JP6181540B2 - Light oil composition - Google Patents

Description

  The present invention relates to a light oil composition using biomass as a raw material.

  2. Description of the Related Art Conventionally, the use of biological resources (so-called biomass) including plant resources as raw materials for gasoline, kerosene, and light oil has been promoted. In particular, biomass fuel derived from plant resources is an organic compound converted from carbon atoms of carbon dioxide taken from the atmosphere by photosynthesis during plant growth, so the biomass fuel derived from plant resources is burned and discharged Carbon dioxide does not lead to an increase in the total amount of carbon dioxide in the atmosphere. Thus, the biomass fuel derived from plant resources is beneficial from the viewpoint of carbon neutrality.

Fatty Acid Methyl Ester (hereinafter referred to as FAME) FAME, which is an example of biomass fuel, is a transesterification reaction between methanol and animal and vegetable fats and oils having a triglyceride structure in which glycerin and a fatty acid are ester-bonded. Is obtained.
However, practical problems have been pointed out in FAME. For example, FAME has a double bond. Double bonds affect oxidative stability and low temperature fluidity. When the amount of double bonds is large, the oxidation stability is lowered, and when the amount of double bonds is small, low-temperature fluidity is deteriorated. For this reason, it is difficult to adjust the double bond amount so as to achieve both the oxidation stability and the low temperature fluidity.
Moreover, since FAME has many heavier components than general diesel fuel, there was a concern that the burn-out property was poor, and fuel consumption deteriorated and unburned hydrocarbon emissions increased during combustion. Furthermore, since FAME is an oxygen-containing compound, there are concerns that it may deteriorate members such as metal and rubber used in the combustion engine, or increase emission of aldehydes during combustion.
As biomass fuel, hydro-treated biodiesel (HBD) obtained by deoxygenating, isomerizing, and hydrotreating animal and vegetable oils and fats having a triglyceride structure in addition to FAME has been proposed. Yes.
HBD also points out several problems. For example, since HBD has a density lower than that of general diesel fuel, fuel consumption is poor and lubricity is also poor. In addition, since isomerization is required to ensure fluidity at low temperatures, it is difficult to achieve complete carbon neutral when viewed over the entire life cycle.
Thus, there are many problems in the spread of biomass fuels such as FAME and HBD. However, if the ratio at which biomass fuel can be used as a raw material for current fuel oil increases, it will be even more beneficial for reducing carbon dioxide emissions. Thus, in recent years, some of the above-described problems have been improved (see Patent Documents 1 to 5).
However, many problems still remain in order to obtain a biomass fuel satisfying the high calorific value while having the low temperature performance required for the current fuel oil, and further improvements are desired.

JP 2007-153928 A JP 2007-308565 A JP 2007-308566 A JP 2007-308567 A JP 2009-161669 A

  An object of the present invention is to provide a light oil composition having a low calorific value and a high calorific value.

  As a result of intensive studies, the present inventors have found that a light oil composition comprising a fuel oil base material obtained by hydrotreating an oil extracted from biomass having a specific compound has a low temperature performance and a high performance. Based on this finding, the present invention has been completed.

That is, the present invention
[1] A fuel oil base material including a monoalkylbenzene compound (component A) to which an alkyl group having 15 carbons is bonded and a monoalkylcyclohexane compound (component B) to which an alkyl group having 15 carbons is bonded, desulfurized kerosene, and desulfurization A gas oil composition comprising gas oil, wherein the fuel oil base is contained in an amount of 1% by volume to 20% by volume based on the gas oil composition, and the desulfurized kerosene is 40% by volume or more and 59% in terms of the gas oil composition. A monoalkylbenzene compound (component A) containing 40% by volume or more and 49% by volume or less of the desulfurized gas oil based on the gas oil composition and containing an alkyl group having 15 carbon atoms is contained in the gas oil composition. A monoalkylcyclohexane compound (component B) containing 1% by mass or more and 8% by mass or less based on a standard and having an alkyl group having 15 carbon atoms bonded thereto is 1% by mass or more based on a light oil composition. % Include the following, the density of said light oil composition is at most 0.80 g / cm ³ or more 0.88 g / cm ^3, and a boiling point range of 140 ° C. or higher 400 ° C. or less, 90% distillation temperature of 350 ° C. or less , and the sulfur content of not more than 10 mass ppm, a kinematic viscosity at 30 ° C. is not more than 2.0 mm ² / s or more 4.7 mm ² / s, and a cetane index of 45 or more, a flash point of 45 ° C. or higher A light oil composition having a pour point of -20 ° C or lower and a clogging point of -12 ° C or lower,
[2] The light oil composition according to [1], wherein the A component and the B component are contained in an amount of 2% by mass or more and 5% by mass or less based on the gas oil composition, respectively.
[3] The light oil composition according to the above [1] or [2], further comprising a fluidity improver in an amount of 50 mass ppm or more based on the light oil composition,
[4] The light oil composition according to [3], wherein the fluidity improver is an ethylene vinyl copolymer,
[5] The light oil composition according to any one of [1] to [4], wherein the fuel oil base material is a cashew nut-derived component,
I will provide a.

  According to the present invention, it is possible to provide a light oil composition having a low calorific value and a high calorific value.

[Light oil composition]
A light oil composition according to an embodiment of the present invention includes a fuel oil containing a monoalkylbenzene compound (component A) having a C15 alkyl group bonded thereto and a monoalkylcyclohexane compound (B component) having a C15 alkyl group bonded thereto. A gas oil composition comprising a base material, desulfurized kerosene, and desulfurized gas oil, wherein the fuel oil base material is contained in an amount of 1% by volume to 20% by volume based on the gas oil composition, and the desulfurized kerosene is light oil. 40% by volume to 59% by volume based on the composition, the desulfurized gas oil is 40% by volume to 49% by volume based on the gas oil composition, and a monoalkylbenzene having an alkyl group having 15 carbon atoms bonded thereto. A monoalkylcyclohexane compound (component B) containing 1 to 8% by mass of the compound (component A) based on the light oil composition and having an alkyl group having 15 carbon atoms bonded thereto is light. The composition contains reference 1 mass% or more and 8 mass% or less, and the density of said light oil composition 0.80 g / cm ³ or more 0.88 g / cm ³ or less, a boiling range be 140 ° C. or higher 400 ° C. or less , and 90% distillation temperature of 350 ° C. or less, a sulfur content of not more than 10 mass ppm, and a kinematic viscosity at 30 ° C. or less 2.0 mm ² / s or more 4.7 mm ² / s, cetane index of 45 The flash point is 45 ° C. or higher, the pour point is −20 ° C. or lower, and the clogging point is −12 ° C. or lower.

The light oil composition according to the present embodiment contains a fuel oil base to be described later, and desulfurized kerosene and desulfurized light oil as petroleum fractions. The fuel oil base is contained in an amount of 1% by volume or more and 20% by volume or less based on the light oil composition.
When the content of the fuel oil base is less than 1% by volume on the basis of the light oil composition, a sufficient calorific value cannot be obtained, and when it exceeds 20% by volume, the properties become heavy and the combustibility deteriorates. In this respect, the content of the fuel oil base material is preferably 2% by volume or more and 18% by volume or less, and more preferably 5% by volume or more and 16% by volume or less.
Desulfurized kerosene is contained in an amount of 40 vol% or more and 59 vol% or less based on the light oil composition. When the content of desulfurized kerosene is less than 40% by volume on the basis of the light oil composition, the low-temperature startability deteriorates, and when it exceeds 59% by volume, a sufficient calorific value cannot be obtained. From this viewpoint, the content of desulfurized kerosene is preferably 42% by volume or more and 55% by volume or less, and more preferably 43% by volume or more and 50% by volume or less.
Further, the desulfurized gas oil is contained in an amount of 40% by volume to 49% by volume based on the gas oil composition. When the content of the desulfurized gas oil is less than 40% by volume based on the gas oil composition, a sufficient calorific value cannot be obtained, and when it exceeds 49% by volume, the low-temperature fluidity deteriorates. From this viewpoint, the content of desulfurized gas oil is preferably 40% by volume or more and 48% by volume or less, and more preferably 40% by volume or more and 46% by volume or less.

  In the light oil composition according to the present embodiment, a component derived from cashew nuts can be used as the fuel oil base material.

In the light oil composition according to the present embodiment, in addition to the fuel oil base material and the petroleum fraction, the remainder includes additives such as a fluidity improver applicable to other petroleum-based fractions and the light oil composition. It may be included.
The fluidity improver is preferably contained in an amount of 50 mass ppm or more based on the light oil composition. When the fluidity improver is contained in an amount of 50 ppm by mass or more, the clogging point and the cloud point are improved. In this respect, the content of the fluidity improver is more preferably 80 mass ppm or more, and still more preferably 100 mass ppm or more. Since the improvement effect of the clogging point and the pour point reaches a peak, the upper limit value of the content of the fluidity improver is usually 500 ppm by mass.
Examples of the fluidity improver include alkenyl succinic acid amide compounds, polyalkyl methacrylates, polyalkylene fatty acid esters, and ethylene vinyl copolymers. Among these, an ethylene vinyl copolymer is preferable from the viewpoint of obtaining a good improvement effect of the clogging point and the pour point.

Density at 15 ℃ of the gas oil composition according to the present embodiment is less 0.80 g / cm ³ or more 0.88 g / cm ^3, preferably be 0.81 g / cm ³ or more 0.86 g / cm ³ or less , more preferably not more than 0.82 g / cm ³ or more 0.84 g / cm ^3. When the density at 15 ° C. is in the above range, the calorific value can be increased and the combustibility can be improved, so that the fuel consumption can be kept good.
The boiling range is 140 ° C. or higher and 400 ° C. or lower. The 90% distillation temperature of the light oil composition is 350 ° C. or lower. The sulfur content is 10 mass ppm or less. Further, the kinematic viscosity at 30 ° C., at 2.0 mm ² / s or more 4.7 mm ² / s or less. From the viewpoint of maintaining lubricity and ensuring proper spraying, the kinematic viscosity at 30 ° C. is preferably 2.2 mm ² / s or more and 3.8 mm ² / s or less.
Further, the cetane index of the light oil composition is 45 or more, preferably 50 or more. The flash point is 45 ° C. or higher, preferably 50 ° C. or higher. The pour point is -20 ° C or lower, and the clogging point is -12 ° C or lower.

In this embodiment, the density at 15 ° C. is a density measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
The 90% distillation temperature is a value measured according to JIS K 2254 “Petroleum products—Distillation test method (normal pressure method)”.
The kinematic viscosity at 30 ° C. is a value measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The flash point is a value measured according to 3 of JIS K 2265 “How to obtain a flash point—Part 3: Penski-Marten sealing method”.
The pour point and cloud point are values measured by JIS K 2269 “Crude point and petroleum product cloud point test method of crude oil and petroleum products”.
The clogging point is a value measured according to JIS K 2288 "Petroleum product-light oil-clogging point test method".
The cetane number and cetane index are values measured and calculated according to JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
The calorific value is a value measured and calculated according to the estimation formula (clause number 6.3e) 1) of JIS K 2279 “Crude oil and petroleum products—The calorific value test method and calculation estimation method”.
The sulfur content is a value measured by JIS K 2541-6 “Crude oil and petroleum products—Sulfur content test method Part 6: Ultraviolet fluorescence method”.

[Fuel oil base material]
The fuel oil base material includes a monoalkylbenzene compound (component A) to which an alkyl group having 15 carbons is bonded and a monoalkylcyclohexane compound (component B) to which an alkyl group having 15 carbons is bonded.
In a fuel oil base material, it is preferable that the sum total of A component and B component is contained 40 mass% or more with respect to the total mass of a fuel oil base material. The fuel oil base material contains components other than the A component and the B component as the remainder of the A component and the B component.
When the fuel oil base material contains a total of 40% by mass or more of the A component and the B component, a density capable of obtaining a sufficient calorific value can be obtained. In addition, from the above viewpoint, the total of the A component and the B component is preferably 50 to 70% by mass with respect to the total capacity of the fuel oil base material.
Moreover, it is preferable that both A component and B component are contained in a fuel oil base material, and A component is contained 20-35 mass% with respect to the total mass of a fuel oil base material. If the A component content is more than 35% by mass, the total hydrocarbons and carbon monoxide in the exhaust gas increase, and the environmental performance deteriorates. On the other hand, when the content of the component A is less than 20% by mass, the density and the calorific value are lowered, and the fuel efficiency improvement effect becomes insufficient.
In addition, each component including A component and B component in a fuel oil base material can be identified with a GC-MS analyzer. Moreover, A component and B component in a fuel oil base material can be quantified with a GC-FID apparatus.

The density at 15 ° C. of the fuel oil base material is preferably 0.820 to 0.880 g / cm ³ . More preferably, it is 0.840-0.870 g / cm < ³ >, More preferably, it is 0.850-0.865 g / cm < ³ >. When the density at 15 ° C. is in the above range, the calorific value can be increased and the combustibility can be improved, so that the fuel consumption can be kept good.
Moreover, it is preferable that the kinematic viscosity at 30 degreeC of a fuel oil base material is 2.7-12.0 mm < ² > / s, More preferably, it is 5.0-10.0 mm < ² > / s. When the kinematic viscosity at 30 ° C. is in the above range, lubricity can be maintained and proper spraying can be ensured.

The monoalkylbenzene compound (component A) to which an alkyl group having 15 carbon atoms is bonded is contained in an amount of 1% by mass to 8% by mass based on the gas oil composition. Further, the monoalkylcyclohexane compound (component B) to which an alkyl group having 15 carbon atoms is bonded is contained in an amount of 1% by mass or more and 8% by mass or less based on the light oil composition.
If the content of the A component and the B component is in the above range, shrinkage of rubber used for a pump or the like can be suppressed. Moreover, a favorable calorific value can be obtained. From the above viewpoint, the A component and the B component are each preferably contained in an amount of 2% by mass to 5% by mass, more preferably 3% by mass to 4% by mass, based on the light oil composition.

<Method for producing fuel oil base>
The fuel oil base material of the present invention can be produced by hydrotreating oil extracted from cashew nut shells with a hydrotreating catalyst.
Among oils extracted from cashew nut shells, it is preferable that at least one compound selected from anacardic acid, cardol, and cardanol is contained.
Especially, it is preferable to decompose | disassemble anacardic acid by heat-processing beforehand, 0 to 10.0 mass% of anacardic acids, 0 to 25.0 mass% of cardols, and cardanol 65. It is preferable that 0-100 mass% is contained.
In addition, the present invention is not limited to oil extracted from cashew nut shell, and any biomass containing 40% by mass or more of an alkylbenzene compound having an alkyl group having 15 or more carbon atoms or a phenol compound having an alkyl group having 15 or more carbon atoms bonded thereto may be used. It is advantageous to obtain the fuel oil base of the invention.

(Hydroprocessing catalyst)
As the mixture constituting the carrier constituting the hydrotreating catalyst, a porous inorganic oxide containing alumina can be used.
The active component constituting the hydrotreating catalyst includes at least one selected from Group 6 metal elements of the periodic table, at least one selected from Group 9 metal elements of the periodic table, and Group 10 metals. Examples thereof include an active metal selected from at least one selected from elements.
The active component of Group 6 of the periodic table is preferably molybdenum or tungsten. Molybdenum compounds supporting these active ingredients on a carrier are preferably molybdenum trioxide, ammonium molybdate and the like, and tungsten compounds are preferably tungsten trioxide, ammonium tungstate and the like.
The active ingredients of Groups 9 and 10 of the periodic table are cobalt and nickel. Effective cobalt compounds for supporting these active ingredients on a carrier are preferably cobalt carbonate, basic cobalt carbonate, cobalt nitrate, and the like, and nickel compounds are preferably nickel carbonate, basic nickel carbonate, nickel nitrate, and the like. The amount of the Group 9 and Group 10 metal elements supported is preferably 2 to 5% in terms of oxide in terms of the total mass ratio of the hydrotreating catalyst. Among the active components described above, a nickel molybdenum catalyst in which nickel and molybdenum are combined is preferable. Moreover, it is preferable to use the above-mentioned hydrotreating catalyst after hydrogen reduction treatment at 300 to 400 ° C. for 1 to 36 hours in a hydrogen atmosphere.

(Hydrogenation conditions)
The reaction conditions for hydrotreating the feedstock oil using the hydrotreating catalyst described above are as follows: treatment temperature: 300 to 390 ° C., feedstock oil flow rate (LHSV): 0.5 to 2.0 h ⁻¹ , hydrogen / Raw material ratio: It is preferable to set it as 500-2400NL / kL. The ratio of the A component and the B component can be changed by changing the feed oil flow rate or the hydrogen / feed oil ratio in the hydrotreating conditions.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
[Evaluation method]
Properties of each fuel oil base material, petroleum fraction, and light oil composition were evaluated by the following methods.
<Identification and quantification of A component and B component>
A component and B component were identified (GC-MS) and quantified (GC-FID) under the following conditions using 7890A GC System (Agilent Technologies).
Column: VF-5ms (Agilent Technologies) GC-MS measurement Inlet temperature: 300 ° C
Oven temperature: 300 ° C. (heated from 40 ° C. at 6 ° C./min)
Carrier gas: He
Injection volume: 0.1 μl

<Density at 15 ° C>
The density at 15 ° C. is a density measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
<Distillation>
Distillation is a value measured according to JIS K 2254 “Petroleum Products—Distillation Test Method (Normal Pressure Method)”.
<Kinematic viscosity at 30 ° C.>
The kinematic viscosity at 30 ° C. is a value measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
<Flash point>
The flash point is a value measured according to JIS K 2265-3 “How to determine the flash point—Part 3: Penschramten sealing method”.

<Pour point and cloud point>
The pour point and cloud point are values measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
<Clogging point>
The clogging point is a value measured according to JIS K 2288 “Petroleum products—light oil—clogging point test method”.
<Cetane number and cetane index>
The cetane number and the cetane index are values measured and calculated according to JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
<Heat generation amount>
The calorific value is a value measured and calculated according to the estimation formula (clause number 6.3e) 1) of JIS K 2279 “Crude oil and petroleum products—Test method of calorific value and estimation method by calculation”. A calorific value of 37300 J / L or higher was accepted, and a calorific value less than 37300 J / L was rejected.
<Sulfur content>
The sulfur content is a value measured by JIS K 2541-6 “Crude oil and petroleum products—Sulfur content test method Part 6: Ultraviolet fluorescence method”.

[Manufacture of fuel oil base]
<Production Example 1>
The center part of the high-pressure fixed bed flow type bench scale reactor (total length: 500 mm) is filled with 5 cc of the hydrotreating catalyst, the inlet side and the outlet side are sandwiched with quartz wool, and the ceramic balls other than the part filled with the catalyst And quartz wool was placed at the open end to form a reaction tube.
An oil component (trade name “CX-1000” manufactured by Cashew Co., Ltd.) extracted from cashew nut shell and heat-treated was used as a raw material oil. As a hydrotreating catalyst, the NiMo catalyst described in Example 2 of JP-A-2004-16975 was sized to 16 to 32 mesh, and subjected to hydrogen reduction treatment at 360 ° C. for 24 hours in a hydrogen atmosphere. Things were used. The reaction conditions for the hydrogenation treatment were as follows.
Processing temperature: 370 ° C
Raw material oil flow rate (LHSV): 1.0 h ^-1
Hydrogen / raw oil ratio: 2200NL / kL
Table 2 shows the properties of the obtained fuel oil base material (cashew nut oil).

<Comparative Production Example 1>
Vegetable oils and fats having the properties shown in Table 1 were reacted with methanol to obtain methylated products of vegetable oils and fats. Here, an ester exchange reaction was used in which stirring was performed at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate) to directly react with an alkyl alcohol to obtain an ester compound. Table 2 shows the properties of the obtained fuel oil base material (FAME).

[Preparation of light oil composition]
The petroleum component of the property shown in Table 1 and the fuel oil base material produced in Production Example 1 are mixed to produce the light oil compositions of Examples 1 to 4 and Comparative Examples 1 to 7, and the above evaluation The method was evaluated.

[Evaluation results]
The characteristics of the light oil compositions of Examples 1 to 4 and Comparative Examples 1 to 7 were evaluated by the evaluation method described above. The results are shown in Table 3.

  According to the fuel oil compositions of Examples 1 to 4, it was found that when the cashew nut oil was mixed, the calorific value was increased, and the calorific value was increased by increasing the ratio of the cashew nut oil. It was also found that the low temperature fluidity can be enhanced by adding a fluidity improver.

Claims (5)

A fuel oil base material comprising a monoalkylbenzene compound (component A) to which an alkyl group having 15 carbons is bonded and a monoalkylcyclohexane compound (component B) to which an alkyl group having 15 carbons is bonded, desulfurized kerosene, and desulfurized gas oil A light oil composition comprising:
The fuel oil base is contained in an amount of 1 to 20% by volume based on the light oil composition, the desulfurized kerosene is contained in an amount of 40 to 59% by volume based on the light oil composition, and the desulfurized light oil is 40% to 49% by volume based on diesel oil composition,
A monoalkylbenzene compound (component A) to which an alkyl group having 15 carbon atoms is bonded is contained in an amount of 1 to 8% by mass based on the light oil composition;
A monoalkylcyclohexane compound (component B) to which an alkyl group having 15 carbon atoms is bonded is contained in an amount of 1 to 8% by mass based on the light oil composition
The density of said light oil composition is at most 0.80 g / cm ³ or more 0.88 g / cm ^3, a boiling point range is at 140 ° C. or higher 400 ° C. or less, and 90% distillation temperature of 350 ° C. or less, sulfur content There is 10 mass ppm or less, kinematic viscosity at 30 ° C. is not more than 2.0 mm ² / s or more 4.7 mm ² / s, and a cetane index of 45 or more, a flash point of 45 ° C. or higher, a pour point Is a gas oil composition having a clogging point of -12 ° C or lower.   The light oil composition according to claim 1, wherein the A component and the B component are each contained in an amount of 2% by mass or more and 5% by mass or less based on the gas oil composition.   Furthermore, the light oil composition of Claim 1 or 2 in which a fluidity improver is contained 50 mass ppm or more on the basis of the light oil composition.   The light oil composition according to claim 3, wherein the fluidity improver is an ethylene vinyl copolymer.   The light oil composition according to any one of claims 1 to 4, wherein the fuel oil base material is a component derived from cashew nuts.