JP2018039010A - Manufacturing method of hydrocarbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of hydrocarbon using saturated hydrocarbon as a raw material without needs for high temperature for proceeding a reaction compared to a reaction accompanying hydrogen molecule generation in a condensation reaction of saturated hydrocarbon accompanying generation of a compound with high atom efficiency and/or high value as a chemical compared to generation of water, having reduced by-products such as oxide of ethylene, CO or COthan in unsaturated hydrocarbon manufacturing using saturated hydrocarbon and oxygen as raw materials and without needs for severe concentration control of introduction raw materials for safety.SOLUTION: There is provided a manufacturing method of hydrocarbon including a process X for reacting a mixed gas containing saturated hydrocarbon a having molar fraction of 0.05 to 0.999 and 1 to 6 carbon atoms and unsaturated hydrocarbon x having molar fraction of 0.001 to 0.95 and 2 to 12 carbon atoms in a presence of a catalyst to manufacture hydrocarbon b having a carbon skeleton equal to a carbon skeleton of the unsaturated hydrocarbon x.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing hydrocarbons.

In recent years, there is a concern about the price increase and depletion of petroleum, and therefore development of a method for producing chemical products using carbon compounds as a raw material instead of petroleum is required. In particular, methane, which is abundant in natural gas and shale gas, has attracted attention as a candidate for a raw material for producing chemicals that replaces petroleum.
Conventionally, methods for producing hydrocarbons, which are chemicals with higher added value, such as ethylene and aromatic compounds, using methane as a raw material have been studied.

  As one of the techniques for producing unsaturated hydrocarbons from methane, a synthesis reaction of aromatic compounds such as benzene by condensation of methane accompanied by generation of hydrogen molecules is known (see Patent Document 1).

  In addition, a method for producing a hydrocarbon having 2 or more carbon atoms by an oxidative coupling reaction of methane is known (see Patent Document 2).

JP 2001-334152 A JP 2011-32257 A

  However, the method for synthesizing unsaturated hydrocarbons from methane described in Patent Document 1 is a large endothermic reaction, so there are large thermodynamic restrictions, and a high temperature condition of about 750 ° C. is required to obtain a high yield. Is desirable. Under this high temperature condition, carbon compounds due to excessive dehydrogenation are produced as by-products.

Patent Document 2 describes that ethylene and water are produced by reacting methane and oxygen. Hydrogen produced by the condensation of methane is reacted with oxygen to form water. From the viewpoint of atomic efficiency and the value of the product as a chemical, hydrogen can be added to a hydrocarbon or obtained as a hydrogen molecule. desirable. Further, the product ethylene may react with oxygen introduced as a raw material to produce ethylene oxide, CO, CO _{2 and the} like as by-products. Furthermore, since methane is a flammable gas, strict concentration control is required for methane and oxygen as raw materials in order to prevent explosion due to reaction with oxygen.

The present invention has been devised in view of such conventional circumstances, and an object of the present invention is to produce a compound having higher atomic efficiency and / or higher chemical value than water production. Compared to the reaction involving the generation of hydrogen molecules in the condensation reaction of saturated hydrocarbons, which does not require a high temperature for the reaction to proceed, and from the production of unsaturated hydrocarbons using saturated hydrocarbons and oxygen as raw materials The present invention also provides a method for producing hydrocarbons using saturated hydrocarbons as raw materials in which ethylene oxide, by-products such as CO and CO ₂ are reduced, and strict control of the concentration of the introduced raw materials is not required for safety. That is.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention by reacting a product with a mixed gas containing a specific amount of a highly recyclable raw material. is there.

That is, the present invention is as follows.
[1]
A saturated hydrocarbon a having a mole fraction of 0.05 or more and 0.999 or less and having 1 to 6 carbon atoms;
A mixed gas containing an unsaturated hydrocarbon x having 2 to 12 carbon atoms and having a molar fraction of 0.001 or more and 0.95 or less, in the presence of a catalyst,
A method for producing a hydrocarbon, comprising at least a step X of producing at least a hydrocarbon b having a carbon skeleton having a carbon skeleton equal to that of the unsaturated hydrocarbon x.
[2]
The method for producing a hydrocarbon according to [1], wherein the degree of unsaturation of carbon-carbon bonds in the hydrocarbon b is lower than that of the unsaturated hydrocarbon x.
[3]
The method for producing a hydrocarbon according to [1] or [2], wherein the saturated hydrocarbon a is methane or ethane.
[4]
The method for producing a hydrocarbon according to any one of [1] to [3], wherein the unsaturated hydrocarbon x is an alkene.
[5]
The method for producing a hydrocarbon according to [4], wherein the alkene has one unsaturated bond between carbons.
[6]
The method for producing a hydrocarbon according to [5], wherein the alkene is ethylene and the hydrocarbon b is ethane.
[7]
The method for producing a hydrocarbon according to [5], wherein the alkene is butene and the hydrocarbon b is butane.
[8]
The method for producing a hydrocarbon according to [4], wherein the alkene has a plurality of unsaturated bonds between carbons.
[9]
The method for producing a hydrocarbon according to [8], wherein the alkene is butadiene and the hydrocarbon b is butane or butene.
[10]
The method for producing hydrocarbons according to any one of [1] to [3], wherein the unsaturated hydrocarbon x is alkyne.
[11]
The method for producing a hydrocarbon according to [10], wherein the alkyne is acetylene and the hydrocarbon b is ethane or ethylene.
[12]
The method for producing hydrocarbons according to any one of [1] to [3], wherein the unsaturated hydrocarbon x is a hydrocarbon having an aromatic ring.
[13]
The hydrocarbon production method according to [12], wherein the hydrocarbon having an aromatic ring is benzene, and the hydrocarbon b is cyclohexane, cyclohexene, or cyclohexadiene.
[14]
The method for producing hydrocarbons according to [13], wherein the hydrocarbon having an aromatic ring is toluene, and the hydrocarbon b is methylcyclohexane, methylcyclohexene, or methylcyclohexadiene.
[15]
The method for producing a hydrocarbon according to any one of [1] to [14], wherein the reaction temperature in the step X is 30 ° C. or higher and 440 ° C. or lower.
[16]
The method for producing hydrocarbons according to any one of [1] to [15], wherein the reaction pressure in the step X is not less than atmospheric pressure and not more than 50 MPa.
[17]
The method for producing hydrocarbons according to any one of [1] to [16], wherein the catalyst is a heterogeneous catalyst.
[18]
The method for producing hydrocarbons according to any one of [1] to [17], wherein in step X, the molar fraction of the saturated hydrocarbon a to be introduced is 0.1 or more and 0.95 or less.
[19]
The process for producing hydrocarbons according to any one of [1] to [18], wherein in step X, the molar fraction of unsaturated hydrocarbon x to be introduced is 0.05 or more and 0.90 or less.
[20]
In the step X, the ratio of the saturated hydrocarbon a to the unsaturated hydrocarbon x to be introduced (unsaturated hydrocarbon x / saturated hydrocarbon a) is 0.001 or more and 10 or less, [1] to [19] The method for producing a hydrocarbon according to any one of the above.
[21]
The method for producing a hydrocarbon according to any one of [1] to [20], wherein hydrogen is introduced in the step X.
[22]
The method for producing a hydrocarbon according to [21], wherein the hydrogen introduced in the step X is 100 or less in molar ratio with respect to the sum of the saturated hydrocarbon a and the unsaturated hydrocarbon x.
[23]
In the step X, the mixed gas of the saturated hydrocarbon a and the unsaturated hydrocarbon x to be introduced is
Including hydrogen having a molar fraction of 0.0001 or more and 0.5 or less,
When the number of carbon atoms of the unsaturated hydrocarbon x is m, the hydrocarbon of any one of [1] to [22], which produces an unsaturated hydrocarbon y having a carbon number of 2 m or more and 8 m or less. Production method.
[24]
In the step X, the first gas containing the saturated hydrocarbon a and the unsaturated hydrocarbon x is introduced into the reaction system in which the catalyst exists in an introduction time of 3 seconds or more and 10 minutes or less. Step A to obtain hydrocarbon b by
Step B, in which a second gas containing hydrogen having a molar fraction of 0.02 or more and 1 or less is introduced into the reaction system at an introduction time of 1 second or more and 5 minutes or less, [1] to [23] The process for producing a hydrocarbon according to any one of [23].
[25]
After step A and before step B, a step α for introducing a third gas containing an inert gas into the reaction system with an introduction time of 1 second or more and 90 seconds or less. In addition,
The third gas has an inert gas molar fraction of 0.01 or more and 1 or less, and an unsaturated hydrocarbon x molar fraction of the unsaturated hydrocarbon x in the first gas. The method for producing hydrocarbons according to [24], which is smaller than the molar fraction of 0.01 by 0.01 or more.
[26]
The method for producing an unsaturated hydrocarbon according to [25], wherein in the step α, the introduction time of the third gas is 5 seconds or more and 70 seconds or less.
[27]
After the step B, further comprising a step β of introducing a fourth gas containing an inert gas into the reaction system with an introduction time of 1 second or more and 90 seconds or less,
The fourth gas has an inert gas molar fraction of 0.01 or more and 1 or less, and an unsaturated hydrocarbon x molar fraction of the unsaturated hydrocarbon x in the first gas. The method for producing hydrocarbons according to any one of [24] to [26], which is 0.01 or more smaller than the molar fraction of.
[28]
The method for producing hydrocarbons according to [27], wherein in the step β, the introduction time of the fourth gas is 5 seconds or longer and 70 seconds or shorter.
[29]
The method for producing hydrocarbons according to any one of [24] to [28], wherein in the step A, the introduction time of the first gas is 3 seconds or more and 60 seconds or less.
[30]
The method for producing an unsaturated hydrocarbon according to any one of [24] to [29], wherein in the step B, the introduction time of the second gas is 3 seconds or longer and 30 seconds or shorter.
[31]
The method for producing hydrocarbons according to any one of [24] to [30], wherein Step B is performed after Step A, and Step A and Step B are each repeated twice or more.
[32]
A saturated hydrocarbon production catalyst comprising at least one element selected from Group 4 to Group 13 elements other than Al and comprising zeolite having a Si / Al molar ratio of 1 or more and 1000 or less.
[33]
The saturated hydrocarbon production catalyst according to [32], wherein the saturated hydrocarbon produced using the saturated hydrocarbon production catalyst has 2 to 6 carbon atoms.
[34]
The saturated hydrocarbon production catalyst according to [32] or [33], wherein the saturated hydrocarbon produced using the saturated hydrocarbon production catalyst has 2 carbon atoms.
[35]
The saturated hydrocarbon production catalyst according to any one of [32] to [34], wherein the zeolite is of MFI type.
[36]
The saturated carbonization according to any one of [32] to [35], wherein an element consisting of a group of Group 4 to Group 13 elements other than Al contained in the zeolite is 0.01 wt% or more and 50 wt% or less. Hydrogen production catalyst.
[37]
The saturated hydrocarbon production catalyst according to any one of [32] to [36], wherein the zeolite contains at least one of Group 8 to Group 10 elements.
[38]
The saturated hydrocarbon production catalyst according to any of [32] to [37], wherein the zeolite contains at least one of Pt and Ni.
[39]
The method for producing hydrocarbons according to any one of [1] to [31], wherein the catalyst used in the step X is the catalyst according to any one of [32] to [38].
[40]
Furthermore, the manufacturing method of the hydrocarbon in any one of [1]-[31] and [39] provided with the process Y which manufactures the said unsaturated hydrocarbon x from the said hydrocarbon b at least.
[41]
The method for producing a hydrocarbon according to [40], wherein the reaction temperature in the step Y is 300 ° C. or higher and 1300 ° C. or lower.
[42]
The method for producing hydrocarbon according to [40] or [41], wherein no catalyst is used in the step Y.
[43]
The method for producing hydrocarbons according to any one of [40] to [42], wherein at least a part of the mixed gas produced in the step Y is used as a raw material in the step X.
[44]
The method for producing hydrocarbons according to [43], wherein at least a part of the unsaturated hydrocarbon x produced in the step Y is used as the unsaturated hydrocarbon x in the step X.
[45]
The method for producing a hydrocarbon according to [43] or [44], wherein at least a part of the hydrogen produced in the step Y is used as the hydrogen in the step X.
[46]
The hydrocarbon production according to any of [43] to [45], which is directly used as a mixed gas of the raw material in the step X without changing the composition of the component contained in the mixed gas produced in the step Y. Method.
[47]
The method for producing hydrocarbons according to any one of [40] to [46], comprising at least a step of performing the step Y after the step X.
[48]
The method for producing hydrocarbons according to any one of [40] to [47], comprising at least a step of performing the step X after the step Y.
[49]
After the step X, the step Y is performed, and at least a part of the unsaturated hydrocarbon x and / or hydrogen produced in the step Y is used as the unsaturated hydrocarbon x and / or the hydrogen of the step X. The method for producing hydrocarbons according to any one of [40] to [48], comprising a step of repeating the step used as 2 or more times.
[50]
In the repeating step, the hydrocarbon production method according to [49], wherein a molar fraction of hydrogen contained in the raw material gas of Step X that is performed first is less than 0.0001.
[51]
In the repeating step, the hydrocarbon production method according to [49], wherein a molar fraction of hydrogen contained in the raw material gas in the first step X is 0.0001 or more.
[52]
In the repeating step, the hydrocarbon production method according to any one of [49] to [51], wherein a molar fraction of hydrogen contained in the raw material gas in the first and subsequent steps X is 0.0001 or more.

According to the present invention, by reacting a mixed gas containing a specific amount of a highly recyclable raw material with a product, the reaction proceeds in a saturated hydrocarbon condensation reaction as compared with a reaction involving hydrogen molecule generation. In addition to the production of hydrocarbons using saturated hydrocarbons and oxygen as raw materials, carbon oxides, CO and CO _{2 and} other byproducts are reduced, and strict introduction for safety is required. It is possible to provide a hydrocarbon production method that does not require the concentration control of the raw material.

Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, In the range of the summary, various deformation | transformation can be implemented.
This embodiment
A saturated hydrocarbon a having 1 to 6 carbon atoms having a mole fraction of 0.05 or more and 0.999 or less; and a carbon number of 2 to 2 having a mole fraction of 0.001 or more and 0.95 or less. Production of a hydrocarbon comprising at least a step X in which a mixed gas containing 12 unsaturated hydrocarbons x is reacted in the presence of a catalyst to produce at least a hydrocarbon b having a carbon skeleton equal to the unsaturated hydrocarbon x. Method.

According to this embodiment, by reacting a mixed gas containing a specific amount of unsaturated hydrocarbon x, which is a highly recyclable raw material, with hydrocarbon b, which is a product, in the condensation reaction of saturated hydrocarbons, hydrogen molecules Compared to the reaction involving the production of carbon, it does not require a high temperature for the reaction to proceed, and carbon dioxide, CO, CO _{2, and the} like are produced in comparison with hydrocarbon production using saturated hydrocarbons and oxygen as raw materials. It is possible to provide a method for producing hydrocarbons in which living organisms are reduced and strict control of the concentration of introduced raw materials is not required for safety.

  The hydrocarbon b which is the product obtained by the process X is not only industrially useful than the saturated hydrocarbon a which is a raw material, but also, for example, the process Y (detailed below from the hydrocarbon b). As in the process of producing saturated hydrocarbon x, it can be a raw material for producing a more industrially useful compound than hydrocarbon b in another process.

For example, in step X, ethane (hydrocarbon b) is produced from methane (saturated hydrocarbon a) and ethylene (unsaturated hydrocarbon x), and in step Y, ethane (hydrocarbon b) is ethylene (unsaturated). Saturated hydrocarbons x) and hydrogen molecules can be produced. More specifically, in Step X, two molecules of methane (hydrocarbon b) are produced by reacting two molecules of methane as the saturated hydrocarbon a and one molecule of ethylene as the unsaturated hydrocarbon x (formula 1). ). In Step Y, these two molecules of ethane (hydrocarbon b) are converted into two molecules of ethylene (unsaturated hydrocarbon x) and two molecules of hydrogen (when formula 2 is 2 equivalents). At this time, out of the two molecules of ethylene, one molecule of ethylene can be used as the raw material of the process X, and the total reaction at that time produces one molecule of ethylene and two molecules of hydrogen from two molecules of methane. (Equation 3) Therefore, the ethane (hydrocarbon b) produced in the step X is also useful from the viewpoint of high reusability.
2CH ₄ + C ₂ H ₄ → 2C ₂ H ₆ (Formula 1)
C ₂ H ₆ → C ₂ H ₄ + H ₂ (Formula 2)
2CH ₄ → C ₂ H ₄ + 2H ₂ (Formula 3)

In the reaction for directly producing ethylene by condensation of methane (Equation 3), the standard free energy change ΔG ⁰ is ΔG ⁰ = 170 kJ / mol and the standard entropy change ΔS ⁰ = 108 J K ⁻¹ mol ⁻¹ . When the reaction of Formula 3 is divided into a plurality of steps, it is desirable that the endothermic amount in one step is small, and that the standard entropy change in each step is large, it is easy to obtain a large yield in a high temperature reaction. It is desirable from the viewpoint. In step X of the present invention, for example, a reaction for producing ethane from methane and ethylene (formula 1) and a reaction for producing ethylene by dehydrogenation of ethane in step Y (formula 2) are respectively ΔG ⁰ = − 32 kJ / mol, ΔG ⁰ = 101 kJ / mol, and the endothermic amount in each step is lower than the endothermic amount in the reaction of Formula 3 described above. In particular, in the reaction of Formula 2, ΔS ⁰ = 120 J K ⁻¹ mol ^−1, which is larger than that of the reaction in which ethylene is directly produced by condensation of methane. For this reason, ethylene production from methane (Formula 3) can be divided into two-stage reactions with less thermodynamic restrictions in each step.

In particular, the reaction for directly producing ethane from methane (formula 4, ΔG ⁰ = 69 kJ / mol, ΔS ⁰ = −12J K ⁻¹ mol ⁻¹ ) is an endothermic reaction and the standard entropy change is negative. Moreover, it is difficult to obtain a high yield under equilibrium conditions even under high temperature conditions, and there are significant thermodynamic restrictions. On the other hand, since the reaction of producing ethane from methane and ethylene using ethylene of formula 1 as a hydrogen acceptor is an exothermic reaction, it is useful from the viewpoint that ethane can be advantageously produced thermodynamically. It is a reaction.
2CH ₄ → C ₂ H ₆ + H ₂ (Formula 4)

In the step X, the unsaturated hydrocarbon x can be condensed to produce an unsaturated hydrocarbon y having a larger carbon number. The unsaturated hydrocarbon y production is useful from the viewpoint that the unsaturated hydrocarbon y having a larger number of carbon atoms can be a chemical with a higher added value than the unsaturated hydrocarbon x. Furthermore, the unsaturated hydrocarbon x produced using the saturated hydrocarbon a as a raw material through the steps X and Y can be condensed to produce an unsaturated hydrocarbon y having a larger carbon number. For example, for the ethylene produced using methane as a raw material through the step X and the step Y, such as the above (formula 1) and (formula 2), or (formula 3), etc. In step X, butene (formula 5) and higher unsaturated hydrocarbons having more carbon atoms can be produced by this ethylene condensation. In this case, as the total reaction, higher unsaturated hydrocarbons using methane as a raw material, such as butene production from methane (Formula 6, the sum of Formula 3 and Formula 5), can be produced. Note that, for example, the synthesis reaction of 1-butene by the condensation of ethylene (Formula 5) is an exothermic reaction of ΔG ⁰ = −65 kJ / mol. Therefore, ethane production from methane and ethylene (Formula 1) and ethane dehydrogenation are performed. In combination with ethylene production by (Formula 2), 1-butene production from methane (Formula 6, ΔG ⁰ = 275 kJ / mol), which has a large endothermic reaction and large thermodynamic constraints, is more thermodynamically constrained. The reaction can be divided into a few three-stage reactions (Formula 1, 2 equivalents of Formula 2, Formula 5).
2C ₂ H ₄ → C ₄ H ₈ (Formula 5)
4CH ₄ → C ₄ H ₈ + 4H ₂ (Formula 6)

In the present embodiment, for example, the saturated hydrocarbon a can be a saturated hydrocarbon having a larger carbon number than methane, and the unsaturated hydrocarbon x can be an unsaturated hydrocarbon having a larger carbon number than ethylene. Specifically, when saturated hydrocarbon a is ethane, unsaturated hydrocarbon x is butene, and hydrocarbon b is butane, two molecules of ethane (saturated hydrocarbon a) and one molecule of butene ( 2 molecules of butane (hydrocarbon b) is produced from unsaturated hydrocarbon x) (formula 7), and in step Y, butane (hydrocarbon b) produced in step X is dehydrogenated to produce butene (unsaturated). Saturated hydrocarbon x) is produced (Equation 8). Then, one molecule of butene (unsaturated hydrocarbon x) produced in the process Y is used as the raw material of the process X, and as a total reaction, the production of butene and hydrogen molecules from ethane (formula) 9). That is, even when the saturated hydrocarbon a is a saturated hydrocarbon having a carbon number larger than that of methane and the unsaturated hydrocarbon x is an unsaturated hydrocarbon having a carbon number larger than that of ethylene, dehydrogenation from ethane is also performed. The accompanying butene production can be divided into two more thermodynamically easier steps.
2C ₂ H ₆ + C ₄ H ₈ → 2C ₄ H ₁₀ (Formula 7)
C ₄ H ₁₀ → C ₄ H ₈ + H ₂ (Formula 8)
2C ₂ H ₆ → C ₄ H ₈ + 2H ₂ (Formula 9)

In the present embodiment, for example, the unsaturated hydrocarbon x can be an alkyne and the hydrocarbon b can be an alkene. Specifically, when the saturated hydrocarbon a is methane, the unsaturated hydrocarbon x is acetylene, and the hydrocarbon b is ethylene, two molecules of methane (saturated hydrocarbon a) and one molecule of acetylene ( A molecule of ethylene (hydrocarbon b) and ethane are produced from unsaturated hydrocarbon x) (Equation 10), and in step Y, ethylene (hydrocarbon b) produced in step X is dehydrogenated to produce acetylene. (Unsaturated hydrocarbon x) is produced (Formula 11). Then, by using the acetylene (unsaturated hydrocarbon x) produced in this step Y as the raw material of the step X, ethane and hydrogen molecules can be produced from methane (Formula 4) as a total reaction. Also, when hydrocarbon b is ethane, the ethane produced in step X is dehydrogenated in step Y to form acetylene (formula 12), so that the total reaction of ethylene and hydrogen molecules from methane Production (Formula 3) can be used. That is, even when the unsaturated hydrocarbon x is alkyne, ethane or ethylene production accompanied by dehydrogenation from methane can be divided into two steps that are thermodynamically easier.
2CH ₄ + C ₂ H ₂ → C ₂ H ₆ + C ₂ H ₄ (Formula 10)
C ₂ H ₄ → C ₂ H ₂ + H ₂ (Formula 11)
C ₂ H ₆ → C ₂ H ₂ + 2H ₂ (Formula 12)

In the present embodiment, for example, the unsaturated hydrocarbon x can be a hydrocarbon having a plurality of unsaturated bonds between carbons. Specifically, when the saturated hydrocarbon a is ethane, the unsaturated hydrocarbon x is butadiene, and the hydrocarbon b is butene, two molecules of ethane (saturated hydrocarbon a) and one molecule of butadiene ( One molecule of butene (hydrocarbon b) and one molecule of butane are produced from the unsaturated hydrocarbon x) (formula 13), and in step Y, the butene produced in step X (hydrocarbon b) is dehydrogenated. Thus, butadiene (unsaturated hydrocarbon x) is produced (Formula 14). Then, by using the butadiene (unsaturated hydrocarbon x) produced in Step Y as the raw material of Step X, butane production from ethane (Formula 15) can be performed as a total reaction. When the hydrocarbon b is butane, the butane produced in the process X is dehydrogenated in the process Y to form butadiene (Formula 16), thereby producing butene and hydrogen molecules from ethane as a total reaction ( Equation 17) can be obtained. That is, even when the unsaturated hydrocarbon x is alkyne, the production of butene or butadiene accompanied by dehydrogenation from ethane can be divided into two steps that are easier to thermodynamically.
2C ₂ H ₆ + C ₄ H ₆ → C ₄ H ₁₀ + C ₄ H ₈ (Formula 13)
C ₄ H ₈ → C ₄ H ₆ + H ₂ (Formula 14)
2C ₂ H ₆ → C ₄ H ₁₀ + H ₂ (Formula 15)
C ₄ H ₁₀ → C ₄ H ₆ + 2H ₂ (Formula 16)
2C ₂ H ₆ → C ₄ H ₈ + 2H ₂ (Formula 17)

  In the present embodiment, for example, the unsaturated hydrocarbon x can be a hydrocarbon having an aromatic ring. Specifically, the unsaturated hydrocarbon x can be toluene or benzene, and the hydrocarbon b can be methylcyclohexane, methylcyclohexene, methylcyclohexadiene, cyclohexane, cyclohexene, or cyclohexadiene. In particular, since toluene, benzene, and the like are used as hydrogen storage materials, they have excellent hydrogen accepting ability, and methylcyclohexane, cyclohexane, and the like are used as hydrogen hydrides thereof, and thus have excellent dehydrogenating ability. In particular, since the reaction energy difference between hydrogen acceptance from toluene and benzene and dehydrogenation from methylcyclohexane and cyclohexane is relatively small, the dehydrogenation reaction in step Y can proceed with relatively small energy. From this viewpoint, a production method in which the unsaturated hydrocarbon x is toluene or benzene and the hydrocarbon b is methylcyclohexane, methylcyclohexene, methylcyclohexadiene, or cyclohexane, cyclohexene, cyclohexadiene is preferable. From a comparatively excellent viewpoint, a production method in which the unsaturated hydrocarbon x is toluene and the hydrocarbon b is methylcyclohexane, methylcyclohexene, or methylcyclohexadiene is more preferable.

  Some examples of the raw material in the present production method are given above. From the viewpoint that the effect of alleviating the thermodynamic restriction by reaction splitting is large, and from the viewpoint that relatively many raw materials exist on the earth, saturated carbonization is performed. A production method in which hydrogen a is methane and / or ethane, and unsaturated hydrocarbon x is ethylene and / or butene and / or butadiene is preferred. From the viewpoint of relatively abundant raw materials, saturated hydrocarbon a is methane. And a production method in which the unsaturated hydrocarbon x is ethylene is more preferable. Further, from the viewpoint that the saturated hydrocarbon having a larger number of carbon atoms has a smaller activation energy for activation on the catalyst and facilitates the progress of the step X, the saturated hydrocarbon a is ethane, and the unsaturated hydrocarbon x More preferred is a production method in which is a butene and / or butadiene. In particular, in the process X, the condensation reaction between saturated hydrocarbons a having only a saturated bond proceeds by the same mechanism as the reaction using saturated hydrocarbons a as methane, so that the carbon number is 2 or more and 6 or less. The reaction proceeds similarly for the saturated hydrocarbons.

(Saturated hydrocarbon a)
The saturated hydrocarbon a becomes a raw material for the hydrocarbon b produced in the step X. One of the reaction mechanisms in which the saturated hydrocarbon a condenses is that the saturated hydrocarbon a is adsorbed on the catalyst, thereby generating dehydrogenated active hydrocarbon species and dissociated hydrogen and / or hydrogen molecules. It is conceivable that two or more hydrocarbon active species are condensed to produce hydrocarbon b and / or unsaturated hydrocarbon y.
The carbon number of the saturated hydrocarbon a is 1 or more and 6 or less. The saturated hydrocarbon a is a saturated hydrocarbon from the viewpoint of being a component such as natural gas or from the viewpoint of reducing the steric hindrance for hydrocarbon adsorption on the catalyst as the number of carbons is reduced when activated on the catalyst. The carbon number of a is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, still more preferably 1 or more and 2 or less, and most preferably 1.

Specific examples of such saturated hydrocarbons a include methane, ethane, propane, butane, pentane, hexane, and isomers thereof. As described above, from the viewpoint of reducing steric hindrance during adsorption onto the catalyst, the saturated hydrocarbon a is preferably methane, ethane, propane, normal butane, and isobutane, more preferably methane, ethane, and propane, and methane. Ethane is more preferred and methane is most preferred.
As the saturated hydrocarbon a, the same type may be used alone, or a plurality of different types may be mixed and used. When the saturated hydrocarbon a is used by mixing a plurality of different types, for example, when using natural gas or shale gas as a raw material gas, it is preferable to use this main component as a raw material, The saturated hydrocarbon a is preferably methane and ethane.

(Unsaturated hydrocarbon x)
The unsaturated hydrocarbon x is a raw material for the unsaturated hydrocarbon y. Moreover, it can be used as the raw material of the saturated hydrocarbon b produced | generated by hydrogenating at the process X etc. The unsaturated hydrocarbon x that reacts in the step X can react in a molecular state or by being adsorbed on a catalyst.
In the present invention, the unsaturated hydrocarbon x has 2 or more and 12 or less carbon atoms. When activated on the catalyst, the carbon number of the unsaturated hydrocarbon x is preferably 2 or more and 8 or less from the viewpoint that the smaller the number of carbons, the smaller the steric hindrance for hydrocarbon adsorption on the catalyst. More preferably, it is 2 or more and 6 or less, More preferably, it is 2 or more and 4 or less, Most preferably, it is 2.

Examples of the unsaturated hydrocarbon x in the present embodiment include alkenes, alkynes, and hydrocarbons having an aromatic ring. Alkenes and alkynes are preferable from the viewpoint of easy adsorption to the catalyst, and alkenes are most preferable from the viewpoint of easy dehydrogenation in Step Y.
More specifically, the unsaturated hydrocarbon x of the present embodiment is ethylene, propylene, butene, pentene, hexene, heptene, octene, acetylene, propyne, butyne, butadiene, benzene, toluene, xylene, naphthalene and isomers thereof. Examples include the body. From the viewpoint of reducing steric hindrance during adsorption to the catalyst, the unsaturated hydrocarbon x is preferably ethylene, acetylene, propylene, 1-butene, 2-butene, or butadiene, and more preferably ethylene, acetylene, Propylene, propyne, most preferably ethylene and acetylene.

(Hydrocarbon b)
The number of carbon atoms of the hydrocarbon b produced in the step X is a saturated hydrocarbon or an unsaturated hydrocarbon having the same carbon skeleton as the unsaturated hydrocarbon x used as a raw material. From the viewpoint of advantageous reaction control, the hydrocarbon b is preferably a saturated hydrocarbon.

  Examples of the production of the hydrocarbon b include condensation of the saturated hydrocarbon a and hydrogen addition by dissociated hydrogen and / or hydrogen molecules to the unsaturated hydrocarbon x. More specifically, the hydrogen addition to the unsaturated hydrocarbon x is a dissociated hydrogen dehydrogenated from the saturated hydrocarbon a, or a hydrogen molecule is added to the unsaturated hydrocarbon x to produce a saturated hydrocarbon b. A mechanism is considered.

  The carbon skeleton in the present application refers to a carbon chain structure, and even if the carbon skeleton is equal, the degree of unsaturation of the carbon-carbon bond may be different. Further, the unsaturation degree of the carbon bond in the present application is the sum of the unsaturation degree of the unsaturated bond in the carbon bond in the carbon skeleton. For example, the saturated hydrocarbon such as ethane is 0, ethylene, butene, etc. Is 1, and acetylene, butadiene and the like are 2. From the viewpoint that the unsaturated hydrocarbon x can be a hydrogen acceptor of the saturated hydrocarbon a, the degree of unsaturation of the hydrocarbon-b intercarbon bond is preferably lower than that of the unsaturated hydrocarbon x.

  Saturated hydrocarbon a and unsaturated hydrocarbon x are generated as raw materials, and dimerization is easy from the collision probability of active species on the catalyst, or can be generated by hydrogen addition to unsaturated hydrocarbon x. From a preferable viewpoint, the carbon number of the hydrocarbon b is preferably 2 or more and 12 or less, more preferably 2 or more and 8 or less, still more preferably 2 or more and 4 or less, and most preferably 2. is there.

  Specific examples of the hydrocarbon b of the present embodiment include ethane, ethylene, propane, butane, butadiene, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decalin, and isomers thereof. Etc. Saturated hydrocarbon a is used as a raw material, condensed and generated, and dimerization is easy from the collision probability of active species on the catalyst, from the viewpoint of generation by hydrogen addition to unsaturated hydrocarbon x, and to the catalyst From the viewpoint of reducing steric hindrance during adsorption, the hydrocarbon b is preferably ethane, propane, butane, pentane, hexane, cyclohexane, methylcyclohexane, and isomers thereof, and ethane, propane, normal butane, isobutane. Is more preferred and ethane is most preferred.

(Unsaturated hydrocarbon y)
The unsaturated hydrocarbon y can be produced by condensation of the unsaturated hydrocarbon x in the step X. The carbon number of the unsaturated hydrocarbon y is 2 m or more and 8 m or less, where m is the carbon number of the unsaturated hydrocarbon x. The greater the number of unsaturated hydrocarbons x to be condensed, the greater the amount of heat generated, and from the viewpoint of supplying reaction heat to the condensation reaction of the saturated hydrocarbon a, it is preferably 3 m or more, and more preferably 4 m or more. Moreover, from a viewpoint of the collision probability of unsaturated hydrocarbon, 6 m or less is preferable and 4 m or less is more preferable.

The unsaturated hydrocarbon y is preferably alkene, alkyne, or aromatic, more preferably alkene, alkyne, more preferably alkene. The carbon chain of the unsaturated hydrocarbon y is preferably a straight chain or branched chain unsaturated hydrocarbon, more preferably a straight chain unsaturated hydrocarbon, and only a straight chain unsaturated hydrocarbon. More preferred is hydrogen.
More specifically, the unsaturated hydrocarbon y of the present embodiment includes butene, hexene, octene, acetylene, butyne, butadiene, benzene, naphthalene, and isomers thereof. From the viewpoint of reducing steric hindrance during adsorption to the catalyst, the unsaturated hydrocarbon y is preferably 1-butene, hexene, octene, 2-butene, butadiene, more preferably 1-butene, octene, 2-butene is most preferably 1-butene.

(Mixed gas)
The mixed gas of the present embodiment includes at least a saturated hydrocarbon a and an unsaturated hydrocarbon x. In the mixed gas, as described above, the mole fraction of the saturated hydrocarbon a is 0.05 or more and 0.999 or less, and the mole fraction of the unsaturated hydrocarbon x is 0.001 or more and 0.95 or less. is there.

  From the viewpoint of efficiently activating the saturated hydrocarbon a with a catalyst, the molar fraction of the saturated hydrocarbon a is preferably 0.2 or more, more preferably 0.3 or more, and most preferably 0.5 or more. . Further, from the viewpoint of purification cost of the saturated hydrocarbon a to be introduced, 0.940 or less is preferable, 0.920 or less is more preferable, and 0.900 or less is more preferable.

  From the viewpoint of efficiently adsorbing the unsaturated hydrocarbon x to the catalyst, the molar fraction of the unsaturated hydrocarbon x is preferably 0.01 or more, more preferably 0.07 or more, and most preferably 0.11 or more. It is. Further, from the viewpoint of suppressing the covering of the catalyst active sites with the unsaturated hydrocarbon x, 0.8 or less is preferable, 0.7 or less is more preferable, 0.6 or less is further preferable, and 0.5 or less is most preferable.

  The ratio of the saturated hydrocarbon a to the unsaturated hydrocarbon x (unsaturated hydrocarbon x / saturated hydrocarbon a) of the mixed gas is preferably 0.01 or more and 10 or less. From the viewpoint of efficiently activating the saturated hydrocarbon a with a catalyst, the ratio of the saturated hydrocarbon a to the unsaturated hydrocarbon x (unsaturated hydrocarbon x / saturated hydrocarbon a) is more preferably 0.005 or more, 0.01 or more is more preferable, and 0.05 or more is most preferable. From the viewpoint of efficiently adsorbing the unsaturated hydrocarbon x to the catalyst, the ratio of the saturated hydrocarbon a to the unsaturated hydrocarbon x (unsaturated hydrocarbon x / saturated hydrocarbon a) is more preferably 5 or less, 1 or less is more preferable, and 0.5 or less is most preferable.

  In this embodiment, hydrogen is introduced in step X, for example, in addition to saturated hydrocarbon a and unsaturated hydrocarbon x (for example, methane and ethylene) as a raw material mixed gas, hydrogen is included to produce unsaturated hydrocarbon y. From the viewpoint of improving the activity, it is preferable. Surprisingly, it is surmised that the addition of hydrogen in the process X is presumed that the unsaturated bond of the resulting unsaturated hydrocarbon y is hydrogenated to promote the reaction to become a saturated hydrocarbon. Production activity of unsaturated hydrocarbon y (for example, butene) was improved. The production of the unsaturated hydrocarbon y derived from the saturated hydrocarbon a is useful from the viewpoint of producing a higher value-added chemical product. The inventors do not want to be bound by a specific theory about the production improvement of the unsaturated hydrocarbon y, but presume the following mechanism.

  The condensation reaction of the saturated hydrocarbon a is performed on the catalyst in a steady state as compared with the case where only the saturated hydrocarbon a is introduced into the catalyst in order to introduce the unsaturated hydrocarbon x together with the saturated hydrocarbon a as a hydrogen acceptor. It is conceivable that the hydrogen concentration decreases. For this reason, by introducing a gas containing hydrogen molecules, hydrogen that is considered to be deficient as compared with the case of introducing only saturated hydrocarbon a can be constantly supplied onto the catalyst. As a result, precipitation of hydrocarbon-derived carbon compounds on the active points could be suppressed, and it is assumed that the production activity of unsaturated hydrocarbon y by the condensation reaction of unsaturated hydrocarbon x was improved.

In addition to the above effects, the hydrogenation reaction to the unsaturated hydrocarbon x is a large exothermic reaction. For example, when unsaturated hydrocarbon x is ethylene (formula 18), ΔG ⁰ = −101 kJ / mol. For this reason, the temperature on the catalyst rises during the reaction, and it is estimated that the reaction rate of the production reaction of the unsaturated hydrocarbon y by the condensation reaction of the unsaturated hydrocarbon x is improved. On the same catalyst, for example, when the saturated hydrocarbon a is methane and the unsaturated hydrocarbon x is ethylene, when the reaction of Formula 3 or Formula 4, which is an endothermic reaction, occurs, heat is supplied to these reactions, The effect of promoting the reaction is also speculated.
C ₂ H ₄ + H ₂ → C ₂ H ₆ (Formula 18)

  Examples of hydrogen contained in the mixed gas include hydrogen molecules, atomic hydrogen, hydrogen plasma, and the like, and hydrogen molecules are preferable from the viewpoint of easy introduction. The molar fraction of hydrogen is preferably 0.0001 or more and 0.5 or less from the viewpoint of enhancing the effect of improving the production rate of unsaturated hydrocarbon y. From the viewpoint of enhancing the effect of improving the production rate of unsaturated hydrocarbon y and suppressing the deactivation of the hydrocarbon production activity, the molar fraction of hydrogen is preferably 0.001 or more, more preferably 0.005. More preferably, it is 0.01 or more, and most preferably 0.02 or more. Further, from the viewpoint of improving the partial pressure of the saturated hydrocarbon a and the unsaturated hydrocarbon x, 0.4 or less is preferable, 0.3 or less is more preferable, 0.25 or less is more preferable, and 0.2 or less is the most. preferable.

  As a method of obtaining a mixed gas, there are a method of mixing a predetermined amount of each raw material, a method of obtaining a gas obtained by reacting methane or the like that is relatively easily available, directly or through a separation or purification process, etc. Can be mentioned. For example, in step Y, which will be described later, unsaturated hydrocarbon x and hydrogen molecule are generated from hydrocarbon b, and this unsaturated hydrocarbon and hydrogen molecule are used as unsaturated hydrocarbon x and hydrogen of the mixed gas. A method is mentioned.

(catalyst)
The catalyst used in the present invention refers to a homogeneous catalyst, a heterogeneous catalyst, a catalyst in which a homogeneous catalyst is fixed to a support or a heterogeneous catalyst, and the like. From the viewpoint of easy separation of the catalyst and the product, a heterogeneous catalyst is preferable. Specifically, the heterogeneous catalyst is a metal catalyst, a metal compound catalyst such as a metal oxide, a zeolite, a catalyst in which a metal or a metal compound is supported or ion-exchanged on a support, a metal complex, activated carbon, etc., preferably a support. A catalyst having a metal compound supported thereon is preferred. The zeolite catalyst in the present application refers to a catalyst having at least a part of a zeolite skeleton.

The element constituting the catalyst preferably contains at least one element from Group 3 to Group 15 in the new IUPAC notation. When utilizing the d-orbital electrons of the metal catalyst for the reaction with the raw material, the group 6 to group 12 is preferred, and the group 7 to group 12 is more preferred from the viewpoint that the larger number of d electrons is advantageous for the reaction. 8 to 12 are more preferable. From the viewpoint of the number of d electrons and the viewpoint of toxicity of metals and metal ions to the human body, groups 8 to 11 are most preferable. The element constituting the catalyst can be composed of one or more elements. The elements constituting the catalyst are, for example, La, Y, Sm, V, Si, Al, In, Sn, Ge, Mo, W, Cr, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os. , Mn, Re, Cu, Ag, Au and the like. From the viewpoint of the use of d electrons in the metal catalyst, the elements constituting the catalyst are Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os, Mn, Re, Cr, Mo, W, Cu, Ag, Au From the viewpoint of catalytic activity, Pt, Ni, Co, Pd, Ru, and Cu are more preferable, Pt, Pd, Ni, Co, and Ru are more preferable, and Pt and Ni are most preferable.
The chemical state of the metal species is not limited to a metal, and may be a compound, a complex, or the like. A material having a higher charge density that contributes to donating electrons to the adsorption substrate is preferably in a metal state from the viewpoint of being advantageous for activation of the unsaturated hydrocarbon. In addition, the compound is preferably a compound from the viewpoint that an anion species bonded to the metal species can be an active point and the electrophilicity of the metal species can be enhanced.

  A catalyst having a metal compound supported on a carrier will be described. Uses single metal oxides or single metal oxides doped with different metal species, composite metal oxides composed of two or more metal elements such as spinel type and perovskite type, zeolite, activated carbon, etc. it can. From the viewpoint of being chemically stable, metal oxides and zelite are preferable, and from the viewpoint of relatively easily increasing the specific surface area, zeolite is more preferable. Specific examples of the metal compound include titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, lanthanum oxide, cerium oxide, and magnesium oxide.

  A phosphorus-containing compound, boron-containing compound, alkali metal compound, alkaline earth metal compound, or the like can be added to the catalyst as an auxiliary agent.

  The catalyst preparation method includes a method of supporting a metal species on a support such as an impregnation method, a method using a solid phase reaction, a flux method, a hydrothermal synthesis method, changing the pH of a solution containing a catalyst raw material, or a compound Examples include a coprecipitation method, a uniform precipitation method, a chemical vapor deposition method, a physical vapor deposition method, and the like in which a catalyst or a precursor thereof is precipitated by adding ions that form a catalyst.

<Zeolite catalyst>
When the hydrocarbon b is a saturated hydrocarbon, preferably a saturated hydrocarbon having 2 to 6 carbon atoms, more preferably ethane, it contains at least one element selected from the group consisting of Group 4 to Group 13 elements, It has been found that the use of a catalyst composed of MFI-type zeolite having a Si / Al molar ratio of 1 or more and 1000 or less shows particularly high activity in the production of saturated hydrocarbons. The inventors do not want to be bound by a specific theory as to why this zeolite catalyst exhibits an excellent saturated hydrocarbon production activity, but consider the following theory.

  The larger the Si / Al molar ratio of the zeolite, the stronger the acid strength of the Bronsted acid point in the zeolite and the lower the acid point number. The zeolite with a specific Si / Al molar ratio showed excellent saturated hydrocarbon generation activity this time. The discovered Si / Al molar ratio zeolite accidentally had an acid strength at an acid point suitable for this reaction, This may be because the number of acid points has been reached. In addition, it is considered that some of the Group 4 to Group 13 elements contained in the zeolite were ion-exchanged with the Bronsted acid point of the zeolite to form an active site. The interaction with the ion-exchanged metal species was suitable for this reaction, so it is considered that the compound exhibited excellent activity.

  The elements contained in the zeolite preferably include Group 4 to Group 13 elements of the new IUPAC. From the viewpoint of excellent activity, Group 8-12 is more preferred, Group 9-11 is more preferred, and Group 10 is most preferred. Specifically, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Pt, Ag, Cd, In, Sn Fe, Co, Ni, Cu, Zn, Ga, Ge, Ru, Rh, Pd, Pt, Ag, In, and Sn are more preferable, Ni, Cu, Zn, and Pt are more preferable, and Pt and Ni are the most preferable preferable.

  The content of Group 4 to Group 13 elements contained in the zeolite catalyst of this embodiment is preferably 0.01 wt% or more and 50 wt% or less. From the viewpoint of increasing the Bronsted acid point, 30 wt% or less is preferable, 15 wt% or less is more preferable, and 10 wt% is more preferable. In addition, the higher the content of the Group 4 to Group 13 elements, the more advantageous it is for the adsorption of the saturated hydrocarbon a or the unsaturated hydrocarbon x to the catalyst, from the viewpoint that it is advantageous for increasing the active sites per unit weight. From a certain viewpoint, 0.05 wt% or more is preferable, 0.5 wt% or more is more preferable, and 1 wt% or more is more preferable. In addition, content of the element in the catalyst in this application is a value calculated as the said element is a metal state.

  The zeolite preferably has a pore structure, and in the structure code of the International Zeolite Society, the MFI type structure is preferable, and the structure of ZSM-5 is more preferable. The Si / Al ratio is usually preferably 1 or more and 1000 or less. From the viewpoint of many Bronsted acid points and advantageous for increasing the number of active sites, 200 or less is preferable, 80 or less is more preferable, and 30 or less is more preferable. Further, from the viewpoint that the stronger acid strength at the Bronsted acid point is advantageous for charging the ion-exchanged metal species, 5 or more is preferable, 10 or more is more preferable, and 15 or more is more preferable.

  The saturated hydrocarbon produced by the zeolite catalyst of the present embodiment preferably has 2 or more and 6 or less carbon atoms from the viewpoint that it can be produced using the inside of the pores of the zeolite. From the viewpoint that the generated hydrocarbon is advantageous for diffusion in the zeolite pores, the saturated hydrocarbon produced by the zeolite catalyst preferably has 4 or less carbon atoms, and more preferably 2 carbon atoms. Further, from the viewpoint that the generated hydrocarbon is advantageous for diffusion in the pores of the zeolite, the carbon chain of the saturated hydrocarbon produced by the zeolite catalyst is preferably a straight chain.

  Examples of the preparation method for introducing a group 4-14 element into zeolite include a wet method, a solid phase method, a chemical vapor phase method, and a physical vapor phase method. From the viewpoint of simple and easy introduction of metal species into the zeolite, a wet method is preferable. The wet method is, for example, a method of reacting a solution containing a group 4-14 element with zeolite, and examples thereof include an impregnation method, an ion exchange method, and a hydrothermal synthesis method. The ion exchange method is preferable from the viewpoint that elements can be introduced in a highly dispersed manner and that metal cations can be introduced into the sites of Bronsted acid sites.

  About the preparation method which introduce | transduces the 4-14 group element into the said zeolite, it is preferable that the precursor of the 4-14 group element to introduce | transduces from a viewpoint which is easy to form a metal cation, and is a water-system wet method. It is preferable that it is water-soluble from a viewpoint suitable for this. Specifically, nitrates, sulfates, carbonates, chlorides, and phosphates are preferable, and nitrates and sulfates are more preferable from the viewpoint of relatively little anion species remaining in the zeolite.

  It is preferable to perform a calcination treatment as a post-treatment for introducing the elements of Groups 4 to 14 into the zeolite. The firing atmosphere is preferably an atmosphere containing an oxidizing substance such as oxygen from the viewpoint of introducing a Group 4-14 element as a metal cation, and is more preferably fired in the air for simplicity. The firing temperature is preferably 150 ° C. or higher from the viewpoint of decomposing the precursor salt, and 900 ° C. or lower is preferable from the viewpoint of preventing the decomposition of zeolite and the convenience of equipment. From the viewpoint of removing adsorbed water of zeolite, 250 ° C. or higher is more preferable, and 350 ° C. or higher is more preferable. From the viewpoint of preventing the decomposition of zeolite and the viewpoint of simplicity of equipment, 750 ° C. or lower is more preferable, and 650 ° C. or lower is further preferable.

  Examples of the synthesis method of the zeolite include a solid phase method, a coprecipitation method, a hydrothermal synthesis method, a sol-gel method, and the like, but the hydrothermal synthesis method is preferable from the viewpoint of being able to synthesize at a relatively low temperature. The reaction temperature during zeolite synthesis is preferably 100 ° C. or higher and 1150 ° C. or lower. 150 degreeC or more is preferable from a viewpoint of reaction rate, and 200 degreeC or more is more preferable. 800 degreeC or less is preferable and 600 degreeC or less is more preferable from a viewpoint which prevents the simplicity of an apparatus and aggregation of particle | grains.

  When performing the reaction using the zeolite catalyst, it is preferable not to perform the reduction pretreatment from the viewpoint of the simplicity of the process and the cost of the reactant used for the pretreatment.

When producing 1-butene (unsaturated hydrocarbon x) from normal butane (hydrocarbon b) in step Y described later, it is preferable to use a catalyst in which Pt species is supported on MgAl ₂ O ₄ . This catalyst can be prepared by a solid phase method using MgO, Al ₂ O ₃ or the like as a precursor, and chloroplatinic acid or the like can be used as a Pt-type precursor to be supported.

  In step Y described later, when producing butadiene (unsaturated hydrocarbon x) from butene (hydrocarbon b), about 5 wt% of potassium is supported on alumina-chromia having a molar ratio of Al / Cr = 5. It is preferable to use a catalyst.

  The catalyst in the present invention can be used by mixing with other catalysts. At that time, the content of the Group 4 to Group 14 element contained in the catalyst defined in the present invention does not include the amount of the Group 4 to Group 14 element contained in the other catalyst to be mixed.

  A phosphorus-containing compound, a boron-containing compound, an alkali metal compound, an alkaline earth metal compound, or the like can be added to the catalyst as an auxiliary agent. As an element constituting the catalyst, it can be composed of one or more elements.

  The catalyst is present in the reactor. Specifically, the catalyst is packed into the reactor as a fixed bed, fluidized bed, slurry bed, moving bed, or simulated moving bed. The reactor may be filled with one type of catalyst, or a plurality of types of catalysts having different activities or a catalyst mixture in which an inert inorganic substance is mixed may be used as the catalyst. Catalysts having different activities and the catalyst mixture may be installed in stages from the reactor inlet to the outlet.

<Process X>
In step X of the present embodiment, a mixed gas containing saturated hydrocarbon a and unsaturated hydrocarbon x is reacted in the presence of a catalyst to produce hydrocarbon b and / or unsaturated hydrocarbon y. The reaction in Step X includes condensation of saturated hydrocarbon a, hydrogenation of hydrogen derived from saturated hydrocarbon a and hydrogen derived from introduced hydrogen to unsaturated hydrocarbon x, condensation of unsaturated hydrocarbon x, and the like. Conceivable.

In Step X, a mixed gas containing at least a saturated hydrocarbon a and an unsaturated hydrocarbon x is introduced into a reaction system in which a catalyst exists to produce a hydrocarbon b and / or an unsaturated hydrocarbon y.
From the viewpoint that hydrogen is a higher energy material than saturated hydrocarbon a and unsaturated hydrocarbon x, the amount of hydrogen to be introduced should be 100 or less with respect to the sum of saturated hydrocarbon a and unsaturated hydrocarbon x. Is preferably 10 or less, more preferably 1 or less. Here, the hydrogen introduced during the reaction in the step X is hydrogen after the process of first introducing the saturated hydrocarbon a or the unsaturated hydrocarbon x into the reactor, and is introduced before the catalyst pretreatment or the like before that. Do not include hydrogen.
During the reaction in the step X, a gas other than the saturated hydrocarbon a and the unsaturated hydrocarbon x may be introduced, and examples thereof include water vapor, oxygen, an inert gas such as nitrogen and argon, and the like. Among them, an inert gas is preferable in order to prevent the catalyst from deteriorating and to replace the gas in the reaction system.

  In the process X, the gas to be introduced (hydrocarbon raw material gas, hydrogen and other gases) is not limited in its production process and production process, but is a gas produced by refining petroleum, natural gas, exhaust gas from a factory, air Gases such as gas recovered from the inside and shale gas recovered from the formation can be used.

  In the step X, the total volume flow rate of the gas to be introduced (mixed gas) is preferably 0.0001 to 100000000 L / h, more preferably 0.001 to 10000000 L / h, more preferably 1 g of the catalyst present in the reactor. Is 0.01 to 1000000 L / h.

  In the case of the reactor for fixing the catalyst in the process X, the ratio of the average diameter (D) of the catalyst part in the direction perpendicular to the raw material flow path direction to the catalyst part length (L) in the raw material flow path direction, L / D is 0.0000001 or more and 1,000,000 or less are preferable, and 0.0001 or more and 1000000 or less are more preferable.

  In Step X, the reaction temperature is preferably 30 ° C. or higher, more preferably 110 ° C. or higher, further preferably 160 ° C. or higher, and most preferably 210 ° C. or higher from the viewpoint of the reaction rate. Further, from the viewpoint of preventing yield reduction due to catalyst sintering, etc., and from the viewpoint of being advantageous for the equilibrium yield of hydrocarbon b, it is preferably 440 ° C. or lower, more preferably 390 ° C. or lower, further preferably 340 ° C. or lower, Most preferably below ℃. The reaction temperature here refers to the temperature in the reaction system.

  In the process X, the reaction pressure is, for example, not less than atmospheric pressure and not more than 50 MPa. The lower the pressure is, the less energy is required to carry out the pressure condition, so 30 MPa or less is preferable, more preferably 20 MPa or less, still more preferably 10 MPa or less, and most preferably 5 MPa or less. When using a hydrocarbon that liquefies in the pressure range, the pressure is preferably less than the liquefaction pressure. The pressure described in this specification indicates a relative pressure (gauge pressure) with respect to the atmospheric pressure. The reaction pressure here refers to the pressure in the reactor.

  The reaction conditions in step X, for example, the conditions for introducing the raw material, temperature, pressure, etc. can be stationary or unsteady. It is preferable that the raw material gas to be introduced is introduced constantly from the viewpoint of simplicity of the process. On the other hand, it is preferable to make it unsteady from the viewpoint of suppressing the decrease in activity and promoting the reaction relatively easily. The term “unsteady” refers to, for example, a condition for alternately introducing saturated hydrocarbon a and unsaturated hydrocarbon x gas, or introducing a catalyst regeneration step. In addition, when the introduction condition of the raw material is unsteady, for example, as the first gas, a mixed gas of saturated hydrocarbon a and unsaturated hydrocarbon x is introduced. Introducing a gas containing hydrogen as the second gas.

  When making the process X unsteady, the process A and the process B can be included. A process α described later is provided between the process A and the process B, a process β described later is provided after the process B, or a process A, a process B, a process α, and a process β are included between the processes. Other processes other than can also be performed.

(Process A)
Step A introduces a first gas containing a saturated hydrocarbon a and an unsaturated hydrocarbon x into a reaction system in which a catalyst exists in an introduction time of 3 seconds or more and 10 minutes or less. This is a step of obtaining b.
By introducing the first gas that is a mixed gas of the saturated hydrocarbon a and the unsaturated hydrocarbon x, the saturated gas is saturated as compared with the case where the gas containing only the saturated hydrocarbon a or the gas containing only the unsaturated hydrocarbon x is introduced. The collision probability between the hydrocarbon a and the unsaturated hydrocarbon x can be improved. Further, the gas containing the saturated hydrocarbon a and the unsaturated hydrocarbon x is advantageous from the viewpoint that it does not require purification or does not require strict purification and can be used as a raw material.

  In the first gas, the molar fraction of the saturated hydrocarbon a is 0.05 or more and 0.99 or less. From the viewpoint of efficiently activating the saturated hydrocarbon a with a catalyst, the molar fraction of the saturated hydrocarbon a is preferably 0.2 or more, more preferably 0.3 or more, and most preferably 0.5 or more. . Moreover, 0.9 or less is preferable, 0.8 or less is more preferable, and 0.7 or less is more preferable from a viewpoint of the refinement | purification cost of the saturated hydrocarbon a to introduce | transducing, and a viewpoint of raising the density | concentration of unsaturated hydrocarbon x.

In the first gas, the molar fraction of unsaturated hydrocarbon x is 0.01 or more and 0.95 or less. From the viewpoint of efficiently adsorbing the unsaturated hydrocarbon x to the catalyst, the molar fraction of the unsaturated hydrocarbon x is preferably 0.02 or more, more preferably 0.05 or more, and most preferably 0.1 or more. It is. Further, from the viewpoint of suppressing the covering of the catalyst active sites with the unsaturated hydrocarbon x and from the viewpoint of increasing the concentration of the saturated hydrocarbon a, 0.8 or less is preferable, 0.7 or less is more preferable, and 0.6 or less Is more preferable, and 0.5 or less is most preferable.
The molar ratio of hydrogen in the first gas is preferably 1 or less with respect to the sum of the saturated hydrocarbon a and the unsaturated hydrocarbon x. From the viewpoint that hydrogen is a high-energy substance with respect to the saturated hydrocarbon a and the unsaturated hydrocarbon x, the molar ratio of hydrogen is preferably 0.6 or less, and more preferably 0.3 or less.

  The introduction time of the first gas in step A is 3 seconds or more and 10 minutes or less. From the viewpoint of ease of switching from the process B, the process β and the other processes to the process A, or from the process A to the process B, the process α, and other processes, the saturated hydrocarbon a and the unsaturated carbonization From the viewpoint of increasing the amount of reaction with hydrogen x, it is preferably 3 seconds or longer, more preferably 5 seconds or longer, and even more preferably 11 seconds or longer. Also, from the viewpoint of enhancing the effects of processes other than process A, such as process B, and from the viewpoint of reducing the amount of deposition on the saturated hydrocarbon a and / or unsaturated hydrocarbon catalyst in process A, 300 seconds or less is more Preferably, it is 240 seconds or less, more preferably 120 seconds or less, and most preferably 60 seconds or less.

(Process B)
Step B is a step of introducing a second gas containing hydrogen having a molar fraction of 0.02 or more and 1 or less into the reaction system of Step A with an introduction time of 1 second or more and 5 minutes or less. is there. The hydrogen introduced in Step B promotes the desorption of the saturated hydrocarbon a and unsaturated hydrocarbon x adsorbed on the catalyst, or hydrogenates the hydrocarbon dehydrogenated species to regenerate the catalyst activity. The effect is speculated. Moreover, the effect of the hydrocarbon b production | generation by condensation of the saturated hydrocarbon a produced | generated on the catalyst and / or the dehydrogenation seed | species of the saturated hydrocarbon a is also estimated.

  The second gas may include a gas other than hydrogen. Examples of the gas other than hydrogen include water vapor, oxygen, inert gas such as nitrogen and argon, and the like. Among these, an inert gas such as nitrogen or argon is preferable from the viewpoint that a hydrogen dilution gas for reducing the residual amount of hydrogen in the step A is preferable and that the aggregation of the catalyst due to the reaction between hydrogen and the catalyst is suppressed.

  From the viewpoint of promoting the desorption of the saturated hydrocarbon a and the unsaturated hydrocarbon x adsorbed on the catalyst and / or promoting the effect of hydrogenating the hydrocarbon dehydrogenated species, the molar fraction of hydrogen is preferably 0.00. 05 or more, more preferably 0.1 or more, still more preferably 0.5 or more. In addition, from the viewpoint of the cost of hydrogen to be introduced, and from the viewpoint of suppressing the reduction of unsaturated bonds of unsaturated hydrocarbons produced by the reaction between the carbon compound deposited on the catalyst and hydrogen, 0.9 or less is 0.9 or less. Preferably, 0.8 or less is more preferable, and 0.7 or less is more preferable.

  The introduction time of the second gas in the process B is 1 second or more and 5 minutes or less. From the viewpoint of ease of switching from step A, step α and other steps to step B, or from step B to step β, step A, and other steps, introduction of hydrogen and carbonization on the catalyst From the viewpoint of being advantageous for desorption of hydrogen adsorbing species, it is preferably 3 seconds or longer, more preferably 5 seconds or longer, and even more preferably 11 seconds or longer. Moreover, since it will distribute | circulate without reacting from the viewpoint which raises the effect of processes other than process B, such as process A, or excess hydrogen in process B, in order to improve reaction efficiency, From the viewpoint that the shorter introduction is advantageous, it is preferably 3 minutes or less, more preferably 90 seconds or less, further preferably 45 seconds or less, and most preferably 30 seconds or less.

(Process α)
The process α is a process performed after the process A and before the process B. Step α includes an unsaturated hydrocarbon x having a mole fraction smaller than or equal to 0.01 and smaller than a mole fraction of unsaturated hydrocarbon x contained in the first gas, and a mole fraction not smaller than 0.01 and not greater than 1. This is a step of introducing a third gas containing an inert gas into the reaction system with an introduction time of 1 second or more and 90 seconds or less.
Reaction in which unsaturated hydrocarbon x introduced in step A and hydrogen introduced in step B react to form hydrocarbon b (for example, when unsaturated hydrocarbon x is ethylene and saturated hydrocarbon b is ethane, Equation 18) is the reverse reaction of step Y (for example, Equation 2), and from the viewpoint of energy efficiency, it is desirable that this reaction amount be small.
In step α, by introducing a gas having a lower molar fraction of unsaturated hydrocarbon x than in step A, hydrogenation reaction to unsaturated hydrocarbon x by hydrogen introduction in subsequent step B (for example, the formula Since step 18) can be reduced, step α is preferably performed.

The inert gas in the third gas is a gas that does not react with the saturated hydrocarbon a and the unsaturated hydrocarbon x under the reaction conditions carried out in the step α. For example, nitrogen, helium, argon, water vapor, etc. Is mentioned.
The molar fraction of the inert gas in the third gas is preferably 0.1 or more, more preferably 0.5 or more, from the viewpoint of efficiently reducing the molar fraction of the unsaturated hydrocarbon x in the reactor. preferable. On the other hand, from the viewpoint of the purification cost of the inert gas, 0.99 or less is more preferable, and 0.95 or less is more preferable.

  From the viewpoint of reducing the amount of reaction between the unsaturated hydrocarbon x and the hydrogen introduced in Step B, the molar fraction of the unsaturated hydrocarbon x in the third gas is the unsaturated hydrocarbon contained in the first gas. The molar fraction is preferably 0.03 or less smaller than x, preferably 0.05 or smaller, more preferably 0.1 or smaller, and most preferably 0.2 or smaller.

  The molar fraction of unsaturated hydrocarbon x contained in the third gas is preferably 0.0001 or more and 0.8 or less. From the viewpoint of the purification cost of the third gas, 0.0005 or more is preferable, 0.001 or more is more preferable, and 0.005 or more is more preferable. From the viewpoint of increasing the effect of reducing the mole fraction of unsaturated hydrocarbon as described above, 0.6 or less is preferable, 0.3 or less is more preferable, and 0.1 or less is more preferable.

  The molar ratio of unsaturated hydrocarbon x to inert gas (unsaturated hydrocarbon x / inert gas) contained in the third gas is preferably 0.0001 or more and 0.8 or less. From the viewpoint of the purification cost of the third gas, 0.0005 or more is preferable, 0.001 or more is more preferable, and 0.005 or more is more preferable. From the viewpoint of increasing the effect of reducing the mole fraction of unsaturated hydrocarbon x as described above, 0.5 or less is preferable, 0.2 or less is more preferable, and 0.1 or less is more preferable.

  The introduction time of the third gas in the process α is such that the reaction system is changed to the process α and other processes, or from the viewpoint of simplicity of gas introduction switching from the process α to the process B and other processes. From the viewpoint of preferably replacing with a gas having a lower molar fraction of unsaturated hydrocarbon x, 5 seconds or more is preferable, 8 seconds or more is more preferable, 10 seconds or more is further preferable, and 20 seconds or more is most preferable. Further, from the viewpoint of shortening the total reaction time, it is preferably 70 seconds or shorter, more preferably 60 seconds or shorter, further preferably 50 seconds or shorter, and most preferably 35 seconds or shorter.

(Process β)
Step β is a step performed after step B. Step β is an unsaturated hydrocarbon x having a mole fraction smaller than or equal to 0.01 than the mole fraction of unsaturated hydrocarbon x contained in the first gas, and a mole fraction of 0.01 or more and 1 or less. A fourth gas containing an inert gas is introduced into the reaction system in an introduction time of 1 second or more and 90 seconds or less. As will be described later, the process β is preferably performed before the process A when the process A is performed again after the process B.
The reaction (eg, Formula 18) in which the unsaturated hydrocarbon x introduced in Step A and the hydrogen introduced in Step B react to form hydrocarbon b is the reverse reaction of Step Y (eg, Formula 2). In view of energy efficiency, it is desirable that this reaction amount be small.
In step β, by introducing a gas having a lower molar fraction of unsaturated hydrocarbon x than in step A, hydrogenation reaction to unsaturated hydrocarbon x by introduction of hydrogen in subsequent step A (for example, the formula Since step 18) can be reduced, step β is preferably performed.

The inert gas in the fourth gas is a gas that does not react with the saturated hydrocarbon a and the unsaturated hydrocarbon x under the reaction conditions performed in step β. For example, nitrogen, helium, argon, water vapor Etc.
The molar fraction of the inert gas in the fourth gas is preferably 0.01 or more and 1 or less, more preferably 0.1 or more, and further preferably 0.5 or more. On the other hand, from the viewpoint of the purification cost of the inert gas, 0.99 or less is more preferable, and 0.95 or less is more preferable.

  The molar fraction of unsaturated hydrocarbon x in the fourth gas is 0.01 or more smaller than the unsaturated hydrocarbon x contained in the first gas. From the viewpoint of reducing the amount of reaction between the unsaturated hydrocarbon x and the hydrogen introduced in the step B, the molar fraction of the unsaturated hydrocarbon x is higher than that of the unsaturated hydrocarbon x contained in the first gas. Is preferably 0.03 or less, preferably 0.05 or more, more preferably 0.1 or more, and most preferably 0.2 or more.

  The molar fraction of unsaturated hydrocarbon x contained in the fourth gas is preferably 0.0001 or more and 0.8 or less. From the viewpoint of the purification cost of the fourth gas, 0.0005 or more is preferable, 0.001 or more is more preferable, and 0.005 or more is more preferable. From the viewpoint of increasing the effect of reducing the mole fraction of unsaturated hydrocarbon as described above, 0.6 or less is preferable, 0.3 or less is more preferable, and 0.1 or less is more preferable.

  The molar ratio of unsaturated hydrocarbon x and inert gas (unsaturated hydrocarbon x / inert gas) contained in the fourth gas is preferably 0.0001 or more and 0.8 or less. From the viewpoint of the purification cost of the third gas, 0.0005 or more is preferable, 0.001 or more is more preferable, and 0.005 or more is more preferable. From the viewpoint of increasing the effect of reducing the mole fraction of unsaturated hydrocarbon as described above, 0.5 or less is preferable, 0.2 or less is more preferable, and 0.1 or less is more preferable.

  The introduction time of the fourth gas in step β is preferably 1 second or longer and 90 seconds or shorter. From the viewpoint of ease of switching from the process B and other processes to the process β or from the process β to the process A and other processes, and a gas having a lower molar fraction of the unsaturated hydrocarbon x Is preferably 5 seconds or longer, more preferably 8 seconds or longer, further preferably 10 seconds or longer, and most preferably 20 seconds or longer. Further, from the viewpoint of shortening the total reaction time, it is preferably 70 seconds or shorter, more preferably 60 seconds or shorter, further preferably 50 seconds or shorter, and most preferably 35 seconds or shorter.

As for the production of the hydrocarbon b in the process X including the process A and the process B, the mechanism generated in the process A and the mechanism generated in the process B are estimated as described above. In the step A, for example, as in the reaction of the above formula 1, the hydrogen generated by the condensation of the saturated hydrocarbon a is received by the unsaturated hydrocarbon x as a hydrogen acceptor, thereby generating a bimolecular hydrocarbon b. Is given as an example. In addition, a mechanism in which hydrocarbon b is generated by unsaturated hydrocarbon x acting as a hydrogen acceptor with respect to hydrogen generated by other reactions that occur simultaneously is also speculated. For example, a reaction (for example, Equation 19) that generates an unsaturated hydrocarbon having a carbon number larger than that of the unsaturated hydrocarbon x, accompanied by formation of a carbon-carbon bond between the saturated hydrocarbon a and the unsaturated hydrocarbon x is Although it is useful from the viewpoint of increasing the number of carbon atoms in the raw material hydrocarbon, for example, since Equation 19 has an endothermic reaction and the standard production entropy difference is negative, thermodynamic restrictions are large. However, by reacting the hydrogen active species and / or hydrogen molecules generated in Formula 19 with unsaturated hydrocarbon x as a hydrogen acceptor to generate hydrocarbon b together (for example, Formula 20), unsaturated hydrocarbons are produced. The reaction for producing unsaturated hydrocarbons having a carbon number greater than x can be an exothermic reaction. For example, C ₂ H ₆ produced in Equation 20 is combined with a dehydrogenation reaction (Equation 2) in which the standard production entropy difference due to Step Y is positive, so that the total reaction is propylene production from methane and ethylene (Equation 20) It can be. That is, according to the present embodiment, the reaction of Equation 19 is divided into Equation 20 and Equation 2 that are easier to proceed, so that a product can be obtained with less thermodynamic constraints. On the other hand, in step B, the reaction between the condensed species of the dehydrogenated saturated hydrocarbon a species (for example, CH ₂ ^* ) generated on the catalyst by hydrogen introduced in the catalyst (for example, Formula 21), or on the catalyst The mechanism of ethane generation by hydrogenation reaction (for example, Formula 22) to the adsorbed unsaturated hydrocarbon x active species is presumed.
CH ₄ + C ₂ H ₄ → C ₃ H ₆ + H ₂ (Formula 19)
CH ₄ + 2C ₂ H ₄ → C ₂ H ₆ + C ₃ H ₆ (Formula 20)
2CH ₂ ^* + H ₂ → C ₂ H ₆ (Formula 21)
C ₂ H ₄ + H ₂ → C ₂ H ₆ (Formula 22)

  In the process A of the present embodiment, by reacting the mixed gas of the saturated hydrocarbon a and the unsaturated hydrocarbon x, the gas of only the saturated hydrocarbon a and the gas of the unsaturated hydrocarbon x are switched and reacted. Compared to the case, the collision probability between the hydrogen active species derived from the saturated hydrocarbon a and the unsaturated hydrocarbon x is improved, and it is presumed that this is advantageous for the reaction of Formula 1, for example. On the other hand, since it is estimated that the unsaturated hydrocarbon x has a stronger adsorption power to the catalyst than the saturated hydrocarbon a, more unsaturated hydrocarbon x may be adsorbed on the catalyst with the passage of time in step A. Conceivable. Therefore, it is presumed that it is important to perform the process B along with the process A under appropriate conditions.

  The process A and the process B can be repeated a plurality of times. From the viewpoint that hydrocarbon b can be produced by desorbing the condensed adsorbing species of saturated hydrocarbon a on the catalyst produced in step A, step B is preferably performed after step A. From the viewpoint of being advantageous for the productivity of hydrocarbon b, Step A and Step B are preferably repeated twice or more, more preferably 4 times or more, and even more preferably 8 times or more.

  After the step A, the step B is performed, and at least a part of the unsaturated hydrocarbon x and / or hydrogen produced in the step B is used as the unsaturated hydrocarbon x and / or the hydrogen in the step X. It is preferable to repeat the process to be used from the viewpoint of increasing the carbon number of the saturated hydrocarbon a as a raw material.

  In the process X, the switching operation between the process A, the process B, the process α, the process β, and other processes is performed in a reaction mode in which the catalyst moves in the reaction system, such as a fluidized bed, a moving bed, and a simulated moving bed. There is a region in the reaction system that is a component composition of each gas such as the first gas, the second gas, the third gas, and the fourth gas, and the catalyst stays in that region for a predetermined time. Thus, each of the steps can be performed. In this case, the time required for each step means the average residence time of the catalyst in that region in the reaction step.

<Process Y>
Step Y of the present embodiment is a step of producing unsaturated hydrocarbon x from hydrocarbon b. The reaction in step Y can be a dehydrogenation reaction from hydrocarbon b.

The gas introduced into the reaction system in step Y is composed of hydrocarbon b and a gas other than hydrocarbon b.
Here, examples of the gas other than hydrocarbon b include hydrocarbons such as saturated hydrocarbon a and unsaturated hydrocarbon x, hydrogen, water vapor, oxygen, inert gases such as nitrogen and argon, and the like. Among them, oxygen and water vapor are preferable for promoting dehydrogenation for the production of unsaturated hydrocarbon x.
The reaction conditions in step Y, for example, the conditions for introducing the raw material, temperature, pressure, etc. can be stationary or unsteady. As for the introduction conditions of the gas to be introduced into the reaction system in the step Y, it is preferable to introduce it constantly from the viewpoint of simplicity of the process. Moreover, it is preferable to set it as unsteady from a viewpoint which can produce | generate unsaturated hydrocarbon x more than an equilibrium yield which can suppress activity fall, a reaction promotion, etc. comparatively easily.

  In step Y, the molar fraction of hydrocarbon b introduced into the reactor is preferably 0.0001 or more and 0.999 or less, and the higher the concentration of the raw material to be introduced, the more the unsaturated hydrocarbon x is produced. From an advantageous viewpoint, 0.001 or more is preferable, 0.1 or more is more preferable, 0.2 or more is further preferable, and 0.4 or more is most preferable. Moreover, from the viewpoint of the purification cost of hydrocarbon b, 0.9 or less is preferable, 0.8 or less is more preferable, 0.7 or less is more preferable, and 0.6 or less is most preferable.

  In step Y, a catalyst may or may not be used, for example, the catalyst may or may not be present in the reactor. From the viewpoint of reducing the activation energy of the target reaction, it is preferable to use a catalyst and to have a catalyst in the reactor. Moreover, it is preferable not to use a catalyst from a viewpoint which does not have the possibility of sintering to a reactor of a catalyst, a viewpoint which simplifies a process, and a viewpoint which does not reduce the activation energy of a side reaction.

  In the process Y, the total volume flow rate of the gas to be introduced is preferably 50 to 10000000000000 L / h, more preferably 100 to 5000000000000 L / h, and further preferably 500 to 1000000000000 L / h per 1 L of the reactor volume.

  In the case of the reactor in which the catalyst is fixed in the process Y, the ratio of the average diameter (D) of the catalyst part in the direction perpendicular to the raw material flow path direction to the catalyst part length (L) in the raw material flow path direction, L / D is 0.0000001 or more and 1,000,000 or less are preferable, and 0.0001 or more and 1000000 or less are more preferable.

  In step Y, the reaction temperature is, for example, 300 ° C. or higher and 1300 ° C. or lower. 400 degreeC or more is preferable from a viewpoint of reaction rate, 500 degreeC or more is more preferable, 600 degreeC or more is further more preferable, and 700 degreeC or more is the most preferable. Further, from the viewpoint of simplicity of the reactor, suppression of side reactions, and prevention of sintering of the catalyst, 1300 ° C. or lower is preferable, 1300 ° C. or lower is more preferable, 1200 ° C. or lower is further preferable, and 1100 ° C. or lower is preferable. Is most preferred. The reaction temperature here refers to the temperature in the reactor.

  In step Y, the reaction pressure is, for example, not less than atmospheric pressure and not more than 50 MPa. From the viewpoint of not requiring energy for implementing the pressure condition, the pressure is preferably 30 MPa or less, more preferably 20 MPa, and even more preferably 10 MPa or less, as the pressure is lower. When using a hydrocarbon that liquefies in the pressure range, the pressure is preferably less than the liquefaction pressure. The reaction pressure here refers to the pressure in the reactor.

  Between the step X and the step Y, steps such as purification and storage of the gas after the reaction obtained in the step X and / or the step Y by separation of a raw material and a product can be included. From the viewpoint of gas purification cost, it is preferable to use all or part of the gas containing hydrocarbon b produced in Step X for part or all of the raw material of Step Y without purification.

  Part or all of the unsaturated hydrocarbon x obtained in the step Y is preferably used as the unsaturated hydrocarbon x in the step X. Moreover, it is preferable to use part or all of the hydrogen obtained in the step Y as hydrogen in the step X.

  Until the gas containing unsaturated hydrocarbon x and / or hydrogen obtained in the step Y is used as a raw material in the step X after the step Y, steps such as storage, separation, and purification can be included. From the viewpoint of gas purification cost, it is preferable to use all or part of the gas containing the unsaturated hydrocarbon x and hydrogen molecule produced in Step Y for part or all of the raw material of Step X without purification. .

  After the step X, the step Y can be performed. Further, after the step Y, the step X can be performed. From the viewpoint that unsaturated hydrocarbon x and hydrogen molecules can be produced from the hydrocarbon b produced in the step X, the step Y is preferably performed after the step X. Moreover, it is preferable to perform the said process X after the said process Y from a viewpoint which can manufacture the hydrocarbon b from the unsaturated hydrocarbon x.

  Step X and Step Y can be performed in a batch-type and / or flow-type reactor. A viewpoint that does not require replacement of the catalyst during the transition from the process X to the process Y, and a viewpoint that does not require time and energy for changing the reactor conditions when the reaction conditions of the process X and the process Y are different. From the viewpoint of easy temperature control such as heat removal, the step X and the step Y are preferably flow reactors.

  The process X and the process Y can be repeated a plurality of times. In particular, after the step X, the step Y is performed, and at least a part of the unsaturated hydrocarbon x and / or hydrogen produced in the step Y is used as the unsaturated hydrocarbon x in the step X, and / or It is preferable to repeat the step of using as hydrogen from the viewpoint of increasing the number of carbon atoms of the saturated hydrocarbon a as a raw material. The number of repetitions of the step X and the step Y is preferably 2 or more from the viewpoint that it is advantageous by increasing the number of carbon atoms of the raw material saturated hydrocarbon a.

  From the viewpoint that shale gas, natural gas, or the like can be directly used as a raw material, in the step X, it is preferable that the molar fraction of hydrogen contained in the raw material gas of the step X performed first is less than 0.0001.

  From the viewpoint that the gas after dehydrogenation treatment, such as shale gas or natural gas, can be directly used as a raw material, the mole fraction of hydrogen contained in the raw material gas of the first step X in the step X is 0. It is preferable that it is 0.0001 or more.

  From the viewpoint that the gas produced by performing the process Y after the process X can be directly used as the raw material, the molar fraction of hydrogen contained in the raw material gas of the process X performed after the second time in the process X is 0.0001 or more. It is preferable that

According to the method of the present embodiment, in the condensation reaction of saturated hydrocarbons, which involves generation of a compound having higher atomic efficiency and / or higher chemical value than water generation, the reaction involving hydrogen generation. Compared to unsaturated hydrocarbon production using saturated hydrocarbons and oxygen as raw materials, ethylene oxide, CO and CO _{2 and} other by-products are reduced compared to the production of unsaturated hydrocarbons using saturated hydrocarbons and oxygen as raw materials. It is possible to provide a method that does not require strict control of the concentration of the introduced raw material for safety.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
The synthesis was performed under the following conditions, and the production activity and production rate of unsaturated hydrocarbons and hydrogen were evaluated.
In addition, the molar fraction, production | generation rate, and production | generation activity of each component were measured as follows.

1. Molar fraction The hydrocarbon and hydrogen mole fractions were evaluated by gas chromatography (GC). The conditions are as follows.
(Online GC)
[apparatus]
490GC (manufactured by Agilent)
[Column types and conditions]
・ CP-Sil5 (manufactured by Agilent)
Temperature: 40 ° C., carrier gas: He (0.55 MPa)
Molsive 5A PLOT (manufactured by Agilent)
Temperature: 100 ° C., carrier gas: Ar (0.55 MPa)
The temperature was measured under steady conditions.

2. Production Activity In the process X of this example and the comparative example, the production activity of the hydrocarbon b and the unsaturated hydrocarbon y was calculated from the following formula. The reaction time was 20 minutes.
The amount of the produced saturated hydrocarbon b, the amount of unsaturated hydrocarbon y, and the amount of unreacted hydrogen were determined by the online GC, and the amount of introduced gas was controlled by a mass flow meter.
[Production activity (mol mol ⁻¹ h ⁻¹ )] = ([Production hydrocarbon amount (mol)] / [Reaction time (h)]) / [Catalytic activity species amount (mol)]
The amount of catalytically active species was calculated using the supported metal species as the catalytically active species.

3. Production rate In step Y of each example and comparative example, the production rate of unsaturated hydrocarbon x was calculated from the following equation. The production amount was determined by the online GC. The reaction time was 20 minutes.
[Production rate (mol h ⁻¹ )] = [Production amount (mol)] / [Reaction time (h)]
The gas production rate of the unsaturated hydrocarbon x in the process Y was determined by subtracting the amount of the unsaturated hydrocarbon x contained after the reaction from the amount of the unsaturated hydrocarbon x of the raw material to be introduced.

4). Deactivation ratio In step X of each example and comparative example, the deactivation ratio was calculated from the following equation.
[Deactivation ratio (%)] = ([Production activity 5 minutes after reaction start (mol mol ⁻¹ h ⁻¹ )] − [Activity 20 minutes after reaction start (mol mol ⁻¹ h ⁻¹ )]) * 100 / [activity 5 minutes after starting the reaction (mol mol ⁻¹ h ⁻¹ )]
Therefore, a smaller deactivation ratio is desirable because there is less deactivation of the hydrocarbon production activity.

5. Ethane yield The yield of ethane (hydrocarbon b), the amount of hydrogen consumed, and the amount of introduced hydrocarbon were calculated from the following equations.
Since it is desirable in the present application that the amount of the produced hydrocarbon b excluding the hydrocarbon b produced by the reaction of the unsaturated hydrocarbon x and hydrogen among the saturated hydrocarbon b produced in the step X is desirable in the present application, the following The yield of hydrocarbon b determined by the equation was used as an index of the examples.
The amount of produced hydrocarbon b and the amount of unreacted hydrogen were determined by online GC, and the amount of introduced gas (hydrogen, saturated hydrocarbon a, unsaturated hydrocarbon x) was calculated by controlling with a mass flow meter.
[Hydrocarbon b yield (%)] = ([Amount of produced hydrocarbon b (mol)] − [Amount of consumed hydrogen (mol)]) × 100 / (Amount of introduced hydrocarbon (mol))
[Hydrogen consumption (mol)] = [Amount of introduced hydrogen (mol)] − [Amount of unreacted hydrogen (mol)]
[Introduced hydrocarbon amount (mol)] = [Introduced saturated hydrocarbon a amount (mol)] + [Introduced unsaturated hydrocarbon x amount (mol)]

(Amount of metal element in catalyst)
20 mg of the catalyst was sampled, and a mixed solution of 3 mL of ultrapure water, 2 mL of 30 vol% hydrochloric acid, and 3 mL of 98 vol% sulfuric acid was mixed in a Teflon (registered trademark) container and kept at 1000 W and 240 ° C. for 30 minutes. The catalyst was dissolved in the solution, and the solution was evaluated by the following ICP. The concentration of each element in the cleaning solution was obtained based on a calibration curve prepared by three-point calibration.
(ICP device)
SP352UV-DD (manufactured by Seiko Instruments Inc.)
(conditions)
High frequency power: 1.2kW
Carrier gas: Ar

<Example 1>
A catalyst was prepared by impregnating a titanium oxide carrier with an aqueous solution in which a metal salt was dissolved as follows. After suspending 10.0 g of rutile-type titanium oxide in 100 mL of 25 mmol / L chloroplatinic acid aqueous solution, the platinum species was supported by evaporating to dryness. Thereafter, a powder fired in the air at 500 ° C. was obtained. A pellet was obtained by applying a pressure of 20 MPa to this powder, and after pulverizing, the powder was classified to 0.25 to 0.50 mm to obtain a catalyst. The amount of platinum supported on this catalyst was 5 wt%.

(Process X)
A distribution system reactor in which 0.5 g of a catalyst was sandwiched between quartz wool in a central part of a SUS tube (outer diameter: 1/4 inch, wall thickness: 0.5 mm) was used.
At 400 ° C, under a hydrogen flow condition of 20 mL / min, a reduction treatment for 1 hour was performed as a pretreatment of the catalyst. After purging the reaction tube with Ar, the reaction temperature was 200 ° C, CH ₄ and C ₂ H ₄ A mixed gas of H ₂ and H ₂ was circulated for 30 minutes. The distribution conditions at this time were CH ₄ : 50 mL / min, C ₂ H ₄ : 5 mL / min, and the molar fraction of H ₂ : 0.001 or less.
The ethane production activity in Step X was 2.1 mol mol ⁻¹ h ⁻¹ . Moreover, CO, formation of carbon oxides such as CO ₂ was not confirmed.

<Example 2>
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 300 ° C. Formation of carbon oxides such as CO and CO ₂ was not confirmed.

<Example 3>
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was 400 ° C. Formation of carbon oxides such as CO and CO ₂ was not confirmed.

  In Examples 4 to 6, the gas after the reaction (after Step X) performed in Examples 1 to 3 was reacted in the following Step Y, respectively.

<Example 4>
As step Y, the mixed gas obtained in the downstream of the reactor of step X in Example 1 is circulated through a quartz tube (outer diameter: 6 mm, wall thickness: 1 mm) having no catalyst at a reaction temperature of 850 ° C. The reaction rate was stored, the gas after the reaction was stored in an aluminum gas bag, and the components were evaluated by gas chromatography to determine the production rate. As a result, the ethylene production rate in Step Y was 1.9 mol h ⁻¹ . Formation of carbon oxides such as CO and CO ₂ was not confirmed.

<Example 5>
The reaction was performed in the same manner except that the gas reacted in Step Y of Example 4 was a mixed gas obtained in the downstream of the reactor of Step X in Example 2. As a result, the ethylene production rate was 2.6 mol h ⁻¹ . Formation of carbon oxides such as CO and CO ₂ was not confirmed.

<Example 6>
The reaction was performed in the same manner except that the gas reacted in Step Y of Example 4 was a mixed gas obtained downstream of the reactor in Step X in Example 3. As a result, the ethylene production rate was 2.4 mol h ⁻¹ . Formation of carbon oxides such as CO and CO ₂ was not confirmed.

<Comparative Example 1>
The reaction was performed in the same manner as in Example 3 except that the reaction gas was a gas containing only CH ₄ (CH ₄ : 10 mL / min). The ethane production activity was 100 mmol mol ⁻¹ h ⁻¹ or less.

  About each Example, the evaluation result of the ethane production | generation activity in the process X and the ethylene production | generation activity in the process Y is shown in Table 1 with reaction conditions.

For Examples 1 to 3, by satisfying the embodiment of the present application, the saturated hydrocarbon a (CH ₄ ) and the unsaturated hydrocarbon x (C ₂ H ₄ ) are used as raw materials, despite the low temperature conditions, It was shown that hydrocarbon b (C ₂ H ₆ ) can be produced without producing carbon oxides such as CO and CO ₂ .

  Comparing the results of the reactions performed under different conditions except for the reaction temperatures of Examples 1 to 3, when the reaction temperature was increased from 200 ° C. to 300 ° C., the production activity of ethane (hydrocarbon b) was improved, but from 300 ° C. By setting the temperature to 400 ° C., the production activity of ethane (hydrocarbon b) decreased. Although the reaction rate increases as the temperature increases, the equilibrium yield is more advantageous as the temperature decreases. For example, the equilibrium yields at 750 ° C., 450 ° C., 400 ° C., 350 ° C., and 300 ° C. in this reaction (Formula 1) are about 0.06%, about 2%, about 5%, about 13%, respectively. From the viewpoint of the equilibrium yield, the reaction under a lower temperature condition is desirable. As described above, from the viewpoints of the results of Examples 1 to 3 and the equilibrium yield, it was shown that the reaction under the temperature condition of about 390 ° C. or less is more preferable in Step X.

  In Comparative Example 1, the ethane production activity when ethane was produced at 400 ° C. using only methane as the raw material without introducing ethylene into the raw material gas was significantly smaller than Examples 1-3. It can be seen that 3 is excellent in ethane production activity. Therefore, it was shown that satisfying the step X of the present embodiment is advantageous for the production of the hydrocarbon b using the saturated hydrocarbon a as a raw material.

  As shown in Examples 4 to 6, ethylene can be produced by reacting the gas produced in Examples 1 to 3 in Step Y, and unsaturated hydrocarbon x is produced from hydrocarbon b. It was shown that it can be generated. That is, following the process X, the process Y is performed to produce the unsaturated hydrocarbon x (ethylene) from the saturated hydrocarbon a (for example, methane) (formula 3). It was shown that the reaction can be produced by dividing into two reactions of (Equation 1) and (Equation 2), which have smaller thermodynamic constraints than the direct synthesis reaction. In particular, in the step Y of Examples 4 to 6, from the viewpoint that the unsaturated hydrocarbon x can be produced without using a catalyst, it is not necessary to cause sintering of the catalyst to the reactor at a high temperature, and the process can be simplified. It was shown that it can be done.

  In addition, it is shown that the faster the production activity and production rate of hydrocarbon b (ethane) in Step X, the faster the production rate of unsaturated hydrocarbon x in Step Y, and the production activity and production rate of hydrocarbon b. It was shown that the more the step X is, the more useful the production method for the production of the unsaturated hydrocarbon x using the saturated hydrocarbon a as a raw material.

In Examples 7 to 21, the saturated hydrocarbon a (CH ₄ ) was reacted with the unsaturated hydrocarbon x (C ₂ H ₄ ) using various catalysts.
<Example 7>
In the catalyst preparation of Example 1, the reaction was carried out in the same manner as in Example 1 except that the 25 mmol / L chloroplatinic acid aqueous solution was changed to a 25 mmol / L cobalt nitrate aqueous solution. When the supported cobalt species was assumed to be in a metal state, the supported amount was 2 wt%.

<Example 8>
The reaction was conducted in the same manner as in Example 7 except that the reaction temperature was 300 ° C.

<Example 9>
In the catalyst preparation of Example 1, the reaction was performed in the same manner except that the 25 mmol / L chloroplatinic acid aqueous solution was changed to a 25 mmol / L ruthenium chloride aqueous solution. Assuming that the supported ruthenium species was in a metallic state, the supported amount was 3 wt%.

<Example 10>
The reaction was conducted in the same manner as in Example 9 except that the reaction temperature was 300 ° C.

<Example 11>
In the catalyst preparation, the reaction was performed in the same manner as in Example 1 except that the 25 mmol / L chloroplatinic acid aqueous solution was changed to a 25 mmol / L palladium chloride aqueous solution. The supported palladium species was in a metallic state, and the supported amount was 3 wt%.

<Example 12>
The reaction was conducted in the same manner as in Example 11 except that the reaction temperature was 300 ° C.

<Example 13>
In the catalyst preparation, the reaction was performed in the same manner as in Example 1 except that the 25 mmol / L chloroplatinic acid aqueous solution was changed to a 25 mmol / L nickel nitrate aqueous solution. The supported nickel species was in a metallic state, and the supported amount was 2 wt%.

<Example 14>
The reaction was carried out in the same manner as in Example 1 except that the catalyst was zeolite (H-ZSM-5, Si / Al molar ratio = 24).

<Example 15>
The reaction was conducted in the same manner as in Example 14 except that the reaction temperature was 300 ° C.

<Example 16>
The reaction was carried out in the same manner as in Example 1 except that the catalyst was platinum-supported alumina (Pt metal support amount: 5 wt%).

  About each Example, the evaluation result of the production | generation activity of the ethane in the process X is shown in Table 2 with reaction conditions.

In Examples 17 to 21, Step X was performed using a catalyst in which a metal species other than Si and Al was introduced into zeolite, and ethane production activity was evaluated.
<Example 17>
The titanium oxide used in the preparation of the catalyst of Example 2 was zeolite (H-ZSM-5, Si / Al molar ratio = 24), and was the same as Example 2 except that the catalyst was not subjected to reduction treatment before the reaction. The reaction was performed. The amount of Pt supported in the catalyst was 5 wt% (Pt: converted as a metal state).

<Example 18>
The reaction was performed in the same manner as in Example 17 except that the Si / Al molar ratio of the zeolite used in preparing the catalyst of Example 17 was 1500. The amount of Pt supported in the catalyst was 5 wt% (Pt: converted as a metal state).

<Example 19>
During the catalyst preparation of Example 17, zeolite (H-ZSM-5, Si / Al molar ratio = 24) was stirred in 50 g, 49 mmol nickel nitrate aqueous solution for 2 hours, washed with suction filtration and ion-exchanged water, and then in the atmosphere. The reaction was conducted in the same manner as in Example 17 except that the catalyst was prepared by baking at 500 ° C. for 2 hours. The amount of Ni supported in the catalyst was 0.25 wt% (Ni: converted as a metal state).

<Example 20>
During the catalyst preparation of Example 17, zeolite (H-ZSM-5, Si / Al molar ratio = 24) was stirred in 50 g, 49 mmol zinc nitrate aqueous solution for 2 hours, washed with suction filtration and ion-exchanged water, and then in the atmosphere. The reaction was conducted in the same manner as in Example 17 except that the catalyst was prepared by baking at 500 ° C. for 2 hours. The amount of Zn supported in the catalyst was 1.2 wt% (Zn: converted as a metal state).

<Example 21>
During the catalyst preparation of Example 17, zeolite (H-ZSM-5, Si / Al molar ratio = 24) was stirred in 50 g, 49 mmol zinc nitrate aqueous solution for 2 hours, washed with suction filtration and ion-exchanged water, and then in the atmosphere. The reaction was carried out in the same manner as in Example 17 except that the catalyst was prepared by repeating the calcination for 2 hours at 500 ° C. and the stirring, washing and calcination operations three times. The amount of Cu supported in the catalyst was 2 wt% (Cu: converted as a metal state).

About each Example, the evaluation result of the production | generation activity of the ethane in the process X is shown in Table 3 with reaction conditions.

  From the results of Examples 17 to 21, it was shown that various catalysts and carriers can be applied to this reaction. It is shown that the zeolite catalyst of this embodiment is excellent in the production activity of saturated hydrocarbons. Particularly, the comparison between Examples 17 and 18 shows that the Si / Al ratio is preferably 1 or more and 1000 or less. It was. As the metal active species, Pt species, Ru species, Ni species, Pd species, and Co species are preferable, Pt species and Ni species are more preferable, and Pt is particularly preferable.

  In addition, when a zeolite catalyst was used, it was shown that this reaction has an excellent activity without requiring a reduction pretreatment. Not requiring pretreatment is useful for industrial applications.

  In Examples 22 to 26, reactions were carried out under various composition ratios of saturated hydrocarbons a and unsaturated hydrocarbons x of raw material gases and reaction pressures.

<Example 22>
Example 16 except that the reaction gas was a mixed gas of CH ₄ and C ₂ H ₄ (CH ₄ : 50 mL / min, C ₂ H ₄ : 25 mL / min, hydrogen molar fraction: 0.001 or less). The reaction was performed in the same manner.

<Example 23>
Example 16 except that the reaction gas was a mixed gas of CH ₄ and C ₂ H ₄ (CH ₄ : 50 mL / min, C ₂ H ₄ : 50 mL / min, molar fraction of hydrogen: 0.001 or less). The reaction was performed in the same manner.

<Example 24>
The reaction was conducted in the same manner as in Example 16 except that the reaction pressure was 0.4 MPa.

<Example 25>
The reaction was conducted in the same manner as in Example 16 except that the reaction pressure was 0.8 MPa.

  About each Example, the evaluation result of the production | generation activity of the ethane in the process X is shown in Table 4 with reaction conditions.

  In Step X, Examples 26 to 29 were studied under conditions for introducing a mixed gas containing hydrogen.

<Example 26>
Except that the mixed gas of the example was a mixed gas of CH ₄ (saturated hydrocarbon a): 36 mL / min, C ₂ H ₄ (unsaturated hydrocarbon x): 18 mL / min, H ₂ : 1 mL / min, The reaction was carried out in the same manner as in the examples.

<Example 27>
The reaction was performed in the same manner as in Example 1 except that the amount of H ₂ introduced into the raw material was 2.5 mL / min.

<Example 28>
The reaction was performed in the same manner as in Example 1 except that the amount of H ₂ introduced into the raw material was 5 mL / min.

<Example 29>
The reaction was performed in the same manner as in Example 1 except that the amount of H ₂ introduced into the raw material was 10 mL / min.

  About each Example, the evaluation result of the production | generation activity of the ethane in process X, 1-butene, and 2-butene is shown in Table 5 with reaction conditions.

  As shown in Table 5, when Example 23 was compared with Examples 26 to 29, the production activity of ethane, 1-butene, and 2-butene in Example 23 in which hydrogen was not introduced was introduced with hydrogen. Compared to Examples 26 to 29, each of the deactivation ratios was large. Therefore, it was shown that inclusion of hydrogen in the raw material gas is advantageous for the generation of hydrocarbon b and unsaturated hydrocarbon y.

  Furthermore, as shown in Examples 26 to 29, by changing the amount of hydrogen to be introduced in Step X, the production activity of ethane, 1-butene, and 2-butene, and the deactivation ratio of each, changed. In Examples 26 to 29, the production activity of ethane, 1-butene and 2-butene was improved by increasing the mole fraction of introduced hydrogen. Moreover, the deactivation ratio of ethane production | generation activity was all 0 of Examples 26-29, and big deactivation was not observed. The deactivation ratio of 1-butene and 2-butene formation activity tends to decrease particularly greatly when the molar fraction of hydrogen is 0.04 or more and the molar ratio of hydrogen / unsaturated hydrocarbon is 0.16 or more. However, the hydrogen concentration on the catalyst is sufficient to suppress deactivation and / or the reaction rate improvement effect using the heat of reaction due to the hydrogenation reaction of ethylene has become significant. It is presumed that this was improved and deactivation was suppressed. It is also speculated that the improvement in the ethane production activity due to the increase in the amount of hydrogen introduced was due to the increase in the amount of reaction heat used for the reaction of the butene production reaction from ethylene for the production of ethane accompanying the improvement in the butene production activity. As the amount of ethane generated in the process X increased, the ethylene production rate in the process Y tended to improve.

  In Examples 30 to 37, the reaction conditions of Step X were set to be unsteady, and in Examples to in particular, the reaction was carried out under the condition that hydrogen was introduced unsteadyly.

<Example 30>
The reaction was performed in the same manner as in Example 16 except that the introduction conditions of the raw material gas were changed to the following reaction steps.
The conditions for introducing the reaction gas were such that CH ₄ was allowed to flow at 50 mL / min (first gas) for 30 seconds, and then C ₂ H ₄ was allowed to flow at 50 mL / min (second gas) for 3 seconds. The reaction was carried out in the same manner as in Example 16 except for repeating. The mole fraction of hydrogen as a raw material gas phase component was 0.001 or less. As a result of the reaction, ethane generating activity of 1.9 mmol mol ⁻¹ h ⁻¹ was observed.

<Example 31>
The reaction was performed in the same manner as in Example 16 except that the introduction conditions of the raw material gas were changed to the following reaction steps.
A mixed gas (first gas) of CH ₄ : 50 mL / min and C ₂ H ₄ : 5 mL / min was circulated for 240 seconds (step A), and 500 mL / min of Ar (third gas) was circulated for 30 seconds ( Step α), a mixed gas (second gas) of H ₂ : 10 mL / min, Ar: 90 mL / min is circulated for 120 seconds (Step B), and Ar (fourth gas) of 500 mL / min is circulated for 30 seconds ( The operation of step β) was repeated 3 times.
The ethane yield in Step X was 1.3%.

<Example 32>
The reaction was performed in the same manner as in Example 16 except that the gas introduction time in each step described in Example 16 was changed as follows. Step A: 120 seconds, step α: 30 seconds, step B: 120 seconds, and step β: 30 seconds were repeated four times.

<Example 33>
The reaction was performed in the same manner as in Example 16 except that the gas introduction time in each step described in Example 16 was as follows. Step A: 30 seconds, step α: 30 seconds, step B: 15 seconds, step β: 30 seconds, and repeated 11 times.

<Example 34>
The reaction was performed in the same manner as in Example 16 except that the gas introduction time in each step described in Example 16 was as follows. Step A: 6 seconds, step α: 30 seconds, step B: 3 seconds, step β: 30 seconds, and repeated 17 times.

<Example 35>
The reaction was performed in the same manner as in Example 1 except that the gas introduction time in each step described in Example 16 was as follows, and the gas in Step B was a mixed gas of H ₂ : 15 mL / min and Ar: 85 mL / min. Went. Step A: 30 seconds, step α: 10 seconds, step B: 10 seconds, step β: 10 seconds, and repeated 20 times.

<Example 36>
The reaction was performed in the same manner as in Example 5 except that the gas introduction time in each step described in Example 35 was as follows. Step A: 12 seconds, step α: 6 seconds, step B: 6 seconds, and step β: 6 seconds were repeated 40 times.

<Example 37>
The reaction was performed in the same manner as in Example 33 except that the catalyst described in Example 33 was changed to Ru-supported TiO ₂ described in Example 10.

  About each Example, the evaluation result of an ethane yield is shown in Table 6 with reaction conditions.

Comparing Example 16 and Examples 31-36, in Example 31-36 in which Step A and Step B were performed together with Example 16 in which only Step A was performed, the ethane yield and ethylene production were It can be seen that the speed improvement is remarkably effective.
Further, even when Example 10 and Example 37 using Ru as a catalyst are compared, performing both Step A and Step B has a remarkable effect on improving the ethane yield and the rate of ethylene production. I understand that.

In the examples, the ethane yield in step X and the ethylene production rate in step Y varied depending on the conditions of step A, step B, step α, and step β. Comparing Examples 31 to 34, under the conditions where Step A is 6 seconds to 240 seconds and Step B is 3 seconds to 120 seconds, the ethane yield and the ethylene production rate are reduced by reducing the time of Step A and Step B. Improved. This is presumably because the amount of the saturated hydrocarbon a and / or unsaturated hydrocarbon b deposited on the catalyst in Step A could be reduced.
Further, by introducing a gas having a low molar fraction of unsaturated hydrocarbon x in step α and step β, hydrogenation reaction to unsaturated hydrocarbon x due to hydrogen introduction in the subsequent step can be reduced, Ethane yield and ethylene production rate can be improved. In particular, when Examples 33 to 36 were compared, the ethane yield and the ethylene production rate tended to decrease by shortening the time of step α and step β. This is because the step α and the step β are carried out for a longer time, so that the unsaturated hydrocarbon x or a gas having a lower mole fraction of hydrogen can be substituted, and the reaction between the unsaturated hydrocarbon x and hydrogen is suppressed. It is presumed that it was possible to do.

<Example 38>
(Process X)
The reaction was performed in the same manner as in Example 33 except that Ar described in Example 33 was changed to nitrogen.
As a result, the same ethane yield and ethylene production rate as in Example 33 were obtained.

  From Example 38, it was shown that gases other than Ar can be applied to the embodiment of the present application as the inert gas.

  Although the embodiment of the present invention has been described above, the present invention is not limited to this, and can be appropriately changed without departing from the spirit of the invention.

By using the method for producing hydrocarbons according to the present invention, hydrogen production in the condensation reaction of saturated hydrocarbons involving the production of compounds having higher atomic efficiency and / or higher chemical value than water production. Compared with the reaction involving NO, it does not require a high temperature for the reaction to proceed, and is more suitable than the production of unsaturated hydrocarbons using saturated hydrocarbons and oxygen as raw materials, such as ethylene oxide, CO and CO _2. It can be widely used as a method for producing hydrocarbons using saturated hydrocarbons as raw materials in which living organisms are reduced and strict control of the concentration of the introduced raw materials is not required for safety.

Claims (8)

  A saturated hydrocarbon production catalyst comprising at least one element selected from Group 4 to Group 13 elements other than Al and comprising zeolite having a Si / Al molar ratio of 1 or more and 1000 or less.   The saturated hydrocarbon production catalyst according to claim 1, wherein the saturated hydrocarbon produced using the saturated hydrocarbon production catalyst has 2 or more and 6 or less carbon atoms.   The saturated hydrocarbon production catalyst according to claim 1 or 2, wherein the saturated hydrocarbon produced using the saturated hydrocarbon production catalyst has 2 carbon atoms.   The saturated hydrocarbon production catalyst according to any one of claims 1 to 3, wherein the zeolite is MFI type.   The saturated carbonization according to any one of claims 1 to 4, wherein an element consisting of a group of Group 4 to Group 13 elements other than Al contained in the zeolite is 0.01 wt% or more and 50 wt% or less. Hydrogen production catalyst.   The saturated hydrocarbon production catalyst according to any one of claims 1 to 5, wherein the zeolite contains at least one of Group 8 to Group 10 elements.   The saturated hydrocarbon production catalyst according to any one of claims 1 to 6, wherein the zeolite contains at least one of Pt and Ni. A saturated hydrocarbon a having a mole fraction of 0.05 or more and 0.999 or less and having 1 to 6 carbon atoms;
A mixed gas containing an unsaturated hydrocarbon x having 2 to 12 carbon atoms and having a molar fraction of 0.001 or more and 0.95 or less, in the presence of a catalyst,
At least a step X of producing a hydrocarbon b having a carbon skeleton equal to the carbon skeleton of the unsaturated hydrocarbon x,
A method for producing a hydrocarbon, wherein the catalyst used in the step X is the catalyst according to any one of claims 1 to 7.