Method for forming carbon fibers

Claim 2

In a process for preparing carbon fibers in a gaseous phase reaction in a reactor, the improvement comprising: a) forming a mixture consisting essentially of a gaseous hydrocarbon, ammonia, hydrogen sulfide, and an iron-containing compound decomposable to form iron nucleation sites, the hydrocarbon being selected from the group consisting of methane, high methane natural gas having a methane content of at least 90 volume percent, and mixtures thereof; the hydrocarbon and the ammonia each being present in an amount sufficient to provide a ratio of carbon atoms (C) to nitrogen atoms (N) in a range of about 1:1 to about 3:1; b) heating the mixture in the reactor for a time and at a temperature sufficient to cause decomposition of the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers and to thereby form carbon fibers having an average diameter of about 0.05 to about 0.5 micron and containing carbon and nitrogen; and c) substantially continuously recovering the carbon fibers.

Claim 3

The process according to claim 1, wherein the decomposable compound consists essentially of iron pentacarbonyl dispersed in a carrier.

Claim 4

The process according to claim 1, wherein the hydrogen sulfide is present in an amount at least as great as the amount of the iron in the decomposable compound.

Claim 5

The process according to claim 2, wherein the the carrier gas is helium.

Claim 6

The process according to claim 1, wherein the temperature of step (b) is at least about 1050° C.

Claim 7

A process of continuously forming carbon fibers in a reactor by the steps consisting of: a) forming a mixture consisting essentially of a gaseous hydrocarbon, a compound decomposable to form iron nucleation sites, a gaseous sulfur-containing compound and ammonia, and flowing the mixture through the reactor at a first pressure; the hydrocarbon being selected from the group consisting of methane, natural gas having a methane content of at least 90 volume percent, and mixtures thereof, the hydrocarbon and the ammonia each being present in an amount sufficient to provide a ratio of carbon atoms (C) to nitrogen atoms (N) in a range of about 1:1 to about 3:1; b) heating the mixture in the reactor for a time and at a temperature sufficient to cause decomposition of the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers and to thereby form carbon fibers having an average diameter of about 0.05 to about 0.5 micron and containing carbon and nitrogen; and c) intermittently interrupting the flow of the mixture of step (a) and, during the interruption, flowing an inert gas selected from the group consisting of helium, argon, and nitrogen through the reactor at a pressure sufficient to forcibly move at least a portion of any of the fibers plugging the reactor out of the reactor, and then flowing an oxygen-containing gas through the reactor for a time and at a temperature sufficient to oxidize at least a portion of any unreacted or partially reacted material in the reactor; and d) recovering the fibers formed in the reactor.

Claim 8

A process of continuously forming carbon fibers in a reactor by the steps consisting of: a) forming a mixture consisting essentially of a gaseous hydrocarbon, a compound decomposable to form iron nucleation sites, a gaseous sulfur-containing compound and ammonia, and flowing the mixture through the reactor at a first pressure; the hydrocarbon being selected from the group consisting of methane, natural gas having a methane content of at least 90 volume percent, and mixtures thereof, the hydrocarbon and the ammonia each being present in an amount sufficient to provide a ratio of carbon atoms (C) to nitrogen atoms (N) in a range of about 1:1 to about 3:1; b) heating the mixture in the reactor for a time and at a temperature sufficient to cause decomposition of the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers and to thereby form carbon fibers having an average diameter of about 0.05 to about 0.5 micron and containing carbon and nitrogen; and c) intermittently interrupting the flow of the mixture of step (a) and, during the interruption, flowing an inert gas selected from the group consisting of helium, argon, and nitrogen through the reactor at a pressure sufficient to forcibly move at least a portion of any of the fibers plugging the reactor out of the reactor, and then flowing an oxygen-containing gas through the reactor for a time and at a temperature sufficient to oxidize at least a portion of any unreacted or partially reacted material in the reactor; and d) recovering the fibers formed in the reactor.

Claim 9

The process according to claim 6, wherein the mixture of step (a) comprises: the decomposable compound consisting essentially of iron pentacarbonyl dispersed in a carrier; and the gaseous sulfur-containing compound consisting essentially of hydrogen sulfide in an amount at least as great as the amount of iron in the iron pentacarbonyl.

Claim 10

The process according to claim 7, wherein the carrier gas is helium.

Claim 11

The process according to claim 6, wherein the inert gas is nitrogen.

Claim 12

The process according to claim 6, wherein the temperature of step (b) is at least about 1050° C.

Claim 13

A process of continuously forming carbon fibers in a reactor by the steps consisting of: a) forming a mixture consisting essentially of a gaseous hydrocarbon, a compound decomposable to form iron nucleation sites, a gaseous sulfur-containing compound and ammonia, and flowing the mixture through the reactor at a first velocity; the hydrocarbon being selected from the group consisting of methane, natural gas having a methane content of at least 90 volume percent, and mixtures thereof, the hydrocarbon and the ammonia each being present in an amount sufficient to provide a ratio of carbon atoms (C) to nitrogen atoms (N) in a range of about 1:1 to about 3:1; b) heating the mixture in the reactor for a time and at a temperature sufficient to decompose the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers and to thereby form carbon fibers having an average diameter of about 0.05 to about 0.5 micron and containing carbon and nitrogen; c) changing the velocity of the flowing mixture with the particles entrained therein to a second velocity less than the first velocity to enhance fiber growth on the particles; d) intermittently interrupting the flow of the mixture of step (a) and, during the interruption, injecting one or more pulses of air through the reactor at a pressure sufficient to forcibly move at least a portion of any of the fibers plugging the reactor out of the reactor, and for a time at a temperature sufficient to oxidize at least a portion of any unreacted or partially reacted material in the reactor; and e) recovering the fibers formed in the reactor.

Claim 14

A process of continuously forming carbon fibers in a reactor by the steps consisting of: a) forming a mixture consisting essentially of a gaseous hydrocarbon, a compound decomposable to form iron nucleation sites, a gaseous sulfur-containing compound and ammonia, and flowing the mixture through the reactor at a first velocity; the hydrocarbon being selected from the group consisting of methane, natural gas having a methane content of at least 90 volume percent, and mixtures thereof, the hydrocarbon and the ammonia each being present in an amount sufficient to provide a ratio of carbon atoms (C) to nitrogen atoms (N) in a range of about 1:1 to about 3:1; b) heating the mixture in the reactor for a time and at a temperature sufficient to decompose the decomposable compound to form particles of nanometer size iron nucleation sites dispersed and entrained in the gaseous mixture which induce growth of carbon fibers and to thereby form carbon fibers having an average diameter of about 0.05 to about 0.5 micron and containing carbon and nitrogen; c) changing the velocity of the flowing mixture with the particles entrained therein to a second velocity less than the first velocity to enhance fiber growth on the particles; d) intermittently interrupting the flow of the mixture of step (a) and, during the interruption, injecting one or more pulses of air through the reactor at a pressure sufficient to forcibly move at least a portion of any of the fibers plugging the reactor out of the reactor, and for a time at a temperature sufficient to oxidize at least a portion of any unreacted or partially reacted material in the reactor; and e) recovering the fibers formed in the reactor.

Claim 15

The process according to claim 11, wherein the mixture of step (a) comprises: the decomposable compound consisting essentially of iron pentacarbonyl dispersed in a carrier; and the gaseous sulfur-containing compound consisting essentially of hydrogen sulfide in an amount at least as great as the amount of iron in the iron pentacarbonyl.

Claim 16

The process according to claim 12, wherein the carrier gas is helium.

Claim 17

The process according to claim 11, wherein the temperature of step (b) is at least about 1050° C.