Deep Desulfurization of Hydrocarbons Using Peroxy Acids and Ionic Liquids
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Solution Overview
Problem
Existing desulfurization technologies, such as hydrodesulfurization (HDS) and oxidative desulfurization (ODS), face challenges including high operating temperatures and pressures, excessive use of hydrogen, and environmental concerns due to the use of volatile organic compounds and flammable oxidants, which hinder the efficient removal of sulfur compounds from hydrocarbon materials to ultra-low levels.
Innovation Solution
A process involving the use of organic and inorganic peroxy acids as oxidants in conjunction with aqueous extractants, followed by ionic liquids, to oxidize sulfur compounds to sulfones and extract them, minimizing hydrogen consumption and operating conditions, and allowing for efficient phase separation and recovery of sulfur compounds.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Manufacturing precision
If hydrodesulfurization (HDS) is used to remove sulfur compounds, then sulfur removal efficiency is improved, but operating temperature and pressure increase significantly
Solution Approach 1:
The patent changes the chemical parameters of the oxidation process by using peracetic acid as oxidant and controlling pH levels, enabling sulfur removal at ambient temperature and pressure conditions rather than requiring high temperature and pressure HDS conditions
Solution Approach 2:
The patent employs peracetic acid, a strong oxidant, to accelerate the oxidation of sulfur compounds to sulfones and sulfonates, achieving effective desulfurization under mild conditions without requiring the high energy input of conventional HDS
2Manufacturing precision
If hydrodesulfurization (HDS) is used to remove sulfur compounds, then sulfur removal efficiency is improved, but hydrogen consumption increases significantly
Solution Approach 1:
The patent extracts sulfur compounds from hydrocarbons by oxidizing them to polar sulfone and sulfonate derivatives that can be separated through liquid-liquid extraction, eliminating the need for large quantities of hydrogen required in HDS processes
Solution Approach 2:
The patent introduces peracetic acid as an intermediary oxidant that converts non-polar sulfur compounds into polar forms that can be extracted by aqueous or ionic liquid phases, providing an alternative pathway that bypasses hydrogen consumption
3Manufacturing precision
If aqueous hydrogen peroxide and organic carboxylic acids are used for oxidative desulfurization, then sulfur removal is achieved, but large amounts of flammable and volatile organic compounds are required
Solution Approach 1:
The patent uses peracetic acid solution as a stable, non-flammable oxidant that can be handled safely under ambient conditions, replacing the need for large amounts of flammable organic solvents and oxidants while maintaining effective sulfur removal
Solution Approach 2:
The patent changes the physical state and chemical stability parameters by using peracetic acid in aqueous solution, which has lower volatility and flammability compared to pure hydrogen peroxide and organic acid mixtures, thereby reducing harmful factors
4Manufacturing precision
If formic acid is used as extractant in oxidative desulfurization, then sulfur compounds are extracted, but recovery becomes difficult due to azeotrope formation with water
Solution Approach 1:
The patent employs ionic liquids as extractants that can be easily recovered and reused through simple phase separation, avoiding the complex distillation processes required to break azeotropes formed by formic acid and water
Solution Approach 2:
The patent uses ionic liquids, which are composite materials with unique properties including immiscibility with hydrocarbons and water, enabling efficient extraction and easy separation without forming problematic azeotropes
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 process effectively reduces sulfur content in hydrocarbons to low ppm levels with reduced capital and operational costs, minimal waste generation, and environmentally benign conditions, using near-stoichiometric oxidant amounts and non-toxic by-products, while avoiding the limitations of traditional methods.
Implementation Method 1
contacting the hydrocarbon material with an oxidant selected from organic peroxy acids, organic peroxides, inorganic peroxides and mixtures thereof, in at least a stochiometric amount and for a time sufficient to oxidise a sulfur compound to a sulfone compound
Implementation Method 2
contacting the hydrocarbon material with an aqueous extractant for a time and under conditions sufficient to allow at least a portion of the oxidised sulfur compounds to be extracted into the aqueous extractant
Implementation Method 3
contacting ionic liquids with HCs such as diesel fuels, in which they are immiscible
Implementation Method 4
After gravity separation of the S-laden IL extractant and repeated extraction steps
Data Source
AI summary
A process for the deep desulfurisation of hydrocarbons (HC), in particular Natural Gas Condensate (NGC), and HC comprising diesel, pre-extracted diesel and naphtha, is described which is capable of reducing the sulfur content of these HC from 500 to 30 ppm. The process comprises contacting the hydrocarbon material with an oxidant selected from organic peroxy acids, organic peroxides, inorganic peroxides and mixtures thereof, in at least a stochiometric amount sufficient to oxidise a sulfur compound to a sulfone compound; contacting the hydrocarbon material with an aqueous extractant to allow at least a portion of the oxidised sulfur compounds to be extracted into the aqueous extractant, and separating the hydrocarbon material from the aqueous extractant to give a hydrocarbon material of reduced sulfur content. Optionally, the process may include a second and subsequent extractions with the aqueous extractant to further reduce sulfur content. A final extraction with an IL may be conducted. The invention also provides for substitution of the aqueous extractant with an IL in one or more of the other extraction steps. The extractants and by products generated during f01 oxidation can be recovered by simple distillation techniques.