Hydrotreating Catalysts via Partial Calcination

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Solution Overview

Problem

Conventional hydrotreating catalysts are not sufficiently reactive and effective for removing sulfur and nitrogen from hydrocarbon streams, necessitating the development of more advanced catalysts for improved hydrodesulfurization and hydrodenitrogenation processes.

Innovation Solution

A method involving the preparation of a catalyst composition with a partially oxidized metal-organic component, comprising a Group VIB metal and a Group VIII metal, supported on an inorganic catalyst support, with a specific carbon-as-carboxyl to total residual carbon ratio, achieved through a unique post-metal calcination method and subsequent sulfiding, enhancing the catalyst's activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional hydrotreating catalysts are used, then the catalyst structure is simple and easy to manufacture, but the catalyst activity for removing sulfur and nitrogen is insufficient

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst preparation process
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent applies preliminary action by performing a controlled calcination treatment before sulfiding to partially decompose the organic acid and create carboxyl groups on the catalyst surface. This pre-treatment step prepares the catalyst in a specific partially oxidized state that enhances subsequent sulfiding efficiency and final catalytic activity for hydrodesulfurization and hydrodenitrogenation

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent employs parameter changes by precisely controlling the calcination temperature (400-600°C) and atmosphere to achieve partial decomposition of the organic acid, maintaining a specific loss on ignition (1-10 wt%) and carboxyl carbon ratio (≥0.10). These parameter optimizations create the desired catalyst surface chemistry that dramatically improves heteroatom removal activity

Inventive Principle:
Principle #35Parameter changes

2Reliability

If complete calcination is performed to remove all organic content, then the catalyst is fully oxidized and stable, but the catalyst loses the reactive carboxyl groups needed for high activity

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst oxidation state
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent applies partial action by performing controlled calcination that removes only a portion of the organic acid content, maintaining 1-10 wt% loss on ignition and ≥0.10 carboxyl carbon ratio. This partial decomposition preserves the essential carboxyl groups and metal-organic components needed for high catalytic activity while providing sufficient structural stability, avoiding complete oxidation that would eliminate the reactive sites

Inventive Principle:
Principle #16Partial or excessive action

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

The resulting catalyst exhibits improved hydrodesulfurization and hydrodenitrogenation activity, achieving higher desulfurization and denitrogenation levels compared to conventional catalysts, as demonstrated by increased reaction activity and efficiency in hydrotreating processes.

Implementation Method 1

calcining the dried catalyst precursor in an oxygen-containing atmosphere for a time and temperature sufficient to oxidize some but not all of the organic portion of the metal-organic component

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 2

thermally treated to partially decompose the organic acid

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Implementation Method 3

sulfiding the partially oxidized catalyst precursor at sulfiding conditions in the presence of a sulfiding agent

Methodology Applied
Scientific EffectSulfidation: Chemical Bonding

Implementation Method 4

Hydrotreating processes are used by petroleum refiners to remove heteroatoms, such as sulfur and nitrogen, from hydrocarbon streams

Methodology Applied
Scientific EffectHydrotreating: Catalysis

Data Source

PatentEP3134205B1High activity hydrotreating catalysts
Publication Date: 2020.11.04 ADVANCED REFINING TECHNOLOGIES LLC

AI summary

This disclosure relates to supported multi-metallic catalysts for use in the hydrotreating of hydrocarbon feeds, as well as a method for preparing such catalysts. The catalysts are prepared from a catalyst precursor comprised of at least one Group VIB metal, at least one Group VIII metal and an organic acid. The catalyst precursor is thermally treated to partially decompose the organic acid, then sulfided. The catalysts have a high carbon-as-carboxyl to total carbon ratio (C carboxy /C total ) as a result of a unique post-metal calcination method employed during the manufacture of the catalyst. As a result, the hydrotreating catalysts have lower percent weight loss-on-ignition, higher activity and longer catalyst life.