NO325093B1 - Method and use in determining the amount of oil or condensate in water or in aqueous samples by means of an extractant - Google Patents
Method and use in determining the amount of oil or condensate in water or in aqueous samples by means of an extractant Download PDFInfo
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- NO325093B1 NO325093B1 NO20060530A NO20060530A NO325093B1 NO 325093 B1 NO325093 B1 NO 325093B1 NO 20060530 A NO20060530 A NO 20060530A NO 20060530 A NO20060530 A NO 20060530A NO 325093 B1 NO325093 B1 NO 325093B1
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- oil
- ftir
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- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 230000003595 spectral effect Effects 0.000 claims abstract description 19
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 13
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004566 IR spectroscopy Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000004587 chromatography analysis Methods 0.000 claims 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 abstract 1
- 238000012421 spiking Methods 0.000 abstract 1
- 238000010561 standard procedure Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 37
- 238000001228 spectrum Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000000513 principal component analysis Methods 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 238000002460 vibrational spectroscopy Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
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- 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
- G01N33/18—Water
- G01N33/1826—Water organic contamination in water
- G01N33/1833—Oil in water
-
- 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
-
- 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
- G01N2021/3595—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using FTIR
Abstract
Foreliggende oppfinnelse vedrører en metode for å benytte FTIR og et hydrokarbonbasert løsemiddel til å ekstrahere olje-/kondensatkomponenter fra vann eller en vandige prøve, oppkonsentrere ekstraktet, og deretter analysere dirkekte på FTIR. Oppfinnelsen har vist at det overraskende nok eksisterer ett eller flere selektive spektrale områder innen området 400-4000 cm-1 som er egnet for å kvantifisere mengde olje- /kondensat komponenter. Når disse er funnet, kan det utvikles kvantitative rutine metoder. Kalibrering kan skje enten ved å spike olje/kondensatfrie vannprøver, eller ved hjelp av nesten tilsvarende standard addisjon på reelle prosessprøver, eller ved å kalibrere opp mot standardmetoder.The present invention relates to a method of using FTIR and a hydrocarbon-based solvent to extract oil / condensate components from water or an aqueous sample, concentrate the extract, and then analyze direct on FTIR. The invention has shown that, surprisingly, one or more selective spectral ranges exist in the range of 400-4000 cm -1 which are suitable for quantifying the amount of oil / condensate components. Once these are found, quantitative routine methods can be developed. Calibration can be done either by spiking oil / condensate-free water samples, or by using almost equivalent standard addition to real process samples, or by calibrating against standard methods.
Description
Bestemmelse av olje i vann ved hjelp av spektroskopiske målemetoder krever først en ekstraksjon av oljekomponenter fra vannfase. Det stilles derfor krav til ekstraksjonsmiddelet at det skal være uløselig i vann, samtidig som det skal være egnet til å ekstrahere ut oljeløselige komponenter fra vannfasen. Dernest kreves en påfølgende toppkonsentrasjon vha f.eks inndampning. Ekstraksjonsmiddelet må derfor være relativt flyktig for at ekstraktet skal kunne dampes inn uten at for mye av oljekomponentene går tapt som følge av flyktighet. Etter oppkonsentrasjon av ekstraksjonsmiddelet er prøven klar for kvantitativ analyse vha vibrasjonsspektroskopi. Determination of oil in water using spectroscopic measurement methods first requires an extraction of oil components from the water phase. The extraction agent is therefore required to be insoluble in water, while at the same time being suitable for extracting oil-soluble components from the water phase. Next, a subsequent peak concentration is required using, for example, evaporation. The extractant must therefore be relatively volatile so that the extract can be evaporated without too much of the oil components being lost as a result of volatility. After concentration of the extractant, the sample is ready for quantitative analysis using vibrational spectroscopy.
Kombinasjon av freon (diklordifluorometan) som ekstraksjonsmiddel og såkalt Fourier ►Transformert Infra Rød spektroskopi (FTIR) er lenge vært en populær metode for kvantitativ analyse av olje i vann. Freon løser oljekomponentene svært bra, og gir ingen interferens på FTIR signalet i det interessante spektrale området. Dette muliggjør kvantitativ analyse av olje på FTIR selv om freon er tilstede i relativt store mengder. Problemet er at freon er ødeleggende for miljøet (ozonnedbrytende effekt), og er i dag •enten tatt ut av bruk eller under utfasing (Se f.eks, The Vienna convention for the protection of the ozone layer (2001), ISDN 92-807-2121-6). Combination of freon (dichlorodifluoromethane) as extraction agent and so-called Fourier Transformed Infrared spectroscopy (FTIR) has long been a popular method for quantitative analysis of oil in water. Freon dissolves the oil components very well, and does not interfere with the FTIR signal in the interesting spectral range. This enables quantitative analysis of oil on FTIR even if freon is present in relatively large quantities. The problem is that freon is destructive to the environment (ozone-depleting effect), and is today either taken out of use or being phased out (See, for example, The Vienna convention for the protection of the ozone layer (2001), ISDN 92-807 -2121-6).
Utfasing av freon og andre halogenholdige hydrokarboner som ekstraksjonsmiddel for olje-i-vann analyser har skapt et problem for bruk av vibrasjonsspektroskopisk kvantitativ (analyse. Det viser seg at gode og egnede ekstraksjonsmidler for å få oljekomponenter ut av vannfasen, også har kraftig interferens med oljekomponentene i den påfølgende vibrasjonsspektroskopiske analysen. Som eksempel; særlig egnet til ekstraksjon er lite eller mindre vannløselige oljekomponenter med kokepunkt over ca. 0°C og under ca. 170°C. Eksempler er butan, pentan, heksan, isooktan, sykloheksan og toluene. Et ekstrakt i med f.eks en av disse oljekomponenter vil imidlertid gi et så kraftig signal i en vibrasjonsspektroskopisk analyse, at den vil kamuflere helt de oljeholdige komponentene som er ekstrahert ut av vannfasen. Spesielt vil interferens inntreffe der løsningsmiddelets molekylære struktur inneholder en eller flere karbon-hydrogen bindinger, såkalte hydrokarboner. En kvantitativ analyse av oljeholdige komponenter i et slikt løsningsmiddel Ibasert på selektive spektrale områder er derfor, ut i fra lærebøker i spektroskopi og den generelle oppfatning i fagmiljøer, å anse som umulig. Av denne grunn tilrådes bestandig 100% inndampning av hydrokarbonløsemidler, før den spektroskopiske analysen. Et eksempel på en slik analysator er beskrevet av Wilks Enterprise for deres TOG/TPH analysator (www.wilksir.com). The phasing out of freon and other halogen-containing hydrocarbons as extractants for oil-in-water analyzes has created a problem for the use of vibrational spectroscopic quantitative (analysis. It turns out that good and suitable extractants for getting oil components out of the water phase also have strong interference with the oil components in the subsequent vibrational spectroscopic analysis. As an example, particularly suitable for extraction are little or less water-soluble oil components with a boiling point above about 0°C and below about 170°C. Examples are butane, pentane, hexane, isooctane, cyclohexane and toluene. A extract with, for example, one of these oil components will, however, give such a strong signal in a vibrational spectroscopic analysis that it will completely camouflage the oily components that have been extracted from the water phase. In particular, interference will occur where the molecular structure of the solvent contains one or more carbons -hydrogen bonds, so-called hydrocarbons A quantitative analysis of oily components of such a solvent based on selective spectral ranges is therefore, based on textbooks in spectroscopy and the general opinion in professional circles, to be considered impossible. For this reason, 100% evaporation of hydrocarbon solvents is always recommended before the spectroscopic analysis. An example of such an analyzer is described by Wilks Enterprise for their TOG/TPH analyzer (www.wilksir.com).
Hovedformålet med foreliggende oppfinnelse er todelt; 1) å undersøke om det eksisterer spektrale områder hvor det kan finnes selektiv innformasjon om andre oljekomponenter enn det hydrokarbonbaserte løsningsmiddelet, 2) dernest eventuelt å undersøke om det selektive området kan brukes til å kvantifisere oljekomponenter vha FTIR spektroskopi i selv om det hydrokarbonholdige ekstraksjonsmiddelet er tilstede i prøvecellen. The main purpose of the present invention is twofold; 1) to investigate whether there exist spectral areas where selective information can be found about oil components other than the hydrocarbon-based solvent, 2) next, possibly to investigate whether the selective area can be used to quantify oil components using FTIR spectroscopy even if the hydrocarbon-containing extractant is present in the sample cell.
For å undersøke om det fantes selektiv spektral informasjon ble en råolje fra Nordsjøen løst i destillert vann, tilnærmet (men nøyaktig) 10,20,30, 50,70, og 90 mg råolje per liter vann. Deretter ble 30 ml isooktan tilsatt hver vannprøve, blandingen ble ristet og lisooktanfasen ble separert fra vannfasen. Isooktanfasen ble dampet inn til nøyaktig 2 ml, og analysert på et FTIR instrument. De spektrale data ble importert til programvaren MUST Analyze! (www.must.as). De ble benyttet i en tradisjonell multivariatstatistisk metode som prinsipal komponent analyse for å lete etter selektive spektrale områder. Foruten å gjenta forsøkene og på forskjellige konsentrasjonsnivå, ble forsøkene også i verifisert ved å gjenta eksperimentene med et lyst og lett kondensat fra Nordsjøen. To investigate whether there was selective spectral information, a crude oil from the North Sea was dissolved in distilled water, approximately (but exactly) 10, 20, 30, 50, 70, and 90 mg of crude oil per liter of water. Then 30 ml of isooctane was added to each water sample, the mixture was shaken and the isooctane phase was separated from the water phase. The isooctane phase was evaporated to exactly 2 ml, and analyzed on an FTIR instrument. The spectral data were imported into the software MUST Analyze! (www.must.as). They were used in a traditional multivariate statistical method as principal component analysis to look for selective spectral areas. Besides repeating the experiments and at different concentration levels, the experiments were also verified by repeating the experiments with a bright and light condensate from the North Sea.
Begge serier av eksperimenter gav meget overraskende og gode resultater, ved at vi påviste et spektral selektivt område for oljekomponenter. Noe slikt som et selektivt spektralt område i FTIR for oljekomponenter med et hydrokarbonbasert løsningsmiddel tilstede i prøvecellen, er hittil ikke omtalt i litteraturen. Vi fant i tillegg meget gode kvantitative Both series of experiments gave very surprising and good results, in that we demonstrated a spectrally selective area for oil components. Something like a selective spectral range in FTIR for oil components with a hydrocarbon-based solvent present in the sample cell has not yet been discussed in the literature. We also found very good quantitative ones
•sammenhenger mellom størrelsen på signalet i disse spektrale områdene og mengde av oljekomponenter (råolje eller kondensat) som ble tilsatt vannprøvene. De to eksemplene beskrevet under forteller konkret hva som ble gjort, og hvordan dette løste problemene med kvantifisering av oljekomponenter vha FTIR spektroskopi, når •oljekomponentene er løst i et karbon-hydrogen holdig løsningsmiddel. Beskyttelsesomfanget og de spesielle trekk ved oppfinnelsen er som definert i de tilknyttede patentkrav. •correlation between the size of the signal in these spectral areas and the amount of oil components (crude oil or condensate) that were added to the water samples. The two examples described below tell concretely what was done, and how this solved the problems with quantification of oil components using FTIR spectroscopy, when • the oil components are dissolved in a carbon-hydrogen containing solvent. The scope of protection and the special features of the invention are as defined in the associated patent claims.
Hovedtrekket ifølge oppfinnelsen er kvantitativ bestemmelse av oljekomponenter vha IFTIR, når oljekomponentene er tilstede i et løsningsmiddel som inkluderer en eller flere hydrokarboner. The main feature according to the invention is the quantitative determination of oil components using IFTIR, when the oil components are present in a solvent that includes one or more hydrocarbons.
Et spesielt trekk ved oppfinnelsen er at den inkluderer kvantifisering av så vel lyse lette kondensat til tyngre mørke oljer. Oppfinnelsen er ytterligere forklart i forbindelse med i følgende eksempler, ett for olje og ett for kondensat. Begge prøvetyper ble opparbeidet som beskrevet over, og analysert på FTIR (0,1 med mer NaCl celle) i isooktan ekstrakt nøyaktig inndampet til 2ml. Alle spektrale data med intensiteter fra alle bølgelengder i området 400 - 4000 cm"' ble analysert. A special feature of the invention is that it includes quantification of light light condensates as well as heavier dark oils. The invention is further explained in connection with in the following examples, one for oil and one for condensate. Both sample types were processed as described above, and analyzed on FTIR (0.1 with more NaCl cell) in isooctane extract precisely evaporated to 2ml. All spectral data with intensities from all wavelengths in the range 400 - 4000 cm"' were analyzed.
Eksempel 1 Example 1
Figur 1 viser spektra fra analyser av de åtte prøvene med oljekomponenter, samt de to rene (spektra av isooktan. Som vi ser fra Figur 1, synes det ikke som om det er forskjeller mellom prøvene. Med andre ord synes det som om den kvantitative informasjonen om oljekomponentene drukner i signalet fra løsemiddelet isooktan i hele det undersøkte spektrale området, som forventet fra lærebøker i spektroskopi. Figure 1 shows spectra from analyzes of the eight samples with oil components, as well as the two pure (spectra of isooctane. As we can see from Figure 1, it does not seem as if there are differences between the samples. In other words, it seems that the quantitative information whether the oil components drown in the signal from the solvent iso-octane in the entire investigated spectral range, as expected from textbooks in spectroscopy.
Overraskende nok, fant vi ved hjelp av prinsipal komponent analyse at det likevel var •systematiske forkjeller mellom prøvene i det spektrale området som svarer til f.eks ca. 650 -1120 cm"'. Dette er vist i Figur 2. En av isooktan-spekterene (oljekomponenter = 0 ppm) er markert med sort stiplet linje, sammen med spekteret av mengde oljekomponenter svarende til 92 ppm olje. Som vi ser faller alle de øvrige prøvene innefor disse to, samtidig som det er en tendens til at jo mer olje i vann i prøven, jo høyere signal. Surprisingly enough, we found with the help of principal component analysis that there were still •systematic differences between the samples in the spectral range which corresponds to, for example, approx. 650 -1120 cm"'. This is shown in Figure 2. One of the iso-octane spectra (oil components = 0 ppm) is marked with a black dotted line, together with the spectrum of the amount of oil components corresponding to 92 ppm oil. As we can see, all the other samples within these two, while there is a tendency for the more oil in water in the sample, the higher the signal.
( (
Ved å plotte signalet mot konsentrasjon, får vi en kalibreringslinje som vist i Figur 3. En R<2>på hele 0,996 tilsier en meget god og lineær modell. By plotting the signal against concentration, we get a calibration line as shown in Figure 3. An R<2> of a whopping 0.996 indicates a very good and linear model.
Overraskende nok var det flere lokale områder innenfor det spektrale området 400-4000 •cm"<1>, som viste selektivitet på lik linje som det som her er vist for det spektrale området på ca. 650 - 1120 cm*<1>. Vi viser ikke alle områdene her, men konkluderer med at det er fullt mulig å finne kvantitativ informasjon på oljekomponenter fra FTIR spektra, selv om det brukes hydrokarboner som løsningsmiddel. Surprisingly, there were several local areas within the spectral range 400-4000 •cm"<1>, which showed selectivity similar to that shown here for the spectral range of approximately 650 - 1120 cm*<1>. We does not show all the areas here, but concludes that it is entirely possible to find quantitative information on oil components from FTIR spectra, even if hydrocarbons are used as solvent.
Eksempel 2 Example 2
Forsøket som beskrevet for Nordsjøoljen, ble gjentatt på et lyst kondensat fra Nordsjøen. Spektra som viser hele prøvene er identisk med det som er vist for isooktan og olje i Figur il, og vises ikke her. På samme måte som for spektrene fra oljeeksperimentene, ble disse analysert vha ordinær prinsipal komponent analyse. Igjen ble oppfinner overrasket over den gode selektiviteten i området svarende til ca. 650 - 1120 cm'<1>. Som for spektra fra oljekomponenter i isooktan, ble det også påvist andre selektive områder mellom 400-4000 cm'<1>helt i strid med hva som står beskrevet i lærebøker. Figur 4 viser den kvantitative (informasjonen fra det selektive området svarende til ca. 650 - 1120 cm<1>. Figur 5 viser at ved å plotte signalet mot konsentrasjon, får vi en meget god og lineær modell (R<2>på hele 0,967). The experiment as described for North Sea oil was repeated on a light condensate from the North Sea. Spectra showing the entire samples are identical to that shown for isooctane and oil in Figure 11, and are not shown here. In the same way as for the spectra from the oil experiments, these were analyzed using ordinary principal component analysis. Again, the inventor was surprised by the good selectivity in the area corresponding to approx. 650 - 1120 cm'<1>. As for spectra from oil components in isooctane, other selective areas between 400-4000 cm'<1> were also detected, completely contrary to what is described in textbooks. Figure 4 shows the quantitative information from the selective range corresponding to approx. 650 - 1120 cm<1>. Figure 5 shows that by plotting the signal against concentration, we get a very good and linear model (R<2> of a whopping 0.967 ).
De to eksemplene viser overraskende nok at det er fullt ut mulig å identifisere selektive iområder for olje- og kondensatområder i FTIR spektra, selv om det benyttes hydrokarboner som ekstraksjonsmiddel og løsemiddel for FTIR instrumentet. The two examples surprisingly show that it is entirely possible to identify selective areas for oil and condensate areas in the FTIR spectra, even if hydrocarbons are used as extraction agent and solvent for the FTIR instrument.
Videre viser beskrivelsen i dette patentet at det er relativt enkelt å utvikle kvantitative modeller når de selektive områdene først er bestemt. Vi har vist slike modeller i en enkelt (form, ved å velge snitt signal ved 727 cm"<1>±10 bølgelengder uten noen form for forbehandling av spektra. Forsøk viser at det kan oppnås langt mer robuste og presise metoder vha egnede forbehandlingsmetoder av spektra i kombinasjon med mulitvariate regresjonsmetoder. Dog er dette ikke vist her, da poenget med denne oppfinnelsen er å vise at det overraskende nok finnes selektivitet ved olje-/kondensat analyser på FTIR selv om idet benyttes hydrokarboner som ekstraksjons og løsningsmiddel. Videre viser oppfinnelsen at disse selektive områdene er egnet til å hente ut kvantitativ informasjon om olje-/ kondensatkomponenter i området 0-100 ppm. Furthermore, the description in this patent shows that it is relatively easy to develop quantitative models once the selective areas have been determined. We have shown such models in a single (form, by choosing the average signal at 727 cm"<1>±10 wavelengths without any form of pre-processing of the spectra. Experiments show that far more robust and precise methods can be achieved using suitable pre-processing methods of spectra in combination with multivariate regression methods. However, this is not shown here, as the point of this invention is to show that, surprisingly enough, there is selectivity in oil/condensate analyzes on FTIR even though hydrocarbons are used as extraction and solvent. Furthermore, the invention shows that these selective areas are suitable for extracting quantitative information about oil/condensate components in the range 0-100 ppm.
I praktisk bruk bør først olje/kondensat prøver først analyseres på et FTIR instrument med den beskrevne metode, for å bestemme optimalt område for kvantifisering. Det kan da ►velges et eller flere områder mellom 400 - 4000 cm-1, og gjerne en multivariat metode for å optimal presisjon og mest mulig robusthet. Deretter bør det lages en kalibreringsmodell hvor metoden videremodifiseres og kalibreres mot en godkjent/validert metode som f.eks In practical use, oil/condensate samples should first be analyzed on an FTIR instrument with the described method, in order to determine the optimal range for quantification. ►One or more areas between 400 - 4000 cm-1 can then be selected, and preferably a multivariate method for optimal precision and the greatest possible robustness. A calibration model should then be created where the method is further modified and calibrated against an approved/validated method such as
GC-FID. GC-FID.
Vi har vist oppfinnelsens muligheter til kvantitativ bestemmelse ved å bruke isooktan som iekstraksjons- og løsningsmiddel for FTIR. Isookan er en 100% forgrenet parafin (dvs molekylet innholder ikke noen rettkjedete -CH2-CH2- fragment), så de overraskende selektive signalene vi observerer i de spektrale områder kommer mest sannsynlig fra komponenter i olje-kondensat som ikke er 100% forgrenete parafiner. Tilsvarende vil vi nok få andre selektive områder om det benyttes heksan, sykloheksan eller toluen som løsningsmiddel. Dog har vi vist, at selv om det benyttes hydrokarboner som løsningsmiddel, så er det likevel overraskende nok mulig å identifisere selektive spektrale områder i et FTIR spekter. We have shown the possibilities of the invention for quantitative determination by using isooctane as extraction and solvent for FTIR. Isookan is a 100% branched paraffin (ie the molecule does not contain any straight-chain -CH2-CH2- fragment), so the surprisingly selective signals we observe in the spectral ranges most likely come from components in oil condensate that are not 100% branched paraffins. Correspondingly, we will probably get other selective areas if hexane, cyclohexane or toluene are used as solvent. However, we have shown that even if hydrocarbons are used as solvent, it is still surprisingly possible to identify selective spectral areas in an FTIR spectrum.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO20060530A NO325093B1 (en) | 2006-02-01 | 2006-02-01 | Method and use in determining the amount of oil or condensate in water or in aqueous samples by means of an extractant |
| PCT/NO2007/000029 WO2007089154A1 (en) | 2006-02-01 | 2007-01-29 | Method and application to determine the amount of oil or condensate in water or in water-based samples with the help of an extractive agent |
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| Application Number | Priority Date | Filing Date | Title |
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| NO20060530A NO325093B1 (en) | 2006-02-01 | 2006-02-01 | Method and use in determining the amount of oil or condensate in water or in aqueous samples by means of an extractant |
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| NO20060530L NO20060530L (en) | 2007-08-02 |
| NO325093B1 true NO325093B1 (en) | 2008-02-04 |
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| AT503665B1 (en) * | 2007-01-31 | 2007-12-15 | Jordan Philipp Mag | Determination of the concentration of hydrocarbons in samples e.g. water, comprises extracting the hydrocarbons from the sample with a solvent, and quantitatively measuring the hydrocarbons by infrared or near-infrared absorption |
| US7703527B2 (en) | 2007-11-26 | 2010-04-27 | Schlumberger Technology Corporation | Aqueous two-phase emulsion gel systems for zone isolation |
| GB2467124B (en) * | 2009-01-21 | 2011-04-27 | Schlumberger Holdings | Concentration of minor constituent of wellbore fluid |
| US9297747B2 (en) | 2013-07-18 | 2016-03-29 | Saudi Arabian Oil Company | Method to determine trace amounts of crude oil by spectroscopic absorption |
| CN104502301A (en) * | 2014-12-26 | 2015-04-08 | 北京伊普国际水务有限公司 | Method for determining oil in coal chemical engineering wastewater |
| DE102015104531A1 (en) * | 2015-03-25 | 2016-09-29 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | analyzer |
| JP2019143971A (en) * | 2016-05-18 | 2019-08-29 | 株式会社堀場製作所 | Oil content measuring method and oil content measuring apparatus |
| US10324077B2 (en) | 2017-03-09 | 2019-06-18 | Saudi Arabian Oil Company | Systems and methods for real-time spectrophotometric quantification of crude oil |
| AR116162A1 (en) * | 2019-04-17 | 2021-04-07 | Ypf Sa | METHOD FOR THE DETERMINATION OF THE CONCENTRATION OF OIL IN WATER |
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| US3118299A (en) * | 1964-01-21 | J-dimethylbutane | ||
| US2854396A (en) * | 1954-11-24 | 1958-09-30 | Jersey Prod Res Co | Petroleum prospecting |
| US3496350A (en) * | 1966-07-18 | 1970-02-17 | Mobil Oil Corp | Method of geochemical exploration by the infrared analysis of selected atoms of isolated aromatic hydrocarbons |
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| WO2007089154A1 (en) | 2007-08-09 |
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