EP3964557A1 - Verfahren und system zur schätzung der eigenschaften eines vakuumrückstands und zur homologisierung eines rohöls - Google Patents

Verfahren und system zur schätzung der eigenschaften eines vakuumrückstands und zur homologisierung eines rohöls Download PDF

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Publication number
EP3964557A1
EP3964557A1 EP20305976.1A EP20305976A EP3964557A1 EP 3964557 A1 EP3964557 A1 EP 3964557A1 EP 20305976 A EP20305976 A EP 20305976A EP 3964557 A1 EP3964557 A1 EP 3964557A1
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EP
European Patent Office
Prior art keywords
values
property data
crude oil
penetrability
value
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EP20305976.1A
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English (en)
French (fr)
Inventor
Nicolas Lenepveu
Christelle KLEIN
Mersaka BENKHALED
Christophe Bolliet
Carine BOULANGER
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TotalEnergies Onetech SAS
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Total Raffinage Chimie SAS
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Priority to EP20305976.1A priority Critical patent/EP3964557A1/de
Publication of EP3964557A1 publication Critical patent/EP3964557A1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/06—Vacuum distillation

Definitions

  • the present invention relates to bitumen and more specifically to homologation methods used to homologate crude oils for producing bitumen, in particular bitumen able to be used in the field of road construction or civil engineering (paving grade bitumen).
  • Bitumen is the main hydrocarbon constituent used in the field of road construction or civil engineering. Bitumen can be defined as being a mixture of several "bitumen bases". Two or more bitumen bases can be mixed to form a composition formed of bitumen bases. A composition formed of bitumen bases can form bitumen. Two or several compositions formed of bitumen bases can also be mixed in order to obtain bitumen.
  • a bitumen base is regarded as being the product resulting from a refining process.
  • a bitumen base can be produced by refining a crude oil, in particular a crude oil homologated to produce bitumen.
  • This crude oil is heated to 300°C, partially vaporized in an oven and transferred into an atmospheric distillation column in which the separation of the different fractions is carried out.
  • the lightest fraction vaporizes while the heaviest fraction (atmospheric residue) remains at the column bottom and passes into a second heat exchanger system before treatment in a vacuum distillation column.
  • the bitumen base is recovered at the bottom of this vacuum distillation column.
  • the bitumen base corresponds, for example, to the 560°C+ cut of the vacuum distillation.
  • bitumen bases In order to produce "bitumen bases", crude oils homologated to produce bitumen are normally selected as a function of their ability to produce the said bases. Thus, among all the crude oils referenced, only less than 10% make it possible to produce "bitumen bases”.
  • the said bases are generally obtained from residues resulting from vacuum distillation of crude oil. The main criteria for choosing the crude oils homologated to produce bitumen are:
  • the penetrability is usually measured according to Standard NF EN 1426 (January 2018).
  • the needle penetrability is the depth, expressed in tenths of a millimetre, to which a standardized needle with a diameter of 1 mm, under a load of 100 g, applied for 5s to a bitumen sample maintained at 25°C or at 15°C, drives into the sample.
  • the softening point more specifically the ring and ball (RBT) softening point, usually measured according to Standard NF EN 1427 (January 2018), is a second fundamental characteristic of a bitumen : a small steel ball weighing 3.5 g and with a diameter of 9.5 mm is placed on a bitumen disk cast beforehand in a ring with an internal diameter of 19.8 mm, itself placed on a standardized support. The combined assembly is introduced in a water bath, the initial and stabilized temperature of which is 5°C. The lower face of the bitumen ring occurs at 25.4 mm from the upper surface of the plate of the bottom of the support, which corresponds to the distance which the ball falls during the test.
  • RBT ring and ball
  • the bath is heated at a constant rate of 5°C/min, with stirring, and the ring and ball softening point (often denoted RBT) is the temperature at which the bitumen pocket, formed during the fall of the ball, touches the reference plate placed (as has been said) at 25.4 mm under the bitumen ring.
  • RBT ring and ball softening point
  • the penetration index (PI), according to Standard NF EN 12591 (december 2009), makes it possible to determine the thermal susceptibility of a bitumen.
  • the PI is calculated by means of a formula from the value of the penetrability at 25°C and from the RBT softening point value of a given bitumen. The result is expressed without dimensions.
  • the present invention relates to a method and a system for estimating properties of a vacuum residue issued from crude oils that can be used for homologating this crude oil, in particular for paving bitumen application.
  • the method of the invention allows estimation of properties useful for characterization of paving bitumen from properties which are usually not used for characterizing paving bitumen.
  • the method and the system of the invention can be integrated respectively in a method and a system for homologating a crude oil, in particular for paving bitumen application.
  • a vacuum residue of a crude oil is defined as the residue of vacuum distillation of an atmospheric residue resulting from the atmospheric distillation of a crude oil.
  • a residue is defined as the bottom of the distillation unit resulting from the distillation of a product.
  • a vacuum residue usually corresponds to the 560+ cut, but may correspond to 520+ cut or 570+ cut or have still another cut point value depending on unit performance. The man skilled in the art is able to determine a cut point appropriate for a vacuum residue, in particular as a function of the performance of the unit considered.
  • Clarke oil (or “crude”) means oil from a natural reservoir that is extracted in liquid form at atmospheric pressure. It is therefore a natural product before refining, but which has already lost some of its initial composition, as the fraction of light hydrocarbons leaves the liquid phase at the point of extraction.
  • Asphaltenes are defined as the heavy products contained in crude oil which are insoluble in n-heptane and soluble in toluene. In general, asphaltenes contain carbon, hydrogen, nitrogen, oxygen, sulfur, vanadium and nickel.
  • a method for estimating properties of a vacuum residue issued from a crude oil comprises :
  • the method according to the invention allows to characterize properties of the vacuum residue which are used to determine if such vacuum residue is usable for a particular application, in particular as paving bitumen, for example as defined in NF EN12591 (dec 2009).
  • the penetrability value estimated is an estimate of the penetrability value at 25°C, expressed in 1/10mm, as defined in NF EN 1426 (January 2018) and the estimated softening point value is an estimate of the RBT softening point, expressed in °C, as defined in NF EN 1427 (January 2018).
  • the set of property data values received in step (a) can be measured values, estimated values or both, preferably measured values.
  • the kinematic viscosity values (at 100°C and 135°C) may be measured according to NF EN 12595 (December 2014).
  • the kinematic viscosity values are expressed in mm 2 /s.
  • the sulphur content value may be measured according to ASTM D2622-16.
  • the asphaltene content value may be measured according to NF T60-115 (January 2020).
  • the sulphur and asphaltene contents are expressed in weight %.
  • the first and second correlations may correlate the estimated value with the same set of properties or with different set of properties.
  • the invention is not limited to such correlations and any other appropriate correlation may be used.
  • step (b) may comprise a step of constructing the estimating model, comprising :
  • N of vacuum residues used in steps (i) and (ii) will be chosen so as to be superior to the number of property data in the correlation and preferably so as to be statistically representative of the existing vacuum residues for which an estimate is needed.
  • N may be equal to 10 or more, preferably equal to 50 or more, more preferably of more than 90 or 100.
  • statically representative we mean a number N sufficient for the property data values to be representative.
  • the first and second sets of property data values received in steps (i) and (ii) can be measured values, estimated values or both, preferably measured values.
  • each of the vacuum residues may be issued from a single crude oil.
  • Several crude oils may however be used to obtain each of the vacuum residues.
  • the vacuum residues may present any cut point value (i.e. any initial boiling point) allowing obtaining a vacuum residue.
  • the statistical methods used for generating the correlation include multivariate statistical analysis techniques such as Partial Least Squares, Multiple Linear Regression, Reduced Rank Regression, Principal Component Analysis and the like, or neural networks, preferably multiple linear regressions, in particular a forward stepwise regression. These statistical analysis techniques or neural networks are well known to those skilled in the art and will therefore not be described in detail.
  • the property data of the first set of data property values may preferably be uncorrelated property data. Uncorrelated property data may be identified by calculating correlation matrix or by using any other appropriate method such as Ridge regression, partial least squares, principal component regression.
  • the property data values used to construct the model may be submitted to a mathematical treatment allowing linearization of the problem to solve for the construction of the estimating model.
  • the estimating model is constructed on the basis of a set of values which are between minima and maxima values.
  • the vacuum residues for which an estimate of the penetrability and of the softening point is needed may preferably be chosen among vacuum residues which present values of the kinematic viscosity at 100°C, the kinematic viscosity at 135°C, the sulphur content, and optionally of the asphaltene content, within the minima and maxima of the values used to construct the model.
  • the set of values used to construct the estimating model and the values of the vacuum residue to estimate using the model should preferably be measured using the same standards. These standards may be the standards mentioned in the specification or other versions of these standards, or any other existing standards, provided the same standards are used for the values used for constructing the model and the values used for estimation purpose.
  • the step of constructing the model may include a step (iv) of validation in which for a number M of vacuum residues, which are different from the N vacuum residues used to generate the correlations, penetrability and softening point values are estimated by implementing the correlations obtained in step (iii) from the set of property data values of the M vacuum residues, and compared to measured values of penetrability and softening point for these M vacuum residues.
  • This number M of residues may be of 5 or more, preferably of 10 or more.
  • the first correlation of the estimating model may correlate the penetrability property data value to the values of the kinematic viscosity at 100°C, the kinematic viscosity at 135°C and the sulphur content.
  • the second correlation of the estimating model may correlate the softening point property data value to the values of the kinematic viscosity at 100°C, the kinematic viscosity at 135°C, the sulphur content and the asphaltene content.
  • a method for homologating a crude oil which comprises :
  • threshold values of step (B) may consist of a lower limit, an upper limit, or both. These threshold values may for example correspond to the values required for classification of a bitumen or a bitumen base in one of the grades defined in the standard NF EN 12591 (December 2009), or to any other specification required by a national requirement, a standard or a use.
  • the decision step (D) may comprise, or consist of, a step (D1) comprising deciding a crude oil is homologated to produce a vacuum residue for said particular application when the estimated values comply with said threshold values, otherwise deciding the crude oil is not homologated.
  • homologating method is not limited to homologation for paving bitumen but could be used for homologating a crude oil for any other application for which the knowing of the penetrability value and of the softening point value is of importance.
  • the invention is not limited to a particular standard, and the threshold values may be chosen by the man skilled in the art according to other standards or national requirements, or to values required for particular applications.
  • step (D) may comprise further steps to take such decision.
  • the deciding step (D) may then comprise, or consist of: a step (D'1) comprising :
  • the measures made when the estimated values are within the thresholds ranges can include measurements of further properties. For example, for a vacuum residue intended to be used as a paving grade, all the properties mentioned in the standard NF EN 12591 can be measured.
  • a system for estimating properties of a vacuum residue issued from a crude oil is proposed.
  • this estimating system is arranged to implement the steps of the method for estimating properties according to the invention.
  • This estimating system comprises :
  • the receiving means may be input or input/output interfaces. They can be wireless communication interfaces (Bluetooth, WIFI or other) or connectors (network port, USB port, serial port, Firewire ® port, SCSI port or other).
  • wireless communication interfaces Bluetooth, WIFI or other
  • connectors network port, USB port, serial port, Firewire ® port, SCSI port or other.
  • the treatment means may be one or several processors, for example microprocessors or microcontrollers.
  • the processor(s) may have storage means which may be random access memory (RAM), Electrically-Erasable Programmable Read-Only Memory (EEPROM), flash memory, external memory, or other. These storage devices can store, among other things, received data, estimated data and estimating model and computer program(s).
  • the estimating system may be arranged to perform a step of constructing the estimating model as disclosed above in respect of the estimating method of the invention.
  • the estimating system may then comprise :
  • the treatment means generating the model may be the same or different than the treatment means calculating the estimates.
  • the receiving means may be the same or different than the previously mentioned receiving means. These treatment means and receiving means may be as previously defined.
  • the estimating model may be as previously disclosed with respect to the estimating method and the treatment means arranged for generating first and second correlations as previously disclosed.
  • this homologating system may be arranged to implement the homologation method according to the invention.
  • This homologating system comprises :
  • the receiving means and treatment means may be defined as the previously mentioned receiving means and treatment means.
  • the receiving means may be arranged to receive estimated data from said estimating system, for example by appropriate communication means such as wiring elements or wireless communication elements.
  • the treatment means are arranged to decide the homologation of the crude oil as explained above for the homologating method.
  • such homologating system may further include the estimating system of the invention and the receiving means may be arranged to receive estimated data from said estimating system.
  • the receiving means and treatment means of the homologating system may include the receiving means and treatment means of the estimating system.
  • a computer program product comprising the instructions for carrying out the steps of the estimating method of the invention or of the homologating method of the invention, when said instructions are executed by one or more processors.
  • the above methods may indeed be implemented in a treatment device such as a processor, for example a microprocessor, a microcontroller or else.
  • Figure 1 represents a flowchart of a method for homologating a crude oil including a method for estimating properties according to one embodiment.
  • property data values of a vacuum residue issued from crude oil to homologate are provided, these property data values are : VC135 and VC100 as previously defined, Sulf for the wt% content of sulfur, Asph for the wt% content of asphaltenes.
  • STEP 1 and STEP 2 can be implemented by the estimating system of the invention.
  • the penetrability index is calculated from PEN_estimate and RTB_estimate, as defined in EN 12591.
  • PEN_estimate, RTB_estimate and PI_estimate are compared with threshold from specifications, here from specifications of EN12591.
  • the process goes to STEP 6 : the vacuum residue is considered as not homologated, more particularly not suitable for being homologated, the process is stopped.
  • STEP 5 the vacuum residue and the crude oil from which it is issued is homologated to produce a bitumen, in particular a bitumen of a specific grade and the process is stopped. Alternatively, it can be considered in STEP 5', that the vacuum residue (and the crude oil from which it is issued) is a good candidate for such homologation and the process then goes to STEP 7.
  • STEP 7 the crude oil is submitted to an atmospheric distillation and the atmospheric residue is submitted to a vacuum distillation to obtain a 560+cut.
  • the 560+cut then undergoes at least penetrability and softening point measurements, and preferably a measure of all the other properties required by the specifications for homologating a vacuum residue. Measured values of penetrability (PEN_measure) and of the softening point (RTB_measure) are then obtained.
  • PEN_measure penetrability
  • RTB_measure softening point
  • the PI index is calculated from PEN_measure and RTB_measure, the value obtained is noted PI_measure.
  • PEN_measure, RTB_measure and PI_measure are compared with threshold from specifications, here from specifications of EN12591.
  • the crude oil can be distilled (by atmospheric and vacuum distillation) to isolate several vacuum residues covering the penetrability ranges of all of the grades of EN12591, the properties of each of the vacuum residues being then measured according to the specifications.
  • STEP 3 to STEP 10 can be implemented by the homologating system of the invention.
  • Measured values VC135, VC100, Sulf, Asph, PEN (penetrability at 25°C) and RTB (softening point) have been collected from 69 vacuum residues issued from 50 crude oils.
  • the vacuum residues used for constructing the models have a penetrability at 25°C from 34 to 226 (1/10 mm).
  • the values VC100, VC135 and Sulf of these vacuum residues are within the minima and maxima collected in table 1.
  • Table 1 Minima and maxima of property data values of vacuum residues used for generating the model VC100 VC135 Sulf Asph mm 2 /s mm 2 /s wt% wt% MIN 253 63.1 0.345 0.02 MAX 122494 5369 9.060 29.50
  • f A , f B , f' A , f' B are distinct functions correlating PEN and RTB to the properties.
  • RMSE Root mean square Error
  • MAD Median of absolute values of deviations from data's median
  • PEN and RTB values have been estimated for a 560+cut of a crude using the models A of example 1.
  • the below table 9 gives the estimated values and measured values.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP20305976.1A 2020-09-03 2020-09-03 Verfahren und system zur schätzung der eigenschaften eines vakuumrückstands und zur homologisierung eines rohöls Withdrawn EP3964557A1 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11767478B1 (en) * 2022-10-26 2023-09-26 Saudi Arabian Oil Company Systems and methods for processing hydrocarbon feedstocks

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6011095A (en) * 1996-05-10 2000-01-04 Elf Antar France Method for preparing bitumen/polymer compositions and use thereof
US20100174494A1 (en) * 2007-05-02 2010-07-08 Peter De Peinder Method for predicting a physical property of a residue obtainable from a crude oil
US20140156241A1 (en) * 2012-01-06 2014-06-05 Bharat Petroleum Corporation Ltd. Prediction of refining characteristics of oil
WO2015173205A1 (fr) * 2014-05-15 2015-11-19 Total Marketing Services Composition bitumineuse performante a basse temperature et a temperature intermediaire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6011095A (en) * 1996-05-10 2000-01-04 Elf Antar France Method for preparing bitumen/polymer compositions and use thereof
US20100174494A1 (en) * 2007-05-02 2010-07-08 Peter De Peinder Method for predicting a physical property of a residue obtainable from a crude oil
US20140156241A1 (en) * 2012-01-06 2014-06-05 Bharat Petroleum Corporation Ltd. Prediction of refining characteristics of oil
WO2015173205A1 (fr) * 2014-05-15 2015-11-19 Total Marketing Services Composition bitumineuse performante a basse temperature et a temperature intermediaire

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11767478B1 (en) * 2022-10-26 2023-09-26 Saudi Arabian Oil Company Systems and methods for processing hydrocarbon feedstocks

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