JP6742020B2 - Process for producing hydrocarbon composition and catalyst - Google Patents

Description

The present invention relates to a method for producing a hydrocarbon composition and a catalyst.

BACKGROUND ART Conventionally, there is known a technique of producing a composition containing a hydrocarbon by subjecting natural fats and oils or their derivatives to a hydrogenation treatment using a metal catalyst or an alloy catalyst.

For example, as a method for producing hydrocarbons using natural fats and oils or their derivatives and edible waste oil as raw materials, natural fats and oils, waste natural fats and oils or their derivatives, and activated hydrogen are used as metal catalysts, alloy catalysts, and metal-supported catalysts. There is known a method for producing hydrocarbons, which comprises reacting in the presence of a catalyst selected from the group consisting of and an alloy-supported catalyst (see, for example, Patent Document 1).

Further, as a light oil composition containing an environmentally low-loading diesel oil base material produced by using a triglyceride-containing hydrocarbon, which is a component derived from animal and vegetable oils and fats, as a raw material oil containing a component derived from animal and vegetable oils and/or animal fats and oils. Of the Periodic Table Group 6A and/or Group 8 metal with a hydrorefining catalyst containing an inorganic oxide having acidic properties under hydrogen pressure and at the same time/afterwards a carrier containing a crystalline molecular sieve. 50% by mass of a chain saturated hydrocarbon having 15 to 18 carbon atoms, which is obtained by contacting with an isomerization catalyst containing a metal of Group 6A and/or Group 8 of the periodic table supported under hydrogen pressure. Light oil containing the above and having a value of 0.7 or more obtained by dividing the chain saturated hydrocarbon content having a side chain of 15 or more carbon atoms by the linear saturated hydrocarbon content of 15 or more carbon atoms and satisfying a specific formula A composition is known (for example, refer to Patent Document 2).

A supported or unsupported catalyst comprising an active phase constituted by a sulfur-containing Group VIB element as a catalyst for converting a distillate of a renewable origin into a fuel of excellent quality, comprising: The Group VIB element is molybdenum, which, in the case of supported catalysts, has a Group VIB element content of 17-35% by weight of the oxide of the Group VIB element with respect to the total mass of the catalyst, and from phosphorus, boron and silicon. There is known a catalyst that further includes a selected doping element supported on the carrier (see, for example, Patent Document 3).

As a way to maximize the yield of gas oil and accelerate the mechanism of hydrodeoxygenation of carboxyl groups to alkyl groups, it comes from renewable sources with decarboxylation/decarbonylation conversion limited to at most 10%. A method of hydrodeoxygenation of a feedstock using a bulk or supported catalyst comprising an active phase comprising at least one element from Group VIB and at least one element from Group VIII Is in the form of a sulphide and the atomic ratio of the metal(s) from Group VIII to the metal(s) from Group VIB is strictly greater than 0 and less than 0.095, Is a temperature in the range of 120 to 450° C., a pressure in the range of ^{1 to} 10 MPa, an hourly liquid hourly space velocity in the range of 0.1 to 10 h ⁻¹ , and the hydrogen/feeding material ratio is the volume of the charging material (m ³ ). A method is known, which is carried out in the presence of the total amount of hydrogen mixed with the charged raw material so that the hydrogen content is 50 to 3000 Nm ³ per unit (for example, refer to Patent Document 4).

Also, the use of a composition containing a hydrocarbon as a cold heat storage agent utilizing latent heat has been studied.
For example, normal paraffin components with a carbon number _{C n} (A) and comprising respectively 10 wt% or more of the two components of the carbon number of _{C n + 2} of the normal paraffin component (B), normal paraffin component of _{C n + 1} carbon atoms (C) Content of less than 10% by weight, (A)+(B)+(C)=100% by weight, and n is in the range of 10 to 16, substantially in the above (A) and (B). A cold storage heat agent composed of a mixture of normal paraffin components is known (see, for example, Patent Document 5).

Moreover, when hydrogen-treating animal and vegetable oils and fats, the production of by-products including both n-paraffins with odd carbon atoms and branched-paraffins is suppressed at the same time, and n-paraffins with even carbon atoms are produced in high yield. As a method for producing a latent heat storage base hydrocarbon composition capable of producing a decarboxylation/decarbonylation and branched-paraffin production, a by-product combining both is limited to 10% at most, and derived from animal or vegetable oils and fats. A hydrodeoxygenation method of a raw material liquid containing an oxygen-containing hydrocarbon compound, comprising an active phase containing at least one element from a Group 6A element and at least one element from a Group 8 element Using a bulk or supported catalyst, the element is in the form of a sulphide and the atomic ratio of the metal(s) from the Group 8 element to the metal(s) from the Group 6A element is exactly 0. Less than 0.06, the catalyst further comprises phosphorus and/or boron in an amount of 1 to 6% by weight of the oxide P ₂ O ₅ or B ₂ O ₃ based on the total catalyst weight. The raw material liquid contains 1 to 250 ppm by weight of sulfur (calculated as elemental sulfur), a temperature in the range of 250 to 350° C., a pressure in the range of ^{1 to} 10 MPa, and a liquid in the range of 0.1 to 10 h ^−1. A method for producing a latent heat storage base hydrocarbon composition that is performed at a space velocity is known (see, for example, Patent Document 6).

JP, 2003-171670, A JP, 2007-308573, A JP, 2010-149118, A JP, 2010-209330, A JP, 6-234967, A JP, 2005-30822, A

However, when producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, decarboxylation/decarbonylation reactions and isomerization reactions, which are side reactions, are suppressed, and hydrogen, which is a main reaction, is suppressed. It is desirable that a method other than the method described in Patent Document 6 be provided as a method for producing a hydrocarbon composition having excellent selectivity for chemical deoxygenation reaction.

An object of one embodiment of the present invention is to suppress a decarboxylation/decarbonylation reaction and an isomerization reaction, which are side reactions in producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition. The present invention provides a method for producing a hydrocarbon composition and a catalyst which are excellent in selectivity of the hydrodeoxygenation reaction which is a main reaction.

Specific means for solving the above problems include the following aspects.
<1> A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms. And the step of preparing
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to Providing an active phase that is 0.30, and a catalyst comprising:
A step of sulfiding the catalyst,
By contacting the sulfur-treated catalyst with the raw material liquid and hydrogen, and subjecting the oxygen-containing hydrocarbon composition in the raw material liquid to hydrodeoxygenation, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. Producing a hydrocarbon composition comprising
A method for producing a hydrocarbon composition having:
<2> The element X1 is at least one of Mo and W,
The method for producing a hydrocarbon composition according to <1>, wherein the element X2 is Co.
<3> The carrier further contains an oxide of at least one element X3 selected from the group consisting of Group 4 elements in an amount of 1% by mass to 30% by mass based on the total amount of the carrier <1. > Or <2>, the method for producing the hydrocarbon composition.
<4> The method for producing a hydrocarbon composition according to <3>, wherein the element X3 is at least one of Ti and Zr.
<5> The method for producing a hydrocarbon composition according to any one of <1> to <4>, wherein the porous material is γ-alumina.
<6> In the step of producing the hydrocarbon composition, the sulfurating treatment of the catalyst, the raw material liquid, and hydrogen are performed at a temperature of 200° C. to 450° C., a pressure of 0.1 MPa to 10 MPa, and a liquid space velocity of 0.1 h ^{−. The} method for producing the hydrocarbon composition according to any one of <1> to <5>, which is brought into contact under the condition of ^{1 to 10} h ⁻¹ .
<7> The method for producing a hydrocarbon composition according to any one of <1> to <6>, wherein the oxygen-containing hydrocarbon composition is a composition derived from animal and vegetable fats and oils.
<8> The method for producing a hydrocarbon composition according to any one of <1> to <7>, in which the hydrocarbon composition is used as a latent heat storage material.
<9> The carbonization according to any one of <1> to <8>, in which the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1 mass% with respect to the total amount of the catalyst. Method for producing hydrogen composition.
A carrier having a specific surface area by <10> BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on the carrier, which is at least one element X1 selected from the group consisting of elements of Group 6 and at least one selected from the group consisting of elements of Groups 8 to 10 An active phase containing the element X2 and the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30,
A catalyst containing.

According to one embodiment of the present invention, when producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition, side reactions such as decarboxylation/decarbonylation reaction and isomerization reaction are suppressed. A method for producing a hydrocarbon composition and a catalyst having excellent selectivity in the hydrodeoxygenation reaction, which is a main reaction, are provided.

In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the present specification, the term “step” is included in this term as long as the intended purpose of the step is achieved not only as an independent step but also when it cannot be clearly distinguished from other steps. Be done.

The production method of the hydrocarbon composition of the present disclosure (hereinafter, also referred to as “production method of the present disclosure”) is
A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms is prepared. Process (hereinafter, also referred to as "raw material liquid preparation process"),
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to A step of preparing a catalyst containing an active phase of 0.30 (hereinafter, also referred to as “catalyst preparation step”),
A step of subjecting the catalyst to sulfurization treatment (hereinafter, also referred to as “sulfurization treatment step”);
By contacting the sulfur-treated catalyst with the raw material liquid and hydrogen, and subjecting the oxygen-containing hydrocarbon composition in the raw material liquid to hydrodeoxygenation, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. A step of producing a hydrocarbon composition containing (hereinafter, also referred to as “hydrodeoxygenation treatment step”),
Have.
The catalyst of the present disclosure includes the carrier and the active phase.

As a result of intensive studies by the present inventor, the oxygen-containing hydrocarbon composition was treated as a catalyst by hydrodeoxygenation (HDO) treatment with a catalyst containing an active phase containing an element X1 and an element X2. When a catalyst in which the atomic ratio of the element X2 to the element X1 is 0.06 to 0.30 is used, the decarboxylation/decarbonylation reaction which is a side reaction and the isomerization reaction are suppressed, and the hydrogenation desorption which is a main reaction is suppressed. It was found that the selectivity of oxygen reaction was improved.
That is, according to the production method of the present disclosure and the catalyst of the present disclosure, the decarboxylation/decarbonylation reaction and the isomerization reaction that are side reactions are suppressed, and the selectivity of the hydrodeoxygenation reaction that is the main reaction is improved. To do.
More specifically, according to the hydrodeoxygenation reaction (main reaction), a linear fatty acid having an even number of carbon atoms and/or an ester derived from a linear fatty acid having an even number of carbons is used as a raw material in the raw material. A straight-chain hydrocarbon having the same number of carbon atoms as the straight-chain fatty acid of (or the straight-chain fatty acid for forming the ester) (that is, an even number of carbon atoms) is produced.
According to the decarboxylation/decarbonylation reaction (side reaction), the number of carbon atoms from the above raw material is one less than the number of carbon atoms of the straight chain fatty acid (or the straight chain fatty acid for forming the above ester) in the above raw material. Hydrocarbons having atoms (ie, having an odd number of carbon atoms) are produced.
According to the isomerization reaction (side reaction), branched chain hydrocarbons are produced from the above raw materials.

Hereinafter, each step of the manufacturing method of the present disclosure will be described.

<Catalyst preparation step>
The catalyst preparation step is a step of preparing the catalyst of the present disclosure.
The catalyst of the present disclosure is
A carrier having a specific surface area by BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on a carrier, which is at least one element X1 selected from the group consisting of Group 6 elements and at least one element selected from the group consisting of Group 8 to Group 10 elements An active phase containing the element X2 and having an atomic ratio of the element X2 to the element X1 (hereinafter, also referred to as “atomic ratio [element X2/element X1]”) of 0.06 to 0.30;
including.
The catalyst preparation step is a step for convenience.
That is, the catalyst preparation step may be a step of producing the catalyst of the present disclosure or may be a step of simply preparing a catalyst of the present disclosure produced in advance.

(Active phase)
The catalyst of the present disclosure is an active phase supported on a carrier described later, which contains the elements X1 and X2 and has an atomic number ratio [element X2/element X1] of 0.06 to 0.30. including.
In the active phase of the catalyst, when the atomic ratio [element X2/element X1] is 0.06 to 0.30, the atomic ratio [element X2/element X1] is less than 0.06 and the atomic ratio Compared with the case where [element X2/element X1] is more than 0.30, side reactions such as decarboxylation/decarbonylation reaction and isomerization reaction are suppressed, and the main reaction of hydrodeoxygenation reaction is suppressed. Selectivity is improved.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the atomic ratio [element X2/element X1] is preferably 0.06 to 0.25, and more preferably 0.06 to 0.20.

The element X1 is at least one element selected from the group consisting of Group 6 elements.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the element X1 is preferably at least one selected from the group consisting of Mo, W, and Cr, and is at least one of Mo and W. Is more preferable, and Mo is particularly preferable.

The element X2 is at least one element selected from the group consisting of elements of Group 8 to Group 10.
From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the element X2 is
It is preferably at least one selected from the group consisting of Co, Rh, Tr, Fe, Ru, Os, Ni, Pd, and Pt,
More preferably, it is at least one selected from the group consisting of Co, Fe, Ni, Pd, and Pt,
More preferably at least one selected from the group consisting of Co, Fe, and Ni,
More preferably at least one of Co and Ni,
Particularly preferred is Co.

From the viewpoint of further improving the selectivity of the hydrodeoxygenation reaction, the combination of the element X1 and the element X2 is particularly preferably a combination in which the element X1 is at least one of Mo and W and the element X2 is Co. ..

The element X1 is preferably contained in the active phase in the form of an oxide of the element X1 from the viewpoint of the suitability for production of the active phase.
The content of the oxide of the element X1 is not particularly limited, but is preferably 1% by mass to 50% by mass, and 5% by mass to 40% by mass, based on the total amount of the catalyst (that is, the total amount of the carrier and the active phase). Is more preferable and 10 mass%-30 mass% is still more preferable.

The element X2 is preferably contained in the active phase in the form of an oxide of the element X2 from the viewpoint of the suitability for production of the active phase.
The content of the oxide of the element X2 is not particularly limited, and can be appropriately adjusted in consideration of the content of the oxide of the element X1 and the atomic ratio [element X2/element X1].

Examples of a method for supporting an active phase on a carrier described later (for example, a carrier made of a porous material, a carrier containing a porous material and an oxide of the element X3, etc.)
(1) The carrier described below is impregnated with a solution containing a precursor of the oxide of the element X1 and an oxide of the element X2, and the resulting composite is baked to oxidize the element X1 to the carrier. And an active phase containing an oxide of the element X2,
(2) The carrier described below is impregnated with one of the precursor solution of the oxide of the element X1 and the solution containing the oxide of the element X2, and then with the other, and the resulting composite is fired. A method of supporting an active phase containing an oxide of the element X1 and an oxide of the element X2 on the carrier by
(3) The element X1 (or its oxide) and the element X2 (or its oxide) are attached to the carrier described later by vapor deposition, CVD (chemical vapor deposition), or sputtering, respectively. Method,
(4) A method of mixing a carrier to be described later, the element X1 (or its oxide), and the element X2 (or its oxide),
Etc.
Above all, the method of (1) or (2) above is preferable from the viewpoint of forming an active phase having excellent catalytic activity and the suitability for producing the active phase.
Examples of the oxide precursor of the element X1 include a salt containing the element X1 and an oxygen atom.
Examples of the oxide precursor of the element X2 include salts containing the element X2 and an oxygen atom.
The solution containing the oxide precursor of the element X1 and/or the oxide of the element X2 is preferably an aqueous solution or an alcohol solution, and particularly preferably an aqueous solution.

(Carrier)
The catalyst of the present disclosure comprises a carrier having a specific surface area by BET method (hereinafter, simply referred to as "specific surface area") contains a porous material which is 100m ² / g~400m ² / g.
When the specific surface area of the porous material is 100 m ² /g or more, the activity of the catalyst containing the carrier of the present disclosure (hereinafter, also simply referred to as “catalytic activity”) is improved.
When the specific surface area of the porous material is 400 m ² /g or less, it is advantageous in terms of strength of the carrier, suitability for manufacturing the carrier, and the like.
The specific surface area of the porous material ^is preferably 100m ² / g~350m 2 / ^g, and more preferably 150m ² / g~300m 2 / g.

The above-mentioned porous material may be only one kind or two or more kinds.
Examples of the porous material include alumina, silica, silica-alumina, zirconia, ceria, zeolite, clay and activated carbon from the viewpoint of effectively exhibiting catalytic activity, and alumina is preferred.
As alumina, η-alumina, δ-alumina, or γ-alumina is preferable, and γ-alumina is particularly preferable.

The content of the porous material in the carrier is preferably 60% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 80% by mass to 100% by mass with respect to the total amount of the carrier. It is particularly preferable that

It is preferable that the carrier further contains an oxide of at least one element X3 selected from the group consisting of Group 4 elements.
When the carrier further contains the oxide of the element X3, the selectivity of the hydrodeoxygenation reaction is further improved. The reason for this is not clear, but it is considered that when the carrier further contains an oxide of the element X3, the acidity of the catalyst is further reduced, and as a result, side reactions (particularly isomerization reaction) can be further reduced. To be

When the carrier contains an oxide of the element X3, the content of the oxide of the element X3 is preferably 1% by mass to 30% by mass, and 3% by mass to 30% by mass with respect to the total amount of the carrier. It is more preferable that the amount is 5% by mass to 30% by mass, further preferably 10% by mass to 30% by mass.
When the content of the oxide of the element X3 is 1% by mass or more, the effect of the oxide of the element X3 described above is more effectively exhibited, and the selectivity of the hydrodeoxygenation reaction is further improved.
When the content of the oxide of the element X3 is 30% by mass or less, it is advantageous in terms of carrier productivity (for example, raw material cost, simplification of carrier manufacturing process, etc.).

The element X3 is at least selected from the group consisting of Ti, Zr, and Hf from the viewpoint of more effectively exerting the effect of the oxide of the element X3 described above and further improving the selectivity of the hydrodeoxygenation reaction. It is preferably one kind, more preferably at least one of Ti and Zr, and particularly preferably Ti.

As a method of producing a carrier containing a porous material and an oxide of the element X3,
(1) A carrier containing a porous material and an oxide of the element X3 is obtained by impregnating a porous material with a solution containing a precursor of an oxide of the element X3 and firing the obtained composite. How to manufacture,
(2) A method of attaching an oxide of the element X3 to the porous material by vapor deposition, CVD, or sputtering,
(3) A method of mixing the porous material and the oxide of the element X3,
Etc.
Above all, the method of (1) above is preferable because the effects of the manufacturing method of the present disclosure are more effectively exhibited.
As the precursor of the oxide of the element X3, the alkoxide of the element X3 is preferable.
As the solution containing the oxide precursor of the element X3, an alcohol solution is preferable.

The catalyst (support and/or active phase) of the present disclosure may include components other than the components described above.
The catalyst of the present disclosure may include P ₂ O ₅ and B ₂ O ₃ described in JP-A-2015-30822, for example.
However, according to the catalyst of the present disclosure, the selectivity of the hydrodeoxygenation reaction is improved by setting the atomic ratio [element X2/element X1] to 0.06 to 0.30. Therefore, in the catalyst of the present disclosure, even when the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1% by mass with respect to the total amount of the catalyst, an excellent hydrodeoxygenation reaction is achieved. The selectivity of is maintained. The fact that the total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst is less than 1% by mass with respect to the total amount of the catalyst means that the productivity of the catalyst (for example, simplification of the production process, raw material cost) is reduced. Is advantageous.
The total content of P ₂ O ₅ and B ₂ O _{3 in} the catalyst may be less than 0.5% by mass, may be less than 0.1% by mass, and may be 0% by mass, based on the total amount of the catalyst. % (Ie the catalyst may be free of P ₂ O ₅ and B ₂ O ₃ ).

<Raw material liquid preparation process>
The raw material liquid preparation step includes an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbons and esters derived from straight-chain fatty acids having an even number of carbons. This is a step of preparing a raw material liquid to be used.
The raw material liquid preparation step is a step for convenience.
That is, the raw material liquid preparation step may be a step of producing the raw material liquid, or may be a step of simply preparing a preliminarily produced raw material liquid.

(Oxygen-containing hydrocarbon composition)
Among the raw material liquids, the oxygen-containing hydrocarbon composition is a substantial raw material of a target hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms.
That is, in the production method of the present disclosure, the oxygen-containing hydrocarbon composition is hydrodeoxygenated to produce a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms.

When the oxygen-containing hydrocarbon composition contains a straight-chain fatty acid having an even number of carbon atoms, the number of straight-chain fatty acids having an even-number of carbon atoms contained in the oxygen-containing hydrocarbon composition is two, if only one. It may be more.
Further, in this case, the oxygen-containing hydrocarbon composition is at least one selected from the group consisting of linear fatty acids having 14 carbon atoms, linear fatty acids having 16 carbon atoms, and linear fatty acids having 18 carbon atoms (preferably, It is preferable to include two or more kinds).

Hereinafter, the carbon number n (for example, carbon number 18) may be referred to as “Cn” (for example, “C18”).

The linear fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition may be a saturated fatty acid or an unsaturated fatty acid.
The straight-chain fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition preferably has 12, 14, 16, 18, or 20 carbon atoms.
Examples of the straight-chain fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition include lauric acid (C12:0), myristic acid (C14:0), palmitic acid (C16:0), and stearic acid (C18). :0), oleic acid (C18:1), linoleic acid (C18:2), arachidic acid (C20:0), gadoleic acid (C20:1), and the like.
Here, the expression "Cn:m" (for example, "C18:1") means that the number of carbon atoms is n (for example, 18) and the number of unsaturated bonds is m (for example, 1).

When the oxygen-containing hydrocarbon composition contains an ester derived from a straight-chain fatty acid having an even number of carbon atoms, the ester derived from a straight-chain fatty acid having an even number of carbon atoms contained in the oxygen-containing hydrocarbon composition is 1 There may be only one kind or two or more kinds.
Further, in this case, the oxygen-containing hydrocarbon composition is selected from the group consisting of an ester derived from a C14 linear fatty acid, an ester derived from a C16 linear fatty acid, and an ester derived from a C18 linear fatty acid. It is preferable to contain at least one type (preferably two or more types).
Here, the "ester derived from a straight-chain fatty acid having an even number of carbon atoms" means an ester formed by the reaction of a straight-chain fatty acid having an even number of carbon atoms and an alcohol.
The alcohol is preferably glycerin or methanol. That is, the “ester derived from a straight-chain fatty acid having an even number of carbon atoms” is preferably a fatty acid glycerin ester (eg, fatty acid triglyceride) or a fatty acid methyl ester.

The preferred embodiment of the linear fatty acid in the ester derived from the linear fatty acid having an even number of carbon atoms is the same as the preferred embodiment of the linear fatty acid having an even number of carbon atoms that can be contained in the oxygen-containing hydrocarbon composition described above. is there.

The oxygen-containing hydrocarbon composition is a component other than an ester derived from a linear fatty acid having an even number of carbons and a linear fatty acid having an even number of carbons (for example, a linear fatty acid having an odd number of carbons, a carbon number of An ester derived from an odd-numbered linear fatty acid, a branched chain fatty acid, an ester derived from a branched chain fatty acid, and the like) may be included.
However, from the viewpoint of more effectively obtaining the effect of the production method of the present disclosure, in an oxygen-containing hydrocarbon composition, a linear fatty acid having an even number of carbons and an ester derived from a linear fatty acid having an even number of carbons The total content is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 97% by mass or more, based on the total amount of the oxygen-containing hydrocarbon composition.

Further, in the hydrodeoxygenation treatment step described below, when a hydrocarbon composition containing a C16 straight chain hydrocarbon and a C18 straight chain hydrocarbon is produced, the C16 straight chain in the oxygen-containing hydrocarbon composition is used. The total content of the fatty acid, the ester derived from the C16 linear fatty acid, the C18 linear fatty acid, and the ester derived from the C18 linear fatty acid is 90% by mass or more based on the total amount of the oxygen-containing hydrocarbon composition. It is preferably present, more preferably 95% by mass or more, and particularly preferably 97% by mass or more.

From the viewpoint of biomass utilization, the oxygen-containing hydrocarbon composition is preferably a composition derived from animal and vegetable oils and fats.
Examples of the composition derived from animal and vegetable oils and fats include animal and vegetable oils and fats, compositions obtained by refining (for example, distilling) animal and vegetable oils and fats, waste oil after using animal and vegetable oils, and the like.
Examples of animal and vegetable oils and fats include coconut oil, sunflower oil, soybean oil, olive oil, cottonseed oil, rapeseed oil, palm oil, jatropha oil, and the like.
The oxygen-containing hydrocarbon composition may be a composition derived from one type of animal or vegetable oil or fat, or may be a composition derived from two or more types of animal or vegetable oil or fat.
The oxygen-containing hydrocarbon composition is preferably palm oil, jatropha oil, or PFAD (Palm Fatty Acid Distillate).

(Sulfur element)
The raw material liquid preferably contains elemental sulfur. As a result, the activity of the catalyst can be further increased in the hydrodeoxygenation treatment step described below.
When the raw material liquid contains elemental sulfur, the elemental sulfur may be contained in the raw material liquid in the form of a simple substance of sulfur, may be contained in the form of a sulfur compound, or may be contained in the form of a simple substance of sulfur and a sulfur compound. May be contained in the form of The sulfur compound that may be contained in the raw material liquid may be only one kind or two or more kinds.
The specific examples and preferred embodiments of the sulfur compound here are the same as the specific examples and preferred embodiments of the sulfur compound that can be used in the sulfurization treatment described later.

When the raw material liquid contains elemental sulfur, the content of elemental sulfur relative to the total amount of the raw material liquid is preferably 1 mass ppm or more.
When the content of the elemental sulfur is 1 mass ppm or more, the catalytic activity can be sufficiently expressed in the hydrodeoxygenation treatment step described later, and as a result, the selectivity of the hydrodeoxygenation reaction is improved. .. The content of elemental sulfur is preferably 5 mass ppm or more, more preferably 10 mass ppm or more.
When the raw material liquid contains elemental sulfur, the content of elemental sulfur relative to the total amount of the raw material liquid is preferably 1000 mass ppm or less.
When the content of the elemental sulfur is 1000 mass ppm or less, the productivity of the hydrocarbon composition (target product) is improved. The content of elemental sulfur is more preferably 500 mass ppm or less, further preferably 400 mass ppm or less, further preferably 300 mass ppm or less, and particularly preferably 250 mass ppm or less.

<Sulfidation process>
The sulfurating treatment step is a step of subjecting the above-mentioned catalyst to sulfurizing treatment.
This causes the metal in the catalyst (preferably the active phase) to be sulphided so that the catalyst exhibits hydrodeoxygenation reaction activity.

The sulfurating treatment can be performed by bringing the above-mentioned catalyst into contact with elemental sulfur.
In the sulfurating treatment, elemental sulfur may be used in the form of simple substance of sulfur, in the form of sulfur compound, or in the form of simple substance of sulfur and in the form of sulfur compound. Only one sulfur compound may be used in the sulfurization treatment, or two or more sulfur compounds may be used.
The sulfur compound that can be used in the sulfurization treatment is not particularly limited, but a sulfur-containing hydrocarbon compound is preferable, and sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, dibenzyl polysulfide, or a derivative thereof, or sulfur. Petroleum hydrocarbon fractions containing fractions are preferred.

As the sulfur compound that can be used in the sulfurating treatment, a compound represented by the following formula (S1) is also preferable.
_R-S n -R '... formula (S1)
In formula (S1), n represents 1 to 10, and R and R′ each independently represent an organic group.

In formula (S1), n is preferably 2 to 7, and more preferably 4 to 6.
In the formula (S1), the total number of carbon atoms of the organic group represented by R and the number of carbon atoms of the organic group represented by R′ is preferably 2 to 150, more preferably 2 to 60. , 2 to 20 is particularly preferable.
R and R′ are each independently preferably a linear or branched hydrocarbon group (preferably an alkyl group), an aryl group, an alkylaryl group, or an arylalkyl group.

Specific examples of the compound represented by formula _{(S1), C 8 H 17} -S 4.8 -C 8 H 17 ( di (1,1,3,3-tetramethylbutyl) polysulfide; DIC Corp. CS -40), dimethyl disulfide (DMDS), and the like.

The sulfurization treatment of the catalyst may be performed in situ or ex situ.

<Hydrodeoxidation process>
In the hydrodeoxygenation treatment step, the catalyst that has been subjected to sulfurization, the raw material liquid and hydrogen are brought into contact with each other, and the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated to have a carbon number of A step of producing a hydrocarbon composition containing an even number of straight-chain hydrocarbons.

In the hydrodeoxygenation treatment step, general conditions can be applied as conditions for contacting the sulfurized catalyst, the raw material liquid, and hydrogen, but particularly preferable conditions are a temperature of 200°C to 450°C. , Pressure ¹ MPa to 100 MPa, and liquid space velocity 0.1 h ^{−1 to} 10 h ⁻¹ .

As described above, the temperature (hereinafter, also referred to as "reaction temperature") at which the sulfurating catalyst is brought into contact with the raw material liquid and hydrogen is preferably 200°C to 450°C.
When the reaction temperature is 200° C. or higher, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) proceeds more effectively.
When the reaction temperature is 450° C. or lower, side reactions (decarboxylation/decarbonylation reaction, isomerization reaction, etc.) can be further suppressed.
The reaction temperature is more preferably 200°C to 400°C, particularly preferably 250°C to 350°C.

The pressure (hereinafter, also referred to as “reaction pressure”) for bringing the sulfurized catalyst, the raw material liquid, and hydrogen into contact with each other is preferably 0.1 MPa to 10 MPa, as described above.
When the reaction pressure is 0.1 MPa or more, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) effectively proceeds, and side reactions (decarboxylation/decarbonylation reaction, isomerization reaction, etc.) are suppressed. It
When the reaction pressure is 10 MPa or less, a reactor for performing hydrodeoxygenation treatment can be manufactured with an inexpensive material, and the structure of the reactor can be simplified, resulting in excellent productivity.
The reaction pressure is preferably 1 MPa to 10 MPa.

As described above, the liquid hourly space velocity at the time of contacting the sulfurized catalyst, the raw material liquid, and hydrogen is preferably 0.1 h ^{−1 to} 10 h ⁻¹ .
When the liquid hourly space velocity is 0.1 h ⁻¹ or more, the volume of the reactor can be further reduced, and therefore the productivity is excellent.
When the liquid hourly space velocity is 10 h ^-1 or less, the hydrodeoxygenation treatment (hydrodeoxygenation reaction) effectively proceeds.

Further, when the catalyst subjected to the sulfurization treatment and the raw material liquid and hydrogen are brought into contact with each other, the ratio of the flow rate of hydrogen to the flow rate of the raw material liquid [hydrogen flow rate/raw material solution flow rate] is 50 Nm ³ /m ^{3 to} 3000 Nm ³ / ^{m 3} are ^preferred, more preferably ^{70Nm 3 / m 3 ~2000Nm 3 /} m 3, more preferably ^{150Nm 3 / m 3 ~1500Nm 3 /} m 3, particularly preferably 300 Nm ³ / m 3 1000 nm ³ / ^{m 3} ..

In the hydrodeoxygenation treatment step, the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated by contacting the sulfurized catalyst, the raw material liquid and hydrogen.
The above contact (that is, hydrodeoxygenation treatment) can be performed in a fixed bed reactor or a boiling bed reactor, but is preferably performed in a fixed bed reactor.

In the hydrodeoxygenation treatment process, the oxygen-containing hydrocarbon composition in the raw material liquid is hydrodeoxygenated to produce a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms as a target product. To do.
Specifically, in this step, the linear fatty acid having an even number of carbon atoms and/or the ester derived from the linear fatty acid having an even number of carbons contained in the oxygen-containing hydrocarbon composition is hydrodeoxygenated. As a result, a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms is produced.
At this time, by the action of the catalyst described above, side reactions (decarboxylation/decarbonylation reaction and isomerization reaction) are suppressed, and the main reaction (hydrodeoxygenation reaction) in the hydrodeoxygenation process proceeds with high selectivity. To do.
Therefore, according to this step, a hydrocarbon composition containing a linear hydrocarbon having the same carbon number as the carbon number of the linear fatty acid and/or the ester in the raw material liquid can be easily produced.
For example, when a raw material liquid containing a C16 straight-chain fatty acid or an ester thereof and a C18 straight-chain fatty acid or an ester thereof is used as a raw material liquid, a C16 straight-chain hydrocarbon and a C18 straight-chain hydrocarbon are used. A hydrocarbon composition containing the same can be easily produced.

There is no particular limitation on the use of the target product (hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms).
Examples of the intended use of the object include light oil or a latent heat storage material (PCM; phase change material), and the latent heat storage material is particularly preferable.
Here, the latent heat storage material means latent heat associated with phase transition (for example, heat of solidification released during phase transition from liquid phase to solid phase and/or heat of fusion absorbed during phase transition from solid phase to liquid phase). The heat storage material used. The latent heat storage material is superior to the heat storage material that uses sensible heat in that the volume of the heat storage material is reduced and the heat loss is reduced. In recent years, a large number of heat storage type air conditioners, heat storage type building materials, various heat retaining devices, devices, and the like have been proposed that utilize latent heat storage materials. Regarding the latent heat storage material, the description in paragraphs 0001 to 0005 of JP-A-2015-30822 can be referred to.
That is, the production method of the present disclosure is particularly suitable as a method for producing a hydrocarbon composition containing a straight-chain hydrocarbon having an even number of carbon atoms as a latent heat storage material by a simple production process.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

[Example 1]
<Preparation of catalyst>
As a catalyst carrier, an alumina carrier (γ-alumina carrier, manufactured by Nippon Ketjen Co., Ltd., specific surface area 275 m ² /g) was prepared. This alumina carrier (50 g) was placed in an eggplant-shaped flask.
In an eggplant-shaped flask containing an alumina carrier (50 g), ammonium molybdate tetrahydrate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O) and cobalt nitrate hexahydrate (Co(NO ₃ ) ₂ · An aqueous solution containing 6H ₂ O) was injected to impregnate the alumina carrier.
While heating the obtained composite, water was evaporated from the composite by a rotary evaporator. The solid obtained was dried at 120° C. for 1 hour and then calcined at 500° C.
As described above, a catalyst having a structure in which an active phase composed of molybdenum oxide (MoO ₃ ) and cobalt oxide (CoO) was supported on the alumina carrier (50 g) was obtained.
As a result of X-ray fluorescence analysis (XRF), in the obtained catalyst, the content of molybdenum oxide was 20% by mass with respect to the total amount of the catalyst (that is, the total amount of the carrier and the active phase). The atomic number ratio [Co/Mo] in the active phase was 0.06 as shown in Table 4.

<Preparation of raw material liquid>
As the oxygen-containing hydrocarbon composition, PFAD (Palm Fatty Acid Distillate) having a fatty acid composition shown in Table 1 below was prepared.

Each of the fatty acids shown in Table 1 is contained in PFAD in the amount of about 80% by mass in the form of fatty acid and about 20% by mass in the form of fatty acid triglyceride.

Di(1,1,3,3-tetramethylbutyl)polysulfide (CS-40; DIC Co., Ltd.), which is a sulfur compound, was added to the above-mentioned PFAD in such a manner that the content of elemental sulfur relative to the total amount of the raw material liquid produced was A raw material liquid was obtained by adding 50 mass ppm.

<Sulfidation treatment and hydrodeoxygenation treatment>
The catalyst prepared above was placed in a fixed bed reactor.
Next, the catalyst in the fixed bed reactor was subjected to sulfurization treatment for 5 hours by supplying a hydrocarbon mixture containing 2 mass% of CS-40 corresponding to a gas oil fraction to the fixed bed reactor. The conditions of the sulfurization treatment were a temperature of 350° C., a pressure of 1 MPa, and a liquid space velocity of 5.0 h ⁻¹ .
Next, the substance supplied to the fixed bed reactor is switched from the hydrocarbon mixture corresponding to the above gas oil fraction to the above raw material liquid (that is, the mixture of PFAD and CS-40) for hydrodeoxygenation treatment. , A liquid product was obtained. The conditions of the hydrodeoxygenation treatment are a reaction temperature of 300° C., a reaction pressure of 3 MPa, a liquid space velocity of 1.0 h ⁻¹ , and a ratio of a hydrogen gas flow rate to a raw material liquid flow rate (hydrogen gas flow rate/raw material liquid flow rate) 1000 Nm ³ /M ³ .

The liquid product after the hydrodeoxygenation treatment was recovered, oil-water separation was performed, and then the oil content (that is, the target hydrocarbon composition) was analyzed by gas chromatography.
As a result, the oxygen atoms in the oxygen-containing hydrocarbon composition (PFAD) in the raw material liquid were almost removed by the hydrodeoxygenation reaction. Further, in the obtained hydrocarbon composition (target product), there were few hydrocarbons having a C14 or less and hydrocarbons having a C19 or more, and most of the hydrocarbon compositions were C15 to C18 hydrocarbons. Specifically, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (object), and C15 to The total content of C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).

Next, as a breakdown of C15 to C18 hydrocarbons in the hydrocarbon composition,
The total number of moles Pe of carbon atoms in the C16 linear hydrocarbon and the C18 linear hydrocarbon produced by the hydrodeoxygenation reaction (that is, the main reaction) Pe,
The total number of moles Po of carbon atoms in the C15 straight chain hydrocarbon and the C17 straight chain hydrocarbon produced by the decarboxylation/decarbonylation reaction (ie, side reaction), and the isomerization reaction (ie, side reaction) The total number of moles Pi of carbon atoms in the C15 to C18 branched chain hydrocarbon was determined, and the selectivity of the hydrodeoxygenation reaction was determined by the following formula (1).
The results are shown in Table 4.
Selectivity of hydrodeoxygenation reaction (mol %)=(Pe/(Pe+Po+Pi))×100 Formula (1)

The selectivity of the hydrodeoxygenation reaction obtained by the formula (1) is determined by the products of the main reaction of the hydrodeoxygenation reaction (that is, the C16 straight chain hydrocarbon and the C18 straight chain hydrocarbon) in the C15 to C18 hydrocarbon. (Hydrocarbon) means the ratio (mol %).
The higher the selectivity of the hydrodeoxygenation reaction, the better the selectivity of the hydrodeoxygenation reaction.

[Examples 2-5, Comparative Examples 1-2]
In the preparation of the catalyst, by changing the amount of cobalt nitrate hexahydrate _{(Co (NO 3) 2 ·} 6H 2 O), the atomic ratio of the active phase in the [Co / Mo] As shown in Table 4 The same operation as in Example 1 was performed except that the changes were made.
The results are shown in Table 4.

Further, in any of the examples, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (target product). Yes, the total content of C15 to C18 hydrocarbons was more than 90 mass% with respect to the total amount of the hydrocarbon composition (object).

[Example 6]
The oxygen-containing hydrocarbon composition (PFAD) in the feedstock was changed to jatropha oil having the fatty acid composition of triglyceride shown in Table 2, and the sulfur compound (CS-40) used in the activation treatment and the hydrodesorption treatment was dimethyl. The same operation as in Example 1 was carried out except that the disulfide (DMDS) was changed and the hydrodeoxygenation conditions (reaction temperature, reaction pressure, and liquid hourly space velocity) were changed as shown in Table 4.
The results are shown in Table 4.

Moreover, in Example 6, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10% by mass with respect to the total amount of the hydrocarbon composition (target product). , The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).

Each fatty acid shown in Table 2 is actually contained in jatropha oil in the form of fatty acid triglyceride.

[Example 7]
The oxygen-containing hydrocarbon composition in the feedstock was changed to palm oil having the fatty acid composition of triglyceride shown in Table 3, and the conditions for the hydrodeoxygenation treatment (reaction temperature, reaction pressure, and liquid hourly space velocity) were changed. The same operation as in Example 1 was performed except that the changes were made as shown in Table 4.
The results are shown in Table 4.

Moreover, in Example 7, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10% by mass with respect to the total amount of the hydrocarbon composition (object). , The total content of C15 to C18 hydrocarbons was more than 90% by mass with respect to the total amount of the hydrocarbon composition (object).

Each fatty acid shown in Table 3 is actually contained in palm oil in the form of fatty acid triglyceride.

[Examples 8 to 10]
In the production of the catalyst, the same operation as in Example 1 was carried out except that the alumina support was changed to the titania-added alumina support produced as follows (that is, the active phase was loaded on the titania-added alumina support). went.
The results are shown in Table 4.

Further, in any of the examples, the total content of the product containing oxygen, the hydrocarbon of C14 or less, and the hydrocarbon of C19 or more is less than 10 mass% with respect to the total amount of the hydrocarbon composition (target product). Yes, the total content of C15 to C18 hydrocarbons was more than 90 mass% with respect to the total amount of the hydrocarbon composition (object).

<Preparation of titania-added alumina carrier (Examples 8 to 10)>
In Examples 8 to 10, the titania-added alumina carrier was prepared as follows.
An ethanol solution of titanium isopropoxide _{(Ti (OCH (CH 3)} 4)) were prepared and placed in a recovery flask. The alumina carrier (50 g) used in Example 1 was put therein and left standing at room temperature for 2 hours to impregnate the alumina carrier with an ethanol solution of titanium isopropoxide.
Next, ethanol was evaporated from the alumina carrier impregnated with the above ethanol solution by a rotary evaporator, and then an appropriate amount of water was added thereto, and titanium isopropoxide was hydrolyzed at room temperature for 12 hours.
Water was evaporated from the obtained product by a rotary evaporator, then dried at 120° C. for 2 hours, and then calcined at 600° C. for 4 hours to obtain an alumina carrier to which titania (TiO ₂ ) was added (that is, titania). (Added alumina carrier) was obtained.
Regarding the concentration of the ethanol solution of titanium isopropoxide described above, the content of titania with respect to the entire titania-added alumina carrier finally obtained is 5% by mass (Example 8), 15% by mass (Example 9), and The content was adjusted to 20% by mass (Example 10). The content of titania in the entire titania-added alumina carrier was confirmed by fluorescent X-ray analysis (XRF).

As shown in Table 4, in Examples 1 to 10 in which the atom number ratio [Co/Mo] in the active phase of the catalyst is 0.06 to 0.30, the straight chain hydrocarbon of C16 in the hydrocarbon of C15 to C18. And the proportion (Ce/(Pe+Po+Pi))×100) of C18 straight-chain hydrocarbons (mol %) was 90.3 mol% or more, and the selectivity of the hydrodeoxygenation reaction was excellent.
On the other hand, in Comparative Example 1 in which the atom number ratio [Co/Mo] in the active phase of the catalyst is less than 0.06, the C16 linear hydrocarbon and the C18 linear hydrocarbon in the C15 to C18 hydrocarbons are The ratio (Pe/(Pe+Po+Pi))×100) (mol %) was 88.5 mol %, and the selectivity of the hydrodeoxygenation reaction was poor.
Further, in Comparative Example 2 in which the atomic ratio [Co/Mo] in the active phase of the catalyst is more than 0.30, the proportion of the C16 linear hydrocarbon and the C18 linear hydrocarbon in the C15 to C18 hydrocarbons ( Pe/(Pe+Po+Pi))×100) (mol %) was 84.8 mol %, and the selectivity of the hydrodeoxygenation reaction was poor.

Further, from the comparison between Examples 1 and 8 to 10, it is understood that the use of the TiO ₂ (titania)-added alumina carrier (Examples 8 to 10) further improves the selectivity of the hydrodeoxygenation reaction.

Claims (9)

A raw material liquid containing an oxygen-containing hydrocarbon composition containing at least one selected from the group consisting of straight-chain fatty acids having an even number of carbon atoms and esters derived from straight-chain fatty acids having an even number of carbon atoms is prepared. Process,
A carrier having a specific surface area by BET method contains a porous material which is 100m 2 ^/ g~400m 2 ^{/ g,} a supported active phase on the support is selected from the group consisting of elements of Group 6 At least one element X1 and at least one element X2 selected from the group consisting of Group 8 to Group 10 elements are contained, and the atomic ratio of the element X2 to the element X1 is 0.06 to Providing a catalyst comprising an active phase of 0.20 ,
A step of sulfiding the catalyst,
By contacting the sulfurized catalyst and the raw material liquid and hydrogen, and hydrodeoxygenating the oxygen-containing hydrocarbon composition in the raw material liquid, a straight-chain hydrocarbon having an even number of carbon atoms is obtained. Producing a hydrocarbon composition comprising
Have
The element X1 is Mo ,
The element X2 is Co,
Process for producing hydrocarbon composition. The carrier further contains 1% by mass to 30% by mass of an oxide of at least one element X3 selected from the group consisting of Group 4 elements, based on the total amount of the carrier. A method for producing the hydrocarbon composition of. The method for producing a hydrocarbon composition according to claim 2, wherein the element X3 is at least one of Ti and Zr. The method for producing a hydrocarbon composition according to any one of claims 1 to 3, wherein the porous material is γ-alumina. In the step of producing the hydrocarbon composition, the sulfurating treatment of the catalyst, the raw material liquid, and hydrogen are performed at a temperature of 200° C. to 450° C., a pressure of 0.1 MPa to 10 MPa, and a liquid space velocity of 0.1 h ^{−1 to} 10 h. ^The method for producing the hydrocarbon composition according to any one of claims 1 to 4, wherein the contact is made under the condition of ^-1 . The method for producing a hydrocarbon composition according to any one of claims 1 to 5, wherein the oxygen-containing hydrocarbon composition is a composition derived from animal and vegetable fats and oils. The method for producing a hydrocarbon composition according to any one of claims 1 to 6, wherein the hydrocarbon composition is used as a latent heat storage material. The total content of P ₂ O ₅ and B ₂ O ₃ in the catalyst is, relative to the total amount of the catalyst, the hydrocarbon composition according to any one of claims 1 to claim 7 is less than 1 wt% Method of manufacturing things. A catalyst used in a reaction for producing a hydrocarbon composition by hydrodeoxygenating an oxygen-containing hydrocarbon composition,
A carrier having a specific surface area by BET method contains a porous material which is 100m ² / g~400m ² / g,
An active phase supported on the carrier, which is at least one element X1 selected from the group consisting of elements of Group 6 and at least one selected from the group consisting of elements of Groups 8 to 10 An active phase containing the element X2 and the atomic ratio of the element X2 to the element X1 is 0.06 to 0.20 ,
Only including,
The element X1 is Mo ,
The element X2 is Co,
catalyst.