WO2014087359A1 - Methodology for detection of kerosene adulteration in gasoline, motor spirit, aviation turbine fuel and diesel with intrinsic marker - Google Patents

Methodology for detection of kerosene adulteration in gasoline, motor spirit, aviation turbine fuel and diesel with intrinsic marker Download PDF

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Publication number
WO2014087359A1
WO2014087359A1 PCT/IB2013/060654 IB2013060654W WO2014087359A1 WO 2014087359 A1 WO2014087359 A1 WO 2014087359A1 IB 2013060654 W IB2013060654 W IB 2013060654W WO 2014087359 A1 WO2014087359 A1 WO 2014087359A1
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Prior art keywords
kerosene
fuel
gasoline
sulphur
adulteration
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PCT/IB2013/060654
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French (fr)
Inventor
Naduhatty SELAI RAMAN
Narayanam SESHUBABU
Dheer SINGH
Anurag Ateet Gupta
Santanam Rajagopal
Ravinder Kumar Malhotra
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Indian Oil Corporation Limited
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Publication of WO2014087359A1 publication Critical patent/WO2014087359A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/003—Marking, e.g. coloration by addition of pigments
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1616—Hydrocarbons fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine
    • 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
    • G01N33/2882—Markers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/16—Tracers which serve to track or identify the fuel component or fuel composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/60—Measuring or analysing fractions, components or impurities or process conditions during preparation or upgrading of a fuel
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
    • G01N2030/8854—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds involving hydrocarbons

Definitions

  • the present invention relates to a method for detection of kerosene adulteration in gasoline, motor spirit, aviation turbine fuel or diesei. More particularly the invention relates to a method of detection of kerosene content in gasoline or motor spirit, aviation turbine fuel or diesei in the concentration range of 0.5vol% or above by tracking intrinsic sulfur molecule/molecules.
  • US Patent No. 5229298 disclosed the method of analyzing the concentration of nitrogen bearing marker dye in liquid fuels selected from the group consisting of l-(4-morphiolino)-3-alpha- napthylamino-propane and l-(4-morpholino)-3-beta naptliylamino-propane.
  • the concentration of marker is further analyzed by gas chromatography equipped with nitrogen phosphorescence detector.
  • US5958780 patent disclosed the method of introducing miscible markers into gasoline or other oil byproducts, and subsequently analyzing the concentration of the marker by absorption spectrometry.
  • US2010305885 patent application disclosed a method to detect the fuel adulteration by transmitting wireless signals into bottom of fuel tank.
  • the returned wireless signals reflected off a bottom of the tank are received to determine whether the material has been adulterated using the level of the material in the tank.
  • US20100208243 patent disclosed the optical sensing system for identifying various types of liquid fuels based on refractive index principle of liquid fuels.
  • a light source is transmitted acutely onto optical fiber which is in contact with the fuel to the test probe.
  • the resulting optical signal derived from the interaction between light and fuel is a function of refractive indexes of the optical fiber and the fuel, the wavelength of light used and the fuel temperature.
  • the method has only discussed the detection of gasoline and diesel adulteration with ethanol and biodiesel respectively. However, the method has not disclosed gasoline or diesel adulteration with kerosene fuel. Further, the disclosed method is applicable for high volumetric ratios of over 5% adulteration.
  • marker protocols appear to be promising for detection of fuel adulteration, nevertheless utility of marker protocols are limited because of various shortcomings associated with marker such as high cost of preparation, high polarity, ability to be tampered or removed from the fuel.
  • the present invention provides a method to detect kerosene adulteration in gasoline, motor spirit, aviation turbine fuel or diesei by tracking intrinsic sulfur molecules with the help of gas chromatography and analysis of sulfur compounds in petroleum fractions.
  • the present invention provides a method for detection of kerosene adulteration in gasoline, motor spirit and diesei by tracking of inherent characteristic molecules of kerosene, preferably intrinsic sulfur molecules.
  • the present invention provides a method for detecting kerosene adulteration in gasoline, motor spirit, aviation turbine fuel, or diesei fuel, wherein the method comprises detecting the presence of sulfur molecules in the fuel by gas chromatography and measuring the peaks, wherein the presence of discernible peaks in the range of 5-10 minutes of retention time indicates the adulteration of fuel by kerosene.
  • the term 'discernible peaks' refers to the peaks which are attributed to the 'intrinsic sulphur molecules * of kerosene.
  • the sulphur molecules showing peaks in the range of 5-10 minutes of retention time are selected from thiophenes, substituted thiophenes, benzothiophenes, mono, di and tri alkyl substituted benzothiophenes and their isomeric mixtures.
  • the intrinsic sulphur molecules are tracked by gas chromatography.
  • gas chromatography is selected from sulphur chemiluminiscence detector, atomic emission detector, flame photometric detector or pulsed flame photometric detector.
  • the sulphur molecules are tracked by gas chromatography with or without mass spectroscopy.
  • the sulphur molecules that are detected are selected from thiophenes, substituted thiophenes, benzothiophenes, mono, di and tri alkyl substituted benzothiophenes and their isomeric mixture thereof.
  • the mono-, di- and tri- methyl benzothiophenes present inherently in kerosene are detected.
  • the concentration of inherent sulphur molecules present in kerosene ranges from 1000-2500 ppm.
  • the process of the present invention detects kerosene adulteration to as low as 0.5 vol % of kerosene or above.
  • the GC-SCD profile peak is observed in 5-6 min, 6.5-7.5 min and 8- 9.5 min for detecting the intrinsic sulphur molecules namely mono-, di- and tri- substituted methyl benzothiophenes, respectively.
  • Fig 1 Sulphur molecular distribution in various petroleum fractions; (Source; C. Song, Catalysis Today 86 (2003) 211)
  • Fig 2 GC-SCD profiles of gasoline, gasoline-kerosene blend and neat kerosene fuels
  • Fig 3 GC-SCD profiles of kerosene adulterated low sulphur diesel fuels
  • Fig 4 GC-SCD profiles of Kerosene adulterated high sulphur Diesel fuels
  • Fig 5 GC-SCD profile of acid, base and adsorbent treated kerosene fuel
  • the present invention discloses a method to detect the kerosene content in gasoline, motor spirit, aviation turbine fuel or diesel in the concentration of 0.5vol% or above by tracking intrinsic sulphur molecules.
  • the term 'intrinsic sulphur molecules refers to the sulphur containing molecules that are invariably present in kerosene in detectable amount, and are not present in premium fuels like gasoline, motor spirit, aviation turbine fuel or diesel in detectable amount.
  • the method relates to detection of intrinsic sulphur molecules which are invariably present in kerosene selected from a group comprising of thiophene, substituted thiophenes, benzothiophene, mono and di and tri substituted alkyl benzothiophenes, dibenzo thiophene, and mixture thereof.
  • kerosene fuel in wide range of concentrations i.e. from 1000-2500 ppm.
  • Fig. 1 illustrates group of typical sulphur molecules present in various petroleum fractions such as gasoline, kerosene and diesel.
  • the sulphur molecules are present in sourced crude oils and get distributed in various petroleum fractions according to their boiling points during the process of crude distillation.
  • catalytic hydro treatment is identified as one of notable process for removal of hetero atoms such as S, N and O in gasoline, diesel and aviation fuel.
  • the total sulphur content of petrol and diesel is mostly in the range of 500 ppm to 10 ppm maximum across the globe, which is due to the effect of hydrotreating process.
  • kerosene which is not used for transportation purposes, has total sulphur content in the range of 1000-2500 ppm, especially in India.
  • the presence of these sulphur molecules have been exploited for the detection of adulteration by kerosene in Gasoline or other fuel.
  • the detection method involves the tracking of the aforesaid molecules in adulterated fuels employing gas chromatography with or without mass spectroscopy.
  • the gas chromatography preferably operates with Sulphur Chemiluminescence Detector (SCD), flame photometry, Pulsed Flame Photometry Detector (PFPD) or using electrochemical detector.
  • SCD Sulphur Chemiluminescence Detector
  • PFPD Pulsed Flame Photometry Detector
  • gasoline, aviation turbine fuel and diesel that are produced by hydrotreatment or hydrodesulphurization process are the fuels for which the process of the present invention would be useful in detecting kerosene adulteration.
  • Gas chromatography with specific detector has been preferred for characterization and detailed analysis of sulphur compounds in petroleum fractions, more preferably in gasoline, kerosene and HSD fuels.
  • Specific detectors can be selected from the group of flame photometric detector (FPD), atomic emission detector (AED) or sulphur chemiluminescence detector (SCD).
  • FPD flame photometric detector
  • AED atomic emission detector
  • SCD sulphur chemiluminescence detector
  • SCD sulphur chemiluminescence detector
  • GC-SCD technique The potential utility of GC-SCD technique was witnessed as it is capable of sorting out the different sulphur compounds such as mercaptans, aliphatic sulfides, cyclic sulfides and thiophenic compounds according to their structural organization, polarity and boiling point.
  • the first embodiment comprises the homogeneous mixing of gasoline and kerosene with concentration as low as 0.5 vol% of kerosene or above.
  • diesel also mixed with kerosene with concentration ranging from 0.5 vol% and above.
  • the inherent sulphur molecules present in neat kerosene and kerosene adulterated gasoline or diesel fuel were tracked employing gas chromatography embedded with SCD. The method unveils the presence of characteristic inherent sulphur compounds in kerosene adulterated fuel samples.
  • known volume of neat gasoline or diesel fuels and kerosene adulterated fuels are injected into GC equipped with SCD under the stated operating conditions.
  • the GC- SCD profiles reveal the distribution of different sulphur compounds in neat and kerosene adulterated fuels.
  • the GC-SCD profile displayed various peaks eluted in accordance with increase of boiling point and polarity, and each peak is attributed to unique sulphur compounds existing in hydrocarbon fuel.
  • the GC-SCD profile of neat kerosene fuel showed the characteristic peaks distributed in the range of 2-10 min of retention time.
  • a series of 1 to 3 vol% or more concentration of kerosene were mixed with gasoline and diesel and ensured the fuel blend is uniformly homogenized.
  • the resultant fuel composite was further characterized by GC-SCD in order to know the sulphur speciation pattern.
  • the key feature of this invention is tracking of inherent sulphur molecules, namely benzothiophene and substituted benzothiophene molecules and the mixture thereof in kerosene adulterated grade gasoline and diesel fuels, as these sulphur molecules are invariably present in the neat kerosene. Therefore one can detect the adulteration in the fuel like gasoline and diesel by tracking benzothiophene and substituted benzothiophene molecules applying the aforesaid methodology.
  • a neat kerosene fuel (1200 ppm of sulphur) has been used as adulterant for gasoline and diesel fuel.
  • the said kerosene fuel is characterized by Gas chromatography embedded with sulphur chemiluminescence detector (GC-SCD) in order to know the distribution of various characteristic sulphur compounds.
  • GC-SCD Gas chromatography embedded with sulphur chemiluminescence detector
  • the GC-SCD profile of neat kerosene fuel shown in Fig 2a and 3a which reveals the presence of characteristic peaks, which are attributed to the presence of thiophenes and benzothiophenes including mono, di and tri- methyl substituted isomers of benzothiophenes and their mixture thereof besides various other sulphur compounds.
  • a neat diesel fuel (25 ppm of sulphur) is characterized by GC-SCD technique to know the type of sulphur compounds distribution.
  • the resulted GC profiles of diesel (Fig 3b) fuels had shown no characteristic peaks pertinent to benzothiophenes including mono, di and tri methyl substituted benzothiophenes components and their mixtures in the range of 5-10 min of retention times.
  • the absence of these characteristic peaks pertinent to benzothiophene molecules in diesel fuels is due to effect of diesel hydrotreating process.
  • lvol% and 3vol% of kerosene is mixed with 99vol% and 97vol% of gasoline fuel and resulted fuel blend is characterized by GC-SCD.
  • GC-SCD profile (Fig 2c & 2d) of both 1 vol% and 3 vol% of kerosene adulterated gasoline fuel has shown the presence of well-defined characteristic peaks pertinent to mono, di and tri methyl benzothiophenes in range of retention times of 5 to 10 min as depicted in figure 3c.
  • intensity of peak pertinent to said benzothiophene molecules increased marginally in case of 3vol% kerosene in gasoline as compared to lvol% of kerosene content in gasoline.
  • lvol% and 3vol% of kerosene fuel is mixed with neat low sulphur diesel (25ppm of sulphur) and then ensured the fuel mixture is well homogenized.
  • the resulted fuel blend is characterized by GC-SCD in order to know the sulphur distribution. It is noteworthy to mention here that, GC-SCD profiles (Fig 3c & 3d) shown the discernible peaks is in the range of 5-10 min of retention times, and these peaks are attributed due to presence of mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures. Therefore, the presence of characteristic peaks is due to effect of kerosene addition to diesel fuel. In addition, molecular intensity of peak pertinent to said benzothiophenes increased marginally in case of 3 vol% kerosene in diesel as compared to 1 vol% of kerosene content in diesel.
  • kerosene fuel 0.5vol%, lvol%, 3vol% and 5vol% of kerosene fuel is mixed with neat high sulphur diesel (65 ppm of sulphur) and then ensured the fuel mixture is well homogenized.
  • the resulted fuel blend is characterized by GC-SCD in order to know the sulphur distribution. It is noteworthy to mention here that, GC-SCD profiles (Fig 4) showed that the discernible peaks is in the range of 5-10 min of retention times, and these peaks are attributed due to presence of mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures thereof. Therefore, the presence of characteristic peaks is due to effect of kerosene addition to diesel fuel. In addition, molecular peak intensity pertinent to said benzothiophenes increased marginally with increase of kerosene concentration in diesel.
  • the resultant acid and base treated kerosene fuel subsequently analyzed by GC-SCD in order to know the concentrations of benzothiophenes (BTs).
  • BTs benzothiophenes
  • the said kerosene fuel (100 ml) is added to 5 g of activated charcoal and clay in separate beakers. Then fuel solutions are kept under stirring for 1 h, further kerosene fuel is filtered. The resultant activated charcoal and clay treated kerosene fuel subsequently analyzed by GC-SCD in order to know the concentrations of BTs.
  • the GC-SCD profiles indicates that there is no significant laundering of benzothiophenes (BTs) observed (Fig 5).

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Abstract

The present invention provides a method to detect kerosene adulteration in gasoline, motor spirit, aviation turbine fuel or diesel by tracking intrinsic sulphur molecule with the help of gas chromatography and analysis of sulphur compounds in petroleum fractions.

Description

METHODOLOGY FOR DETECTION OF KEROSENE ADULTERATION IN
GASOLINE, MOTOR SPIRIT, AVIATION TURBINE FUEL AND DIESEL WITH
INTRINSIC MARKER
FIELD OF THE INVENTION
The present invention relates to a method for detection of kerosene adulteration in gasoline, motor spirit, aviation turbine fuel or diesei. More particularly the invention relates to a method of detection of kerosene content in gasoline or motor spirit, aviation turbine fuel or diesei in the concentration range of 0.5vol% or above by tracking intrinsic sulfur molecule/molecules.
BACKGROUND OF THE INVENTION
All over the globe, oil firms are putting enormous investments to produce the fuels such as gasoline, aviation turbine fuel, diesei etc. meeting the desired quality. However, fuel adulteration at the sales point has become an acute problem all over the world. Fuel adulteration is mixing of low premium fuel, i.e. kerosene with high premium fuel, such as gasoline or diesei, resulting in the deterioration of the fuel quality. In addition, it further impedes the engines performance and other internals, eventually engine life minimizes. Fuel adulteration also causes to increase the pollution as it results in emissions of hydrocarbon and sulfur. The major reason behind this malpractice is the substantial fuel price differential between kerosene and gasoline and diesei.
Adulteration of fuel has been wide spread all over the globe, which swindle the customers out of what they are paying for regular grade premium products. In addition, governments and oil firms have incurred massive losses of their revenues due to fuel adulteration. Therefore, a suitable and efficient method to detect adulteration of fuel has become necessary.
Globally, many efforts have been made by various researchers to develop method for detection of fuel adulteration, one of them being introduction of a chemical marker into the fuel and thereafter determining its concentration by physicochemical or spectroscopic methods. Few of prominent references are described below. Canada Patent No. 2773774 described the method of using azadipyrromethene dyes in petroleum product as covert dye in fuels and then ascertaining its presence by spectroscopy. US Patent No, 5358873 described the method to detect gasoline adulteration by using Rhodamine B base as marker dye. The method unveiled the fuel adulteration if gasoline containing dye is mixed with any undesired fuel followed by treating with silica, turns into red color.
US Patent No. 5229298 disclosed the method of analyzing the concentration of nitrogen bearing marker dye in liquid fuels selected from the group consisting of l-(4-morphiolino)-3-alpha- napthylamino-propane and l-(4-morpholino)-3-beta naptliylamino-propane. The concentration of marker is further analyzed by gas chromatography equipped with nitrogen phosphorescence detector.
US5958780 patent disclosed the method of introducing miscible markers into gasoline or other oil byproducts, and subsequently analyzing the concentration of the marker by absorption spectrometry.
US2010305885 patent application disclosed a method to detect the fuel adulteration by transmitting wireless signals into bottom of fuel tank. The returned wireless signals reflected off a bottom of the tank are received to determine whether the material has been adulterated using the level of the material in the tank.
US20100208243 patent disclosed the optical sensing system for identifying various types of liquid fuels based on refractive index principle of liquid fuels. A light source is transmitted acutely onto optical fiber which is in contact with the fuel to the test probe. The resulting optical signal derived from the interaction between light and fuel is a function of refractive indexes of the optical fiber and the fuel, the wavelength of light used and the fuel temperature. The method has only discussed the detection of gasoline and diesel adulteration with ethanol and biodiesel respectively. However, the method has not disclosed gasoline or diesel adulteration with kerosene fuel. Further, the disclosed method is applicable for high volumetric ratios of over 5% adulteration. The marker involved in the above disclosed methods require the doping of chemical markers into the fuel so that the concentration of marker may be measured by using appropriate spectroscopic methods. Although marker protocols appears to be promising for detection of fuel adulteration, nevertheless utility of marker protocols are limited because of various shortcomings associated with marker such as high cost of preparation, high polarity, ability to be tampered or removed from the fuel.
Therefore it is desirable to present a suitable method for detection of fuel adulteration in a cost effective manner and also for detection of lower levels of adulterant. SUMMARY OF THE INVENTION
The present invention provides a method to detect kerosene adulteration in gasoline, motor spirit, aviation turbine fuel or diesei by tracking intrinsic sulfur molecules with the help of gas chromatography and analysis of sulfur compounds in petroleum fractions.
The present invention provides a method for detection of kerosene adulteration in gasoline, motor spirit and diesei by tracking of inherent characteristic molecules of kerosene, preferably intrinsic sulfur molecules.
The present invention provides a method for detecting kerosene adulteration in gasoline, motor spirit, aviation turbine fuel, or diesei fuel, wherein the method comprises detecting the presence of sulfur molecules in the fuel by gas chromatography and measuring the peaks, wherein the presence of discernible peaks in the range of 5-10 minutes of retention time indicates the adulteration of fuel by kerosene. The term 'discernible peaks' refers to the peaks which are attributed to the 'intrinsic sulphur molecules* of kerosene.
In one specific aspect, the sulphur molecules showing peaks in the range of 5-10 minutes of retention time are selected from thiophenes, substituted thiophenes, benzothiophenes, mono, di and tri alkyl substituted benzothiophenes and their isomeric mixtures. In an aspect the intrinsic sulphur molecules are tracked by gas chromatography.
In another aspect the gas chromatography is selected from sulphur chemiluminiscence detector, atomic emission detector, flame photometric detector or pulsed flame photometric detector.
In another aspect the sulphur molecules are tracked by gas chromatography with or without mass spectroscopy. In the present invention, the sulphur molecules that are detected are selected from thiophenes, substituted thiophenes, benzothiophenes, mono, di and tri alkyl substituted benzothiophenes and their isomeric mixture thereof. In a specific aspect of the present invention, the mono-, di- and tri- methyl benzothiophenes present inherently in kerosene are detected.
In still another aspect, the concentration of inherent sulphur molecules present in kerosene ranges from 1000-2500 ppm.
The process of the present invention detects kerosene adulteration to as low as 0.5 vol % of kerosene or above.
In a specific aspect of the present invention, the GC-SCD profile peak is observed in 5-6 min, 6.5-7.5 min and 8- 9.5 min for detecting the intrinsic sulphur molecules namely mono-, di- and tri- substituted methyl benzothiophenes, respectively.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
Fig 1 : Sulphur molecular distribution in various petroleum fractions; (Source; C. Song, Catalysis Today 86 (2003) 211)
Fig 2: GC-SCD profiles of gasoline, gasoline-kerosene blend and neat kerosene fuels;
Fig 3: GC-SCD profiles of kerosene adulterated low sulphur diesel fuels;
Fig 4: GC-SCD profiles of Kerosene adulterated high sulphur Diesel fuels;
Fig 5: GC-SCD profile of acid, base and adsorbent treated kerosene fuel
DETAILED DESCRIPTION OF THE INVENTION
The present invention discloses a method to detect the kerosene content in gasoline, motor spirit, aviation turbine fuel or diesel in the concentration of 0.5vol% or above by tracking intrinsic sulphur molecules. The term 'intrinsic sulphur molecules" refers to the sulphur containing molecules that are invariably present in kerosene in detectable amount, and are not present in premium fuels like gasoline, motor spirit, aviation turbine fuel or diesel in detectable amount. The method relates to detection of intrinsic sulphur molecules which are invariably present in kerosene selected from a group comprising of thiophene, substituted thiophenes, benzothiophene, mono and di and tri substituted alkyl benzothiophenes, dibenzo thiophene, and mixture thereof.
These intrinsic organo sulphur molecules are present in kerosene fuel in wide range of concentrations i.e. from 1000-2500 ppm. Fig. 1 illustrates group of typical sulphur molecules present in various petroleum fractions such as gasoline, kerosene and diesel. The sulphur molecules are present in sourced crude oils and get distributed in various petroleum fractions according to their boiling points during the process of crude distillation.
Among the petroleum fractions, gasoline and diesel fractions are used for transportation purpose. Therefore, sulphur and nitrogen content in these fuels is regulated by the pollution control. Accordingly, oil refineries are adopting various catalytic processes to curtail the sulphur and nitrogen emissions. Of several treatments, catalytic hydro treatment is identified as one of notable process for removal of hetero atoms such as S, N and O in gasoline, diesel and aviation fuel. The total sulphur content of petrol and diesel is mostly in the range of 500 ppm to 10 ppm maximum across the globe, which is due to the effect of hydrotreating process.
On the other hand kerosene, which is not used for transportation purposes, has total sulphur content in the range of 1000-2500 ppm, especially in India. The presence of these sulphur molecules have been exploited for the detection of adulteration by kerosene in Gasoline or other fuel. Further, the detection method involves the tracking of the aforesaid molecules in adulterated fuels employing gas chromatography with or without mass spectroscopy. The gas chromatography preferably operates with Sulphur Chemiluminescence Detector (SCD), flame photometry, Pulsed Flame Photometry Detector (PFPD) or using electrochemical detector. In the disclosed invention gasoline, aviation turbine fuel and diesel that are produced by hydrotreatment or hydrodesulphurization process are the fuels for which the process of the present invention would be useful in detecting kerosene adulteration.
Gas chromatography with specific detector has been preferred for characterization and detailed analysis of sulphur compounds in petroleum fractions, more preferably in gasoline, kerosene and HSD fuels. Specific detectors can be selected from the group of flame photometric detector (FPD), atomic emission detector (AED) or sulphur chemiluminescence detector (SCD). Of these, SCD is widely used for the analysis of sulphur compounds in petroleum fuels because of its linearity, equimolar response to all kind of sulphur molecules, as well as its excellent sensitivity and selectivity as hydrocarbon interference is negligible. The potential utility of GC-SCD technique was witnessed as it is capable of sorting out the different sulphur compounds such as mercaptans, aliphatic sulfides, cyclic sulfides and thiophenic compounds according to their structural organization, polarity and boiling point.
The first embodiment comprises the homogeneous mixing of gasoline and kerosene with concentration as low as 0.5 vol% of kerosene or above. Similarly diesel also mixed with kerosene with concentration ranging from 0.5 vol% and above. The inherent sulphur molecules present in neat kerosene and kerosene adulterated gasoline or diesel fuel were tracked employing gas chromatography embedded with SCD. The method unveils the presence of characteristic inherent sulphur compounds in kerosene adulterated fuel samples.
In another embodiment, known volume of neat gasoline or diesel fuels and kerosene adulterated fuels are injected into GC equipped with SCD under the stated operating conditions. The GC- SCD profiles (Fig 2 and 3) reveal the distribution of different sulphur compounds in neat and kerosene adulterated fuels. The GC-SCD profile displayed various peaks eluted in accordance with increase of boiling point and polarity, and each peak is attributed to unique sulphur compounds existing in hydrocarbon fuel. The GC-SCD profile of neat kerosene fuel showed the characteristic peaks distributed in the range of 2-10 min of retention time. A close look at these profiles reveals that, discernible peaks appeared in 5-6 min, 6.5-7.5 min and 8-9.5 min of retention times, attributed to mono, di and tri substituted methyl benzothiophenes, respectively. The appearance of these specific sulphur compounds in kerosene is obvious as total sulphur in kerosene would be around 1000-2500 ppm. On the other hand, no discernible peaks observed in the range of 5-10 min of retention times in both neat gasoline and diesel fuels evidencing the absence of mono, di and tri methyl substituted benzothiophenes. The absence of these characteristic peaks is obvious in gasoline and diesel fuels, which is due to the effect of hydro treating process.
In another embodiment, a series of 1 to 3 vol% or more concentration of kerosene were mixed with gasoline and diesel and ensured the fuel blend is uniformly homogenized. The resultant fuel composite was further characterized by GC-SCD in order to know the sulphur speciation pattern. These profiles further demonstrated that, characteristic peaks pertinent to thiophene and benzothiophene were apparently displayed in all concentrations of kerosene mixed gasoline and diesel fuels, albeit with different intensities. It is noteworthy that, the appearance of thiophene and benzothiophene peaks in the range of 5-10 min of retention times in adulterated gasoline and diesel fuel is evident of the gasoline or diesel fuel being adulterated with kerosene. The key feature of this invention is tracking of inherent sulphur molecules, namely benzothiophene and substituted benzothiophene molecules and the mixture thereof in kerosene adulterated grade gasoline and diesel fuels, as these sulphur molecules are invariably present in the neat kerosene. Therefore one can detect the adulteration in the fuel like gasoline and diesel by tracking benzothiophene and substituted benzothiophene molecules applying the aforesaid methodology.
The detection of kerosene content in gasoline or diesel is detected in most reliable manner through this methodology. Moreover, the method is amicable and facile, and requires small quantity of fuel. The relative peak intensity of distinctive sulphur molecule in adulterated gasoline and diesel to the same in neat kerosene would imply the scale of fuel adulteration. The following examples are given by way of illustration and should not be construed to limit the scope of the present invention.
Example 1:
1. A neat kerosene fuel (1200 ppm of sulphur) has been used as adulterant for gasoline and diesel fuel. The said kerosene fuel is characterized by Gas chromatography embedded with sulphur chemiluminescence detector (GC-SCD) in order to know the distribution of various characteristic sulphur compounds. The GC-SCD profile of neat kerosene fuel shown in Fig 2a and 3a, which reveals the presence of characteristic peaks, which are attributed to the presence of thiophenes and benzothiophenes including mono, di and tri- methyl substituted isomers of benzothiophenes and their mixture thereof besides various other sulphur compounds. Furthermore, the characteristic peaks pertinent to above said benzothiophenes including mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures displayed in the range of 5 to 10 min of retention times. A neat gasoline fuel (15 ppm of sulphur) analyzed by GC-SCD technique in order to know the distribution of various typical molecules, preferably sulphur molecules. The resulted GC profiles of neat gasoline fuel (Fig 2b), unlike in kerosene, had shown no discernible peaks pertinent to benzothiophenes including mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures in the range of 5-10 min of retention time. The commercial gasoline available is made available in open market only after being treated by various processes in refinery like hydrotreating and therefore mono, di and tri substituted benzothiophenes are virtually absent in gasoline.
A neat diesel fuel (25 ppm of sulphur) is characterized by GC-SCD technique to know the type of sulphur compounds distribution. The resulted GC profiles of diesel (Fig 3b) fuels had shown no characteristic peaks pertinent to benzothiophenes including mono, di and tri methyl substituted benzothiophenes components and their mixtures in the range of 5-10 min of retention times. The absence of these characteristic peaks pertinent to benzothiophene molecules in diesel fuels is due to effect of diesel hydrotreating process. lvol% and 3vol% of kerosene is mixed with 99vol% and 97vol% of gasoline fuel and resulted fuel blend is characterized by GC-SCD. It is noteworthy to mention here that, GC-SCD profile (Fig 2c & 2d) of both 1 vol% and 3 vol% of kerosene adulterated gasoline fuel has shown the presence of well-defined characteristic peaks pertinent to mono, di and tri methyl benzothiophenes in range of retention times of 5 to 10 min as depicted in figure 3c. The presence of peaks pertinent to benzothiophenes indicates that gasoline fuel is adulterated by kerosene. Whereas gasoline fuel does not have characteristic peaks in the said retention time range (Fig 2a). in addition, intensity of peak pertinent to said benzothiophene molecules increased marginally in case of 3vol% kerosene in gasoline as compared to lvol% of kerosene content in gasoline.
lvol% and 3vol% of kerosene fuel is mixed with neat low sulphur diesel (25ppm of sulphur) and then ensured the fuel mixture is well homogenized. The resulted fuel blend is characterized by GC-SCD in order to know the sulphur distribution. It is noteworthy to mention here that, GC-SCD profiles (Fig 3c & 3d) shown the discernible peaks is in the range of 5-10 min of retention times, and these peaks are attributed due to presence of mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures. Therefore, the presence of characteristic peaks is due to effect of kerosene addition to diesel fuel. In addition, molecular intensity of peak pertinent to said benzothiophenes increased marginally in case of 3 vol% kerosene in diesel as compared to 1 vol% of kerosene content in diesel.
Example 2%
0.5vol%, lvol%, 3vol% and 5vol% of kerosene fuel is mixed with neat high sulphur diesel (65 ppm of sulphur) and then ensured the fuel mixture is well homogenized. The resulted fuel blend is characterized by GC-SCD in order to know the sulphur distribution. It is noteworthy to mention here that, GC-SCD profiles (Fig 4) showed that the discernible peaks is in the range of 5-10 min of retention times, and these peaks are attributed due to presence of mono, di and tri methyl substituted benzothiophenes and their isomeric mixtures thereof. Therefore, the presence of characteristic peaks is due to effect of kerosene addition to diesel fuel. In addition, molecular peak intensity pertinent to said benzothiophenes increased marginally with increase of kerosene concentration in diesel.
Example 3:
Laundering treatments on kerosene:
This is to demonstrate that the intrinsic markers are highly resistant to removal by typical laundering procedures involving treatment with various chemical reagents like HQ, H2SO4, HNO3, KOH. Moreover the surface adsorption tendency of the disclosed intrinsic markers on various notable adsorbents like activated carbon, clay etc. is found to be negligible which augments their potential application for detection of adulteration. a) The said kerosene fuel (100 ml) is treated with each 100 ml of 1M concentration of acids (HNO3, H2SO4) and base (KOH) by concomitant mixing of both solutions. The resultant fuel composite is kept under stirring for 1 h, further both aqueous and hydrocarbon phase were allowed to separate. The resultant acid and base treated kerosene fuel subsequently analyzed by GC-SCD in order to know the concentrations of benzothiophenes (BTs). The GC-SCD profiles reveal that there is no significant laundering of BTs observed in both acid and base treated kerosene fuel (Fig 5).
The said kerosene fuel (100 ml) is added to 5 g of activated charcoal and clay in separate beakers. Then fuel solutions are kept under stirring for 1 h, further kerosene fuel is filtered. The resultant activated charcoal and clay treated kerosene fuel subsequently analyzed by GC-SCD in order to know the concentrations of BTs. The GC-SCD profiles indicates that there is no significant laundering of benzothiophenes (BTs) observed (Fig 5).

Claims

We claim:
1. A method for detecting kerosene adulteration in gasoline, motor spirit, aviation turbine fuel, or diesel fuel, the method comprising detecting the presence of intrinsic sulphur molecules in the fuel by gas chromatography and measuring the peaks, wherein the presence of discernible peaks in the range of 5-10 minutes of retention time indicates the presence of kerosene adulteration.
2. The method as claimed in claim 1, wherein the gas chromatography is selected from sulphur chemiluminiscence detector, atomic emission detector, flame photometric detector or pulsed flame photometric detector.
3. The method as claimed in claim 2, wherein the gas chromatography is conducted with or without mass spectroscopy.
4. The method as claimed in claim 1 , wherein the intrinsic sulphur molecules showing peaks in the range of 5-10 minutes of retention time are thiophenes, substituted thiophenes, benzothiophenes, mono, di and tri alkyl substituted benzothiophenes or their isomeric mixtures.
5. The method as claimed in claim 1, wherein the intrinsic sulphur molecules present in kerosene are in the range from 1000-2500 ppm.
6. The method as claimed in claim 1, wherein the method detects kerosene adulteration as low as 0.5 vol % of kerosene or above.
7. The method as claimed in claim 1, wherein the discernible peaks are observed in 5-6 min, 6.5-7.5 min and 8-9.5 min of retention time in GC-SCD profile, detecting mono, di and tri substituted methyl benzothiophenes respectively.
PCT/IB2013/060654 2012-12-06 2013-12-05 Methodology for detection of kerosene adulteration in gasoline, motor spirit, aviation turbine fuel and diesel with intrinsic marker WO2014087359A1 (en)

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