# US 5,348,717 A · Synthesis gas from particulate catalysts, and admixtures of particulate catalysts and heat transfer solids

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- Number: US 5,348,717 A
- Document ID: US5348717A
- Status: Granted
- Kind: A
- Application number: 08/060,332
- Filed: 1993-05-11
- Granted: 1994-09-20
- Earliest claimed: 1993-05-11
- Assignees: Exxon Research & Engineering Co.
- Inventors: LeRoy R. Clavenna; Stephen M. Davis; Geoffrey R. Say; Rocco A. Fiato
- Web page: https://patentgrep.com/patent/US5348717A

## CPC

- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- C01B 3/40: characterised by the catalyst
- C01B 3/42: using moving solid particles, e.g. fluidised bed technique
- C01B 32/40: Carbon monoxide
- C01B 2203/1052: Nickel or cobalt catalysts
- C01B 2203/1064: Platinum group metal catalysts
- C01B 2203/1082: Composition of support materials
- Y02P 20/52: using catalysts, e.g. selective catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process utilizing a particulate catalyst, or particulate catalyst admixed with particulate heat transfer solids for conducting high temperature fluidized bed syn gas operations. Hydrogen and carbon monoxide are produced from a low molecular weight hydrocarbon by contact thereof, at high temperature in the presence of oxygen, or steam and oxygen, with a fluidized bed comprising said particulate solids. In one of its forms, barium hexaluminate is employed as a heat transfer solid, in concentrations ranging generally from about 10 wt. % to about 99.9 wt. %, in admixture with a particulate catalyst containing a metal, or metals, component catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons contacted with a fluidized bed of the catalyst at high temperature hydrothermal conditions. The catalyst, suitably one having a barium hexaluminate carrier component, is employed in concentration ranging generally from about 0.1 wt. % to about 90 wt. %. Such an admixture provides a particularly useful catalytic contact mass for conducting fluidized bed synthesis gas generation operations. This type of bed promotes continuous, highly efficient heat and mass transfer within the reacting gas phase. The presence of the catalyst having a barium hexaluminate carrier component, or barium hexaluminate heat transfer solid as a bed component maintains excellent bed fluidization characteristics, suppressing the normal tendency of the catalyst to sinter or agglomerate; tendencies which promote defluidization of the bed. Moreover, the heat transfer particles of the bed are highly attrition resistant, and are chemically compatible with the catalyst particles of the admixture.

## Claims

### Claim 1

In a process for the production of hydrogen and carbon monoxide from a low molecular weight hydrocarbon by contact with a fluidized bed of catalyst at elevated temperature in the presence of oxygen, or both steam and oxygen, the improvement wherein the fluidized bed is comprised of
an admixture of
a particulate consisting essentially of non-leachable barium hexaluminate solids of fluidizable particle diameter in concentration ranging from about 10 percent to about 99.9 percent, based on the weight of the admixture, and
a catalyst comprised of a carrier component composited with a metal, or metals, component catalytic for the production of hydrogen and carbon monoxide from low molecular weight hydrocarbons when contacted with a fluidized bed of the catalyst, in concentration ranging from about 0.1 percent to about 90 percent, based on the weight of the admixture.

### Claim 2 (depends on 1)

The process of claim 1 wherein the average particle diameter of both the barium hexaluminate and catalyst particles of the admixture ranges from about 30 microns to about 150 microns.

### Claim 3 (depends on 2)

The process of claim 2 wherein the average particle diameter of both the barium hexaluminate and catalyst particles of the admixture ranges from about 60 microns to about 90 microns.

### Claim 4 (depends on 1)

The process of claim 1 wherein the concentration of the barium hexaluminate component of the admixture ranges from about 80 percent to about 99.5 percent, and the catalyst component ranges from about 0.5 percent to about 20 percent.

### Claim 5 (depends on 1)

The process of claim 1 wherein the metal, or metals, component of the catalyst is comprised of nickel, platinum, or ruthenium.

### Claim 6 (depends on 5)

The process of claim 5 wherein the metal component of the catalyst is nickel, and the nickel is composited with the carrier component in concentration ranging from about 1 percent to about 20 percent, based on the weight of the catalyst.

### Claim 7 (depends on 6)

The process of claim 6 wherein the nickel component is composited with the carrier in concentration ranging from about 5 percent to about 10 percent.

### Claim 8 (depends on 1)

The process of claim 1 wherein the catalyst component of the admixture is barium hexaluminate composited with nickel, and the barium hexaluminate is one having an Al.sub.2 O.sub.3 :BaO mole ratio of 100:(1-16).

### Claim 9 (depends on 8)

The process of claim 8 wherein the nickel-on-barium hexaluminate catalyst contains from about 1 percent to about 20 percent nickel, based on the weight of the catalyst.

### Claim 10 (depends on 9)

The process of claim 9 wherein the catalyst contains from about 5 percent to about 10 percent nickel.

### Claim 11 (depends on 1)

The process of claim 1 wherein the average particle diameter of the barium hexaluminate component of the admixture ranges from about 60 microns to about 90 microns, and the barium hexaluminate component ranges in concentration from about 80 percent to about 99.5 percent within the admixture; and the catalyst component of the admixture is nickel-on-barium hexaluminate containing from about 5 percent to about 10 percent nickel, and the catalyst is present within the admixture in concentration ranging from about 0.5 percent to about 20 percent.

### Claim 12 (depends on 1)

The process of claim 1 wherein the barium hexaluminate solids of the admixture are precalcined at temperatures ranging from about 1200.degree. C. to about 1700.degree. C.