WO2013186338A1 - Procédé d'analyse - Google Patents

Procédé d'analyse Download PDF

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Publication number
WO2013186338A1
WO2013186338A1 PCT/EP2013/062332 EP2013062332W WO2013186338A1 WO 2013186338 A1 WO2013186338 A1 WO 2013186338A1 EP 2013062332 W EP2013062332 W EP 2013062332W WO 2013186338 A1 WO2013186338 A1 WO 2013186338A1
Authority
WO
WIPO (PCT)
Prior art keywords
lubricating oil
total basicity
absorption spectra
calculating
calculated
Prior art date
Application number
PCT/EP2013/062332
Other languages
English (en)
Inventor
Durmus OZDEMIR
Ayse AYBEY
Vedat AKGUN
Original Assignee
Opet Petrolculuk Anonim Sirketi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Opet Petrolculuk Anonim Sirketi filed Critical Opet Petrolculuk Anonim Sirketi
Publication of WO2013186338A1 publication Critical patent/WO2013186338A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/26—Oils; Viscous liquids; Paints; Inks
    • G01N33/28—Oils, i.e. hydrocarbon liquids
    • G01N33/2835—Specific substances contained in the oils or fuels
    • G01N33/2876—Total acid number
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water

Definitions

  • the present invention relates to an analysis method for calculating the total basicity number particularly of lubricating oils.
  • Acidic waste products may result from the combustion of fuels in internal combustion engines, particularly in automobile engines (e.g. sulphuric acid or nitrogen oxide due to the presence of sulfur and nitrogen in the fuel, respectively).
  • the acidic waste products affect specifically the metallic parts of the engine and these parts become damaged in time (e.g. as a result of corrosion).
  • lubricating oils with a high basicity number are employed in the engines running with fuel. These lubricating oils balance (i.e. neutralize) the acidic waste products resulting from the combustion of the fuel and thus protect the metallic parts against damage.
  • the basicity number of the lubricating oil may decrease as a result of running the engine over time. Therefore, the basicity number of the lubricating oil must be measured at certain times to ensure a safe operation for the engine.
  • a lubricating oil of which the total basicity number is to be calculated is mixed with an acid in a beaker.
  • the bases present in the lubricating oil react with the acids and generate a gas (e.g. carbon dioxide).
  • a gas e.g. carbon dioxide
  • the amount of this generated gas is measured such that the total basicity number of the lubricating oil is calculated.
  • this method may also give rise to erroneous results due to human errors (e.g. using an incorrect amount of lubricating oil).
  • the acid present in the beaker may damage the person conducting the test.
  • the total basicity number of lubricating oils is calculated using Fourier transform infrared spectroscopy in the method according to the present invention. Thus, the calculation process can be carried out in a rapid and reliable manner.
  • the object of the present invention is to develop a method for calculating the total basicity number of lubricating oils.
  • Another object of the present invention is to develop a rapid and reliable method for calculating the total basicity number of lubricating oils.
  • Acidic waste products are produced in internal combustion engines as a result of the reaction (i.e. combustion) of the fuel with the oxygen in the air.
  • the lubricating oil used in the engines for neutralizing these acidic waste products which may damage the engine must have basic properties.
  • the basicity of the lubricating oil decreases over the running period of engines. For this reason, the total basicity number of lubricating oils must be calculated at certain time intervals to determine the reliability thereof.
  • an analysis method is developed according to the present invention to provide a rapid and reliable calculation of the total basicity number of lubricating oils.
  • the absorption spectra of the lubricating oils are measured using the Fourier transform infrared (FTIR) spectroscopy method. Then, the absorption spectra obtained as a result of the measurement is entered to a previously generated chemometric multivariable calibration model.
  • the calibration model with preset parameters calculates the total basicity number of the lubricating oil according to the measured absorption spectra. Thus, the total basicity number can be calculated without having to mix the lubricating oil with different chemicals.
  • the chemometric multivariable calibration model is generated using a plurality of lubricating oil samples of which the total basicity numbers are known (i.e. the total basicity numbers are measured using conventional methods).
  • the absorption spectra of each of the lubricating oil samples are measured using the Fourier transform infrared spectroscopy method.
  • the chemometric multivariable calibration model is generated through the genetic algorithm based inverse least squares (GILS) method using the total basicity number and the measured absorption spectra of each lubricating oil. Said calibration model can thus be generated in a reliable manner.
  • GILS genetic algorithm based inverse least squares
  • the Fourier transform infrared spectroscopy method according to the present invention is widely used nowadays (e.g. in biotechnology, analytical process technologies, microanalysis, recycling industry, nuclear power industry, geomorphology, drug and food industries, polymer plastics industries, academic and agricultural researches, process control etc.) for identifying the molecular structures of substances by analyzing the functional groups thereof, examining the mixture compositions, clarifying the molecular interactions, etc..
  • this method is one of the most important test methods giving rapid results as used for identifying the hydrocarbon distribution constituting the basic structure of organic and inorganic substances and mineral oils, monitoring the production processes, reference-based check processes, and determining undesired foreign contaminants in mineral oils.
  • the absorption spectra of samples are measured and the measured values are modeled using various methods.
  • this modeling is made using genetic algorithm based inverse least squares method instead of conventional methods such as the classical least squares (CLS) method, the inverse least squares (ILS) method (sometimes called as the multi linear regression (MLR) method), the partial least squares (PLS) method and the principal components regression (PCR) method.
  • CLS classical least squares
  • ILS inverse least squares
  • MLR multi linear regression
  • PLS partial least squares
  • PCR principal components regression
  • the genetic algorithm based inverse least squares method used in the analysis method according to the present invention is a combined form of the inverse least squares (ILS) method with a genetic algorithm.
  • the modeling for a spectrum of m calibration sample comprising I components with n wavelengths is calculated generally as below:
  • C represents the concentration matrix with a size of m x I
  • A represents the spectral absorption matrix with a size of m x n
  • P represents the coefficients correlating the absorbance values in each wavelength of n x I with the concentration
  • E c represents the residual matrix of m x I which cannot be modeled.
  • c and p each are one vector and c represents the concentration of the calibration samples of any component.
  • the estimation of the vector p is calculated as given in the equation 3 below:
  • the superscript (') represents a transposition operation of the matrix
  • the superscript (-1 ) on the parenthesis is the inverse of the multiplication of matrixes.
  • the present invention makes use of the genetic algorithm based inverse least squares (GILS) method obtained by combining the least squares method with a genetic algorithm.
  • GILS genetic algorithm based inverse least squares
  • the most suitable multivariable calibration models can be obtained for the Fourier transform infrared spectroscopy analysis of the total basicity number of the mixtures of lubricating oils (e.g. mineral oils).
  • Genetic algorithms are universal research and optimization methods based on natural evolution and selection principles.
  • the term gene is used for describing the solution of a given problem, and the population, in turn, for describing a collection of genes collected from a valid generation. After an initial population is created according to a predetermined suitability value for the potential solutions, new modified populations are created according to the natural selection principle. The modification is iterated for the best solution according to the suitability criterion.
  • the entire operations of a genetic algorithm are completed in 5 steps. These steps are as follows;
  • the first step in the GILS method is the initiation of the gene population.
  • a user first determines the number of genes to be created, provided that an even number is determined.
  • the length of each gene is randomly determined, provided that the sample number in the calibration set is not exceeded and that the length is at least two. For example, if the length of the first selected gene (G1 ) is randomly determined as 9, nine elements of this gene are constituted from randomly selected data points through the FTIR spectra in the calibration set as given in equation 5.
  • G1 (A3450, A2560, A1763, A892, A1243, A756, A2632, A1587, A3921 ) (5)
  • the letter A signifies the absorbance value at the wavelength indicated in the number accompanying the letter A.
  • these genes are put in sequence from the best to the worst according to a suitability function (the inverse of standard error of calibration (SEC), i.e.1 /SEC) in the step of evaluating the population.
  • SEC standard error of calibration
  • these 30 genes are placed on a roulette wheel according to the suitability values they possess, such that 30 genes are selected by turning the roulette wheel 30 times such that in each turn one gene is selected among these 30 genes according to the roulette method.
  • the selection probability of the genes having a higher suitability value can be relatively higher, some genes can be selected more than once, and some genes may never be selected.
  • a step is carried out by which new generation genes are created using a single point cross-linking method for these genes. This step can be conducted e.g. as given below.
  • G1 (A3450, A2560, A1763, A892, A1243, / A756, A2632, A1587, A3921 )
  • G2 (A2512, A1678, A978, / A754, A1345)
  • G1 and G2 above represent the first two genes selected from the roulette wheel method
  • first each gene is cut from a point close to the middle of its length, as illustrated with the symbol (/).
  • the first part of the first gene and the second part of the second gene after being cut are combined to give yG1
  • the second part of G1 and the first part of G2 are taken to give the new generation yG2 as follows.
  • yG1 (A3450, A2560, A1763, A892, A1243, A754, A1345)
  • yG2 ( A756, A2632, A1587, A3921 , A2512, A1678, A978)
  • the calibration models are created using the absorption values of these wavelengths.
  • the success criterion of this calibration is the standard error of calibration (SEC) and is calculated according to the following equation.
  • q represents the real concentration values
  • c. represents the predicted concentration values
  • m represents the sample number.
  • SEP standard error of prediction
  • the closeness of the regression coefficient to 1 represents an indication of the success of the calibration model.
  • the analysis method according to the present invention makes use of the Fourier transform infrared spectroscopy analysis to measure the total basicity number particularly of lubricating oils.
  • the duration of the calculation which is around one hour according to conventional methods is reduced to around half a minute.
  • the lubricating oil is directly analyzed in the method according to the present invention in place of adding dissolving chemicals to the lubricating oil which is the case of conventional methods.
  • the analysis is rendered reliable in terms of the person conducting the analysis and the results of the analysis.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

La présente invention concerne un procédé d'analyse permettant de calculer l'indice de basicité totale d'huiles lubrifiantes. Le procédé comprend les étapes consistant à calculer les indices de basicité totale de plusieurs échantillons d'huile lubrifiante selon des procédés connus ; à mesurer les spectres d'absorption de chaque échantillon d'huile lubrifiante à l'aide d'un procédé de spectroscopie infrarouge à transformée de Fourier ; à générer un modèle d'étalonnage multivarié chimiométrique à l'aide des indices de basicité totale calculés et des spectres d'absorption mesurés dans une méthode des moindres carrés inversés à base d'algorithmes génétiques ; à mesurer les spectres d'absorption de l'huile lubrifiante dont l'indice de basicité totale doit être calculé à l'aide du procédé de spectroscopie infrarouge à transformée de Fourier et à calculer l'indice de basicité totale de l'huile lubrifiante par l'application des spectres d'absorption mesurés de l'huile lubrifiante au modèle d'étalonnage créé.
PCT/EP2013/062332 2012-06-15 2013-06-14 Procédé d'analyse WO2013186338A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR201207028 2012-06-15
TR2012/07028 2012-06-15

Publications (1)

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WO2013186338A1 true WO2013186338A1 (fr) 2013-12-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017017082A1 (fr) * 2015-07-27 2017-02-02 Avenisense Procédé de détermination en ligne d'un indice de basicité d'un corps liquide et utilisation de ce procédé pour un lubrifiant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006034072A1 (fr) * 2004-09-17 2006-03-30 Bp Oil International Limited Procédé d’analyse d’une charge d’alimentation contenant un hydrocarbure

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006034072A1 (fr) * 2004-09-17 2006-03-30 Bp Oil International Limited Procédé d’analyse d’une charge d’alimentation contenant un hydrocarbure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AL-GHOUTI M A ET AL: "Application of chemometrics and FTIR for determination of viscosity index and base number of motor oils", TALANTA, ELSEVIER, AMSTERDAM, NL, vol. 81, no. 3, 15 May 2010 (2010-05-15), pages 1096 - 1101, XP026966421, ISSN: 0039-9140, [retrieved on 20100206] *
YALCIN A ET AL: "Determination of aluminum rolling oil additives and contaminants using infrared spectroscopy coupled with genetic algorithm based multivariate calibration", VIBRATIONAL SPECTROSCOPY, ELSEVIER SCIENCE, AMSTERDAM, NL, vol. 54, no. 1, 18 September 2010 (2010-09-18), pages 10 - 20, XP027208096, ISSN: 0924-2031, [retrieved on 20100608] *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017017082A1 (fr) * 2015-07-27 2017-02-02 Avenisense Procédé de détermination en ligne d'un indice de basicité d'un corps liquide et utilisation de ce procédé pour un lubrifiant
FR3039648A1 (fr) * 2015-07-27 2017-02-03 Avenisense Procede de determination en ligne d'un indice de basicite d'un corps liquide et utilisation de ce procede pour un lubrifiant
US10634610B2 (en) 2015-07-27 2020-04-28 Wika Tech S.a.S. Method for on-line determination of a basicity index of a liquid body and use of said method for a lubricant

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