# US 2021/0340447 A1 · Process for preparing liquid hydrocarbons by the fischer-tropsch process integrated into refineries

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- Number: US 2021/0340447 A1
- Document ID: US20210340447A1
- Status: Published application
- Kind: A1
- Application number: 17/274,647
- Filed: 2019-09-11
- Published: 2021-11-04
- Earliest claimed: 2018-09-11
- Assignees: Petroleo Brasileiro S.A. - Petrobras
- Applicants: Petroleo Brasileiro S.A. - Petrobras
- Inventors: Roberto Carlos PONTES BITTENCOURT
- Web page: https://patentgrep.com/patent/US20210340447A1

## CPC

- C10G 2/332: {of the iron-group}
- B01J 12/00: Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor (B01J3/08, B01J8/00, B01J19/08 take precedence)
- B01J 16/00: Chemical processes in general for reacting liquids with non- particulate solids, e.g. sheet material; Apparatus specially adapted therefor (B01J19/08 takes precedence)
- B01J 21/04: Alumina
- B01J 21/06: Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J 21/08: Silica
- B01J 23/02: of the alkali- or alkaline earth metals or beryllium
- B01J 23/42: Platinum
- B01J 23/46: Ruthenium, rhodium, osmium or iridium
- B01J 23/75: Cobalt
- C01B 3/38: using catalysts
- C01B 3/48: followed by reaction of water vapour with carbon monoxide
- C01B 3/56: by contacting with solids; Regeneration of used solids
- C01B 32/50: Carbon dioxide
- C10G 2/00: Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G 2/333: {of the platinum-group}
- C10G 2/50: {from carbon dioxide with hydrogen}
- C10L 1/02: essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L 1/08: for compression ignition
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
- C01B 2203/062: Hydrocarbon production, e.g. Fischer-Tropsch process
- C01B 2203/0827: at least part of the fuel being a recycle stream
- C01B 2203/1058: Nickel catalysts
- C01B 2203/1241: Natural gas or methane
- C01B 2203/148: involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
- C10G 2300/4006: Temperature
- C10G 2300/4056: Retrofitting operations
- C10G 2300/4081: Recycling aspects
- C10G 2300/42: Hydrogen of special source or of special composition
- C10G 2300/70: Catalyst aspects
- C10G 2400/02: Gasoline
- C10G 2400/04: Diesel oil
- C10G 2400/10: Lubricating oil
- Y02P 20/52: using catalysts, e.g. selective catalysts
- 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
- 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}
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention relates to a process for preparing liquid hydrocarbons by the Fischer-Tropsch process integrated into refineries, in particular comprising recycling streams from the steam reforming hydrogen production process as the feedstock for the Fischer-Tropsch process.

## Claims

### Claim 1

A process for preparing liquid hydrocarbons by the Fischer-Tropsch process integrated into refining units, wherein it comprises recycling the gaseous stream from the steam-reforming hydrogen generation process as feedstock in the Fischer-Tropsch process, in which the carbon dioxide content is at least 20% and the hydrogen content is lower than 50% v/v.

### Claim 2 (depends on 1)

The process of claim 1, wherein the gaseous stream from the steam-reforming hydrogen generation process is from the PSA section.

### Claim 3 (depends on 1)

The process of claim 1, wherein the gaseous stream from the steam-reforming hydrogen generation process is a purge gas stream comprising 25 to 35% hydrogen, 35 to 55% carbon dioxide, 10 to 30% methane, and 8 to 15% carbon monoxide.

### Claim 4 (depends on 3)

The process of claim 3, wherein the Hz:CO ratio is of about 1.2 and about 5.5 mol/mol.

### Claim 5 (depends on 1)

The process of claim 1, wherein the Fischer-Tropsch process comprises:
compression of the feedstock, coming from the steam-reforming hydrogen generation process, with pressure lower than about 0.5 kgf/cm2 (0.049 MPa) to about 4 to 40 kgf/cm2 (0.39 MPA to 3.92 MPa),
feeding said compressed feedstock into a Fischer-Tropsch reactor and contact with a catalyst, and
optionally, separation of the liquid products obtained in an oleaginous stream, comprising liquid hydrocarbons, and an aqueous stream.

### Claim 6 (depends on 3)

The process of claim 3, wherein part of the uncompressed purge gas stream is sent to comprise the reformer fuel.

### Claim 7 (depends on 1)

The process of claim 1, wherein the unconverted residual gaseous fraction containing light hydrocarbons returns to the hydrogen generation process with the fuel from the reformer, or optionally, it is sent to a light olefins recovery section.

### Claim 8 (depends on 5)

The process of claim 5, wherein the catalyst used in the Fischer-Tropsch reaction is selected from cobalt compounds based on alumina, titanium, aluminates, silica, zirconia, or mixtures thereof.

### Claim 9 (depends on 8)

The process of claim 8, wherein said catalyst additionally contains noble metals selected from Pt, Re or Ru as promoters.

### Claim 10 (depends on 5)

The process of claim 5, wherein the catalyst used in the Fischer-Tropsch reaction is selected from amongst iron compounds containing, optionally, the promoters of silica, copper, noble metals and alkaline metals selected from amongst potassium oxide, copper oxides, silica, zinc oxide, or a combination thereof.

### Claim 11 (depends on 5)

The process of claim 5, wherein the Fischer-Tropsch reactor is selected from slurry, fluidized, fixed-bed, or moveable bed-type reactors.

### Claim 12 (depends on 1)

The process of claim 1, wherein the Fischer-Tropsch reaction temperature is between about 180° C. and 300° C., and pressures between about 4 and 30 kgf/cm2 (0.39 and 2.94 MPa).

### Claim 13 (depends on 1)

The process of claim 1, wherein the Fischer-Tropsch reaction temperature is between about 250° C. and 400° C.

### Claim 14 (depends on 1)

The process of claim 1, wherein the liquid hydrocarbons are gasoline, diesel, or lubricants.

### Claim 15 (depends on 1)

The process of claim 1, wherein the gaseous stream from the steam-reforming hydrogen generation process is from already-existing refining units.

### Claim 16 (depends on 1)

The process of claim 1, wherein the oleaginous stream containing liquid hydrocarbons obtained in the Fischer-Tropsch process are recycled into the existing refinery sections.

### Claim 17 (depends on 5)

The process of claim 5, wherein the aqueous stream generated in the Fischer-Tropsch process is recycled to an existing acid water unit of the refinery.

### Claim 18 (depends on 11)

The process of claim 11, wherein the Fischer-Tropsch reactor is a mili or micro-channel type compact reactor.

### Claim 19 (depends on 12)

The process of claim 12, wherein the Fischer-Tropsch reaction temperature is between about 190° C. and 250° C.

### Claim 20 (depends on 16)

The process of claim 16, wherein the oleaginous stream containing liquid hydrocarbons obtained in the Fischer-Tropsch process are recycled into distillation, hydrotreatment and effluent treatment sections.