# US 6,284,807 B1 · Slurry hydrocarbon synthesis process with increased catalyst life

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- Number: US 6,284,807 B1
- Document ID: US6284807B1
- Status: Granted
- Kind: B1
- Application number: 09/134,304
- Filed: 1998-08-14
- Granted: 2001-09-04
- Earliest claimed: 1995-08-05
- Assignees: Exxon Research & Engineering Co.
- Inventors: Stephen C. Leviness; Charles J. Mart; William C. Behrmann; Stephen J. Hsia; Daniel R. Neskora
- Web page: https://patentgrep.com/patent/US6284807B1

## CPC

- C10K 1/34: by catalytic conversion of impurities to more readily removable materials
- B01D 53/14: by absorption
- B01D 53/8621: {Removing nitrogen compounds}
- C01B 3/52: by contacting with liquids; Regeneration of used liquids
- C01B 3/56: by contacting with solids; Regeneration of used solids
- C01B 3/58: including a catalytic reaction
- C10G 2/30: {from carbon monoxide with hydrogen}
- B01D 2255/20707: Titanium
- B01D 2257/406: Ammonia
- B01D 2257/408: Cyanides, e.g. hydrogen cyanide (HCH)
- C01B 2203/0415: Purification by absorption in liquids
- C01B 2203/0435: Catalytic purification
- C01B 2203/0465: Composition of the impurity
- C10K: PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES

## Abstract

A slurry catalytic hydrocarbon synthesis process which employs a catalyst comprising a supported cobalt component achieves a short term catalyst half life of more than 10 days, by using a syngas feed which contains less than fifty parts per billion of a combined total amount of HCN and NH3.

## Claims

### Claim 1

A slurry hydrocarbon synthesis process, with reduced rejuvenation hydrogen consumption, for making hydrocarbons from a synthesis gas comprising a mixture of H2 and CO which also contains HCN, NH3 or mixture thereof, said process comprising passing said synthesis gas into a slurry hydrocarbon synthesis reactor and reacting said H2 and CO in the presence of a hydrocarbon synthesis catalyst in a slurry comprising said catalyst and gas bubbles in a hydrocarbon slurry liquid, under reaction conditions effective to form hydrocarbons from said H2 and CO, at least a portion of which are liquid at said reaction conditions and comprise said slurry liquid, wherein said HCN, NH3 or mixture thereof reversibly deactivates said catalyst and causes it to lose a portion of its catalytic activity, and wherein at least a portion of said lost catalytic activity is restored by contact with hydrogen in-situ in said slurry liquid, said catalyst comprising a catalytically active metal component and a particulate inorganic refractory oxide support component, and wherein the total amount of said HCN, NH3 or mixture thereof present in said synthesis gas passed into said reactor is less than 20 vppb, to achieve a reversibly deactivated short term catalyst half life of at least 20 days.

### Claim 2 (depends on 1)

A process according to claim 1 wherein said catalyst exhibits a productivity of at least 150 hr−1.

### Claim 3 (depends on 2)

A process according to claim 2 wherein said synthesized hydrocarbons which are liquid at the synthesis reaction temperature and pressure comprise primarily C5+ paraffinic hydrocarbons.

### Claim 4 (depends on 3)

A process according to claim 3 wherein said catalyst exhibits less than 10 mole % methane selectivity.

### Claim 5 (depends on 4)

A process according to claim 4 wherein said catalytically active metal component comprises cobalt.

### Claim 6 (depends on 5)

A process according to claim 5 wherein said support component comprises titania.

### Claim 7 (depends on 6)

A process according to claim 6 wherein said total amount of said HCN, NH3 or mixture thereof present in said synthesis gas fed into said reactor is less than 10 vppb, to achieve a catalyst short term half life greater than 40 days.

### Claim 8 (depends on 7)

A process according to claim 7 wherein said catalyst productivity is at least 500 hr−1.

### Claim 9

A method for increasing the productivity of a hydrocarbon synthesis reactor producing hydrocarbons from a synthesis feed gas comprising a mixture of H2 and CO, by passing said feed gas into said reactor, in which said H2 and CO react in the presence of a hydrocarbon synthesis catalyst therein at reaction conditions effective to produce hydrocarbons, a portion of which are liquid at the reaction conditions, wherein said feed gas contains NH3, HCN or mixture thereof in a total amount of greater than 20 vppb which reversibly deactivates said catalyst to produce a catalyst short term half life of less than 20 days, and wherein said catalytic activity is at least partially restored by continuously or intermittently rejuvenating said reversibly deactivated catalyst with hydrogen, said method comprising producing a synthesis gas having a total amount of said NH3, HCN or mixture thereof of less than 20 vppb, before it is passed into said reactor, to achieve a catalyst short term half life of at least 20 days, and thereby increase said reactor productivity.

### Claim 10 (depends on 9)

A process according to claim 9 wherein said catalyst exhibits a productivity of at least 150 hr−1.

### Claim 11 (depends on 10)

A process according to claim 10 wherein said synthesized hydrocarbons which are liquid at the synthesis reaction temperature and pressure comprise primarily C5+ paraffinic hydrocarbons.

### Claim 12 (depends on 11)

A process according to claim 11 wherein said catalyst exhibits less than 10 mole % methane selectivity.

### Claim 13 (depends on 12)

A process according to claim 12 wherein said catalyst comprises a catalytically active cobalt metal component.

### Claim 14 (depends on 13)

A process according to claim 13 wherein said catalyst includes a titania support component.

### Claim 15 (depends on 14)

A process according to claim 14 wherein said total amount of said HCN, NH3 or mixture thereof present in said synthesis gas fed into said reactor is less than 10 vppb, to achieve a catalyst short term half life greater than 40 days.

### Claim 16 (depends on 15)

A process according to claim 15 wherein said catalyst productivity is at least 500 hr−1.