JP6426711B2 - Method for producing unsaturated hydrocarbon - Google Patents

Description

  The present invention relates to a process for producing unsaturated hydrocarbons by conducting a dehydrogenation reaction of hydrocarbons.

  Unsaturated hydrocarbons, in particular olefins and dienes, are very useful as base materials for various derivatives in the petrochemical industry. Representative lower olefins and dienes include propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and the like. These lower olefins and dienes are also known to be produced by dehydrogenating the corresponding paraffins and / or olefins, for example catalysts supported on chromium oxide on alumina support, alumina support or zinc aluminate It is known that such a catalyst having platinum supported on a spinel support is suitable for its production (Non-patent Document 1). Further, Patent Documents 1 to 9 disclose that a catalyst having platinum and zinc supported on a zeolite carrier exhibits high activity for a long time as compared with other catalyst systems.

  On the other hand, since the melting point of metallic zinc is as low as about 420 ° C. and it has a high vapor pressure, metallic dehydrogenation catalysts containing metallic zinc as an active component are metallic zinc under typical dehydrogenation reaction conditions requiring high temperature and low pressure. Continues to volatilize from the catalyst, resulting in irreversible deterioration of the catalyst.

  As a method of suppressing the volatilization of zinc from above the catalyst, for example, the main text of Patent Document 7 describes that the addition of a Group IVB element such as zirconium is effective. In Patent Document 10, a method in which gallium is added to a zeolite supporting zinc as a propane aromatization catalyst is used, and in Patent Document 11, a zeolite containing zinc as a lower hydrocarbon aromatization catalyst is used. There is disclosed a method of supplying carbon dioxide, steam, thiophene and the like together with a source gas. Further, Patent Document 12 discloses that the formation of zinc aluminate due to the reaction of the zinc component contained in the aromatization catalyst and alumina greatly contributes to the stabilization of zinc.

U.S. Pat. No. 4,962,266 U.S. Pat. No. 5,126,502 U.S. Pat. No. 5,208,201 U.S. Pat. No. 5,324,702 U.S. Patent No. 5,453,558 U.S. Patent No. 6,197,717 U.S. Patent No. 6,555,724 International Publication 2012/020743 JP 2012-026197 A U.S. Pat. No. 4,490,569 U.S. Pat. No. 4,849,568 JP 10-52646 A

Industrial Organic Chemicals, Third Edition, Wiley, page 214

  However, when the inventors of the present invention apply the zinc volatilization suppression technology found in the development of these aromatization catalysts to a dehydrogenation catalyst, the effects obtained are all small, or the activity is greatly reduced. It has been found that the above-mentioned zinc volatilization suppression technology is hardly satisfactory. Therefore, establishment of an effective zinc stabilization method applicable to a dehydrogenation catalyst is desired.

  Therefore, the present invention is a method of dehydrogenating hydrocarbons using a dehydrogenation catalyst to produce unsaturated hydrocarbons, and effectively suppressing the volatilization of zinc from the dehydrogenation catalyst over a long period of time An object of the present invention is to provide a method for stably producing unsaturated hydrocarbons, ie, olefins or dienes.

  As a result of intensive studies to solve the above problems, the present inventors contacted the raw material-containing gas with metallic zinc and / or zinc compound and then brought them into contact with a catalyst, or alternatively, used the raw material-containing gas containing zinc vapor as a catalyst. It has been found that the contact effectively suppresses the volatilization of zinc from the catalyst, and as a result, unsaturated hydrocarbons, that is, olefins and dienes can be stably produced over a long period of time.

  That is, one aspect of the present invention is to contact a hydrocarbon-containing feedstock-containing gas (1) with metallic zinc or zinc compound or both, and then with a dehydrogenation catalyst containing zinc as one of the active components. It is a method for producing unsaturated hydrocarbon (hereinafter also referred to as “production method (1)”) including the step of producing the unsaturated hydrocarbon by performing the dehydrogenation reaction of the hydrocarbon.

In another aspect of the present invention, the feed gas containing hydrocarbon (2) containing hydrocarbon and zinc vapor is contacted with a dehydrogenation catalyst containing zinc as one of the active components to carry out the dehydrogenation reaction of the hydrocarbon. It is a manufacturing method (it is also called the following "manufacturing method (2).") Of unsaturated hydrocarbon including the process of performing and manufacturing unsaturated hydrocarbon.
The raw material-containing gas (2) can be obtained by bringing the raw material-containing gas (1) into contact with metallic zinc or zinc compound or both of them.

It is preferable that the reaction temperature of the said dehydrogenation reaction is 300-800 degreeC, and the reaction pressure is 0.01-1 Mpa.
The partial pressure of zinc vapor contained in the raw material-containing gas (2) is equal to or less than the vapor pressure of zinc at the reaction temperature of the dehydrogenation reaction. As a source of zinc vapor, metallic zinc or zinc oxide or both are preferred.

The hydrocarbon which is a raw material is preferably at least one selected from propane, n-butane and isobutane, or n-butene.
In the production method (1), the raw material-containing gas (1) preferably further contains water vapor and / or hydrogen.
In the production method (2), the raw material-containing gas (2) preferably further contains water vapor and / or hydrogen.

  A preferred form of the dehydrogenation catalyst is a catalyst having a zeolite as a carrier and zinc and a Group VIIIA metal supported as active components. The amount of zinc contained in such a catalyst is preferably 0.01 to 15% by weight, based on 100% by weight of the total weight of the catalyst, and the amount of Group VIIIA metal corresponds to the weight of the total weight of the catalyst If it is 100% by weight, it is preferably 0.01 to 5% by weight. Further, platinum is preferable as the Group VIIIA metal.

  The zeolite is preferably silicalite or borosilicate, more preferably one having an MFI structure. A further preferable zeolite support is a silicate obtained by removing at least a part of boron atoms from MFI-type borosilicate, and the residual ratio of boron atoms in the silicate is 80% or less of the total amount of boron atoms in MFI-type borosilicate Some are particularly preferred.

  According to the present invention, the volatilization of zinc from the dehydrogenation catalyst can be effectively suppressed by a very simple method, and as a result, high activity of the dehydrogenation catalyst can be obtained over a long period of time, which is economically significant. It becomes possible to predominantly produce unsaturated hydrocarbons, ie olefins or dienes.

Propylene yield of the case where zinc oxide was packed on the upstream side of the gas flow in the reaction tube with respect to the catalyst layer (Example 1, plot by ○) and when not packed (comparative example 1, plot by ●) It is a figure which shows the difference in a time-dependent change.

Hereinafter, the present invention will be described in detail.
The method for producing unsaturated hydrocarbon according to the present invention (production method (1)) comprises contacting a raw material-containing gas (1) containing hydrocarbon with metallic zinc or zinc compound or both, and then one of the active components And C. contacting with a dehydrogenation catalyst containing zinc to carry out a dehydrogenation reaction of the hydrocarbon to produce an unsaturated hydrocarbon.

In another aspect of the present invention, the method for producing unsaturated hydrocarbon according to the present invention (production method (2)) comprises using a raw material-containing gas (2) containing hydrocarbon and zinc vapor as one of the active components And C. contacting with a dehydrogenation catalyst containing zinc to carry out a dehydrogenation reaction of the hydrocarbon to produce an unsaturated hydrocarbon.
The following description applies to both the production method (1) and the production method (2) unless otherwise noted.

  The reaction temperature in the dehydrogenation reaction is preferably in the range of 300 to 800 ° C, more preferably 400 to 700 ° C, and particularly preferably 450 to 650 ° C. When the reaction temperature is equal to or higher than the lower limit, unsaturated hydrocarbons are produced in a high yield in a single pass because hydrocarbons as a raw material are converted to unsaturated hydrocarbons at a high equilibrium conversion rate. In addition, when the reaction temperature is lower than the above upper limit value, the coking rate does not increase, and the catalyst activity deterioration can be suppressed.

  The reaction pressure is preferably in the range of 0.01 to 1 MPa, more preferably 0.01 to 0.5 MPa. The lower the reaction pressure, the higher the equilibrium conversion of the feedstock hydrocarbon and the greater the yield of unsaturated hydrocarbons in one pass.

Since the production method of the present invention is carried out in the gas phase, it is preferable to carry out the reaction in a continuous reactor. At this time, it is convenient and appropriate to express the amount of the catalyst used by weight hourly space velocity WHSV (the weight of catalyst and the feed weight of the raw material hydrocarbon). Although the range of WHSV in the present invention is not particularly limited, it is preferably 0.01 to 50 h ^-1 , more preferably 0.1 to 20 h ^-1 .

  The present invention is characterized in that, in the production method (2), a raw material-containing gas containing zinc vapor is brought into contact with a catalyst containing zinc as one of the active components. By contacting the catalyst with zinc vapor, the volatilization of zinc on the catalyst is suppressed, and as a result, the catalyst can exhibit stable performance over a long period of time. The partial pressure of zinc vapor contained in the raw material-containing gas in contact with the catalyst is below the vapor pressure of zinc at the reaction temperature, and the concentration (based on volume) of zinc vapor contained in the raw material-containing gas is greater than 0% Preferably it is 0.01% or more, More preferably, it is 0.05% or more.

  Sources of zinc vapor include, for example, metallic zinc, zinc oxide, zinc nitrate, zinc chloride, zinc acetate, zinc aluminate and the like, and zinc zinc and / or zinc oxide or both are preferred because zinc vapor is easily generated. preferable.

  The source of zinc vapor is heated to generate zinc vapor of a predetermined partial pressure, but its temperature range is preferably 300 ° C. or more and the reaction temperature or less, more preferably 400 ° C. or more and the reaction temperature or less. Particularly preferably, it is 450 ° C. or more and the reaction temperature or less.

  There is no particular limitation on the method of supplying the zinc vapor to the raw material-containing gas, and for example, the metallic zinc and / or zinc compound is heated to a predetermined temperature in a separate room from the reactor (that is, the vessel for dehydrogenating hydrocarbon). By passing a mixed gas consisting of the hydrocarbon gas which is the raw material and the inert gas optionally used there, the hydrocarbon gas which is the raw material and the inert gas of the zinc vapor at maximum vapor pressure It may be included in the mixed gas consisting of Further, a catalyst layer containing the catalyst is formed in the reaction tube, and a layer of zinc oxide or zinc aluminate is provided on the upstream side of the gas flow in the reaction tube with respect to the catalyst layer. Zinc vapor is generated from this layer by heating in the presence of hydrogen gas, and the raw material hydrocarbon gas, optionally used inert gas, and optionally unreacted unreacted reducing gas This mixed gas may contain zinc vapor at a maximum vapor pressure just before the mixed gas contacts the catalyst layer.

The supply of zinc vapor may be continuous or intermittent, but in the case of intermittent supply, it is necessary to provide a separate chamber from the reactor.
In the present invention, a hydrocarbon which is converted to unsaturated hydrocarbon by dehydrogenation reaction is supplied to the reactor. The unsaturated hydrocarbon produced in the present invention is preferably an olefin (unsaturated hydrocarbon in which one double bond exists in one molecule) and a diene (one double bond) from the viewpoint of industrial utility. (2) unsaturated hydrocarbons). That is, the process for producing unsaturated hydrocarbons of the present invention is preferably a process for producing olefins or dienes.

  Particularly preferable compounds as the raw material hydrocarbon are propane, n-butane, isobutane, 1-butene, 2-butene and a mixture thereof, and particularly preferable compounds as the unsaturated hydrocarbon are propylene, 1-butene, 2 Butene, isobutene, 1,3-butadiene and mixtures thereof. The mixture of 1-butene and 2-butene is usually called n-butene.

  The hydrocarbon gas, which is a raw material, may be supplied to the reactor together with other gases that do not inhibit the effects of the present invention, and examples of the other gases include water vapor, nitrogen gas, carbon dioxide gas, hydrogen gas, methane gas, etc. Can be mentioned. Among these, water vapor is particularly preferable in that the life of the dehydrogenation catalyst can be extended. Also, as the other gas, the residue of hydrogen gas used to generate zinc vapor from zinc oxide may be supplied. There is no particular limitation on the mixing method and mixing ratio of the hydrocarbon gas and the other gas.

  The reaction type used in the present invention is not particularly limited, and known methods can be adopted, and examples thereof include fixed bed, moving bed, fluidized bed and the like. From the viewpoint of process design easiness, the fixed bed type is particularly preferred.

  In the present invention, a dehydrogenation catalyst containing zinc as one of the active components is used, preferably a catalyst using a zeolite as a carrier and supporting zinc and a Group VIIIA metal as an active component.

  Zinc and Group VIIIA metals can be supported on zeolites using, for example, metal compounds such as the corresponding metal nitrates, metal chlorides or metal complexes. The support on the zeolite can be carried out by a known method such as an ion exchange method or an impregnation method, and the order of the support is not particularly limited.

Examples of the zinc compound include zinc oxide, zinc nitrate, zinc chloride and zinc acetate. Examples of the group VIIIA metal compound include chloroplatinic acid, tetraammine platinum chloride, tetraammine platinum hydroxide, and tetraammine platinum nitrate.

  The range of the amount of zinc contained in the dehydrogenation catalyst is preferably 0.01 to 15% by weight, and more preferably 0.05 to 15% by weight, as a ratio of the weight of zinc metal atoms to the weight (100% by weight) of the total catalyst. It is 5% by weight, particularly preferably 0.1 to 3% by weight.

  The range of the amount of Group VIIIA metal contained in the dehydrogenation catalyst is preferably 0.01 to 5% by weight, more preferably as a ratio of the weight of Group VIIIA metal atom to the total weight (100% by weight) of the catalyst. Is 0.05 to 3% by weight, particularly preferably 0.1 to 1.5% by weight.

  The ratio of zinc to the Group VIIIA metal is usually 0.5 or more, preferably 0.5 to 50, more preferably 1 to 30, further as the molar ratio (the number of moles of Zn / the number of moles of the Group VIIIA metal) Preferably it is 1-20.

  The Group VIIIA metal is a notation of the old IUPAC method, and in the IUPAC method, it is a metal of Groups 8 to 10. Examples of metals of Group VIIIA include platinum, palladium, ruthenium, iridium, rhodium, nickel and the like. Among these, platinum is preferable from the viewpoint of catalytic activity.

  In one example of the method for producing the dehydrogenation catalyst, the zinc compound and optionally the Group VIIIA metal compound are supported on zeolite, and then drying and calcination are performed. Although the drying conditions are not particularly limited, the drying is usually carried out at 80 to 150 ° C. for a predetermined time. The firing conditions are also not particularly limited, but the firing is usually performed at a temperature of 400 to 600 ° C. for a predetermined time. The atmosphere at the time of firing is also not particularly limited, but usually, drying and firing are carried out under air flow.

  The zeolite is a name used as a generic name of crystalline porous aluminosilicates, and is classified by a structural code according to topology. For each structural code, information about structure, composition, crystallographic data is known (eg Atlas of Zeolite Structure Types, 4th Ed., Elsevier 1996, etc., Collection of Simulated XRD Powder Patterns for Zeolites, Elsevier 1996). ). In addition, as compounds other than aluminosilicates having similar crystal structures, zeolites that do not contain aluminum, metallosilicates that contain iron, gallium, titanium, etc. instead of aluminum are also included in the zeolite (for example, And Engineering, Kodansha Scientific).

  In the present invention, it is preferable to use borosilicate which is a metallosilicate containing boron instead of aluminium-free silicalite or aluminum as a catalyst support.

The aluminum content in the silicalite or borosilicate used in the present invention is not particularly limited, but the silica / alumina molar ratio (mole number of SiO ₂ / mole number of Al ₂ O ₃ ) in these zeolites is 100 or more. Is more preferably 500 or more, particularly preferably 1000 or more, and most preferably 2000 or more. When the silica / alumina molar ratio is 100 or more, side reactions such as oligomerization which proceed on an acid point caused by aluminum are suppressed. If the silica / alumina molar ratio is 2000 or more, such side reactions can be suppressed more effectively.

  The boron content in the borosilicate is not particularly limited, but is preferably 100 to 30,000 ppm, more preferably 500 to 10,000 ppm, and particularly preferably 1,000 to 8,000 ppm.

  The content of alkali metal and alkaline earth metal in silicalite or borosilicate is not particularly limited, but it is preferable that these metals be substantially absent. "Substantially absent" indicates that the content of alkali metal and alkaline earth metal in silicalite or borosilicate is 300 ppm or less, respectively.

Furthermore, it is preferable that the silicalite and the borosilicate have an MFI structure.
Although a borosilicate having an MFI structure (hereinafter also referred to as "MFI-type borosilicate") may be used as a carrier as it is, a silicate obtained by removing at least a part of boron atoms from the MFI-type borosilicate is used as a carrier It is preferred to use.

  The residual ratio of boron atoms in the silicate after removing at least a part of the boron atoms from the MFI-type borosilicate is preferably 80% or less of the total amount of boron atoms in the borosilicate, and is 50% or less Is more preferable, 30% or less is particularly preferable, and 20% or less is most preferable.

  The residual ratio of boron atoms is calculated by comparing the content of boron atoms in the borosilicate before removing the boron atoms with the content of boron atoms in the silicate after removing the boron atoms. There is no limitation on the method of removing at least a part of the boron atom from the borosilicate, and a known method such as a method of treating with an aqueous solution of an inorganic acid or an organic acid may be employed.

  The catalyst loaded into the reactor may be in the form of powder or in the form of a molded body. There is no restriction on the molding method, and known methods such as extrusion molding, tableting molding, coating molding and the like are adopted.

  After loading the catalyst into the reactor and prior to the start of the reaction, pretreatment may be carried out to activate the catalyst, which usually involves reducing the catalyst such as hydrogen or reducing gas such as carbon monoxide Contact These reducing gases may be used without dilution, or may be appropriately diluted with the above-mentioned inert gas.

  When a certain time has passed from the start of the reaction and a decrease in catalyst activity is confirmed, the reaction may be stopped and the catalyst may be reactivated by a method called regeneration treatment. The method is not particularly limited, but usually, a method is employed in which heavy substances of hydrocarbon called coke deposited on the catalyst surface are burned off by contacting a gas containing oxygen with a catalyst at a predetermined temperature.

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
(Catalyst preparation 1)
After 10 g of MFI-type borosilicate containing 3200 ppm of boron atoms was stirred in 200 ml of 1 N aqueous nitric acid solution at 80 ° C. for 2 hours, it was filtered and separated into a cake and a filtrate. Furthermore, after stirring the filtered cake in 200 ml of 1 N nitric acid aqueous solution at 80 ° C. for 2 hours, the procedure of filtering and fractionating into a cake and a filtrate is repeated twice, and then the filtered cake is used The resultant was washed with distilled water until the washings became neutral. The washed cake is dried for 3 hours in a static electric furnace kept at 120 ° C. by circulating air, and subsequently calcined at 500 ° C. for 4 hours to obtain at least one of MFI-type borosilicate and boron atoms. Part of the removed silicate was obtained. The boron atom weight in the obtained silicate was 260 ppm, and the boron atom residual ratio at this time was 8%.

(Catalyst preparation 2)
To 2 g of the silicate obtained in Catalyst Preparation 1, 0.66 g of an aqueous solution containing 0.058 g of zinc nitrate hexahydrate was added to impregnate zinc ions by the incipient-wetness method. The silicate impregnated with zinc ions is dried for 3 hours in a stationary electric furnace kept at 120 ° C. by circulating air, and subsequently calcined at 500 ° C. for 4 hours to carry out the zinc-loaded silicate Prepared.

(Catalyst preparation 3)
0.375 g of an aqueous solution containing 0.0127 g of chloroplatinic acid hexahydrate was added to 1.5 g of the zinc-supported silicate obtained in Catalyst Preparation 2 to impregnate platinum ions by the incipient-wetness method. The The silicate ion impregnated with platinum ions was dried for 3 hours in a stationary electric furnace kept at 120 ° C. by flowing air, and subsequently calcined at 500 ° C. for 4 hours to support platinum and zinc. The powder of the silicate catalyst was obtained. The supported amount of platinum of this silicate catalyst was 0.32% by weight, and the supported amount of zinc was 0.64% by weight.

Example 1
0.2 g of the platinum and zinc supported silicate catalyst obtained in Catalyst Preparation 3 is packed in a SUS tube equipped with an inner tube of alumina with an inner diameter of 6 mm, and then the silica wool is sandwiched and oxidized on the upstream side of the catalyst A reaction tube was manufactured by charging 0.1 g of zinc (manufactured by Sigma Aldrich) and packing alumina balls before and after them to fix the catalyst and zinc oxide. After pretreating the catalyst by flowing a mixed gas consisting of 20 sccm of hydrogen and 0.064 g / min of steam at a temperature of 600 ° C. under normal pressure for 2 hours, the reaction tube was pretreated with 2.1 sccm of hydrogen, 13.55 sccm of propane and 0. Dehydrogenation of propane was initiated by feeding 022 g / min. The reaction temperature was raised to 650 ° C. with the start of the reaction.
The catalyst showed stable activity over time and showed a 60% propylene yield over about 120 hours.

Comparative Example 1
A reaction tube was manufactured in the same manner as in Example 1 except that zinc oxide was not loaded, and the propane dehydrogenation reaction was initiated under the same pretreatment conditions and reaction conditions as in Example 1. The catalyst showed a propylene yield of 60% over about 60 hours.

Comparative Example 2
A reaction tube was manufactured in the same manner as in Example 1 except that the silicate catalyst was not loaded, and in the same manner as in Example 1, 20 sccm of hydrogen and 0.064 g / min of steam were added to the reaction tube at 600.degree. The mixed gas was allowed to flow for 2 hours, and then, at 650 ° C., 2.1 sccm of hydrogen, 13.55 sccm of propane and 0.022 g / min of water vapor were supplied. Zinc oxide showed no catalytic activity in the propane dehydrogenation reaction.
From the above results, it is clear that while zinc oxide loaded upstream of the catalyst itself has no catalytic activity, the catalyst exhibits high activity over a long period due to the presence of zinc oxide.

[Reference example]
A reaction tube was manufactured in the same manner as in Comparative Example 2 except that a quartz tube processed for fixing the catalyst was used instead of the SUS tube to which the alumina inlaid tube was attached, and the alumina ball was not filled. Then, similarly to Comparative Example 2, after flowing a mixed gas consisting of 20 sccm of hydrogen and 0.064 g / min of water vapor at 600.degree. C. and normal pressure for 2 hours in a reaction tube, then 2.1 sccm of hydrogen and propane at 650.degree. 13.55 sccm, and 0.022 g / min of water vapor were supplied. As in Comparative Example 2, zinc oxide did not exhibit any catalytic activity in the dehydrogenation reaction of propane, but a silver-colored and band-like film was formed at the lower part of the quartz tube after the reaction. As a result of analyzing the solution after dissolving this film with dilute nitric acid by ICP (inductively coupled plasma), it was confirmed that the silver-colored and band-shaped film is zinc.

  From the above results, it is clear that at least part of the zinc oxide is reduced during the pretreatment and reaction to metal zinc, from which zinc vapor is generated to move in the gas phase. It is also apparent that the partial pressure of zinc vapor at this time is equal to or less than the vapor pressure of zinc at the reaction temperature of 650 ° C.

Claims (18)

The hydrocarbon containing raw material containing gas (1) is brought into contact with metallic zinc or zinc compound or both, and then with a dehydrogenation catalyst containing zinc as one of the active components to carry out the dehydrogenation reaction of the hydrocarbon. the process of manufacturing a performed unsaturated hydrocarbons seen including,
The hydrocarbon is a hydrocarbon which is converted to unsaturated hydrocarbon by dehydrogenation reaction,
The zinc compound is zinc oxide,
The method for producing an unsaturated hydrocarbon , wherein the dehydrogenation catalyst is a catalyst having a zeolite as a carrier and zinc and a Group VIIIA metal supported as an active component .   The method for producing unsaturated hydrocarbon according to claim 1, wherein the raw material-containing gas (1) further contains water vapor.   The method for producing unsaturated hydrocarbon according to claim 1 or 2, wherein the raw material-containing gas (1) further contains hydrogen.   A feed containing gas (1) containing hydrocarbon is brought into contact with metal zinc or zinc compound or both to obtain a feed containing gas (2) containing hydrocarbon and zinc vapor, and the feed containing gas (2) is obtained by The method for producing unsaturated hydrocarbon according to claim 1, comprising the step of dehydrogenating said hydrocarbon to produce unsaturated hydrocarbon in contact with a dehydrogenation catalyst containing zinc as one of the active components. .   The method for producing unsaturated hydrocarbon according to claim 4, wherein the partial pressure of zinc vapor contained in the raw material-containing gas (2) is equal to or less than the vapor pressure of zinc at the reaction temperature of the dehydrogenation reaction.   The method for producing unsaturated hydrocarbon according to claim 4 or 5, wherein the raw material-containing gas (2) further contains water vapor.   The method for producing unsaturated hydrocarbon according to any one of claims 4 to 6, wherein the raw material-containing gas (2) further contains hydrogen.   The method for producing an unsaturated hydrocarbon according to any one of claims 1 to 7, wherein the reaction temperature in the dehydrogenation reaction is 300 to 800 ° C, and the reaction pressure is in the range of 0.01 to 1 MPa.   The method for producing an unsaturated hydrocarbon according to any one of claims 1 to 8, wherein the hydrocarbon is selected from propane, n-butane, isobutane, 1-butene, 2-butene and a mixture thereof. The method for producing an unsaturated hydrocarbon according to any one of claims 1 to 8 , wherein the hydrocarbon is at least one hydrocarbon selected from propane, n-butane and isobutane. The method for producing unsaturated hydrocarbon according to any one of claims 1 to 8 , wherein the hydrocarbon is n-butene. The unsaturated hydrocarbon according to any one of claims 1 to 11 , wherein the amount of zinc contained in the dehydrogenation catalyst is 0.01 to 15% by weight based on 100% by weight of the total weight of the catalyst. Manufacturing method. The amount of Group VIIIA metal contained in the dehydrogenation catalyst is 0.01 to 5% by weight, based on 100% by weight of the total weight of the catalyst, the non-dehydrogenation catalyst according to any one of claims 1 to 12. Process for producing saturated hydrocarbons. The method for producing an unsaturated hydrocarbon according to any one of claims 1 to 13 , wherein the Group VIIIA metal is platinum. The method for producing unsaturated hydrocarbon according to any one of claims 1 to 14 , wherein the zeolite is silicalite or borosilicate. The method for producing unsaturated hydrocarbon according to claim 15 , wherein the silicalite and the borosilicate have an MFI structure. The method for producing unsaturated hydrocarbon according to any one of claims 1 to 14 , wherein the zeolite is a silicate obtained by removing at least a part of boron atoms from MFI-type borosilicate. The method for producing unsaturated hydrocarbon according to claim 17 , wherein the residual ratio of boron atoms in the silicate is 80% or less of the total amount of boron atoms in the MFI-type borosilicate.

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