Method for determining normalized carbon deposition tendency of substance mixture and for calculating representative index of total carbon deposition tendency

Abstract

A method for determining a normalized carbon deposition tendency of a mixture of substances and for calculating a representative index of a total carbon deposition tendency. The invention relates to a method for determining the tendency to carbon deposition by means of a Reformulyzer analysis using a gas chromatography composition analysis of a substance mixture, in particular of the hydrocarbon type of a fuel (F) or of an additive (B), and of oxygenates. It is provided that the normalized total carbon deposition yield index (YSITotal) of the substance mixture according to the equation (1) YSITotal = sigma YSIi Vi / 100 is determined, in which the volume ratio (Vi) of each Reformyzer subset (i) is multiplied by the carbon deposition yield index (YSIi) associated with the Reformyzer subset (i), whereby the determined values are added up to obtain the total carbon deposition yield index (YSITotal). Furthermore, a method variant for determining a carbon deposition yield index (YSIi-M, YSIi-Mid, YSIi-GewM) representative of the carbon deposition yield index (YSIi) associated with a subset (i) is described.

Description

[0001] The present invention relates to a method for determining carbon deposition tendency using gas chromatographic compositional analysis of hydrocarbon types and oxygen-containing compounds of a substance mixture.

[0002] Nowadays, the topic of carbon particle formation of fuels is very critical, because emissions or carbon particle formation of motor vehicles are to be further reduced. This is particularly linked to the tightening of the guidelines related to the EU7 reform. New guidelines for motor vehicles or fuels must be met and a series of different fuels must be tested. In addition, for example, for urban fuels, the supply efficiency must be checked. The YSI (carbon yield index) is a good basis for describing the carbon tendency. In German, the YSI is called the "Ruβbildungsneigungs-Index". This index is currently difficult to determine. Based on this, it is possible to determine the carbon yield index by individual component analysis of the fuel. Disadvantageously, when determining the carbon index, an individual component analysis must therefore be performed. This analysis involves a large amount of data and is very time-consuming and costly. In addition, there is the problem that in this method, not all components can be assigned and are listed as unknown. Disadvantageously, this ultimately leads to deviations in the calculation.

[0003] DE 689 27 133 T2 is known from the prior art. It proposes a method for determining the aromatic carbon content in a hydrocarbon-containing solution containing more than one aromatic compound, in which the procedure is as follows. (a) The solution is separated into its constituent parts by liquid chromatography. (b) Each constituent part is irradiated separately with UV light in a wavelength range, at least a portion of which is in the range from 200 to 400 nanometers. (c) The absorption of the UV light by the aromatic hydrocarbons in each constituent part is measured. (d) The absorption integral is then determined as a function of the photon energy at the energy corresponding to the wavelength range. (e) Finally, the aromatic carbon content is determined from the absorption integral.

[0004] EP 1 953 545 A1 discloses a method for the quantitative analysis of a mixture of molecular compounds by two-dimensional gas chromatography, wherein a two-dimensional chromatogram (CHR) is generated from the chromatographic signals (SB) and the chromatographic peaks are selected with the aid of polygons.

[0005] For at least one polygon, the method comprises the steps of: fitting the polygon by identifying the portion of the chromatographic signal contained in the polygon, with the following further steps: (a) determining the start time, the end time and the largest chromatographic peak present on the portion. (b) setting the polygon by moving the intersection point between the polygon and these portions according to the start time, the end time and the largest chromatographic peak. (c) determining the amount of at least one molecular compound by calculating the area of ​​the polygon fitted in this way.

[0006] WO 1997 / 01142A1 describes a method for predicting a physical, sensory, performance or chemical property of a complex hydrocarbon mixture, the method comprising: (a) selecting at least one property of the hydrocarbon mixture. (b) selecting a reference sample, wherein the reference sample comprises a characteristic compound type present in the complex hydrocarbon mixture and has a known value of one or more properties selected in step (a). (c) creating a sample set using the following steps: (1) injecting each reference sample into a gas chromatograph connected to a mass spectrometer so that at least a portion of the hydrocarbon mixture is separated into chemical components. (2) introducing the chemical components of each reference sample into the mass spectrometer under dynamic flow conditions. (3) obtaining a series of time-resolved mass chromatograms for each reference sample. (4) calibrating the mass chromatograms to correct for retention times. (5) selecting a series of corrected retention time windows. (6) selecting a series of molecular and / or fragment ions within each retention time window, wherein the ions represent the expected characteristic compounds or molecular classes within the retention time window. (7) recording the total amount of each characteristic compound or group of compounds selected in step c(6). (8) Creating the data from steps c(6) and c(7) in an X block matrix. (9) Creating the data selected in (a) for the reference sample selected in (b) in a Y block matrix. (10) Analyzing the data from steps c(8) and c(9) using a multivariate correlation technique (including partial least squares, principal component regression, or ridge regression) to produce a series of coefficients. (d) Performing steps c(1) to c(3) on the unknown hydrocarbon mixture in the same manner as for the reference sample to produce a series of time-resolved mass chromatograms. (e) Repeating steps c(4) to c(8) for each mass spectrum of step (d), and (f) Multiplying the matrix from step (e) by the coefficients from step c(10) to produce predicted values ​​for one or more properties.

[0007] In summary, in the prior art according to DE 689 27 133 T2, (molecular) group formation is proposed, whereas according to EP 1 953 545 A1, peak groups are determined, wherein, finally, WO 1997 / 01142 A1 discloses the selection of molecules and / or fragment ions for the analysis of hydrocarbon mixtures.

[0008] The invention is based on the object of developing a simplified method for determining the carbon deposition tendency index of a material mixture, which consists of a plurality of individual components, in particular hydrocarbon types and oxygen-containing compounds, which differ in material and overall volume, wherein the method results in being suitable for inputting the carbon deposition tendency of the material mixture to be compared into a standardization in the form of a carbon deposition tendency index associated with the material mixture.

[0009] The starting point for the method according to the invention is the ISO 22854:2016 standard entitled “Liquid petroleum products—Determination of hydrocarbon types and oxygenates in automotive-motor gasoline and inethanol (E85)—Multidimensional gas chromatography method”.

[0010] Reformulyzer analysis according to ISO 222854 exists for most fuels that appear today. Therefore, there is usually no individual component analysis, but a Reformulyzer analysis according to the ISO 22854 standard. Gas chromatography is performed according to ISO 22854. The results are then displayed in a so-called Reformulyzer output as a so-called Reformulyzer. In the Reformulyzer analysis according to ISO 22854, the individual components are classified into functional supergroups and Reformulyzer groups, wherein the Reformulyzer analysis contains Reformulyzer group i that is differentiated according to the number of carbon atoms. Reformulyzer group i classified according to the number of carbon atoms is also called Reformulyzer subgroup.

[0011] Multidimensional gas chromatography also provides the volume percentage V of the corresponding Reformulyzer subgroup i i .

[0012] In order to determine the carbon deposition tendency using a gas chromatographic composition analysis of the hydrocarbon types and oxygenates of a substance mixture, in particular a fuel (F) or an additive (B), by means of a Reformulyzer analysis, the following steps are provided: (I) classification of the hydrocarbon types and oxygen-containing compounds of the substance mixture determined within the composition analysis into functional Reformulyzer supergroups, (II) Classification of the determined hydrocarbon types and oxygenates according to the number of carbon atoms into Reformulyzer subgroups (i), which are associated with functional Reformulyzer supergroups, (III) Determine the volume percentage (V) of the corresponding Reformulyzer subgroup (i) from the total volume of the substance mixture i ).

[0013] According to the present invention, a further step is provided, which (IV) Assign a carbon yield index (YSI) to each Reformulyzer subgroup (i)i ),as well as (V) According to equation (1) YSI Total =∑YSI i ·V i / 100 to determine the total carbon yield index (YSI Total ), where the volume ratio (V i ) multiplied by the carbon yield index (YSI) associated with that Reformulyzer subgroup (i) i ), and the determined values ​​are added to obtain the total carbon yield index (YSI Total ).

[0014] Preferred embodiments of the method are explained in the dependent claims and in the description.

[0015] The present invention will now be explained using the associated drawings. Figure 1 shows the basic procedure in a schematic overview, and Figure 2 and Figure 3 A Reformulyzer analysis performed according to ISO 222854 is shown.

[0016] Figure 1 The basic procedure is shown in a schematic overview.

[0017] By means of the method according to the invention, gasoline engine fuels F or additives B produced on the basis of hydrocarbons, so-called mixtures which are primarily added to gasoline engine fuels F as additives, are examined with regard to their tendency to deposit carbon.

[0018] In this method, as explained and in Figures 1 to 3 The Reformulyzer analysis performed according to ISO 222854 shown in FIG. 1 provides for the classification of the individual components into functional Reformulyzer supergroups and Reformulyzer subgroups i, wherein within the Reformulyzer analysis according to ISO 222854 the volume percentage V of the respective Reformulyzer subgroup i is determined. i , and can therefore be used to further develop the method.

[0019] The functional Reformulyzer supergroup is cycloalkanes, paraffins, cycloalkenes, olefins, aromatics and oxygenates.

[0020] according to Figure 2 , Reformulyzer subgroup i is associated with the corresponding functional supergroup and has the reference symbol V according to the carbon atom i(V = volume ratio to total volume (in %), i = number of carbon atoms).

[0021] According to the invention, each of these Reformulyzer subgroups i is associated with a carbon yield index, subsequently referred to as YSI i , and is given the reference symbol YSI i Therefore, it may also be called YSI i Subgroup.

[0022] In the Reformulyzer analysis according to ISO 222854, only the group classification i and the volume percentage V i It can be used for individual components, but the carbon yield index of individual components is not the same, so that the carbon yield index YSI of Reformulyzer subgroup i cannot be formed in the end i The value of .

[0023] The method according to the invention overcomes this disadvantage as follows:

[0024] The carbon yield index YSI of the corresponding Reformulyzer subgroup i i Taken from a database available for this purpose, which was created by the applicant by evaluating the individual ingredients belonging to the corresponding Reformulyzer subgroup i.

[0025] In other words, the database includes individual components belonging to Reformulyzer subgroup i with corresponding YSI i , wherein, according to the invention, the corresponding Reformulyzer subgroup i is executed in the database = YSI i of determination.

[0026] In terms of the database, the YSI associated with the corresponding Reformulyzer subgroup i i The volume percentage V is independent of the total volume of the substance mixture under study i And application, where the volume percentage V i Advantageously provided by Reformulyzer analysis according to ISO 222854.

[0027] Different method variants have been proposed to define the YSI to be used i The following is used to determine the YSI i The method variants represent the YSI of the Reformulyzer subgroup i in various ways i wherein the method variant is particularly useful in determining the YSI of the corresponding Reformulyzer subgroup i iAll protocols were successful but differed in the data sets that were retrieved from the database and made available, as explained below in terms of the description of the method variants.

[0028] Principle: According to the invention, a representative carbon deposit yield index is associated with each of the Reformulyzer subgroups i.

[0029] According to the creation of a representative carbon deposition yield index, the present invention proposes the following preferred method variants:

[0030] In a first method variant, the YSI of the individual components of the corresponding Reformulyzer subgroup i is taken from the database. i Value, create a representative carbon yield index YSI for each Reformulyzer subgroup i i -M:

[0031] From their own DHA analysis on the individual components of the corresponding Reformulyzer subgroup i and a database unknown to the applicant, the applicant detected the YSI of the corresponding individual components of the corresponding Reformulyzer subgroup i. i value.

[0032] For example, the Reformulyzer subgroup i=C10 in the Reformulyzer supergroup of aromatic hydrocarbons contains =35 different individual components. Within the Reformulyzer subgroup i=C10, each individual component is related to the YSI i Value associated.

[0033] To simplify the method, the individual components of the Reformulyzer subgroup i are based on the YSI database i The arithmetic mean of the values ​​was created and used as the representative YSI i -M is associated with Reformulyzer subgroup i, which represents YSI i -M Total Carbon Deposition Yield Index (YSI) explained below Total Used as YSI in calculations i .

[0034] In a second method variant, the YSI of the individual components of the corresponding Reformulyzer subgroup i is taken from the database. i Value, create a representative carbon yield index YSI for each Reformulyzer subgroup i i -Mid:

[0035] Database and corresponding individual components of Reformulyzer subgroup i unknown to applicants, with respect to available YSI from their own DHA analysis i Value, the starting position corresponds to the first method variant.

[0036] In contrast to the first method variant, the representative carbon deposit yield index is defined as the average carbon deposit yield index YSI i -Mid (first see Figure 3 ), which is calculated by calculating the minimum YSI of all individual components of Reformulyzer subgroup i i -Min and Max YSI i -Max values. Figure 3 The third column records the associated average carbon yield index YSI i -Mid, which is the total carbon yield index YSI explained below Total Used as YSI in calculations i .

[0037] Therefore, if Figure 3 As shown in, for example, the Reformulyzer subgroup i=C10 in the Reformulyzer supergroup aromatics can contain =35 different individual components. YSI i -Min value = 199.1, and YSI i -Max value = 466.1, whereby in this exemplary embodiment, the representative average carbon yield index average value YSI for Reformulyzer subgroup i = C10 i -Mid gets YSI i -Mid=332.60.

[0038] Average carbon deposition yield index YSI i -Mid as a representative YSI i -Mid is associated with Reformulyzer subgroup i, which is the total carbon yield index YSI explained below Total Used as YSI in calculations i .

[0039] In a third method variant, the YSI of the individual components of the corresponding Reformulyzer subgroup i is taken from the database. i Value, create a representative carbon yield index YSI for each Reformulyzer subgroup i i -GewM.

[0040] For the individual components of the corresponding Reformulyzer subgroup i and a database unknown to the applicant, regarding the available YSI from their own DHA analysis i The starting position of the values ​​corresponds to the first and second method variants.

[0041] According to the invention, in this third method variant, starting from the first method variant of the arithmetic mean, a weighted arithmetic mean is provided for the individual Reformulyzer subgroups i.

[0042] For this purpose, the frequency with which specific individual components occur / were detected in the different substance mixtures investigated (in particular fuel F and additive B) is determined in the database.

[0043] The applicant used a large database with carbon deposit yield indices associated with individual components from at least 60 different conventional fuels F and additives B in the field (i.e. in use), from which it was possible to verify the relevance in terms of the frequency of the respective individual components within the Reformulyzer subgroup i. The respective individual components were assessed to be frequently occurring and therefore relevant if they occurred in at least half of the fuels considered.

[0044] Advantageously, therefore, it is possible to weight the individual components within a Reformulyzer subgroup i relative to their frequency.

[0045] For example, there are 35 individual components, such as aromatic hydrocarbons, in the functional Reformulyzer supergroup.

[0046] For weighted arithmetic mean, the frequency values ​​obtained from the database test are associated with the individual components and a representative weighted arithmetic mean YSI is calculated. i -GewM is taken into account.

[0047] In other words, rarely occurring individual components that occur in less than fifty percent of the fuels previously evaluated in the database are therefore not weighted during determination of the weighted arithmetic mean, such that the representative weighted average arithmetic carbon yield index YSI i -GewM is different from the other carbon yield index YSI of the first and second method variants i -M and YSI i -Mid.

[0048] The subject of the present patent application is therefore: A simplified general method for determining the normalized carbon deposit tendency or the total carbon deposit yield index of a fuel F or an additive B, the total carbon deposit yield index having the reference symbol YSI for the fuel F or the additive B. Total; There is also a way to determine a representative carbon deposition yield index for the corresponding Reformulyzer subgroup i.

[0049] For example, Figure 2 Shows the volume ratio V of the Reformulyzer subgroup i i , which is used to calculate the total carbon yield index according to Equation 1, which has the reference symbol YSI Total . (Equation 1) YSI Total =∑YSI i ·V i / 100 YSI Total →Total carbon deposit yield index of fuel F or additive B YSI i →YSI of the corresponding subgroup i i V i → The determined volume proportion V expressed as a percentage of the corresponding subgroup i i

[0050] Equation 1 again provides the total carbon yield index YSI Total The general solution of .

[0051] Depending on the method variant, the YSI explained above i -M or YSI i -Mid or YSI i - One of the indices of GewM is considered as the YSI of the corresponding Reformulyzer subgroup i i , that is, is used in Equation 1.

[0052] Thus, the various fuels F and / or additives B can be analyzed in a simpler manner than hitherto via the total soot yield index YSI. Total A comparison is made where a higher value of the total YSI characterizes Fuel F or Additive B having a greater tendency to carbon deposit.

[0053] The procedure is simplified in particular in that the conventional complex DHA evaluation (English: DHA=Detailed Hydrocarbon Analysis) of determining all individual components (number > 350) of the corresponding substance mixture (in particular fuel F and / or additive B) for fuel F or additive B is no longer necessary.

[0054] In an advantageous manner, this procedure results in that it is no longer necessary to sum all >350 individual components; instead, the volume percentage V of the corresponding Reformulyzer subgroup i is taken into account. i , only the summation of subgroup i is required.

[0055] Furthermore, by using the Reformulyzer or the output of a Reformulyzer analysis as the basis for the evaluation, advantageously, the problem of many unknowns as described above no longer arises.

[0056] Finally, a more robust determination is thereby possible, wherein the result can be obtained with much less effort, as is clear from the preceding description.

[0057] The method has preferred embodiment variants.

[0058] In a first embodiment variant, provision is made for additionally combining functional Reformulyzer supergroups. For example, the functional Reformulyzer supergroups of olefins and cycloolefins are combined to form a functional Reformulyzer supergroup. Thus, in the last step of the method (i.e. the summation), less data needs to be summed.

[0059] According to a second embodiment variant, Reformulyzer subgroups i that are close to one another and whose values ​​differ by less than 5 volume percent are combined in a functional Reformulyzer supergroup.

[0060] For example, within the functional Reformulyzer supergroup, Reformulyzer subgroups i (e.g. C7 and C8) can be combined into a single Reformulyzer subgroup. Thus, in the final step of the method (i.e. summation), less data needs to be summed.

[0061] According to the third embodiment variant, Reformulyzer subgroups i that are close to each other and whose values ​​differ by less than 5 volume percent are combined into multiple functional Reformulyzer supergroups. Therefore, Reformulyzer subgroups i can be combined into Reformulyzer subgroups i across multiple functional Reformulyzer supergroups (e.g., C7 and C8 to C(7+8) of the Reformulyzer supergroup). Therefore, in the last step (i.e., summation) of the method, less data needs to be summed.

[0062] In a fourth embodiment variant, it is provided that the Reformulyzer subgroups i of all functional Reformulyzer supergroups that are close to each other and whose values ​​differ by less than 5 volume percent are combined. For example, it is possible to combine across all functional Reformulyzer supergroups (e.g. C7 and C8 to C(7+8) of all Reformulyzer supergroups) to create a Reformulyzer subgroup i. Thus, in the last step (summation) of the method, less data needs to be summed.

[0063] The first embodiment variant may be advantageously combined with at least one of the second to fourth embodiments.

[0064] In an advantageous manner, the “combination” according to the explained embodiment variants reduces the calculation accordingly as the selected embodiment variant YSI Total Total carbon yield index YSI as a function of Total of expenses.

[0065] In summary, the advantage of this method is that it reduces the total carbon yield index YSI Total The cost of the method is reduced, since no individual component analysis has to be performed and an existing standard (ISO 22854) can be used. As an advantage of this method, significantly more robust results are also obtained, which do not fail due to unknown input variables, since unknown terms no longer appear when using the results of the Reformulyzer analysis, which means that the results can always be determined. In addition, according to this method, the total YSI index YSI Total The standard determination of YSI advantageously results in a standard and standardized statement about the carbon deposit tendency of each fuel F or additive B. This means that by using the total carbon deposit yield index YSI Total , the total carbon yield index YSI for different fuels F and additives B can be advantageously performed Total and standardized in the standard.

[0066] Finally, according to the invention, by means of this method, all fuels in which the tendency to carbon deposits must be predicted can be checked and evaluated, in particular standardized. Advantageously, the method can already be used during the new development of fuels F or additives B, and can also be used in the testing of stock fuels.

[0067] During operation of the vehicle, according to the invention, it is possible to automatically (e.g. wirelessly) or manually set the total carbon yield index YSI Total The carbon deposit yield index YSI is transmitted to a receiving unit, in particular a control device of a receiving unit of a vehicle. If such a value is present in the engine control unit, the carbon deposit yield index YSI Total It can be used to more accurately determine the control of operating parameters of the internal combustion engine and / or exhaust system. Total It can also be displayed to the user via the HMI, thereby providing the user with standardized information about whether they are using a fuel F or additive B with a high or low carbon deposit tendency.

Claims

1. A method for determining the carbon deposition tendency by gas chromatographic composition analysis of hydrocarbon types and oxygen-containing compounds of a substance mixture, in particular a fuel (F) or an additive (B), by Reformulyzer analysis, said method The following steps are involved: (I) classifying the hydrocarbon types and oxygenates of the substance mixture determined within the compositional analysis into functional Reformulyzer supergroups, (II) classifying determined hydrocarbon types and oxygenates according to the number of carbon atoms into Reformulyzer subgroups (i), said Reformulyzer subgroups (i) being associated with said functional Reformulyzer supergroup, (III) determining the volume percentage (Vi) of the corresponding Reformulyzer subgroup (i) from the total volume of the substance mixture, It is characterized by the following steps: (IV) Assign a carbon yield index (YSI) to each Reformulyzer subgroup (i) i ), (V) According to equation (1) YSl Total =ΣYSI i ·V i / 100 to determine the total carbon yield index (YSI Total ), where the volume ratio (V i ) multiplied by the carbon yield index (YSI) associated with the Reformulyzer subgroup (i) i ), and the determined values ​​are added to obtain the total carbon yield index (YSI Total ).

2. The method according to claim 1, It is characterized in that The carbon yield index (YSI) associated with the corresponding Reformulyzer subgroup (i) i ) is taken from the database, wherein the carbon yield index (YSI) of the corresponding Reformulyzer subgroup (i) i ) are provided based on the corresponding individual components of the Reformulyzer subgroup (i) available in said database.

3. The method according to claim 2, It is characterized in that The carbon yield index (YSI i ) is a database YSI of individual components of the Reformulyzer subgroup (i) i The values ​​are generated as arithmetic means, where, in the corresponding arithmetic mean, The carbon yield index (YSI) of all individual components of the Reformulyzer subgroup (i) i ) values ​​flow into the representative arithmetic mean (YSI i -M), or The carbon yield index (YSI) of all individual components of the Reformulyzer subgroup (i) i ) i Value (YSI i -Min) and Maximum YSI i Value (YSI i -Max) into the representative arithmetic mean (YSI i -Mid), or The carbon yield index (YSI) of all individual components of the Reformulyzer subgroup (i) i ) into the representative arithmetic mean (YSI i -GewM), said representative arithmetic mean weighting the frequency of occurrence of said individual components within said Reformulyzer subgroup (i), wherein during said weighting only individual components occurring in at least 50% of the fuels considered in said database are taken into account.

4. The method according to claim 1, It is characterized in that In determining the total carbon yield index (YSI Total ), at least two or more functional Reformulyzer supergroups are combined into one functional Reformulyzer supergroup.

5. The method according to claim 1, It is characterized in that In determining the total carbon yield index (YSI Total ) before combining Reformulyzer subgroups (i) within the functional Reformulyzer supergroup that are close to each other and whose values ​​differ by less than 5 volume percent.

6. The method according to claim 1, It is characterized in that In determining the total carbon yield index (YSI Total ), combine Reformulyzer subgroups (i) of a plurality of functional Reformulyzer supergroups that are close to each other and whose values ​​differ by less than 5 volume percent.

7. The method according to claim 1, It is characterized in that In determining the total carbon yield index (YSI Total ), combine all Reformulyzer subgroups (i) of the functional Reformulyzer supergroup that are close to each other and whose values ​​differ by less than 5 volume percent.

8. The method according to claim 4, It is characterized in that Combining functional Reformulyzer supergroups into one functional Reformulyzer supergroup in combination with Reformulyzer subgroups (i) according to at least one of claims 5 to 7 which are close in combination to one another, the values ​​of which differ by less than 5 volume percent.

9. The method according to claim 1, It is characterized in that The carbon yield index (YSI Total ) is automatically or manually transmitted to a receiving unit of the vehicle.

10. The method according to claim 9, It is characterized in that The carbon yield index (YSI Total ) are used as additional input variables for more accurately determining the control of operating parameters of the internal combustion engine and / or the exhaust system of the vehicle.

11. The method according to claim 1, It is characterized in that The total carbon yield index (YSI Total ) is used to standardize the carbon deposition tendency of a plurality of at least two different substance mixtures investigated within the method, in particular fuels (F) or additives (B).

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