DE102022110521A1 - Method for determining a standardized tendency of a mixture of substances to form soot - Google Patents

Abstract

The invention relates to a method for determining the tendency to soot formation by means of a gas chromatographic component analysis of hydrocarbon types and oxygenates of a mixture of substances, in particular a fuel (F) or an additive (B), by means of a reformulyzer analysis. It is provided that a normalizable overall soot formation tendency index (YSItotal ) of substance mixtures according to the equation (1) YSItotal = ΣYSIi · Vi / 100, whereby the percentage volumetric proportion (Vi) of each Reformulyzer subgroup (i) with the soot formation tendency index (YSIi) assigned to the Reformulyzer subgroup (i) is multiplied, after which the determined values are added up to form the overall soot formation tendency index (YSItotal). A procedure for determining a soot formation tendency index (YSIi) which represents the soot formation tendency index (YSIi) assigned to the subgroups (i) is also described.

Description

The invention relates to a method for determining the tendency to form soot by means of a gas chromatographic component analysis of hydrocarbon types and oxygenates of a mixture of substances.

The topic of soot particle formation in fuels is very crucial these days, as the emissions and soot particle formation from motor vehicles should be continually reduced. This is particularly due to the tightening of the guidelines in connection with the EU 7 reform. The new guidelines must be met for motor vehicles and fuels and a range of different fuels must be tested. Furthermore, the inventory effectiveness must be checked, for example for City Fuels. The YSI (Yield Sooting Index) represents a good basis for describing the tendency to soot formation. The YSI is referred to in German as the soot formation tendency index. This index is currently complicated to determine. It is then possible to determine the soot formation tendency index by means of an individual component analysis of a fuel. The disadvantage is that an individual component analysis must be carried out when determining the soot formation tendency index. This analysis involves a lot of data and is very time-consuming and costly. There is also the problem that with this method not all components can be assigned and are listed as unknowns. This ultimately leads to disadvantageous deviations in the calculation.

The publication is from the prior art DE 689 27 133 T2 known. It proposes a method for determining the aromatic carbon content of a hydrocarbon-containing solution containing more than one aromatic compound, which proceeds as follows. (a) The solution is separated into fractions using liquid chromatography. (b) Each fraction is irradiated separately with UV light in a wavelength range, at least a part of which is in the range from 200 nm to 400 nm. (c) The absorption of UV light is measured by the aromatic hydrocarbons in each fraction. (d) The integral of the absorption is then determined as a function of the photon energy over the energy corresponding to the wavelength range. (e) Finally, the aromatic carbon content is determined from the absorption integral.

The publication EP 1 953 545 A1 discloses a method for the quantitative analysis of a mixture of molecular compounds by two-dimensional gas chromatography, in which a two-dimensional chromatogram (CHR) is generated from a chromatographic signal (SB), and chromatographic peaks are selected on the polygon aid.

The method includes the following steps for at least one polygon: fitting a polygon by identifying portions of the chromatographic signal contained in the polygon, with the following further steps: (a) determining start times, end times and maximum chromatographic peaks, which are present on the portions. (b) The polygon is adjusted by moving intersections between the polygon and the sections as a function of start times, end times and maximum chromatographic peaks. (c) A quantity of at least one molecular compound is determined by calculating the area of the polygon so fitted.

The publication WO 1997/01142 A1 describes a method for predicting physical, perceptual, performance or chemical properties of a complex hydrocarbon mixture, comprising: (a) selecting at least one property of the hydrocarbon mixture, (b) selecting reference samples, the reference samples containing characteristic compound types that are in the complex hydrocarbon mixture and which have known values of the property or properties selected in step (a), (c) creating a sample set by the steps of: (1) injecting each reference sample into a gas chromatograph connected to a mass spectrometer, whereby at least a partial separation of the hydrocarbon mixture into chemical components is effected. (2) Introducing the chemical components of each reference sample into the mass spectrometer under dynamic flow conditions. (3) Obtain a series of time-resolved mass chromatograms for each reference sample. (4) Calibrate the mass chromatograms to correct retention times. (5) Select a series of corrected retention time windows. (6) selecting a set of molecular and/or fragment ions within each retention time window, the ions being representative of characteristic compounds or classes of molecules expected within the retention time window. (7) Record the total amount of each characteristic compound or group of compounds selected in step c (6). (8) Forming the data from steps c (6) and c (7) into an X-block matrix. (9) Forming the data selected in (a) for reference samples selected in (b) into a Y-block matrix. (10) Analyze the data from steps c(8) and c(9) by multivariate correlation techniques including partial least squares, principal component regression, or ridge regression to produce a series of coefficients. (d) subjecting an unknown hydrocarbon mixture to steps c(I) through c(3) in the same manner as the reference sample to produce a series of time-resolved mass chromatograms. (e) repeating steps c (4) to c (8) for each mass chromatogram of step (d) and (f) multiplying the matrix from step (e) by the coefficients from step c (10) to obtain a predicted value of the To create property or properties.

The prior art is summarized according to the publication DE 689 27 133 T2 a (molecule) group formation was suggested, while the publication EP 1 953 545 A1 the determination in peak groups provides, whereby finally the publication WO 1997/01142 A1 discloses selecting molecular and/or fragment ions to analyze hydrocarbon mixtures.

The invention is based on the object of developing a simplified method for determining a soot formation tendency index for a mixture of substances, which consists of a large number of individual components that differ in terms of material and percentage volume, in particular hydrocarbon types and oxygenates, whereby the method result should be suitable , to incorporate the soot formation tendency of mixtures of substances to be compared into the standardization in the form of a soot formation tendency index assigned to the substance mixtures.

The starting point of the method according to the invention is the ISO 22854:2016 standard with the title “Liquid mineral oil products - Determination of hydrocarbon types and oxygenates in motor vehicle gasoline and in ethanol (E85) - Multidimensional gas chromatography method”.

A reformulyzer analysis according to ISO 22854 is available for most fuels used today. This means that in most cases there is no individual component analysis, but rather a reformulyzer analysis according to the ISO 22854 standard. Gas chromatography is carried out according to ISO 22854. The result is then presented as a so-called Reformulyzer in a so-called Reformulyzer output. In the Reformulyzer analysis according to ISO 22854, the individual components are divided into functional supergroups and Reformulyzer groups, whereby the Reformulyzer analysis contains the Reformulyzer groups i, which are differentiated according to the number of carbon atoms. The Reformulyzer groups i, divided according to the number of carbon atoms, are also referred to as Reformulyzer subgroups.

In multidimensional gas chromatography, the percentage volumetric fraction V _i of the respective Reformulyzer subgroup i is also determined.

• (I) Einteilen der innerhalb der Komponentenanalyse bestimmten Kohlenwasserstofftypen und Oxygenaten des Stoffgemischs in funktionale Reformulyzer-Obergruppen,
• (II) Einteilen der bestimmten Kohlenwasserstofftypen und Oxygenaten nach der Anzahl der Kohlenstoffatome in Reformulyzer-Untergruppen (i), die den funktionalen Reformulyzer-Obergruppen zugeordnet sind,
• (III) Bestimmen des prozentualen volumetrischen Anteils (V_i) der jeweiligen Reformulyzer-Untergruppe (i) vom Gesamtvolumen des Stoffgemischs.

To determine the tendency to form soot by means of a gas chromatographic component analysis of hydrocarbon types and oxygenates of a mixture of substances, in particular a fuel (F) or an additive (B), using a reformulyzer analysis, the following steps are provided:

• (I) dividing the hydrocarbon types and oxygenates of the mixture determined within the component analysis into functional reformulyzer supergroups,
• (II) classifying the specific hydrocarbon types and oxygenates according to the number of carbon atoms into reformulyzer subgroups (i), which are assigned to the functional reformulyzer supergroups,
• (III) Determine the percentage volumetric proportion (V _i ) of the respective Reformulyzer subgroup (i) from the total volume of the substance mixture.

• (IV) Zuordnen eines Rußbildungsneigungs-Index (YSI_i) zu jeder Reformulyzer-Untergruppe (i) und das
• (V) Bestimmen eines Gesamt-Rußbildungsneigungs-Index (YSI_gesamt) nach der Gleichung (1) YSI_Gesamt = Σ YSI_i · V_i / 100, wobei der volumetrische Anteil (V_i) jeder Reformulyzer-Untergruppe (i) mit dem der Reformulyzer-Untergruppe (i) zugeordneten Rußbildungsneigungs-Index (YSI_i) multipliziert wird, wonach die ermittelten Werte zu dem Gesamt-Rußbildungsneigungs-Index (YSI_gesamt) aufsummiert werden.

According to the invention, further steps are provided:

• (IV) assigning a sooting propensity index (YSI _i ) to each Reformulyzer subgroup (i) and that
• (V) Determine an overall soot formation propensity index (YSI _total ) according to the equation (1) YSI _total = Σ YSI _i · V _i / 100, where the volumetric fraction (V _i ) of each Reformulyzer subgroup (i) is the same as that of Reformulyzer subgroup (i) assigned to the soot formation tendency index (YSI _i ) is multiplied, after which the determined values are summed up to form the overall soot formation tendency index (YSI _total ).

Preferred embodiments of the method are explained in the subclaims and in the description.

• 1 eine grundsätzliche Verfahrensweise in einer schematischen Übersichtsdarstellung und
• 2 eine durchgeführte Reformulyzeranalyse nach ISO 22854.

The invention is explained below with reference to the associated drawings. Show it:

• 1 a basic procedure in a schematic overview and
• 2 a reformulyzer analysis carried out according to ISO 22854.

1 shows the basic procedure in a schematic overview.

Using the method according to the invention, gasoline engine fuels F or additives B produced on the basis of hydrocarbons, so-called blends, which are usually added to the gasoline engine fuels F as additives, are examined for their tendency to form soot.

Within the process, a Reformulyzer analysis carried out according to ISO 22854, as explained and in the 1 and 2 is clarified, a division of the individual components into functional Reformulyzer supergroups and into Reformulyzer subgroups i, whereby the percentage volumetric share V _i of the respective Reformulyzer subgroup i is determined within the Reformulyzer analysis according to ISO 22854 and is therefore available for further development of the method.

The functional reformulyzer supergroups are naphthenes, paraffins, cyclic olefins, olefins, aromatics and oxygenates.

The Reformulyzer subgroups i are according to 2 assigned to the respective functional supergroups and sorted according to the number of carbon atoms with the reference symbol V _i (V = volumetric proportion in% of the total volume and i = number of carbon atoms).

According to the invention, each of these Reformulyzer subgroups i is assigned a soot formation tendency index, which is referred to below as YSI _i and is provided with the reference symbol YSI _i . One could therefore also speak of a subgroup YSI.

In the Reformulyzer analysis according to ISO 22854, only the group classification i and the percentage volumetric share V _i are available for the individual components, but not the soot formation tendency index of the individual components, so that ultimately no value for YSI _{i of} a Reformulyzer subgroup i is formed can.

• Der YSI_i der jeweiligen Reformulyzer-Untergruppe i wird aus einer dafür zur Verfügung stehenden Datenbank entnommen werden, welche die Anmelderin durch Auswertung der den jeweiligen Reformulyzer-Untergruppen i gehörenden Einzelkomponenten erstellt hat.

The method according to the invention overcomes this disadvantage as follows:

• The YSI _i of the respective Reformulyzer subgroup i will be taken from a database available for this purpose, which the applicant has created by evaluating the individual components belonging to the respective Reformulyzer subgroups i.

In other words, the database includes the individual components belonging to a Reformulyzer subgroup i with the respective YSI _i of the respective individual components, with the YSI _i for the respective Reformulyzer subgroup i being determined within the database according to the invention.

This YSI _i , assigned to the respective Reformulyzer subgroup i, applies on the database side independently of the percentage volumetric proportion V _i of the total volume of the mixture of substances examined, the percentage volumetric proportion V _i being advantageously provided by the Reformulyzer analysis according to ISO 22854.

The applicant recorded the YSI _i values of the individual components of the respective Reformulyzer subgroups i from its own DHA analyzes of the individual components of the respective Reformulyzer subgroups i and third-party databases.

Only for example, an arithmetic mean is formed from the database-side YSI _i values of the individual components of the respective Reformulyzer subgroup i, which is assigned to the Reformulyzer subgroup i as a representative YSI _i -M, which is used in the calculation of the overall soot formation tendency index explained below YSI _total is used as YSI _i in Equation 1.

The subject of this patent application is the simplified basic method for determining a standardized tendency to soot formation of a fuel F or an additive B or a total soot formation tendency index with the reference symbol YSI _total for a fuel F or an additive B.

YSIGesamt

→ Gesamt-Rußbildungsneigungs-Index des Kraftstoffs F oder des Zusatzstoffes B

YSIi

→ der YSI_i der jeweiligen Untergruppe i

Vi

→ der ermittelte Volumenanteil V_i in Prozent der jeweiligen Untergruppe i

Shows as an example 2 the percentage volumetric proportion V _i of the respective Reformulyzer subgroup i, which is used to calculate the overall soot formation tendency index with the reference symbol YSI _total according to equation 1. $${\text{YSI}}_{\text{In total}}={\displaystyle \sum {\text{YSI}}_{\text{i}}\cdot {\text{v}}_{\text{i}}}/100$$

YSITotal

→ Overall soot formation propensity index of fuel F or additive B

YSIi

→ the YSI _i of the respective subgroup i

Vi

→ the determined volume fraction V _i in percent of the respective subgroup i

Different fuels F and/or additives B can be compared with each other in a simpler manner than before using the _overall soot formation tendency index YSI, with a higher value of the overall YSI leading to more soot formation tending fuel F or additive B.

The simplification of this procedure is, in particular, that for a fuel F or an additive B there is no conventional, complex DHA evaluation (English: DHA = Detailed Hydrocarbon Analysis / German: = Detailed Hydrocarbon Analysis) of all individual components (number > 350) of the respective mixture of substances, in particular a fuel F and/or an additive B, needs to be determined more.

Advantageously, thanks to this procedure, it is no longer necessary to sum up all >350 individual components, but rather only the summation of the subgroups i is necessary, taking into account the percentage volumetric share V _i of the respective Reformulyzer subgroup i.

In addition, by using the Reformulyzer or the output of the Reformulyzer analysis as a basis for the evaluation, the problem of many unknowns, as explained above, no longer arises.

Ultimately, this makes a more robust determination possible, with the result being able to be achieved with significantly less effort, as is clear from the previous description.

The method has preferred embodiment variants.

In a first embodiment variant, it is provided that functional Reformulyzer supergroups are also combined. For example, the functional reformulyzer supergroups of olefins and cyclic olefins are combined into a functional reformulyzer supergroup. This means that less data has to be added up in the last step of the process, summing up.

In a second embodiment variant, it is provided that Reformulyzer subgroups i that are close to one another and whose values are less than five volume percent apart are combined within a functional Reformulyzer supergroup.

For example, within one of the functional Reformulyzer supergroups, the Reformulyzer subgroups i, for example C7 and C8, can be combined into a single Reformulyzer subgroup. This means that less data has to be added up in the last step of the process, summing up.

In a third embodiment variant, it is provided that Reformulyzer subgroups i that are close to one another and whose values are less than five volume percent apart are combined into several functional Reformulyzer supergroups. Thus, Reformulyzer subgroups i can be combined across several functional Reformulyzer supergroups, for example C7 and C8 to C(7+8) of the Reformulyzer supergroups to form a Reformulyzer subgroup i. This means that less data has to be added up in the last step of the process, summing up.

In a fourth embodiment variant, it is provided that Reformulyzer subgroups i that are close to one another and whose values are less than five volume percent apart from all functional Reformulyzer supergroups are combined. For example, across all functional Reformulyzer supergroups, for example C7 and C8 to C(7+8) of all Reformulyzer supergroups can be combined into a Reformulyzer subgroup i. This means that less data has to be added up in the last step of the process, summing up.

The first embodiment variant can be advantageously combined with at least one of the second to fourth embodiment variants.

Advantageously, “combining” according to the explained embodiment variants reduces the effort involved in calculating the overall soot formation tendency index YSI _overall depending on the selected embodiment variant YSI _overall .

In summary, the advantages of the method are that the costs for determining the overall soot formation tendency index YSI are reduced _overall , since no individual component analysis has to be carried out and existing standards (ISO 22854) can be used. Since there are no longer any unknowns when using the results of the Reformulyzer analysis, the advantage of the method is that a significantly more robust result is achieved, which does not fail due to unknown input variables, so that the result can always be determined. According to the method, a standard determination of the overall soot formation tendency index YSI _overall advantageously leads to a standard and standardizable statement about the soot formation tendency for each fuel F or additive B. That is, by means of the overall soot formation tendency index YSI _overall , one can advantageously make a Comparison of the overall soot formation tendency indices YSI _for different fuels F and additives B takes place and are standardized in a standard.

Finally, the invention provides that all fuels for which the tendency to soot formation must be predicted can be examined and evaluated, in particular standardized, using this method. The method can advantageously be used when developing new fuels F or additives B as well as when checking existing fuels.

When operating the vehicles, it is possible according to the invention for the overall soot formation tendency index YSI to be _transmitted either automatically (for example wirelessly) or manually to a receiving unit, in particular a control device with the receiving unit of a vehicle. If such a value is present in the engine control unit, the _total soot formation tendency index YSI can be used for a more precise determination of the control of the operating parameters of the internal combustion engine and/or the exhaust system. The _total soot formation tendency index YSI can also be displayed to the user via the HMI, so that the user has standardized information about whether he is using a fuel F or an additive B that tends to produce a high level of soot formation or a low level of soot formation.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 68927133 T2 [0003, 0007]
• EP 1953545 A1 [0004, 0007]
• WO 199701142 A1 [0006, 0007]

Claims (10)

Method for determining the tendency to soot formation by means of a gas chromatographic component analysis of hydrocarbon types and oxygenates of a mixture of substances, in particular a fuel (F) or an additive (B) by means of a reformulyzer analysis with the steps: (I) Classifying the hydrocarbon types and oxygenates of the mixture of substances determined within the component analysis functional Reformulyzer supergroups, (II) dividing the specific hydrocarbon types and oxygenates according to the number of carbon atoms into Reformulyzer subgroups (i), which are assigned to the functional Reformulyzer supergroups, (III) determining the percentage volumetric fraction (V _i ) of the respective Reformulyzer subgroup (i) from the total volume of the mixture of substances, characterized by the steps: (IV) assigning a sooting propensity index (YSI _i ) to each Reformulyzer subgroup (i), (V) determining an overall sooting propensity index (YSI _total ) according to the equation (1) YSI _Total = Σ YSI _i · V _i / 100, where the volumetric proportion (V _i ) of each Reformulyzer subgroup (i) with the soot formation tendency index (YSI i.) assigned to the Reformulyzer subgroup (i _). ) is multiplied, after which the determined values are added up to form the overall soot formation index (YSI _total ). Procedure according to Claim 1 , characterized in that the soot formation tendency index (YSI _i ) assigned to the respective Reformulyzer subgroup (i) is taken from a database, the value of the soot formation tendency index (YSI _i ) of the respective Reformulyzer subgroup (i) being on the Basis of the individual components of a Reformulyzer subgroup (i) present in the database is provided. Procedure according to Claim 1 , characterized in that before determining the overall soot formation propensity index (YSI _total ), at least two or more functional Reformulyzer supergroups are combined into a functional Reformulyzer supergroup. Procedure according to Claim 1 , characterized in that before determining the overall soot formation propensity index (YSI _total ), Reformulyzer subgroups (i) that are close to each other are combined within a functional Reformulyzer supergroup whose values are less than five percent by volume apart. Procedure according to Claim 1 , characterized in that before determining the overall soot formation propensity index (YSI _total ), closely spaced Reformulyzer subgroups (i) of several functional Reformulyzer supergroups, whose values are less than five percent by volume apart, are combined. Procedure according to Claim 1 , characterized in that before determining the overall soot formation propensity index (YSI _total ), closely spaced Reformulyzer subgroups (i) of all functional Reformulyzer supergroups, whose values are less than five percent by volume apart, are combined. Procedure according to Claim 3 , characterized in that the combining of functional Reformulyzer supergroups into a functional Reformulyzer supergroup with the combining of closely spaced Reformulyzer subgroups (i), whose values are less than five volume percent apart, according to at least one of the Claims 4 until 6 is combined. Procedure according to Claim 1 , characterized in that the overall soot formation tendency index (YSI _total ) is transmitted either automatically or manually to a receiving unit of a vehicle. Procedure according to Claim 8 , characterized in that the soot formation tendency index (YSI _total ) is used as an additional input variable for a more precise determination of the control of the operating parameters of an internal combustion engine and / or an exhaust system of the vehicle. Procedure according to Claim 1 , characterized in that the total soot formation tendency index (YSI _total ) is used for standardization with regard to the soot formation tendency of several, at least two different substance mixtures examined within the process, in particular fuels (F) or additives (B).

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