Sulfur Characterization in Rock Sediments and Petroleum

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Solution Overview

Problem

Current methods are inadequate for accurately quantifying and characterizing sulfur in petroleum products and sedimentary rocks, particularly in heavy oils and distinguishing between organic and mineral sulfur, which is crucial for oil exploration, production, and refining processes.

Innovation Solution

A method involving pyrolysis and oxidation of samples in a non-oxidizing and oxidizing atmosphere, respectively, with continuous measurement of SO2 emissions using UV or IR spectrophotometry to generate a unique sulfur fingerprint, allowing discrimination between different sulfur types and quantification of total sulfur content.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Measurement precision

If multiple separate operations are used to discriminate organic sulfur from mineral sulfur in rocks, then discrimination between sulfur types is achieved, but analysis time and operational complexity increase significantly

Engineering Contradiction:
Improvesulfur type discriminationVSAvoidanalysis time
Core Design Contradiction:
Measurement precisionVSLoss of time

Solution Approach 1:

The patent combines multiple separate analytical operations into a single integrated pyrolysis system. The pyrolysis oven simultaneously performs thermal decomposition, vaporization, and separation of different sulfur types, with the effluent directly introduced into a single detector that continuously measures SO2 evolution. This merging of operations maintains sulfur type discrimination capability while dramatically reducing analysis time from hours to minutes.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The patent segments the sulfur content into different thermal evolution profiles during pyrolysis. By monitoring SO2 evolution at different temperature stages, the system distinguishes between organic sulfur (evolving at lower temperatures) and mineral sulfur (evolving at higher temperatures). This segmentation approach allows simultaneous discrimination of sulfur types without requiring multiple separate operations.

Inventive Principle:
Principle #1Segmentation

2Measurement precision

If conventional measurement methods are used for sulfur in heavy oils, then total sulfur content can be measured, but detailed characterization of different sulfur forms is impossible

Engineering Contradiction:
Improvesulfur characterizationVSAvoidmeasurement system complexity
Core Design Contradiction:
Measurement precisionVSDevice complexity

Solution Approach 1:

The patent introduces pyrolysis as an intermediary process that transforms complex heavy oil sulfur compounds into volatile SO2 gas. The pyrolysis oven acts as a mediator that breaks down refractory sulfur-containing molecules in heavy oils, converting them into detectable gaseous forms. This intermediary step enables detailed sulfur characterization without requiring direct analysis of the complex original compounds, thus avoiding the need for extremely complex measurement systems.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent utilizes temperature as a changing parameter during pyrolysis to differentiate sulfur forms. By progressively increasing temperature and monitoring SO2 evolution rates at each stage, the system characterizes different sulfur types based on their thermal stability. This parameter change approach provides detailed sulfur characterization while keeping the device relatively simple, as it relies on temperature programming rather than complex multi-technique instrumentation.

Inventive Principle:
Principle #35Parameter changes

3Quantity of substance

If high sulfur content samples are analyzed using traditional methods, then quantitative data is obtained, but the ability to identify specific sulfur compound types is lost

Engineering Contradiction:
Improvesulfur quantificationVSAvoidsulfur type information
Core Design Contradiction:
Quantity of substanceVSLoss of information

Solution Approach 1:

The patent employs continuous monitoring of SO2 evolution throughout the pyrolysis process. Rather than taking discrete measurements at different stages, the system continuously records the rate and amount of SO2 released as temperature increases. This continuous action provides both the total sulfur quantity (integrated area under the curve) and sulfur type information (shape and peaks of the evolution profile), preserving information that would be lost in discrete sampling methods.

Inventive Principle:
Principle #20Continuity of useful 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

Enables precise characterization and quantification of sulfur in various samples, including heavy oils, with a short analysis time and low sample quantity, effectively discriminating between organic and mineral sulfur, and providing detailed sulfur information for oil exploration, production, and refining applications.

Implementation Method 1

The sample is pyrolyzed according to a predefined temperature program, in an oven swept by a flow of non-oxidizing gas

Methodology Applied
Scientific EffectPyrolysis: Pyrolysis

Implementation Method 2

The residue is oxidized there according to a predefined temperature program, under a flow of air

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 3

The quantity of SO2 contained in the effluents resulting from said oxidizing heating is continuously measured

Methodology Applied
Scientific EffectAbsorption Spectroscopy: Absorption Spectroscopy

Data Source

PatentEP2342557B1Method and device for rapidly characterising and quantifying sulfur in rock sediments and petrol products
Publication Date: 2014.09.10 IFP ENERGIES NOUVELLES
  • EP2342557B1 patent drawingFigure 1~2-b
  • EP2342557B1 patent drawingFigure 3-a~4

AI summary

The invention relates to a method and to a device for characterising and quantifying sulphur in a sample of sedimentary rock or petroleum product, said method comprising the following steps: heating said sample in a pyrolysis oven (1) in an non-oxidising atmosphere, oxidising a portion of the pyrolysis effluents and continuously measuring the amount of SO2 generated by said pyrolysis after the oxidation, and transferring the pyrolysis residue of said sample into an oxidation oven (11) and continuously measuring the amount of SO2 contained in the effluents resulting from said oxidation heating.