Two-Stage Reforming Process for High Sulfur Fuel Conversion

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Solution Overview

Problem

Current methods for reforming high sulfur-containing liquid fuels are inefficient and complex, leading to lower catalyst performance, increased coke precursor formation, and reduced fuel cell stack reliability, making them unsuitable for field operations and fuel cell applications.

Innovation Solution

A two-stage reforming process involving a catalytic partial oxidation (CPOX) stage followed by an autothermal reforming (ATR) stage, where high molecular weight organosulfur compounds are converted to low molecular weight sulfur compounds, and the reformate is further processed with steam and optional oxidants to produce a sulfur-free gaseous reformate, reducing coke precursor formation and enhancing catalyst longevity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Device complexity

If conventional single-stage reforming is used with high sulfur-containing fuels, then the process is simpler, but catalyst performance deteriorates and coke precursor formation increases

Engineering Contradiction:
Improvereforming process complexityVSAvoidcatalyst performance and endurance
Core Design Contradiction:
Device complexityVSReliability

Solution Approach 1:

The reforming process is divided into two distinct stages: a first reforming stage that handles high sulfur-containing fuels with a sulfur-tolerant catalyst, and a second reforming stage that processes the intermediate reformate with a high-performance catalyst. This segmentation allows each stage to be optimized for its specific function, resolving the contradiction between process simplicity and catalyst performance.

Inventive Principle:
Principle #1Segmentation

2Productivity

If reforming temperature is elevated to compensate for reduced catalytic activity, then fuel conversion improves, but catalyst degradation accelerates

Engineering Contradiction:
Improvefuel conversion efficiencyVSAvoidcatalyst longevity
Core Design Contradiction:
ProductivityVSDuration of action of stationary object

Solution Approach 1:

The two-stage reforming process segments the thermal and catalytic loads. The first stage operates at elevated temperatures with sulfur-tolerant catalysts to ensure complete fuel conversion despite sulfur presence. The second stage operates at lower temperatures with high-performance catalysts to produce clean reformate without excessive catalyst degradation, thus resolving the contradiction between productivity and catalyst longevity.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The intermediate reformate stream from the first stage acts as a mediator that has already undergone partial conversion and sulfur tolerance testing. This intermediate product allows the second stage catalyst to operate under milder conditions, protecting it from both sulfur poisoning and thermal degradation while maintaining high overall conversion efficiency.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Device complexity

If high molecular weight organosulfur compounds are directly reformed, then the process is simpler, but catalyst performance deteriorates and sulfur tolerance decreases

Engineering Contradiction:
Improvereforming process structureVSAvoidsulfur tolerance
Core Design Contradiction:
Device complexityVSAdaptability or versatility

Solution Approach 1:

The reforming process is segmented into two stages where the first stage specifically addresses high molecular weight organosulfur compounds using a sulfur-tolerant catalyst. This segmentation allows the system to maintain simplicity while achieving high sulfur tolerance by dedicating the first stage to handling the most challenging sulfur-containing compounds.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The first reforming stage operates under specific parameters (elevated temperature, controlled residence time) that are optimized for breaking down high molecular weight organosulfur compounds. These parameter changes enable the catalyst to effectively process refractory sulfur compounds without rapid deactivation, improving sulfur tolerance while maintaining process structural simplicity.

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 process achieves complete fuel conversion, low coke precursor formation, and improved sulfur tolerance, allowing for efficient and long-lasting operation with high sulfur-containing fuels, reducing system complexity and cost, and producing a sulfur-free reformate suitable for fuel cell use.

Implementation Method 1

contacting therein said fuel with a first oxidant in the presence of a partial oxidation catalyst under partial oxidation reaction conditions sufficient to produce a first reformate stream comprising a mixture of unconverted hydrocarbons, partially-converted hydrocarbons, and one or more low molecular weight sulfur compounds

Methodology Applied
Scientific EffectCatalytic partial oxidation: Oxidation

Implementation Method 2

contacting therein said first reformate stream with steam and optionally a second oxidant in the presence of an autothermal reforming catalyst under autothermal reforming reaction conditions sufficient to obtain a second reformate stream comprising carbon monoxide, hydrogen

Methodology Applied
Scientific EffectAutothermal reforming: Combustion

Data Source

PatentEP2624937B1Process for reforming a high sulfur-containing liquid fuel
Publication Date: 2018.12.19 PRECISION COMBUSTION INC
  • EP2624937B1 patent drawingFigure 1
  • EP2624937B1 patent drawingFigure 2
  • EP2624937B1 patent drawingFigure 3

AI summary

A reforming process and apparatus exhibiting improved catalyst longevity towards reforming a high sulfur-containing liquid fuel. The process involves contacting in a first reforming zone a first oxidant and a liquid fuel containing high molecular weight organosulfur compounds with a partial oxidation catalyst under CPOX reaction conditions to form a first reformate stream containing a mixture of unconverted and partially-converted hydrocarbons and one or more low molecular weight sulfur compounds; and then contacting in a second reforming zone the first reformate stream with steam and optionally a second oxidant in the presence of an autothermal reforming catalyst under ATR reaction conditions to form a second reformate stream containing carbon monoxide and hydrogen and one or more low molecular weight sulfur compounds. The low molecular weight sulfur compounds can be readily removed from the first and/or second reformate streams by gas phase adsorption methods.