Electrochemical Hydrodesulfurization via NEMCA Catalyst Promotion

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Solution Overview

Problem

Current catalytic hydrodesulfurization processes face challenges such as unintended hydrogenation of olefins, leading to decreased octane ratings and the formation of hydrogen sulfide, which limits sulfur removal efficiency, and struggle with achieving high metal loading and dispersion on catalyst supports like alumina, resulting in suboptimal desulfurization performance.

Innovation Solution

An electrochemical catalytic method using a MoCo-TiO2 catalyst with Non-Faradic Electrochemical Modification of Chemical Activity (NEMCA) in an electrochemical cell with a charge conducting solid electrolyte support, applying electrical potential to enhance reaction rates and selectivity, allowing for in situ control of catalyst activity and precise promoter dosing.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If conventional catalytic hydrodesulfurization is performed at elevated temperature and pressure, then sulfur removal is achieved, but olefin hydrogenation occurs leading to decreased octane rating

Engineering Contradiction:
Improvesulfur removal efficiencyVSAvoidoctane rating loss
Core Design Contradiction:
Quantity of substanceVSObject-generated harmful factors

Solution Approach 1:

The invention changes the operating parameters by applying electrochemical potential to the catalyst surface, modifying the electronic state of catalytic sites to achieve selective sulfur removal without olefin hydrogenation. The electrochemical promotion alters the catalyst's electronic properties, enabling differentiation between sulfur-containing compounds and olefins at milder conditions.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention replaces the traditional thermal-mechanical approach (elevated temperature and pressure) with an electrochemical approach. Instead of relying solely on thermal energy to drive the reaction, electrical potential is applied to the catalyst surface to promote selective hydrodesulfurization, substituting thermal mechanics with electrochemical control.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

2Productivity

If high metal loading is attempted on alumina support, then catalytic activity should increase, but metal dispersion becomes difficult due to strong polarity and limited surface area

Engineering Contradiction:
Improvecatalytic activityVSAvoidmetal dispersion
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The invention uses composite material structures by combining electrochemically active catalyst layers with conductive supports. The catalyst system is designed as a composite where metal species are dispersed on conductive oxides or carbon materials that provide both high surface area and electrochemical activity, rather than using traditional alumina alone.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention employs porous conductive materials as catalyst supports, such as porous carbon or conductive metal oxides with high surface area. These porous structures provide extensive surface area for metal dispersion while maintaining electrical conductivity necessary for electrochemical promotion, solving the dispersion limitation of dense alumina.

Inventive Principle:
Principle #31Porous materials

3Quantity of substance

If basic nitrogen compounds are present in feedstock, then they bind to acidic alumina sites, but this limits available surface sites for sulfur compound desulfurization

Engineering Contradiction:
Improvesulfur desulfurization capacityVSAvoidcatalyst site availability
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

The invention changes the chemical environment of the catalyst surface through electrochemical promotion, altering the electronic state and acid-base properties of catalytic sites. This modification reduces the affinity between basic nitrogen compounds and acidic sites, preventing poisoning and maintaining site availability for sulfur desulfurization.

Inventive Principle:
Principle #35Parameter changes

4Productivity

If electrochemical promotion is applied to enhance reaction rate, then hydrodesulfurization activity increases, but device complexity increases due to electrochemical cell requirements

Engineering Contradiction:
Improvehydrodesulfurization reaction rateVSAvoidelectrochemical cell structure
Core Design Contradiction:
ProductivityVSDevice complexity

Solution Approach 1:

The invention makes the catalyst serve multiple functions: it acts as both the traditional catalytic site for hydrodesulfurization and as an electrode for receiving electrochemical promotion. The catalyst layer is designed to be electronically conductive or semi-conductive, enabling it to function as an electrode while maintaining catalytic activity, thus eliminating the need for separate electrode and catalyst components.

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 significantly enhances hydrodesulfurization reaction rates and selectivity, achieving higher sulfur removal efficiency while maintaining octane ratings by controlling electron density on the catalyst surface, thereby overcoming limitations of traditional catalytic processes.

Implementation Method 1

contacting the petroleum-based hydrocarbon stream with a hydrogen-containing gas in an electrochemical cell employing Non Faradic Electrochemical Modification of Chemical Activity

Methodology Applied
Scientific EffectNon-Faradic Electrochemical Modification of Chemical Activity (NEMCA):

Implementation Method 2

a charge conducting solid electrolyte support selected from YSZ and BCN18

Methodology Applied
Scientific EffectElectrical conduction: Conduction (electrical)

Implementation Method 3

MoCo-TiO2 as an active metal catalyst working electrode

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP2715845B1Electrochemical hydrodesulfurization of hydrocarbons on a solid electrolyte cell
Publication Date: 2019.12.04 SAUDI ARABIAN OIL CO
  • EP2715845B1 patent drawingFigure 1
  • EP2715845B1 patent drawingFigure 2
  • EP2715845B1 patent drawingFigure 3

AI summary

An electrochemical catalytic method for the hydrodesulfurization of a petroleum- based hydrocarbon stream is described involving a hydrogen-containing gas in an electrochemical cell employing Non Faradic Electrochemical Modification of Electrochemcial Activity.