JP6957148B2 - Diesel fuel base material, diesel fuel composition, method for producing diesel fuel base material and method for producing diesel fuel composition - Google Patents

Description

The present invention relates to a diesel fuel base material, a diesel fuel composition containing the diesel fuel base material, a method for producing a diesel fuel base material, and a diesel using a diesel fuel base material produced by the method for producing the diesel fuel base material. The present invention relates to a method for producing a fuel composition.

The world economy relies on fossil resources such as oil for most of its underlying energy supply. However, the continuous use of fossil resources causes serious social problems symbolized by global warming and environmental pollution, and the rapid and global expansion of industry is the foundation of human social development, which is the depletion of fossil resources. It poses a crisis to loosen.
Under these circumstances, promotion of the use of renewable energy instead of fossil fuels has been advocated. As renewable energy, in addition to the use of natural energy (solar energy, wind power, geothermal energy, etc.), the use of biomass that utilizes the capabilities of living organisms is being considered, and technological development for their practical use has been active in recent years. It is done in.

Biomass fuels derived from animal and vegetable fats and oils are attracting attention as fuels using biomass. FAME (Fatty Acid Methyl Ester), which is currently the mainstream of biomass fuel for diesel vehicles, is a biofuel that brings animal and vegetable fats and oils closer to the physical properties of light oil by transesterification reaction. However, since FAME is a fuel having properties different from those of existing petroleum-based fuels, it causes various problems in the engine. Therefore, a biomass fuel having a performance superior to that of FAME is desired.
Under such circumstances, as a biomass fuel conversion technology that replaces FAME, a technology for hydrogenating and reforming animal and vegetable fats and oils to obtain a light oil composition is drawing attention. As such a technique, for example, those described in Patent Documents 1 to 3 are known.

Patent Document 1 describes a method for converting a raw material containing animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils by a combination of a hydrorefining catalyst and a subsequent isomerization catalyst.
In Patent Document 2, a Ni / Mo / alumina catalyst is used as an HDO (hydrodesulfurization) catalyst, and a Ni / W / zeolite catalyst (including alumina) is used in the subsequent stage, and animal and vegetable fats and oils and / or animals and plants are used. A method for obtaining hydrogenated deoxidized oil by hydrogenating and refining a raw material containing a component derived from fats and oils is disclosed.
In Patent Document 3, a Ni / Mo / alumina catalyst is used as an HDO (hydrogenated oxygen scavenger) catalyst, and a raw material containing animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils is hydropurified and hydrogenated in one stage. A method for obtaining deoxidized oil is disclosed.

JP-A-2007-308573 JP-A-2007-153937 Japanese Unexamined Patent Publication No. 2007-308571

However, in the biomass fuel conversion technique described in Patent Document 1, since the method for producing a light oil composition is a two-stage reaction, and as in the examples, the catalyst in the second stage is Pt-Pd, which is a noble metal. Since a catalyst using a crystalline molecular sieve as a carrier is used, there are problems in terms of the complexity of the device (two stages), the increase in energy consumption, and the high catalyst price. The density of the vegetable oil 1HDO treated oil in Table 4 are obtained base gas oil and vegetable fats 2HDO processing oil, respectively low as 781kg / ^{m 3} and 789kg / ^{m 3,} is believed to be low calorific value.
Each density of the HDO treated oil and HDO process oils of vegetable oil 2 of vegetable oil 1 obtained by the fuel technology of biomass that is described in Patent Document 2 as low as 772kg / ^{m 3} and 783kg / ^{m 3,} heat value Is considered to be low. Further, since the hydrogen partial pressure is as high as 11 MPa, the energy efficiency of the hydrogenation treatment is low.
The density of the HDO-treated oil of the vegetable oil 1 obtained by the biomass fueling technique described in Patent Document 3 is as ^{low as 783 kg / m 3,} and it is considered that the calorific value is low. Further, since the light oil composition is obtained by a one-step reaction, the process is simple in that respect, but the energy efficiency of the hydrogenation treatment is low because the reaction pressure is as high as 11 MPa. In addition, since there is no description about the pour point, it is a very high pour point, and it seems that it is not practical. It is also uneconomical that it is necessary to add a sulfur compound to the raw material.
Therefore, in the present invention, a diesel fuel base material having a high calorific value, good oxidation stability, and a high cetan index, a diesel fuel composition containing the diesel fuel base material, and a diesel fuel for obtaining the diesel fuel base material can be obtained. It is an object of the present invention to provide a method for producing a base material and a method for producing a diesel fuel composition using a diesel fuel base material produced by the method for producing a diesel fuel base material.

The present inventors can obtain a dense diesel fuel base material by hydrodeoxidizing a raw material containing components derived from animal and vegetable fats and oils and / or animal and vegetable fats and oils, whereby a diesel fuel group having a high calorific value can be obtained. The present invention was completed by finding that a material can be obtained, that the diesel fuel base material has good oxidative stability and a high cetane number. That is, the present invention is as follows.

(1) A plant and animal oils and / or diesel fuel base stock of the raw material containing components derived from animal or vegetable fats and oils and hydrogenated deoxygenated, density at 15 ℃ is 0.7790g / cm ³ or more 0.8600g / cm ³ The following diesel fuel base material.
(2) The diesel fuel base material according to (1) above, wherein the total calorific value is 36.5 MJ / L or more.
(3) The diesel fuel base material according to (1) or (2) above, wherein the induction period according to the PetroOXY test is 100 minutes or more.
(4) The diesel fuel base material according to any one of (1) to (3) above, wherein the animal and vegetable fat and oil and / or the component derived from the animal and vegetable fat and oil is a fat and oil derived from microalgae.
(5) The diesel fuel base material according to (4) above, wherein the microalgae is Pseudocolicistic ellipsoidia, algae belonging to the genus Pseudococomixa, or algae belonging to the genus Kokkomixa.
(6) A diesel fuel composition containing the diesel fuel base material according to any one of (1) to (5) above.
(7) The diesel fuel composition according to (6) above, further comprising JIS No. 2 light oil.
(8) A diesel fuel base material that includes a step of hydrogenating and deoxidizing a raw material containing fats and oils derived from microalgae and does not include a step of isomerizing a raw material that has been hydrogenated and deoxidized by a hydrogenating and deoxidizing treatment step. Manufacturing method.
(9) The method for producing a diesel fuel base material according to (8) above, wherein the microalgae is a pseudocolicistic ellipsoidia, an alga belonging to the genus Pseudococomixa, or an alga belonging to the genus Kokkomixa.
(10) The method for producing a diesel fuel base material according to (8) or (9) above, wherein the pressure in the step of hydrogenation deoxidation treatment is 2 MPa or more and 8 MPa or less.
(11) The method for producing a diesel fuel base material according to any one of (8) to (10) above, wherein the reaction temperature in the step of hydrogenation deoxidation treatment is 250 ° C. or higher and 450 ° C. or lower.
(12) A diesel fuel composition comprising a step of mixing JIS No. 2 light oil with a diesel fuel base material produced by the method for producing a diesel fuel base material according to any one of (8) to (11) above. Manufacturing method.

According to the present invention, a diesel fuel base material having a high calorific value, good oxidation stability, and a high cetan index, a diesel fuel composition containing the diesel fuel base material, and a diesel fuel for obtaining the diesel fuel base material. It is possible to provide a method for producing a base material and a method for producing a diesel fuel composition using a diesel fuel base material produced by the method for producing a diesel fuel base material.

[Diesel fuel base material]
Hereinafter, the diesel fuel base material of the present invention will be described in detail.
The diesel fuel base material of the present invention is a diesel fuel base material obtained by hydrogenating and deoxidizing a raw material containing animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils, and has a density of 0.7790 g / cm ³ or more at 15 ° C. .8600 g / cm ³ or less. Thereby, the calorific value of the diesel fuel base material can be increased.

(Ingredients derived from animal and vegetable fats and oils and / or animal and vegetable fats and oils)
In the present specification, animal and vegetable fats and oils are fats and oils obtained by pressing animal and plant raw materials or extracting them with an organic solvent. Those obtained from plants are referred to as vegetable fats and oils, and those obtained from animals are animal fats and oils. These are collectively called animal and vegetable fats and oils.
Animal and vegetable fats and oils and / or animal and vegetable fats and oils-derived components used in the diesel fuel base material of the present invention include, for example, palm oil, palm kernel oil, palm oil, cacao butter, flaxseed oil, saflower oil, sesame seed oil, and drill. Derived from oil, cottonseed oil, rapeseed oil, sesame oil, corn oil, soybean oil, sunflower oil, capoc oil, olive oil, mustard oil, peanut oil, sunflower oil, camellia oil, yatrofa oil, camelina oil, carinata oil, mandari oil, microalgae Oil, milk fat, goat milk fat, buffalo milk fat, beef fat, pork fat, sheep fat, fish oil, liver oil, cow leg oil and the like. These can be used alone or in combination of two or more.
The microalgae in the oil derived from microalgae means an alga having a property of converting a part of nutrients in the body into a form of hydrocarbon or fat. Such microalgaes include, for example, Aurantiochytrium, Botryococcus brauny, Pseudocolystistis ellipsoidia, algae belonging to the genus Pseudococomixa, algae belonging to the genus Kokkomixa, chlorella, squid, spirulina, euglena and nanno. Examples include chloropsis.

From the viewpoint of obtaining a dense diesel fuel base material, preferable animal and vegetable fats and oils and / or animal and vegetable fats and oils-derived components are microalgae-derived oils, and more preferable animal and vegetable fats and oils and / or animal and vegetable fats and oils-derived components are, for example, Oil from Pseudochoricystis ellipsoidea N1 strain (accession number FERM BP-10485), Pseudochoricystis ellipsoidea Obi strain (accession number FERM BP-10484), or Pseudococcomyxa sp.KJ Denso strain (accession number FERM BP-22254) For example, it is an oil derived from Coccomoyxa simplex (UTEX274) and Coccomoyxa chodatii (UTEXB266). , Can be confirmed by using a well-known DNA database.

The animal and vegetable fats and oils and / or the components derived from the animal and vegetable fats and oils used in the diesel fuel base material of the present invention are mainly at least one selected from the group consisting of fatty acid triglycerides, fatty acid diglycerides, fatty acid monoglycerides, (free) fatty acids and fatty acid esters. It is an ingredient. In at least one fatty acid moiety selected from the group consisting of the above fatty acid triglyceride, fatty acid diglyceride, fatty acid monoglyceride, (free) fatty acid and fatty acid ester from the viewpoint of increasing the yield of the diesel fuel base material by the hydrodeoxidation treatment. The number of carbon atoms is preferably 16 or more and 18 or less. Further, when the number of carbon atoms is 16 or more and 18 or less, a diesel fuel base material having a boiling point range corresponding to the boiling point range of the gas oil fraction can be obtained.

(material)
The raw material used for the diesel fuel base material of the present invention is not particularly limited as long as it contains the above-mentioned animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils. The proportion of the animal and vegetable fats and oils and / or the components derived from the animal and vegetable fats and oils in the raw material used for the diesel fuel base material of the present invention is preferably 20% by volume or more, more preferably 30% by volume, from the viewpoint of improving the cetane number. % Or more, more preferably 40% by volume or more. The upper limit of the above ratio is 100% by volume. The raw material used for the diesel fuel base material of the present invention is botriocossen, squalane, or carbon-carbon hydrogenated thereof, in which microalgae coexist with animal and vegetable fats and oils in addition to the above-mentioned animal and vegetable fats and oils and / or components derived from animal and vegetable fats and oils. Substances with hydrogenated or partially hydrogenated heavy bonds (eg, squalane), or straight gas oil, desulfurized gas oil (DGO), hydrodesulfurized kerosene (DK), hydrocracked gas oil (HCGO), hydrocracked gas oil It can include at least one selected from the group consisting of (HCK).

(Hydrogen deoxidation treatment)
<Catalyst>
In the hydrogenation deoxidation catalyst used for the hydrogenation deoxidation treatment for obtaining the diesel fuel base material of the present invention, at least one metal selected from the elements of Group 6A and Group 8 was supported on the catalyst carrier. Those are preferable. Phosphorus may be further supported on the catalyst carrier.
Examples of at least one or more metals selected from the preferred Group 6A and Group 8 elements include Ni, Ni-Mo, Ni-W, Co-Mo and Ni-Co-Mo.
On an oxide basis, the supported amount of nickel or cobalt in the hydrogenated deoxidizing catalyst is preferably 1% by mass or more and 10% by mass or less, and the supported amount of molybdenum or tungsten in the hydrogenated deoxidizing catalyst is preferably 10% by mass. % Or more and 40% by mass or less, and the amount of phosphorus supported in the hydrogenation deoxidizing catalyst is preferably 1% by mass or more and 10% by mass or less.

The catalyst carrier preferably contains 50% by mass or more of alumina, and the alumina is preferably γ-alumina. The catalyst carrier may further comprise titania. The average pore size of the catalyst carrier is preferably 5 nm or more and 15 nm or less, and more preferably 6 nm or more and 14 nm or less. The form of the catalyst carrier may be powder, or may be a molded product such as a cylinder, three leaves, or four leaves.

The method of supporting at least one metal selected from the elements of Group 6A and Group 8 on the catalyst carrier is preferably an impregnation method. The nickel compound for supporting nickel on the catalyst carrier by the impregnation method is preferably at least one selected from the group consisting of nickel carbonate, basic nickel carbonate and nickel nitrate. The cobalt compound used to support cobalt on the catalyst carrier in the impregnation method is preferably at least one selected from the group consisting of cobalt carbonate, basic cobalt carbonate and cobalt nitrate. The molybdenum compound used for supporting molybdenum on the catalyst carrier in the impregnation method is preferably at least one selected from the group consisting of molybdenum trioxide and ammonium molybdate. The tungsten compound used to support tungsten on the catalyst carrier in the impregnation method is preferably at least one selected from the group consisting of tungsten trioxide and ammonium tungstate. The phosphorus compound used to support phosphorus on the catalyst carrier in the impregnation method is preferably at least one selected from the group consisting of phosphorus pentoxide and orthophosphoric acid.

The hydrogenated deoxidized catalyst may be reduced under hydrogen prior to using the hydrogenated deoxidized catalyst. The conditions for reduction under hydrogen are that the reduction temperature is preferably 300 ° C. or higher and 400 ° C. or lower, and the reduction time is preferably 1 hour or longer and 36 hours or lower.

The hydrogenation deoxidation catalyst may be used after sulfurization in the reaction system. The sulfurization method hydrodeoxygenation catalyst, for example, a liquid-phase sulfurization performed by supplying the catalyst by mixing the sulfurizing agent such as dimethyl disulfide in the feed is carried out by supplying the H 2 _S gas mixture There is gas phase sulfurization.

<Hydrogen deoxidation conditions>
From the viewpoint of obtaining a diesel fuel base material having a high density at 15 ° C., and from the viewpoint of energy efficiency and oxidative stability of the hydrogenation deoxidation treatment, the pressure in the hydrogenation deoxidation treatment is preferably 2 MPa or more and 8 MPa or less. More preferably, it is 3 MPa or more and 7 MPa or less, and the liquid space velocity (LHSV) is preferably 0.2 hr ^-1 or more and 3.0 hr ^-1 or less, and more preferably 0.3 hr ^-1 or more and 2.0 hr ^-1 or less. The reaction temperature is preferably 250 ° C. or higher and 450 ° C. or lower, and more preferably 330 ° C. or higher and 400 ° C. or lower.

(Density at 15 ° C)
From the viewpoint of obtaining a diesel fuel base material having a high calorific value and satisfying the JIS standard for light oil, the density of the diesel fuel base material of the present invention at 15 ° C. is 0.7790 g / cm ³ or more and 0.8600 g / cm. ^{It is 3} or less, preferably 0.8000 g / cm ³ or more and 0.8600 g / cm ³ or less, and more preferably 0.8100 g / cm ³ or more and 0.8600 g / cm ³ or less.

(Total calorific value)
From the viewpoint of fuel efficiency of the diesel fuel base material, the total calorific value of the diesel fuel base material of the present invention is preferably 36.5 MJ / L or more, more preferably 37.0 MJ / L or more, still more preferably 37. It is .5 MJ / L or more. The upper limit of the range of the total calorific value of the diesel fuel base material of the present invention is not particularly limited, but is, for example, 39.0 MJ / L. The total calorific value of the diesel fuel base material of the present invention can be measured and evaluated according to JIS K 2279 (crude oil and petroleum products-calorific value test method and calculation method-).

(Oxidation stability)
The oxidation stability of the diesel fuel base material of the present invention is estimated by the induction period by the PetroOXY test, and the induction period is preferably 100 minutes or more from the viewpoint of quality stabilization of the diesel fuel base material, which is more preferable. Is 150 minutes or longer, more preferably 200 minutes or longer. The induction period is the time required to fill 5 ml of the sample with a predetermined amount of oxygen, raise the temperature to 140 ° C., and reduce the initial pressure by 10%. Usually, it is good if it is 65 minutes or more, and it is not possible if it is less than 65 minutes.

[Diesel fuel composition]
The diesel fuel composition of the present invention comprises the diesel fuel substrate of the present invention. As a result, a diesel fuel composition containing a biomass fuel having a high calorific value, good oxidative stability, and a high cetane index can be obtained. Then, the fuel efficiency of the diesel fuel composition containing the biomass fuel is improved.

The diesel fuel composition of the present invention may further contain JIS No. 2 gas oil. If the JIS No. 2 diesel fuel produced due to winter demand becomes surplus, it may be used by mixing it with other fuel base materials. By mixing the diesel fuel base material of the present invention with JIS No. 2 light oil, the cetan index is higher and the oxidation stability is higher than when the fuel base material other than the diesel fuel base material of the present invention is mixed with JIS No. 2 light oil. A good diesel fuel composition with a high calorific value can be obtained. The cetane index of the diesel fuel composition is preferably 50 or more, more preferably 60 or more, and further preferably 70 or more.

From the viewpoint of obtaining a diesel fuel composition having a high cetan index, good oxidation stability, and a high calorific value, the volume ratio of the diesel fuel base material of the present invention to the JIS No. 2 light oil in the diesel fuel composition of the present invention ( The diesel fuel base material / JIS No. 2 light oil of the present invention) is preferably 10/90 to 50/50, more preferably 15/85 to 45/55, and even more preferably 20/80 to 40/60. In addition, instead of JIS No. 2 gas oil, straight-run gas oil, desulfurized gas oil (DGO), desulfurized kerosene (DK), hydrogenated gas oil (HCGO), hydrogenated gas oil (HCK) and the like can also be used.

The diesel fuel composition of the present invention is at least one selected from the group consisting of straight-run gas oil, desulfurized gas oil (DGO), desulfurized gas oil (DK), hydrocracked gas oil (HCGO) and hydrogenated gas oil (HCK). May be further included.

[Manufacturing method of diesel fuel base material]
The method for producing a diesel fuel base material of the present invention includes a step of hydrogenating and deoxidizing a raw material containing fats and oils derived from microalgae, and isomerizing the raw material hydrogenated and deoxidized by the hydrogenation deoxidizing treatment step. Does not include the process of

(Raw material containing oils and fats derived from microalgae)
The raw material containing microalgae-derived fats and oils used in the method for producing a diesel fuel base material of the present invention contains the animal and vegetable fats and oils and / or the components derived from animal and vegetable fats and oils described in the above-mentioned diesel fuel base material of the present invention. Since it is the same as a raw material that is a fat or oil derived from microalgae, the description of the raw material containing the fat or oil derived from microalgae is omitted.

(Hydrogen deoxidation treatment)
Since the hydrogenation deoxidation treatment carried out in the method for producing a diesel fuel base material of the present invention is the same as that described above for the diesel fuel base material of the present invention, the description of the hydrogenation deoxidation treatment will be omitted.

(Step of isomerizing the raw material hydrogenated and deoxidized by the hydrogenation deoxidation treatment step)
The step of isomerizing the hydrogenated and deoxidized raw material is at least one fatty acid selected from the group consisting of fatty acid triglyceride, fatty acid diglyceride, fatty acid monoglyceride, (free) fatty acid and fatty acid ester contained in the raw material. A step of branching a long-chain fatty acid portion derived from a portion. By this step, the low temperature performance of the hydrogenated and deoxidized raw material can be improved. In the conventional method for producing a diesel fuel base material derived from biomass, if the isomerization treatment is not performed, the low temperature performance becomes very poor. Therefore, the isomerization treatment is an indispensable treatment in the method for producing a diesel fuel base material. However, the method for producing a diesel fuel base material of the present invention does not include a step of isomerizing a raw material hydrogenated and deoxidized by a hydrogenation deoxidizing treatment step. This is because, by mixing the diesel fuel base material of the present invention with another fuel base material or JIS No. 2 light oil, a diesel fuel base material having good low temperature performance can be obtained without isomerization. This is because the inclusion of the isomerization step lowers the setan index of the diesel fuel base material.

In the step of isomerizing the hydrogenated and deoxidized raw material, a noble metal such as platinum is used as a catalyst, so that the cost for carrying out the isomerization treatment is high. Therefore, the method for producing a diesel fuel base material of the present invention does not include a step of isomerizing the hydrogenated and deoxidized raw material by the hydride deoxidized treatment step, so that the manufacturing cost for manufacturing the diesel fuel base material is not included. Can be reduced.

The method for producing a diesel fuel base material of the present invention may further include a step of removing impurities such as alkali metal, alkaline earth metal and chlorine from the raw material, which is carried out before the step of performing the hydrogenation deoxidation treatment. Impures such as alkali metals, alkaline earth metals and chlorine may become catalytic poisons during the hydrogenation deoxidation treatment and may corrode the reactors that perform the hydrogenation deoxidation treatment. Therefore, it is preferable to remove these impurities from the raw material before performing the hydrogenation deoxidation treatment. As a method for removing these impurities from the raw material, there are column refining using a polar column such as silica, or application of degumming-deoxidation-decolorization-deodorization, which is used as a method for refining edible oil. For degumming-deoxidation-decolorization-deodorization, all four steps may be selected or only a part may be selected. For example, only two or three steps such as degumming-decolorization and degumming-deoxidizing-decoloring are effective in removing impurities.

[Manufacturing method of diesel fuel composition]
The method for producing a diesel fuel composition of the present invention includes a step of mixing JIS No. 2 light oil with a diesel fuel base material produced by the method for producing a diesel fuel base material of the present invention. As a result, it is possible to obtain a diesel fuel composition having a high cetane number and a high calorific value by using JIS No. 2 light oil.

The diesel fuel base material produced by the method for producing a diesel fuel base material of the present invention, straight-run gas oil, desulfurized gas oil (DGO), desulfurized kerosene (DK), hydrocracked gas oil (HCGO) and hydrocracked gas oil. It may further include the step of mixing with at least one selected from the group consisting of (HCK).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

[Evaluation method]
(Oil derived from Pseudocholis cystis ellipsoidia)
The following evaluation was performed on the oil derived from Pseudocorysistis ellipsoidia used in the production of the diesel fuel base material of Example 1.
(Distillation properties)
Distillation properties were measured according to the gas chromatograph method specified in JIS K 2254.
(Sulfur content)
Sulfur content was measured according to JIS K 2541-6.
(Alkali metal content (Na, K))
The alkali metal content (Na, K) was measured by the ICP-OES method after the sample was treated with sulfuric acid, incinerated and acid-decomposed.
(Alkaline earth metal content (Ca, Mg))
The alkaline earth metal content (Ca, Mg) was measured by the ICP-OES method after the sample was treated with sulfuric acid, incinerated and acid-decomposed.
(Halogen content (F, Cl))
Halogen content (F, Cl) was measured by combustion-ion chromatography. The combustion-ion chromatograph method is a method in which a sample is burned in a combustion gas stream containing oxygen, the generated gas is collected in an absorption liquid, and halogen contained in the absorption liquid is separated and quantified by ion chromatography. ..
(moisture)
Moisture was measured according to the volumetric titration method specified in JIS K 2275.

(Diesel fuel base material)
The following evaluations were performed on the diesel fuel base materials of Examples 1 and Comparative Examples 1 to 3.
(Density (15 ° C))
The density at a liquid temperature of 15 ° C. was measured according to JIS K 2249.
(Dynamic viscosity (30 ° C))
The kinematic viscosity at a liquid temperature of 30 ° C. was measured according to the kinematic viscosity test method specified in JIS K 2283.
(Pour point)
The pour point was measured according to the pour point test method specified in JIS K 2283.
(Clogged point)
The clogging point was measured according to JIS K 2288.
(Flash point)
The flash point was measured according to JIS K 2265-3.
(Distillation properties)
Distillation properties were measured according to the atmospheric pressure method specified in JIS K 2254.
(Aroma)
The aroma content was measured according to JPI-5S-49-2007.
(Oxidation stability)
Oxidation stability was expressed as the induction period measured by the PetroOXY test. The induction period is the time required to fill 5 ml of the sample with a predetermined amount of oxygen, raise the temperature to 140 ° C., and reduce the initial pressure by 10%.
(Total calorific value)
The total calorific value was measured according to JIS K 2279.
(Cetane index)
The cetane index was measured according to the cetane number test method specified in JIS K 2280 and the calculation method of the cetane index using a four-variable equation.

(Diesel fuel composition)
The following evaluations were performed on the diesel fuel compositions of Examples 2 to 4. The sulfur content was evaluated by the same method as the above-mentioned oil derived from Pseudochorysistis ellipsoidia. Further, regarding the evaluation of density (15 ° C.), kinematic viscosity (30 ° C.), distillation properties, cetane index, total calorific value, flash point, pour point, clogging point and aroma content, the above-mentioned Example 1 and Comparative Example The evaluation was carried out in the same manner as in the diesel fuel base materials 1 to 3.

[Preparation of sample]
(Diesel fuel base material)
(Diesel fuel base material of Example 1 (HBD100))
<Preparation of hydrogenated oxygen scavenger catalyst>
A catalyst was prepared with reference to JP-A-2010-235944. First, a titanium-containing aqueous solution was prepared based on the pamphlet of International Publication No. 2002/049963. _{12.7 g of titanium hydroxide powder and 70 g of pure water in which the ratio of titanium oxide (IV) (TiO 2} ) obtained by firing at 500 ° C. for 4 hours is 85% by mass are put into a glass beaker having an internal volume of 1 L. It was put in, stirred and made into a slurry. Next, an aqueous solution obtained by mixing 78.7 g of 35% by mass hydrogen peroxide solution and 26.5 g of 26% by mass ammonia water was added to the titanium hydroxide slurry. Then, the mixture was stirred for 3 hours while maintaining 25 ° C. to obtain a yellowish green and transparent titanium-containing aqueous solution. To this, 28.4 g of citric acid primary hydrate was added. Then, after holding at a temperature of 30 ° C. or lower for 6 hours, holding at 80 to 95 ° C. for 12 hours gave 120 g of a transparent titanium-containing aqueous solution having a pH of 6.2. 58.5 g of the obtained titanium-containing aqueous solution was taken and diluted with pure water to make 80 ml, and 100 g of four-leaf γ-alumina was impregnated under normal pressure with a pore capacity of 0.8 ml / g (pore filling method). bottom. Then, under reduced pressure using a rotary evaporator, after drying for 1 hour at 70 ° C., then dried for 3 hours at 120 ° C., finally calcined for 4 hours at 500 ° C., to obtain a _TiO 2 -5 wt% on an alumina support.

Next, 75.3 g of basic nickel carbonate (44.0 g as NiO), 220 g of molybdenum trioxide, positive 250 ml of pure water was added to 34.5 g of phosphoric acid ( _{29.3 g as P 2} O ₅ ), dissolved at 80 ° C. with stirring, cooled at room temperature, and then nickel was added to 264 ml of pure water. -A molybdenum impregnated solution was prepared. The impregnation solution was 60 ml collected with the addition of triethylene glycol 6 g, to meet the water absorption of the TiO 2 _-5 wt% on an alumina support 100 g, was diluted, constant volume with pure water, the atmospheric pressure Impregnated. Then, after drying under reduced pressure using a rotary evaporator at 70 ° C. for 1 hour, heat treatment was performed at 120 ° C. for 16 hours to prepare a catalyst precursor A. The catalyst was 57% by mass of alumina, _{3% by mass of TiO 2} , 6% by mass of NiO, 30% by mass of _{MoO 3} , and 4% by mass of _{P 2} O _{5 in terms of the amount charged.}

<Pretreatment of raw material oil>
The raw material oil obtained by n-heptane extraction from Pseudocorycystis ellipsoidia was purified through a silica column using a mixed solution of isopropyl ether and n-heptane (1:20 by volume) as a developing solvent, and purified at 100 ° C. Volatilized isopropyl ether and n-heptane. The impurity concentration of this raw material oil is as shown in Table 4 below. It was also found that this feedstock oil contained about 90% fatty acid triglyceride and 10% fatty acid (measured using FID gas chromatograph (Agient 7890 series)).

<Hydrogenation deoxygenation reaction>
The fixed-bed flow reactor was filled with 10 cc of the hydrogenation deoxidizing catalyst, and a reduction treatment was carried out at 375 ° C. for 18 hours in a hydrogen stream. Then, the reaction was carried out under the conditions of a reaction temperature of 375 ° C., ^{WHSV of 0.5 hr -1} _{, H 2} / Oil of 2000 NL / L, and a pressure of 6 MPa. Then, the reaction was continued for about 500 hours to obtain 2 L of the diesel fuel base material (HBD100) of Example 1.

(Diesel fuel base material (HBD) of Comparative Example 1)
An oil prepared by adding 5% by mass ppm of a sulfur compound (DMDS; dimethyl disulfide) to a vegetable oil having the properties shown in Table 1 was subjected to a two-step hydrogenation treatment under the reaction conditions shown in Tables 2 and 3, and a comparative example. 1 diesel fuel substrate (HBD) was obtained.

(Diesel fuel base material (FAME) of Comparative Example 2)
The vegetable oil having the properties shown in Table 1 was reacted with methanol to obtain the diesel fuel base material (FAME) of Comparative Example 2. Here, a transesterification reaction was used in which the mixture was stirred at 70 ° C. for about 1 hour in the presence of an alkaline catalyst (sodium methylate) and directly reacted with an alkyl alcohol to obtain an ester compound.

(Diesel fuel base material (GTL) of Comparative Example 3)
A diesel fuel base material having the properties shown in Table 5 was prepared from GTL obtained by FT synthesis.

(Diesel fuel composition)
The diesel fuel oil base material of Example 1 and the straight-run gas oil were mixed at the blending ratio (volume%) shown in Table 6 described later to produce the diesel fuel compositions of Examples 2 to 4.

[Evaluation results]
(Oil derived from Pseudocholis cystis ellipsoidia)
Table 4 below shows the evaluation results of the oil derived from Pseudochorysistis ellipsoidia used in the production of the diesel fuel base material of Example 1.

(Diesel fuel base material)
The evaluation results of the diesel fuel base materials of Examples 1 and Comparative Examples 1 to 3 are shown in Table 5 below.

The diesel fuel base material of Example 1 had good oxidation stability and total calorific value.
On the other hand, the diesel fuel base material of Comparative Example 1 had good oxidation stability, but had a low total calorific value. From this, it was found that the diesel fuel base material obtained by hydrogenating and deoxidizing the raw material containing the animal and vegetable fats and oils and / or the components derived from the animal and vegetable fats and oils has high oxidative stability. Then, it was found that the calorific value of the diesel fuel base material can be increased by increasing the density of the diesel fuel base material.
The diesel fuel base material of Comparative Example 2 had poor oxidation stability and a low total calorific value. From this, it was found that the diesel fuel oil base material obtained by methyl esterifying vegetable oils and fats has poor oxidative stability, and the calorific value does not increase so much even if the density is increased.
Although the diesel fuel base material of Comparative Example 3 was not as good as the diesel fuel base material of Example 1 and the diesel fuel base material of Comparative Example 1, the oxidation stability was good. However, the total calorific value of the diesel fuel base material of Comparative Example 3 was low. From this, it was found that the calorific value of the diesel fuel base material obtained by the GTL (Gas to Liquid) process does not increase so much even if the density is increased.

(Diesel fuel composition)
The evaluation results of the diesel fuel compositions of Examples 2 to 4 and Comparative Examples 4 and 5 are shown in Table 6 below. The straight-run diesel fuel that meets the JIS No. 2 diesel fuel standard was also evaluated in the same manner as the diesel fuel compositions of Examples 2 to 4 and Comparative Examples 4 and 5. The evaluation results are shown in Table 6 as Reference Example 1.
Regarding the cetane index, those with 70 or more are "◎" (excellent), those with 60 or more and less than 70 are "○" (good), those with 50 or more and less than 60 are "△" (possible), and less than 50. Those were evaluated as "x" (impossible).
Regarding the total calorific value, those with 37.5 MJ / L or more are "◎" (excellent), those with 37.0 MJ / L or more and less than 37.5 MJ / L are "○" (good), 36.5 MJ /. Those with L or more and less than 37.0 MJ / L were evaluated as "Δ" (possible), and those with less than 36.5 MJ / L were evaluated as "x" (impossible).
Furthermore, regarding the oxidation stability, those for 100 minutes or more are marked with "◎" (excellent), those for 65 minutes or more and less than 100 minutes are marked with "○" (good), and those for less than 65 minutes are marked with "x" (impossible). Each was evaluated.
Then, when all the evaluations of the cetane index, the total calorific value and the oxidative stability are "◎" (excellent), the comprehensive evaluation is "◎" (excellent), and the evaluation of the cetane number, the total calorific value and the oxidative stability are evaluated. "○" (good) is evaluated as a comprehensive evaluation of only "◎" (excellent) and "○" (good), and "x" (impossible) in the evaluation of cetane number, total calorific value and oxidation stability. There is no), but there is a "△" (possible) as a comprehensive evaluation, and there is an "x" (impossible) in the evaluation of cetane number, total calorific value and oxidation stability. Those were evaluated as "x" (impossible) as a comprehensive evaluation. A diesel fuel composition having an overall evaluation of "◎" (excellent) or "○" (good) can be evaluated as a diesel fuel composition having a high cetane number, good oxidation stability, and a high calorific value. However, a diesel fuel composition having a comprehensive evaluation of "△" (possible) or "×" (impossible) is a diesel fuel composition having a high cetane number, good oxidative stability, and a high calorific value. Cannot be evaluated.

From the above evaluation results of the diesel fuel compositions of Examples 2 to 4 and Comparative Examples 4 and 5, the setan index was obtained by mixing the straight-run gas oil satisfying the JIS No. 2 gas oil standard with the diesel fuel base material of Example 1. It was found that a diesel fuel composition having high calorific value, good oxidative stability, and high calorific value can be obtained.

Claims (11)

A diesel fuel base material obtained by hydrogenating and deoxidizing a raw material containing a fat and oil containing at least one selected from the group consisting of fatty acid triglyceride, fatty acid diglyceride, fatty acid monoglyceride, (free) fatty acid and fatty acid ester. ,
15 Density at ℃ is 0.7790g / cm ³ or more 0.8600g / cm ³ Ri der below,
The fat and oil containing at least one main component selected from the group consisting of the fatty acid triglyceride, the fatty acid diglyceride, the fatty acid monoglyceride, the (free) fatty acid and the fatty acid ester is a fat and oil derived from microalgae, and the fatty acid triglyceride and the fatty acid. A diesel fuel substrate having 16 or more and 18 or less carbon atoms in the fatty acid portion of diglyceride, fatty acid monoglyceride, (free) fatty acid and fatty acid ester. The diesel fuel base material according to claim 1, wherein the total calorific value is 36.5 MJ / L or more. The diesel fuel base material according to claim 1 or 2, wherein the induction period according to the PetroOXY test is 100 minutes or more. The diesel fuel base material according to any one of claims 1 to 3, wherein the microalgae is a pseudocolicistic ellipsoidia, an alga belonging to the genus Pseudococomixa, or an alga belonging to the genus Kokkomixa. A diesel fuel composition containing the diesel fuel base material according to any one of claims 1 to 4. The diesel fuel composition according to claim 5 , further comprising JIS No. 2 light oil. The method for producing a diesel fuel base material according to any one of claims 1 to 4.
Including a step of hydrogenating and deoxidizing the raw material containing fats and oils derived from microalgae.
A method for producing a diesel fuel base material, which does not include a step of isomerizing the raw material hydrogenated and deoxidized by the hydrogenation deoxidation treatment step. The method for producing a diesel fuel base material according to claim 7 , wherein the microalgae is a pseudocolicistic ellipsoidia, an alga belonging to the genus Pseudococomixa, or an alga belonging to the genus Kokkomixa. The method for producing a diesel fuel base material according to claim 7 or 8 , wherein the pressure in the step of the hydrogenation deoxidation treatment is 2 MPa or more and 8 MPa or less. The method for producing a diesel fuel base material according to any one of claims 7 to 9 , wherein the reaction temperature in the step of hydrogenation deoxidation treatment is 250 ° C. or higher and 450 ° C. or lower. A method for producing a diesel fuel composition, which comprises a step of mixing the diesel fuel base material produced by the method for producing a diesel fuel base material according to any one of claims 7 to 10 with JIS No. 2 light oil.