# US 4,397,964 A · Process using fluidized bed catalyst

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- Number: US 4,397,964 A
- Document ID: US4397964A
- Status: Granted
- Kind: A
- Application number: 06/322,679
- Filed: 1981-11-18
- Granted: 1983-08-09
- Earliest claimed: 1978-01-10
- Assignees: The International Nickel Company, Inc.
- Inventors: John K. Pargeter; Umar M. U. Ahmad
- Web page: https://patentgrep.com/patent/US4397964A

## CPC

- B01J 23/755: Nickel
- C07C 1/0435: {containing a metal of group 8 or a compound thereof}
- C07C 2523/755: Nickel
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

An unsupported particulate catalyst especially useful for methanation reactions is prepared by a method comprising fluid-bed roasting agglomerates of nickel sulfide to form a particulate precursor material which can be reduced to composite particles consisting essentially of a nickel-oxide core with a then coherent adherent layer of nickel thereon, the reduced particles being characterized at the surface by the presence of microcapillary pores interconnecting with each other and the outer surface of the particles.

## Claims

### Claim 1

In a catalytic process for converting carbon monoxide and hydrogen contained in a feed gas stream to methane, wherein said feed gas is contacted with a nickel-containing catalyst in a fluidized bed; the improvement comprising contacting said stream with an unsupported particulate catalyst composed of up to about 13% oxygen, less than about 1% sulfur and the balance greater than about 75% nickel, said particulate catalyst having a minimum of fines, said catalyst particles being a composite material consisting essentially of a nickel oxide core and a thin adherent, coherent layer of nickel on said core, the nickel oxide core having been formed as unsupported nickel oxide particles having a particle size of about 0.25 to about 1.2 mm. by a method comprising fluid-bed roasting agglomerates comprised of nickel sulfide in an oxidizing atmosphere, and the nickel layer having been developed under reducing conditions from the nickel oxide particles, said nickel layer being characterized by the presence of microcapillary pores interconnecting with each other and with the outer surface of the particles, said reduced catalyst being non-pyrophoric in the reduced state both before and after use, whereby the feed gas stream can be reacted in the fluidized bed with high throughput in the presence of an active, selective catalyst which is resistant to attrition in said fluidized bed, and whereby said reaction can be carried out without the use of stabilizing equipment for the catalyst.

### Claim 2 (depends on 1)

The process of claim 1, wherein the nickel layer of the catalyst has an average thickness of at least about 1/30th the particle diameter.

### Claim 3 (depends on 1)

The process of claim 1, wherein the catalyst contains up to about 1% cobalt, up to about 3.5% copper, up to about 1.5% iron, up to about 0.1% platinum group metals, and up to a total of about 2% alkali and/or alkaline earth metals.

### Claim 4 (depends on 1)

The process of claim 1, wherein the catalyst, apart from oxygen and sulfur, contains greater than 90% nickel.

### Claim 5

In a methanation process for converting carbon monoxide and hydrogen contained in a feed stream to methane, wherein said feed gas is contacted with a nickel-containing catalyst in a fluidized bed, the improvement comprising contacting said stream with a catalyst developed from an unsupported particulate precursor catalyst material, said precursor catalyst comprising nickel oxide and containing at least about 7% oxygen, less than about 1% sulfur, and the balance predominantly nickel and having a bulk density of less than about 4 g/cc, a particle size of about 0.25 to about 1.2 mm with a minimum of fines, said precursor catalyst material having been formed by fluid-bed roasting nickel sulfide in an oxidizing atmosphere and said precursor catalyst material on being subjected to reducing conditions being converted to a reduced catalyst material having at least a portion of the nickel oxide at least at the surface being reduced to a thin layer of nickel, said nickel being characterized by the presence of microcapillary pores interconnecting with each other and with the outer surface of the particles, and said reduced catalyst material having a nickel content of greater than about 75%, a superficial surface area of at least 0.4 m.sup.2 /g and a pore volume of at least about 0.001 ml/g, and said reduced catalyst being non-pyrophoric in the reduced state before and after use.

### Claim 6 (depends on 5)

The process of claim 5, wherein the sulfur content of the unsupported particulate precursor catalyst material is a small but effective amount to produce the desired microcapillary pore structure up to about 1%.

### Claim 7 (depends on 5)

The process of claim 5, wherein the oxygen content of the unsupported particulate precursor catalyst material is about 15% to about 26%.

### Claim 8 (depends on 7)

The process of claim 7, wherein the oxygen content of the precursor catalyst is above about 20%.

### Claim 9 (depends on 5)

The process of claim 5, wherein the nickel content of the precursor catalyst material is about 68% to about 93%, and sulfur is present.

### Claim 10 (depends on 9)

The process of claim 9, wherein the precursor catalyst material contains up to about 1% cobalt, up to about 3.5% copper, up to about 1.5% iron, up to 0.1% platinum group metal, and up to about 2% alkali and/or alkaline earth material.

### Claim 11 (depends on 5)

The process of claim 5, wherein the bulk density unsupported particulate precursor catalyst material is about 2.5 to about 3.6 g/cc.

### Claim 12 (depends on 5)

The process of claim 5, wherein the precursor catalyst material has a level of fines of less than about 1%.

### Claim 13

In a catalytic methanation process comprising reacting carbon monoxide and hydrogen in a fluidized bed reaction zone containing a nickel-containing catalyst material, the improvement comprising contacting said reactants in said fluidized bed with an unsupported catalyst containing greater than about 75% nickel and prepared by a method comprising fluid-bed roasting agglomerates comprised of nickel sulfide in an oxidizing atmosphere at a temperature of at least about 600.degree. C. up to about 1500.degree. C. to form a particulate precursor catalyst material comprising nickel oxide, said nickel oxide containing at least about 7% oxygen, and subjecting said precursor catalyst material to reducing conditions to convert at least a part of the nickel oxide at the surface of the particles to elemental nickel, said reduced catalyst being non-pyrophoric in the reduced state both before and after use, whereby said process can be carried out without the use of stabilizing equipment for the catalyst.

### Claim 14 (depends on 13)

A process according to claim 13, wherein the agglomerates are formed from a nickel-sulfide powder derived from a nickel matte containing at least about 7% sulfur.

### Claim 15 (depends on 14)

A process according to claim 14, wherein the nickel matte contains more than about 15% up to about 26% sulfur.

### Claim 16 (depends on 13)

A process according to claim 13, wherein the particulate precursor catalyst material formed by fluid-bed roasting contains at least 15% oxygen.

### Claim 17 (depends on 13)

A process according to claim 13, wherein the particulate precursor catalyst material comprising nickel oxide formed by fluid-bed roasting has a particle size of about 0.25 to about 1.2 mm with a minimum of fines.

### Claim 18 (depends on 15)

A process according to claim 15, wherein the level of fines is less than about 1%.

### Claim 19 (depends on 15)

A process according to claim 15, wherein the particle size of said reduced catalyst material is between about 0.25 mm and about 1.2 mm.

### Claim 20 (depends on 13)

A process according to claim 13, wherein the reduction is carried out at a temperature of about 200.degree. C. to about 500.degree. C.

### Claim 21 (depends on 13)

A process according to claim 13, wherein reduction is carried out in a fluidized bed.

### Claim 22 (depends on 16)

A process according to claim 16, wherein the precursor catalyst material is maintained at reducing conditions for a period of time sufficient to lower the oxygen content to about 13% and less.

### Claim 23 (depends on 13)

A process according to claims 13, wherein the particulate precursor catalyst material comprising nickel oxide is treated to obtain a reduced catalyst material by subjecting the precursor catalyst material to reducing conditions to convert at least a part of the nickel oxide at the surface of the particles to a thin layer of nickel, said reduced nickel layer being characterized by the presence of microcapillary pores interconnecting with each other and with the outer surface of the particles.

### Claim 24 (depends on 23)

A process according to claim 23, wherein said particulate precursor catalyst material comprising nickel oxide contains a small but effective amount of sulfur to obtain said pore structure in the reduced catalyst material up to about 1% sulfur.

### Claim 25 (depends on 13)

A process according to claim 13, wherein said particulate precursor catalyst material comprising nickel oxide contains about 0.02% up to about 0.5% sulfur.

### Claim 26 (depends on 13)

A process according to claim 13, wherein the reduced catalyst material has a sulfur content of less than about 0.2%.

### Claim 27 (depends on 13)

A process according to claim 13, wherein said particulate precursor catalyst material comprising nickel oxide contains a refractory oxide in a small but effective amount to minimize sintering of the reduced nickel on temperature excursions above the normal operating temperatures for the catalyst, said refractory oxide being introduced into the agglomerates comprising nickel sulfide prior to fluid-bed roasting of said agglomerates.

### Claim 28 (depends on 27)

A process according to claim 27, wherein the refractory oxide is present in an amount of up to about 25%.

### Claim 29 (depends on 27)

A process according to claim 27, wherein the refractory oxide is at least one oxide of the metals consisting of zirconium, calcium, magnesium, silicon, aluminum, thorium and chromium.

### Claim 30 (depends on 27)

A process according to claim 27, wherein the reduced catalyst material contains, in addition to nickel, at least one element or compound from the groups of the Periodic Table IA, IB, IIA, IIB, IVA, IVB, VB, VIB, VIII, and rare earth metals, and wherein the oxygen content is up to about 13% and the sulfur content is less than about 1%.

### Claim 31 (depends on 13)

A process according to claim 13, wherein the particulate precursor catalyst material contains about 68% to about 93% nickel, up to about 1% cobalt, up to about 1.5% iron, up to about 3.5% copper, up to about 2% alkali and/or alkaline earth metals, and up to about 0.1% platinum group metals, said particulate precursor catalyst material having an average particle size of about 0.25 to about 1.2 mm, and said particulate precursor catalyst material on being subjected to reducing conditions, equivalent to a period of about 1/2 to 2 hours at a temperature of about 315.degree. C. to about 425.degree. C., converting to a reduced catalyst material having an oxygen content of about 19% to about 2%, a sulfur content of less than about 0.2%, a surface area of at least about 0.4 m.sup.2 /g and a pore volume of at least about 0.001 ml/g.

### Claim 32 (depends on 23)

A process according to claim 23, wherein the thin layer of nickel is an adherent, coherent coating having an average thickness of about 1/30th the particle diameter.