WO2007064019A1

WO2007064019A1 - Liquefied fuel gas composition

Info

Publication number: WO2007064019A1
Application number: PCT/JP2006/324306
Authority: WO
Inventors: Manabu Watanabe; Masanori Hirose
Original assignee: Nippon Oil Corporation
Priority date: 2005-11-30
Filing date: 2006-11-29
Publication date: 2007-06-07
Also published as: CN101341232A; JP2007153940A; KR20080071580A; JP4925653B2

Abstract

Disclosed is a liquefied fuel gas composition as a fuel derived from a biomass, which is obtained by bringing a raw material oil into contact with a hydrogenolysis catalyst under hydrogen pressure. The raw material oil is composed of animal and plant fats and oils and/or a hydrocarbon distillate containing a component derived from animal and plant fats and oils; and the hydrogenolysis catalyst contains at least one metal selected from group 6A and group 8 elements of the periodic table and an inorganic oxide having acidic properties. The liquefied fuel gas composition contains a hydrocarbon having a sulfur content of not more than 10 ppm by mass, not less than 1.0 mol% but not more than 99.0 mol% of hydrocarbons with 3 carbon atoms, and not less than 1.0 mol% but not more than 99.0 mol% of hydrocarbons with 4 carbon atoms.

Description

Liquefied fuel gas composition

[Technical field]

The present invention relates to a liquefied fuel gas composition, and in particular, using at least one metal selected from Groups 6A and 8 of the Periodic Table using a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats as a feedstock. And hydrogen containing an inorganic oxide with acid properties

The present invention relates to a liquefied fuel gas composition containing hydrocarbons obtained by contacting a hydrocracking catalyst with hydrogen under pressure.

-Thread

Rice field

[Background]

In recent years, as the air pollution situation worsens, regulations on automobile exhaust gas have been tightened, and there has been a situation where the use of diesel vehicles that use light oil as fuel, especially diesel trucks, is restricted. In response to this, an exhaust gas purification system for diesel vehicles has been developed, but alternatives to low-emission vehicles with cleaner emissions are also being considered, and liquefied petroleum gas (LPG) is used as fuel. Trucks are expected to replace diesel trucks. Furthermore, in taxis, LPG has been used as the main fuel for nearly 40 years. (For example, see Non-Patent Document 1.) In addition, regarding the quality of liquefied petroleum gas (autogas) for automobiles, there are examples that have been studied with the aim of further reducing exhaust gas (see, for example, Patent Document 1), but examples of studies on reducing carbon dioxide. There is no.

Patent Document 1: Japanese Patent Laid-Open No. 10-1 2 10 70

Non-Patent Document 1: Γ LP Gas 'Data Required (LP Gas' Data Required Editorial Committee) ", industry bulletin, supervised by the Science and Technology Agency, Resource Bureau, 1 96 4 years, p. 1 6 6 Used in Japan About one-quarter of LPG is provided by domestic production and about 34 by import. In recent years, attempts have been made to expand import destinations in order to diversify import LPG supply sources, and domestic production is separated from oil refineries at the time of crude oil distillation. Some of these are obtained from by-products from other plants, etc., and the LPG quality is not necessarily the same as before. That is not the case. However, they were all limited to those derived from fossil fuels.

In order to respond to global warming issues while reducing emissions, there is a need for effective fuel properties to reduce carbon dioxide, and one of the solutions is to replace biomass-derived fuel, which is the most renewable energy. Use as a fuel is being studied. Currently, fuels that can be mixed directly with gasoline and light oil, which are conventional fossil fuels, such as bioethanol, ETB, and biodiesel are being investigated. However, there are no examples or knowledge of biomass-derived liquefied fuel gas compositions that can be directly mixed with conventional liquefied petroleum gas.

[Disclosure of the Invention] '

As a result of intensive research on the above problems, the present inventors have used hydrocarbon fractions containing animal and vegetable fats and animal fats and oils as feedstocks, starting from groups 6A and 8 of the periodic table. A liquefied fuel gas composition using a hydrocarbon obtained by contacting a hydrocracking catalyst containing at least one selected metal and an inorganic oxide having acid properties with hydrogen under pressure is found, and the present invention Has been completed. That is, the present invention provides a feedstock consisting of a hydrocarbon fraction containing a component derived from animal and vegetable fats and / or animal fats and at least one metal selected from Groups 6A and 8 of the periodic table. Sulfur content of 10 mass ppm or less and carbon number of 3 hydrocarbons of 1.0 mol% or more obtained by contacting a hydrocracking catalyst containing an inorganic oxide with acid properties under hydrogen pressure The present invention relates to a liquefied fuel gas composition characterized by containing a hydrocarbon having 9 9.0 mol% or less and a C 4 hydrocarbon of 1.0 mol% or more and 99.0 mol% or less.

The present invention also provides a mixed oil obtained by mixing a hydrocarbon hydrocarbon fraction containing a component derived from animal and vegetable fats and oils and Z or animal fats and a petroleum hydrocarbon fraction having a kerosene fraction purified from crude oil or the like at an arbitrary ratio. A feedstock comprising: a hydrocracking catalyst containing at least one metal selected from Groups 6A and 8 of the Periodic Table and an inorganic oxide having acid properties under hydrogen pressure. A sulfur content of 10 mass ppm or less and a carbon number of 3 hydrocarbons obtained by the above is 1.0 mol% or more and 99.0 mol. /. Hereinafter, the hydrocarbon having 4 carbon atoms is 1.0 mol% or more and 99.0 mol. Contains hydrocarbons that are less than or equal to ₀ The present invention relates to a liquefied fuel gas composition.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

In the present invention, a hydrocarbon fraction containing animal and vegetable fats and oils and components derived from Z or animal fats is used as a raw material oil. .

In the present invention, a mixed oil obtained by mixing animal and vegetable oils and / or hydrocarbon fractions containing animal fats and oils at an arbitrary ratio is used as a raw material oil.

The animal and vegetable fats and oils and animal fats and oils-derived components in the present invention refer to animal and vegetable fats and oils and animal and vegetable fats and oils components that are produced or manufactured naturally or artificially. Examples of animal fats and animal oils include beef tallow, milk lipid (batter), pork tallow, sheep fat, whale oil, fish oil, liver oil, etc. Vegetable oils and vegetable oil ingredients include coconut palm, olive palm, olive, There are seeds and other parts such as banana, rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, Amami, etc. There is no problem in use. These raw oils may be solid or liquid, but it is preferable to use vegetable oils or vegetable oils as raw materials because of easy handling and high carbon dioxide absorption. In the present invention, waste oils obtained by using these animal oils and vegetable oils for consumer use, industrial use, food use, etc. can be used as raw materials after adding a step for removing impurities.

Typical compositions of the fatty acid part of the glyceride compounds contained in these raw materials include butyric acid (C ₃ H ₇ COOH) and caproic acid, which are fatty acids having no unsaturated bonds in the molecular structure called saturated fatty acids. (CsHnCOOH force prillic acid (C?! ^ ₅ COOH), capric acid (C ₉ H ₁₉ COOH), lauric acid (C i

Myristic acid (C! ₃ H ₂₇ COOH), palmitic acid (C! ₅ H ₃ i COOH), stearic acid (C ₁₇ H ₃₅ COOH), and unsaturated fatty acids with one or more unsaturated bonds Examples include oleic acid (C ₇ H ₃₃ COOH), linoleic acid (C ₁₇ H ₃₁ COO H), linolenic acid (C i ₇ H ₂₉ COOH), and ricinolenic acid (C ₁₇ H ₃₂ (OH) CO OH). The hydrocarbon part of these fatty acids in natural substances is generally straight chain, but as long as the properties defined in the present invention are satisfied in the present invention, even a structure having a side chain, that is, an isomer is used. can do. Also, The position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties specified in the present invention are satisfied in the present invention, but are also set at arbitrary positions by chemical synthesis. It can also be used.

The above-mentioned raw oils (components derived from animal and vegetable fats and oils and animal fats and oils) have one or more of these fatty acids, and the fatty acids they have differ depending on the raw materials. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid. .

Petroleum hydrocarbon fractions with kerosene fractions refined from crude oil, etc. used by mixing them in any proportion with hydrocarbon fractions containing animal and vegetable fats and / or animal fats and oils. The fraction obtained in the refining process can be used. For example, the fraction hydrodesulfurization apparatus, hydrocracking apparatus, hydrocracking apparatus, and residual oil direct desulfurization corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus. A fraction having a corresponding boiling range obtained from an apparatus, a fluid catalytic cracker, or the like may be mixed alone, or corresponding fractions from a plurality of apparatuses may be mixed. The petroleum hydrocarbon fraction has at least a boiling point

It is desirable to contain a fraction with a temperature of 300 ° C or higher, and it is more desirable not to contain a fraction with a boiling point higher than 70 ° C. If the petroleum hydrocarbon fraction does not contain a fraction of 300 ° C or higher, there is a risk that a sufficient liquid yield may not be obtained due to excessive decomposition, which is heavier than 700 ° C. When a fraction is included, the active component is covered by the carbon component formation on the catalyst by the heavy component, which may lead to a decrease in activity. The boiling point range in this specification is a value measured according to the method described in JI S K 2 2 5 4 “Distillation test method” or A STM — D 8 6.

Petroleum containing raw material oil consisting of hydrocarbon fractions containing components derived from animal and vegetable oils and fats or animal oils, or hydrocarbons containing components derived from animal and vegetable oils and / or animal oils and oils having kerosene fractions refined from crude oil, etc. The mixed oil in which the hydrocarbon fractions are mixed in an arbitrary ratio is the raw material oil. Next, an inorganic oxide having at least one metal selected from Group 6A and Group 8 of the periodic table and an acid property is used. The hydrocracking catalyst contained is brought into contact with hydrogen under pressure.

The hydrocracking catalyst contains at least one type of metal selected from Group 6A and Group 8 metals of the periodic table, and preferably two or more types from Group 6A and Group 8. Contains the above metals. For example, C o—M o, N i -M o, N i—C o—M o, N i—W are preferable, N i—M o, N i—C o—M o, N i— W is selected. In hydrocracking, these metals are converted into sulfides and used in the same manner as the pretreatment catalyst for hydrogenation.

As the carrier for the hydrocracking catalyst, an inorganic oxide having an acid property is adopted, but it is desirable to contain at least two of silica, alumina, polya, zirconia, magnesia, and zeolite. For example, silica-alumina, titania-alumina, poly-alumina, zirco-alumina, titania-zirconia-alumina, silica-bora-alumina, silica-zirco-alumina, silica-titania-alumina, silica-tita-zirconia-alumina Silica-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina, silica-boria-alumina, silica-zircoua-alumina, silica-titania-alumina are more desirable, silica-alumina, silica-zirconia —Alumina is even more desirable. It is most desirable that these composite oxides contain zeolite. When alumina is included, the ratio of alumina to other components can be any ratio to the support, but the alumina content is 96% of the support weight. / ₀ or less, preferably 90 weight. It is more desirable that it be less than ₀ . When the alumina content exceeds 96% by weight, sufficient acidity cannot be obtained, and it tends to be difficult to exhibit a predetermined hydrocracking activity.

In addition to silica, there are alumina, titania, polya, gallium, and other components that form the zeolite crystal skeleton used in hydrocracking catalysts. Is desirable. Many types of crystal structures of zeolite have been reported, such as faujasite, beta, mordenite, and pentasil. In the present invention, the faujasite type, beta type, and pentasil type are more preferable, and particularly the faujasite type and beta type are even more desirable in that sufficient hydrocracking activity is exhibited. As these zeolites, those having an alumina content adjusted according to the stoichiometric ratio of raw materials at the start of synthesis, or those subjected to a predetermined hydrothermal treatment and / or acid treatment can be used. Of these, ultra-stabilized Y type that is super-stabilized by hydrothermal treatment and / or acid treatment is most desirable. This ultra-stabilized Y-type 2 In addition to the fine pore structure called Miku mouth pores below OA, new pores are formed in the range of 20 to 10 OA, which provides a good reaction field for converting the oxygen content of fats and oils. The volume of the pores having the pore diameter is preferably 0.03 ml / g or more, more preferably 0,04 4 m 1 / g. The pore volume mentioned here can be generally determined by a mercury intrusion method. Known conditions can be used as the hydrothermal treatment conditions. As the physical property of the ultra-stabilized Y type, the molar ratio of silica and alumina is preferably 10 to 120, more preferably 15 to 70, and even more preferably 20 to 50. If the molar ratio of silica Z-alumina is higher than 120, the acidity is low, and sufficient hydrocracking activity may not be exhibited. On the other hand, when the molar ratio of silica Z alumina is lower than 10, the acidity is too strong, and there is a risk that the activity is rapidly lowered by promoting the coke formation reaction. The content of zeoli cake is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the weight of the carrier. If the zeolite content is less than the lower limit, the hydrocracking activity may not be exhibited. If the zeolite content exceeds the upper limit, the acidity is too strong and the coke formation reaction There is a risk of promoting.

In the present invention, when the feedstock is subjected to contact treatment under hydrogen pressure, a hydrogenation pretreatment catalyst containing at least one metal selected from Group 6A and Group 8 of the periodic table and hydrogen pressure is used. It is preferable to contact with the hydrocracking catalyst under hydrogen pressure after contacting with.

The active metal of the hydrogenation pretreatment catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably selected from Group 6A and Group 8 Contains two or more metals. For example, Co-Mo, Ni-M--o, Ni-Co-Mo, Ni--W, and these metals are converted to sulfide during the pretreatment of hydrogenation. To use.

A porous inorganic oxide is used as the support for the hydrogenation pretreatment catalyst. Generally, it is a porous inorganic oxide containing alumina, and other carrier constituents include siri force, titania, zircoua, and polya. Desirably, it is a complex oxide containing at least one selected from alumina and other constituent components. Moreover, phosphorus may be included as another component. Preferably the total free Yuryou ingredient other than alumina is 1 to 2 0 weight ^_0/0, 2-1 5 to contain by weight% Is more desirable. If the content is less than 1% by weight, a sufficient catalyst surface area cannot be obtained, and the activity may be lowered. If the content exceeds 20% by weight, the acidity of the support increases. There is a risk of reducing the activity due to the generation of the core. When phosphorus is included as a carrier constituent, its content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.

There are no particular limitations on the raw material that is a precursor of silica, titania, zircoure, and polya, which are carrier constituents other than alumina, and a solution containing general silicon, titanium, zirconium, and boron can be used. For example, calcium for acid, water glass, silica sol, titanium sulfate for titanium, titanium tetrachloride and various alkoxide salts, zirconium for zirconium sulfate and various alkoxide salts, boron for boric acid, etc. Can be used. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.

It is desirable that the raw materials for the carrier constituents other than these aluminas are added in any step prior to the firing of the carrier. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. Although it may be added to the step of adding and kneading, a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the support, and some sort of active metal. It is considered that the activity is affected by the interaction.

The active metal content is, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide conversion. is there. If the total supported amount of W and Mo is less than the lower limit, the activity may decrease due to a decrease in the number of active points.If the upper limit is exceeded, the metal is not effectively dispersed, Similarly, the activity may be reduced. The total supported amount of 0 and ^ 1 is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of cobalt and nickel is less than 1.5% by weight, a sufficient promoter effect may not be obtained and the activity may decrease. If it is higher than% by weight, the metal will not disperse effectively and may lead to activity as well o

The catalytic reaction conditions under hydrogen pressure are as follows: hydrogen pressure 5 to 20 MPa, liquid space velocity (LHSV) 0.:! To 2.2 h ¹ , hydrogen Z oil ratio 300 to: I 500 N LZL Desirable conditions are: hydrogen pressure 6.5 to 18 MPa, liquid space velocity 0.2 to 2.0 h ¹ , hydrogen / oil ratio 300 to 1 500 NL / L. Pressure 8 ~ 15MPa, Liquid space velocity 0.3 ~: I.5h Hydrogen Oil ratio 350 ~ 1000N LZL and when the conditions are even more desirable.

By contact treatment under hydrogen pressure, sulfur content 10 mass p pm or less, carbon number 3 hydrocarbons 1.0 mol% to 99.0 mol%, carbon number 4 hydrocarbons 1.0 mol % To 99.0 mol% of hydrocarbon is obtained.

The liquefied fuel gas composition of the present invention contains such a hydrocarbon, and its content is at least 1.0% by volume, preferably at least 20.0% by volume, more preferably at 98.0%. It is more than volume%.

The liquefied fuel gas composition of the present invention comprises a propane mixture which is a hydrocarbon having 3 carbon atoms as a main component and a butane mixture which is a hydrocarbon having 4 carbon atoms. The ratio of the two can be arbitrarily defined according to the location of use and season. The propane mixture is mainly composed of propane and propylene, and the butane mixture is mainly composed of butane and butylene. In addition to these, the composition of the liquefied fuel gas composition of the present invention can contain a small amount of ethane mixture, butadiene, pentane and the like. The ethane mixture is composed of ethane and ethylene, and the content of the ethane mixture in the liquefied fuel gas composition is preferably 5 mol% or less. The content of butadiene in the liquefied fuel gas composition is preferably 5 mol ^_0/0 below 0.1, the content of pentane 2 mol ⁰ /. The following is preferable.

The liquefied fuel gas composition of the present invention preferably has a residue at 105 ° C of 10 mass ppm or less. 105. The C residue content is more preferably 5 mass ppm or less, and particularly preferably 2 mass ppm or less from the viewpoint of reducing the deposit generation rate and the frequency of drain extraction.

The residue at 105 ° C here is a value measured according to the method specified in ASTM D 2 1 58, but the initial sample amount is 10 OmL as described in the AS TM method. By changing the set temperature from 38 ° C to 75 ° C and 1,05 ° C in order, and finally weighing the remaining residue at 105 ° C. The value to be measured. At this time, the holding time at each temperature is not 5 minutes described in the AS TM method, but a sufficient time is taken until almost no evaporation is observed at that temperature. The liquefied fuel gas composition of the present invention preferably has a pH of the residue at 105 ° C of 6 or more. If the pH of the residue at 105 ° C is less than 6, there is a risk of increased deposit formation inside the vaporizer. On the other hand, the pH is preferably 8 or less in terms of preventing corrosion between the fuel line and the vaporizer. More preferably, the pH is 6-7, and even more preferably the pH is 7.

Note that “105 at 11 residue” means that the residue at 105 ° C obtained by the above method for measuring the residue at 105 ° C is 1000 times the amount of distilled water (residue is 1 mg). In the following cases, 1 mL of distilled water) is added and stirred, and then the value obtained by measuring the pH of the aqueous phase with a pH test paper.

The sulfur content of the liquefied fuel gas composition of the present invention is preferably 0.02 mass% or less on the basis of the total amount of liquefied fuel gas from the viewpoint of preventing corrosion of the fuel line and preventing sulfur oxide emission into the exhaust gas, More preferably, the content is 0.01% by mass or less, more preferably 0.005% by mass or less, and 0.001% by mass. Most preferably, it is less than or equal to ₀ .

The sulfur content here means a value measured by J I S K 2240 “Liquefied petroleum gas (LP gas) single sulfur content test method”.

The vapor pressure at 40 ° C of the liquefied fuel gas composition of the present invention is preferably 0.28 MPa or more, more preferably 0.38 MPa or more from the viewpoint of securing startability at low temperatures. . On the other hand, from the viewpoint of handling safety, it is preferably 1.55 MPa or less, 1. 25 MPa or less is more preferable, and 0.52 MPa or less is most preferable.

The vapor pressure at 40 ° C here refers to the value measured by J I S K 2240 “Liquid fossil oil gas (LP gas) one vapor pressure test method”.

The density at 15 ° C of the liquefied fuel gas composition of the present invention is preferably 0.500 gZcm ³ or more from the viewpoint of improving fuel efficiency, while it is 0.620 from the viewpoint of preventing heavy components from being mixed. preferably GZC m ³ or less, 0. e OO gZcm ³ below Is more preferable. ,

Here, the density at 15 ° C. means a value measured by J I S K 2 2 40 “Liquefied petroleum gas (L P G) —Density test method”.

The copper plate corrosion of the liquefied fuel gas composition of the present invention is preferably 1 or less, more preferably la, from the viewpoint of preventing corrosion of fuel piping.

In addition, copper plate corrosion here means the value measured by JISK 2240. “Liquefied petroleum gas (LP gas) monocopper plate corrosion test method”.

The liquefied fuel gas composition of the present invention can be suitably used as a fuel for automobiles.

[The invention's effect] '

The liquefied fuel gas composition of the present invention comprises at least one selected from Group 6A and Group 8 of the periodic table using a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats as a feedstock. By using hydrocarbons obtained by contacting hydrogenolysis catalysts containing inorganic metals with acid properties with hydrogen metals under hydrogen pressure, emissions are reduced and CO ₂ emissions are reduced. be able to.

[Example]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Inorganic oxide having at least one metal selected from Group A and Group 8 of the Periodic Table and acid properties, consisting of hydrocarbon fractions containing components derived from animal and vegetable fats and / or animal fats The liquefied fuel gas compositions of Examples 1 and 2 were prepared using hydrocarbons obtained by contacting a hydrocracking catalyst containing hydrogen under pressure of hydrogen. On the other hand, a liquefied fuel gas composition of Comparative Example 1 was prepared using butane, propane, imported propane, and imported propane produced from a refinery. Table 1 shows the properties of each liquefied fuel gas composition used in Examples and Comparative Examples. For these liquefied fuel gas compositions, an exhaust gas test was conducted and an exhaust gas evaluation was carried out by the following method. The results are shown in Table 2. Again. Then the discharge of these Examples and Comparative Example 0 ₂ La I conducted Fusaikuru assess the (LCA), were shown in Table 2 by calculating the discharged is C0 _2.

(a) Property measurement

The properties of each liquefied fuel gas composition were measured by the following method.

The composition analysis of propane, butane, etc. is the value measured by JIS K 2240 “Liquefied petroleum gas (LL gas) one composition analysis method (gas chromatograph method)”.

1 For the residue at 05 ° C, the initial sample amount was changed from 10 OmL described in the AS TM method to 4 L according to the method specified in ASTM D 2 1 58, and the set temperature was 38 described in the AS TM method. It is a value measured by weighing the residue remaining at 105 ° C in the order of 75 ° C and 105 ° C in order from ° C.

1 The pH of the residue at 05 ° C is 10 000 times the amount of distilled water (residue content is 1 mg). In the following cases, 1 mL of distilled water) is added and stirred, and then the pH of the aqueous phase is obtained by measuring with a pH test paper (pH test paper manufactured by Toyo Roshi Kaisha).

Sulfur content is a value measured by J I S K 2240 “Liquefied petroleum gas (LP gas) — Sulfur content test method IV”.

Vapor pressure at 40 ° C is a value measured by J I S K 2240 “Liquefied petroleum gas (LΡ gas)-Vapor pressure test method”.

1 Density at 5 ° C is a value measured according to JIS K 2240, “Liquefied Petroleum Gas (LPG) — Density Test Method”.

Copper plate corrosion is a value measured according to JIS K 2240 “Liquid petroleum gas (LP gas) monocopper plate corrosion test method”. .

(b) Emission evaluation

Using the following test vehicle, exhaust gas measurement was performed in the 10 * 15 mode. Table 2 shows the evaluation results of the exhaust gas test and CO ₂ emissions LCA.

(Test vehicle)

Engine: Inline 4 cylinder

Displacement: 1 998 c c

Fuel supply system: Electronically controlled carburetor

Mission: Automatic Transmission table 1

Table 2

As shown in Table 2, it can be seen that the liquefied fuel gas composition of the present invention can reduce exhaust gas components (THC, CO, NO x) compared to conventional LPG fuel.

Furthermore, a life cycle assessment (LCA) of the emitted CO ₂ of these examples and comparative examples was performed, and the C 0 ₂ emitted was calculated. In this example, the biomass-derived component of C0 ₂ generated during combustion becomes zero count, so it was possible to achieve a significant C0 ₂ reduction. .

[Industrial Applicability]-The present invention provides a liquefied fuel gas composition excellent in the effect of reducing exhaust gas and CO ₂ emission from components derived from animal and vegetable fats and oils.

Claims

1. Inorganic oxidation having at least one metal selected from Group 6 and Group 8 of the Periodic Table and acid properties from a feedstock consisting of a hydrocarbon fraction containing components derived from animal and vegetable oils and / or animal oils and fats Sulfur content, 10 mass ppm or less, carbon number, obtained by contacting the hydrocracking catalyst containing the product under hydrogen pressure

The hydrocarbon of 3 is 1.0 mol% or more and 99.0 mol% or less, and the hydrocarbon of 4 carbon atoms is 1.0.

0 mol% or more 99.0 mol. /. Liquid blue characterized by containing hydrocarbons below

Fuel gas composition.

2. Mix hydrocarbon fractions containing components derived from animal and vegetable oils and / or animal fats and petroleum-based hydrocarbon fractions containing kerosene fractions refined from crude oil, etc., in any ratio.

A feedstock composed of the combined oil mixture is selected from groups 6A and 8 of the periodic table.

Sulfur content of 10 mass ppm or less, carbon number 3 carbonized, obtained by contacting under hydrogen pressure with a hydrocracking catalyst containing at least one kind of metal and an inorganic oxide having acid properties Hydrogen is 1.0 mole. /. A liquefied fuel gas composition comprising a hydrocarbon having 9 to 9 mol% or less and a hydrocarbon having 4 carbon atoms of 1.0 mol% or more and 99.0 mol% or less.

3. After contacting the feedstock with a hydrotreating catalyst containing at least one metal selected from Groups 6A and 8 of the periodic table under hydrogen pressure, the hydrocracking catalyst The liquefied fuel gas composition according to claim 1, wherein the liquefied fuel gas composition is contacted with hydrogen under pressure.

4. The hydrocarbon constituting the liquefied fuel gas composition is a mixture of the hydrocarbon of claim 1 or 2 and the hydrocarbon derived from fossil fuel, and the hydrocarbon of claim 1 or 2 is 1 A liquefied fuel gas composition comprising at least mol%.

5. The liquefied fuel gas composition according to any one of claims 1 to 4, which is used for an automobile fuel.

6. The residue at 10 5 ° C is 10 mass ppm or less, and the pH of the residue at 10 5 ° C is 6 or more and 8 or less. The liquefied fuel gas composition as described.