Slurry Catalyst Preparation for Heavy Oil Hydroprocessing

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Solution Overview

Problem

There is a need for improved catalysts with optimum morphology, structure, and enhanced catalytic activity for the conversion of heavy oils and residua, as well as more efficient processes for their preparation, as existing catalysts do not adequately address the challenges of sulfur and nitrogen content in heavy oil feedstocks.

Innovation Solution

The development of slurry catalysts using a combination of Group VIB and Group VIII metal precursors, with specific sulfiding agents and processes such as co-sulfiding, in-situ sulfidation, and high shear mixing, to create catalysts with improved surface area and pore volume, enabling effective hydroconversion of heavy oils.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional hydroprocessing catalysts are used, then basic catalytic activity is achieved, but conversion rate of heavy oils and catalytic activity are insufficient

Engineering Contradiction:
Improveconversion rate of heavy oilsVSAvoidcatalytic activity
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent employs composite catalyst formulations combining Group VIB metals (Mo, W) with Group VIII metals (Co, Ni) and promoter metals (Zn, Fe, Mn) to create synergistic effects that simultaneously enhance conversion rate and catalytic activity. The composite nature of the catalyst allows multiple active sites working together to address the insufficiency of conventional single-metal catalysts.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent optimizes multiple parameters including metal ratios (e.g., Mo:Co:Ni), sulfiding conditions (H2S partial pressure, temperature, time), and support characteristics to achieve maximum catalytic performance. By systematically adjusting these parameters, the catalyst achieves both high conversion rate and sustained catalytic activity.

Inventive Principle:
Principle #35Parameter changes

2Area of stationary object

If catalysts are prepared with standard methods, then basic catalyst structure is obtained, but surface area and pore volume are insufficient

Engineering Contradiction:
Improvesurface areaVSAvoidcatalyst preparation complexity
Core Design Contradiction:
Area of stationary objectVSEase of manufacture

Solution Approach 1:

The patent utilizes porous support materials such as alumina, silica, or mixed oxides with controlled pore structures to provide high surface area for catalyst dispersion. The porous structure allows increased active metal surface area while maintaining ease of manufacture through standard impregnation and calcination procedures.

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The patent employs intermediates such as ammonium heptamolybdate or other soluble metal salts that facilitate uniform metal distribution on the support during preparation. These intermediaries enable controlled deposition of active metals, achieving high surface area catalysts through straightforward wet impregnation methods rather than complex procedures.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Object-affected harmful factors

If heavy oils are processed without adequate hydroprocessing, then processing simplicity is maintained, but sulfur and nitrogen content remain high

Engineering Contradiction:
Improvesulfur and nitrogen contentVSAvoidhydroprocessing process complexity
Core Design Contradiction:
Object-affected harmful factorsVSDevice complexity

Solution Approach 1:

The patent employs hydroprocessing catalysts specifically designed to extract and remove sulfur and nitrogen from heavy oil feedstocks through hydrodesulfurization and hydrodenitrogenation reactions. The catalyst selectively targets these harmful components, converting them to removable forms (H2S, NH3) that can be separated from the processed oil.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent optimizes hydroprocessing conditions including temperature (300-450°C), pressure (500-3000 psi H2S), and catalyst composition to maximize removal of sulfur and nitrogen. By adjusting these parameters, the process achieves effective contaminant removal while managing the complexity of the hydroprocessing operation.

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

The new catalysts achieve high conversion rates of heavy oils, with at least 30% conversion of 1000°F+ materials, and improved catalytic activity in hydroprocessing, reducing sulfur and nitrogen content, and enhancing the quality of heavy oil products.

Implementation Method 1

sulfiding an aqueous mixture of the metal compounds with hydrogen sulfide (H2S) gas

Methodology Applied
Scientific EffectSulfiding: Chemical Bonding

Implementation Method 2

reacting at least a Group VIB metal compound with a Promoter metal compound, sulfiding the intermediate mixture with a sulfiding agent

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 3

treating with hydrogen of various hydrocarbon fractions, or whole heavy feeds, or feedstocks, in the presence of hydrotreating catalysts to effect conversion of at least a portion of the feeds

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 4

treating with hydrogen of various hydrocarbon fractions... to effect conversion of at least a portion of the feeds, or to effect the removal of unwanted components

Methodology Applied
Scientific EffectHydrogenation: Hydrogenation

Implementation Method 5

removal of unwanted components... reducing sulfur and nitrogen content

Methodology Applied
Scientific EffectHydrodesulfurization: Chemical Bonding

Implementation Method 6

removal of unwanted components... reducing sulfur and nitrogen content

Methodology Applied
Scientific EffectHydrodenitrogenation: Chemical Bonding

Implementation Method 7

high shear mixing, to create catalysts with improved surface area and pore volume

Methodology Applied
Scientific EffectShear mixing: Shear Stress

Implementation Method 8

improved surface area and pore volume, enabling effective hydroconversion

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP2658647B1Hydroprocessing catalysts and methods for making thereof
Publication Date: 2024.04.10 CHEVRON USA INC
  • EP2658647B1 patent drawingFigure 1~3
  • EP2658647B1 patent drawingFigure 4~6
  • EP2658647B1 patent drawingFigure 7~9

AI summary

A process for preparing a slurry catalyst for the heavy oil upgrade is provided. The slurry catalyst has a BET total surface area of at least 100 m2/g, a total pore volume of at least 0.5 cc/g and a polymodal pore distribution with at least 80% of pore sizes from 5 to 2,000 Angstroms. In one embodiment, a polar aprotic solvent is mixed with the metal precursor feed to form an oil-dispersible precursor. In another embodiment, the precursor feedstock is selected from any of a pressure leach solution from metal recovery, a rework material, a double metal salt precursor, a single metal precursor. In one embodiment, high shear mixing is employed to generate an emulsion. In another embodiment, sulfiding is carried out at least twice for enhanced sulfiding. In another embodiment, at least a metal precursor feedstock is split into portions for addition in various stages of the process.