SERS Detection of Refinery Amines Using Cyano-Functionalized Gold Nanoparticles

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Solution Overview

Problem

Current methods for monitoring nitrogen-bearing compounds like monoethanolamine (MEA) in refinery effluent streams are inefficient and time-consuming, failing to detect concentrations at parts per million to parts per billion levels, which poses a risk for corrosion and requires a more precise and rapid monitoring solution.

Innovation Solution

The use of Surface Enhanced Raman Spectroscopy (SERS) with functionalized metallic nanoparticles, specifically gold nanoparticles covalently bonded with a cyano group, as a substrate to enhance Raman signals and enable detection and quantification of amines down to parts per billion levels, utilizing a unique Raman peak as an internal standard for calibration.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Measurement precision

If titrimetry or ion-selective electrode methods are used to monitor nitrogen-bearing compounds, then the monitoring can be performed, but the detection precision is insufficient for parts per million to parts per billion levels

Engineering Contradiction:
Improvedetection precisionVSAvoidmonitoring reliability
Core Design Contradiction:
Measurement precisionVSReliability

Solution Approach 1:

The patent changes the detection parameter from conventional titrimetry or ion-selective electrode measurements to Surface Enhanced Raman Spectroscopy (SERS), which operates at different physical principles and provides significantly enhanced detection sensitivity. The SERS technique exploits surface plasmon resonance and Raman scattering effects to achieve parts per billion detection levels, resolving the contradiction between measurement precision and monitoring reliability.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces functionalized metallic nanoparticles as an intermediary substrate that enhances the Raman signal of nitrogen-bearing compounds. These nanoparticles act as a mediator between the analyte and the detection system, providing signal amplification that enables detection at parts per million to parts per billion levels, thereby simultaneously improving both measurement precision and monitoring reliability.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Measurement precision

If chromatography techniques are used to detect refinery chemicals, then detection can be achieved, but the process is tedious and time consuming

Engineering Contradiction:
Improvedetection capabilityVSAvoidanalysis speed
Core Design Contradiction:
Measurement precisionVSProductivity

Solution Approach 1:

The patent replaces the mechanical chromatography separation system with an optical detection system based on SERS. Instead of using complex chromatographic columns, mobile phases, and separation mechanisms, the invention uses functionalized metallic nanoparticles combined with Raman spectroscopy to directly detect and quantify nitrogen-bearing compounds, achieving both high precision and rapid analysis within minutes.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The patent performs preliminary functionalization of metallic nanoparticles with cyano groups before use, creating a ready-to-use SERS substrate that requires no further preparation. This preliminary action enables direct injection and detection of samples, eliminating the time-consuming chromatography steps while maintaining high detection precision.

Inventive Principle:
Principle #10Preliminary action

3Reliability

If conventional detection methods are used, then the monitoring process can be performed, but the time required for analysis is excessive and prevents prompt action

Engineering Contradiction:
Improvemonitoring coverageVSAvoidanalysis time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The patent enables continuous monitoring by establishing a rapid SERS detection protocol that can be repeatedly performed in minutes. The functionalized metallic nanoparticles provide consistent, reproducible signals that allow for continuous sampling and analysis, ensuring reliable monitoring coverage while minimizing analysis time to enable prompt operational responses.

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

This method allows for quick and cost-effective detection and quantification of refinery chemicals at parts per million or parts per billion levels, providing consistent results and reducing the time required for analysis to less than 10 minutes, enabling prompt action to mitigate corrosion risks.

Implementation Method 1

Surface Enhanced Raman Spectroscopy (SERS) to determine concentrations of chemicals

Methodology Applied
Scientific EffectSurface Enhanced Raman Spectroscopy (SERS):

Implementation Method 2

Surface-enhanced Raman scattering detection of toluene and dichlorobenzene vapors

Methodology Applied
Scientific EffectRaman scattering:

Implementation Method 3

functionalized metallic nanoparticles...covalently bonded with a cyano group...as a substrate to enhance Raman signals

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP3510382B1Refinery chemical detection using surface enhanced raman spectroscopy with functionalized nanoparticles
Publication Date: 2023.10.25 BAKER HUGHES CO
  • EP3510382B1 patent drawingFigure 1
  • EP3510382B1 patent drawingFigure 2
  • EP3510382B1 patent drawingFigure 3

AI summary

A method of analyzing a selected refinery chemical at a low concentration comprises contacting a sample with functionalized metallic nanoparticles that contain metallic nanoparticles functionalized with a functional group comprising a cyano group, a thiol group, a carboxyl group, an amino group, a boronic acid group, an aza group, an ether group, a hydroxyl group, or a combination comprising at least one of the foregoing; radiating the sample contacted with the functionalized metallic nanoparticles with electromagnetic radiation at a selected energy level; measuring a Raman spectrum emitted from the sample; and determining the presence or a concentration of a selected refinery chemical in the sample from the Raman spectrum.