JP2016182544A - Catalyst for hydrogenation reaction and method for producing alicyclic compound using the same - Google Patents
Catalyst for hydrogenation reaction and method for producing alicyclic compound using the same Download PDFInfo
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- silica gel
- ruthenium
- hydrogenation reaction
- methylenedianiline
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 150000001334 alicyclic compounds Chemical class 0.000 title abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000741 silica gel Substances 0.000 claims abstract description 27
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 4
- SPJXZYLLLWOSLQ-UHFFFAOYSA-N 1-[(1-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CCCCC1(N)CC1(N)CCCCC1 SPJXZYLLLWOSLQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Abstract
Description
本発明は、芳香核水素化反応に用いられる触媒に関する。 The present invention relates to a catalyst used in an aromatic nucleus hydrogenation reaction.
ビス（アミノシクロヘキシル）メタンは、エポキシ樹脂アミン硬化剤として用いられる（例えば、非特許文献１参照）一方、ポリウレタン原料であるメチレンビス（シクロヘキシルイソシアネート）の原料アミンとしても知られている。 Bis (aminocyclohexyl) methane is used as an epoxy resin amine curing agent (see, for example, Non-Patent Document 1), while it is also known as a raw material amine for methylene bis (cyclohexyl isocyanate), which is a polyurethane raw material.
ビス（アミノシクロヘキシル）メタンの製造方法としては、芳香族ジアミンであるメチレンジアニリンを金属触媒の存在下に高圧で水素添加させ、芳香族を脂環族に変換させる方法が一般的に知られている（例えば、特許文献１、２参照）。 As a method for producing bis (aminocyclohexyl) methane, a method in which methylenedianiline which is an aromatic diamine is hydrogenated at high pressure in the presence of a metal catalyst to convert the aromatic to an alicyclic is generally known. (For example, refer to Patent Documents 1 and 2).
この水素化反応において適用される圧力は、触媒の種類によって異なる。具体的には、高価なロジウム系の触媒を用いた場合には、１．０ＭＰａ未満の低水素圧で反応を進行させることができるが（例えば、特許文献３、４参照）、一方、より安価なルテニウムやニッケル系の触媒では、低水素圧での反応進行例はほとんど知られていない。例外としてラネールテニウム触媒の例（例えば、特許文献５参照）があるものの、この調製は特殊な方法を必要とする。このように、これまでロジウムなどの高価な金属を使用せず、また上記ラネールテニウムのような特殊な触媒調製を必要としない低水素圧で使用可能な触媒は検討されていなかった。 The pressure applied in this hydrogenation reaction varies depending on the type of catalyst. Specifically, when an expensive rhodium-based catalyst is used, the reaction can proceed at a low hydrogen pressure of less than 1.0 MPa (for example, see Patent Documents 3 and 4), but on the other hand, it is cheaper. For ruthenium and nickel-based catalysts, few examples of reaction progress at low hydrogen pressures are known. Although there is an example of Raneruthenium catalyst (see, for example, Patent Document 5), this preparation requires a special method. Thus, a catalyst that does not use an expensive metal such as rhodium and can be used at a low hydrogen pressure that does not require the preparation of a special catalyst such as the above-mentioned raneruthenium has not been studied.
本発明は上記の背景技術に鑑みてなされたものであり、その目的は、低水素圧条件において高い水素化活性を有する安価な芳香核水素化触媒を提供することである。 The present invention has been made in view of the above background art, and an object thereof is to provide an inexpensive aromatic nucleus hydrogenation catalyst having high hydrogenation activity under low hydrogen pressure conditions.
本発明者らは上記課題を解決すべく鋭意検討した結果、特定のシリカゲルを担体としたルテニウム担持触媒が、低水素圧でもメチレンジアニリンの芳香環を水素化できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a ruthenium-supported catalyst using a specific silica gel as a carrier can hydrogenate the aromatic ring of methylenedianiline even at a low hydrogen pressure, thereby completing the present invention. It came to.
すなわち、本発明は、以下に示すとおりのメチレンジアニリンの水素化用触媒およびこれを用いた脂環族化合物の製造方法である。 That is, the present invention is a catalyst for hydrogenation of methylenedianiline and a method for producing an alicyclic compound using the same as shown below.
［１］粒子径が４０乃至１５０マイクロメートルであり、かつ細孔径が５乃至５０ナノメートルであるシリカゲルにルテニウムを担持してなるルテニウム担持シリカゲル触媒。 [1] A ruthenium-supported silica gel catalyst in which ruthenium is supported on silica gel having a particle diameter of 40 to 150 micrometers and a pore diameter of 5 to 50 nanometers.
［２］ルテニウム源が塩化ルテニウムであることを特徴とする上記［１］に記載のルテニウム担持シリカゲル触媒。 [2] The ruthenium-supported silica gel catalyst according to [1], wherein the ruthenium source is ruthenium chloride.
［３］上記［１］または［２］に記載の触媒の存在下、メチレンジアニリンと水素とを反応させることを特徴とするメチレンジアニリンの水素化方法。 [3] A method for hydrogenating methylenedianiline, comprising reacting methylenedianiline with hydrogen in the presence of the catalyst according to [1] or [2].
以下、本発明を詳細に述べる。 The present invention will be described in detail below.
本発明の触媒は、粒子径が４０乃至１５０マイクロメートルであり、かつ細孔径が５乃至５０ナノメートルであるシリカゲルにルテニウムを担持してなるルテニウム担持シリカゲル触媒である。粒子径が１５０マイクロメートルより大きい、細孔径が５０ナノメートルより大きい、または粒子径が４０マイクロメートルより小さい、細孔径が５ナノメートルより小さい場合、水素化反応の転化率が低下する。 The catalyst of the present invention is a ruthenium-supported silica gel catalyst in which ruthenium is supported on silica gel having a particle size of 40 to 150 micrometers and a pore size of 5 to 50 nanometers. When the particle size is larger than 150 micrometers, the pore diameter is larger than 50 nanometers, or the particle diameter is smaller than 40 micrometers, and the pore diameter is smaller than 5 nanometers, the conversion rate of the hydrogenation reaction is lowered.
本発明の触媒において、シリカゲル担体の重量に対するルテニウム金属の含有比率は、０．３重量％以上６重量％以下の範囲が好ましい。６重量％よりも大きい、または０．３重量％よりも小さい場合、触媒の作用効率が低下する傾向にある。 In the catalyst of the present invention, the content ratio of the ruthenium metal with respect to the weight of the silica gel support is preferably in the range of 0.3 wt% to 6 wt%. When it is larger than 6% by weight or smaller than 0.3% by weight, the working efficiency of the catalyst tends to be lowered.
本発明の触媒の調製において、ルテニウム源としては、塩化ルテニウムや硝酸ルテニウムなどを用いることができるが、活性の点で塩化ルテニウムが好ましい。 In the preparation of the catalyst of the present invention, as the ruthenium source, ruthenium chloride, ruthenium nitrate or the like can be used, but ruthenium chloride is preferable in terms of activity.
ルテニウム源をシリカゲルに担持させる方法に関しては特に限定するものではないが、一般的な担持触媒を合成する方法であれば、何れでも用いることができる。 The method for supporting the ruthenium source on silica gel is not particularly limited, but any method for synthesizing a general supported catalyst can be used.
本発明の水素化方法において、基質のメチレンジアニリンに対して用いる触媒の量は特に限定するものではないが、０．３乃至１０重量％の範囲が好ましい。 In the hydrogenation method of the present invention, the amount of catalyst used for the substrate methylenedianiline is not particularly limited, but is preferably in the range of 0.3 to 10% by weight.
本発明の水素化方法において、適用する水素の圧力は特に限定するものではないが、１．０ＭＰａ未満であることが好ましい。 In the hydrogenation method of the present invention, the applied hydrogen pressure is not particularly limited, but is preferably less than 1.0 MPa.
本発明の水素化方法において、適用する反応温度は特に限定するものではないが、８０乃至２５０℃の範囲であることが好ましい。 In the hydrogenation method of the present invention, the reaction temperature to be applied is not particularly limited, but is preferably in the range of 80 to 250 ° C.
本発明の水素化方法において、適用する反応時間は特に限定するものではないが、１乃至４８時間の範囲であることが好ましい。 In the hydrogenation method of the present invention, the reaction time to be applied is not particularly limited, but is preferably in the range of 1 to 48 hours.
本発明の触媒は、低圧で高い水素化活性を示すことから、芳香族化合物の水素化触媒として有用である。 Since the catalyst of the present invention exhibits high hydrogenation activity at a low pressure, it is useful as a hydrogenation catalyst for aromatic compounds.
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.
実施例１ 触媒３の調製および触媒３を用いたメチレンジアニリンの水素化反応
２００ｍＬのナス型フラスコに、シリカゲル担体Ｃ（和光純薬製）を９．５ｇ入れ、次に硝酸ルテニウム水溶液（５０ｇ／Ｌ、田中貴金属製）を１０ｍＬ加えた。さらに純水を１０ｇ加えて流動性を与えた後、ロータリーエバポレーターで水分を留去した。硝酸ルテニウムが担持された乾燥シリカゲルを２００ｍＬのステンレス製オートクレーブに移した後、容器内を窒素で置換してから、さらに水素で置換した。容器を２００℃まで昇温した後、水素圧を１．０ＭＰａに保ちつつ水素の吸収が止まるまで３時間熟成した。冷却後、容器内を窒素で置換し、触媒３を得た。
Example 1 Preparation of Catalyst 3 and Hydrogenation Reaction of Methylenedianiline Using Catalyst 3 In a 200 mL eggplant type flask, 9.5 g of silica gel carrier C (manufactured by Wako Pure Chemical Industries, Ltd.) was placed, and then an aqueous ruthenium nitrate solution (50 g / L, made by Tanaka Kikinzoku) was added. Further, 10 g of pure water was added to give fluidity, and then water was distilled off with a rotary evaporator. After the dried silica gel carrying ruthenium nitrate was transferred to a 200 mL stainless steel autoclave, the inside of the container was replaced with nitrogen, and further replaced with hydrogen. After raising the temperature to 200 ° C., the container was aged for 3 hours until hydrogen absorption stopped while maintaining the hydrogen pressure at 1.0 MPa. After cooling, the inside of the container was replaced with nitrogen to obtain catalyst 3.
内容積２００ｍＬの撹拌装置を備えたステンレス製オートクレーブに、４，４’−メチレンジアニリン（東ソー社製）を５０ｇ、上記で調製した触媒３を２．５ｇ加え、窒素で系内を置換した。さらに系内を水素で置換した後、撹拌下１４０℃まで昇温させた。系内の水素圧を０．９ＭＰａまで昇圧した後、１４０℃で１時間熟成した。反応液を室温まで冷却し、残圧分の水素を抜き、窒素で系内を置換した。スラリーを一部抜き出し、触媒をろ別し、有機成分をガスクロマトグラフで分析した。結果を表１に示す。 50 g of 4,4'-methylenedianiline (manufactured by Tosoh Corporation) and 2.5 g of the catalyst 3 prepared above were added to a stainless steel autoclave equipped with a stirring device having an internal volume of 200 mL, and the inside of the system was replaced with nitrogen. Furthermore, after replacing the system with hydrogen, the temperature was raised to 140 ° C. with stirring. After raising the hydrogen pressure in the system to 0.9 MPa, it was aged at 140 ° C. for 1 hour. The reaction solution was cooled to room temperature, the residual pressure of hydrogen was removed, and the system was replaced with nitrogen. A part of the slurry was extracted, the catalyst was filtered off, and the organic components were analyzed by gas chromatography. The results are shown in Table 1.
実施例２
シリカゲル担体Ｃの代わりにシリカゲル担体Ｆを用いる以外は実施例１と同様にして触媒６を得た。さらに、得られた触媒６を用い、水素化反応を実施した結果を表１に示す。
Example 2
A catalyst 6 was obtained in the same manner as in Example 1 except that the silica gel carrier F was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 6.
実施例３
シリカゲル担体Ｃの代わりにシリカゲル担体Ｇを用いる以外は実施例１と同様にして触媒７を得た。さらに、得られた触媒７を用い、水素化反応を実施した結果を表１に示す。
Example 3
A catalyst 7 was obtained in the same manner as in Example 1 except that the silica gel carrier G was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 7.
比較例１
シリカゲル担体Ｃの代わりにシリカゲル担体Ａを用いる以外は実施例１と同様にして触媒１を得た。さらに、得られた触媒１を用い、水素化反応を実施した結果を表１に示す。
Comparative Example 1
A catalyst 1 was obtained in the same manner as in Example 1 except that the silica gel carrier A was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 1.
比較例２
シリカゲル担体Ｃの代わりにシリカゲル担体Ｂを用いる以外は実施例１と同様にして触媒２を得た。さらに、得られた触媒２を用い、水素化反応を実施した結果を表１に示す。
Comparative Example 2
A catalyst 2 was obtained in the same manner as in Example 1 except that the silica gel carrier B was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 2.
比較例３
シリカゲル担体Ｃの代わりにシリカゲル担体Ｄを用いる以外は実施例１と同様にして触媒４を得た。さらに、得られた触媒４を用い、水素化反応を実施した結果を表１に示す。
Comparative Example 3
A catalyst 4 was obtained in the same manner as in Example 1 except that the silica gel carrier D was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 4.
比較例４
シリカゲル担体Ｃの代わりにシリカゲル担体Ｅを用いる以外は実施例１と同様にして触媒５を得た。さらに、得られた触媒５を用い、水素化反応を実施した結果を表１に示す。
Comparative Example 4
A catalyst 5 was obtained in the same manner as in Example 1 except that the silica gel carrier E was used instead of the silica gel carrier C. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 5.
実施例４
硝酸ルテニウム水溶液の代わりに塩化ルテニウム水溶液（１００ｇ／Ｌ、田中貴金属製）を５ｍＬ用いる以外は実施例２と同様にして触媒８を得た。さらに、得られた触媒８を用い、水素化反応を実施した結果を表１に示す。
Example 4
A catalyst 8 was obtained in the same manner as in Example 2 except that 5 mL of an aqueous ruthenium chloride solution (100 g / L, manufactured by Tanaka Kikinzoku) was used instead of the aqueous ruthenium nitrate solution. Furthermore, Table 1 shows the results of carrying out the hydrogenation reaction using the obtained catalyst 8.
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| WO2009054462A1 (en) * | 2007-10-26 | 2009-04-30 | Asahi Kasei Chemicals Corporation | Composite particle-loaded article, method for producing the composite particle-loaded article, and method for producing compound using the composite particle-loaded article as chemical synthesis catalyst |
| JP2013513477A (en) * | 2009-12-15 | 2013-04-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Aromatic compound hydrogenation catalyst and method |
| WO2014046009A1 (en) * | 2012-09-21 | 2014-03-27 | Ｊｘ日鉱日石エネルギー株式会社 | Fischer-tropsch synthesis catalyst, method for producing same, and method for producing hydrocarbon |
| JP2015097980A (en) * | 2013-11-18 | 2015-05-28 | Ｊｘ日鉱日石エネルギー株式会社 | Method for manufacturing catalyst for fischer-tropsch synthesis and method for manufacturing hydrocarbon |
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