrubbing carbon dioxide may also form one or more clusters, globules, shaped forms, pellets or extrudates. As used herein, the term "shaped form" refers to a three dimensional design or shape which is preconceived as in a molded or sculpted article.
In one embodiment, the adsorbent for scrubbing carbon dioxide may be shaped into a cluster, form, pellet or extrudate having at least one dimension greater than about 0.1 mm. Alternatively, the dimensions may be in the range of about 0.25 mm to about 1 mm. Thus, the adsorbent for scrubbing carbon dioxide can be grouped or packed into a bed and resist movement with the flow of fluids within and about the adsorbent.
Turning to Figure 1, an article of manufacture in the form of a pellet, generally designated by the numeral 11 , embodies the features of the present invention. Pellet 11 comprises an organic amine and support particles. By way of example, pellet 11 has a height, width or depth, depending on the orientation of the pellet and the designation of top and bottom, front or back, which can be arbitrary, that is greater than 0.1 mm. Other embodiments feature at least one dimension up to or exceeding 10 mm, 20 mm, or 50 mm. For example, in the case of spheroids the dimensions are about 0.3 mm to about 1 mm, and alternatively the range may have an upper limit of 3 mm. In the case of extrudates, the diameter is about 0.5 mm to about 1 mm and/or the extrudate may have a length of a few mm, but no more than about 10 mm. A packed bed of pellets (11) can support movement of gases around the individual pellets (11) or through the pellets (11) due to the porous nature of the grouping of individual
support particles. Each pellet (11) has a plurality of support particles which are bonded or affixed to each other wherein the organic amine, by itself or with additional binders covers and bonds the support particles. Without being bound to a method of formation, it is presently contemplated that the organic amine forms bonds with a plurality of particles to bind the particles.
The adsorbent for scrubbing carbon dioxide of the invention comprises at least one organic amine combined with a support particle to form a cluster product capable of capturing or removing carbon dioxide. Optionally, the adsorbent for scrubbing carbon dioxide may also contain additional ingredients such as binders or chemical activators. For example, the binders and chemical activators may facilitate binding the support particles, drying, alter pH levels, and hinder amine oxidation, among other properties.
As used herein unless otherwise defined, the term "organic amine" refers to an organic molecule having at least one amine functional group. Typically, the organic amine has at least one alkane, alkene, alkyne, alkyl, or aryl group. The organic amine may have multiple alkanes, alkenes, alkynes, alkyl, aryl groups, or combinations thereof. While the amine can be a primary, secondary or tertiary amine, preferably the amine is a primary or secondary amine and more preferable a secondary amine. The invention encompasses molecules having a mixture of primary, secondary, and/or tertiary amines.
Typical amines used in the invention include, but are not limited to, polyethylenimine (PEI), aziridine, ethanolamine, diethanolamine (DEA),
triethylenetetramine, tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), 2-amino-2-methyl propanol (AMP), and mixtures thereof. Preferably, the amines include polyethylenimine (PEI), diethanolamine (DEA), triethylenetetramine, tetraethylenepentamine (TEPA), or pentaethylenehexamine. More preferably the amines include polyethylenimine (PEI), diethanolamine (DEA), or
tetraethylenepentamine. Organic amines of the invention may be purchased through commercial vendors such as Sigma Aldrich (Milwaukee, Wisconsin) or BASF (Florham Park, New Jersey).
The support particle includes, but is not limited to, a generally inert particle capable of binding with the organic amine and forming a cluster or shaped form upon extrusion or drying. For example, support particles may have a composition of
carbon, silica, alumina, aluminosilicates, or combinations thereof. In the case of silica, the support particle is preferably of a fumed, pyrolytic, or precipitated type. Similarly, in the case of alumina, the support particle is preferably of a fumed, pyrolytic, or precipitated type. In the case of carbon, the support particle is preferably carbon black, porous carbon, or carbon nanoparticles. The invention also
encompasses mixtures of support particles. Typically, the mixtures are combined in a desired weight ratio. For example, a mixture of fumed silica and fumed alumina may be combined in a weight ratio of about 5: 1, preferably about 4:1, and more preferably about 3: 1.
The support particles can be either manufactured or purchased through commercial vendors. Examples of commercially available silica include Cab-O-Sil© sold by Cabot Corporation (Boston, Massachusetts) or Aerosil© or Sipernat© sold by Evonik Industries (Parsippany, New Jersey). Examples of commercially available carbon is Carbon Pearls sold by Cabot Corporation. Examples of commercially available alumina include the CP product line by BASF Corporation.
The adsorbent for scrubbing carbon dioxide may include one or more chemical activators to the organic amine, support particles or paste. These chemical activators may facilitate wetting or bonding of individual support particles and/or drying of the products. Examples of activator or modifier include, but are not limited to, polyethylene glycol or polyvinyl alcohol. Other examples of chemical activators include, but are not limited to, organic binders, polymerization catalysts and agents, cellulose, and alkaline salts.
The invention also encompasses methods of making an adsorbent for scrubbing carbon dioxide or formaldehyde. The method for making the adsorbent comprises adding at least one organic amine to at least one support particle and water to form a mixture; mixing the mixture, if needed, partially drying the mixture to remove some of the water and form a product in the form of a paste, and extruding or molding the paste to form a shaped solid adsorbent. After shaping, the shaped forms are dried as described herein. Optionally, the method includes an additional step of adding at least one chemical activator to the mixture. The order of mixing may be altered such as combing the organic amine with the water prior to adding the support particle. Hence an alternative embodiment of the method for making the solid adsorbent for scrubbing carbon dioxide comprises adding at least one organic amine
to at least one support particle and water to form a mixture; mixing the mixture, extruding the mixture to form a shaped product, and drying the shaped product to remove the water and forming a solid adsorbent for scrubbing carbon dioxide.
The ratio of organic amine to support particle should be sufficient to coat and bind the support particle in a manner sufficient to impart carbon dioxide adsorbing properties to the material. The ratio of materials will depend on a number of considerations including, but not limited to, surface area, stability, or cost benefit. Increasing the amount of amine is generally expected to increase CO2 capture or removal; however, too much amine can lead to reduced active surface area, thereby undermining the performance. Also, too much amine content may lead to weaker binding of the amines and instability of the material.
Typically, the mixture is about 10% to 60% by weight organic amine and 90% to 40% by weight support particle. Preferably, the mixture is about 20% to 50% by weight organic amine and 80% to 50% by weight support particle. Most preferably, the mixture is about 30% to 50% by weight organic amine and 70% to 50% by weight support particle. However, one of ordinary skill in the art with little or no experimentation can vary the amounts depending upon the amine and support particle used.
The amount of water used in the process will depend on the desired properties of the adsorbent for scrubbing carbon dioxide. For instance, the greater amount of water used the easier it is to mix the ingredients; however, large amounts of water need to be removed after mixing and before a stable paste is obtained and require longer drying times or harsher drying conditions. In contrast, small amounts of water can create a very dense paste that is difficult to mix. Typically, the ratio of dry ingredients to water is about 1 :2-11 by weight. Preferably, the ratio of dry ingredients to water is about 1:5-9 by weight. Most preferably, the ratio of dry ingredients to water is about 1 :7 by weight.
Other volatile solvents can be used instead, including organic alcohols.
However, while organic alcohols may provide good technical results, they also introduce cost and safety disadvantages in a commercial or industrial setting.
The solid adsorbent for scrubbing carbon dioxide is substantially free of organic solvents. As used herein unless otherwise defined, the term "substantially free of organic solvents" refers to a solid adsorbent for scrubbing carbon dioxide
having less than 1% by weight of organic solvents. Preferably, solid adsorbent for scrubbing carbon dioxide having less than 0.5% by weight organic solvents and more preferably, less than 0.1% by weight of organic solvents. By organic solvents it is meant solvents used during the mixing step and not the organic amine.
The drying step may be conducted by any method known in the art as long as the drying process does not damage the adsorbent for scrubbing carbon dioxide. Such drying methods are described in Catalyst Manufacture by Alvin b. Stiles (2d edition, CRC Press, 1995). Commonly, the known drying methods include, but are not limited to, drying during the extrusion process, heat drying, air drying, drying under a vacuum (vacuum processing), and the like. Drying may be carried out at elevated temperatures relative to water until water removal is complete. As recognized by the skilled artisan, drying conditions will depend upon a variety of factors such as the temperature, the amount of water present, whether a vacuum is used, the amount of time for drying, and the amount of acceptable residual water. For example, during heat drying typically the temperature may be about 70 °C to about 120 °C, preferably about 80 °C to about 110 °C, and more preferably the temperature during drying is about 90 °C to about 100 °C. During the heat drying step, typically the time for drying may be about 1 to about 24 hours, preferably about 2 to about 12 hours, and more preferably about 3 to about 6 hours. As recognized by the skilled artisan, if a vacuum is used, then a skilled artisan may use lower temperatures and shorter drying times. For example, the drying step under vacuum may be carried out for about 1 hour at about 70°C.
The duration and temperature of the drying may determine the brittleness of the solid adsorbent for scrubbing dioxide, such as the pellets (11) of Figure 1 or Figure 2. The amount of residual water may affect the adsorption kinetics with water hindering access of gas molecules to the active amine sites, as well as the production costs associated with drying times and energy usage.
The apparatus for drying includes, but is not limited to, a fixed oven, a sealed chamber for vacuum or ambient control, or a moving belt oven.
The extrusion step typically consists of extruding the paste-like mixture from an apparatus to shape the adsorbent. The extrusion step may be carried out using techniques commonly known to the skilled artisan such as those found in Catalyst Manufacture (see above). In one example, the mixture may be extruded into the form
of pellets, filaments, sheets, globules, and other shapes as desired for the end use. Alternatively, the mixture can be extruded into molds or poured into forms including, but not limited to, filaments, sheets, cylinders, spheres, spheroids, ellipsoids, cubes, rectangles, triangles, rings, or discs. The dimensions of the extruded adsorbent for scrubbing carbon dioxide are discussed above.
The optional step of adding at least one chemical activator or inhibitor to the mixture can be performed at any time prior to extrusion. Since the chemical activators may facilitate wetting or bonding of individual support particles and/or drying of the products, a skilled artisan readily knows when to add the chemical activator to achieve the desired purpose. For example, a chemical activator such as polyethylene glycol or polyvinyl alcohol can be added to the mixture, water, organic amine, or support particle during the mixing step. Other examples of chemical activators include, but are not limited to, organic binders, polymerization catalysts and agents, cellulose, and alkaline salts.
The invention also encompasses a method of scrubbing gas to remove carbon dioxide comprising the step of placing a gas comprising carbon dioxide in contact with the solid adsorbent for scrubbing carbon dioxide material in a shaped form, pellet, cluster or extrudate having a reaction product of an organic amine and a support particle wherein said shaped form, pellet, cluster and extrudate has at least one dimension greater than about 0.1 mm. The method also includes a shaped form, pellet, cluster or extrudate constructed and arranged as a fixed bed through which said gas is compelled through.
Having described the invention with reference to certain preferred embodiments, other embodiments will become apparent to one skilled in the art from consideration of the specification. The invention is further defined by reference to the following examples describing in detail the synthesis of solid adsorbent for scrubbing carbon dioxide. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.
Examples
Example 1 : Pellets
The pellets, such as those of Figure 1 (11), are made without the use of organic solvents. Dilute polyethylenimine (PEI) is mixed with deionized water in a weight ratio of 1:7 ΡΕΙ:]¾0. The PEI and water are combined in an industrial mixer, such as those described in Catalyst Manufacture. Once thoroughly blended, fumed silica (Cab-O-Sil© from Cabot Corporation) is gradually added to the mixture in a 10:4 weight ratio of fumed silica:PEI. During mixing the mixture forms a thick paste. This paste is extruded using a simple lab syringe or 1-2 mm mesh screens. The extruded paste forms pellets with 1 mm and 2 mm diameter. Thus, the pellets formed from such extrusions have at least one dimension which is greater than 1 mm. The pellets were dried on a tray in a lab oven.
Example 2: Solid Forms
Solid forms of amine-bound fumed silica (FS) are made without the use of organic solvents. Using the mixing process described in Example 1, a thick paste of water, PEI, and fumed silica was made. Thereafter, the paste is placed in molds shaped as discs. The discs are approximately 50 mm in diameter and 20 mm in height. The drying step was performed on a hot plate.
Example 3: Drying
The pellets or molded shapes of examples 1 and 2 are dried at elevated temperatures for several hours to form a solid adsorbent for scrubbing carbon dioxide. The solid adsorbent for scrubbing carbon dioxide is a brittle, rigid, and highly porous solid that is easy to manipulate and distribute. The discs and pellets were dried at 90 °C for over 4 hours.
Figure 2 illustrates the solid adsorbent for scrubbing carbon dioxide of the invention in the form of pellets.
Example 4: Testing Carbon Dioxide Absorbing Properties
The solid adsorbent for scrubbing carbon dioxide in the shape of pellets was tested to determine the carbon dioxide absorbing properties. The product of example 1 was test under the following conditions: adsorption and desorption repetitive cycles of 30 minutes each. Desorption was carried out at 50 °C under dry compressed air and adsorption was carried out at 30 °C under dry and compressed air containing 1000
ppm carbon dioxide. Figure 4 illustrates a TGA graph of this process, where the change percent in weight of material (X axis) changes as carbon dioxide is adsorbed over time (Y axis).
The results of the above-described testing are graphically illustrated in Figure 3. Figure 3 depicts the results of thermogravimetric analysis (TGA) of the CO2 adsorption properties of the solid sorbent for scrubbing carbon dioxide of the present invention. The material has performance comparable to solvent-formed FS-PEI with CO2 adsorption capacity over 3% weight per weight, and has the mechanical form that is conducive to fixed bed flow adsorption.
Example 5: Order of Mixing
In this example, the order of mixing the reactants of Example 1 is altered. Following the amounts used in Example 1, fumed silica is first mixed with deionized water, and the amine is added to the fumed silica-water mixture to form a paste. This paste is then used to form an extrudate or solid form.
Example 6: Organic Amine
This example illustrates the substitution of other organic amines for PEI or as additional organic amines to PEI. Such other organic amines include but are not limited to ethanolamines, ethyleneamines such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA) or pentaethylenehexamine (PEHA), linear-chain polyethylenimine, and sterically hindered amines such as 2-amino-2-methyl-l- propanol (AMP). Such organic amines are used singularly in place of PEI, or in combination with PEI or in combination with each other.
Example 7: Additives Details
Additives such as polyethylene glycol are added to the paste, or deionized water, or organic amine or to the support particles. Example 8: Fumed Alumina
The pellets, such as those of Figure 1 (11), are made without the use of organic solvents and using a combination of fumed silica and alumina. Dilute
polyethylenimine (PEI) is mixed with deionized water in a weight ratio of 1 :7
PEI:H20. The PEI and water are combined in an industrial mixer. Once thoroughly blended, fumed silica and fumed alumina in a weight ratio of 3: 1 is gradually added to the mixture in a 10:4 weight ratio of fumed silica and fumed alumina to PEI. During mixing the mixture forms a thick paste, which is extruded using a lab syringe of 1-2 mm mesh screen. The extruded paste forms elongated rods with 1 mm and 2 mm diameter and varying lengths. Thus, the elongated rods formed from such extrusions have at least one dimension which is greater than 1 mm. The elongated rods were dried on a tray inside a conventional lab oven at 90°C.
It was found that a mix of 3: 1 (silica to alumina) produced pellets that exhibited greater CO2 adsorption capacity than silica-only pellets.
Claims
1. A paste comprising a liquid amine, a plurality of support particles and a solvent, where the solvent is substantially water.
2. The paste of claim 1, wherein the amine is polyethylenimine (PEI), aziridine, ethanolamine, diethanolamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, or sterically hindered amines
3. The paste of claim 1, wherein the support particles are composed of carbon, silica, alumina, or mixtures thereof.
4. The paste of claim 3, wherein the support particle is fumed, pyrolytic or precipitated.
5. The paste of claim 1, wherein the mass ratio of amine to particle is no less than 1:5 and no more than 2: 1
6. The paste of claim 1 further comprising at least one chemical activator or binder, wherein the chemical activator or binder is incorporated into the paste and the activators are polyethylene glycol, polyvinyl alcohol, cellulose, or a mixture thereof.
7. A solid sorbent for scrubbing air comprising at least one support particle and at least one organic amine, wherein the organic amine and support particles are solidified into shaped forms of a substantially similar shape and dimensions, where the shaped form is larger than the particles and the amine helps bind the particles into the larger shaped forms.
8. The sorbent of claim 7, wherein the organic amine is polyethylenimine
(PEI), aziridine, ethanolamine, diethanolamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, or sterically hindered amines.
9. The sorbent of claim 7, wherein the support particles are composed of carbon, silica, alumina, or mixtures thereof.
10. The sorbent of claim 7, wherein the shaped form has at least one dimension greater than about 0.1 mm.
11. The sorbent of claim 7, wherein the shaped form has at least one dimension greater than about 10 mm.
12. The sorbent of claim 7, wherein the shaped form is a pellet, filament, sheet, globules, cylinder, sphere, spheroid, ellipsoid, cube, rectangle, triangle, ring, or disc.
13. The sorbent of claim 7 further comprising a binder, a chemical activator, or an alkaline base.
14. A method of making a solid sorbent for scrubbing air comprising adding at least one liquid amine to at least one support particle and water to form a wet mixture; forming the wet mixture into shapes of substantially similar form and dimensions; and drying the formed shapes to remove substantially all of the water used in forming the mixture.
15. The method of claim 14, wherein the mixture after drying is about 20% to 60% by weight organic amine and about 40% to 80% by weight support particle.
16. The method of claim 14, wherein the ratio of organic amine and support particle to water is about 1 :2 to 1: 11 by weight.
17. The method of claim 14, wherein the mixture is formed into shapes by extrusion, molding, cutting or pelletization.
18. The method of claim 14, wherein the drying step is performed at a temperature of about 70 °C to about 150 °C and for a time of about 1 hour to about 24 hours.
19. The method of claim 14, wherein the support particles are composed of carbon, silica, alumina, or mixtures thereof.
20. The method of claim 14, wherein the mixture is formed into pellets, filaments, sheets, globules, cylinders, spheres, spheroids, ellipsoids, cubes, blocks, rectangles, pyramids, ring, or discs.
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US14/760,395 US9919287B2 (en) | 2013-01-10 | 2014-01-10 | Articles of manufacture formed of amine-support particles and methods of making thereof |
CN201480006394.XA CN104955562A (en) | 2013-01-10 | 2014-01-10 | Articles of manufacturing formed of amine-support particles, and methods of making and using same |
EP14737604.0A EP2943275A4 (en) | 2013-01-10 | 2014-01-10 | Articles of manufacture formed of amine-support particles, and methods of making and using same |
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US9919287B2 (en) | 2013-01-10 | 2018-03-20 | Massachusetts Institute Of Technology | Articles of manufacture formed of amine-support particles and methods of making thereof |
WO2024133317A1 (en) * | 2022-12-21 | 2024-06-27 | Basf Se | Sorbents for carbon dioxide capture |
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CN104955562A (en) | 2015-09-30 |
US9919287B2 (en) | 2018-03-20 |
US20150352518A1 (en) | 2015-12-10 |
EP2943275A4 (en) | 2016-08-31 |
EP2943275A1 (en) | 2015-11-18 |
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