Fischer-Tropsch Reactor Start-Up Catalyst Deactivation

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Solution Overview

Problem

The activity of Fischer-Tropsch catalysts decreases over time, especially during the start-up phase of a reactor, due to high relative humidity caused by initial high catalyst activity, leading to rapid and irreversible deactivation.

Innovation Solution

Supplying a feed gas stream containing a nitrogen-containing compound, such as ammonia, to the catalyst during the initial stages of reactor operation to decrease catalyst activity and maintain lower relative humidity, thereby slowing down deactivation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If a fresh catalyst with high initial activity is used, then productivity is improved, but the catalyst deactivates rapidly due to high relative humidity during start-up

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent applies preliminary action by introducing a nitrogen-containing compound into the synthesis gas feed stream before the Fischer-Tropsch reaction begins. This pre-treatment step modifies the catalyst surface in advance to reduce its initial activity, preventing the formation of excessive water vapor during start-up. The nitrogen compound adsorbs on active sites, creating a protective effect that stabilizes the catalyst during the critical initial operation phase when high relative humidity would otherwise cause rapid deactivation.

Inventive Principle:
Principle #10Preliminary action

2Reliability

If the reaction temperature is kept low during start-up to avoid high product yield, then catalyst deactivation is reduced, but productivity decreases

Engineering Contradiction:
Improvecatalyst stabilityVSAvoidproduct yield
Core Design Contradiction:
ReliabilityVSProductivity

Solution Approach 1:

The patent applies parameter changes by modifying the chemical composition of the feed stream rather than adjusting temperature parameters. By adding a nitrogen-containing compound to the synthesis gas, the catalyst's effective activity is reduced through chemical modification of the reaction environment. This allows the reaction temperature to be increased during start-up to maintain productivity, while the nitrogen compound continues to suppress water vapor formation and protect the catalyst from deactivation, thus decoupling the temperature-yield-stability relationship.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This method allows for a higher reaction temperature during start-up, maintaining catalyst stability and productivity over a longer period, with the added benefit of improved heat recovery and reduced need for frequent catalyst regeneration.

Implementation Method 1

the activity of the catalyst is decreased by supplying a feed gas stream comprising a nitrogen-containing compound other than molecular nitrogen

Methodology Applied
Scientific EffectAdsorption: Adsorption

Implementation Method 2

converting carbon monoxide and hydrogen supplied with the gaseous feed stream to the reactor into hydrocarbons

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

a lot of water is produced in the Fischer-Tropsch hydrocarbon synthesis, resulting in a high relative humidity at the start of the Fischer-Tropsch process

Methodology Applied
Scientific EffectExothermic reaction: Exothermic Reaction

Data Source

PatentEP3119856B1A method for start-up and operation of a fischer-tropsch reactor
Publication Date: 2025.01.22 SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ BV
  • EP3119856B1 patent drawingFigure 1
  • EP3119856B1 patent drawingFigure 2

AI summary

The invention relates to a method for start-up and operation of a Fischer-Tropsch reactor comprising the steps of: (a) providing a reactor with a fixed bed of reduced Fischer-Tropsch catalyst that comprises cobalt as catalytically active metal; (b) supplying a gaseous feed stream comprising carbon monoxide and hydrogen to the reactor, wherein the gaseous feed stream initially comprises a nitrogen-containing compound other than molecular nitrogen in an initial concentration in the range of from 0.1 to 50 ppmv based on the volume of the gaseous feed stream; (c) converting carbon monoxide and hydrogen supplied with the gaseous feed stream to the reactor into hydrocarbons at an initial reaction temperature, wherein the initial reaction temperature is set at a value of at least 200 °C and hydrocarbons are produced at a first yield; (d) maintaining the initial reaction temperature at the set value and maintaining the first yield by decreasing the concentration of the nitrogen-containing compound in the gaseous feed stream supplied to the reactor; (e) optionally increasing the reaction temperature after the concentration of the nitrogen-containing compound in the gaseous feed stream has decreased to a value below 100 ppbv.