JP7171777B2 - Gasoline production method - Google Patents

Description

The present invention relates to a method for producing gasoline.

Conventionally, there has been known a method for producing a gasoline base material by reforming naphtha to produce a gasoline base material (see, for example, Patent Document 1). In the method for producing a gasoline base material described in Patent Document 1, catalytically reformed gasoline obtained by catalytically reforming naphtha is subjected to a distillation treatment to obtain a low boiling point fraction, a medium boiling point fraction, and a high boiling point fraction. After separation, the low-boiling fraction and the high-boiling fraction are mixed to produce a gasoline base stock with a high octane number.

JP 2015-189890 A

When a mixed fuel is produced by mixing a low boiling point fraction and a high boiling point fraction of catalytically reformed gasoline as in the production method described in Patent Document 1, the octane number of the mixed fuel is mixed with the octane number of each fraction. It is difficult to efficiently produce a high octane mixed fuel.

One aspect of the present invention is a method for producing gasoline, wherein light naphtha is mixed with cyclopentane, and the product of the octane number of light naphtha and the mixing ratio of light naphtha, the octane number of cyclopentane and the mixing ratio of cyclopentane are and calculating the difference between the calculated octane number of gasoline calculated as the sum of the product and the measured octane number of gasoline . The mixture ratio of cyclopentane is determined so that the octane number of gasoline falls within a predetermined range set according to the octane number of regular gasoline, and the mixture ratio at which the difference is maximum is the center, and the difference is a predetermined value or more. is determined within a predetermined range .

According to the present invention, high-octane gasoline can be efficiently produced.

The figure for demonstrating an example of the renewable fuel manufactured using renewable energy. FIG. 4 is a diagram showing an example of octane numbers of mixed fuel prepared by adding cyclopentane to standard fuel. FIG. 4 is a graph showing characteristics of the octane bonus with respect to the mixture ratio of cyclopentane and the octane number of standard fuel. FIG. 4 is a graph showing characteristics of the mixture ratio of cyclopentane and the octane number (actual value) of the mixed fuel with respect to the octane number of the standard fuel. The figure which shows an example of the combustion-test result of mixed fuel. FIG. 4 is a graph showing the characteristics of ignition delay time of mixed fuel with respect to the mixture ratio of cyclopentane and the octane number of standard fuel. FIG. 4 is a diagram for explaining an example of a suitable mixing ratio of cyclopentane when adding cyclopentane to FT light naphtha to produce reformed gasoline. FIG. 5 is a diagram for explaining another example of a suitable mixing ratio of cyclopentane when adding cyclopentane to FT light naphtha to produce reformed gasoline. FIG. 4 is a diagram for explaining still another example of a suitable mixing ratio of cyclopentane when adding cyclopentane to FT light naphtha to produce reformed gasoline. The figure for demonstrating the addition effect of the cyclopentane with respect to a paraffinic hydrocarbon. FIG. 4 is a diagram for explaining the breakdown of OH radicals consumed and produced in the combustion process of each mixed fuel;

An embodiment of the present invention will be described below with reference to FIGS. 1 to 11. FIG. A method for producing gasoline according to an embodiment of the present invention reforms light naphtha with a low octane number to produce reformed gasoline with a high octane number.

Greenhouse gases in the atmosphere keep the average temperature of the earth warm enough for life. Specifically, greenhouse gases absorb part of the heat radiated from the ground surface warmed by sunlight into outer space and radiate it back to the ground surface, keeping the atmosphere warm. it's dripping When the concentration of such greenhouse gases in the atmosphere increases, the average temperature of the earth rises (global warming).

The concentration of carbon dioxide in the atmosphere, which contributes greatly to global warming among greenhouse gases, is the balance between the carbon fixed on and in the ground as plants and fossil fuels and the carbon existing in the atmosphere as carbon dioxide. determined by For example, when carbon dioxide in the atmosphere is absorbed by photosynthesis during the growth process of plants, the concentration of carbon dioxide in the atmosphere decreases, and when carbon dioxide is released into the atmosphere by burning fossil fuels, carbon dioxide in the atmosphere concentration increases. In order to curb global warming, it is necessary to replace fossil fuels with renewable energy such as solar, wind, and biomass to reduce carbon emissions.

FIG. 1 is a diagram for explaining an example of renewable fuel produced using renewable energy, and shows renewable fuel produced via FT (Fischer-Tropsch) synthesis. As shown in FIG. 1, renewable power is generated by photovoltaic power generation or wind power generation, and the renewable power is used to electrolyze water to generate renewable hydrogen. Furthermore, FT synthesis is performed using renewable hydrogen and carbon dioxide recovered from factory exhaust gas or the like to produce FT crude oil.

FT crude oil is fractionated according to boiling range and separated into FT diesel, jet fuel and FT light naphtha. Of these, FT diesel can be used as fuel for diesel engines, and jet fuel can be used as fuel for jet engines. On the other hand, FT light naphtha is mainly composed of linear saturated hydrocarbons (paraffinic hydrocarbons) with about 4 to 6 carbon atoms, so the research octane number is as low as about 60 to 70, so it can be used as fuel for gasoline engines. This may impair the combustion performance of the engine.

In this regard, the inventors have found that adding (mixing) cyclopentane to a paraffinic hydrocarbon increases the octane number to a value greater than expected depending on the octane number and mixing ratio of both. Therefore, in the present embodiment, a gasoline production method will be described in which cyclopentane is added to FT light naphtha for reforming to produce reformed gasoline with a high octane number.

FIG. 2 shows a mixture of fuel prepared by adding cyclopentane (octane number 103.2) to a standard fuel (octane number (research octane number RON) 65) at a different mixing ratio x (% by volume under standard conditions). It is a figure which shows an example of an octane number. The standard fuel is prepared by blending isooctane (octane number 100) and n-heptane (octane number 0), which are both paraffinic hydrocarbons, in an appropriate mixing ratio. Note that, in the present embodiment, an experimental value measured by a test according to JIS standards is used as the octane number of cyclopentane. As shown by the dashed line in FIG. 2, the calculated value RONc of the octane number of the mixed fuel calculated by the following formula (i) based on the mixing ratio of the standard fuel and cyclopentane is linearly proportional to the mixing ratio x of cyclopentane. increase exponentially.
RONc=65(100−x)/100+103.2x/100 (i)

On the other hand, as shown by the plot and solid line in FIG. 2, the measured octane number RONa of the mixed fuel was higher than the calculated value RONc regardless of the mixing ratio x of cyclopentane, and reached a maximum at the mixing ratio x of 50%. . Similar trends were observed for standard fuels with different octane numbers. From this, it is considered that some interaction occurs between the paraffinic hydrocarbon and cyclopentane. Hereinafter, the difference ΔRON between the measured octane number RONa and the calculated octane number RONc is referred to as an "octane bonus".

Thus, the octane bonus ΔRON when cyclopentane is added to the paraffinic hydrocarbon reaches a maximum when the mixing ratio x of cyclopentane is 50%. Therefore, when cyclopentane is added to FT light naphtha to produce reformed gasoline, the mixing ratio x of cyclopentane is preferably 50% or less from the viewpoint of effective use of FT light naphtha.

FIG. 3 is a diagram showing the characteristics of the octane bonus ΔRON with respect to the mixing ratio x of cyclopentane and the octane number of standard fuel. As shown in FIG. 3, the octane bonus ΔRON shows a maximum value when the mixture ratio x of cyclopentane is 50% regardless of the octane number of the standard fuel. The maximum value of the octane bonus ΔRON increases as the octane number of the standard fuel decreases. At an octane number equivalent to FT light naphtha of 60 to 70, the octane bonus ΔRON can be increased to 15 or more by adjusting the mixing ratio x of cyclopentane. When producing reformed gasoline by adding cyclopentane to FT light naphtha, from the viewpoint of fully utilizing the effect of adding cyclopentane, cyclopentane is mixed in a range where the octane bonus ΔRON is a predetermined value (for example, 15) or more. It is preferred to determine the proportion x.

FIG. 4 is a diagram showing the characteristics of the mixture ratio x of cyclopentane and the octane number (actually measured value) RONa of the mixed fuel with respect to the octane number of the standard fuel. As shown in FIG. 4, the octane number RONa of the mixed fuel changes according to the octane number of the standard fuel and the mixing ratio x of cyclopentane. By setting a calibration curve (predetermined characteristic) based on such test results and determining the mixing ratio x of cyclopentane based on it, cyclopentane is added to FT light naphtha to obtain an appropriate octane number. Reformulated gasoline can be produced. For example, reformed gasoline with an octane number of 88 to 95, which is equivalent to regular gasoline, can be produced.

5 and 6 are diagrams showing an example of the combustion test results of the mixed fuel, showing the results of the combustion test using a rapid compression device. In a combustion test using a rapid compression device, a mixture of fuel and air with a stoichiometric air-fuel ratio is introduced into a vacuum combustion chamber, the mixture is compressed to a specified compression ratio, and self-ignition starts after the specified compression ratio is reached. A time (ignition delay time) ti [ms] was measured.

FIG. 5 shows the characteristics of maximum thermal efficiency [%] with respect to ignition delay time ti. As shown in FIG. 5, when the ignition delay time ti is less than 10 ms, the maximum thermal efficiency drops significantly, while when the ignition delay time ti is 10 ms or more, the maximum thermal efficiency tends to be stable. Therefore, when producing reformed gasoline by adding cyclopentane to FT light naphtha, from the viewpoint of ensuring sufficient performance of the applied engine, the mixing ratio of cyclopentane is such that the ignition delay time ti is 10 ms or more Preferably x is determined.

FIG. 6 shows the characteristics of the ignition delay time ti with respect to the mixture ratio x of cyclopentane and the octane number of the standard fuel. As shown in FIG. 6, the ignition delay time ti increases as the cyclopentane mixture ratio x increases, and the cyclopentane mixture ratio x at which the ignition delay time ti reaches 10 ms decreases as the octane number of the standard fuel increases.

7 to 9 are diagrams for explaining an example of a suitable mixing ratio x of cyclopentane when cyclopentane is added to FT light naphtha to produce reformed gasoline. An example of a range of a suitable mixing ratio x for is shown.

The mixing ratio x of cyclopentane is preferably 50% or less from the viewpoint of effective use of FT light naphtha (Fig. 2). Further, from the viewpoint of ensuring sufficient performance of the engine to which the reformed gasoline is applied, it is preferable that the ignition delay time ti is determined to be 10 ms or longer (FIGS. 5 and 6). That is, as shown in the example of FIG. 7, when cyclopentane is added to FT light naphtha to produce reformed gasoline, the mixing ratio x of cyclopentane is 50% or less, and the ignition delay time ti is 10 ms or more. is preferably determined to be

The mixing ratio x of cyclopentane is preferably determined within a range in which the octane bonus ΔRON is equal to or greater than a predetermined value (for example, 15) from the viewpoint of making full use of its addition effect (FIG. 3). Further, from the viewpoint of ensuring sufficient performance of the engine to which the reformed gasoline is applied, it is preferable that the ignition delay time ti is determined to be 10 ms or longer (FIGS. 5 and 6). That is, as shown in the example of FIG. 8, the mixing ratio x of cyclopentane is determined so that the ignition delay time ti is 10 ms or more within a range in which the octane bonus ΔRON is a predetermined value (for example, 15) or more. is preferred.

When cyclopentane is added to FT light naphtha to produce reformed gasoline, the mixing ratio x of cyclopentane can be determined according to the desired octane number of the reformed gasoline (Fig. 4). For example, it can be determined based on predetermined characteristics so that the octane number is 88 to 95, which is equivalent to regular gasoline. In this case, the performance of the engine to which the reformed gasoline is applied is ensured, but it is preferable that the octane bonus ΔRON is determined within a range in which the octane bonus ΔRON is equal to or greater than a predetermined value (for example, 15) from the viewpoint of fully utilizing the effect of the addition. (Fig. 3). That is, as shown in the example of FIG. 9, the mixing ratio x of cyclopentane is predetermined so that the octane number RONa of the mixed fuel falls within a predetermined range within a range in which the octane bonus ΔRON is equal to or greater than a predetermined value (for example, 15). It is preferably determined based on the properties identified.

FIG. 10 is a diagram for explaining the effect of adding cyclopentane to paraffinic hydrocarbons, and shows changes in combustion temperature over time when the fuel composition is changed. As shown in FIG. 10, in a mixed fuel (standard fuel) of 50% isooctane and 50% n-heptane and a mixed fuel of 50% isooctane and 50% cyclopentane, a low-temperature oxidation reaction in which the combustion temperature rises occurs. There was a big difference in the time taken. The low-temperature oxidation reaction is an exothermic reaction caused by a slow oxidation reaction of fuel molecules, and proceeds in a chain reaction through the generation and consumption of OH radicals.

As a result of chemical reaction analysis, in the chemical reaction when general paraffinic hydrocarbons are burned, OH radicals are produced in chemical equivalents slightly less than twice the OH radicals consumed. As described above, in the general combustion of paraffinic hydrocarbons, more OH radicals are produced than consumed OH radicals, so chain reactions tend to proceed, and the low-temperature oxidation reaction proceeds rapidly.

On the other hand, in the chemical reaction when cyclopentane was burned, OH radicals were generated in an amount a little less than 0.65 times as large as the OH radicals consumed. In addition, it was confirmed that 35% of the product became stable cyclopentene, and the rate of termination reaction in which radicals disappeared was high. Thus, in the combustion of cyclopentane, the number of OH radicals produced is less than the number of OH radicals consumed, so the chain reaction is difficult to progress and the low-temperature oxidation reaction is difficult to progress rapidly.

FIG. 11 is a diagram for explaining the breakdown of OH radicals consumed and produced in the combustion process of each mixed fuel, showing the results of chemical reaction analysis. As shown in FIG. 11, in the mixed fuel of 50% isooctane and 50% n-heptane, OH radicals consumed and generated during the combustion process of isooctane, and OH radicals consumed during the combustion process of n-heptane Radicals and generated OH radicals are almost equal. Therefore, the rate of the low-temperature oxidation reaction of n-heptane is not changed by the coexistence of isooctane.

On the other hand, in the mixed fuel of 50% cyclopentane and 50% n-heptane, more OH radicals are consumed in the combustion process of n-heptane than in the combustion process of cyclopentane. is less than the OH radicals generated. That is, when the low-temperature oxidation reaction of n-heptane and the low-temperature oxidation reaction of cyclopentane proceed in parallel, the OH radicals generated during the combustion process of n-heptane are consumed during the combustion process of cyclopentane. Therefore, the low-temperature oxidation reaction of n-heptane is difficult to proceed in the presence of cyclopentane.

In this way, cyclopentane is not only difficult to oxidize as a single substance, but when it is added (mixed) to paraffinic hydrocarbons, it consumes OH radicals generated during the combustion process. It slows down the oxidation reaction and slows down combustion.

According to this embodiment, the following effects can be obtained.
(1) A process for producing gasoline includes blending light naphtha with cyclopentane. The mixing ratio x of cyclopentane is determined based on predetermined characteristics so that the octane number of the reformed gasoline falls within a predetermined range, and the octane number of light naphtha, the octane number of cyclopentane, the light naphtha and cyclopentane The difference ΔRON between the calculated value RONc of the octane number of the reformed gasoline calculated based on the mixture ratio of be.

By determining the mixing ratio x of cyclopentane in a range where the effect of adding cyclopentane due to the interaction between light naphtha and cyclopentane is sufficiently large, the effect of adding cyclopentane can be fully utilized, and high octane gasoline can be efficiently produced. can be manufactured. In addition, by determining the mixing ratio x of cyclopentane based on predetermined characteristics in consideration of the interaction between paraffinic hydrocarbons and cyclopentane, which are the main components of light naphtha, the octane number can be appropriately modified. Gasoline can be produced.

(2) The predetermined range is set according to the octane number of regular gasoline. In this case, the reformed gasoline can be suitably applied to gasoline engines manufactured on the assumption that regular gasoline will be used.

(3) Light naphtha is FT light naphtha obtained by FT synthesis. By using FT light naphtha, the carbon intensity of reformed gasoline can be further suppressed.

In the above embodiment, an example of adding cyclopentane to FT light naphtha, which is a renewable fuel, was described, but cyclopentane may be added to naphtha derived from fossil fuel. Alternatively, renewable cyclopentane derived from renewable fuel may be used as cyclopentane. In this case, the carbon intensity of the reformed gasoline can be further reduced.

In the above embodiment, the octane number of 88 to 95 corresponding to regular gasoline was exemplified as a specific numerical value as the predetermined range of the octane number of the reformed gasoline, but the predetermined range of the octane number of the gasoline is not limited to such. For example, the octane number of gasoline sold in a country or region where reformed gasoline is sold may be used.

The above description is merely an example, and the present invention is not limited by the above-described embodiments and modifications as long as the features of the present invention are not impaired. It is also possible to arbitrarily combine one or more of the above embodiments and modifications, and it is also possible to combine modifications with each other.

Claims (3)

A method for producing gasoline,
Mixing cyclopentane with light naphtha ,
A calculated octane number of the gasoline calculated as the sum of the product of the light naphtha octane number and the light naphtha mixture ratio and the product of the cyclopentane octane number and the mixture ratio of the cyclopentane; Including calculating the difference between the octane number of gasoline and the actual value ,
The mixture ratio of cyclopentane is determined so that the octane number of the gasoline falls within a predetermined range set according to the octane number of regular gasoline, and the mixture ratio at which the difference is maximized is the center. A method for producing gasoline, wherein the value is determined within a predetermined range equal to or greater than a predetermined value. In the method for producing gasoline according to claim 1,
The method for producing gasoline, wherein the predetermined value is 15. In the method for producing gasoline according to claim 1 or 2 ,
The method for producing gasoline, wherein the light naphtha is FT light naphtha obtained by Fischer-Tropsch synthesis.

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