US20050025695A1 - Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures - Google Patents
Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures Download PDFInfo
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- US20050025695A1 US20050025695A1 US10/628,842 US62884203A US2005025695A1 US 20050025695 A1 US20050025695 A1 US 20050025695A1 US 62884203 A US62884203 A US 62884203A US 2005025695 A1 US2005025695 A1 US 2005025695A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title claims description 13
- 229910021392 nanocarbon Inorganic materials 0.000 title claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 28
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000000877 morphologic effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 230000009257 reactivity Effects 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical group 0.000 claims description 12
- 239000002086 nanomaterial Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002717 carbon nanostructure Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 150000002823 nitrates Chemical class 0.000 description 1
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Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/40—
-
- B01J35/613—
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to the production of Nanocarbon materials. More particularly, the present invention relates to an improved catalyst and process to produce Nanocarbon materials in high yield and high selectivity and at reduced reaction temperatures.
- Nano-structured materials are gaining importance for various commercial applications. Such applications include their use to store molecular hydrogen, to serve as catalyst supports, as reinforcing components of polymeric composites, for use in electromagnetic shielding and for use in various types of batteries and other energy storage devices.
- Carbon nano-structure materials are generally prepared from the decomposition of carbon containing gases over selected catalytic metal surfaces at temperatures ranging from about 500° C. to about 1200° C.
- carbon nanofibers can be used in lithium ion batteries, wherein the anode would be comprised of graphitic nanofibers.
- the graphite sheets are substantially perpendicular or parallel to the longitudinal axis of the carbon nanofiber.
- Example of such a use can be found in U.S. Pat. No. 6,503,660 which is contained in the information disclosure statement submitted herewith.
- U.S. Pat. No. 5,879,836 teaches the use of fibrils as a material for the lithium ion battery anode. Fibrils are described as being composed of parallel layers of carbon in the form of a series of concentric tubes disposed about a longitudinal axis rather than as multi-layers of flat graphite sheets.
- the graphite nanofibers possess structures in which the graphite sheets are aligned in the direction either substantially perpendicular or substantially parallel to the fiber axis and designated as platelet and ribbon respectively.
- the exposed surfaces of the nanofibers are comprised of at least 95% edge regions in contrast to conventional graphites that are comprised almost entirely of basal plane regions and very little edge sites.
- a carbon nanofiber system is synthesized with very high purity (above 95%), high crystallinity, selectivity of the carbon morphology, and exceptionally high yield.
- a custom made catalyst with an average single crystal-particle size of ⁇ 10 nm and a high surface area (>50 m 2 /g), provides a higher morphological selectivity and higher reactivity than heretofore attainable. The reactivity of these catalyst particles is maintained even after 24 hours reaction such that yield exceeds 200 g carbon per gram of catalyst.
- the catalysts which are key to the products and yield achieved are prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process as taught in U.S. Pat. No. 6,132,653. The disclosure of U.S. Pat. No. 6,132,653, is totally incorporated herein by reference thereto.
- “Selectivity” is defined as fraction of the carbonaceous product possessing the intended morphology (orientation of graphene layers); and “yield” is defined as weight carbon produced divided by weight of catalysts; in such catalytic processes, this is also sometimes expressed as turnover.
- FIG. 1 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of the Iron oxide catalyst over a 24 hour period;
- FIG. 2 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of an Iron:Nickel catalyst over a 24 hour period;
- FIG. 3 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation to FIG. 1 ;
- FIG. 4 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation to FIG. 1 .
- FIG. 5 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation to FIG. 2 ;
- FIG. 6 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation to FIG. 2 ;
- FIG. 7 is a graph of the production of nanocarbon fibers having platelet morphology prepared with Iron oxide catalyst compared with a conventional catalyst.
- FIG. 8 is a graph of the production of nanocarbon fibers having tubular morphology prepared with Iron:Nickel catalyst compared with a conventional catalyst.
- the Iron oxide catalyst utilized with CO:H 2 ::4::1 at 550° C. produces a specific morphology of the carbon micro structure where the graphite planes are perpendicular to the carbon growth axis as seen in FIGS. 3 and 4 .
- this trial shows a better carbon yield (2 to 3 time higher) and at 50° C. lower synthesis temperature (550° vs 600° C.).
- Morphological selectivity is 100%.
- an Iron:Nickel catalyst was used, with C 2 H 2 :H 2 ::1:4 at 550° C. to produce a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel and/or at an angle to the carbon growth axis, as seen in FIGS. 5 and 6 .
- this trial shows a better carbon yield (2 to 3 times higher) and at 100° C. lower synthesis temperature ( 5500 vs 650° C.). A greater than 99.2% purity of the carbon product can be reached in this system. Morphological selectivity is >95%.
- the catalyst can be a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys.
- a known amount of oxide catalyst (0.1-1.2 g) was placed in a ebullated fluid-bed reactor with Al 2 O 3 (14.9-13.8 g) The reactor was flushed for 30 min with nitrogen gas with a flow rate of 1000 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H 2 (balanced with N 2 ). This was held for 1 h at this temperature then the temperature was increased to a reaction temperature 550° C. for iron-nickel oxide catalyst in 30 min under N 2 flow. Once the set temperature was stabilized, the reaction gas (C 2 H 4 /H 2 ) was introduced into the reactor for a known period of time (2 h). The yield can reach to 140 g carbon/g catalyst.
- FIG. 1 shows the graph of the effect of time on growth of carbon nanofibers utilizing an iron oxide catalyst with CO:H 2 ::4:1 at 550° C.
- the carbon nanofibers produced comprise the carbon platelet morphology as seen in FIGS. 3 and 4 .
- FIG. 1 shows the metal content as a percentage weight of the product decreases to 0.3% and the yield of carbon per gram of catalyst was >300 g/g. It also shows that the catalytic particle was still active even after the 24 hours reaction time.
- FIG. 2 the graph depicts utilizing the iron-nickel catalyst with C 2 H 2 :H 2 ::1:4 at 550° C.
- the carbon nanofibers which were produced as shown in this graph resulted in a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel or at an angle to the growth axis as seen in FIGS. 5 and 6 .
- this shows a better carbon yield and at a 100° C. lower synthesis temperature.
- 99.6% purity of the carbon product and morphological selectivity is >95%.
- the metal content of the product was 0.4% while the yield of carbon was between 200 and 250 g/g catalyst.
- both the Iron catalyst and the Iron:Nickel catalyst respectively produced a carbon nanomaterial platelet or tubular morphology at lower temperature, >95% morphological selectivity, higher yield and lower impurity of metal than the commercial or conventional catalysts.
- the “CCC Produced Conventional” catalyst was prepared utilizing a liquid precipitation process. Iron, nickel, and copper metal nitrates were utilized. The metal nitrates were stoichimetrically mixed in H 2 O and rapidly stirred at room temperature. Ammonium bicarbonate is added to a pH ⁇ 9, and stirred ⁇ 5 minutes.
- a precipitate forms overnight; the precipitate is washed and dried.
- Metal carbonate is dried at 110° C. for 24 hrs. and then calcinated in air for 4 hrs. at 400° C.
- Metal oxides are ball milled for 6 hrs. and reduced in 10% H2 in N2 at 500° C. for 20 hrs. in 200 sccm flow.
- Metal powder is passivated in 2% O 2 in N2 at room temperature for 1 hour. This technique and the reaction taking place, as shown below, are referenced in R. J. Best and W. W. Russel, J. Am. Chem. Soc. 76, 8383 (1954).
- the process for producing nanocarbon materials is undertaken by providing a catalyst with an average particle size of ⁇ 10 nm and a surface area greater than 50 m2/g, although this may vary.
- carbonaceous reactants are reacted in the presence of the catalyst over a given period of time to produce carbon nanofibers with over 99% purity and a morphological selectivity approaching 100% with higher reactivity.
- the catalyst produced by the method described in U.S. Pat. No. 6,123,653, incorporated herein by reference, is a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys. There may be other suitable metal oxides which may be found as experimentation continues.
- the catalyst itself, is prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process; and it possesses a single crystal morphology.
- the resulting yield of carbon nanomaterial is ⁇ 140 g carbon per g catalyst, but it may be more, while the morphology of the carbon micro structure comprises graphite planes of controllable orientation (depending on catalyst composition and carbonaceous feedstock) perpendicular or parallel to the carbon growth axis resulting in the 99.6% purity of the carbon product.
Abstract
Description
- None
- Not applicable
- Not applicable
- 1. Field of the Invention
- The present invention relates to the production of Nanocarbon materials. More particularly, the present invention relates to an improved catalyst and process to produce Nanocarbon materials in high yield and high selectivity and at reduced reaction temperatures.
- 2. General Background of the Invention
- Nano-structured materials, more particular carbon nano structure materials, are gaining importance for various commercial applications. Such applications include their use to store molecular hydrogen, to serve as catalyst supports, as reinforcing components of polymeric composites, for use in electromagnetic shielding and for use in various types of batteries and other energy storage devices. Carbon nano-structure materials are generally prepared from the decomposition of carbon containing gases over selected catalytic metal surfaces at temperatures ranging from about 500° C. to about 1200° C.
- For example, carbon nanofibers can be used in lithium ion batteries, wherein the anode would be comprised of graphitic nanofibers. The graphite sheets are substantially perpendicular or parallel to the longitudinal axis of the carbon nanofiber. Example of such a use can be found in U.S. Pat. No. 6,503,660 which is contained in the information disclosure statement submitted herewith. Furthermore U.S. Pat. No. 5,879,836 teaches the use of fibrils as a material for the lithium ion battery anode. Fibrils are described as being composed of parallel layers of carbon in the form of a series of concentric tubes disposed about a longitudinal axis rather than as multi-layers of flat graphite sheets.
- Furthermore in U.S. Pat. No. 6,485,858 the graphite nanofibers possess structures in which the graphite sheets are aligned in the direction either substantially perpendicular or substantially parallel to the fiber axis and designated as platelet and ribbon respectively. In addition, the exposed surfaces of the nanofibers are comprised of at least 95% edge regions in contrast to conventional graphites that are comprised almost entirely of basal plane regions and very little edge sites.
- Other references include “Catalytic Growth of Carbon Filaments,” which is an article from the Chemical Engineering Department of Auburn University dated 1989, wherein it discusses the formation of filamentous carbon. Another source of information is an article entitled “A Review of Catalytic Grown Carbon Nanofibers,” published by the Material Research Society, in 1993. In that article, carbon nanofibers are discussed as being produced in a relatively large scale through a catalytic decomposition of certain hydrocarbons on small metal particles.
- In all cases, as was discussed above, synthesizing a pure carbon nanomaterial is challenging. Most of the applications of these materials require pure carbon nanomaterials systems. Therefore, it would be beneficial to provide a system of producing pure carbon nanomaterials where the carbon system can be synthesized with very high purity (greater than 95%), high crystallinity, selectivity of the carbon morphology, and exceptionally high yield. Furthermore, a custom made catalyst with a particular particle size and high surface area would give a higher selectivity and higher reactivity.
- In the present invention, a carbon nanofiber system is synthesized with very high purity (above 95%), high crystallinity, selectivity of the carbon morphology, and exceptionally high yield. A custom made catalyst with an average single crystal-particle size of <10 nm and a high surface area (>50 m2/g), provides a higher morphological selectivity and higher reactivity than heretofore attainable. The reactivity of these catalyst particles is maintained even after 24 hours reaction such that yield exceeds 200 g carbon per gram of catalyst. The catalysts which are key to the products and yield achieved are prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process as taught in U.S. Pat. No. 6,132,653. The disclosure of U.S. Pat. No. 6,132,653, is totally incorporated herein by reference thereto.
- For purposes of this application the terms used herein will have the following definitions: “Purity” is defined as carbon content with the impurity understood to comprise the catalyst.
- “Selectivity” is defined as fraction of the carbonaceous product possessing the intended morphology (orientation of graphene layers); and “yield” is defined as weight carbon produced divided by weight of catalysts; in such catalytic processes, this is also sometimes expressed as turnover.
- Therefore, it is a principal object of the present invention to synthesize a pure carbon nanomaterial with extremely high purity, high selectivity, of the carbon morphology and exceptionally high yield.
- It is a further object of the present invention to synthesize a pure carbon nanomaterial in the presence of a custom made catalyst having a particular particle size, surface area, and chemical composition to provide the high morphological selectivity, yield, and purity.
- It is a further object of the present invention to produce a carbon nanomaterial in the presence of a custom made catalyst so that over a given amount of time the yield exceeds 200 g carbon/g of catalyst.
- For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
-
FIG. 1 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of the Iron oxide catalyst over a 24 hour period; -
FIG. 2 is a graph of the Effect of Time on Growth of the carbon nanofiber in the presence of an Iron:Nickel catalyst over a 24 hour period; -
FIG. 3 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation toFIG. 1 ; -
FIG. 4 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron oxide catalyst as described in relation toFIG. 1 . -
FIG. 5 illustrates the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation toFIG. 2 ; -
FIG. 6 is a high resolution view of the specific morphology of the carbon microstructure of the carbon nanofiber produced in the presence of the Iron:Nickel catalyst as described in relation toFIG. 2 ; -
FIG. 7 is a graph of the production of nanocarbon fibers having platelet morphology prepared with Iron oxide catalyst compared with a conventional catalyst; and -
FIG. 8 is a graph of the production of nanocarbon fibers having tubular morphology prepared with Iron:Nickel catalyst compared with a conventional catalyst. - The production of the catalyst utilized in the production of the nanofibers disclosed herein is similar to that disclosed in U.S. Pat. No. 6,132,653, referenced and incorporated earlier herein.
- List of metals that can be used as part of the catalyst are as follows:
-
- Fe, Ni, Co, Mo, Cu, La, Ag, Au and alloys.
- The Nanocarbon Materials Produced with the Catalysts
- Reference is now made to the table and information below which discusses the properties of the material as produced with the new catalyst as described above (flame synthesized) and a conventional catalyst (co-precipitated)
TABLE 2 New Catalyst Conventional or (flame Commercial Catalyst Properties synthesized) (co-precipitation) Chemical form Metal Oxide Pre-reduced Metal with thin cover of oxide Size (nm) ˜10 500-2000 Morphology Single Crystal Polycrystalline Surface area ˜130 <20 (m2/g) Packing density Lower than bulk Same as bulk
Experimental Detail to Achieve Results Above: - a. Conventional or Commercial Catalyst:
- A known amount of pre-reduced catalyst (0.1 g) was placed in a ceramic boat or a quartz cylinder. The boat was then transferred into a quartz reactor (ø=47 mm). The reactor was flushed for 30 min with nitrogen gas with a flow rate of 200 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature. The temperature was then increased to reaction temperature 600° C. for iron or 650° C. for iron-nickel catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (CO/H2 or C2H4/H2) was introduced into the reactor for different periods of time (1, 2, 4, 6, 8 and 24 h).
- b. New Catalyst:
- A known amount of oxide catalyst (0.1 g) was placed in ceramic boat or a quartz cylinder. The boat was then transferred into the quartz reactor (ø=47 mm). The reactor was flushed for 30 min with nitrogen gas with a flow rate of 200 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature than the temperature was increased to
reaction temperature 550° C. for iron oxide and iron-nickel oxide catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (CO/H2 or C2H4/H2) was introduced into the reactor for different periods of time (1, 2, 4, 6, 8 and 24 h). - The Iron oxide catalyst utilized with CO:H2::4::1 at 550° C. produces a specific morphology of the carbon micro structure where the graphite planes are perpendicular to the carbon growth axis as seen in
FIGS. 3 and 4 . In comparison to the commercial catalyst, this trial shows a better carbon yield (2 to 3 time higher) and at 50° C. lower synthesis temperature (550° vs 600° C.). There is a greater than 99.6% purity of the carbon product which can be reached in the system. Morphological selectivity is 100%. - In the second example, an Iron:Nickel catalyst was used, with C2H2:H2::1:4 at 550° C. to produce a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel and/or at an angle to the carbon growth axis, as seen in
FIGS. 5 and 6 . In comparison to other conventional or commercial catalyst, this trial shows a better carbon yield (2 to 3 times higher) and at 100° C. lower synthesis temperature (5500 vs 650° C.). A greater than 99.2% purity of the carbon product can be reached in this system. Morphological selectivity is >95%. In the two examples used above, the catalyst can be a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys. - c. Fluid Bed Process Option:
- A known amount of oxide catalyst (0.1-1.2 g) was placed in a ebullated fluid-bed reactor with Al2O3 (14.9-13.8 g) The reactor was flushed for 30 min with nitrogen gas with a flow rate of 1000 sccm. The reactor was heated up to 450° C. with a heating rate of 5° C./min under 10-20% H2 (balanced with N2). This was held for 1 h at this temperature then the temperature was increased to a
reaction temperature 550° C. for iron-nickel oxide catalyst in 30 min under N2 flow. Once the set temperature was stabilized, the reaction gas (C2H4/H2) was introduced into the reactor for a known period of time (2 h). The yield can reach to 140 g carbon/g catalyst. - Reference is now made to
FIG. 1 which shows the graph of the effect of time on growth of carbon nanofibers utilizing an iron oxide catalyst with CO:H2::4:1 at 550° C. In this graph, the carbon nanofibers produced comprise the carbon platelet morphology as seen inFIGS. 3 and 4 . With reference toFIG. 1 : As the process continues over some 24 hour period, the metal content as a percentage weight of the product decreases to 0.3% and the yield of carbon per gram of catalyst was >300 g/g. It also shows that the catalytic particle was still active even after the 24 hours reaction time. In this particular example, the iron oxide catalyst, with CO:H2::4:1 at 550° C. produced a specific morphology of the carbon micro structure, i.e., where the graphite planes are perpendicular to the carbon growth axis, again as depicted inFIGS. 3 and 4 . Furthermore, in comparison to the commercial catalyst, as stated earlier this trial shows a better carbon yield (2-3 times higher) and at 50° C. lower synthesis temperature. This provides a 99.7 pure carbon product and with a morphological selectivity of 100%. As seen inFIGS. 3 and 4 , the specific morphology of the carbon microstructure shows the graphite planes perpendicular to the carbon growth axis. - Turning now to
FIG. 2 , the graph depicts utilizing the iron-nickel catalyst with C2H2:H2::1:4 at 550° C. The carbon nanofibers which were produced as shown in this graph resulted in a specific morphology of the carbon micro structure, i.e., where the graphite planes are parallel or at an angle to the growth axis as seen inFIGS. 5 and 6 . In comparison to the conventional catalyst, this shows a better carbon yield and at a 100° C. lower synthesis temperature. Again there is a 99.6% purity of the carbon product and morphological selectivity is >95%. At the end of a 24 hour reaction period, the metal content of the product was 0.4% while the yield of carbon was between 200 and 250 g/g catalyst. - In both of these systems, as shown in
FIGS. 1 and 2 , there can be reached a 99% carbon in an 8 hour reaction time. These results are shown in the following tables. - In each of these tables and as depicted in
FIGS. 7 and 8 respectively, both the Iron catalyst and the Iron:Nickel catalyst respectively produced a carbon nanomaterial platelet or tubular morphology at lower temperature, >95% morphological selectivity, higher yield and lower impurity of metal than the commercial or conventional catalysts. - For Platelet Morphology, Catalyst Iron, CO:H2::4:1.
Temperature Selectivity Yield Impurity Catalyst (° C.) (visual) (g/6 h) (metal) Flame 550 100 77 1.3 Commercial 600 90 50 2 (J. T. Baker) - For Tubular Morphology, Catalyst Iron:Nickel::8:2, C2H4:H2::1:4
Temperature Selectivity Yield Impurity Catalyst (° C.) (visual) (g/6 h) (metal) Flame 550 >95 81 1.25 CCC 650 60 26.33 3.8 Produced Conventional
The “CCC Produced Conventional” catalyst was prepared utilizing a liquid precipitation process. Iron, nickel, and copper metal nitrates were utilized. The metal nitrates were stoichimetrically mixed in H2O and rapidly stirred at room temperature. Ammonium bicarbonate is added to a pH ˜9, and stirred ˜5 minutes. A precipitate forms overnight; the precipitate is washed and dried. Metal carbonate is dried at 110° C. for 24 hrs. and then calcinated in air for 4 hrs. at 400° C. Metal oxides are ball milled for 6 hrs. and reduced in 10% H2 in N2 at 500° C. for 20 hrs. in 200 sccm flow. Metal powder is passivated in 2% O2 in N2 at room temperature for 1 hour. This technique and the reaction taking place, as shown below, are referenced in R. J. Best and W. W. Russel, J. Am. Chem. Soc. 76, 8383 (1954).
Powder Catalyst Synthesis by Flame/Plasma Process: - A mixture of nitrate/sulfate salt of metal (Fe, Ni and Cu) ethanolic solution were prepared and vaporized/atomized into either flame or plasma torch and powder of pure oxide or mixed metal oxide were obtained by this process. U.S. Pat. No. 6,123,653 (Oct. 17, 2000).
- In general, the process for producing nanocarbon materials, is undertaken by providing a catalyst with an average particle size of ≦10 nm and a surface area greater than 50 m2/g, although this may vary. Next, carbonaceous reactants are reacted in the presence of the catalyst over a given period of time to produce carbon nanofibers with over 99% purity and a morphological selectivity approaching 100% with higher reactivity.
- The catalyst, produced by the method described in U.S. Pat. No. 6,123,653, incorporated herein by reference, is a metal oxide catalyst selected from the metals including iron, nickel, cobalt, lanthanum, gold, silver, molybdenum, iron-nickel, iron-copper and their alloys. There may be other suitable metal oxides which may be found as experimentation continues. The catalyst, itself, is prepared to specific parameters (size distribution, composition and crystallinity) specified and via a flame synthesis process; and it possesses a single crystal morphology. By utilizing the catalyst from the group identified, the resulting yield of carbon nanomaterial is ≧140 g carbon per g catalyst, but it may be more, while the morphology of the carbon micro structure comprises graphite planes of controllable orientation (depending on catalyst composition and carbonaceous feedstock) perpendicular or parallel to the carbon growth axis resulting in the 99.6% purity of the carbon product.
- The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims.
Claims (19)
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US10/628,842 US20050025695A1 (en) | 2003-07-28 | 2003-07-28 | Catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
CNA2004800219719A CN1833055A (en) | 2003-07-28 | 2004-04-20 | Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
PCT/US2004/012136 WO2005016853A2 (en) | 2003-07-28 | 2004-04-20 | Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
EP04750358A EP1654406A4 (en) | 2003-07-28 | 2004-04-20 | Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
KR1020067001924A KR20060052923A (en) | 2003-07-28 | 2004-04-20 | Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
JP2006521812A JP2007500121A (en) | 2003-07-28 | 2004-04-20 | Improved catalyst and method for producing high yield and high selectivity nanocarbon materials at reduced reaction temperatures |
BRPI0413069-3A BRPI0413069A (en) | 2003-07-28 | 2004-04-20 | improved process and catalyst to produce high selectivity nanocarbon materials with low reaction temperatures |
TW093112404A TW200505788A (en) | 2003-07-28 | 2004-05-03 | Improved catalyst and process to produce nanocarbon materials in high yield and at high selectivity at reduced reaction temperatures |
ARP040101720A AR044387A1 (en) | 2003-07-28 | 2004-05-18 | PROCEDURE TO PRODUCE HIGH PERFORMANCE NANOCARBON MATERIALS AND HIGH SELECTIVITY TO REDUCED REACTION TEMPERATURES |
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