JP4599868B2 - Hydrogenation catalyst and method for producing the same - Google Patents
Hydrogenation catalyst and method for producing the same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims description 102
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004453 electron probe microanalysis Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- 150000001299 aldehydes Chemical class 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- PYLMCYQHBRSDND-VURMDHGXSA-N (Z)-2-ethyl-2-hexenal Chemical compound CCC\C=C(\CC)C=O PYLMCYQHBRSDND-VURMDHGXSA-N 0.000 description 1
- GADNZGQWPNTMCH-NTMALXAHSA-N (z)-2-propylhept-2-enal Chemical compound CCCC\C=C(C=O)\CCC GADNZGQWPNTMCH-NTMALXAHSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- -1 aliphatic aldehydes Chemical class 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- LARSGJZNVQJRMD-UHFFFAOYSA-N methyl 4-formylcyclohexane-1-carboxylate Chemical compound COC(=O)C1CCC(C=O)CC1 LARSGJZNVQJRMD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、水添触媒およびその製造方法に関する。詳しくは、アルデヒドを水素添加して対応するアルコールを製造する反応に用いる水添触媒およびその製造方法に関する。 The present invention relates to a hydrogenation catalyst and a method for producing the same. Specifically, the present invention relates to a hydrogenation catalyst used in a reaction for producing a corresponding alcohol by hydrogenating an aldehyde and a production method thereof.
従来アルデヒドの水添触媒としては、ニッケルを主な触媒成分とするものが工業的に使用されている。その代表的なものの一つは特許文献１に記載されているようなニッケルおよびクロムを触媒成分とするものである。
しかしながら、触媒は同じ方法で製造しても、製造ロットによって得られる触媒の選択率は相当に変化する。一方、選択率の測定は、長時間の反応を実際に行う必要があり、時間がかかるという問題がある。そこで、選択率が高い触媒を安定して製造する方法の開発が望まれている。 However, even if the catalyst is produced by the same method, the selectivity of the catalyst obtained by the production lot varies considerably. On the other hand, the measurement of selectivity has a problem that it takes time to actually perform a long-time reaction. Therefore, development of a method for stably producing a catalyst with high selectivity is desired.
アルデヒド水添触媒は、通常、触媒担体を触媒活性成分を含有する溶液に含浸することによって製造されている。従来、触媒担体を溶液でスラリー状にして含浸する場合には、溶液と触媒担体とを十分に攪拌したり、触媒担体をカラムに詰め溶液を流通させて含浸する場合には溶液の流通速度を早くしたりして、触媒担体と溶液との混合性を良好にすることにより、触媒担体と触媒活性成分との接触する確率が高くなり、より多くの触媒活性成分が触媒担体に担持され、良好な触媒が得られると考えられていた。 Aldehyde hydrogenation catalysts are usually produced by impregnating a catalyst carrier with a solution containing a catalytically active component. Conventionally, when a catalyst carrier is impregnated in a slurry with a solution, the solution and the catalyst carrier are sufficiently agitated, or when the catalyst carrier is packed in a column and the solution is circulated, the solution flow rate is increased. By improving the mixing speed between the catalyst carrier and the solution, the probability of contact between the catalyst carrier and the catalytically active component is increased, and more catalytically active components are supported on the catalyst carrier. It was thought that a good catalyst could be obtained.
ところが、本発明者らが上記課題について鋭意検討した結果、溶液と触媒担体との混合性を低くして得られる、触媒活性成分が表面から中心部に向かってなだらかな濃度勾配をもって担持されている触媒は、選択率が高いことを見出し本発明に到達した。 However, as a result of intensive studies on the above problems by the present inventors, a catalytically active component obtained by reducing the mixing property between the solution and the catalyst carrier is supported with a gentle concentration gradient from the surface toward the center. The catalyst has been found to have high selectivity and has reached the present invention.
すなわち、本発明の要旨は、触媒担体を充填したカラムに、触媒活性成分を含有する溶液を流通して、触媒担体に活性成分を担持するアルデヒドの水添触媒の製造方法において、溶液の線速を３．０ｍ／ｈｒ以下とすることを特徴とするアルデヒド水添触媒の製造方法、および、アルデヒドを水素添加してアルコールを製造するための触媒であって、活性成分としてニッケル、銅、白金、コバルト、パラジウムから選ばれる金属を含有し、Ｘ線マイクロアナライザー（ＥＰＭＡ）で触媒の断面を測定した場合の、活性成分の含有量のチャートにおいて、触媒粒子の表面と中心部分の中間点のおけるピーク強度が触媒粒子の中心部分におけるピーク強度よりも大きいことを特徴とする水添触媒に存する。 That is, the gist of the present invention is to provide a linear velocity of a solution in a method for producing an aldehyde hydrogenation catalyst in which a solution containing a catalytically active component is passed through a column packed with a catalyst carrier to carry the active component on the catalyst carrier. 3.0 m / hr or less, a method for producing an aldehyde hydrogenation catalyst, and a catalyst for producing an alcohol by hydrogenating an aldehyde, wherein the active component is nickel, copper, platinum, The peak at the midpoint between the surface of the catalyst particle and the central part in the active ingredient content chart when the cross section of the catalyst is measured with an X-ray microanalyzer (EPMA) containing a metal selected from cobalt and palladium. It exists in the hydrogenation catalyst characterized by the intensity | strength being larger than the peak intensity in the center part of a catalyst particle.
本発明によれば、アルコール選択率の高い水添触媒およびアルコール選択率の高い水添触媒の製法を提供することができ、工業的に極めて有利である。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a hydrogenation catalyst with high alcohol selectivity and a hydrogenation catalyst with high alcohol selectivity can be provided, and it is industrially very advantageous.
以下に本発明について詳細に説明する。
本発明に係る水添触媒は、触媒活性成分として、ニッケル、銅、白金、コバルト、パラジウムから選ばれる金属を含有するものであり、なかでも触媒活性成分としてニッケルを含むものが好ましい。
The present invention is described in detail below.
The hydrogenation catalyst according to the present invention contains a metal selected from nickel, copper, platinum, cobalt, and palladium as a catalytic active component, and among them, a catalyst containing nickel as the catalytic active component is preferable.
触媒活性成分を含有する溶液としては、ニッケル、銅、白金、コバルト、パラジウムから選ばれる金属の水溶性化合物を、金属として通常１００〜２００ｇ／Ｌの濃度で含有する水溶液が用いられる。触媒活性成分がニッケルの場合は、水溶性化合物としては、硝酸ニッケル、硫酸ニッケル、硝酸ニッケルなどが挙げられる。
触媒担体としては、珪藻土、アルミナ、シリカゲル、シリカアルミナ、活性炭などが挙げられる。触媒担体は表面積が大きいものが活性の点から好ましく、通常１ｍ2／ｇ以上
程度である。また、触媒担体は、直径１〜１０ｍｍφ、長さ１〜２０ｍｍに成形されたものが好ましく用いられる。
As the solution containing the catalytically active component, an aqueous solution containing a metal water-soluble compound selected from nickel, copper, platinum, cobalt and palladium as a metal at a concentration of usually 100 to 200 g / L is used. When the catalytically active component is nickel, examples of the water-soluble compound include nickel nitrate, nickel sulfate, and nickel nitrate.
Examples of the catalyst carrier include diatomaceous earth, alumina, silica gel, silica alumina, activated carbon and the like. A catalyst carrier having a large surface area is preferable from the viewpoint of activity, and is usually about 1 m 2 / g or more. Moreover, the catalyst carrier is preferably used having a diameter of 1 to 10 mmφ and a length of 1 to 20 mm.
本発明に係る水添触媒は、触媒担体に触媒活性成分を含有する溶液を含浸させた後、乾燥、焼成することにより得ることができる。
触媒担体に触媒活性成分を含有する溶液を含浸させる方法は特に限定されないが、触媒担体をつめたカラムに触媒活性成分を含有する溶液を流通させる方法、触媒活性成分を含有する溶液に触媒担体を入れて攪拌混合する方法などが挙げられる。本発明の方法においては、このときの溶液の液線速を３．０ｍ／ｈｒ以下、特には２．５ｍ／ｈｒ以下にすることを特徴とする。液線速の求め方は、カラムにつめた触媒担体に溶液を流通させて含浸させる方法では、カラムの断面積をＳｍ2、溶液の流通速度をＱｍ3／ｈｒとした時にＱ／Ｓで求められる。
The hydrogenation catalyst according to the present invention can be obtained by impregnating a catalyst carrier with a solution containing a catalytically active component, followed by drying and firing.
The method of impregnating the catalyst carrier with the solution containing the catalytically active component is not particularly limited, but the method of circulating the solution containing the catalytically active component through the column packed with the catalyst carrier, the catalyst carrier containing the catalyst carrier in the solution containing the catalytically active component. And a method of stirring and mixing. The method of the present invention is characterized in that the liquid linear velocity of the solution at this time is 3.0 m / hr or less, particularly 2.5 m / hr or less. The liquid linear velocity can be obtained by Q / S when the cross-sectional area of the column is Sm 2 and the flow rate of the solution is Qm 3 / hr in the method in which the solution is passed through the catalyst support packed in the column and impregnated. It is done.
本発明により選択率が高まる理由は明らかではないが、液線速を遅くすると触媒活性成分は触媒担体表面近傍のみならず、中心部にまで順次浸透し、表面から中心部に向けてなだらかな濃度勾配をもって担持される。一方、触媒担体内部は触媒担体表面に比べて水素の供給が乏しいため、触媒担体内部では高沸物等の副生物を生成する反応が起こりやすくなる。本発明の方法により得られる触媒では、副反応を起こす触媒担体内部の触媒活性成分が少ないため、選択率が向上したものと推察される。しかしながら、触媒活性成分を表面のみに担持した場合、多孔質である担体の特長を十分に生かすことができず、低活性の触媒しか得られない。以上のことから、表面に比べて水素の供給が乏しくなる触媒中心部に向かって徐々に触媒活性成分濃度を下げていくことがで、多孔質担体の特長を生かした高活性かつ高選択性の触媒を得ることができるもの推察される。 The reason why the selectivity is increased by the present invention is not clear, but when the liquid linear velocity is decreased, the catalytically active component penetrates not only in the vicinity of the surface of the catalyst carrier but also in the center, and the concentration from the surface toward the center is gentle. Carried with a gradient. On the other hand, since the supply of hydrogen is poor in the catalyst carrier compared to the surface of the catalyst carrier, a reaction that generates by-products such as high boiling matters easily occurs in the catalyst carrier. In the catalyst obtained by the method of the present invention, it is presumed that the selectivity is improved because there are few catalytically active components inside the catalyst carrier that cause side reactions. However, when the catalytically active component is supported only on the surface, the characteristics of the porous carrier cannot be fully utilized, and only a low activity catalyst can be obtained. From the above, it is possible to gradually reduce the concentration of the catalytically active component toward the center of the catalyst where the supply of hydrogen is scarce compared to the surface. It is inferred that a catalyst can be obtained.
担体の触媒活性成分を含有する溶液への浸漬時間は、液線速、溶液の濃度にもよるが、通常、０．５〜２４時間である。浸漬温度は、通常５〜１００℃で行う。
触媒活性成分を含有する溶液を含浸させた触媒担体は、通常３０〜１００℃で１〜２４時間乾燥され、次いで、通常２５０〜４００℃で１〜１０時間焼成を行う。このようにして得られる触媒は、ニッケル、銅、白金、コバルト、パラジウムから選ばれる金属、なかでもニッケルを１０〜２０重量％含有する。
The immersion time of the support in the solution containing the catalytically active component is usually 0.5 to 24 hours, although it depends on the liquid linear velocity and the concentration of the solution. The immersion temperature is usually 5 to 100 ° C.
The catalyst carrier impregnated with the solution containing the catalytically active component is usually dried at 30 to 100 ° C. for 1 to 24 hours, and then usually calcined at 250 to 400 ° C. for 1 to 10 hours. The catalyst thus obtained contains 10 to 20% by weight of a metal selected from nickel, copper, platinum, cobalt and palladium, especially nickel.
得られた水添触媒は、通常、水素気流下、通常２５０〜４５０℃で５〜４０時間還元を行い、触媒活性が付与される。このような還元された触媒は不安定であるため、通常、酸素濃度が０．０５〜２１容量％の窒素流通下、３０〜１５０℃で１〜２４時間加熱し、酸化安定化体とするか、アルコール等の不活性な液体雰囲気で保管する。 The obtained hydrogenation catalyst is usually reduced at 250 to 450 ° C. for 5 to 40 hours under a hydrogen stream to impart catalytic activity. Since such a reduced catalyst is unstable, it is usually heated at 30 to 150 ° C. for 1 to 24 hours under a nitrogen flow of 0.05 to 21% by volume to obtain an oxidized stabilizer. Store in an inert liquid atmosphere such as alcohol.
このようにして得られる触媒は、Ｘ線マイクロアナライザー（ＥＰＭＡ）で、触媒成形体の断面を測定した場合の、触媒活性成分の含有量のチャートにおいて、触媒粒子の表面と中心部分の中間点のおけるピーク強度が触媒粒子の中心部分におけるピーク強度よりも大きく、触媒活性成分が触媒担体の表面から中心部にむけてなだらかな濃度勾配をもって存在している。触媒粒子の表面と中心部分の中間点のおけるピーク強度が触媒粒子の中心部分におけるピーク強度の１．１倍以上、特に１．２倍以上であることが好ましい。なお、チャートが細かな凹凸をもつ場合には、各ピークの頂点を結ぶ接線を引き、この接線を
用いてピーク強度の比を求める。
The catalyst thus obtained is an intermediate point between the surface of the catalyst particle and the central portion in the chart of the content of the catalyst active component when the cross section of the catalyst molded body is measured with an X-ray microanalyzer (EPMA). The peak intensity in the catalyst particles is larger than the peak intensity in the central portion of the catalyst particles, and the catalytically active component is present with a gentle concentration gradient from the surface of the catalyst carrier to the central portion. The peak intensity at the midpoint between the surface of the catalyst particles and the central part is preferably 1.1 times or more, particularly 1.2 times or more than the peak intensity in the central part of the catalyst particles. If the chart has fine irregularities, a tangent line connecting the vertices of each peak is drawn, and the ratio of peak intensities is obtained using this tangent line.
Ｘ線マイクロアナライザーで触媒活性成分の含有量を測定するための試料は、常法に従えばよいが、まず、触媒活物質を担持した触媒担体の成形体を切断した後、エポキシ樹脂で包埋し、切断面を平滑になるまで研磨し、プラチナを蒸着して作製する。
本発明に係る水添触媒は、安全のため活性成分が酸化物の状態で取り扱われるのが普通である。その場合は、通常、水素気流下、１２０〜２００℃で１〜５時間加熱することにより還元して触媒として反応に用いられる。
The sample for measuring the content of the catalytically active component with an X-ray microanalyzer may be in accordance with an ordinary method. First, after cutting the molded body of the catalyst carrier carrying the catalytic active material, the sample is embedded with an epoxy resin. Then, the cut surface is polished until smooth, and platinum is vapor-deposited.
In the hydrogenation catalyst according to the present invention, the active component is usually handled in an oxide state for safety. In that case, it reduces by heating normally at 120-200 degreeC under hydrogen stream for 1 to 5 hours, and is used for reaction as a catalyst.
本発明に係る触媒により水添されるアルデヒドは特に限定されず、飽和アルデヒド、不飽和アルデヒドなどの脂肪族アルデヒド、芳香族アルデヒド等が挙げられる。好ましくは炭素数１〜３０、特に炭素数１〜２０の脂肪族アルデヒドである。このようなアルデヒドの例としては、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、イソブチルアルデヒド、ノルマルブチルアルデヒド、ノルマルバレルアルデヒド、２−エチル−２ヘキセナール、２−プロピル−２−ヘプテナール、４−メトキシカルボニルシクロヘキサンカルボキシアルデヒド等が挙げられる。 The aldehyde hydrogenated by the catalyst according to the present invention is not particularly limited, and examples thereof include aliphatic aldehydes such as saturated aldehydes and unsaturated aldehydes, and aromatic aldehydes. Preferably it is a C1-C30, especially C1-C20 aliphatic aldehyde. Examples of such aldehydes include formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, normal butyraldehyde, normal valeraldehyde, 2-ethyl-2-hexenal, 2-propyl-2-heptenal, 4-methoxycarbonylcyclohexanecarboxaldehyde, etc. Is mentioned.
以下に本発明の具体的態様を実施例により更に詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例によって限定されるものではない。 Specific embodiments of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
＜実施例１＞
直径３〜４ｍｍφ、長さ５〜６ｍｍの珪藻土担体８８０ｋｇを円筒形固定床に充填し、ここに、硝酸ニッケルを金属ニッケルとして１７０ｇ／Ｌ及び重クロム酸アンモニウムを金属クロムとして２３ｇ／Ｌの割合で含有する水溶液を、液線速２．３ｍ／Ｈｒ、室温で７時間循環させた後、乾燥、３３０℃で４時間焼成を行って、触媒を調製した。この触媒を水素気流下３７０℃で還元し、さらに酸素濃度０．１容量％の窒素流通下、８０℃で５時間加熱して酸化安定化体（ニッケル担持量１２％、クロム担持量２％）とした。
<Example 1>
A cylindrical fixed bed is filled with 880 kg of a diatomaceous earth carrier having a diameter of 3 to 4 mmφ and a length of 5 to 6 mm. Here, nickel nitrate is used as metallic nickel at 170 g / L and ammonium bichromate is used as metallic chromium at a rate of 23 g / L. The aqueous solution contained was circulated at a liquid linear velocity of 2.3 m / Hr at room temperature for 7 hours, then dried and calcined at 330 ° C. for 4 hours to prepare a catalyst. This catalyst was reduced at 370 ° C. under a hydrogen stream, and further heated at 80 ° C. for 5 hours under a nitrogen flow with an oxygen concentration of 0.1% by volume (a nickel loading amount of 12% and a chromium loading amount of 2%). It was.
得られた触媒の断面のＮｉ濃度分布を、島津社製Ｘ線マイクロアナライザー「ＥＰＭＡ８７０５」を用い、以下の条件で測定した。測定結果を図１に示す。触媒粒子の表面と中心部分の中間点におけるピーク強度は、触媒粒子の中心部分におけるピーク強度の１．３倍であった。
加速電圧：１５ｋＶ
照射電流：０．１３０μＡ
測定時間：４０ｍｓ／ｐｏｉｎｔ
測定点数：５１２×５１２ｐｏｉｎｔ（間隔１０μｍ、１０μｍ）
The Ni concentration distribution in the cross section of the obtained catalyst was measured under the following conditions using an X-ray microanalyzer “EPMA8705” manufactured by Shimadzu Corporation. The measurement results are shown in FIG. The peak intensity at the midpoint between the surface of the catalyst particles and the central part was 1.3 times the peak intensity at the central part of the catalyst particles .
Acceleration voltage: 15 kV
Irradiation current: 0.130 μA
Measurement time: 40 ms / point
Number of measurement points: 512 × 512 points (interval 10 μm, 10 μm)
この触媒を水素気流下１５０℃に加熱することにより還元活性化を行った。内容量１０００ｍｌのオートクレーブに得られた還元活性化触媒８０ｇ及び、ｎ−ブチルアルデヒドとｎ−ブタノールの混合液（重量比１：５）６００ｍｌを投入し、これに水素ガスを圧入し、反応温度１００℃、反応圧力４．９ＭＰａで２時間反応させた。ｎ−ブタノール選択率は９８．６％であった。 The catalyst was reduced and activated by heating to 150 ° C. in a hydrogen stream. 80 g of the reduced activation catalyst obtained in an autoclave with an internal volume of 1000 ml and 600 ml of a mixed solution of n-butyraldehyde and n-butanol (weight ratio 1: 5) are charged, hydrogen gas is injected into this, and the reaction temperature is 100 The reaction was carried out at 2 ° C. and a reaction pressure of 4.9 MPa for 2 hours. The n-butanol selectivity was 98.6%.
＜実施例２＞
直径３〜４ｍｍφ、長さ５〜６ｍｍの珪藻土担体１０４ｇを円筒形固定床に充填し、そこに、硝酸ニッケルを金属ニッケルとして１７０ｇ／Ｌ及び重クロム酸アンモニウムを金属クロムとして２３ｇ／Ｌの割合で含有する水溶液４５０ｍｌを入れ、水溶液の循環は行わずに（液線速０ｍ／ｈｒ）、常温で７時間浸漬させた他は、実施例１と同様に行って、触媒の酸化安定化体（ニッケル担持量１２％、クロム担持量２％）を調製した。
得られた触媒の断面のＮｉ濃度分布を実施例１と同様の方法で測定した結果を図２に示す。触媒粒子の表面と中心部分の中間点におけるピーク強度は、触媒粒子の中心部分におけるピーク強度の１．２倍であった。
この触媒を実施例１と同様に還元活性化した後、ｎ−ブチルアルデヒドの水添を行った。ｎ−ブタノール選択率は９８．３％であった。
<Example 2>
104 g of diatomaceous earth carrier having a diameter of 3 to 4 mmφ and a length of 5 to 6 mm is packed into a cylindrical fixed bed, and there is nickel nitrate as metallic nickel at 170 g / L and ammonium bichromate as metallic chromium at a rate of 23 g / L. The catalyst was stabilized in the same manner as in Example 1 except that 450 ml of the aqueous solution was added and the aqueous solution was not circulated (liquid linear velocity: 0 m / hr) and immersed for 7 hours at room temperature. A loading amount of 12% and a chromium loading amount of 2%) were prepared.
The results of measuring the Ni concentration distribution in the cross section of the obtained catalyst by the same method as in Example 1 are shown in FIG. The peak intensity at the midpoint between the surface of the catalyst particles and the central portion was 1.2 times the peak intensity at the central portion of the catalyst particles .
This catalyst was reduced and activated in the same manner as in Example 1 and then hydrogenated with n-butyraldehyde. The n-butanol selectivity was 98.3%.
＜比較例１＞
直径３〜４ｍｍφ、長さ５〜６ｍｍの珪藻土担体１０４ｇを円筒形固定床に充填し、硝酸ニッケルを金属ニッケルとして１７０ｇ／Ｌ及び重クロム酸アンモニウムを金属クロムとして２３ｇ／Ｌの割合で含有する水溶液を、液線速３．５ｍ／Ｈｒ、室温で７時間循環した他は実施例１と同様に行って、触媒の酸化安定化体（ニッケル担持量１２％、クロム担持量２％）を調製した。
得られた触媒の断面のＮｉ濃度分布を実施例１と同様の方法で測定した結果を図３に示す。、触媒粒子の表面と中心部分の中間点におけるピーク強度は触媒粒子の中心部分におけるピーク強度の１．０倍であった。
この触媒を実施例１と同様に還元活性化した後、ｎ−ブチルアルデヒドの水添を行った。ｎ−ブタノール選択率は９６．０％であった。
<Comparative Example 1>
An aqueous solution containing 104 g of diatomaceous earth support having a diameter of 3 to 4 mmφ and a length of 5 to 6 mm packed in a cylindrical fixed bed and containing nickel nitrate as metallic nickel at a rate of 170 g / L and ammonium dichromate as metallic chromium at a rate of 23 g / L. Was performed in the same manner as in Example 1 except that the liquid linear velocity was circulated at room temperature for 7 hours at room temperature to prepare an oxidation stabilized body of the catalyst (nickel loading 12%, chromium loading 2%). .
The result of measuring the Ni concentration distribution in the cross section of the obtained catalyst by the same method as in Example 1 is shown in FIG. The peak intensity at the midpoint between the surface and the central part of the catalyst particles was 1.0 times the peak intensity at the central part of the catalyst particles .
This catalyst was reduced and activated in the same manner as in Example 1 and then hydrogenated with n-butyraldehyde. The n-butanol selectivity was 96.0%.
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| JPS5678633A (en) * | 1979-11-06 | 1981-06-27 | Exxon Research Engineering Co | Manufacture of novel nonferrous viii group metallaluminum coprecipitating hydrogenating catalyst and its use |
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