US20100135883A1 - Catalyst supports - Google Patents
Catalyst supports Download PDFInfo
- Publication number
- US20100135883A1 US20100135883A1 US12/555,340 US55534009A US2010135883A1 US 20100135883 A1 US20100135883 A1 US 20100135883A1 US 55534009 A US55534009 A US 55534009A US 2010135883 A1 US2010135883 A1 US 2010135883A1
- Authority
- US
- United States
- Prior art keywords
- metal oxide
- theta
- composite material
- ceo
- oxide felt
- 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
- 239000003054 catalyst Substances 0.000 title abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 54
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 14
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 37
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000003870 refractory metal Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 239000011593 sulfur Substances 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000012824 chemical production Methods 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 17
- 239000003245 coal Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- 239000002737 fuel gas Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 238000002309 gasification Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005486 sulfidation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005200 wet scrubbing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- -1 solid particulates Chemical compound 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- 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
-
- B01J35/30—
-
- B01J35/40—
-
- B01J35/58—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/206—Rare earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/92—Dimensions
- B01D2255/9205—Porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
Definitions
- This invention relates to a catalyst material, and its method of making and manufacture, useful for a diversity of chemical production processes as well as various emission control processes. More specifically, it relates to a catalyst composition, preferably comprising a metal oxide felt substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface, which can be used in the removal of sulfur from hot gases as well as acting to trap solid particulates and metals within these hot gases.
- IGCC Integrated Gasification Combined Cycle
- IGCC plants are to be contrasted to traditional coal powered power plants where the coal is pulverized and then burnt to produce steam to drive a turbine.
- Gasification is the thermal conversion of carbon-based materials at 760° to 1538° C. (1400° to 2800° F.), with a limited supply of pure oxygen, to a synthetic gas, also known as a syngas as compared to combustion which occurs when there is a surplus of oxygen.
- Syngas typically contains about 35% H 2 , 45% CO, 5% H 2 O, 15% CO 2 with a small amount of methane, as well as impurities such as solid particulates, sulfur compounds (mainly H 2 S and COS) and nitrogen compounds as well as smaller quantities of other impurities.
- the syngas can be used as a fuel to generate power, or to make chemicals and fuels.
- the heating value is 264 kjoules (250 Btu/scf).
- the hot exhaust gas from the gasification reaction is sent to a steam turbine which generates steam to produce electricity.
- the syngas is sent to a combustion turbine which turns a generator.
- the combined cycle is the combination of a simple cycle combustion turbine generator plus a steam turbine generator.
- the sulfur compounds need to be removed from the hot exhaust gas.
- IGCC technology produces air emissions that are already considerably lower than required by current U.S. Clean Air standards. Significant reductions in sulfur dioxide (SO 2 ), nitrogen oxides (NO X ) and carbon monoxide (CO) are possible through use of IGCC plants, making them more advantageous than conventional coal power plants. Carbon dioxide (CO 2 ), which is considered a major source of global warming, can be captured more economically with IGCC than with conventional technologies. The CO 2 could be sequestered or sold in part as a by-product. Overall efficiency is approximately 40 to 45% of the energy value of coal converted to electricity. In comparison, conventional coal plants are approximately 30 to 35% efficient. Water requirements are typically about 50% less for IGCC applications than for conventional coal generation.
- IGCC technology requires more frequent maintenance with longer maintenance outages, requiring that power be purchased from other resources when the IGCC plant is unavailable.
- U.S.-based IGCC projects has used Powder River Basin, or western, coal, which is the type used most frequently in the Midwest.
- Powder River Basin, or western, coal which is the type used most frequently in the Midwest.
- the industry is encouraging suppliers to offer performance contracts for next-generation IGCC plants, but for now, the risk of reduced reliability and availability add significant cost to the project's financing.
- IGCC Integrated Gasification Combined Cycle
- Hot gas cleanup may also avoid much of the operational complexity, space requirements, and capital costs associated with cool down/reheating systems or heat exchange systems.
- Other drivers for hot gas clean-up in IGCCs include avoiding the production of sour water (produced if the fuel gas is cooled below the dew point of water) and consequently the sour water treating, avoiding the production of “black-mud” (mixture of water-char ash) produced in water quenching or water scrubbing of particulates from the fuel gas.
- black-mud mixture of water-char ash
- Coal-derived fuel gases used for power generation or cogeneration have to be substantially cleaned before being either burned in a gas turbine or used for chemical synthesis, e.g., methanol, ammonia, urea production, Fischer-Tropsch synthesis.
- Cleanup techniques require removal of solid particulates, sulfur-containing gases, i.e., H 2 S and COS and all trace contaminants resulting from the gasification of coal, i.e., NH 3 , HCN, alkali metals, metal carbonyls, Hg, As, and Se.
- the successful development of hot-gas cleanup techniques depends on the ability to remove all of the above at equally high temperatures.
- This invention discloses a regenerable material acting as a high temperature sulfur sink as well as a filtering media for the solid particulates.
- the support used to disperse the active metal oxide phase is acting as a filtering media for the hot solid particulates and trace metals, and the active metal oxide phase dispersed on the support is acting as the sulfur sink.
- the preferred support material is a ceramic textile composed of 100% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media.
- the zirconia felts are designed for use in extremely corrosive environments, are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts.
- refractory oxide felts such as Ce 2 O 3 , CeO 2 , Y 2 O 3 , TiO 2 , HfO 2 , Al 2 O 3 , Nb 2 O 5 , La 2 O 3 , Yb 2 O 3 , and mixed oxide felts like Al 2 O 3 —SiO 2 , HfO 2 —CeO 2 , Sm 2 O 3 —CeO 2 , Yb 2 O 3 —CeO 2 may be used.
- metal oxide felts such as Ce 2 O 3 , CeO 2 , Y 2 O 3 , TiO 2 , HfO 2 , Al 2 O 3 , Nb 2 O 5 , La 2 O 3 , Yb 2 O 3 , and mixed oxide felts like Al 2 O 3 —SiO 2 , HfO 2 —CeO 2 , Sm 2 O 3 —CeO 2 , Yb 2 O 3 —CeO 2 may be used.
- the metal oxide phase acting as the sulfur sink can be any metal oxide or mixed metal oxides, i.e., oxides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn, dispersed on the zirconia felt using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation. All commercial large-scale hot coal derived gas cleanup demonstration projects have so far failed because, among other reasons, of the poor attrition resistance of the tested sorbent materials. This problem is avoided by dispersing the active metal oxide used to chemically bind sulfur on the flexible felt material. This porous media can also be used to simultaneously trap the hot solid particulates.
- This invention involves a regenerable material acting as a high temperature sulfur sink as well as a filtering media for the solid particulates.
- the support used to disperse the active metal oxide phase is acting as a filtering media for the hot solid particulates and trace metals, and the active metal oxide phase dispersed on the support is acting as the sulfur sink.
- the support is a metal oxide felt substrate comprising a metal oxide selected from the group consisting of ZrO 2 , Ce 2 O 3 , CeO 2 , Y 2 O 3 , TiO 2 , HfO 2 , Al 2 O 3 , Nb 2 O 5 , La 2 O 3 , Yb 2 O 3 , and mixed oxide felts like Al 2 O 3 —SiO 2 , HfO 2 —CeO 2 , Sm 2 O 3 —CeO 2 , Yb 2 O 3 —CeO 2 .
- the preferred support material is a ceramic textile composed of 100% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media.
- the zirconia felts are designed for use in extremely corrosive environments, are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts. They contain no binder and they retain their fibrous nature up to 2480° C.
- refractory (metal) oxide felts such as Ce 2 O 3 , CeO 2 , Y 2 O 3 , TiO 2 , HfO 2 , Al 2 O 3 , Nb 2 O 5 , La 2 O 3 , Yb 2 O 3 , and mixed oxide felts like Al 2 O 3 —SiO 2 , HfO 2 —CeO 2 , Sm 2 O 3 —CeO 2 , Yb 2 O 3 —CeO 2 may be used.
- the metal oxide phase acting as the sulfur sink can be any metal oxide or mixed metal oxides, i.e., oxides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn dispersed on the zirconia felt using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation. All commercial large-scale hot coal derived gas cleanup demonstration projects have so far failed because, among other reasons, of the poor attrition resistance of the tested sorbent materials. This problem is avoided by dispersing the active metal oxide used to chemically bind sulfur on the flexible felt material. This porous media can also be used to simultaneously trap the hot solid particulates.
- the metal oxide felt material used in the present invention may comprise layers having a thickness from about 0.25 to about 6.35 mm and preferably the thickness of the layers is from about 1.27 to about 3.81 mm.
- the metal oxide felt material has a bulk porosity from about 50 to 100% and preferably from about 88 to 96%.
- the bulk density of the metal oxide felt material is from about 128 to 1073 grams/liter and preferably from about 160 to 400 grams per liter.
- the metal oxide felt material has a high melting point in the range from 15000 to 5000° C.
- the catalytic material that is deposited on the metal oxide felt material is selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides and mixed metal sulfides.
- Catalytic materials for use in removal of sulfur compounds are selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides and mixed metal sulfides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn.
- the catalytic active phases for the removal of sulfur compounds are oxides of Mn.
- the catalytic active phase can be deposited on the metal oxide felt material using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation.
- one process of making the active metal oxide phase supported on the refractory metal oxide felt support comprises an aqueous impregnation of the active metal oxide phase onto the metal felt support, followed by a (high temperature of about 800° C.) heat treatment.
- the active metal oxide phase coating the metal oxide felt support fibers is porous, allowing the unhindered diffusion and easy access of the sulfur compounds contained in the gaseous stream to the catalytic active metal oxide sites dispersed on the metal oxide felt support.
- Yet another embodiment of the invention involves the use of the composite materials of the present invention in the treatment of a hot gaseous stream with the exposure of the hot gaseous stream to a composite material comprising a metal oxide felt substrate and a catalytic material wherein the treatment includes removal of sulfur compounds and solid particulates from a hot gas that may be at a temperature from about 250° to 850° C.
- a typical gaseous stream comprises carbon monoxide, carbon dioxide, hydrogen, and sulfur compounds.
- the gaseous stream may comprise a fuel gas or a synthesis gas comprising hydrogen, carbon monoxide, sulfur-containing compounds and impurities like solid particulates and trace metals.
- the Mn oxide supported on yttria stabilized zirconia felt catalyst was prepared by cutting the yttria stabilized zirconia felt into approximately 0.25 inch squares. To the cut felt squares, 36.3 g of an 0.5 M aqueous Mn(OAc) 2 :4H 2 O solution was added slowly with gentle stirring. The felt support squares were allowed to soak in the aqueous Mn acetate solution for 24 hours at room temperature with periodic gentle stirring, after which the mixture was dried at 100° C. for 4 hours. The dry impregnated felt support squares were then calcined in flowing air for 2 hours at 800° C.
- the Mn oxide supported on yttria stabilized zirconia felt catalyst showed characteristic lines at 23.2 ⁇ 0.5 deg. 2-theta, 28.942 ⁇ 0.5 deg. 2-theta, 30.220 ⁇ 0.5 deg. 2-theta, 33.039 ⁇ 0.5 deg. 2-theta, 35.060 ⁇ 0.5 deg. 2-theta, 38.303 ⁇ 0.5 deg. 2-theta, 45.243 ⁇ 0.5 deg. 2-theta, 49.441 ⁇ 0.5 deg. 2-theta, 50.318 ⁇ 0.5 deg. 2-theta, 55.261 ⁇ 0.5 deg. 2-theta, 57.024 ⁇ 0.5 deg. 2-theta, 59.779 ⁇ 0.5 deg. 2-theta, 62.779 ⁇ 0.5 deg. 2-theta, 65.841 ⁇ 0.5 deg. 2-theta, under X-Ray Diffraction.
- the material prepared via the method described in Example 1 was used for the removal of sulfur from a synthetic fuel gas with 1.35% H 2 S.
- the material was tested in 5.5 sulfidation-oxidation cycles at atmospheric pressure in an alumina AD-998 reactor.
- the sulfidation step was done at 750° C. and 1600 h ⁇ 1 space velocity with fuel gas simulating an air-blown gasifier (1.35% H 2 S+13.3% H 2 +13.14% CO+13.5% CO 2 +59% N 2 ). Under these reducing conditions, the active oxide phase for the sulfidation reaction is Mn(II)O.
- the 22 wt-% Mn dispersed on the yttria stabilized zirconia felt support gives a maximum theoretical sulfur capacity of 12 wt-% S.
- the regeneration was performed in-situ with lean air (2% O 2 in N 2 ) at 800° C. and 1600 h ⁇ 1 space velocity.
- the Mn-zirconia felt sorbent can easily be cycled between the oxide and sulfide phases with 100% S uptake, i.e., 11.9 wt-% S in all six sulfidation cycles. With this particular space velocity (1600 h ⁇ 1 ) the sample is fully sulfided in 4 hours and fully regenerated in 2.5 to 3 hours with SO 2 being the only off-gas produced.
- the XRD analysis of the six times sulfided Mn/zirconia felt material suggested that the sulfidation was complete. After a six cycles test, the zirconia felt structure remained intact and the only manganese phase detected was MnS with no MnO left behind. After five oxidation cycles, the reactor was unloaded and re-packed for the sixth sulfidation cycle.
- High Resolution Scanning Electron Microscopy (HR-SEM) image reveals that the Mn metal oxide active phase completely coats the fibers of the zirconia felt support.
- the Backscattered Electron image of a cross-section of the Mn metal oxide on the zirconia felt material indicates that the metal oxide layer is very porous, allowing thus the unhindered diffusion of the S-containing gas to the active Mn metal oxide phase.
- the Mn metal oxide dispersed on the zirconia felt support has more sulfur absorbing capacity than metal on traditional bulk zirconia, freshly precipitated or amorphous.
- Example 2 The material prepared via wet impregnation described in Example 1 was used for the removal of sulfur from a synthetic fuel gas at 750° C. and 800 h ⁇ 1 space velocity with fuel gas simulating an air-blown gasifier (1.35% H 2 S+13.3% H 2 +13.14% CO+13.5% CO 2 +59% N 2 ). Decreasing the space velocity from 1600 to 600 h ⁇ 1 increased the breakthrough time (the time with zero ppm H 2 S in the effluent gas) from about 38 minutes (with 2.65 wt-% S loading) to greater than 180 minutes (with about 5 wt-% S loading). Table 2 summarizes the test results.
Abstract
This invention relates to a catalyst material, and its method of making and manufacture, useful for a diversity of chemical production processes as well as various emission control processes. More specifically, it relates to a catalyst composition, preferably comprising a metal oxide felt substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface, which can be used in the removal of sulfur and sulfur compounds from hot gases as well as acting to trap solid particulates and trace metals within these hot gases.
Description
- This application claims priority from Provisional Application No. 61/138,152 filed Dec. 17, 2008, the contents of which are hereby incorporated by reference.
- This invention relates to a catalyst material, and its method of making and manufacture, useful for a diversity of chemical production processes as well as various emission control processes. More specifically, it relates to a catalyst composition, preferably comprising a metal oxide felt substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface, which can be used in the removal of sulfur from hot gases as well as acting to trap solid particulates and metals within these hot gases.
- IGCC (Integrated Gasification Combined Cycle) is a type of power plant that gasifies coal into synthetic gas (syngas) to power a gas turbine. In these plants there is a need to remove a variety of impurities, including sulfur compounds from the syngas. After the impurities are removed, the heat from the gas turbine exhaust generates steam to run a steam turbine.
- The integration of the combination of coal gasification, gas turbines, and steam turbines into electric power plants is new and presents engineering challenges. IGCC plants are to be contrasted to traditional coal powered power plants where the coal is pulverized and then burnt to produce steam to drive a turbine. Gasification is the thermal conversion of carbon-based materials at 760° to 1538° C. (1400° to 2800° F.), with a limited supply of pure oxygen, to a synthetic gas, also known as a syngas as compared to combustion which occurs when there is a surplus of oxygen.
- Syngas typically contains about 35% H2, 45% CO, 5% H2O, 15% CO2 with a small amount of methane, as well as impurities such as solid particulates, sulfur compounds (mainly H2S and COS) and nitrogen compounds as well as smaller quantities of other impurities. The syngas can be used as a fuel to generate power, or to make chemicals and fuels. The heating value is 264 kjoules (250 Btu/scf).
- The hot exhaust gas from the gasification reaction is sent to a steam turbine which generates steam to produce electricity. In addition, the syngas is sent to a combustion turbine which turns a generator. The combined cycle is the combination of a simple cycle combustion turbine generator plus a steam turbine generator. The sulfur compounds need to be removed from the hot exhaust gas.
- IGCC technology produces air emissions that are already considerably lower than required by current U.S. Clean Air standards. Significant reductions in sulfur dioxide (SO2), nitrogen oxides (NOX) and carbon monoxide (CO) are possible through use of IGCC plants, making them more advantageous than conventional coal power plants. Carbon dioxide (CO2), which is considered a major source of global warming, can be captured more economically with IGCC than with conventional technologies. The CO2 could be sequestered or sold in part as a by-product. Overall efficiency is approximately 40 to 45% of the energy value of coal converted to electricity. In comparison, conventional coal plants are approximately 30 to 35% efficient. Water requirements are typically about 50% less for IGCC applications than for conventional coal generation. Marketable by-products from the IGCC process can be sold, such as sulfur. However, IGCC facilities are more expensive to build than conventional coal plants. Only recently have suppliers begun to emerge that can offer comprehensive, integrated designs with packaged systems and compatible equipment. Due to the industry's limited experience with the technology, truly accurate cost estimates for construction and operating costs are not yet available for use in planning future facilities.
- IGCC technology requires more frequent maintenance with longer maintenance outages, requiring that power be purchased from other resources when the IGCC plant is unavailable. Neither of the U.S.-based IGCC projects has used Powder River Basin, or western, coal, which is the type used most frequently in the Midwest. The industry is encouraging suppliers to offer performance contracts for next-generation IGCC plants, but for now, the risk of reduced reliability and availability add significant cost to the project's financing.
- Only a few IGCC projects have been built world-wide despite the potential benefits of the technology. Among the improvements that are sought are methods of cleaning up the hot coal derived gases produced in an IGCC project. In prior art systems, wet scrubbing techniques have been used to clean up the gases. Unfortunately, these systems require first cooling of the gas and then a subsequent reheating step.
- The clean-up of hot coal-derived gases originating from an Integrated Gasification Combined Cycle (IGCC) avoids the sensible heat loss due to the cooling and subsequent reheating associated with the wet scrubbing techniques using either chemical or physical solvents. If the fuel gas is cleaned with the conventional cold gas cleanup, the penalties in both thermal and overall process efficiencies will be larger for air-blown gasifiers compared to O2-blown gasifiers, because the former produces over twice the volume of fuel gas produced by the latter. But nevertheless, both air- and O2-blown gasifiers would benefit from the successful development of hot-gas cleanup techniques. Ideally, the clean-up is done at the highest inlet temperature at which the gas turbine fuel control and delivery systems can de be designed at. Hot gas cleanup may also avoid much of the operational complexity, space requirements, and capital costs associated with cool down/reheating systems or heat exchange systems. Other drivers for hot gas clean-up in IGCCs include avoiding the production of sour water (produced if the fuel gas is cooled below the dew point of water) and consequently the sour water treating, avoiding the production of “black-mud” (mixture of water-char ash) produced in water quenching or water scrubbing of particulates from the fuel gas. Also, if the particulates are removed dry via dry filtration systems, they could be recycled to the gasifier to improve fuel utilization and process efficiency.
- Coal-derived fuel gases used for power generation or cogeneration have to be substantially cleaned before being either burned in a gas turbine or used for chemical synthesis, e.g., methanol, ammonia, urea production, Fischer-Tropsch synthesis. Cleanup techniques require removal of solid particulates, sulfur-containing gases, i.e., H2S and COS and all trace contaminants resulting from the gasification of coal, i.e., NH3, HCN, alkali metals, metal carbonyls, Hg, As, and Se. The successful development of hot-gas cleanup techniques depends on the ability to remove all of the above at equally high temperatures.
- This invention discloses a regenerable material acting as a high temperature sulfur sink as well as a filtering media for the solid particulates. The support used to disperse the active metal oxide phase is acting as a filtering media for the hot solid particulates and trace metals, and the active metal oxide phase dispersed on the support is acting as the sulfur sink. The preferred support material is a ceramic textile composed of 100% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media. The zirconia felts are designed for use in extremely corrosive environments, are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts. They contain no binder and they retain their fibrous nature up to 2480° C. In addition to zirconia, other refractory (metal) oxide felts, such as Ce2O3, CeO2, Y2O3, TiO2, HfO2, Al2O3, Nb2O5, La2O3, Yb2O3, and mixed oxide felts like Al2O3—SiO2, HfO2—CeO2, Sm2O3—CeO2, Yb2O3—CeO2 may be used. The metal oxide phase acting as the sulfur sink can be any metal oxide or mixed metal oxides, i.e., oxides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn, dispersed on the zirconia felt using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation. All commercial large-scale hot coal derived gas cleanup demonstration projects have so far failed because, among other reasons, of the poor attrition resistance of the tested sorbent materials. This problem is avoided by dispersing the active metal oxide used to chemically bind sulfur on the flexible felt material. This porous media can also be used to simultaneously trap the hot solid particulates.
- This invention involves a regenerable material acting as a high temperature sulfur sink as well as a filtering media for the solid particulates. The support used to disperse the active metal oxide phase is acting as a filtering media for the hot solid particulates and trace metals, and the active metal oxide phase dispersed on the support is acting as the sulfur sink. The support is a metal oxide felt substrate comprising a metal oxide selected from the group consisting of ZrO2, Ce2O3, CeO2, Y2O3, TiO2, HfO2, Al2O3, Nb2O5, La2O3, Yb2O3, and mixed oxide felts like Al2O3—SiO2, HfO2—CeO2, Sm2O3—CeO2, Yb2O3—CeO2.
- The preferred support material is a ceramic textile composed of 100% yttria-stabilized zirconia fibers which are mechanically interlocked to give a light weight, very flexible and porous media. The zirconia felts are designed for use in extremely corrosive environments, are stable in strong oxidizing or reducing conditions, and are not reactive to alkali vapors or salts. They contain no binder and they retain their fibrous nature up to 2480° C. In addition to zirconia, other refractory (metal) oxide felts, such as Ce2O3, CeO2, Y2O3, TiO2, HfO2, Al2O3, Nb2O5, La2O3, Yb2O3, and mixed oxide felts like Al2O3—SiO2, HfO2—CeO2, Sm2O3—CeO2, Yb2O3—CeO2 may be used. The metal oxide phase acting as the sulfur sink can be any metal oxide or mixed metal oxides, i.e., oxides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn dispersed on the zirconia felt using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation. All commercial large-scale hot coal derived gas cleanup demonstration projects have so far failed because, among other reasons, of the poor attrition resistance of the tested sorbent materials. This problem is avoided by dispersing the active metal oxide used to chemically bind sulfur on the flexible felt material. This porous media can also be used to simultaneously trap the hot solid particulates.
- The metal oxide felt material used in the present invention may comprise layers having a thickness from about 0.25 to about 6.35 mm and preferably the thickness of the layers is from about 1.27 to about 3.81 mm. The metal oxide felt material has a bulk porosity from about 50 to 100% and preferably from about 88 to 96%. The bulk density of the metal oxide felt material is from about 128 to 1073 grams/liter and preferably from about 160 to 400 grams per liter. The metal oxide felt material has a high melting point in the range from 15000 to 5000° C.
- The catalytic material that is deposited on the metal oxide felt material is selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides and mixed metal sulfides. Catalytic materials for use in removal of sulfur compounds are selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides and mixed metal sulfides of Zn, Fe, Cu, Co, Ni, Mo, Ca, Sr, Ba, Ce, Ti, V, W, or Mn. Preferably the catalytic active phases for the removal of sulfur compounds are oxides of Mn. The catalytic active phase can be deposited on the metal oxide felt material using any of the methods known in the art, i.e., wet impregnation, metal vapor deposition and subsequent metal oxidation.
- In an embodiment of the present invention, one process of making the active metal oxide phase supported on the refractory metal oxide felt support is disclosed. The process comprises an aqueous impregnation of the active metal oxide phase onto the metal felt support, followed by a (high temperature of about 800° C.) heat treatment.
- In another embodiment of the present invention, the active metal oxide phase coating the metal oxide felt support fibers is porous, allowing the unhindered diffusion and easy access of the sulfur compounds contained in the gaseous stream to the catalytic active metal oxide sites dispersed on the metal oxide felt support.
- Yet another embodiment of the invention, involves the use of the composite materials of the present invention in the treatment of a hot gaseous stream with the exposure of the hot gaseous stream to a composite material comprising a metal oxide felt substrate and a catalytic material wherein the treatment includes removal of sulfur compounds and solid particulates from a hot gas that may be at a temperature from about 250° to 850° C. A typical gaseous stream comprises carbon monoxide, carbon dioxide, hydrogen, and sulfur compounds. The gaseous stream may comprise a fuel gas or a synthesis gas comprising hydrogen, carbon monoxide, sulfur-containing compounds and impurities like solid particulates and trace metals.
- The Mn oxide supported on yttria stabilized zirconia felt catalyst was prepared by cutting the yttria stabilized zirconia felt into approximately 0.25 inch squares. To the cut felt squares, 36.3 g of an 0.5 M aqueous Mn(OAc)2:4H2O solution was added slowly with gentle stirring. The felt support squares were allowed to soak in the aqueous Mn acetate solution for 24 hours at room temperature with periodic gentle stirring, after which the mixture was dried at 100° C. for 4 hours. The dry impregnated felt support squares were then calcined in flowing air for 2 hours at 800° C.
- The Mn oxide supported on yttria stabilized zirconia felt catalyst showed characteristic lines at 23.2±0.5 deg. 2-theta, 28.942±0.5 deg. 2-theta, 30.220±0.5 deg. 2-theta, 33.039±0.5 deg. 2-theta, 35.060±0.5 deg. 2-theta, 38.303±0.5 deg. 2-theta, 45.243±0.5 deg. 2-theta, 49.441±0.5 deg. 2-theta, 50.318±0.5 deg. 2-theta, 55.261±0.5 deg. 2-theta, 57.024±0.5 deg. 2-theta, 59.779±0.5 deg. 2-theta, 62.779±0.5 deg. 2-theta, 65.841±0.5 deg. 2-theta, under X-Ray Diffraction.
- The material prepared via the method described in Example 1 was used for the removal of sulfur from a synthetic fuel gas with 1.35% H2S. The material was tested in 5.5 sulfidation-oxidation cycles at atmospheric pressure in an alumina AD-998 reactor. The sulfidation step was done at 750° C. and 1600 h−1 space velocity with fuel gas simulating an air-blown gasifier (1.35% H2S+13.3% H2+13.14% CO+13.5% CO2+59% N2). Under these reducing conditions, the active oxide phase for the sulfidation reaction is Mn(II)O. The 22 wt-% Mn dispersed on the yttria stabilized zirconia felt support gives a maximum theoretical sulfur capacity of 12 wt-% S. The regeneration was performed in-situ with lean air (2% O2 in N2) at 800° C. and 1600 h−1 space velocity. The Mn-zirconia felt sorbent can easily be cycled between the oxide and sulfide phases with 100% S uptake, i.e., 11.9 wt-% S in all six sulfidation cycles. With this particular space velocity (1600 h−1) the sample is fully sulfided in 4 hours and fully regenerated in 2.5 to 3 hours with SO2 being the only off-gas produced. The oxidation reaction is extremely exothermic (Delta H=−133.7 kcal/mol at 800° C.), however the exotherm was only 4° C. because of the low O2 concentration in the regeneration gas. In accordance with the gas chromatograph analysis and the S LECO measurements, the XRD analysis of the six times sulfided Mn/zirconia felt material suggested that the sulfidation was complete. After a six cycles test, the zirconia felt structure remained intact and the only manganese phase detected was MnS with no MnO left behind. After five oxidation cycles, the reactor was unloaded and re-packed for the sixth sulfidation cycle. The XRD spectra of the five times oxidized material indicated that the sulfided Mn was completely oxidized to Mn2O3 (which is further fully reduced to Mn(II)O in the presence of the reducing fuel gas during the sulfidation cycle).
- High Resolution Scanning Electron Microscopy (HR-SEM) image reveals that the Mn metal oxide active phase completely coats the fibers of the zirconia felt support. The Backscattered Electron image of a cross-section of the Mn metal oxide on the zirconia felt material indicates that the metal oxide layer is very porous, allowing thus the unhindered diffusion of the S-containing gas to the active Mn metal oxide phase. As a result, the Mn metal oxide dispersed on the zirconia felt support has more sulfur absorbing capacity than metal on traditional bulk zirconia, freshly precipitated or amorphous.
- The test results are summarized in Table 1.
-
TABLE 1 Wt-% S loading before Cycle sulfur breakthrough Wt-% total S loading 1 2.65 12 2 2.65 11.9 3 2.65 11.3 6 2.65 11.5 - The material prepared via wet impregnation described in Example 1 was used for the removal of sulfur from a synthetic fuel gas at 750° C. and 800 h−1 space velocity with fuel gas simulating an air-blown gasifier (1.35% H2S+13.3% H2+13.14% CO+13.5% CO2+59% N2). Decreasing the space velocity from 1600 to 600 h−1 increased the breakthrough time (the time with zero ppm H2S in the effluent gas) from about 38 minutes (with 2.65 wt-% S loading) to greater than 180 minutes (with about 5 wt-% S loading). Table 2 summarizes the test results.
-
TABLE 2 Space Velocity Wt-% S loading before (h−1) sulfur breakthrough Wt-% total S loading 800 2.65 11.9 1600 5 12
Claims (20)
1. A composite material comprising a support structure and a catalytic material deposited on said support structure, wherein said support structure comprises a metal oxide felt material.
2. The composite material of claim 1 wherein said metal oxide felt material is selected from the group consisting of inorganic refractory metal oxide felts selected from the group consisting of ZrO2, Ce2O3, CeO2, Y2O3, TiO2, HfO2, Al2O3, Nb2O5, La2O3, Yb2O3, and mixed oxide felts selected from the group consisting of Al2O3—SiO2, HfO2—CeO2, Sm2O3—CeO2, Yb2O3—CeO2.
3. The composite material of claim 2 wherein said metal oxide felt material is ZrO2.
4. The composite material of claim 3 wherein said metal oxide felt material further comprises yttrium.
5. The composite material of claim 1 wherein said metal oxide felt material comprises layers having a thickness from about 0.25 to about 6.35 mm.
6. The composite material of claim 1 wherein said metal oxide felt material comprises layers having a thickness from about 1.27 to about 3.81 mm.
7. The composite material of claim 1 wherein said metal oxide felt material has a bulk porosity from about 50 to 100%.
8. The composite material of claim 1 wherein said metal oxide felt material has a bulk porosity from about 88 to 96%.
9. The composite material of claim 1 wherein said metal oxide felt material has a bulk density of about 128 to 1073 grams/liter.
10. The composite material of claim 1 wherein said metal oxide felt material has a bulk density of about 160 to 400 grams/liter.
11. The composite material of claim 1 wherein said metal oxide felt material has a melting point between about 1500° and 5000° C.
12. The composite material of claim 1 wherein said catalytic material is selected from the group consisting of metals, metal oxides, metal sulfides, mixed metal oxides, mixed metal sulfides.
13. The composite material of claim 12 wherein said metals, said mixed metals and said mixed metal sulfides comprise metals selected from the group consisting of Zn, Fe, Cu, Co, Ni, Mo, Mn, Ca, Sr, Ba, Ce, Ti, V, and W.
14. A method for treating a hot gas comprising exposing said hot gas to a composite material comprising a metal oxide felt substrate and a catalytic material wherein said treating includes removal of sulfur compounds, and solid particulates, and metals from said hot gas.
15. The method of claim 14 wherein said hot gas is at a temperature from about 250° to 850° C.
16. The method of claim 14 wherein said hot gas is a synthesis gas.
17. The method of claim 14 wherein said composite material both catalyzes a reaction to remove sulfur compounds and traps solid particulates and metals contained in said hot gas.
18. The method of claim 14 wherein said metal oxide felt substrate comprises a metal oxide selected from the group consisting of ZrO2, Ce2O3, CeO2, Y2O3, TiO2, HfO2, Al2O3, Nb2O5, La2O3, and Yb2O3, or a mixed metal oxide selected from the group consisting of Al2O3—SiO2, HfO2—CeO2, Sm2O3—CeO2, and Yb2O3—CeO2.
19. The method of claim 14 wherein said metal oxide felt substrate comprises ZrO2.
20. The method of claim 14 wherein said metal oxide felt substrate comprises ZrO2 and the catalytic material comprises oxides of Mn, and said metal oxide felt substrate and catalytic material shows characteristic lines at 23.2±0.5 deg. 2-theta, 28.942±0.5 deg. 2-theta, 30.220±0.5 deg. 2-theta, 33.039±0.5 deg. 2-theta, 35.060±0.5 deg. 2-theta, 38.303±0.5 deg. 2-theta, 45.243±0.5 deg. 2-theta, 49.441±0.5 deg. 2-theta, 50.318±0.5 deg. 2-theta, 55.261±0.5 deg. 2-theta, 57.024±0.5 deg. 2-theta, 59.779±0.5 deg. 2-theta, 62.779±0.5 deg. 2-theta, 65.841±0.5 deg. 2-theta, under X-Ray Diffraction.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/555,340 US20100135883A1 (en) | 2008-12-17 | 2009-09-08 | Catalyst supports |
PCT/US2009/063466 WO2010077432A1 (en) | 2008-12-17 | 2009-11-06 | Catalyst supports |
US13/160,168 US8883108B2 (en) | 2008-12-17 | 2011-06-14 | Catalyst supports |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13815208P | 2008-12-17 | 2008-12-17 | |
US12/555,340 US20100135883A1 (en) | 2008-12-17 | 2009-09-08 | Catalyst supports |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/160,168 Division US8883108B2 (en) | 2008-12-17 | 2011-06-14 | Catalyst supports |
Publications (1)
Publication Number | Publication Date |
---|---|
US20100135883A1 true US20100135883A1 (en) | 2010-06-03 |
Family
ID=42222995
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/555,340 Abandoned US20100135883A1 (en) | 2008-12-17 | 2009-09-08 | Catalyst supports |
US13/160,168 Active 2030-06-24 US8883108B2 (en) | 2008-12-17 | 2011-06-14 | Catalyst supports |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/160,168 Active 2030-06-24 US8883108B2 (en) | 2008-12-17 | 2011-06-14 | Catalyst supports |
Country Status (2)
Country | Link |
---|---|
US (2) | US20100135883A1 (en) |
WO (1) | WO2010077432A1 (en) |
Citations (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US405848A (en) * | 1889-06-25 | Joseph s | ||
US3663182A (en) * | 1968-03-29 | 1972-05-16 | Union Carbide Corp | Metal oxide fabrics |
US4173549A (en) * | 1978-09-22 | 1979-11-06 | Dart Industries Inc. | Catalyst composition for decomposing ozone |
US4193793A (en) * | 1974-12-26 | 1980-03-18 | Union Carbide Corporation | Porous metal-alumina composite |
US4215011A (en) * | 1979-02-21 | 1980-07-29 | Chemical Research And Licensing Company | Catalyst system for separating isobutene from C4 streams |
US4220625A (en) * | 1976-10-20 | 1980-09-02 | Matsushita Electric Industrial Co., Ltd. | Exhaust gas control equipment |
US4544534A (en) * | 1981-12-17 | 1985-10-01 | Societe Nationale Elf Aquitaine | Catalytic desulfurization process of an acid gas containing H2 S |
US4735788A (en) * | 1984-12-12 | 1988-04-05 | Societe Nationale Elf Aquitaine (Production) | Process of removing of COS and CS2 compounds contained in an industrial gas |
US4791079A (en) * | 1986-06-09 | 1988-12-13 | Arco Chemical Company | Ceramic membrane for hydrocarbon conversion |
US5114898A (en) * | 1990-01-18 | 1992-05-19 | Board Of Trustees Operating Michigan State University | Layered double hydroxide sorbents for the removal of SOx from flue gas and other gas streams |
US5130100A (en) * | 1989-02-27 | 1992-07-14 | Usui Kokusai Sangyo Kabushiki Kaisha | Exhaust gas cleaning device |
US5413704A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a mixture of a supported metal chelate and a solid base |
US5916531A (en) * | 1997-04-29 | 1999-06-29 | Pan; Chuen Yong | Spiral fixed-bed module for adsorber and catalytic reactor |
US5942323A (en) * | 1995-01-27 | 1999-08-24 | Purafil, Inc. | Fiber filter and methods of use thereof |
US6379437B1 (en) * | 1997-09-19 | 2002-04-30 | Valtion Teknillinen Tutkimuskeskus | Filter for gases |
US7316782B2 (en) * | 2001-10-11 | 2008-01-08 | Honeywell International, Inc. | Filter apparatus for removing sulfur-containing compounds from liquid fuels, and methods of using same |
US7604719B2 (en) * | 2006-05-25 | 2009-10-20 | Uop Llc | In situ generation of hydrogen peroxide |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3811845A (en) | 1970-07-30 | 1974-05-21 | Matsushita Electric Ind Co Ltd | Vehicle exhaust control equipment |
US4200609A (en) | 1978-04-03 | 1980-04-29 | Mcdonnell Douglas Corporation | Ozone removal filter containing manganese dioxide and ceric oxide catalysts |
US4585899A (en) | 1985-01-22 | 1986-04-29 | Chem Systems Inc. | Hydrogenation of carboxylic acid compounds to aldehydes using MnO2 on gamma alumina as catalyst |
US5075160A (en) * | 1988-06-13 | 1991-12-24 | Martin Marietta Energy Systems, Inc. | Ceramic fiber reinforced filter |
US5221484A (en) * | 1991-01-10 | 1993-06-22 | Ceramem Separations Limited Partnership | Catalytic filtration device and method |
US5196120A (en) * | 1991-05-13 | 1993-03-23 | Minnesota Mining And Manufacturing Company | Ceramic-ceramic composite filter |
US6183852B1 (en) * | 1992-09-15 | 2001-02-06 | The Boeing Company | Refractory fibrous ceramic insulation and process of making same |
US5804153A (en) | 1994-12-16 | 1998-09-08 | The Hong Kong University Of Science & Technology | Catalytic removal of sulfur dioxide form flue gas |
KR100283551B1 (en) * | 1996-01-21 | 2001-03-02 | 클라우스 렌네벡 | Hollow microfiber of ceramic material, a process for its manufacture and its use |
US5914455A (en) | 1997-09-30 | 1999-06-22 | The Boc Group, Inc. | Air purification process |
TW396052B (en) | 1997-11-12 | 2000-07-01 | Babcock Hitachi Kk | Exhaust emission control catalyst element, catalyst structure, production method thereof, exhaust emission control apparatus and exhaust emission control method using the apparatus |
US6440895B1 (en) * | 1998-07-27 | 2002-08-27 | Battelle Memorial Institute | Catalyst, method of making, and reactions using the catalyst |
US20020004450A1 (en) * | 2000-01-21 | 2002-01-10 | Gaffney Anne M. | Thermal shock resistant catalysts for synthesis gas production |
US7052532B1 (en) * | 2000-03-09 | 2006-05-30 | 3M Innovative Properties Company | High temperature nanofilter, system and method |
WO2003033136A2 (en) | 2001-10-15 | 2003-04-24 | Catalytic Distillation Technologies | Hydrogenation catalyst and hydrogenation process |
-
2009
- 2009-09-08 US US12/555,340 patent/US20100135883A1/en not_active Abandoned
- 2009-11-06 WO PCT/US2009/063466 patent/WO2010077432A1/en active Application Filing
-
2011
- 2011-06-14 US US13/160,168 patent/US8883108B2/en active Active
Patent Citations (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US405848A (en) * | 1889-06-25 | Joseph s | ||
US3663182A (en) * | 1968-03-29 | 1972-05-16 | Union Carbide Corp | Metal oxide fabrics |
US4193793A (en) * | 1974-12-26 | 1980-03-18 | Union Carbide Corporation | Porous metal-alumina composite |
US4220625A (en) * | 1976-10-20 | 1980-09-02 | Matsushita Electric Industrial Co., Ltd. | Exhaust gas control equipment |
US4173549A (en) * | 1978-09-22 | 1979-11-06 | Dart Industries Inc. | Catalyst composition for decomposing ozone |
US4215011A (en) * | 1979-02-21 | 1980-07-29 | Chemical Research And Licensing Company | Catalyst system for separating isobutene from C4 streams |
US4544534A (en) * | 1981-12-17 | 1985-10-01 | Societe Nationale Elf Aquitaine | Catalytic desulfurization process of an acid gas containing H2 S |
US4735788A (en) * | 1984-12-12 | 1988-04-05 | Societe Nationale Elf Aquitaine (Production) | Process of removing of COS and CS2 compounds contained in an industrial gas |
US4791079A (en) * | 1986-06-09 | 1988-12-13 | Arco Chemical Company | Ceramic membrane for hydrocarbon conversion |
US5130100A (en) * | 1989-02-27 | 1992-07-14 | Usui Kokusai Sangyo Kabushiki Kaisha | Exhaust gas cleaning device |
US5114898A (en) * | 1990-01-18 | 1992-05-19 | Board Of Trustees Operating Michigan State University | Layered double hydroxide sorbents for the removal of SOx from flue gas and other gas streams |
US5413704A (en) * | 1993-11-15 | 1995-05-09 | Uop | Process for sweetening a sour hydrocarbon fraction using a mixture of a supported metal chelate and a solid base |
US5942323A (en) * | 1995-01-27 | 1999-08-24 | Purafil, Inc. | Fiber filter and methods of use thereof |
US6265024B1 (en) * | 1995-01-27 | 2001-07-24 | Purafil, Inc. | Fiber filter and methods of use thereof |
US5916531A (en) * | 1997-04-29 | 1999-06-29 | Pan; Chuen Yong | Spiral fixed-bed module for adsorber and catalytic reactor |
US6379437B1 (en) * | 1997-09-19 | 2002-04-30 | Valtion Teknillinen Tutkimuskeskus | Filter for gases |
US7316782B2 (en) * | 2001-10-11 | 2008-01-08 | Honeywell International, Inc. | Filter apparatus for removing sulfur-containing compounds from liquid fuels, and methods of using same |
US7604719B2 (en) * | 2006-05-25 | 2009-10-20 | Uop Llc | In situ generation of hydrogen peroxide |
Also Published As
Publication number | Publication date |
---|---|
US8883108B2 (en) | 2014-11-11 |
WO2010077432A1 (en) | 2010-07-08 |
US20110243824A1 (en) | 2011-10-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhu et al. | Perovskites as geo-inspired oxygen storage materials for chemical looping and three-way catalysis: a perspective | |
Ma et al. | Effects of supports on hydrogen production and carbon deposition of Fe-based oxygen carriers in chemical looping hydrogen generation | |
Aravind et al. | Evaluation of high temperature gas cleaning options for biomass gasification product gas for solid oxide fuel cells | |
Bashan et al. | Perovskite catalysts for methane combustion: applications, design, effects for reactivity and partial oxidation | |
Din et al. | The fate of SOFC anodes under biomass producer gas contaminants | |
Hervy et al. | Evolution of dolomite composition and reactivity during biomass gasification | |
Vamvuka et al. | Flue gas desulfurization at high temperatures: A review | |
JP5550715B2 (en) | CO shift catalyst, CO shift reaction apparatus, and purification method of gasification gas | |
JP5659537B2 (en) | Catalyst for reforming tar-containing gas, method for producing the same, and method for reforming tar-containing gas | |
CN102427879A (en) | Catalyst for reforming tar-containing gas, method for producing catalyst for reforming tar-containing gas, method for reforming tar-containing gas using catalyst for reforming tar-containing gas, and method for regenerating catalyst for reforming tar | |
JP7445925B2 (en) | combustion system | |
KR20110010118A (en) | Catalytic process for control of nox emissions using hydrogen | |
Pan et al. | Regenerable Co-ZnO-based nanocomposites for high-temperature syngas desulfurization | |
Liu et al. | Catalytic combustion of soot over the highly active (La0. 9K0. 1CoO3) x/nmCeO2 catalysts | |
Ding et al. | Synthesis and characteristics of BaSrCoFe-based perovskite as a functional material for chemical looping gasification of coal | |
JP2013237049A (en) | Modifying catalyst for tar-containing gas, method for manufacturing the same, and modifying method for tar-containing gas | |
Valsamakis et al. | Stability of lanthanum oxide-based H2S sorbents in realistic fuel processor/fuel cell operation | |
Atimtay | Cleaner energy production with integrated gasification combined cycle systems and use of metal oxide sorbents for H2S cleanup from coal gas | |
US8883108B2 (en) | Catalyst supports | |
Ma et al. | Investigation of combined catalyst and oxygen carrier systems for the partial oxidation of naphthalene as model tar from biomass gasification | |
Flytzani-Stephanopoulos et al. | Kinetics of sulfidation reactions between H2S and bulk oxide sorbents | |
CN104507570B (en) | The process for purification of CO reforming catalysts, CO conversion reactions device and gasification gas | |
JPWO2010131358A1 (en) | CO shift catalyst, method for producing the same, and CO shift reaction apparatus using the CO shift catalyst | |
Valechha et al. | Improved oxygen carriers for cleaner energy generation through chemical looping combustion | |
CN104507571A (en) | Co shift catalyst, co shift reactor, and method for purifying gasification gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UOP LLC,ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SERBAN, MANUELA;KING, LISA M;BHATTACHARYYA, ALAKANANDA;AND OTHERS;SIGNING DATES FROM 20091103 TO 20091104;REEL/FRAME:023490/0253 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |