Multi-Zone Catalytic Reforming with Alkali Segmentation

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Solution Overview

Problem

The catalytic reforming of hydrocarbons faces challenges in achieving high activity, selectivity, and stability, particularly due to increased operating severities which lead to catalyst deactivation and reduced yields of desired gasoline-range products.

Innovation Solution

A multi-catalyst-zone reforming process is employed, with an initial zone containing platinum, rhenium, or germanium, along with an alkali metal or alkaline earth metal and halogen on a solid catalyst support, and a terminal zone lacking alkali metals, using platinum, rhenium, or germanium, and halogen on a solid catalyst support, to enhance hydrocarbon conversion efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If higher operating severities are used to meet increased octane needs, then catalyst activity is improved, but catalyst deactivation accelerates and stability deteriorates

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The reforming catalyst system is divided into multiple zones with different compositional characteristics. The first zone contains catalyst with higher alkali metal content for dehydrogenation, while subsequent zones contain catalyst with lower alkali metal content for dehydrocyclization and isomerization. This segmentation allows each zone to be optimized for its specific function, maintaining overall stability while achieving high activity through the combined effect of all zones.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

Different regions of the catalyst system are given different local qualities in terms of alkali metal content and catalytic function. The first zone has higher alkali metal content (0.01-0.15%) optimized for dehydrogenation activity, while later zones have progressively lower alkali metal content optimized for dehydrocyclization and isomerization. This local quality differentiation resolves the contradiction by allowing high activity where needed without compromising overall stability.

Inventive Principle:
Principle #3Local quality

2Productivity

If higher operating severities are used to meet increased octane needs, then desired product yield is improved, but coke formation increases and catalyst deactivation accelerates

Engineering Contradiction:
Improvedesired product yieldVSAvoidcoke formation
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The catalyst system is segmented into zones with different alkali metal contents to control the distribution of harmful coke formation. By having the first zone with higher alkali metal content and subsequent zones with lower content, the system optimizes product yield while controlling coke accumulation in specific regions, thereby extending catalyst life and maintaining stability under high severity operating conditions.

Inventive Principle:
Principle #1Segmentation

3Device complexity

If a single-catalyst system is used, then device complexity is reduced, but the ability to balance yield and activity is limited

Engineering Contradiction:
Improvecatalyst system complexityVSAvoidyield-activity balance capability
Core Design Contradiction:
Device complexityVSAdaptability or versatility

Solution Approach 1:

The catalyst system is divided into multiple zones with different compositional characteristics, allowing the system to balance yield and activity across different reaction stages. This segmentation provides the adaptability needed to optimize for both yield and activity simultaneously, overcoming the limitations of a single-catalyst system.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The reforming catalyst system uses a composite approach by combining catalyst zones with different alkali metal contents and catalytic properties. This composite material strategy allows the system to achieve both high yield and high activity balance, with the first zone providing dehydrogenation activity and subsequent zones providing dehydrocyclization and isomerization activities.

Inventive Principle:
Principle #40Composite materials

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 approach results in significant yield improvements of C5+ hydrocarbons while maintaining activity, achieving a balance between higher yields and lower activity losses, thereby addressing the limitations of single-catalyst systems.

Implementation Method 1

The catalytic reforming of hydrocarbon feedstocks in the gasoline range is an important commercial process... The multi-functional catalyst composite employed in catalytic reforming contains a metallic hydrogenation-dehydrogenation component on a porous, inorganic oxide support which provides acid sites for cracking and isomerization.

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

Naphthene dehydrogenation takes place principally in the first catalyst zones... dehydrogenation of naphthenes to aromatics

Methodology Applied
Scientific EffectDehydrogenation: Hydrogenation

Implementation Method 3

dehydrocyclization of paraffins... dehydrocyclization is largely accomplished in later catalyst zones

Methodology Applied
Scientific EffectDehydrocyclization: Chemical Bonding

Implementation Method 4

isomerization of paraffins and naphthenes... isomerization takes place principally in the first catalyst zones

Methodology Applied
Scientific EffectIsomerization: Chemical Bonding

Implementation Method 5

hydrocracking of paraffins to light hydrocarbons

Methodology Applied
Scientific EffectHydrocracking: Chemical Bonding

Implementation Method 6

formation of coke which is deposited on the catalyst... The principal cause of deactivation of a dual-function catalyst in a catalytic reforming operation is the aforementioned formation of coke on the surface of the catalyst.

Methodology Applied
Scientific EffectCoke formation: Deposition (physical)

Data Source

PatentEP3645669B1Reforming process employing a catalyst system with front catalyst zones containing higher levels of alkali
Publication Date: 2024.03.27 UOP LLC

AI summary

The invention provides a process for the catalytic reforming of hydrocarbons comprising contacting the hydrocarbon feed in two or more sequential catalyst zones. The initial catalyst zone is a fixed-bed system and contains an initial catalytic composition comprising a platinum component, a germanium or rhenium component, a refractory inorganic oxide, potassium and a halogen component and then there is a terminal catalyst zone with a terminal catalyst composition that has a similar composition but with an essential lack of potassium. The addition of potassium was found to improve the yield of C5+ hydrocarbons.