JP3568372B2 - Method for producing solid acid catalyst - Google Patents

Description

【００２９】
［平均粒径の測定方法］
日機装（株） ＭＩＣＲＯＴＲＡＣ粒度分析計を用い、湿式測定法で測定した。これは、流れる粉体群にレーザ光を照射し、その前方散乱光により粒度分析を行うものである。
【００３０】
（実施例１） 触媒の調製例
ＭＥＬ社製水酸化ジルコニウムＸＺＯ６３１／０１を乾燥させ、平均粒径１．２μｍの乾燥水和ジルコニアを得た。この乾燥水和ジルコニア粉３００ｇに平均粒径１０μｍの水和アルミナ（擬ベーマイト）粉３００ｇを加え、攪拌羽根のついた混練機で水を加えながら２時間混練を行った。得られた混練物を直径１．６ｍｍの円形の穴の開いた押出機より押し出し、乾燥後６００℃で２時間焼成してジルコニアアルミナ担体を得た。この担体中のジルコニアの結晶種は正方晶で、単斜晶は全く認められなかった。この担体５０ｇに白金０．２５ｇを含有する塩化白金酸水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、６００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ａ）を得た。
【００３１】
（実施例２） 触媒の調製例
実施例１と同様にして得たジルコニアアルミナ担体５０ｇに白金０．２５ｇと硫酸６．１３ｇを含有する塩化白金酸と硫酸の混合水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、６００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｂ）を得た。
【００３２】
（実施例３） 触媒の調製例
実施例１と同様にして得たジルコニアアルミナ担体５０ｇに白金０．２５ｇを含有する塩化白金酸水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、５５０℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｃ）を得た。
【００３３】
（実施例４） 触媒の調製例
実施例１と同様にして得たジルコニアアルミナ担体５０ｇに白金０．２５ｇを含有する塩化白金酸と塩酸の混合水溶液を添加した。これを乾燥後、５００℃で２時間焼成して白金含有ジルコニアアルミナ担体を得た。この担体に０．５ｍｏｌ／ｌ硫酸水溶液７５０ｍｌを加えて接触させた後過剰硫酸を濾過により除去し、乾燥後、６００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｄ）を得た。
【００３４】
（実施例５） 触媒の調製例
実施例４と同様にして得た白金含有ジルコニアアルミナ担体５０ｇに０．５ｍｏｌ／ｌ硫酸水溶液７５０ｍｌを加えて接触させた後過剰硫酸を濾過により除去し、乾燥後、５００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｅ）を得た。
【００３５】
（比較例１） 触媒の調製例
実施例１と同じ乾燥水和ジルコニア粉３００ｇに水和アルミナ（擬ベーマイト）粉３００ｇを加え、攪拌羽根のついた混練機で水を加えながら２時間混練を行った。得られた混練物を直径１．６ｍｍの円形の穴の開いた押出機より押し出し、乾燥後４００℃で２時間焼成してジルコニアアルミナ担体を得た。この担体は非晶質であり、正方晶、単斜晶のジルコニアは認められなかった。この担体５０ｇに白金０．２５ｇを含有する塩化白金酸水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、６００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｆ）を得た。
【００３６】
（比較例２） 触媒の調製例
比較例１と同様の方法で調製したジルコニアアルミナ担体５０ｇに白金０．２５ｇを含有する塩化白金酸水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、５００℃で２時間焼成し、白金含有硫酸ジルコニアアルミナ触媒（触媒Ｇ）を得た。
【００３７】
（比較例３） 触媒の調製例
実施例１と同様の方法で調製した乾燥水和ジルコニア粉５０ｇに、白金０．２５ｇを含有する塩化白金酸水溶液１２５ｍｌを添加した。これを乾燥後、０．５ｍｏｌ／ｌ硫酸水溶液１２５ｍｌを添加し、乾燥後、６００℃で２時間焼成して白金含有硫酸ジルコニア触媒（触媒Ｈ）を得た。
【００３８】
異性化反応例（１）
１６〜２４ｍｅｓｈの粒に成形した白金含有触媒４ｃｃを、長さ５０ｃｍ、内径１ｃｍの固定床流通式反応器中でｎ−ヘキサンの異性化反応を行った。反応条件は次の通りである。
水素還元（触媒前処理）条件：３００℃、１時間
反応温度：２００℃、反応圧力（ゲージ圧）：１０ｋｇｆ／ｃｍ^２
ＬＨＳＶ＝１．５ｈｒ^−１１、Ｈ_２／Ｏｉｌ：５（ｍｏｌ／ｍｏｌ）
【００３９】
通油開始１．５時間後の反応管出口組成をガスクロマトグラフィーにより分析した結果を以下に示す。
ｎ−ヘキサン転化率
触媒Ａ（実施例）：８２％
触媒Ｂ（実施例）：８２％
触媒Ｃ（実施例）：８５％
触媒Ｄ（実施例）：８０％
触媒Ｆ（比較例）：６５％
触媒Ｈ（比較例）：７６％
【００４０】
異性化反応例（２）
１６〜２４ｍｅｓｈの粒に成形した白金含有触媒４ｃｃを、長さ５０ｃｍ、内径１ｃｍの固定床流通式反応器中でパラフィン混合溶液（ｎ−ヘキサン７０質量％、ｎ−ヘプタン１５質量％、シクロヘキサン１５質量％）の異性化反応を行った。反応条件は次の通りである。
水素還元（触媒前処理）条件：３００℃、１時間
反応温度：２２０℃、反応圧力（ゲージ圧）：４．８ｋｇｆ／ｃｍ^２
ＬＨＳＶ＝５．０ｈｒ^−１、Ｈ_２／Ｏｉｌ：５（ｍｏｌ／ｍｏｌ）
【００４１】
通油開始１．５時間後の反応管出口組成をガスクロマトグラフィーにより分析した結果を以下に示す。
ｎ−ヘキサン転化率
触媒Ｅ（実施例）：５５％
触媒Ｇ（比較例）：３３％
触媒Ｈ（比較例）：５０％
ｎ−ヘキサン転化率＝［１−（生成油中に占めるｎ−ヘキサンの質量％／原料油中に占めるｎ−ヘキサンの重量％）］×１００（％）
【００４２】
本発明の触媒は、ジルコニアとアルミナを組み合わせることにより、驚くべきことに粉体の白金含有硫酸ジルコニア固体酸触媒（触媒Ｈ）と同等以上の活性を示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a solid acid catalyst useful for a reaction requiring an acid catalyst, particularly a solid acid having high activity in the isomerization reaction of hydrocarbons, easy handling, and excellent stability of the catalyst during the reaction. The present invention relates to a method for producing a catalyst.
[0002]
[Prior art]
In the chemical industry, many reactions requiring an acid catalyst such as an alkylation reaction, an esterification reaction, and an isomerization reaction are known. Conventionally, acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, phosphoric acid, and paratoluenesulfonic acid have been used in this type of reaction. However, these acid catalysts have a property of corroding metals, so that it is necessary to use expensive corrosion-resistant materials or to perform a corrosion-resistant treatment. In addition, it is usually difficult to separate the reactants from the reactants after the reaction, and it is necessary to perform a waste acid treatment, which requires a complicated process such as alkali washing, which has a serious environmental problem. It was also very difficult to reuse the catalyst.
[0003]
In order to solve such a problem, a sulfate group-containing solid acid catalyst has been proposed in which a Group IV metal hydroxide or hydrated oxide is brought into contact with a sulfuric acid-containing solution and then calcined at 350 to 800 ° C. (Japanese Patent Publication No. 59-6181). This solid acid catalyst has a higher acid strength than 100% sulfuric acid (Hammet's acidity function H0 is -11.93). These solid acid catalysts have high catalytic performance for various acid catalyzed reactions due to their strong acid strength, are low in corrosiveness, can be easily separated from reactants, do not require waste acid treatment, and can be used for catalyst regeneration. It has the advantage that it can be used, and is expected to replace conventional acid catalysts in various industrial reactions.
[0004]
It is also known that, even for elements other than Group IV of the periodic table, oxides containing sulfuric acid show an acid strength stronger than 100% sulfuric acid. For example, a solid acid catalyst obtained by adding a sulfuric acid-containing compound to an aluminum hydroxide or oxide and calcining the compound shows a stronger acid strength than 100% sulfuric acid (JP-A-5-96171, Arata, Trends in Physical Chemistry Volume 2, Item 1, (1991)). In the case of alumina, it is reported that a method of once calcining and crystallizing at about 700 ° C. and treating with sulfuric acid has the highest activity. It is obvious that catalysts obtained by adding a metal having hydrogenation ability to these solid acid catalysts also exhibit good hydrocarbon isomerization activity. However, it has also been found that the acid strength of these is weaker than that of the zirconia sulfate solid acid catalyst.
[0005]
Japanese Patent Publication Nos. 5-29503, 5-29504, 5-29505 and 5-29505 disclose a method for producing a catalyst mainly supporting isomerization by carrying a platinum group metal on the above catalyst. It is disclosed in JP-A-5-29506. These are a method for producing a group IV metal or group III metal hydroxide, a treating agent containing a sulfate group, and a sulfate group-containing solid acid catalyst using a group VIII metal as a main raw material. The resulting catalyst is said to be a catalyst having excellent catalyst stability in isomerization reactions of linear hydrocarbons, alkylation reactions of hydrocarbons, and the like, and having less decomposition reaction than conventional solid acid catalysts. However, these sulfuric acid-containing solid acid catalysts are produced in powder form and need to be formed into a suitable size when used in a conventional industrial reactor, for example, a fixed bed flow reactor.
[0006]
Japanese Patent Application Laid-Open No. Hei 9-38494 discloses a method for producing a sulfated metal oxide catalyst molded article. This is a catalyst molding using alumina as a binder, which is performed by molding using a metal hydroxide and boehmite, pre-firing the molded body at a temperature of 300 ° C. or more and 500 ° C. or less, and then performing a sulfate treatment. Is the way. However, since the catalyst activity was formed by adding boehmite, the activity was lower than that of the powder catalyst without adding boehmite. Thus, the activity is said to be lower than that of the catalyst without alumina. It is also disclosed that a catalyst obtained by mixing a platinum-supported zirconia sulfate catalyst powder with a boehmite powder, adding water, kneading the mixture, and then molding and calcining the mixture further greatly reduces the catalytic activity.
[0007]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above problems, and is a method for producing a molded solid acid catalyst having a high activity equivalent to or higher than that of a powder catalyst while being a molded product of a solid acid catalyst containing sulfuric acid. Is to provide.
[0008]
[Means for Solving the Problems]
As a result of the inventor's intensive studies, it was found that when zirconium hydroxide and alumina hydrate (pseudo-boehmite) were kneaded and molded, and calcined at 600 ° C., tetragonal zirconia, which is preferable for exhibiting the activity of the catalyst, was easily formed. The inventors have found that, by supporting a sulfuric acid component or the like on the calcined molded body, the molded body has a hydrocarbon isomerization activity equal to or higher than that of a solid acid catalyst of powdered zirconia, and completed the present invention.
[0009]
That is, the method for producing a solid acid catalyst according to the present invention comprises (a) kneading a hydroxide and / or a hydrated oxide of zirconium and a hydrated oxide of aluminum having a boehmite structure to form a molded body, b) firing the molded article thereof at a temperature tetragonal zirconia is obtained, then there is then burned in (c) carrying a sulfureous component-containing compound in the molded body, a temperature lower than 700 ° C. higher than 300 ° C. (C) supporting at least one metal compound selected from Group 8, Group 9, and Group 10 when supporting a sulfuric acid-containing compound on the molded body; or (a) water of zirconium; When kneading an oxide and / or a hydrated oxide and a hydrated oxide of aluminum having a boehmite structure, kneading at least one metal compound selected from Group 8, Group 9, and Group 10 It is .
[0011]
[Action and Effect of the Invention]
ADVANTAGE OF THE INVENTION According to this invention, the production | generation of the tetragonal zirconia which can obtain high catalytic activity, and the formation of the strong acid point by the sulfuric acid content in the sintered compact can be performed separately. This is considered to have resulted in the expression of high activity of the sulfuric acid-containing solid acid catalyst of the present invention. At the same time, by adding a hydrated aluminum oxide having a boehmite structure, a molded body that can be easily handled as a catalyst is obtained.
[0012]
The catalyst of the present invention not only has high catalytic activity as a molded solid acid catalyst particularly for a hydrocarbon isomerization reaction, but also has a high mechanical strength of the molded catalyst. Further, since the molded article is used, it has a special effect that the separation from the reactants is easy and the catalyst can be reused. Further, since the production is carried out by a kneading method which is industrially easy to adapt, it has high industrial utility value.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
It is preferable that the aluminum hydrated oxide having a boehmite structure is so-called pseudo-boehmite in order to obtain high catalytic activity and sufficient crushing strength. However, when α-alumina or γ-alumina is used, for example, the crushing strength is lowered and monoclinic zirconia is mixed into the catalyst, so that the catalytic activity is reduced. The content of alumina in the total amount of zirconia and alumina in the catalyst is preferably from 10 to 90% by mass, particularly preferably from 20 to 80% by mass. If the content is less than 10% by mass, not only the effect of adding the hydrated oxide of aluminum on the tetragonal crystal of zirconia is reduced, but also the crushing strength of the molded catalyst is reduced. On the other hand, if it exceeds 90% by mass, the activity may decrease. Aluminum hydrated oxide is usually a powder, preferably having a mean particle size of 0.5 to 50 μm, particularly preferably 0.5 to 20 μm, in order to improve the crushing strength and specific surface area of the catalyst. .
[0014]
The hydroxide or hydrated oxide of zirconium may be produced in any manner, but in general, these salts and organic metal compounds such as oxychloride, alcoholate, chloride, sulfate, nitrate, oxysulfate And the like can be obtained by neutralizing or hydrolyzing them. Further, these hydroxides and / or hydrated oxides may be used as composite metal hydroxides and / or composite metal hydrated oxides. A hydroxide and / or hydrated oxide and / or salt of another metal may be added to the hydroxide and / or hydrated oxide and / or salt of zirconium. As other metals, titanium, hafnium, vanadium, chromium, manganese, iron, silicon, tin, aluminum, gallium, and boron are preferably used. These other metal compounds may be complex metal compounds. The zirconia content in the total amount of zirconia and alumina in the catalyst is preferably 10 to 90% by mass, particularly preferably 20 to 80% by mass. If the amount is less than 10% by mass, the activity decreases. On the other hand, if the content exceeds 90% by mass, the effect of improving the activity by the addition of the hydrated aluminum oxide is weakened, and not only monoclinic crystals may be mixed into zirconia, but also the crushing strength of the formed catalyst is weakened. The zirconium hydroxide or hydrated oxide can be made amorphous without a clear crystal structure by X-ray and electron beam diffraction, because the crushing strength of the catalyst is improved and zirconia is easily stabilized. preferable. The hydroxide or hydrated oxide of zirconium is usually a powder, preferably having a shape having an average particle size of 0.5 to 50 μm, particularly 0.5 to 20 μm. Preferred for improvement.
[0015]
Next is kneading, which may be any kneading machine that is generally used for catalyst preparation, but usually, water is added to the raw materials, and the mixture is mixed with a stirring blade. A suitable method is suitably used. Water is usually added during kneading, but the liquid to be added may be an alcohol such as ethanol or isopropanol, or a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone.
[0016]
Similarly, as long as the catalytic properties of the present invention are maintained, an acid such as nitric acid or a base such as ammonia, an organic compound, a binder, a ceramic fiber, a surfactant, a zeolite or the like may be added and kneaded. I do not care. However, the catalyst of the present invention has sufficient strength and high catalytic activity even when such additives are not added during kneading.
[0017]
For molding after kneading, a known device such as a screw type extruder can be used. In particular, extrusion molding using a screw type extruder or the like is preferably used because it can be efficiently formed into an arbitrary shape such as a pellet shape or a honeycomb shape. Although the size of the molded product is not particularly limited, it is usually molded to have a cross-sectional length of 0.5 mm or more. For example, if it is a columnar pellet, a pellet having a diameter of about 0.5 to 10 mm and a length of about 0.5 to 15 mm can be easily obtained. Since the crushing strength after firing is greatly affected by kneading, it is desirable to previously determine the water content, kneading time, electric energy, and the like during the kneading.
[0018]
After kneading and molding the hydroxide and / or hydrated oxide of zirconium, the hydrated oxide of aluminum having a boehmite structure, and firing in a gas atmosphere such as air or nitrogen, zirconia Is crystallized. Normally, it is preferable to set the firing temperature to a temperature higher than 500 ° C. and lower than 800 ° C., and to set the firing time to 0.5 to 10 hours, since monoclinic zirconia is less likely to occur and most of the zirconia is tetragonal zirconia. A monoclinic structure may partially exist. This crystal structure can be confirmed by X-ray diffraction. Specifically, the X-ray diffraction peak area ratio of 2θ = 28.2 ° and 2θ = 30.2 ° by CuKα ray (hereinafter abbreviated as S28.2 / S30.2 ratio. S28.2 is 2θ = 28) (The area of the peak of monoclinic zirconia at 0.2 °, S30.2 is the area of the peak of tetragonal zirconia at 2θ = 30.2 °) is 1.0 or less, preferably 0.05 or less. Higher catalytic activity is obtained when almost no monoclinic structure is present. If the firing temperature is too high, the proportion of monoclinic crystals in the crystal structure of zirconium oxide increases, and the peak area ratio of 2θ = 28.2 ° and 2θ = 30.2 ° may exceed 1, resulting in a catalyst. It is not preferable because the activity also decreases. On the other hand, if the firing temperature is too low, zirconium oxide does not crystallize, and the catalytic activity decreases, which is not preferable. Usually, after forming and before firing, drying is performed at a temperature of 80C to 200C.
[0019]
Examples of the sulfuric acid-containing compound include sulfuric acid, ammonium sulfate, sulfurous acid, ammonium sulfite, thionyl chloride, and the like. However, ammonium sulfate and ammonium sulfite are preferable because of low corrosiveness of the production apparatus. The sulfuric acid-containing compound may be used as it is or as a solution such as an aqueous solution. Further, there is no particular limitation on the concentration of the solution. The amount of the sulfuric acid-containing compound to be added is preferably such that the sulfur content in the finally obtained solid acid catalyst is 0.5 to 10%. The method of addition is not particularly limited, but an impregnation method such as spraying or dipping is preferably used.
[0020]
Depending on the use of the solid acid catalyst, it is preferable to add one or more metal compounds selected from Group 8, Group 9, and Group 10 to the catalyst. As an element selected from Group 8, Group 9, and Group 10, platinum, palladium, ruthenium, and the like are particularly preferably used as a catalyst for the isomerization reaction. It is preferable that one or more metals selected from Group 8, Group 9, and Group 10 be in the form of a compound rather than the metal itself. These metal compounds can be used both as anhydrides and hydrates. Further, these metal compounds may be one kind or a mixture of two or more kinds. These metal compounds can be preferably added to the catalyst by (c) supporting the compound containing sulfuric acid on the molded body, or (a) kneading the metal compound when kneading the raw materials. .
[0021]
The method of supporting these metal compounds is not particularly limited, but an impregnation method such as spraying or immersion, or an ion exchange method is preferably used. Either one or more of the metal compounds selected from Group 8, Group 9, and Group 10 and the sulfuric acid-containing compound may be carried first. In addition, a method of simultaneously using a mixed solution is also suitably used. Further, between or after loading of these compounds, after loading, drying at a temperature of 80 ° C to 200 ° C or firing at a temperature higher than 300 ° C and lower than 700 ° C for 0.5 to 10 hours is performed. No problem. Further, a reduction treatment with hydrogen may be performed. These metal components should be added so that the total amount of the Group VIII, Group IX, and Group X elements in the finally obtained solid acid catalyst is 0.05 to 10% by weight. Is preferred.
[0022]
Finally, it is calcined at a temperature higher than 300 ° C. and lower than 700 ° C. to obtain a target solid acid catalyst. The firing time is usually 0.5 to 10 hours.
[0023]
In addition, the loading of one or more metal compounds selected from Group VIII, Group IX, and Group X may be carried out by mixing the metal compounds at the time of kneading during the production method. In this case, after kneading and molding, firing in a gas atmosphere such as air or nitrogen, crystallizing zirconia, adding a sulfuric acid-containing compound and drying, and then higher than 300 ° C and lower than 700 ° C Calcination at a temperature gives the desired solid acid catalyst.
[0024]
The solid acid catalyst thus obtained contains zirconia and alumina as main components. The total amount of zirconia and alumina in the catalyst is preferably 70% by mass or more, and more preferably 80% by mass or more, from the viewpoints of catalytic activity and strength of the molded product. It is practically preferable that the molding strength is 3 kg or more as the side crushing strength of a cylindrical pellet having a diameter of 1.5 mm. Since the crushing strength is greatly affected by the kneading, it is desirable to previously determine the water content, the kneading time, the electric energy, and the like during the kneading.
[0025]
The solid acid catalyst obtained in the present invention is a solid superacid having an acid strength higher than 100% sulfuric acid and an acid strength Ho (Hammet acidity function) higher than -11.93. It can be used as a catalyst for various acid-catalyzed reactions such as isomerization, alkylation, acylation, esterification, etherification, acetalization, hydration, dehydration, polymerization, decomposition, nitration, etc. Preferably used. A major feature of this method for producing a catalyst is that calcination for crystallization of zirconia and calcination for formation of strong acid sites by sulfuric acid are separated. That is, due to its high acid strength and the effect of adding pseudo-boehmite, the catalyst exhibits excellent catalytic performance particularly in the isomerization reaction of hydrocarbons. In particular, the catalyst has sufficient strength to be used as a molded article, so that it is easy to handle the catalyst and can be used for a reaction in a fixed bed.
[0026]
The catalyst of the present invention is preferably used for isomerizing a hydrocarbon compound. In particular, it is preferably used as a catalyst for isomerizing a linear hydrocarbon in a petroleum fraction having a boiling point of about -20 ° C to 110 ° C as a hydrocarbon compound into a branched hydrocarbon in the presence of hydrogen. The isomerization conditions in this case are as follows: reaction temperature: 140 to 240 ° C., reaction pressure: 1 to 50 kgf / cm ² , LHSV: 0.2 to 10 hr ⁻¹ , hydrogen / raw material ratio: 0.2 to 10 mol / mol. A range is preferred.
【Example】
[0027]
Hereinafter, an embodiment will be described in detail. First, an evaluation method will be described.
[0028]
[Method of calculating crystal seed ratio by X-ray diffraction]
The tetragonal and monoclinic zirconia peaks were separated from the X-ray diffraction chart, and the area of the monoclinic zirconia peak at 2θ = 28.2 ° and the area of the tetragonal zirconia peak at 2θ = 30.2 °. (S28.2 / S30.2 ratio) was calculated. When the S28.2 / S30.2 ratio was 0.02 or less, the monoclinic peak was unclear and could not be detected.

[0029]
[Measurement method of average particle size]
It was measured by a wet measurement method using a Nikkiso Co., Ltd. MICROTRAC particle size analyzer. In this technique, a flowing powder group is irradiated with a laser beam, and the particle size is analyzed by forward scattered light.
[0030]
(Example 1) Preparation example of catalyst Zirconium hydroxide XZO631 / 01 manufactured by MEL was dried to obtain dried hydrated zirconia having an average particle diameter of 1.2 µm. 300 g of hydrated alumina (pseudo-boehmite) powder having an average particle size of 10 μm was added to 300 g of the dried hydrated zirconia powder, and the mixture was kneaded for 2 hours while adding water using a kneader equipped with stirring blades. The obtained kneaded material was extruded from an extruder having a circular hole with a diameter of 1.6 mm, dried and fired at 600 ° C. for 2 hours to obtain a zirconia alumina carrier. The crystal seed of zirconia in this carrier was tetragonal, and no monoclinic crystal was observed. To 50 g of the carrier, 125 ml of an aqueous solution of chloroplatinic acid containing 0.25 g of platinum was added. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added. After drying, the mixture was calcined at 600 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst A).
[0031]
(Example 2) Preparation example of catalyst To 50 g of a zirconia alumina carrier obtained in the same manner as in Example 1, 125 ml of a mixed aqueous solution of chloroplatinic acid and sulfuric acid containing 0.25 g of platinum and 6.13 g of sulfuric acid was added. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added. After drying, the mixture was calcined at 600 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst B).
[0032]
Example 3 Catalyst Preparation Example 125 ml of a chloroplatinic acid aqueous solution containing 0.25 g of platinum was added to 50 g of a zirconia alumina carrier obtained in the same manner as in Example 1. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added. After drying, the mixture was calcined at 550 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst C).
[0033]
Example 4 Catalyst Preparation Example A mixed aqueous solution of chloroplatinic acid and hydrochloric acid containing 0.25 g of platinum was added to 50 g of a zirconia alumina carrier obtained in the same manner as in Example 1. After drying, this was fired at 500 ° C. for 2 hours to obtain a platinum-containing zirconia alumina support. After adding 750 ml of a 0.5 mol / l sulfuric acid aqueous solution to the carrier and bringing it into contact, excess sulfuric acid was removed by filtration, dried, and calcined at 600 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst D). .
[0034]
(Example 5) Catalyst Preparation Example 0.5 mol / l sulfuric acid aqueous solution (750 ml) was added to 50 g of a platinum-containing zirconia alumina carrier obtained in the same manner as in Example 4, and the mixture was contacted. At 500 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (Catalyst E).
[0035]
(Comparative Example 1) Catalyst Preparation Example 300 g of hydrated alumina (pseudo-boehmite) powder was added to 300 g of dry hydrated zirconia powder as in Example 1, and kneading was performed for 2 hours while adding water using a kneader equipped with stirring blades. Was. The obtained kneaded material was extruded from an extruder having a circular hole having a diameter of 1.6 mm, dried and calcined at 400 ° C. for 2 hours to obtain a zirconia alumina carrier. This support was amorphous, and no tetragonal or monoclinic zirconia was observed. To 50 g of the carrier, 125 ml of an aqueous solution of chloroplatinic acid containing 0.25 g of platinum was added. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added, followed by drying and calcining at 600 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst F).
[0036]
Comparative Example 2 Catalyst Preparation Example 125 ml of an aqueous chloroplatinic acid solution containing 0.25 g of platinum was added to 50 g of a zirconia alumina carrier prepared in the same manner as in Comparative Example 1. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added, followed by drying and calcining at 500 ° C. for 2 hours to obtain a platinum-containing zirconia alumina sulfate catalyst (catalyst G).
[0037]
Comparative Example 3 Catalyst Preparation Example To 50 g of dry hydrated zirconia powder prepared in the same manner as in Example 1, 125 ml of an aqueous chloroplatinic acid solution containing 0.25 g of platinum was added. After drying, 125 ml of a 0.5 mol / l sulfuric acid aqueous solution was added, followed by drying and calcining at 600 ° C. for 2 hours to obtain a platinum-containing zirconia sulfate catalyst (catalyst H).
[0038]
Example of isomerization reaction (1)
4 cc of the platinum-containing catalyst formed into particles of 16 to 24 mesh was subjected to n-hexane isomerization reaction in a fixed bed flow reactor having a length of 50 cm and an inner diameter of 1 cm. The reaction conditions are as follows.
Hydrogen reduction (catalyst pretreatment) conditions: 300 ° C., 1 hour Reaction temperature: 200 ° C., reaction pressure (gauge pressure): 10 kgf / cm ^{2
_{LHSV = 1.5hr -1 1, H 2}} / Oil: 5 (mol / mol)
[0039]
The result of analyzing the composition of the reaction tube outlet 1.5 hours after the start of oil passage by gas chromatography is shown below.
n-Hexane conversion catalyst A (Example): 82%
Catalyst B (Example): 82%
Catalyst C (Example): 85%
Catalyst D (Example): 80%
Catalyst F (comparative example): 65%
Catalyst H (comparative example): 76%
[0040]
Example of isomerization reaction (2)
In a fixed bed flow reactor having a length of 50 cm and an inner diameter of 1 cm, a paraffin mixed solution (70% by mass of n-hexane, 15% by mass of n-heptane, 15% by mass of cyclohexane) was placed in a fixed bed flow reactor having a length of 50 cm and an inner diameter of 1 cm. %). The reaction conditions are as follows.
Hydrogen reduction (catalyst pretreatment) conditions: 300 ° C., 1 hour Reaction temperature: 220 ° C., reaction pressure (gauge pressure): 4.8 kgf / cm ²
LHSV = 5.0 hr ⁻¹ , H ₂ / Oil: 5 (mol / mol)
[0041]
The result of analyzing the composition of the reaction tube outlet 1.5 hours after the start of oil passage by gas chromatography is shown below.
n-hexane conversion catalyst E (Example): 55%
Catalyst G (comparative example): 33%
Catalyst H (comparative example): 50%
n-hexane conversion rate = [1- (mass% of n-hexane in product oil / weight% of n-hexane in feed oil)] × 100 (%)
[0042]
By combining zirconia and alumina, the catalyst of the present invention surprisingly exhibits activity equal to or higher than that of the powdered platinum-containing zirconia sulfate solid acid catalyst (catalyst H).

Claims (2)

Of zirconium hydroxide and / or hydrated oxide with aluminum having boehmite structure
The hydrated oxide is kneaded and formed into a compact, and the compact is heated at a temperature at which tetragonal zirconia is obtained.
After sintering, the molded product is loaded with a sulfuric acid-containing compound.
Supports one or more metal compounds selected from Group 0 and is higher than 300 ° C and lower than 700 ° C
A method for producing a solid acid catalyst , comprising calcination at a temperature . Of zirconium hydroxide and / or hydrated oxide with aluminum having boehmite structure
The hydrated oxide is kneaded, and at that time, one or more metal compounds selected from Group VIII, Group 9 and Group 10 are kneaded and formed into a molded body, and the molded body is made of tetragonal zirconia. Firing at the resulting temperature
Then, a sulfuric acid-containing compound is supported on the molded body, and is higher than 300 ° C. and lower than 700 ° C.
A method for producing a solid acid catalyst , comprising calcination at a temperature .