PRODUCTION OF CARBON NANOTUBES

• US 20090099016A1
• Filed: 12/19/2006
• Published: 04/16/2009
• Est. Priority Date: 12/19/2005
• Status: Active Grant

• Current Assignee: ZEON Corporation
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Xu, Xueping, Carruthers, J. Donald, Wang, Luping
• Granted Patent: US 8,562,937 B2
• Time in Patent Office: Days
• US Class Current: 502/416
• CPC Class Codes: B01J 20/20 comprising free carbon; comprising carbon obtained by carbonising processes
• CPC Class Codes: B01J 20/205 Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 23/74 Iron group metals
• CPC Class Codes: B01J 23/881 and iron
• CPC Class Codes: B01J 23/882 and cobalt
• CPC Class Codes: B01J 23/883 and nickel
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 2202/02 Single-walled nanotubes
• CPC Class Codes: C01B 2202/08 Aligned nanotubes
• CPC Class Codes: C01B 2202/36 Diameter
• CPC Class Codes: C01B 32/162 characterised by catalysts
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

A method and apparatus for manufacture of carbon nanotubes, in which a substrate is contacted with a hydrocarbonaceous feedstock containing a catalytically effective metal to deposit the feedstock on the substrate, followed by oxidation of the deposited feedstock to remove hydrocarbonaceous and carbonaceous components from the substrate, while retaining the catalytically effective metal thereon, and contacting of the substrate having retained catalytically effective metal thereon with a carbon source material to grow carbon nanotubes on the substrate. The manufacture can be carried out with a petroleum feedstock such as an oil refining atmospheric tower residue, to produce carbon nanotubes in high volume at low cost. Also disclosed is a composite including porous material having single-walled carbon nanotubes in pores thereof.

Claims

1-134. -134. (canceled)

135. A method of forming carbon nanotubes, selected from among the following methods (A), (B), (C) and (D):

(A) a method of forming carbon nanotubes, comprising;

depositing catalytically effective metal for carbon nanotube growth on a substrate to produce a catalytically effective metal-containing substrate; and

contacting the catalytically effective metal-containing substrate with a carbon source material that in contact with such substrate enables growth of carbon nanotubes thereon, for sufficient time and under sufficient conditions to grow carbon nanotubes on the substrate;

(B) a method of forming carbon nanotubes, comprising;

contacting a catalytically effective metal-containing feedstock with a substrate to deposit said feedstock on the substrate;

exposing the substrate having metal-containing feedstock thereon to elevated temperature effecting burnoff of carbon in the feedstock on the substrate and yielding a catalytic metal-containing substrate; and

contacting the catalytic metal-containing substrate with a nanotube-forming carbon source material under conditions producing carbon nanotubes on the substrate;

(C) a method of forming carbon nanotubes, comprising;

contacting a substrate with hydrocarbonaceous feedstock containing a catalytically effective metal to deposit said feedstock thereon;

oxidizing the feedstock deposited on the substrate to remove hydrocarbonaceous and carbonaceous components thereof from the substrate, but retaining the catalytically effective metal thereon; and

contacting the substrate having retained catalytically effective metal thereon with a carbon source material to grow carbon nanotubes on the substrate; and

(D) a method of forming carbon nanotubes, comprising;

providing a substrate including metal that is catalytically effective for carbon nanotube growth on the substrate;

contacting the catalytically effective metal-containing substrate with a carbon source material, for sufficient time and under sufficient conditions to grow carbon nanotubes on the substrate; and

recovering the carbon nanotubes from the substrate.

136. The method of claim 135(A), wherein the metal comprises nickel or iron, and the carbon source material comprises a hydrocarbon material.

137. The method of claim 135(A), wherein said catalytically effective metal comprises nickel, and is deposited on said substrate by contacting said substrate with a reduced crude oil containing nickel porphyrins therein.

138. The method of claim 135(A), wherein the carbon source material comprises a petroleum feedstock, a residual oil feedstock, or an oil refining atmospheric tower residue.

139. The method of claim 135(B), wherein contacting the catalytically effective metal-containing feedstock with the substrate is conducted at temperature in a range of from about 480 to about 750°

C., and at feedstock weight hourly space velocity, WHSV, in a range of from about 5 to about 20 kg feedstock/hr, with residence time of the feedstock in the contacting being in a range of from about 0.5 to about 144 seconds, and wherein said elevated temperature burnoff of carbon is conducted in a burnoff zone through which oxidant is flowed at flow rate in a range of from 1 to 10 standard cubic feet per minute (CFM) per kilogram of solid and wherein said oxidant has a residence time in said burnoff zone in a range of from 5 to 30 minutes.

140. The method of claim 135, further comprising manufacturing a product incorporating the carbon nanotubes.

141. The method of claim 135(C), wherein said carbon source material comprises a same material as said hydrocarbonaceous feedstock, or said same material having a lower amount of catalytically effective metal therein.

142. The method of claim 135 (D), wherein the substrate comprises spent fluid catalytic cracking catalyst, further comprising recycling the substrate for contacting with the carbon source material after recovering the carbon nanotubes from the substrate.

143. A method of forming a single-walled nanotube composite, selected from among the following methods (A), (B) and (C):

(A) a method of forming a single-walled nanotube composite, comprising impregnating a porous activated carbon with a catalyst precursor, reducing the catalyst precursor to form active catalyst in pores of the activated carbon, and catalytically growing single-walled carbon nanotubes in the pores of the activated carbon to form a single-walled nanotube/activated carbon composite;

(B) a method of forming a single-walled nanotube composite, comprising impregnating a porous substrate with a catalyst precursor, reducing the catalyst precursor to form active catalyst in pores of the substrate, and catalytically growing single-walled carbon nanotubes in the pores of the porous substrate; and

(C) a method of forming a single-walled nanotube composite including forming single-walled nanotubes in pores of a porous material, said method comprising;

(a) dissolving a metal catalyst precursor in a solvent to form a precursor solution;

(b) contacting the porous material with the precursor solution to introduce the precursor solution into the pores of the porous material;

(c) drying the porous material to remove solvent from the pores;

(d) reducing the metal catalyst in the pores of the porous material to an active metal catalyst form;

(e) contacting the porous material with a carbon source vapor at sufficient temperature and for sufficient time to catalytically form single walled nanotubes in the pores of the porous material.

144. The method of claim 143, further comprising treating the composite to open the carbon nanotubes therein.

145. The method of claim 143 (C), wherein the active catalyst comprises a metal selected from the group consisting of iron, nickel, cobalt, and molybdenum, and combinations including two or more of the foregoing.

146. A carbon nanotube product, selected from among the following carbon nanotube products (A), (B) and (C):

(A) a microsphere having an array of carbon nanotubes grown thereon;

(B) a composite comprising porous material having single-walled carbon nanotubes in pores thereof; and

(C) a fluid storage system, comprising a composite including a porous material having single-walled carbon nanotubes in pores thereof, and a dispenser adapted to discharge fluid from the composite under dispensing conditions effecting desorption of fluid from the composite.

147. The carbon nanotube product of claim 146(A), comprising a microsphere formed of carbon or kaolin.

148. The carbon nanotube product of claim 146(B), wherein the porous material comprises carbon.

149. The carbon nanotube product of claim 146(C), wherein said composite is of discontinuous form and defines a bed of the porous material comprising porous carbon having single-walled carbon nanotubes in pores of the porous carbon, said bed being disposed in a vessel, and said dispenser being coupled to said vessel.

150. The carbon nanotube product of claim 149, wherein said dispenser is coupled to flow circuitry joined to a fluid-utilizing apparatus, and said fluid-utilizing apparatus comprises an apparatus selected from the group consisting of combustion engines and fuel cells.

151. A method of reversibly storing fluid, comprising contacting said fluid with a composite comprising a porous material having single-walled carbon nanotubes in pores thereof, so that said fluid is taken up by said composite and is releasable from the composite under dispensing conditions involving desorption of the fluid therefrom.

152. The method of claim 151, comprising dispensing fluid from the composite under dispensing conditions therefor.

153. The method of claim 152, wherein said dispensing conditions comprise establishing a reduced pressure at a dispensing locus in relation to pressure at said composite to effect pressure-mediated dispensing of fluid from said composite.

154. An apparatus for manufacturing carbon nanotubes, comprising:

a first vessel adapted to contain a bed of particles therein;

a source of a feedstock containing catalytically effective metal for forming carbon nanotubes from a carbon source material therefor, joined in feed relationship with the first vessel for flow of the feedstock through the bed of particles in the first vessel to deposit the feedstock containing catalytically effective metal on the particles;

a source of oxidant arranged in feed relationship with the first vessel and adapted for flow of oxidant through the first bed of particles after termination of flow of feedstock therethrough, and burnoff of the feedstock to yield particles having catalytically effective metal thereon in said first vessel; and

a second vessel adapted to contain a bed of particles containing catalytically effective metal thereon, wherein said second vessel is coupled in fluid flow relationship with the first vessel and adapted to receive fluid from the first vessel comprising flow of feedstock to contact the bed of particles in the second vessel, for growth of carbon nanotubes thereon.