JP2011083701A - Hydrogenation catalyst exhibiting excellent anti-poison property to impurity in hydrogen source and method for producing the catalyst - Google Patents

Abstract

Even if a low-grade hydrogen containing a poisoning component of a metal catalyst such as a sulfur compound or carbon monoxide is used as a hydrogen source used in an aromatic hydrogenation reaction, Provided are an aromatic hydrogenation catalyst having a high anti-toxicity against these catalyst poisons, particularly sulfur compounds, and thereby reducing the load for removing the catalyst poisons, and a method for producing the same.
SOLUTION: Nickel (Ni) is supported on a catalyst support made of a metal oxide at a ratio of 10 to 40% by weight in terms of metal, and tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ) as a second catalyst metal. ) Is added in an amount of 5 to 30%, and the catalyst carrier has a predetermined surface area, pore volume, average pore diameter, and ratio of pores having an average pore diameter of ± 30 mm to the total pore volume. A hydrogen-containing catalyst having a physical property of 0.1 to 3.0% by weight and a sulfur-containing catalyst carrier having excellent anti-poisoning properties against hydrogen source impurities and a method for producing the same.
[Selection figure] None

Description

  The present invention relates to a hydrogenation catalyst used for an aromatic hydrogenation reaction such as benzene, toluene and naphthalene, and a method for producing the same. Specifically, a sulfur compound and / or monoxide that becomes a poisonous substance of a catalyst as a hydrogen source in an aromatic hydrogenation reaction such as cyclohexane production from benzene, methylcyclohexane production from toluene, and decalin production from naphthalene. The present invention relates to a hydrogenation catalyst for an aromatic hydrogenation reaction using low-grade hydrogen containing carbon as a hydrogen source and a method for producing the same.

  The hydrogenation reaction of organic compounds is generally called a hydrogenation reaction, and the aromatic hydrogenation reaction has long been put into practical use as an industrial production method for cyclohexane, methylcyclohexane, decalin, and the like. In particular, cyclohexane was found to be a raw material for ε-caprolactam and adipic acid, which are the raw materials for nylon, and the demand for cyclohexane increased rapidly. As of 2001, domestic production was approximately 700,000 tons / year. More than 90% is consumed for nylon raw materials, and most of the rest is consumed for adipic acid raw materials.

  These industrial aromatic hydrogenation reactions are described in “Petrochemical Process”, Petroleum Society (2001) (Non-patent Document 1), “Process Handbook”, Petroleum Society (1986) (Non-Patent Document 2), etc. It has been introduced. All the processes do not require special high-temperature and high-pressure conditions, and are performed under relatively mild conditions such as a reaction temperature of 250 ° C. or lower and a reaction pressure of about 10 to 20 atm. In addition, the purity of the product is 99% or higher, and the yield is also highly established as a process with a very high productivity of 97-100%. The hydrogen source includes sulfur, carbon monoxide, etc. A high-purity hydrogen source (high-grade hydrogen) that does not contain any catalyst poisoning component is used.

  Typical aromatic hydrogenation reaction processes include production of methylcyclohexane using toluene as a raw material, production of cyclohexane using benzene as a raw material, and production process of decalin using naphthalene as a raw material. Here, the hydrogenation reaction of toluene and benzene is a reaction in which 3 mol of hydrogen is added to an aromatic ring, and the hydrogenation reaction of naphthalene, which is a bicyclic aromatic, is a hydrogenation reaction in which 5 mol of hydrogen is added. It becomes. In addition, these hydrogenation reactions are exothermic reactions, and the heat of reaction during the hydrogenation reaction of toluene and cyclohexane to which 3 mol of hydrogen is added is 205 kJ / mol, 206 kJ / mol, and that of naphthalene to which 5 mol of hydrogen is added. The heat of hydrogenation reaction is 332 kJ / mol.

  As described above, since the hydrogenation reaction involves a large exotherm, the raw material hydrogen is diluted with an inert gas such as nitrogen in order to prevent an increase in the reaction temperature due to the reaction heat, a runaway reaction, etc. The reaction is controlled by introducing them. In addition, the heat generated by the exothermic reaction is effectively used as energy necessary for processes such as preheating of raw materials, and surplus is recovered and used. Therefore, when a hydrogenation reaction is carried out using a small amount of catalyst in a laboratory or the like, the reaction is often carried out by mixing the catalyst with a diluent such as glass beads in order to prevent an increase in temperature due to an exothermic reaction.

  Methylcyclohexane is mainly used as a low-toxic industrial solvent, and the annual domestic demand is about 4,000 tons / year, which is the same process as the hydrogenation process of benzene. In many cases, the raw material is changed to toluene. Decalin production by hydrogenation of naphthalene is carried out under the conditions of a liquid phase reaction and is mainly used as an aroma-free industrial solvent, and the annual domestic production is about 500 tons / year.

  On the other hand, in recent technological development aimed at the use of hydrogen energy, the establishment of a method for storing and transporting hydrogen at a low cost has been urgently underway, and research and development of various hydrogen storage media has been vigorously carried out ( Non-Patent Document 3). One of these hydrogen storage / transport technologies under development is the organic chemical hydride method (see Non-Patent Document 4).

  In this method, hydrogen, which is the lightest gas, is fixed to an aromatic substance such as toluene by a chemical reaction by the above-mentioned hydrogenation reaction of the aromatic, thereby forming an organic chemical hydride such as methylcyclohexane that is liquid at room temperature and normal pressure. Converted and transported to the place where hydrogen is used in the form of this organic chemical halide and stored at this place of use. Also, dehydrogenation is performed at this place of use to generate and use hydrogen, which is generated by the dehydrogenation reaction. Aromatic substances such as toluene are collected and reused. Since toluene and methylcyclohexane, which are components of gasoline, are used, hydrogen storage and transport can be handled in the same way as gasoline, and the existing gasoline distribution infrastructure can be diverted.

  This method has been studied as the methylcyclohexane (MCH) method in the Euro-Québec project, which transports hydrogen produced by cheap hydroelectric power in Canada for about 15 years from 1980 and exports it to Europe. However, since no dehydrogenation catalyst that stably generates hydrogen was developed at that time, it was not put into practical use, and it is a method that has not been technically established at present. However, Japanese Patent No. 4,142,733 (see Patent Document 1) discloses a dehydrogenation catalyst that overcomes the carbon deposition of the dehydrogenation catalyst, which has been a concern, and a method for producing the dehydrogenation catalyst. In recent years, this method can be established. It has been introduced that the development of dehydrogenation catalysts is gradually progressing (see Non-Patent Document 5).

  As described above, the aromatic hydrogenation reaction using high-quality and high-purity hydrogen as a hydrogen source has already been industrialized, and high-quality hydrogen is transported even in hydrogen storage and transport systems using the organic chemical hydride method. In some cases, it can be put to practical use by applying an existing aromatic hydrogenation process.

By the way, approximately 30 billion Nm ³ of hydrogen is used annually in Japan, of which 60% is used for petroleum refining. These hydrogens are produced by a hydrogen production device in a refinery and used for catalytic cracking, catalytic reforming, and hydrodesulfurization processes in petroleum refining. Many of these hydrogen production systems were built by the 1980s, and as a result of the reduction of hydrogen consumption due to the efficiency of the hydrogen utilization process, the operating rate of domestic hydrogen production systems reached about 60%. Has been reduced. Accordingly, the petroleum industry has the capability of supplying about 6.4 billion Nm ³ of high-purity hydrogen by increasing the operating rate of the hydrogen production device in accordance with future hydrogen demand.

Other high-grade hydrogen sources include by-product hydrogen generated during salt electrolysis. However, the annual hydrogen generation is as low as about 1.2 billion Nm ³ , of which the amount of hydrogen sold outside the country is only 180 million Nm ³ , which is about 15%, and most of it is consumed as fuel by itself. Yes.

On the other hand, as a hydrogen source, not only the above-described high-quality and high-purity hydrogen hydrogen source, but also a low-quality and low-purity hydrogen source exists.
For example, the refineries mentioned above use high-grade hydrogen produced by hydrogen production equipment, as well as bleed gas after being used in catalytic cracking, catalytic reforming and hydrodesulfurization processes in petroleum refining. It contains a significant amount of hydrogen and is currently consumed in-house as fuel.

  Also in the steelworks, by-product gas containing a lot of hydrogen is generated in the coke production process, the process of producing pig iron from iron ore and coke, and the process of refining pig iron into steel with a converter. For example, coke oven gas (COG) that is recovered when coke is produced by carbonizing coal in a coke oven contains about 55% hydrogen. The blast furnace gas and the converter gas generated when refining in the converter contain about 3% hydrogen. In this way, most of the hydrogen in the by-product gas generated at steelworks is present in the coke oven gas, and hydrogen equivalent to 40% of the hydrogen used in Japan is these steelworks. It is generated in hydrogen.

These refinery bleed gas and steelworks by-product gas contain a large amount of hydrogen sulfide and carbon monoxide, which are poisonous substances for the catalyst. It is necessary to separate and purify the sulfur content and carbon monoxide. However, these low-grade hydrogen sources are present in relatively large quantities, the amount of hydrogen in refinery bleed gas is about ³ billion Nm ³ per year, and the amount of hydrogen in coke oven gas is about 7.8 billion per year. It is said to be Nm ³ .

  When these low-grade hydrogen is recovered and reused, it is often purified using a PSA process after the pretreatment to remove solids and the like, and further, a high-purity hydrogen is produced through a deoxygenation step. There are few cases where economic efficiency is realized due to restrictions on the hydrogen recovery rate and scale-up, and this is a major factor in consuming low-grade hydrogen simply as fuel. Therefore, the development of a catalyst capable of reducing the burden when reusing these low-grade hydrogen sources and performing an aromatic hydrogenation reaction has great significance from the viewpoint of hydrogen utilization in the petroleum industry.

  JP-A-62-215,540 (Patent Document 2) discloses a method for producing cyclohexane by reacting hydrogen in a coke oven gas with benzene, after reducing the sulfur compound in the coke oven gas to 1 ppm or less. Disclosed is a method for producing cyclohexane using hydrogen in a coke oven gas, characterized in that the carbon monoxide concentration in the gas is reduced to 1% or less by a shift reaction to react with benzene, and nickel is used as an active metal It is disclosed that the conversion of the reaction is not affected when the concentration of carbon monoxide is 1% or less.

  Japanese Patent Laid-Open No. 2003-277,003 (Patent Document 3) discloses a hydrogen-rich gas having a hydrogen concentration of 20 to 80% by volume using a raw material mainly containing naphthalene having a sulfur concentration of 50 ppm or less. A method of producing decalin by the hydrogenation reaction used and subjecting it to a dehydrogenation reaction to produce high purity hydrogen is disclosed. As an example, naphthalene hydrorefined to a sulfur content of 15 ppm and hydrogen purity of 70 are disclosed. An example is disclosed in which hydrogenation reaction is performed using palladium-supported activated carbon as a catalyst with a gas having a nitrogen concentration of 30% and a nitrogen concentration of 30%.

  Furthermore, Japanese Patent Application Laid-Open No. 2004-277,250 (Patent Document 4) similarly discloses a method in which hydrogen in a mixed gas containing hydrogen is hydrogenated with an aromatic compound and then taken out by dehydrogenation. However, the naphthalenes reacted with the mixed gas are preferably desulfurized, and it is desirable that the sulfur concentration be 100 ppm or less, more preferably 10 ppm or less. In this example, purified naphthalene (sulfur concentration 10 ppm) An example is disclosed in which a hydrogenation reaction is performed on desulfurized coke oven gas (sulfur concentration 10 ppm) using Raney nickel as a catalyst.

  As described above, when hydrogenation of aromatic compounds is performed using hydrogen in a hydrogen-containing gas such as a by-product gas according to the prior art, sulfur and carbon monoxide, which are poisonous substances for metal catalysts, are used. In particular, regarding the sulfur content in the reaction system, it is necessary to carry out a hydrogenation reaction after performing a treatment with a concentration of 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. is there.

Japanese Patent No. 4,142,733 JP-A-62-215,540 Japanese Patent Laid-Open No. 2003-277,003 JP 2004-277,250 A

“Petrochemical Process”, Petroleum Institute, p.94 (2001) "Process Handbook", Petroleum Institute, p.141 (1986) "Hydrogen technology that can be understood well", Nihon Kogyo Publishing, p.80 (2008) "Characteristics and Future of Hydrogen Storage / Supply System Using Organic Hydride", Junko Umezawa, Petrotech, vol.29, No.4, 253-257 (2006) “Global Hydrogen Supply Chain Concept and Development of Organic Chemical Hydride Hydrogen Storage and Transport System”, Yoshimi Okada, Masashi Saito, Nobuhiro Onda, Junichi Sakaguchi, Hydrogen Energy System vol.33, No.4, p.8 (2008)

  By the way, as an aromatic hydrogenation catalyst, a catalyst in which nickel is supported on a carrier such as alumina or silica alumina is the most representative, and the reason is that the decomposition activity is not as high as that of a noble metal and it is an inexpensive metal. It is done. However, since transition metals such as precious metals and nickel react with sulfur compounds to produce sulfides, sulfur compounds are very often poisonous substances for catalysts. In addition, it is known that metal sulfides are not easily decomposed, and sulfur compounds are extremely poisonous substances against catalysts even in reforming reactions carried out in the highest temperature range as a chemical reaction process.

Carbon monoxide (CO) is also known to form a carbonyl compound with a metal such as nickel, and is a typical metal catalyst poison as well as a sulfur compound. However, carbonyl compounds decompose under high temperature conditions and hydrogen-rich conditions to produce carbon monoxide (CO), and in the presence of a nickel catalyst, carbon monoxide (CO) reacts with hydrogen (H ₂ ) to produce methane. The methanation reaction to produce (CH ₄ ) proceeds. Therefore, under the reaction conditions in which the methanation reaction proceeds, low concentrations of carbon monoxide (CO) are not as poisonous as sulfur compounds, and generally less than 1% has problems with aromatic hydrogenation reactions. It is known that there are few.

  Therefore, the present inventors contain by-product gas containing hydrogen derived from fossil fuels in steelworks and refineries, mixed gas containing hydrocarbon-derived hydrogen such as waste plastic, or hydrogen derived from bio raw materials. To develop a hydrogenation catalyst that enables hydrogenation of aromatics even when using a low-grade hydrogen source derived from a mixed gas, etc., thereby reducing the burden of removing sulfur and carbon monoxide As a result of intensive studies, the catalyst-supporting sulfur-containing catalyst carrier having a predetermined physical property and containing a sulfur content in a predetermined ratio supports nickel as an active metal in a predetermined ratio and supports the second component of the catalyst. Thus, the inventors have found that the object can be achieved and completed the present invention.

  Accordingly, an object of the present invention is to use a sulfur compound or a monovalent compound as a hydrogen source used in an aromatic hydrogenation reaction for producing methylcyclohexane, cyclohexane, decalin, etc. by an aromatic hydrogenation reaction such as toluene, benzene, or naphthalene. Even when using low-grade hydrogen containing metal catalyst poisoning components such as carbon oxide, it is very strong against catalyst poisoning substances such as sulfur compounds and carbon monoxide, especially catalysts. An object of the present invention is to provide an aromatic hydrogenation catalyst which has high anti-toxicity against sulfur compounds having poisoning action and thereby can reduce the load for removing catalyst poisoning substances, and a method for producing the same.

That is, the present invention supports nickel (Ni) as an active metal in a ratio of 10 to 40% by weight in terms of metal on a catalyst support made of a metal oxide of a support metal, and from a metal oxide of a second catalyst metal. A hydrogenation catalyst to which 5 to 30% by weight of tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ) is added, and the catalyst support has a surface area of 150 m ² / g or more and a pore volume. 0.4 cc / g or more, average pore diameter of 40 to 300 mm, and the proportion of pores having an average pore diameter of ± 30 mm with respect to the total pore volume is 60% or more. It is a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities, characterized in that it is a sulfur-containing catalyst carrier containing 0.0 wt% sulfur content.

In the present invention, the surface area is 150 m ² / g or more, the pore volume is 0.4 cc / g or more, the average pore diameter is 40 to 300 mm, and the proportion of the average pore diameter is ± 30 mm relative to the total pore volume. A catalyst carrier having a physical property of 60% or more contains one or more sulfur or sulfur compounds selected from sulfur (S), sulfuric acid, and sulfates, and has a sulfur content of 0.1 to 3.0. A sulfur-containing catalyst carrier containing% by weight is prepared, and the resulting sulfur-containing catalyst carrier is impregnated with a nickel compound solution and dried to prepare a nickel compound-supported dried material. It is fired after impregnating and drying an aqueous solution of a metal compound of the metal, or the nickel compound-supported dry product is calcined to prepare a nickel-supported calcined product. Compound aqueous solution A hydrogen source impurity characterized in that nickel (Ni) is supported at a rate of 10 to 40% by weight in terms of metal and a metal oxide of a second catalytic metal is supported by calcination after immersion and drying It is a manufacturing method of the hydrogenation catalyst excellent in the anti-poisoning property with respect to.

  In the present invention, for the metal oxide used as the catalyst support, for example, aluminum (Al), silicon (Si), zirconium (Zr), magnesium (Mg), calcium (Ca), titanium (Ti), vanadium (V) , Chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), yttrium (Y), niobium (Nb) , Metal oxides containing one or more metals selected from molybdenum (Mo), tungsten (W), lanthanum (La), and cerium (Ce), preferably alumina, silica, Titania, zirconia, ceria, and the like are preferable, and alumina or silica, and silica alumina that is a composite oxide thereof are more preferable.

  In the present invention, since a relatively large amount of nickel metal needs to be supported on the catalyst support, a catalyst support with controlled pores can be used to maintain a good adsorbed and dispersed state in the impregnation step. In order to prepare a catalyst having high activity, it is necessary that the pores do not cause clogging or the like by the supported metal, and the prepared catalyst has a pore size suitable for the target reaction. In order to maintain a good dispersion state on the catalyst support, a relatively large amount of nickel metal supported on the catalyst support has a uniform pore size and a sharp pore distribution that selectively has a narrow range of pores. In addition to using the catalyst support, it is necessary that a sulfur content as a dispersant for the active metal is present on the pore surface of the catalyst support in advance.

  Therefore, in the present invention, for example, when the catalyst support is alumina, as disclosed in, for example, Japanese Patent Publication No. 6-72,005, a slurry of aluminum hydroxide generated by neutralization of an aluminum salt is filtered. A porous γ-alumina carrier obtained by washing and dehydrating and drying the obtained alumina hydrogel, followed by firing at 400 to 800 ° C. for about 1 to 6 hours, more preferably the pH value of the alumina hydrogel. Of alumina hydrogel by adding an alumina hydrogel-forming substance during the pH change from at least one pH region to the other pH region, and alternately changing between the alumina hydrogel dissolution pH region and the boehmite gel precipitation pH region. It is a porous γ-alumina support obtained through a pH swing process for growing .

  The porous γ-alumina support obtained through such a pH swing process has excellent uniformity of pore distribution, and there is little variation in physical properties even in the alumina support pellets after molding, and the physical properties of each pellet are Excellent in that it is stable, and has a narrow pore distribution with a uniform pore size and a uniform pore structure across the interior of the carrier. Therefore, the dispersibility when impregnating the metal is excellent.

In the dehydrogenation catalyst used in the present invention, the porous γ-alumina support used as the catalyst support has a surface area of 150 m ² / g or more, preferably 200 m ² / g or more, and a pore volume of 0.40 cc / g or more, Preferably, it is 0.65 cm ³ / g or more, the average pore diameter is 90 to 300 mm, preferably 90 to 200 mm, and the occupation ratio of pores with an average pore diameter of ± 30 mm is 60% or more, preferably 80%. If the surface area is less than 150 m ² / g, the activity after catalysis is not sufficient, and if the pore volume is less than 0.40 cc / g, it is difficult to uniformly carry the active metal component. Yes, if the average pore diameter is smaller than 90 mm, the surface area increases, but the pore volume is not sufficient. Conversely, if the average pore diameter is larger than 300 mm, the surface area becomes extremely small and the pore volume becomes extremely large. And these correlations As a result of comprehensive consideration, an average pore diameter of 90 to 300 mm is appropriate. Further, when the occupation ratio of pores having an average pore diameter of ± 30 mm is less than 60%, the effect of the present invention is reduced in catalyst performance.

  The sulfur or sulfur compound dispersed and contained in advance in such a catalyst carrier has elemental sulfur and is uniformly dispersed in the catalyst carrier at the time of preparation of the catalyst carrier or after preparation of the catalyst carrier. There is no particular limitation as long as it can be contained in the state, and examples thereof include sulfur crystal powder and sulfur-containing compounds such as sulfates such as sulfuric acid and ammonium sulfate, and sulfur is easily dispersed on the support. From the viewpoint, a sulfur compound that is soluble in water or an organic solvent is preferable, and examples of such a sulfur compound include sulfuric acid and ammonium sulfate.

  The amount of sulfur to be contained in the carrier is preferably 0.1% by weight or more and 3% by weight or less, more preferably 0.15% by weight or more and 2.0% by weight or less as the sulfur (S) content. When the sulfur content is less than 0.1% by weight, the effect is low in the degree that the metal is uniformly supported over the center of the catalyst, and when the sulfur content exceeds 3% by weight, sulfur locally aggregates. It is easy to cause a problem that the metal is not dispersed and supported on such local portions. From these, the most suitable range of the sulfur content in the effect of uniformly dispersing and supporting the metal is preferably 0.15 to 2.0% by weight.

  In the present invention, the method for preparing the sulfur-containing catalyst carrier containing sulfur or a sulfur compound is not particularly limited as long as it can contain sulfur or a sulfur compound in a state of being dispersed throughout the carrier cross section. Examples of the methods A to E can be exemplified.

[Method A]
A method in which a sulfur powder is kneaded into a metal hydroxide gel that is a precursor of a metal oxide obtained at the time of preparation of a catalyst carrier, shaped into a predetermined shape, dried, and calcined.

[Method B]
A metal hydroxide gel that is a precursor of a metal oxide containing a sulfur content is prepared using a metal sulfate and / or sulfuric acid at the time of preparation of the catalyst carrier, formed into a predetermined shape, dried and fired. How to prepare

[Method C]
A sulfur-containing catalyst carrier is mixed with a metal hydroxide gel that is a precursor of a metal oxide, and then a sulfur compound solution is mixed and then fired after molding and drying, or a metal hydroxide gel that is a precursor of a metal oxide Is formed into a predetermined shape, then dried to obtain a dry metal hydroxide, and the dry metal hydroxide is impregnated with a sulfur compound solution and then fired and prepared.

[Method D]
A metal hydroxide gel that becomes a precursor of the metal oxide during the preparation of the catalyst carrier is formed into a predetermined shape, and then dried to obtain a dry metal hydroxide. The dry metal hydroxide is impregnated with a sulfur compound solution. After baking

[Method E]
A metal hydroxide gel, which is a precursor of a metal oxide, is formed into a predetermined shape, then dried to obtain a dry metal hydroxide gel, and then the fired metal obtained by firing this dry metal hydroxide gel A method of preparing an oxide and impregnating the calcined metal oxide with a sulfur compound solution such as an aqueous sulfuric acid solution or an aqueous ammonium sulfate solution, followed by firing again

  Further, regarding the firing conditions when preparing this sulfur-containing catalyst carrier, the firing temperature is usually 100 ° C. or higher and 1,000 ° C. or lower, preferably 350 ° C. or higher and 800 ° C. or lower, and the firing time is 0.5. The time is not less than 48 hours, preferably not less than 1 hour and not more than 24 hours. When the calcination temperature is lower than 350 ° C., the conversion from hydroxide to oxide may not be sufficiently performed. On the other hand, when the calcination temperature is higher than 800 ° C., the surface area after calcination may be significantly reduced.

  As a method of preparing a nickel-supported fired product by supporting nickel metal on such a sulfur-containing catalyst carrier, the sulfur-containing catalyst carrier is impregnated with a solution such as an aqueous solution of a nickel compound, and the nickel compound is applied to the pore surface of the carrier. Adsorbed, dried, and dried to prepare a nickel compound-supported dried product, and the resulting nickel compound-supported dried product was calcined in the presence of air in a muffle furnace or other firing furnace, thereby containing sulfur. There is a method in which the nickel compound adsorbed on the pore surface of the catalyst support is decomposed and converted into an oxide, and nickel oxide particles are supported on the support.

  The supported amount of nickel is preferably 10% by weight or more and 40% by weight or less as the metal equivalent amount of nickel. When the supported amount of nickel is 10% by weight or less in terms of metal, sufficient hydrogenation activity cannot be obtained. Conversely, when 40% by weight or more of nickel is supported, it is difficult to prepare a catalyst. Hydrogenation activity tends to be low.

  The nickel source used when the nickel metal is supported on the carrier is not particularly limited as long as it is a nickel compound that is water-soluble or soluble in an organic solvent. For example, nickel nitrate, nickel sulfate, nickel chloride, Examples thereof include nickel acetate, nickel carbonate and nickel hydroxy carbonate.

  The nickel concentration when the catalyst support is impregnated with such a nickel compound solution is not particularly limited as long as the nickel compound is uniformly dissolved. However, if the amount of the solvent is large, excessive energy is required for removing the solvent. Therefore, it is better to be able to impregnate with a small amount of solution. Further, when using an organic solvent, there are many cases where it takes time and cost for prevention of volatile diffusion at the time of removal and disposal, and it is preferable to use an aqueous solvent as an impregnation solution using a water-soluble nickel reagent. .

  The method for removing the solvent is not particularly limited, but since the amount of nickel metal supported is relatively large, it is difficult for the nickel compound to be completely adsorbed on the catalyst support. Therefore, since there is a nickel compound dissolved in the solvent even after impregnation with the nickel compound solution, the removal of the solvent can be forcibly removed with an apparatus equipped with a heating function in order not to make the preparation time longer than necessary. Necessary. At this time, if the solvent is removed too quickly at a high temperature, the dispersibility of the nickel metal is lowered. Therefore, it is preferable to use a device such as a rotary evaporator or a rotary kiln that can expand the sales of the entire catalyst carrier while heating.

  It is preferable that the dried nickel compound-supported product from which the solvent is removed and the nickel compound is adsorbed on the catalyst support is additionally dried. If a large amount of solvent such as moisture remains in the dried nickel compound-supported product, the solvent is evaporated at the time of firing. Usually, drying is performed at a temperature of 100 ° C. or less, preferably 60 to 90 ° C. for 0.5 to 24 hours, preferably 0.5 to 12 hours, more preferably 1 to 5 hours using a dryer. Is good.

  The dried nickel compound-supported dried product thus additionally dried is further baked in a firing furnace such as a muffle furnace to form a nickel-supported fired product. The atmosphere at the time of firing may be air, and it is preferable to circulate in the furnace. The firing temperature is usually from 100 ° C. to 1,000 ° C., preferably from 350 ° C. to 800 ° C., more preferably from 350 ° C. to 600 ° C., and the firing time is 0.5 hours or more. 48 hours or less, preferably 1 hour or more and 24 hours or less. When the calcination temperature is lower than 350 ° C., the conversion from hydroxide to oxide may not be sufficiently performed. On the other hand, when the calcination temperature is higher than 800 ° C., the surface area after calcination may be significantly reduced.

  The thus-fired nickel-supported fired product is in a state where nickel oxide particles are supported on the pore surfaces of the catalyst carrier. Therefore, in order to develop a high catalytic activity for hydrogenation, it is necessary to reduce the oxide particles to nickel metal particles. The method for reducing the nickel oxide particles is not particularly limited, but usually reduction using hydrogen gas is preferred.

  The temperature for hydrogen reduction is preferably 250 to 600 ° C., more preferably 300 to 450 ° C., and preferably 350 to 400 ° C. in a hydrogen stream. Reduction at a high temperature of 600 ° C. or higher leads to a reduction in the surface area of the catalyst, and at a temperature of 250 ° C. or lower, it is difficult to perform sufficient reduction. Regarding the reduction time, it is preferable to perform the reduction sufficiently for 3 hours or more, more preferably 15 hours or more. However, if the reduction is performed for a longer time, it takes a lot of time to prepare the catalyst and the production cost becomes high, so that a reduction time of 10 to 24 hours is preferable.

  A second catalyst metal is further supported on the nickel-supported fired product prepared as described above. There are two methods for supporting the second catalyst metal on the nickel-supported calcined product, and the first method is to impregnate the dried nickel compound-supported product with the metal compound aqueous solution of the second catalyst metal and dry it. The second method is a method of firing later, and the second method is a method of firing after impregnating a nickel-supported fired product with an aqueous metal compound aqueous solution of the second catalyst metal. The nickel compound-carrying dried product or nickel-carrying calcined product when the second catalyst metal is supported is reduced in advance with hydrogen before supporting the second catalyst metal, and the nickel compound-carrying dried product or nickel-carrying product is supported. It is preferable to convert the nickel oxide particles supported on the surface of the sulfur-containing catalyst carrier in the fired product into nickel metal particles.

Examples of the metal oxide of the second catalytic metal supported on the nickel-supported fired product obtained above include tungstic acid (WO ₃ ) and molybdic acid (MoO ₃ ).

When the metal oxide of the second catalytic metal is tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ), the amount added is within the range of 5 to 30% by weight as the amount of metal oxide. preferable. If the addition amount of tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ) is less than 5% by weight, a sufficient addition effect cannot be obtained, and if the addition amount is more than 30% by weight, the addition effect becomes rather low. .

In addition, as a tungsten compound that can be used when adding tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ), ammonium tungstate [5 (NH ₄ ) ₂ · 12WO ₃ · 5H ₂ O], tungsten chloride, etc. There is no particular limitation as long as it is a tungsten compound containing only tungsten as a metal species. However, since a tungsten compound generally has low solubility, it is necessary to select a solvent, preferably ammonium tungstate [5 (NH ₄ ) _2. [12WO ₃ · 5H ₂ O] is preferably dissolved in an aminoethanol aqueous solution.

The molybdenum compounds that can be used when adding molybdic acid (MoO ₃ ) include ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O], molybdic acid (H ₂ MoO ₄ · H ₂ O), There is no particular limitation as long as it is a molybdenum compound containing only molybdenum as a metal species such as molybdenum chloride, molybdenum oxychloride compound, etc., but it is necessary to select a solvent as in the case of tungstic acid, preferably ammonium molybdate. [(NH ₄ ) ₆ Mo ₇ O ₂₄ · 4H ₂ O] is preferably used by dissolving in water.

After impregnating a nickel-supported catalyst with a solution of these tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ), the solution was allowed to stand for 1 hour or more, preferably 3 hours or more, and then the solvent was removed using an evaporator or a similar apparatus. To do. The nickel catalyst impregnated with tungstic acid or molybdic acid thus obtained is further dried in a drier and then baked in a baking apparatus such as an electric furnace. The firing temperature is preferably 150 to 800 ° C, more preferably 150 to 300 ° C, and preferably about 200 ° C.

The catalyst to which tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ) calcined as described above is added is used after being reduced with hydrogen during the reaction. The temperature for hydrogen reduction is preferably 250 to 600 ° C., more preferably 300 to 450 ° C., and preferably 350 to 400 ° C. in a hydrogen stream. Reduction at a high temperature of 600 ° C. or more causes a reduction in the surface area of the catalyst, and at a temperature of 250 ° C. or less, it is difficult to perform sufficient reduction. Regarding the reduction time, it is preferable to perform the reduction sufficiently for 3 hours or more, more preferably 15 hours or more. However, if the reduction is performed for a longer time, it takes a lot of time to prepare the catalyst and the production cost becomes high, so that a reduction time of 10 to 24 hours is preferable.

In addition, the reduction operation of the catalyst to which tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ) is added is preferably performed after being charged into the reactor when being subjected to the reaction. Since the catalyst taken out from the reducing apparatus and brought into contact with air is exposed to an oxidized state including the surface of nickel metal, the catalyst activity tends to be reduced by forming a passive film. Although hydrogen-rich conditions during the hydrogenation reaction, the aromatic hydrogenation reaction is carried out at a relatively low reaction temperature of 250 ° C. or lower, so that the conditions for reduction again after the start of the reaction are not sufficient. is there.

  The catalyst thus prepared has high toxicity against sulfur compounds and carbon monoxide, particularly sulfur compounds, contained in a low-grade hydrogen source. However, since sulfur compounds have very high poisoning characteristics, there are limitations on the conditions for using the catalyst, and preferably the sulfur concentration in the hydrogen source to be hydrogenated is 1,000 ppm or less, more preferably 500 ppm or less, It is desirable that the sulfur concentration is reduced to about 100 to 200 ppm.

  The hydrogenation catalyst of the present invention has excellent catalytic activity and selectivity in hydrogenation reactions of aromatic hydrocarbons even when a low-grade hydrogen source containing impurities such as hydrogen sulfide and carbon monoxide is used as the hydrogen source. Can be stably exhibited for a long time. Moreover, according to the manufacturing method of this invention, such a hydrogenation catalyst can be manufactured industrially easily.

  Hereinafter, preferred embodiments of the present invention will be described in detail based on examples, test examples, and comparative examples.

[Preparation of catalyst support]
First, the following five types of catalyst carriers A to E were prepared or prepared as catalyst carriers used in Examples and Comparative Examples of the present invention.

(1) Catalyst carrier A (Manufacture of silica carrier)
In addition to preparing 3,900 cc of nitric acid having a concentration of 8.01 mol / L, 3,900 cc of an aqueous solution of J sodium silicate having a concentration of 8.01 mol / L based on the concentration of sodium hydroxide was prepared. Next, 20 L of pure water was put into a 30 liter (L) enamel container, heated to 70 ° C. while stirring, and further stirred, 650 cc of the nitric acid aqueous solution was added and stirred for 5 minutes (pH: 3.0 or less), and then 6500 cc of the aqueous sodium silicate solution was added and stirred for 5 minutes (pH value: 10.4). The pH swing operation was repeated 6 times. The obtained slurry aqueous solution was filtered to collect a cake, and then the washing operation of redispersing the cake in 20 L of pure water and filtering again was repeated three times to obtain a washed cake. Next, the washed cake is air-dried to adjust the moisture content, then formed into a 1.6 mm diameter rod with an extruder, dried at 120 ° C. for 3 hours, and then pulverized to a length of about 1 cm. , Prepared by firing in a muffle furnace at 500 ° C. for 3 hours, and the surface area (m ² / g), pore volume (cc / g), average pore diameter (Å) and total fineness shown in Table 1 A silica carrier (catalyst carrier A) having a ratio (%) of pores having an average pore diameter of ± 30 mm to the pore volume was used.

(2) Catalyst carrier B (Manufacture of silica-alumina carrier)
In addition to preparing 3,900 cc of nitric acid with a concentration of 8.01 mol / L, a mixed aqueous solution of 3,900 cc with sodium silicate at 5.34 mol / L and sodium aluminate at 2.67 mol / L was prepared. Next, 20 L of pure water was put into a 30 liter (L) enamel container, heated to 70 ° C. while stirring, and further stirred, 650 cc of the aqueous aluminum nitrate solution was added and stirred for 5 minutes (pH Value: 3.0 or less), and then 650 cc of the above mixed aqueous solution was added and stirred for 5 minutes (pH value: 10.2). The pH swing operation was repeated 6 times. The obtained slurry aqueous solution was filtered to collect a cake, and then the washing operation of redispersing the cake in 20 L of pure water and filtering again was repeated three times to obtain a washed cake. Next, the washed cake is air-dried to adjust the moisture content, then formed into a 1.6 mm diameter rod with an extruder, dried at 120 ° C. for 3 hours, and then pulverized to a length of about 1 cm. , Prepared by firing in a muffle furnace at 500 ° C. for 3 hours, and the surface area (m ² / g), pore volume (cc / g), average pore diameter (Å) and total fineness shown in Table 1 A silica-alumina carrier (catalyst carrier B) having a ratio (%) of pores having an average pore diameter of ± 30 mm to the pore volume was obtained.

(3) Catalyst support C (alumina support having a wide range of pore distribution)
As catalyst carrier C, the surface area (m ² / g), pore volume (cc / g), average pore diameter (Å), and pores having an average pore diameter of ± 30Å with respect to the total pore volume are shown in Table 1. A commercially available γ-alumina support having an occupying ratio of 60% or less was used.

(4) Catalyst carrier D (alumina carrier having a narrow pore distribution with controlled pores)
3900 cc of an aqueous aluminum nitrate solution having a concentration of 2.67 mol / L was prepared, and 3900 cc of an aqueous ammonia solution having a concentration of 14% was prepared. Next, 20 L of pure water was put into a 30 liter (L) enamel container, heated to 70 ° C. while stirring, and further stirred, 650 cc of the aqueous aluminum nitrate solution was added and stirred for 5 minutes (pH Value: 2.0), and then 650 cc of the aqueous ammonia solution was added and stirred for 5 minutes (pH value: 7.4). The pH swing operation was repeated 6 times. The obtained aluminum hydroxide slurry aqueous solution is filtered to recover a cake, and then the washing operation of redispersing the cake in 20 L of pure water and filtering again is repeated three times to obtain an aluminum hydroxide washed cake. It was. Next, the washed cake is air-dried to adjust the moisture content, then formed into a 1.6 mm diameter rod with an extruder, dried at 120 ° C. for 3 hours, and then pulverized to a length of about 1 cm. And calcining in a muffle furnace at 500 ° C. for 3 hours to obtain a γ-alumina carrier (catalyst carrier D).

(Properties of alumina carrier with sharp pore distribution)
The surface area (m ² / g), pore volume (cc / g), average pore diameter (Å), and average pore diameter of the obtained γ-alumina carrier (catalyst carrier D) ± 30Å Table 1 shows the ratio (%) occupied by the pores. Further, the pore distribution of the γ-alumina carrier (catalyst carrier D) is shown in FIG. 1 together with the pore distribution of the γ-alumina carrier (catalyst carrier C).

(5) Catalyst carrier E (Sulfur-containing catalyst carrier)
The above γ-alumina support (catalyst support D) was impregnated with an aqueous ammonium sulfate solution having a concentration of 0.38 mol / L so that the sulfur content after calcination was 0.5% by weight, and then the solvent was removed with an evaporator. Sulfur-containing γ-alumina, dried at 120 ° C for 3 hours, calcined at 500 ° C for 3 hours, and containing 0.5% by weight (sulfur content) of sulfur as sulfur element (S) A carrier (catalyst carrier E) was obtained.

[Examples 1-2 and Comparative Examples 1-5]
Next, hydrogenation catalysts No. 1 to No. 7 (Comparative Examples 1 to 7) according to Comparative Examples 1 to 5 and Examples 1 to 2 were used as described below, using the above five types of catalyst carriers A to E. 5: Hydrogenation catalysts No. 1 to No. 5; Examples 1-2: Hydrogenation catalysts No. 6 to No. 7) were prepared.

(1) Preparation of hydrogenation catalysts No. 1 to No. 5 Using the above five types of catalyst carriers A to E, each of the catalyst carriers A to E was added to 97 cc of a nickel nitrate aqueous solution prepared to a concentration of 0.5 mol / L. After impregnating 100 g of E and allowing to stand in a sealed container for 12 hours, water was removed at room temperature with an evaporator, and the mixture was baked in an electric furnace at 200 ° C. for 3 hours in air. Each fired product in which nickel (Ni) was supported on ~ E was obtained. Next, each of these calcined products is filled in a flow-type hydrogen reduction device, and hydrogen reduction is performed under conditions of 370 ° C. and 15 hours under a hydrogen stream, and hydrogenated catalysts No. 1 to No. 5 (Comparative Examples 1 to 5). ) And hydrogenation catalyst No. 6 (Example 1) and hydrogenation catalyst No. 7 (Example 2) were obtained.

Table 1 shows the nickel supported amount (Ni supported amount) in terms of metallic Ni in the obtained hydrogenation catalysts No. 1 to No. 5.
In addition, for the hydrogenation catalyst No. 5, the presence concentration of sulfur element (S) and nickel (Ni) element on the cross section of the catalyst using EPMA was quantified by surface analysis and line analysis. As a result, these sulfur element (S) It was also found that the nickel (Ni) element was supported with almost the same distribution and almost uniformly dispersed.
Furthermore, as a result of measuring the particle diameter of the nickel (Ni) element by the X-ray diffraction method, the particle diameter was about 4 nanometers or less.

(2) Preparation of hydrogenation catalyst No. 6 (Example 1) 21.57 g of ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ per 100 g of the hydrogenation catalyst No. 5 obtained above・ After impregnating an aqueous solution of 4H ₂ O dissolved in 65.92 cc of pure water and leaving it in a sealed container for 12 hours, water was removed at room temperature with an evaporator, and 200 ° C. in air in an electric furnace. The calcined product is then calcined for a period of time, and then the calcined product is charged into a flow-type hydrogen reduction device, and reduced with hydrogen in a hydrogen stream at 370 ° C. for 15 hours, so that molybdic acid (MoO ₃ ) Hydrogenation catalyst No. 6 added at a ratio of 15% by weight based on .5 was prepared.
Table 1 shows the nickel supported amount (Ni supported amount) and molybdic acid (MoO ₃ ) supported amount (MoO ₃ supported amount) in terms of metallic Ni in the obtained hydrogenation catalyst No. 6.

(3) Preparation of hydrogenation catalyst No. 7 (Example 2) To 100 g of the hydrogenation catalyst No. 5 obtained above, 14.17 g of ammonium tungstate [5 (NH ₄ ) ₂ · 12WO ₃ · 5H ₂ O] was impregnated with an aqueous solution of 65.92 cc of aminoethanol in water and allowed to stand in a sealed container for 12 hours, after which moisture was removed at room temperature with an evaporator, and in an electric furnace at 200 ° C. in air for 3 hours. Then, the calcined product was charged into a flow-through hydrogen reduction device, and hydrogen-reduced under conditions of 370 ° C. and 15 hours under a hydrogen stream, whereby tungstic acid (WO ₃ ) was converted into a hydrogenation catalyst No. Hydrogenation catalyst No. 7 added at a ratio of 15% by weight based on 5 standards was prepared.
Table 1 shows the nickel supported amount (Ni supported amount) and the tungstic acid (WO ₃ ) supported amount (WO ₃ supported amount) in the hydrogenation catalyst No. 7 obtained.

[Test Example 1: Hydrogenation Test 1]
About each hydrogenation catalyst No.1-No.7 obtained in each said Comparative Examples 1-5 and Examples 1-2, it diluted 10 times using the glass bead so that the removal of reaction heat might become easy. Thereafter, the diluted hydrogenation catalysts No. 1 to No. 7 are filled into the reaction tube of the flow-type catalytic reaction test apparatus, and the raw material toluene is supplied to the reaction tube under the condition of LHSV: 10 h ^−1. Then, a mixed hydrogen gas containing 100 ppm of impurity hydrogen sulfide as a hydrogen source is supplied under the conditions of GHSV: 22800 h ⁻¹ , and a flow-type hydrogenation reaction test 1 for 6 hours under the conditions of a reaction temperature of 200 ° C. and a reaction pressure of 0.2 MPa. went.

In this hydrogenation test, 1 hour after the start of the flow test and 6 hours after the start of the flow test, the product was externally cooled with ice water and collected separately into gas and liquid, and each sample collected was subjected to gas chromatography. Thus, the conversion rate of toluene and the selectivity of the target product, methylcyclohexane, were determined.
The results are shown in Table 2.

  From Table 2, the conversion rates of catalysts 1 and 2 with nickel supported on silica support and silica alumina support are as low as 32% and 37% at the beginning of the reaction time of 1 hour, and decrease to 12% and 16% after 6 hours of reaction. This indicates that the activity is low and the catalyst deterioration is large.

  Catalyst 3 and catalyst 4 using alumina as a catalyst carrier have higher initial activity than catalysts 1 and 2, and catalyst 4 using an alumina carrier having a narrow pore distribution and a sharp pore distribution, It can be seen that the initial activity is high and the deterioration of the activity after 6 hours of reaction is small compared to the catalyst 3 using the alumina support having a broad pore distribution and a broad pore distribution.

  Furthermore, it can be seen that the catalyst 5 in which the sulfur content is added to the alumina carrier has almost the same catalytic performance as the catalyst 4 not containing the sulfur content. The catalyst performance of catalyst 6 (Example 1) in which molybdic acid was added to catalyst 5 was as low as 51% in the initial activity, but the addition rate after 6 hours of the reaction was maintained at 48%, and the activity degradation was It can be seen that it has been relaxed.

  Further, the catalyst 7 (Example 2) obtained by adding tungstic acid to the catalyst 5 has the highest initial activity of 71% compared to the other catalysts, and the conversion rate after 6 hours of the reaction is maintained at 69%. It can be seen that despite the presence of 100 ppm of hydrogen sulfide, which is a sulfur compound, it has high conversion and high anti-poisoning properties. In addition, the selectivity has a high selectivity of 99% or more in all the above-described reaction tests, indicating that the presence of hydrogen sulfide does not affect the selectivity.

[Test Example 2: Hydrogenation reaction test 2]
Comparative Examples 1 to 5 were performed in the same manner as in the hydrogenation reaction test 1 of Test Example 1 except that a mixed hydrogen gas containing 100 ppm of impurity hydrogen sulfide and 1,000 ppm of carbon monoxide (CO) was used as the hydrogen source. And the hydrogenation reaction test 2 about the hydrogenation catalyst No.1-No.7 of Examples 1-2 was conducted.
The results are shown in Table 3.

  From Table 3, even when carbon monoxide having a high concentration of 1,000 ppm, which is 10 times the concentration of hydrogen sulfide of 100 ppm, was present, the degree of activity deterioration of each catalyst during the 6-hour reaction was the same as that of Test Example 1. It turns out that it does not change greatly. However, when tungstic acid is added and the initial activity of the catalyst 7 is only hydrogen sulfide in Test Example 1, the initial activity is about 52% when carbon monoxide is present in this Test Example. It is shown that it is characteristic to decrease.

[Examples 3 to 5 and Comparative Examples 6 to 7]
Using the hydrogenation catalyst No. 5 obtained above, the second component tungstic acid (WO ₃ ) was added in various proportions in the same manner as in the case of the hydrogenation catalyst No. 7 in Example 2 above. Addition amount (WO ₃ addition amount) based on the weight of tungstic acid (WO ₃ ) is 3 wt% (Comparative Example 6: hydrogenation catalyst No. 8), 5 wt% (Example 3: hydrogenation catalyst No. 9) 10 wt% (Example 4: hydrogenation catalyst No. 10), 20 wt% (Example 5: hydrogenation catalyst No.11), and 26 wt% (Comparative Example 7: hydrogenation catalyst No.12) Certain hydrogenation catalysts No. 8 to No. 12 were prepared.

For the hydrogenation catalysts No. 9 to No. 11 of each of Examples 3 to 5 and the hydrogenation catalysts No. 8 and No. 12 of Comparative Examples 6 to 7, the hydrogenation reaction test 1 of Test Example 1 and Similarly, a hydrogenation reaction test 3 was performed.
The results are shown in Table 4.

From Table 4, since the addition amount of tungstic acid (WO ₃ ) is 5% or less based on the weight of tungstic acid, the effect of suppressing the deterioration of activity is small, and when the addition amount exceeds 25%, the conversion rate decreases. It has been shown that the addition amount of tungstic acid (WO ₃ ) is preferably 5 to 25%.

  The hydrogenation catalyst of the present invention stably exhibits excellent catalytic activity and selectivity even when a low-grade hydrogen source containing impurities such as hydrogen sulfide and carbon monoxide is used as the hydrogen source. It is suitably used as a hydrogenation catalyst for hydrogen storage reaction used in a hydride method hydrogen supply system or the like, or as a hydrogenation catalyst for aromatic hydrocarbons. Moreover, according to the manufacturing method of this invention, such a hydrogenation catalyst can be manufactured industrially easily.

FIG. 1 is a graph showing the pore distribution of the catalyst carrier C and the catalyst carrier D.

Claims (17)

A catalyst carrier made of a metal oxide of a support metal carries nickel (Ni) as an active metal at a rate of 10 to 40% by weight in terms of metal, and a second component made of a metal oxide of a second catalyst metal is added. The catalyst support has a surface area of 150 m ² / g or more, a pore volume of 0.4 cc / g or more, an average pore diameter of 40 to 300 mm, and an average pore diameter of ± 30 mm with respect to the total pore volume. Anti-poisoning against hydrogen source impurities characterized by being a sulfur-containing catalyst carrier having a physical property of 60% or more of the pores and containing 0.1 to 3.0% by weight of sulfur content Hydrogenation catalyst with excellent characteristics. 2. The hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to claim 1, wherein the second component comprising the metal oxide of the second catalyst metal is tungstic acid (WO ₃ ) or molybdic acid (MoO ₃ ). .   The hydrogenation catalyst excellent in the anti-poisoning property with respect to the hydrogen source impurity of Claim 1 or 2 by which the 2nd component is added in the ratio of 5-30 weight% as a metal oxide of a 2nd catalyst metal.   The catalyst support is a metal oxide of one or more support metals selected from aluminum (Al), silicon (Si), titanium (Ti), zirconium (Zr), and cerium (Ce). The hydrogenation catalyst excellent in the anti-poisoning property with respect to the hydrogen source impurity in any one of 1-3.   The hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to any one of claims 1 to 4, wherein the catalyst carrier is a molded body or powder made of porous γ-alumina.   The hydrogen source according to any one of claims 1 to 5, wherein the sulfur component contained in the sulfur-containing catalyst carrier is one or more sulfur or sulfur compounds selected from sulfur (S), sulfuric acid, and sulfate. Hydrogenation catalyst with excellent anti-poisoning properties against impurities. Physics with a surface area of 150 m ² / g or more, a pore volume of 0.4 cc / g or more, an average pore diameter of 40 to 300 mm, and a ratio of pores with an average pore diameter of ± 30 mm to the total pore volume of 60% or more Sulfur containing 0.1 to 3.0% by weight of sulfur containing sulfur or sulfur compound selected from sulfur (S), sulfuric acid and sulfate in a catalyst carrier having properties A catalyst carrier is prepared, and the resulting sulfur-containing catalyst carrier is impregnated with a nickel compound solution and dried to prepare a nickel compound-carrying dried material. Next, a metal compound aqueous solution of the second catalyst metal is added to the nickel compound-carrying dried material. It is impregnated and dried and then fired, or this nickel compound-supported dried product is calcined to prepare a nickel-supported calcined product, and the resulting nickel-supported calcined product is impregnated with a metal compound aqueous solution of the second catalyst metal and dried. Let Anti-poisoning property against hydrogen source impurities, characterized by supporting nickel (Ni) in a proportion of 10 to 40% by weight in terms of metal and supporting a metal oxide of the second catalytic metal by firing later For producing a hydrogenation catalyst excellent in water.   The sulfur-containing catalyst carrier is prepared by kneading a sulfur powder into a metal hydroxide gel that is a precursor of the metal oxide of the catalyst carrier, forming the sulfur powder into a predetermined shape, drying and firing. 8. A method for producing a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to 7.   A sulfur-containing catalyst carrier is prepared by preparing a metal hydroxide gel that is a precursor of a metal oxide using an aqueous solution of metal sulfate and / or sulfuric acid, forming it into a predetermined shape, and then drying and firing. The method for producing a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to claim 7.   A sulfur-containing catalyst carrier is mixed with a metal hydroxide gel that is a precursor of a metal oxide, and then a sulfur compound solution is mixed and then fired after molding and drying, or a metal hydroxide gel that is a precursor of a metal oxide 8. The hydrogen according to claim 7, wherein the hydrogen is prepared by molding into a predetermined shape and then drying to form a dry metal hydroxide, impregnating the dry metal hydroxide with a sulfur compound solution, and firing. A method for producing a hydrogenation catalyst having excellent anti-poisoning properties against source impurities.   A sulfur-containing catalyst carrier is obtained by forming a metal hydroxide gel, which is a precursor of a metal oxide, into a predetermined shape, then drying to form a dry metal hydroxide, and then firing the dry metal hydroxide. The water having excellent anti-poisoning properties against hydrogen source impurities according to claim 7, wherein the fired metal oxide is prepared by impregnating the fired metal oxide with a sulfur compound solution and then firing again. A method for producing a catalyst.   The method for producing a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to claim 10 or 11, wherein the sulfur compound solution is an aqueous sulfuric acid solution or an aqueous ammonium sulfate solution.   The method for producing a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to any one of claims 7 to 12, wherein the sulfur-containing catalyst carrier is a sulfur-containing porous γ-alumina carrier.   The calcining conditions for preparing the sulfur-containing catalyst support are a calcining temperature of 350 to 800 ° C and a calcining time of 1.0 to 24 hours. A method for producing an excellent hydrogenation catalyst.   After reducing nickel (Ni) compound-supported dried product or nickel (Ni) -supported calcined product with hydrogen, metal compound of one or more second catalyst metals selected from tungsten (W) or molybdenum (Mo) The method for producing a hydrogenation catalyst having excellent anti-poisoning properties against hydrogen source impurities according to any one of claims 7 to 14, wherein the aqueous solution is impregnated, dried and calcined, and then reduced again with hydrogen.   A method for hydrogenating aromatics, comprising hydrogenating aromatics using the hydrogenation catalyst according to any one of claims 1 to 6.   The fragrance according to claim 16, wherein the aromatic is a monocyclic aromatic hydride, a bicyclic aromatic, a compound having three or more aromatic rings, or a mixture of two or more. A method for hydrogenating tribes.

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