Hydroprocessing Bulk Catalyst Composite Design

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Solution Overview

Problem

The petroleum industry faces challenges in upgrading heavy oils and residua due to their high sulfur and nitrogen content, requiring improved catalysts with optimal morphology and structure for high yield conversions, as well as efficient processes for catalyst preparation.

Innovation Solution

A novel bulk catalyst composition based on sulfides of 'd' block metals, specifically formulated as (R p< ) ¡ (M t< ) a (L u< ) b (S v< ) d (C w< ) e (H x< ) f (O y< ) g (N z< ) h, where M and L are different 'd' block element metals, is developed, along with a process involving the combination of metal precursors and a sulfiding agent to form the catalyst, which can be mixed with hydrocarbon compounds for sulfidation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional hydrotreating catalysts are used for heavy oils and residua, then the basic upgrading function is achieved, but the catalytic activity and conversion yield are insufficient due to high sulfur and nitrogen content

Engineering Contradiction:
Improveconversion yieldVSAvoidcatalytic activity
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent employs composite catalyst systems combining multiple metal sulfides (e.g., Ni-Mo, Co-W, Fe-Zn) with specific surface area characteristics. These composite materials synergistically enhance both catalytic activity and conversion yield by distributing active sites across different metal phases, allowing simultaneous improvement of productivity and reliability in harsh hydroprocessing conditions

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention optimizes catalyst parameters including metal composition ratios, surface area (5-50 m²/g), pore volume, and particle size distribution. By adjusting these physical and chemical parameters, the catalyst maintains high activity and stability despite the challenging feedstock composition, resolving the contradiction between conversion yield and catalytic reliability

Inventive Principle:
Principle #35Parameter changes

2Reliability

If catalysts with optimized morphology and structure are developed, then catalytic activity and conversion yield improve, but the complexity of catalyst preparation increases

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

Solution Approach 1:

The patent uses pre-sulfided metal oxides or hydroxides as starting materials, where the sulfide phase is already formed before catalyst preparation. This preliminary sulfidation step simplifies the overall process by eliminating the need for complex in-situ sulfidation procedures, reducing preparation complexity while maintaining high catalytic activity and reliable performance

Inventive Principle:
Principle #10Preliminary action

3Object-affected harmful factors

If heavy oils and residua are upgraded to remove sulfur and nitrogen, then product quality improves, but the process requires considerable upgrading effort and multiple treatment steps

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

Solution Approach 1:

The patent develops universal catalyst formulations capable of performing multiple functions simultaneously: hydrodesulfurization, hydrodenitrogenation, hydrocracking, and hydrogenation. This multi-functionality allows a single catalyst system to address all harmful components (sulfur, nitrogen, metals) in heavy oils and residua, simplifying the upgrading process while improving product quality without requiring separate treatment units for each contaminant

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

The catalyst composition demonstrates enhanced catalytic activity and efficiency in converting heavy oils and residua, achieving high yield conversions and improving the quality of upgraded products by reducing sulfur and nitrogen content.

Implementation Method 1

The upgrading or refining is accomplished by hydrotreating processes, i.e., 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 2

combining at least two different metal precursors of 'd' block element metals with a sulfiding agent forming at least a sulfided catalyst precursor

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 3

mixing the metal precursors with a hydrocarbon compound under conditions sufficient for the oil dispersible sulfur containing organic ionic compound to thermally decompose, releasing sulfur for the sulfidation of the metal precursors

Methodology Applied
Scientific EffectThermal decomposition: Thermolysis

Data Source

PatentEP2504099B1Hydroprocessing bulk catalyst, it's use and methods of making thereof
Publication Date: 2021.08.11 CHEVRON USA INC
  • EP2504099B1 patent drawingFigure 1~3
  • EP2504099B1 patent drawingFigure 4~6
  • EP2504099B1 patent drawingFigure 7~9

AI summary

A hydroprocessing bulk catalyst is provided. A process to prepare hydroprocessing bulk catalysts is also provided. The hydroprocessing catalyst has the formula (Rp)i(Mt)a(Lu)b(Sv)d(Cw)e(Hx)f(Oy)g(Nz)h, wherein M is at least a "d" block element metal; L is also at least a "d" block element metal, but different from M; t, u, v, w, x, y, z representing the total charge for each of the components (M, L, S, C, H, O and N, respectively); R is optional and in one embodiment, R is a lanthanoid element metal; 0 &lt;= i &lt;= 1; pi+ta+ub+vd+we+xf+yg+zh=0; 0 &lt; b; 0 &lt; b / a = &lt; 5; 0.5 (a + b) &lt;= d &lt;= 5(a + b); 0 &lt; e &lt;= 11(a+b); 0 &lt; f &lt;= 7(a+b); 0 &lt; g &lt;= 5(a + b); 0 &lt; h &lt;= 2(a + b). The catalyst has an X-ray powder diffraction pattern with at least three diffractions peak located at 2-θ angles of greater than 25°. In one embodiment, the catalyst is prepared by forming at least a sulfided catalyst precursors from at least two "d" block element metals; and mixing the catalyst precursor with a hydrocarbon compound to form the hydroprocessing catalyst composition. In another embodiment, the catalyst is prepared by the thermal decomposition of an oil dispersible sulfur containing organic metal precursor upon contact with a hydrocarbon oil, generating a slurry catalyst. In yet another embodiment, the catalyst is prepared from an in-situ or ex-situ sulfidation of "d block element metal precursors in a solvent carrier.