US20180117522A1 - Surface-Modified Carbon and Sorbents for Improved Efficiency in Removal of Gaseous Contaminants - Google Patents
Surface-Modified Carbon and Sorbents for Improved Efficiency in Removal of Gaseous Contaminants Download PDFInfo
- Publication number
- US20180117522A1 US20180117522A1 US15/802,971 US201715802971A US2018117522A1 US 20180117522 A1 US20180117522 A1 US 20180117522A1 US 201715802971 A US201715802971 A US 201715802971A US 2018117522 A1 US2018117522 A1 US 2018117522A1
- Authority
- US
- United States
- Prior art keywords
- porous sorbent
- accordance
- carbon
- manganese oxide
- mnox
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002594 sorbent Substances 0.000 title claims abstract description 43
- 239000000356 contaminant Substances 0.000 title description 16
- 150000001721 carbon Chemical class 0.000 title description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 195
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 146
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 77
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 159000000011 group IA salts Chemical class 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 59
- 239000010457 zeolite Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 229910001414 potassium ion Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 89
- 239000002105 nanoparticle Substances 0.000 abstract description 19
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000007246 mechanism Effects 0.000 abstract description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 42
- 239000003570 air Substances 0.000 description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000002243 precursor Substances 0.000 description 20
- 238000001914 filtration Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 239000000835 fiber Substances 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229940071125 manganese acetate Drugs 0.000 description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- 230000000274 adsorptive effect Effects 0.000 description 7
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- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 229940099596 manganese sulfate Drugs 0.000 description 7
- 235000007079 manganese sulphate Nutrition 0.000 description 7
- 239000011702 manganese sulphate Substances 0.000 description 7
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000012286 potassium permanganate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
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- 229960001841 potassium permanganate Drugs 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- -1 without limitation Substances 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- NCYCYZXNIZJOKI-OVSJKPMPSA-N Retinaldehyde Chemical compound O=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-OVSJKPMPSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
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- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3238—Inorganic material layers containing any type of zeolite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/324—Inorganic material layers containing free carbon, e.g. activated carbon
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3268—Macromolecular compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2101/02—Carbon filters
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- B01D—SEPARATION
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- B01D2253/25—Coated, impregnated or composite adsorbents
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- B01D—SEPARATION
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/06—Polluted air
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/45—Gas separation or purification devices adapted for specific applications
- B01D2259/4508—Gas separation or purification devices adapted for specific applications for cleaning air in buildings
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the invention relates generally to materials used to remove contaminants from a gas, and more particularly to materials used to remove contaminant gases, such as aldehydes, from air.
- Aldehydes are highly reactive organic compounds, and include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, tolualdehyde, and retinaldehyde, among others.
- Formaldehyde is harmful if inhaled by humans at sufficient levels and is considered a volatile organic compound, or VOC.
- Aldehydes are sometimes found in air around newly manufactured polymers, which are present in residential buildings. It is therefore desirable to remove aldehydes from air in residential buildings.
- One common way of removing contaminants from the air in a residential building, such as a house, is to treat a filter used in the central heating and cooling system of the house with materials that will adsorb contaminants from the air as it is circulated through the house.
- Such heating and cooling systems are known to use a fan to move air into each room of the home while simultaneously drawing air out of most or all of the same rooms. In this manner, air is circulated through the central system and while the filter strains out and/or otherwise removes particulate from the air, the treatment materials adsorb the contaminant gas molecules from the air as the air passes through the filter.
- Prior art filters have included activated carbon treated for an adsorptive (physisorption or chemisorption) mechanism to filters used in the central heating and cooling system of building. These filters use carbon in large mesh size or in pellet form to adsorb contaminants, such as formaldehyde. Thus, the prior art removes formaldehyde by carbon treated for adsorptive mechanisms. It is desirable to remove more formaldehyde, or remove formaldehyde at faster rates, in order to reduce the negative impact of formaldehyde on the occupants of any building.
- activated carbon and other porous sorbents with surface modifications which may be carried out by impregnation with transition metals, metal oxides and complexes.
- These surface-modified porous sorbents receive the metal oxides in their pores and may be placed in contact with room air, such as by being added to an HVAC filter. This results in higher adsorption of VOCs, and in catalytic activity in the oxidation of VOCs, and especially formaldehyde, in the air passing through the filter or other air-contacting structure, thereby removing the VOCs from the air stream that will be breathed by the occupants of the building.
- Activated carbon is one contemplated porous sorbent, as are titania, molecular sieves, zeolites and alumina.
- Activated carbon may be impregnated with MnOx-based nano particles, which may be previously prepared or prepared in-situ, to give an additional mechanism of catalytic oxidation of VOCs, such as formaldehyde and other aldehydes.
- VOCs such as formaldehyde and other aldehydes.
- This combination of MnOx nano particles and activated carbon has a higher capacity for oxidation at faster kinetics, which results in higher filtration efficiency and longer filter life.
- Porous substrates in addition to activated carbon may be impregnated with Manganese-based particles and/or nanoparticles, including, without limitation, zeolite.
- a fibrous structure such as a woven sheet, a non-woven batt, or a web of fibers, which may be polymeric.
- the fibrous structure may have a coating of metal oxide and ionic suspensions that create catalytic sites on the fibrous structure.
- This fibrous structure may be placed in a frame and installed as a filter in a central heating and cooling system. It is contemplated to use the resulting filtration media as air filtration media for the oxidation of volatile organic compounds (VOC), especially formaldehyde, in an air stream.
- VOC volatile organic compounds
- HVAC heating, air conditioning and ventilation
- the polymeric web coated with catalytic nano metal oxide has enhanced efficiency in the removal of molecular gas and/or VOCs by adsorption and catalysis of the contaminant into less-harmful substances.
- a polymeric web media may be coated with nano-sized manganese oxide and potassium ions.
- the filtration media may be used alone, or in combination with activated carbon, in an HVAC system.
- the media may be treated with activated carbon impregnated with commercially-available or in-situ-prepared MnOx-based nano particles as described herein to give a mechanism for removing VOCs/gases by catalytic oxidation of VOCs, such as formaldehyde. This results in a higher capacity of removal at faster kinetics, resulting in higher filtration efficiency and longer filter life.
- the advantage of this polymeric web coated with nano particles of manganese oxide is that the coated web can decompose more VOCs, and at faster kinetics, to support accomplishing higher CADR and CCM.
- the polymeric fibrous structure coated with manganese oxide acts as a strong catalyst for the decomposition and/or oxidation of VOCs (especially formaldehyde) from the air stream into CO 2 .
- VOCs especially formaldehyde
- the web has higher catalytic capacity than prior art structures to remove gaseous contaminants (including formaldehyde vapors and other gases) by using a catalytic coated web alone or in combination with activated carbon in an air filtration system. Also disclosed is technology to synthesize nano manganese oxide particles (MnOx) and coat the polymeric web.
- the filtration media disclosed herein adding catalytic activity removes formaldehyde and molecular gases and/or vapors from an air stream.
- Catalytic activity may be added to a carbon filter by using a polymeric web layer coated with catalytic manganese oxide and potassium ions.
- catalytic activity may be added to a particulate filter by entrapping granular sorbent impregnated with MnOx between two layers or attaching activated carbon with MnOx impregnated therein to a fibrous web.
- the air filtration media for the gaseous phase may be a combination of a particulate filter web and a carbon filter, which may be carbon in the form of pellets, granules or immobilized carbon in sheet form to react with (and/or adsorb) and thereby remove the gaseous contaminants from the air stream.
- the products disclosed herein should meet the emerging standards of air filters in terms of higher filtration efficiency to remove formaldehyde and other Volatile Organic Compounds (VOCs).
- VOCs Volatile Organic Compounds
- the GBT 18801 test protocol introduced by Chinese authorities to remove formaldehyde at higher clean air delivery rate (CADR) is desirably met by the disclosed products.
- Disclosed herein is a high filtration media that immobilizes the surface-modified carbon described herein to accomplish the higher adsorption and catalytic activity to remove formaldehyde and other vapors/gases from the air stream.
- FIG. 1 is a schematic cross-sectional view illustrating a highly porous carbon granule onto which particles of MnOx are dispersed.
- FIG. 2 is a graphical representation of experimental data resulting from an experiment in which the amount of time required for multiple different substances to remove formaldehyde from a volume of air.
- FIG. 3 is a graphical representation of experimental data resulting from an experiment in which the time for breakthrough of a filter by contaminants is shown for each of four samples.
- FIG. 4 is a schematic side view illustrating an embodiment of the invention.
- FIG. 5 is a schematic side view illustrating an embodiment of the invention.
- FIG. 6 is a schematic end view in section illustrating the embodiment of the invention of FIG. 5 through the line 5 - 5 .
- FIG. 7 is a schematic side view illustrating an embodiment of the invention.
- FIG. 8 is a schematic end view in section illustrating the embodiment of the invention of FIG. 7 through the line 8 - 8 .
- FIG. 9 is a schematic illustration of a heating, ventilation and cooling system with an embodiment of the invention in place therein.
- Activated carbon in any particle size distribution from as coarse as 4 mm to as fine as 10 micron may be treated, such as by being impregnated, with manganese oxide (MnOx) and such complexes prepared as their finely dispersed nano particles.
- MnOx manganese oxide
- the nanoparticles of MnOx are preferably in the range of 100-400 nanometers.
- nano particles are commercially available and may be applied to the activated carbon or other substrate.
- the particles may be formed in situ by chemical/reducing agents with their precursors, such as potassium/sodium permanganate, manganese acetate, manganese oxalate and/or manganese sulfate and others known by the person of ordinary skill.
- chemical/reducing agents with their precursors, such as potassium/sodium permanganate, manganese acetate, manganese oxalate and/or manganese sulfate and others known by the person of ordinary skill.
- One may blend this MnOx impregnated carbon with a proportion (10-60%) of carbon impregnated with ionic alkaline salts, such as KOH and KCl, to increase the activity for the catalytic oxidation.
- ionic alkaline salts such as KOH and KCl
- the resulting MnOx impregnated activated carbon or other substrates have catalytic properties in addition to adsorptive properties.
- One proposed MnOx impregnated substrate is activated carbon with a concentration of MnOx particles in the range of 0.5-5.0% by weight of the carbon.
- a proposed impregnated substrate is zeolite with a concentration of MnOx particles in the range of 0.5-2.0% by weight of the zeolite.
- the porous carbon or other substrate is impregnated with manganese oxide and possibly also hydroxides on finer carbon particles and accomplished uniform dispersion of the catalytic sites of manganese crystallites.
- This MnOx impregnated carbon may be blended with a proportion of ionic alkaline salts (such as KOH and KCl) impregnated carbon to further increase the activity for the catalytic oxidation.
- the air filtration media for the gaseous phase may be a combination of particulate filters and carbon filters.
- Carbon filters may be formed of carbon pellets, granules or immobilized carbon in sheet form, which may have a honeycomb structure to retain the granules.
- the manganese oxide may be prepared by dissolving manganese precursor compounds (such as potassium/sodium permanganate, manganese acetate, manganese oxalate and manganese sulfate) with their reducing agents (such as ammonium oxalate, ammonium hydroxide and aniline) in aqueous phase.
- manganese precursor compounds such as potassium/sodium permanganate, manganese acetate, manganese oxalate and manganese sulfate
- their reducing agents such as ammonium oxalate, ammonium hydroxide and aniline
- the reaction rate forming manganese oxide particles affects the particle size. If the precursor and reducing agents are combined rapidly, large particles will precipitate, which is undesirable. However, if the precursor and reducing agents are combined in a controlled manner, for example in diluted form (in water) with the reducing agent deliberately kept at a low concentration to slow the reaction, the particles formed are extremely small, as desired.
- the carbon with alkaline ionic charges may be prepared by dissolving potassium precursor compounds, such as potassium hydroxide/chloride/iodide, in water. The carbon is impregnated or soaked with this solution for about an hour and then dried in the same way at a temperature lower than 150° C.
- the manganese precursor is typically used in the range between 0.5 and 5 wt % of the carbon to be impregnated and prepared using de-ionized water in 1-100% (e.g., 20%) excess of the carbon's incipient volume.
- Reducing agents like ammonium hydroxide, ammonium oxalate, oleic acid or aniline are used to convert manganese precursors into manganese oxide particles of very small size.
- the carbon is impregnated with this water suspension containing fine manganese oxide nano particles, using a spraying and/or soaking process that evenly spreads the manganese oxide nano particles over the activated carbon.
- the alkaline/K+ ionic precursor is typically used in the range between 0.5 and 10 wt % of the carbon and prepared using de-ionized water in 1-100% excess of the carbon's incipient volume, as above.
- MnO 4 manganese oxide
- the described carbon impregnated with manganese oxide has both adsorptive as well as catalytic properties to remove VOCs, especially formaldehyde, from the air stream.
- the manganese oxide is prepared in fine particles by a wet process and dispersed in the pores of activated carbon granules.
- the formaldehyde (HCHO) molecules are adsorbed and react with the catalytic MnOx particles and are oxidized to CO 2 and H 2 O, by the mechanism proposed below:
- the surface modified carbon acts as a strong catalyst for the decomposition/oxidation of formaldehyde into CO 2 and the decomposition and/or oxidation of other VOCs. Furthermore, the material acts as a high efficiency sorbent to adsorb such organic gaseous molecules by physisorption and chemisorption in the gas phase filtration.
- MnOx e.g., MnO 2 and other manganese oxides
- FIG. 1 The resulting form of the surface modified carbon loaded with MnOx (e.g., MnO 2 and other manganese oxides) is sketched in FIG. 1 .
- MnOx particles are widely and evenly distributed within the pores of the porous substrate granule, and on or toward the outer surface thereof.
- MnOx particles on the carbon substrate have catalytic properties in addition to adsorptive properties.
- These MnOx particles may be mounted in a filter to remove formaldehyde and other VOCs from ambient air that is flowing through the filter that is mounted in a conventional HVAC system or a room or building filtration device.
- the catalyzation of formaldehyde oxidizes the harmful chemical into much less harmful CO 2 and H 2 O.
- the adsorptive feature removes the VOC from the air by adsorption. This combination arises due to the surface area per unit mass of the extremely small particles of MnOx.
- the MnOx particles may be in the range of 100-400 nanometers in size.
- the activated carbon also has a high surface area per unit mass, and may be in the range of 800-1,300 m 2 /g.
- the preferred activated carbon has a surface area of about 1,000 m 2 /g.
- the resulting carbon can decompose more VOCs, and at faster kinetics, than other products due to the combination of adsorptive and catalytic activities.
- Another advantage is that the carbon can be in any size particles from coarser to finer mesh sizes.
- the carbon can be immobilized, such as between two layers, in a nonwoven filtration media to impart these benefits in the given space of a filter.
- the invention differs from the prior art by the existence of nano manganese oxide particles (MnOx) dispersed in carbon or other sorbent substrate pores to result in the specific morphology and properties of the combination. This results in adsorption and catalytic activity to remove gaseous contaminants including formaldehyde vapors and other gases.
- MnOx nano manganese oxide particles
- the combination of MnOx impregnated in carbon and blended with a proportion of ionic alkaline salts (such as KOH and KCl) impregnated in other carbon particles further increases the activity for catalytic oxidation.
- the structural integrity of the media and its formulation with treated carbon and binder is significant.
- the invention contemplates including a proportion of the surface-modified sorbents in addition to carbon, such as titania, molecular sieves, zeolites and alumina to result in synergy to give even higher performance.
- a method of preparing MnOx particles in aqueous phase may begin with manganese precursors, such as potassium permanganate or manganese acetate or manganese sulfate, and results in impregnating carbon particles with these finely suspended MnOx particles.
- the starting carbon particle size can be as coarse as 4 mm to as fine as 10 micron with high micro-porosity and textural properties. Due to the uniform dispersion of the fine catalytic MnOx particles on the carbon, resulting filters have higher life at higher filtration efficiency of gaseous contaminants.
- nMnOx nano manganese oxide
- formaldehyde is a basic compound in the class of “Aldehyde” compounds.
- acetaldehyde which has similar properties and is considered to be an equally or more toxic air pollutant.
- the same nMnOx impregnated carbon may remove acetaldehyde as well as formaldehyde, by catalytic oxidation. It is in this context that the product is extended to the catalytic oxidation of VOCs such as the aldehyde group of compounds, which include formaldehyde and acetaldehyde.
- the activated carbon granules can be any mesh size and any form, but preferably is in the ranges of 4-8 mm, 8-16 mm, 20-50 mm and 50-200 mm U.S. mesh size. If zeolite is used, the preferred size is 12-30 mm mesh size. Activated carbon pellets may be used in the range of 2-3 mm in size. This MnOx impregnated carbon may be blended with another carbon impregnated with ionic alkaline salts like KOH and KCl to increase the activity for the catalytic oxidation.
- An objective is to remove the gaseous species from the air stream by higher adsorption and catalysis by the activated carbon.
- the said higher adsorption and catalytic activity can be created by different chemical treatments and impregnation with active metal/oxides.
- the chemical treatments we create different functional groups on the carbon basal plane, which are considered to be the chemisorption active sites. These sites are occupied by the gaseous molecules to form a bond between a functional group and the gas molecules and gradually become saturated.
- the chemically-treated carbon e.g., activated carbon with potassium ions
- the catalytic carbon prepared by the explained method of impregnation with nMnOx particles has the capability to decompose the gaseous molecules and the remaining active sites are regenerated after every cycle.
- a first approach is to physically blend the two carbons: the chemically-treated carbon and nMnOx-impregnated catalytic carbons can be mixed in various proportions to combine the effects. It is observed that the formaldehyde and other gaseous removal efficiency increases significantly by blending the chemisorption and catalytic carbons. The effects add up significantly, as can be seen in FIG. 3 , which shows the results of experiments to determine formaldehyde breakthrough and saturation capacity of various blends. The shortest breakthrough time is by catalytic nMnOx carbon alone, the next shortest time is by chemically treated carbon alone.
- the longest time to breakthrough is the physical blend in 50/50 mixture of carbon impregnated with nMnOx and carbon chemically-treated with ionic alkaline salts, such as potassium ions (e.g., KCl, KOH, KI).
- ionic alkaline salts such as potassium ions (e.g., KCl, KOH, KI).
- the second highest time is the blend of 40% carbon impregnated with nMnOx and 60% carbon chemically-treated with ionic alkaline salts.
- the longest time until breakthrough of contaminants is thus found in the blend of 50% activated carbon impregnated with nMnOx and 50% carbon chemically-treated with ionic alkaline salts.
- the second approach is to create dual effects of chemisorption and catalysis on the same carbon by impregnating first with catalytic manganese oxide and then treating with chemical reagents.
- the first step of preparing nMnOx carbon is explained herein.
- the second treatment is carried out on the same carbon.
- the chemical reagents like KI, KOH, etc., are dissolved in water in the 10-25% volume of the carbon to be treated and then sprayed uniformly on the nMnOx carbon.
- Another embodiment may be created by coating polymeric fibrous structures with the same manganese oxide particles and potassium ions described herein to give additional catalytic activity in the air filters for oxidizing VOCs, when in use individually or in combination with carbon filters described herein.
- One may prepare MnOx particles in aqueous phase (starting with manganese precursors such as potassium permanganate, manganese acetate, or manganese sulfate) and impregnate carbon with these finely suspended MnOx particles.
- the next step is to coat the MnOx particles on the polymeric web to accomplish the higher CADR and CCM for removing molecular gas contaminants/VOCs from the air stream.
- the manganese precursor compound is dissolved in water in the range between 1 and 30% w/v
- the potassium ion precursor is dissolved in the range between 10 and 30% w/v for the coating on the fibers.
- the nano manganese oxide loading is 1-5%.
- FIG. 4 The product resulting from coating fibers with impregnated carbon is shown schematically in FIG. 4 , in which a filter media, such as a non-woven batt 100 , is placed in a stream of gas flow 110 .
- a magnified view of the media shows the porous sorbent particles 120 in the non-woven batt 100 .
- the particle 120 may be impregnated with MnOx, treated with potassium ions, both, or a combination of some impregnated and some treated.
- a batt 200 of fibrous media has interposed within it a sheet or panel 210 of material in which the impregnated carbon particles are retained.
- the panel 210 may be two sheets of woven or non-woven, gas-permeable material.
- the batt 200 filters particulate while the impregnated carbon particles retained in the panel 210 catalyze the conversion of VOCs and adsorb the same, thereby removing the VOC from the gas passing through the media batt 200 .
- a media batt 300 which may be polymer fibers formed in a non-woven structure, has had porous, sorbent particles adhered to the fibers of the batt 300 .
- the sorbent particles are impregnated with metal oxide nano particles according to the disclosure herein, and some sorbent particles may be treated by ionic alkaline salts.
- the manganese oxide coating may be prepared in multiple steps, starting with coating the fibrous structure with a colloidal solution of manganese compounds, such as potassium/sodium permanganate. These may be the same as the precursors used in formation of MnOx nano particles that coat the activated carbon granules as described herein.
- the nano manganese oxide particles are applied to the resulting web structure, such as by applying the suspension of MnOx nano particles to the web structure.
- the metal oxide complex solution is thus prepared with manganese oxide (MnOx) using chemical/reducing agents with their precursors as potassium/sodium permanganate or manganese acetate or manganese sulfate, and the nano manganese oxide particles that were prepared in aqueous form coat the polymeric fibers or web.
- MnOx manganese oxide
- the manganese oxide may be prepared by dissolving manganese precursor compounds such as potassium permanganate, manganese acetate and manganese sulfate and their redox reactions with chemicals agents including ammonium oxalate, ammonium hydroxide and aniline in aqueous phase, as described herein.
- manganese precursor compounds such as potassium permanganate, manganese acetate and manganese sulfate and their redox reactions with chemicals agents including ammonium oxalate, ammonium hydroxide and aniline in aqueous phase, as described herein.
- Polymeric fibrous structures with different concentrations of MnOx particles in different concentrations start with manganese precursors, such as potassium permanganate, manganese acetate, or manganese sulfate.
- This nano manganese oxide coated fibrous web may be coated in conventional honeycomb filters to synergize the catalytic activity.
- the manganese oxide precursor may be applied to the fibers when the precursor is diluted in water or some other liquid.
- the manganese oxide nano particles may be applied to the fibers by applying the suspension described above to the fibers.
- the manganese oxide precursor on the fibers may have some effect of catalyzing VOCs, and the manganese oxide nano particles also on the fibers may have some effect of catalyzing VOCs.
- the catalyzing effect of a resulting product can be enhanced by adding to the fibers so coated (with manganese oxide precursor and manganese oxide nano particles) an activated carbon filter which may be as shown in U.S. Pat. No. 9,199,189 and/or United States Patent Application Publication No. 2016/0023186, both of which are incorporated herein by reference.
- HVAC heating, ventilation and cooling
- the HVAC system 400 holds a filter 420 adjacent an air handling furnace 430 , in which a blower fan 440 draws air through an air return 410 from rooms in a building, through the filter 420 , through the air handling furnace 430 and out a supply 450 to rooms of the building.
- Any filter described herein, and any filter media or additive to media or a filter may be positioned where the filter 420 is located as shown in FIG. 9 .
- Air, or any other gas thereby flows through the filter 420 and VOCs, such as formaldehyde, is catalyzed in a reaction to H 2 O and CO 2 , and adsorbs to, the additives described herein.
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US15/802,971 US20180117522A1 (en) | 2016-11-03 | 2017-11-03 | Surface-Modified Carbon and Sorbents for Improved Efficiency in Removal of Gaseous Contaminants |
US17/087,716 US20210046417A1 (en) | 2016-11-03 | 2020-11-03 | Surface-Modified Carbon And Sorbents For Improved Efficiency In Removal Of Gaseous Contaminents |
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US201662416899P | 2016-11-03 | 2016-11-03 | |
US201662422943P | 2016-11-16 | 2016-11-16 | |
US201762463144P | 2017-02-24 | 2017-02-24 | |
US15/802,971 US20180117522A1 (en) | 2016-11-03 | 2017-11-03 | Surface-Modified Carbon and Sorbents for Improved Efficiency in Removal of Gaseous Contaminants |
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2017
- 2017-11-03 JP JP2019545706A patent/JP7294755B2/ja active Active
- 2017-11-03 KR KR1020197015781A patent/KR20190079654A/ko active Application Filing
- 2017-11-03 CN CN201780071754.8A patent/CN109963639A/zh active Pending
- 2017-11-03 WO PCT/US2017/059902 patent/WO2018102069A1/en active Application Filing
- 2017-11-03 CN CN202210964222.XA patent/CN115282940A/zh active Pending
- 2017-11-03 KR KR1020227005927A patent/KR102615619B1/ko active IP Right Grant
- 2017-11-03 KR KR1020247013801A patent/KR20240057456A/ko active Search and Examination
- 2017-11-03 US US15/802,971 patent/US20180117522A1/en not_active Abandoned
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- 2020-11-03 US US17/087,716 patent/US20210046417A1/en active Pending
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CN112619607A (zh) * | 2021-01-07 | 2021-04-09 | 深圳市奇信集团股份有限公司 | 甲醛吸附剂 |
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WO2023093655A1 (en) * | 2021-11-24 | 2023-06-01 | Rht Limited | Catalyst compositions and methods for decomposing formaldehyde thereof |
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KR20190079654A (ko) | 2019-07-05 |
US20210046417A1 (en) | 2021-02-18 |
CN109963639A (zh) | 2019-07-02 |
KR20240057456A (ko) | 2024-05-02 |
WO2018102069A1 (en) | 2018-06-07 |
KR20220028166A (ko) | 2022-03-08 |
JP7294755B2 (ja) | 2023-06-20 |
KR102615619B1 (ko) | 2023-12-20 |
JP2019534159A (ja) | 2019-11-28 |
CN115282940A (zh) | 2022-11-04 |
JP7344270B2 (ja) | 2023-09-13 |
WO2018102069A9 (en) | 2018-07-19 |
JP2022045928A (ja) | 2022-03-22 |
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