FR2619629A1 - Method for on-line, real-time determination of the compositions of the supply and of the distillation yields obtained during the distillation of crude oils and their mixtures by near-infrared spectrophotometric analysis of the supply - Google Patents
Method for on-line, real-time determination of the compositions of the supply and of the distillation yields obtained during the distillation of crude oils and their mixtures by near-infrared spectrophotometric analysis of the supply Download PDFInfo
- Publication number
- FR2619629A1 FR2619629A1 FR8711685A FR8711685A FR2619629A1 FR 2619629 A1 FR2619629 A1 FR 2619629A1 FR 8711685 A FR8711685 A FR 8711685A FR 8711685 A FR8711685 A FR 8711685A FR 2619629 A1 FR2619629 A1 FR 2619629A1
- Authority
- FR
- France
- Prior art keywords
- distillation
- sep
- compositions
- yields
- supply
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 238000004821 distillation Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000010779 crude oil Substances 0.000 title claims abstract description 9
- 238000002798 spectrophotometry method Methods 0.000 title description 3
- 230000003595 spectral effect Effects 0.000 claims abstract description 4
- 238000002835 absorbance Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 238000009825 accumulation Methods 0.000 claims description 4
- 238000011481 absorbance measurement Methods 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 2
- 239000013307 optical fiber Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000000424 optical density measurement Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010223 real-time analysis Methods 0.000 description 1
- 230000001373 regressive effect Effects 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
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
- G01N33/2829—Oils, i.e. hydrocarbon liquids mixtures of fuels, e.g. determining the RON-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
-
- 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
- G01N21/359—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using near infrared light
Abstract
Description
Procédé de détermination en ligne et en temps réel des compositions de l'alimentation et des rendements de distillation obtenus lors de la distillation des pétroles bruts et de leurs mélanges par analyse spectrophotométrique proche infrarouge de l'alimentation.Process for determining on-line and in real time the compositions of the feed and the distillation yields obtained during the distillation of crude oils and their mixtures by near infrared spectrophotometric analysis of the feed.
L'invention concerne la détermination en ligne et en temps réel des compositions des alimentations et des rendements de distillation des pétroles bruts et de leurs mélanges. The invention relates to the on-line and real-time determination of feed compositions and distillation yields of crude oils and mixtures thereof.
Dans la pratique courante actuelle, les rendements de distillation sont connus pour des bruts connus. I1 est par contre difficile de connaître les proportions des différents pétroles bruts qui alimentent une unité de distillation et les rendements des diverses coupes de distillation. Les rendements sont constatés après plusieurs heures et, en cas de réglage inadéquat, on peut obtenir de grandes quantités de produits ne correspondant pas à ce qui pourrait être obtenu avec un réglage optimal. In current practice, the distillation yields are known for known crudes. On the other hand, it is difficult to know the proportions of the various crude oils which feed a distillation unit and the yields of the various distillation cuts. The yields are observed after several hours and, in the event of inadequate adjustment, one can obtain large quantities of products not corresponding to what could be obtained with an optimal adjustment.
L'objet de la présente invention est de résoudre ces difficultés. The object of the present invention is to resolve these difficulties.
Conformément à l'invention, ce résultat est obtenu en mettant en oeuvre un procédé rapide et précis permettant d'obtenir les informations nécessaires par une analyse en ligne et en temps réel de l'alimentation de l'unité de distillation. In accordance with the invention, this result is obtained by implementing a rapid and precise method making it possible to obtain the necessary information by an on-line and real-time analysis of the feed to the distillation unit.
Le procédé suivant l'invention utilise la spectrophotométrie dans le domaine du proche infrarouge couplée éventuellement à un dispositif de traitement de signaux permettant une accumulation numérique du spectre par transformée de FOURIER. The method according to the invention uses spectrophotometry in the near infrared range optionally coupled to a signal processing device allowing digital accumulation of the spectrum by FOURIER transform.
Ce procédé qui traite la charge à l'entrée de l'unité n'induit aucun délai de réponse et permet de ce fait une conduite assistée par ordinateur réalisée effectivement en temps réel. This process, which processes the load at the input of the unit, does not induce any response delay and therefore enables computer-assisted driving effectively carried out in real time.
Le procédé suivant l'invention permet par une analyse en ligne et en temps réel, avec utilisation éventuelle de fibres optiques, de la charge d'alimentation d'une unité de distillation, de déterminer les rendements distillatoires de cette même unité en ses diverses fractions : distillat léger, kérogène, gazole, résidu. The method according to the invention makes it possible, by online analysis in real time, with optional use of optical fibers, of the feedstock of a distillation unit, to determine the distillation yields of this same unit in its various fractions. : light distillate, kerogen, gas oil, residue.
On a établi qu'il existe de très bonnes corrélations entre la structure du spectre dans le proche infrarouge de l'alimentation de l'unité et les rendements distillatoires de cette même unité. It has been established that there are very good correlations between the structure of the near infrared spectrum of the feed to the unit and the distillation yields of the same unit.
Un autre objet de l'invention est de déterminer - dans le cas de mélanges de plusieurs bruts dont les origines sont connues - les compositions pondérales de divers bruts dans le mélange à partir du spectre de l'alimentation dans le proche infrarouge. Another object of the invention is to determine - in the case of mixtures of several crudes whose origins are known - the weight compositions of various crudes in the mixture from the spectrum of the feed in the near infrared.
Du point de vue contrôle de procédé et conduite de procédé, ce type de corrélation est précieux puisqu'il concerne la qualification de la charge et l'anticipation en temps réel du rendement potentiel de l'unité en les diverses fractions. From the point of view of process control and process control, this type of correlation is valuable since it concerns the qualification of the load and the real-time anticipation of the potential yield of the unit in the various fractions.
L'information peut être obtenue en moins d'une minute alors que les rendements sont constatés plusieurs heures après. The information can be obtained in less than a minute while the returns are observed several hours later.
Le procédé s'applique à diverses possibilités de coupes distillatoires et aux bruts ou mélanges de bruts d'origine diverses ou à des coupes de constitutions variées. The process applies to various possibilities of distillation cuts and to crudes or mixtures of crudes of various origins or to cuts of various constitutions.
L'obtention d'une information instantanée relative au rendement potentiel en les diverses coupes désirées permet d'obtenir sans retard un réglage optimal de la distillation. Obtaining instantaneous information relating to the potential yield in the various desired cuts makes it possible to obtain an optimum adjustment of the distillation without delay.
Dans la suite du texte, on appellera
- distillat léger : la fraction distillant du pentane à 149"C. In the remainder of the text, we will call
- light distillate: the fraction distilling pentane at 149 ° C.
- kérosène : la fraction distillant entre 149 et 232"C. - kerosene: the fraction distilling between 149 and 232 "C.
- gazole : la fraction distillant entre 232 et 342"C. - diesel: the fraction distilling between 232 and 342 "C.
- résidu : la fraction ayant un point de distillation supérieur à 3420 C. - residue: the fraction having a distillation point higher than 3420 C.
La spectrophotométrie dans le proche infrarouge est alors un marqueur fidèle de la qualité du brut effectivement traité à un moment donné n'induisant pas de délais dans l'analyse de la charge. Near infrared spectrophotometry is then a reliable marker of the quality of the crude actually treated at a given moment, which does not lead to delays in the analysis of the load.
Le procédé selon l'invention est caractérisé par le fait
a) que l'on utilise un spectrophotomètre apte à opérer dans le proche infrarouge;
b) que l'on réalise avec cet appareil les mesures d'absorbance dans la zone spectrale de 12500 à 3840 cm-l (0,8 à 2,6 microns) sur le produit reçu à l'alimentation de l'unité;
c) que l'on sélectionne dans cette zone un certain nombre n de fréquences choisies pour établir des corrélations statistiques avec les caractéristiques recherchées; et
d) que l'on calcule directement les valeurs recherchées par l'application d'une relation corrélative avec les n valeurs d'absorbance mesurées, cette corrélation étant déterminée expérimentalement par regression muitivariable et ne dépendant que du type de spectromètre utilisé, du type de valeur caractéristique recherchée, du nombre n de fréquences retenues parmi les plus -significatives ainsi que des caractéristiques et réglages de l'unité de distillation utilisée.The method according to the invention is characterized by the fact
a) that a spectrophotometer capable of operating in the near infrared is used;
b) that the absorbance measurements are carried out with this apparatus in the spectral region of 12500 to 3840 cm-1 (0.8 to 2.6 microns) on the product received at the feed to the unit;
c) that a certain number n of frequencies chosen are selected in this zone in order to establish statistical correlations with the characteristics sought; and
d) that the desired values are calculated directly by applying a correlative relationship with the n measured absorbance values, this correlation being determined experimentally by multi-variable regression and depending only on the type of spectrometer used, on the type of characteristic value sought, the number n of frequencies selected from among the most significant as well as the characteristics and settings of the distillation unit used.
D'autres particularités de l'invention apparaîtront dans la description qui va suivre d'un mode de mise en oeuvre particulier. Other features of the invention will appear in the following description of a particular embodiment.
La première particularité de l'invention consiste à utiliser pour les mesures un rayonnement dans le proche infrarouge, c'est-à-dire la bande de 0,81u à 2,6 r, qui est inutilisée habituellement car étant constituée de bandes d'absorption fusionnées de manière complexe, mais qui au contraire, assure une meilleure répétabilité pour la mise en oeuvre du procédé selon l'invention. The first feature of the invention consists in using for the measurements a radiation in the near infrared, that is to say the band from 0.81u to 2.6 r, which is usually unused because it consists of bands of. absorption merged in a complex manner, but which on the contrary ensures better repeatability for the implementation of the method according to the invention.
On utilise de préférence la bande 2,1 à 2,5,,u. The band 2.1 to 2.5,, u is preferably used.
Les meilleurs résultats ont été obtenus en utilisant les 15 fréquences suivantes, exprimées en nombre d'ondes par cm. The best results have been obtained using the following 15 frequencies, expressed as number of waves per cm.
F1 = 4670 cm-l
F2 = 4640 cm-l
F3 = 4615 cm-l
F4 = 4585 cm-l
F5 = 4485 cm-l
F6 = 4385 cm-l
F7 = 4332 cm-i
F8 = 4305 cm-l
Fg = 4260 cml
F10 = 4210 cm-l
Fil = 4170 cm-l
F12 = 4135 cm-l
F13 = 4100 c-l
F14 = 4060 cml
F15 = 4040 cm-l
La fréquence correspondante exprimée en unités légales (Hz) s'obtiendrait en multipliant ces valeurs par 3.10101 vitesse de la lumière en cm/s.F1 = 4670 cm-l
F2 = 4640 cm-l
F3 = 4615 cm-l
F4 = 4585 cm-l
F5 = 4485 cm-l
F6 = 4385 cm-l
F7 = 4332 cm-i
F8 = 4305 cm-l
Fg = 4260 cml
F10 = 4210 cm-l
Thread = 4170 cm-l
F12 = 4135 cm-l
F13 = 4100 cl
F14 = 4060 cml
F15 = 4040 cm-l
The corresponding frequency expressed in legal units (Hz) would be obtained by multiplying these values by 3.10101 speed of light in cm / s.
On utilise un spectrophotomètre à proche infrarouge, dont le pouvoir de résolution est de 4 cm-l, couplé à un ordinateur. A near infrared spectrophotometer is used, the resolving power of which is 4 cm-1, coupled to a computer.
Par le procédé classique, on détermine, pour chaque fréquence, l'absorbance, c' est-à-dire le logarithme du rapport d'affaiblissement entre le rayonnement incident et le ragonnement ayant traversé la cuve. By the conventional method, the absorbance is determined for each frequency, that is to say the logarithm of the attenuation ratio between the incident radiation and the coarseness which has passed through the tank.
Ce choix n'est ni limitatif, ni exclusif. Le choix d'autres longueurs d'ondes n'altère en rien le procédé mais conduirait à l'utilisation d'autres coefficients dans les modèles permettant de calculer les propriétés recherchées à partir des spectres. This choice is neither limiting nor exclusive. The choice of other wavelengths in no way alters the process but would lead to the use of other coefficients in the models making it possible to calculate the desired properties from the spectra.
Le temps d'analyse et de traitement des données est inférieur à 1 minute. Data analysis and processing time is less than 1 minute.
La ligne de base (considérée comme corespondant à une absorbance nulle) est prise à 4780 cm-l . The baseline (considered to correspond to zero absorbance) is taken at 4780 cm-l.
Le spectromètre utilisé effectue les mesures d'absorbances pour les 15 fréquences sélectionnées et on obtient directement par régression multivariée les valeurs recherchées. The spectrometer used performs absorbance measurements for the 15 frequencies selected and the desired values are obtained directly by multivariate regression.
Dans une conduite assistée par ordinateur d'une unité de distillation, le spectre proche infrarouge de la charge entrante est donc saisi en temps réel et traité comme un vecteur information qualifiant en continu les propriétés distillatoires de l'alimentation dans l'opération de distillation. La richesse du spectre proche infrarouge et la précision expérimentale découlant de l'accumulation spectrale par transformée de Fourier rapide font que cette information est sûre et très pertinente vis-à-vis des opérations physiques impliquées dans la distillation. Le spectre proche infrarouge est donc un marqueur numérique de l'aptitude de la charge aux opérations de distillation. In computer-aided operation of a distillation unit, the near infrared spectrum of the incoming feed is therefore captured in real time and processed as an information vector continuously qualifying the distillation properties of the feed in the distillation operation. The richness of the near infrared spectrum and the experimental precision resulting from the spectral accumulation by fast Fourier transform make this information certain and very relevant to the physical operations involved in the distillation. The near infrared spectrum is therefore a digital marker of the suitability of the feed for distillation operations.
La preuve de cette précieuse propriété du spectre proche infrarouge est administrée par les exemples qui suivent, où l'on montre que pour un réglage fixé de l'unité, les variations de rendements des produits formés et de composition de la charge sont corrélables, moyennant un traitelnent numérique plus ou moins élaboré, avec les variations du spectre proche infrarouge de la charge. The proof of this valuable property of the near infrared spectrum is given by the examples which follow, where it is shown that for a fixed setting of the unit, the variations in yields of the products formed and in the composition of the charge are correlable, with a more or less elaborate digital processing, with variations in the near infrared spectrum of the load.
Dans les exemples non limitatifs suivants, les coupes pétrolières sont obtenues par distillation au moyen d'une colonne à distiller d'efficacité 14 plateaux théoriques. In the following nonlimiting examples, the petroleum cuts are obtained by distillation using a distillation column with an efficiency of 14 theoretical plates.
EXEMPLE 1
On réalise le spectre dans le proche infrarouge de trois pétroles bruts. Les valeurs des absorbances pour ces trois bruts sont les suivantes aux fréquences utilisées, la ligne de base étant prise à 4780 cm-1.
The near infrared spectrum of three crude oils is produced. The absorbance values for these three crudes are as follows at the frequencies used, the baseline being taken at 4780 cm-1.
<tb><tb>
<SEP> BRUT <SEP> ABSORBANCES <SEP> Ai
<tb> <SEP> Iranien <SEP> Zakum <SEP> Djeno <SEP> Mélange
<tb> <SEP> lourd <SEP> 50-35-15
<tb> Fréquences
<tb> Fi <SEP> cm-1 <SEP>
<tb> F3 <SEP> : <SEP> 4615 <SEP> 0,02736 <SEP> 0,0248 <SEP> 0,01758 <SEP> -0,0251 <SEP>
<tb> F4 <SEP> : <SEP> 4585 <SEP> 0,02671 <SEP> 0,02562 <SEP> 0,01895 <SEP> 0,0255
<tb> F5 <SEP> : <SEP> 4485 <SEP> 0,03811 <SEP> 0,03981 <SEP> 0,03172 <SEP> 0,0379
<tb> F7 <SEP> : <SEP> 4332 <SEP> 0, <SEP> 93621 <SEP> 0,96899 <SEP> 0, <SEP> 94434 <SEP> 0,9494
<tb> Fg <SEP> : <SEP> 4260 <SEP> 0,77561 <SEP> O, <SEP> 79598 <SEP> 0,80701 <SEP> 0,7876
<tb> F11 <SEP> : <SEP> 4170 <SEP> 0,55478 <SEP> O, <SEP> 56599 <SEP> 0,57862 <SEP> O, <SEP> 5622 <SEP>
<tb> F13 <SEP> :<SEP> 4100 <SEP> 0,49855 <SEP> O, <SEP> 50971 <SEP> 0,51222 <SEP> 0,5050
<tb> F14 <SEP> : <SEP> 4060 <SEP> 0,53475 <SEP> 0,54304 <SEP> O, <SEP> 52624 <SEP> 0,5361
<tb> F15 <SEP> : <SEP> 4040 <SEP> 0,41833 <SEP> 0,42156 <SEP> 0,41788 <SEP> 0,4196
<tb>
On réalise un mélange homogène des trois pétroles bruts dans les proportions suivantes
Iranien lourd : 50% poids - Zakum : 35% poids
Djeno : 15% poids.<SEP> GROSS <SEP> ABSORBANCES <SEP> Ai
<tb><SEP> Iranian <SEP> Zakum <SEP> Djeno <SEP> Mixture
<tb><SEP> heavy <SEP> 50-35-15
<tb> Frequencies
<tb> Fi <SEP> cm-1 <SEP>
<tb> F3 <SEP>: <SEP> 4615 <SEP> 0.02736 <SEP> 0.0248 <SEP> 0.01758 <SEP> -0.0251 <SEP>
<tb> F4 <SEP>: <SEP> 4585 <SEP> 0.02671 <SEP> 0.02562 <SEP> 0.01895 <SEP> 0.0255
<tb> F5 <SEP>: <SEP> 4485 <SEP> 0.03811 <SEP> 0.03981 <SEP> 0.03172 <SEP> 0.0379
<tb> F7 <SEP>: <SEP> 4332 <SEP> 0, <SEP> 93621 <SEP> 0.96899 <SEP> 0, <SEP> 94434 <SEP> 0.9494
<tb> Fg <SEP>: <SEP> 4260 <SEP> 0.77561 <SEP> O, <SEP> 79598 <SEP> 0.80701 <SEP> 0.7876
<tb> F11 <SEP>: <SEP> 4170 <SEP> 0.55478 <SEP> O, <SEP> 56599 <SEP> 0.57862 <SEP> O, <SEP> 5622 <SEP>
<tb> F13 <SEP>: <SEP> 4100 <SEP> 0.49855 <SEP> O, <SEP> 50971 <SEP> 0.51222 <SEP> 0.5050
<tb> F14 <SEP>: <SEP> 4060 <SEP> 0.53475 <SEP> 0.54304 <SEP> O, <SEP> 52624 <SEP> 0.5361
<tb> F15 <SEP>: <SEP> 4040 <SEP> 0.41833 <SEP> 0.42156 <SEP> 0.41788 <SEP> 0.4196
<tb>
A homogeneous mixture of the three crude oils is produced in the following proportions
Iranian heavy: 50% weight - Zakum: 35% weight
Djeno: 15% weight.
La dernière colonne du tableau ci-dessus indique les absorbances obtenues par analyse du mélange. The last column of the above table indicates the absorbances obtained by analysis of the mixture.
Par une méthode des moindres carrés, on résout les neuf équations par rapport aux trois inconnues (% poids de chacun des bruts du mélange). By a method of least squares, the nine equations are solved with respect to the three unknowns (% by weight of each of the crudes of the mixture).
Les valeurs ainsi calculées sont les suivantes en % poids
Iranien lourd : 51,4% - Zakum : 34,2% - Djeno : 14,4 %.The values thus calculated are as follows in% by weight
Iranian heavy: 51.4% - Zakum: 34.2% - Djeno: 14.4%.
La précision par rapport au mélange témoin est donc tout à fait satisfaisante, les écarts observés étant acceptables et dus & la répétabilité des mesures de densité optique. The precision with respect to the control mixture is therefore quite satisfactory, the differences observed being acceptable and due to the repeatability of the optical density measurements.
Ce procédé permet de doser en temps réel la composition d'un mélange de bruts connus. This process makes it possible to measure in real time the composition of a mixture of known crudes.
I1 est ainsi possible, si on alimente l'unité à partir de bacs contenant divers bruts, de connaître en temps réel la composition du mélange de bruts qui entre effectivement dans l'unité de distillation. It is thus possible, if the unit is fed from tanks containing various crudes, to know in real time the composition of the crude mixture which actually enters the distillation unit.
Cette technique peut s'appliquer au comptage des approvisionnements sur bruts mixtes. This technique can be applied to the counting of supplies on mixed crude.
EXEMPLE 2
On utilise un pétrole brut DJENO, on mesure les absorbances Ai pour 12 fréquences Fi. Les résultats sont rassemblés dans le tableau ci-après
F2 : (4640 cm-1) A2 = 0,01364
F3 : (4615 cm-l) A3 = 0,01758
F4 : (4585 cm-1) A4 = 0,01895
F5 : (4485 cm-l) As = 0,03172
F6 : (4385 cm-1) A6 = 0,45629
F7 : (4332 cm-l) A7 = O, 94434
F8 : (4305 cm-1) A8 = O,63842
Fg : (4260 cm-1) Ag = 0,80701
F11: (4170 cm-1) A11= 0, 57862
F13: (4100 cm-l) A13= 0,51222
F14: (4060 cm'l) A14= O, 52624
F15: (4040 cm'l) A15= O, 41788
Les rendements des coupes définies antérieurement obtenus par régression multivariée sont exprimés en fonction des absorbances Ai des diverses alimentations par les expressions suivantes
Rendement en résidu = 359,88 - 1385,51 A2 - 441,15 A6 - 291,84 A7 + 225,1 A8 + 12S,33 t15
Rendement en distillat léger = - 113,6 + 541,26 A2 + 108,75 A6 + 122,71 A7 - 55,49 A8 - 31,64 A15
Rendement en gazole = - 51,03 + 373,77 A2 + 199,13 A6 + 67,77 A7 - 101,61 A8 - 57,92 A15
Le calcul effectué à partir des formules précédentes et des absorbances donne les résultats suivants comparés aux valeurs expérimentales observées pour le brut DJENo examiné ici
Calculé Observé
Rendement en résidu % poids 61,4% 63%
Distillat léger 10,6% 9,1%
Gazole 16,8% 16,2%
Si on étend ce type de technique régressive à l'ensemble de la découpe distillatoire, il devient possible de recalculer en temps réel la courbe distillatoire et la température moyenne de distillation de l'alimentation considérée.EXAMPLE 2
A DJENO crude oil is used, the absorbances Ai are measured for 12 frequencies Fi. The results are collated in the table below
F2: (4640 cm-1) A2 = 0.01364
F3: (4615 cm-W) A3 = 0.01758
F4: (4585 cm-1) A4 = 0.01895
F5: (4485 cm-l) As = 0.03172
F6: (4385 cm-1) A6 = 0.45629
F7: (4332 cm-W) A7 = O, 94434
F8: (4305 cm-1) A8 = O, 63842
Fg: (4260 cm-1) Ag = 0.80701
F11: (4170 cm-1) A11 = 0.57862
F13: (4100 cm-l) A13 = 0.51222
F14: (4060 cm'l) A14 = O, 52624
F15: (4040 cm'l) A15 = O, 41788
The yields of the previously defined cuts obtained by multivariate regression are expressed as a function of the absorbances Ai of the various feeds by the following expressions
Residue yield = 359.88 - 1385.51 A2 - 441.15 A6 - 291.84 A7 + 225.1 A8 + 12S, 33 t15
Yield of light distillate = - 113.6 + 541.26 A2 + 108.75 A6 + 122.71 A7 - 55.49 A8 - 31.64 A15
Diesel yield = - 51.03 + 373.77 A2 + 199.13 A6 + 67.77 A7 - 101.61 A8 - 57.92 A15
The calculation made from the previous formulas and absorbances gives the following results compared to the experimental values observed for the raw DJENo examined here
Calculated Observed
Residue yield% weight 61.4% 63%
Light distillate 10.6% 9.1%
Diesel 16.8% 16.2%
If this type of regressive technique is extended to the whole of the distillation cutting, it becomes possible to recalculate in real time the distillation curve and the mean distillation temperature of the feed considered.
Cette technique s'applique aussi au cas de mélanges et d'alimentations de constitutions variées. This technique also applies to the case of mixtures and feeds of various constitutions.
Claims (8)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8711685A FR2619629B1 (en) | 1987-08-18 | 1987-08-18 | METHOD FOR DETERMINING ONLINE AND REAL-TIME FEEDING COMPOSITIONS AND DISTILLATION YIELDS OBTAINED BY DISTILLATION OF CRUDE OILS AND THEIR MIXTURES BY NEAR INFRARED SPECTROPHOTOMETRIC ANALYSIS |
| AT88307462T ATE146880T1 (en) | 1987-08-18 | 1988-08-11 | METHOD FOR DIRECT DETERMINATION OF THE PHYSICAL PROPERTIES OF HYDROCARBON PRODUCTS |
| DE3855720T DE3855720T2 (en) | 1987-08-18 | 1988-08-11 | Method for the direct determination of the physical properties of hydrocarbon products |
| ES88307462T ES2095205T3 (en) | 1987-08-18 | 1988-08-11 | METHOD FOR THE DIRECT DETERMINATION OF PHYSICAL PROPERTIES OF HYDROCARBON PRODUCTS. |
| EP88307462A EP0304232B1 (en) | 1987-08-18 | 1988-08-11 | Method for the direct determination of physical properties of hydrocarbon products |
| AU20953/88A AU603919B2 (en) | 1987-08-18 | 1988-08-16 | Method for the direct determination of physical properties of hydrocarbon products |
| CA000575011A CA1333447C (en) | 1987-08-18 | 1988-08-17 | Method for the direct determination of physical properties of hydrocarbon products |
| NO883671A NO304330B1 (en) | 1987-08-18 | 1988-08-17 | Method and apparatus for the direct determination of, inter alia, the properties and / or yield of a product in a hydrocarbon conversion or separation process |
| JP63203936A JP3070608B2 (en) | 1987-08-18 | 1988-08-18 | A direct method for measuring the physical properties of hydrocarbon products. |
| US08/357,047 US5452232A (en) | 1987-08-18 | 1994-12-13 | Method and apparatus for determining a property or yield of a hydrocarbon product based on NIRA of the feedstock |
| GR970400220T GR3022532T3 (en) | 1987-08-18 | 1997-02-12 | Method for the direct determination of physical properties of hydrocarbon products |
| JP09276313A JP3110358B2 (en) | 1987-08-18 | 1997-10-08 | How to determine quantitative composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8711685A FR2619629B1 (en) | 1987-08-18 | 1987-08-18 | METHOD FOR DETERMINING ONLINE AND REAL-TIME FEEDING COMPOSITIONS AND DISTILLATION YIELDS OBTAINED BY DISTILLATION OF CRUDE OILS AND THEIR MIXTURES BY NEAR INFRARED SPECTROPHOTOMETRIC ANALYSIS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2619629A1 true FR2619629A1 (en) | 1989-02-24 |
| FR2619629B1 FR2619629B1 (en) | 1992-10-16 |
Family
ID=9354280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR8711685A Expired - Fee Related FR2619629B1 (en) | 1987-08-18 | 1987-08-18 | METHOD FOR DETERMINING ONLINE AND REAL-TIME FEEDING COMPOSITIONS AND DISTILLATION YIELDS OBTAINED BY DISTILLATION OF CRUDE OILS AND THEIR MIXTURES BY NEAR INFRARED SPECTROPHOTOMETRIC ANALYSIS |
Country Status (1)
| Country | Link |
|---|---|
| FR (1) | FR2619629B1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2926253A (en) * | 1954-12-22 | 1960-02-23 | Distillers Co Yeast Ltd | Radiation analysis |
| US3121677A (en) * | 1960-10-28 | 1964-02-18 | Gulf Research Development Co | Process for controlling carbon residue content of oil |
| FR1465253A (en) * | 1965-01-25 | 1967-01-06 | Exxon Research Engineering Co | Improved hydroforming process to control the formation of coke deposits on a catalyst |
| US3666932A (en) * | 1970-12-30 | 1972-05-30 | Texaco Inc | Means and method for on-line determination of the aromatic, naphthene and paraffin contents of charge oil |
| FR2545938A1 (en) * | 1983-05-12 | 1984-11-16 | Broken Hill Pty Co Ltd | METHOD AND APPARATUS FOR EVALUATING CHARACTERISTICS AND HANDLING MULTI-CONSTITUENT SUBSTANCES |
-
1987
- 1987-08-18 FR FR8711685A patent/FR2619629B1/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2926253A (en) * | 1954-12-22 | 1960-02-23 | Distillers Co Yeast Ltd | Radiation analysis |
| US3121677A (en) * | 1960-10-28 | 1964-02-18 | Gulf Research Development Co | Process for controlling carbon residue content of oil |
| FR1465253A (en) * | 1965-01-25 | 1967-01-06 | Exxon Research Engineering Co | Improved hydroforming process to control the formation of coke deposits on a catalyst |
| US3666932A (en) * | 1970-12-30 | 1972-05-30 | Texaco Inc | Means and method for on-line determination of the aromatic, naphthene and paraffin contents of charge oil |
| FR2545938A1 (en) * | 1983-05-12 | 1984-11-16 | Broken Hill Pty Co Ltd | METHOD AND APPARATUS FOR EVALUATING CHARACTERISTICS AND HANDLING MULTI-CONSTITUENT SUBSTANCES |
Non-Patent Citations (2)
| Title |
|---|
| ANALYTICAL CHEMISTRY, vol. 59, no. 9, 1er mai 1987, pages 624A-637A, American Chemical Society; J.B. CALLIS et al.: "Process analytical chemistry" * |
| APPLIED SPECTROSCOPY REVIEWS, vol. 21, no. 1/2, 1985, pages 1-43, Marcel Dekker, Inc., New York, US; L.G. WEYER: "Near-infrared spectroscopy of organic substances" * |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2619629B1 (en) | 1992-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sirven et al. | Laser-induced breakdown spectroscopy of composite samples: comparison of advanced chemometrics methods | |
| FR2611911A1 (en) | METHOD FOR DIRECT DETERMINATION OF OCTANE INDEX | |
| US7404411B2 (en) | Method and apparatus for analysis of relative levels of biodiesel in fuels by near-infrared spectroscopy | |
| EP0304232B1 (en) | Method for the direct determination of physical properties of hydrocarbon products | |
| EP0877923B1 (en) | Mutivariate sample analysis | |
| EP2350615B1 (en) | Method for predicting hydrocarbon process stream stability using near infrared spectra | |
| JPH07301599A (en) | Method to analyze hydrocarbon by near-infrared spectroscopy analysis | |
| CN107976419B (en) | Method for predicting properties of oil product by near infrared spectrum | |
| CN106932378A (en) | The on-line detecting system and method for a kind of sour gas composition based on Raman spectrum | |
| CN101027554A (en) | Method of assaying a hydrocarbon-containing feedstock | |
| CN112782146A (en) | Gasoline olefin content analysis method based on Raman spectrum | |
| EP2992314B1 (en) | Method for characterising a product by topological spectral analysis | |
| FR2619629A1 (en) | Method for on-line, real-time determination of the compositions of the supply and of the distillation yields obtained during the distillation of crude oils and their mixtures by near-infrared spectrophotometric analysis of the supply | |
| FR2619628A1 (en) | Method for on-line and real-time determination of the characteristics of the supply and of the products obtained during catalytic cracking of petroleum fractions by near-infrared spectrophotometric analysis of the supply | |
| JPH04233439A (en) | Method and apparatus for measuring amount of one component of fluid mixture in other component or fluid mixture itself using spectroscope after sepa-rating fluid mixture into its component | |
| Chen et al. | Improvement of predicting precision of oil content in instant noodles by using wavelet transforms to treat near-infrared spectroscopy | |
| FR2619630A1 (en) | Method for on-line, real-time determination of the characteristics of the supply and of the products obtained during distillation of crude oils by near-infrared spectrophotometric analysis of the supply | |
| FR2619627A1 (en) | Method for on-line and real-time determination of the characteristics of the supply and of the yields of products obtained during catalytic cracking of petroleum fractions by near-infrared spectrophotometric analysis of the supply | |
| FR2619625A1 (en) | Method for on-line, real-time determination of the degree of olefin unsaturation of the supply and of the products obtained during hydrogenation of light petroleum fractions by near-infrared spectrophotometric analysis | |
| FR2619626A1 (en) | Method for on-line and real-time determination of the characteristics of the supply and of the yields of products obtained during catalytic hydrogen treatment of petroleum fractions by near-infrared spectrophotometric analysis of the supply | |
| FR2634283A1 (en) | Method for on-line and real-time determination of the characteristics of the supply and yields and qualities of the products obtained during thermal treatment of heavy petroleum products by near-infrared spectrophotometric analysis of the supply | |
| FR2619624A1 (en) | Method for determining the octane indices of a complex mixture of fuels or the composition of such a mixture of fuels having an octane index determined by near-infrared spectrophotometric analysis of the constituents of the mixture | |
| Khofar et al. | Trends of forensic analysis of pen ink using attenuated total reflectance fourier transform infrared (ATR-FTIR) spectroscopy | |
| FR2632409A1 (en) | Method for determining the properties of a fuel oil obtained from a complex mixture based on petroleum products, or the constitution of such a product having properties defined by near-infrared spectrophotometric analysis of the constituents of the mixture | |
| FR2685775A1 (en) | Method for determining the level of aromatic polycyclics from a mixture of hydrocarbons by near-infrared spectrophotometric analysis of the constituents of the mixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TP | Transmission of property | ||
| ST | Notification of lapse |
Effective date: 20060428 |