JP3244605B2 - Precious metal carbon catalyst with adjusted particle size - Google Patents
Precious metal carbon catalyst with adjusted particle sizeInfo
- Publication number
- JP3244605B2 JP3244605B2 JP00824595A JP824595A JP3244605B2 JP 3244605 B2 JP3244605 B2 JP 3244605B2 JP 00824595 A JP00824595 A JP 00824595A JP 824595 A JP824595 A JP 824595A JP 3244605 B2 JP3244605 B2 JP 3244605B2
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- catalyst
- activated carbon
- less
- filtration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002245 particle Substances 0.000 title claims description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 61
- 239000003054 catalyst Substances 0.000 title claims description 60
- 229910052799 carbon Inorganic materials 0.000 title claims description 9
- 239000010970 precious metal Substances 0.000 title 1
- 230000001186 cumulative effect Effects 0.000 claims description 18
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000010419 fine particle Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006264 debenzylation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、特定の粒度分布を有
し、工業的な化学反応に有用な貴金属炭素触媒に関す
る。The present invention relates to a noble metal carbon catalyst having a specific particle size distribution and useful for industrial chemical reactions.
【０００２】[0002]
【従来の技術】粉末状の貴金属炭素触媒は、一般に反応
液中に分散した状態で用いられる。例えば水素添加反応
では、反応系に水素と反応液と触媒とがそれぞれ気相、
液相、固相において互に接触する状態で触媒反応が進行
する。このため、各相の接触性、および分散性が反応速
度に与える影響は大きい。一般に触媒の平均粒子径を小
さくすることにより、触媒単位重量当たりの触媒個数が
増え、分散性が向上する。このようにして高活性な触媒
を製造することができる。2. Description of the Related Art Generally, a powdery noble metal carbon catalyst is used in a state of being dispersed in a reaction solution. For example, in a hydrogenation reaction, hydrogen, a reaction solution, and a catalyst are each in a gas phase,
The catalytic reaction proceeds in a state where the liquid phase and the solid phase are in contact with each other. For this reason, the influence of the contact property and dispersibility of each phase on the reaction rate is large. In general, by reducing the average particle size of the catalyst, the number of catalysts per unit weight of the catalyst increases, and the dispersibility improves. Thus, a highly active catalyst can be produced.
【０００３】一方、工業的に用いる触媒は、濾過分離性
がすぐれていることも重要である。すなわち、反応終了
後には反応液と触媒との濾過分離工程があり、反応液は
次の工程へ進み、ろ別された触媒は活性が低下するまで
再使用される。触媒の使用量が多い場合には濾過時間が
長くなり生産性が低下することになる。このとき触媒活
性を高くして反応時間を短縮しても、濾過時間がそれを
上回るようであると、このような触媒は工業用触媒とし
ては高性能なものとは言えない。濾過性の良い触媒を製
造しようとすれば粒子径は粗いものが有利となるが、前
述の通り反応液中における分散性に問題がありかつ活性
の点でも不利である。[0003] On the other hand, it is also important that a catalyst used industrially has excellent filtration and separation properties. That is, after the completion of the reaction, there is a filtration separation step of the reaction solution and the catalyst, the reaction solution proceeds to the next step, and the filtered catalyst is reused until the activity decreases. When the amount of the catalyst used is large, the filtration time is prolonged, and the productivity is reduced. At this time, even if the reaction time is shortened by increasing the catalyst activity, if the filtration time seems to exceed it, such a catalyst cannot be said to be high-performance as an industrial catalyst. In order to produce a catalyst having good filterability, a catalyst having a large particle diameter is advantageous, but as described above, there is a problem in dispersibility in a reaction solution and disadvantageous in terms of activity.
【０００４】通常用いられるろ紙やろ布の捕捉粒子径は
２〜３μｍであるので、３μｍ未満の微粒子の存在は濾
過漏れや濾過面の目詰まりを起こし、濾過速度の低下を
招く。このような場合、濾過助材を濾過面にコーティン
グすることで対処できるが、触媒を再使用できなくなる
という問題を生ずる。[0004] Since the filter particles or filter cloth used usually have a trapped particle size of 2 to 3 µm, the presence of fine particles of less than 3 µm causes filtration leakage and clogging of the filtration surface, leading to a reduction in filtration speed. In such a case, the problem can be solved by coating the filter surface with a filter aid, but there is a problem that the catalyst cannot be reused.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、高活性でし
かも濾過性に優れた、粒度調整された貴金属炭素触媒を
提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a noble metal carbon catalyst having a high activity and excellent filterability, the particle size of which is controlled.
【０００６】[0006]
【課題を解決するための手段】本発明者らは上述の見地
から、触媒の粒度をコントロールすることによって活性
と濾過性を両立した触媒が得られることを見いだし本発
明を完成させた。Means for Solving the Problems From the above viewpoints, the present inventors have found that a catalyst having both activity and filterability can be obtained by controlling the particle size of the catalyst, and have completed the present invention.
【０００７】一般に粒状触媒は１〜１０００μｍの範囲
の体積粒度分布を有している。触媒活性を上げるために
は平均粒子径が可能な限り細かい方が有利である。細か
くするに従い活性は向上するが濾過漏れや濾過面の目詰
まりの原因となる微細粒子の量が多くなり、濾過分離工
程に支障をきたす。また濾過分離工程に支障を来す微細
粒子をあらかじめ除去する場合、触媒製造工程の経済性
が低下する。Generally, particulate catalysts have a volume particle size distribution in the range of 1-1000 μm. In order to increase the catalytic activity, it is advantageous that the average particle diameter is as small as possible. As the size is reduced, the activity increases, but the amount of fine particles causing filtration leakage and clogging of the filtration surface increases, which hinders the filtration separation process. In addition, if fine particles that interfere with the filtration / separation step are removed in advance, the economics of the catalyst production step will decrease.
【０００８】本発明の貴金属炭素触媒は活性炭粒子から
なる担体と、それに担持されている貴金属触媒成分とを
含み、前記活性炭粒子が、その体積粒度分布における累
積９０％が、６０μｍ以下の粒子サイズを有し、かつそ
の個数粒度分布において３．３μｍ以下の粒子サイズを
有する微粒子の累積値が４０％未満であるように粒度調
整されていることを特徴とするものである。[0008] The noble metal carbon catalyst of the present invention comprises a support comprising activated carbon particles and a noble metal catalyst component supported thereon, wherein the activated carbon particles have a particle size of 60 µm or less in a 90% cumulative volume particle size distribution. The particle size is adjusted so that the cumulative value of the fine particles having a particle size of 3.3 μm or less in the number particle size distribution is less than 40%.
【０００９】本発明の触媒において、前記貴金属触媒成
分がパラジウムまたは白金を含有していることが好まし
い。In the catalyst of the present invention, it is preferable that the noble metal catalyst component contains palladium or platinum.
【００１０】[0010]
【作用】本発明の触媒においては、活性炭素担体の粒子
サイズが３．３μｍ以下の微細粒子の個数粒度分布累積
値が４０％未満に調整され、かつ粒子サイズ６０μｍ以
下の粒子の体積分布累積値が９０％に達しているため、
得られる貴金属炭素触媒は、実用上すぐれた触媒活性
と、濾過分離性とを併せ有し、化学反応工程の効率、生
産性を著しく向上させることができる。また、本発明の
触媒を用いると、濾過助剤の使用が不必要となるため触
媒の再使用が可能となる。In the catalyst of the present invention, the cumulative value of the number particle size distribution of fine particles having an activated carbon carrier particle size of 3.3 μm or less is adjusted to less than 40% and the volume distribution cumulative value of particles having a particle size of 60 μm or less. Has reached 90%,
The resulting noble metal carbon catalyst has both practically excellent catalytic activity and filtration separation properties, and can significantly improve the efficiency and productivity of the chemical reaction process. Further, when the catalyst of the present invention is used, the use of a filter aid is not required, so that the catalyst can be reused.
【００１１】本発明において、活性炭素担体の体積粒度
分布において、累積９０％が、６０μｍ以下の粒子サイ
ズを有し、かつ活性炭素担体の個数粒度分布において、
３．３μｍ以下の微細粒子の累積値が、４０％未満にす
るためには、活性炭の原料炭について、それを所望の粒
子サイズ（６０μｍ以下）になるように粉砕し、分級機
を用いて微細粒子の除去を行えばよい。上記粉砕および
分級は、活性炭について行ってもよい。In the present invention, in the volume particle size distribution of the activated carbon carrier, 90% of the particles have a particle size of 60 μm or less, and in the number particle size distribution of the activated carbon carrier,
In order to make the cumulative value of fine particles of 3.3 μm or less less than 40%, the raw coal of activated carbon is pulverized to a desired particle size (60 μm or less), and then finely divided using a classifier. What is necessary is just to remove particles. The above pulverization and classification may be performed on activated carbon.
【００１２】本発明において、活性炭素担体の体積粒度
分布において、累積９０％に含まれる粒子のサイズが６
０μｍより大きくなると、得られる触媒の活性が不十分
になる。また、本発明において、活性炭素担体の個数粒
度分布において、３．３μｍ以下の微細粒子の累積値
が、４０％以上になると、濾過分離工程に要する時間の
増大という不都合を生ずる。In the present invention, in the volume particle size distribution of the activated carbon carrier, the size of particles contained in 90% of the total is 6%.
If it is larger than 0 μm, the activity of the obtained catalyst becomes insufficient. In the present invention, when the cumulative value of the fine particles having a size of 3.3 μm or less in the number particle size distribution of the activated carbon carrier is 40% or more, there is a disadvantage that the time required for the filtration and separation step is increased.
【００１３】本発明に用いられる活性炭素担体の粒度調
整（分級）は、一般に、触媒製造前に行うことが好まし
いが、触媒製造間に行われてもよい。後者の場合には、
湿式または乾式の分級機による分級をすることにより粒
度調整を行うことができる。The particle size adjustment (classification) of the activated carbon carrier used in the present invention is generally preferably performed before the production of the catalyst, but may be carried out during the production of the catalyst. In the latter case,
The particle size can be adjusted by performing classification using a wet or dry classifier.
【００１４】本発明に用いられる活性炭素としては、木
質材料、ピート、タール、椰子殻などから製造されたも
のを用いることができる。As the activated carbon used in the present invention, those produced from wood materials, peat, tar, coconut shell, etc. can be used.
【００１５】本発明において、貴金属触媒成分として
は、パラジウム、白金、ルテニウム、ロジウム、イリジ
ウム、オスミウム、金、銀、およびレニウムなどを用い
ることができるが、パラジウム又は白金を用いることが
好ましい。In the present invention, palladium, platinum, ruthenium, rhodium, iridium, osmium, gold, silver, rhenium and the like can be used as the noble metal catalyst component, but palladium or platinum is preferably used.
【００１６】本発明の触媒を製造するには、たとえば活
性炭素担体を水に懸濁させ、貴金属の水溶性塩を滴下し
て完全に吸着させた後、ホルマリン、ギ酸、またはナト
リウムボロハイドライド等の還元剤で還元させる方法を
行えばよい。In order to produce the catalyst of the present invention, for example, an activated carbon carrier is suspended in water, a water-soluble salt of a noble metal is added dropwise and completely adsorbed. What is necessary is just to perform the method of reducing with a reducing agent.
【００１７】本発明の触媒において、貴金属触媒成分の
担持量は、金属換算で１〜２０％（重量）であることが
好ましい。また、本発明の触媒には貴金属成分の他に、
添加成分、例えばＫ，Ｎａ，Ｌｉ，Ｐｂ、およびＳｂの
１種以上が含まれていてもよい。In the catalyst of the present invention, the amount of the noble metal catalyst component carried is preferably 1 to 20% (weight) in terms of metal. The catalyst of the present invention, in addition to the noble metal component,
Additional components, for example, one or more of K, Na, Li, Pb, and Sb may be included.
【００１８】[0018]
【実施例】以下実施例を挙げて、本発明を更に詳細に説
明する。粒度測定には、日機装株式会社製マイクロトラ
ックII ＳＲＡ（０．７〜７００μｍ）を使用した。本
文中では測定装置から出力された「粒度分布測定結果」
を「体積粒度分布」により表し、「個数分布演算結果」
を「個数粒度分布」として表し、「ＭＶ」を「体積加重
平均粒子径」と表す。また「頻度」とは、ある粒子径範
囲の度数（％）であり、「累積」とは、ある粒子径以下
の頻度全体を加えあわせた値である。「累積９０％」と
は粒子径頻度の累積の値が９０％であることを表す。The present invention will be described in more detail with reference to the following examples. Nikkiso Co., Ltd. Microtrac II SRA (0.7-700 μm) was used for the particle size measurement. In the text, "Results of particle size distribution measurement" output from the measuring device
Is represented by “volume particle size distribution” and “number distribution calculation result”
Is represented as “number particle size distribution”, and “MV” is represented as “volume weighted average particle size”. “Frequency” is the frequency (%) of a certain particle size range, and “cumulative” is a value obtained by adding the entire frequency below a certain particle size. “Cumulative 90%” indicates that the cumulative value of the particle diameter frequency is 90%.
【００１９】実施例１ パラジウム１．６ｇを王水に溶解した後、これを濃縮し
て１５wt％塩化パラジウム溶液を得た。２．８〜１７６
μｍの体積粒度分布を有し、累積９０％の粒子径が５
９．０５μｍ以下、体積加重平均粒子径が２８．６２μ
ｍ、個数粒度分布において、３．３μｍ以下の微粒子の
累積値が３４．０６％に調整された活性炭３０ｇを、３
００mlの水で懸濁させながら、この中に前記の塩化パラ
ジウム溶液を滴下した。１６時間後、２０wt％苛性ソー
ダ水溶液を、混合系のpHが１３になるまで加えた。２時
間後、この混合物に３７wt％ホルマリン水溶液７mlを加
えて１時間９０℃に保って前記パラジウム化合物を還元
した後、濾過、水洗、乾燥して５％パラジウム炭素触媒
を調製した。 Example 1 1.6 g of palladium was dissolved in aqua regia and concentrated to obtain a 15 wt% palladium chloride solution. 2.8-176
It has a volume particle size distribution of μm and a 90% cumulative particle size of 5
9.05 μm or less, volume-weighted average particle diameter is 28.62 μm
m, 30 g of activated carbon in which the cumulative value of fine particles having a particle size of 3.3 μm or less was adjusted to 34.06% in the number particle size distribution,
The above-mentioned palladium chloride solution was added dropwise thereto while being suspended in 00 ml of water. After 16 hours, a 20 wt% aqueous sodium hydroxide solution was added until the pH of the mixed system reached 13. Two hours later, 7 ml of a 37 wt% formalin aqueous solution was added to the mixture, and the above-mentioned palladium compound was reduced at 90 ° C. for 1 hour, followed by filtration, washing with water and drying to prepare a 5% palladium-carbon catalyst.
【００２０】この触媒５ｇを３０℃のイオン交換水３０
０mlに懸濁し、この懸濁液を、濾過面が直径３cmの円形
ろ紙（東洋濾紙株式会社No131 ）により、０．１ kgf／
cm2の窒素圧をかけた条件下の濾過に供し、濾紙から窒
素が噴出するまでの濾過時間を測定したところ、１２分
であった。5 g of this catalyst was mixed with 30 ° C. ion-exchanged water 30
0 ml, and the suspension was filtered with a filter paper having a filtration surface of 3 cm in diameter (Toyo Roshi Kaisha No. 131) at 0.1 kgf / kg.
The mixture was subjected to filtration under a condition of applying a nitrogen pressure of cm 2 , and the filtration time required until nitrogen was ejected from the filter paper was measured, to be 12 minutes.
【００２１】別に、ジニトロトルエン０．９１ｇをエタ
ノールで溶解し、液量を２５mlとし、この溶液中に上記
触媒５０mgを加えた。この反応系を反応容器に入れ、さ
らにエタノールを１０ml加えた。反応容器及びそれに通
じる水素ライン全体を３０℃にした後、窒素置換し、さ
らに水素置換して、この容器を振盪させながら、ジニト
ロトルエンのニトロ基に水素添加反応を施した。このと
き、圧力が常圧を保つように水素を追加しながら１５分
間の触媒活性試験を行ったところ、水素吸収量は５５０
mlであった。Separately, 0.91 g of dinitrotoluene was dissolved in ethanol to make the volume 25 ml, and 50 mg of the above catalyst was added to this solution. This reaction system was placed in a reaction vessel, and 10 ml of ethanol was further added. After the entire temperature of the reaction vessel and the hydrogen line leading to the reaction vessel was set at 30 ° C., the atmosphere was replaced with nitrogen and further replaced with hydrogen. The nitro group of dinitrotoluene was subjected to a hydrogenation reaction while shaking the vessel. At this time, the catalyst activity test was performed for 15 minutes while adding hydrogen so that the pressure was maintained at normal pressure.
ml.
【００２２】比較例１ ２．８〜５００μｍの体積粒度分布を有し、累積９０％
の粒子の径が２２５．２６μｍ以下、体積加重平均粒子
径が７０．５３μｍ、３．３μｍ以下の微粒子が個数粒
度分布で５０．２１％の粒度を有する活性炭を用いたこ
とを除き、実施例１と同様にして５％パラジウム炭素触
媒を調製した。実施例１と同様にして、得られた触媒の
濾過試験を行ったところ濾過時間３０分であり、またジ
ニトロトルエンによる触媒活性試験においては、水素吸
収量は５００mlであった。 Comparative Example 1 A powder having a volume particle size distribution of 2.8 to 500 μm and a cumulative 90%
Example 1 except that activated carbon having a particle size of 225.26 μm or less, a volume-weighted average particle size of 70.53 μm, and a particle size of 3.3 μm or less having a particle size distribution of 50.21% was used. A 5% palladium carbon catalyst was prepared in the same manner as described above. A filtration test was performed on the obtained catalyst in the same manner as in Example 1. The filtration time was 30 minutes. In the catalyst activity test using dinitrotoluene, the hydrogen absorption was 500 ml.
【００２３】実施例２ パラジウム３．３８ｇを王水に溶解した後、濃縮して１
５wt％塩化パラジウム溶液を得た。実施例１で用いた粒
度調製活性炭３０ｇを３００mlの水で懸濁させ、この中
に前記の塩化パラジウム溶液を滴下した。１６時間後、
２０wt％苛性ソーダ水溶液をpH＝１３になるまで加え
た。２時間後、３７wt％ホルマリン水溶液７mlを加えて
１時間９０℃に保って前記パラジウム化合物を還元した
後、濾過水洗乾燥して１０％パラジウム炭素触媒を調製
した。 Example 2 3.38 g of palladium was dissolved in aqua regia and concentrated to give 1
A 5 wt% palladium chloride solution was obtained. 30 g of the activated carbon particle size used in Example 1 was suspended in 300 ml of water, and the palladium chloride solution was added dropwise thereto. 16 hours later,
A 20 wt% aqueous sodium hydroxide solution was added until pH = 13. Two hours later, 7 ml of a 37 wt% formalin aqueous solution was added, and the above-mentioned palladium compound was reduced at 90 ° C. for 1 hour, followed by filtration, washing with water and drying to prepare a 10% palladium-carbon catalyst.
【００２４】別に安息香酸ベンジル５ｇにエタノールを
加えて液量を２５mlとし、その中に前記触媒２００mgを
加えた。この溶液を反応容器に入れ、さらにエタノール
を１０ml加えた。反応容器及びそれに通じる水素ライン
全体を３０℃にした後、窒素置換、さらに水素置換し
て、この容器を振盪させながら脱ベンジル反応を行い、
圧力が常圧を保つように水素を追加しながら３０分間の
活性試験を行ったところ、水素吸収量は４００mlであっ
た。Separately, ethanol was added to 5 g of benzyl benzoate to make the liquid volume 25 ml, and 200 mg of the catalyst was added thereto. This solution was put into a reaction vessel, and 10 ml of ethanol was further added. After the entire reaction vessel and the hydrogen line leading to it at 30 ° C., the atmosphere was replaced with nitrogen and further replaced with hydrogen, and a debenzylation reaction was carried out while shaking the vessel.
When an activity test was performed for 30 minutes while adding hydrogen so that the pressure was maintained at normal pressure, the hydrogen absorption amount was 400 ml.
【００２５】比較例２ 比較例１の活性炭を用いたことを除き、実施例２と同様
にして１０％パラジウム炭素触媒を調製した。実施例２
と同様に安息香酸ベンジルの活性試験を行ったところ、
水素吸収量は３５０mlであった。 Comparative Example 2 A 10% palladium carbon catalyst was prepared in the same manner as in Example 2 except that the activated carbon of Comparative Example 1 was used. Example 2
When the activity test of benzyl benzoate was performed in the same manner as
The hydrogen absorption was 350 ml.
【００２６】比較例３ ２．８〜１２５μｍの体積粒度分布を有し、累積９０％
の粒子の粒子径が４４．１６μｍ以下、体積加重平均粒
子径が２２．９７μｍ、３．３μｍ以下の微粒子の累積
値が個数粒度分布で４４．０５％になるように粒度調整
された活性炭を用いたことを除き、実施例１と同様にし
て５％パラジウム炭素触媒を調製した。実施例１と同様
に濾過試験を行ったところ、濾過時間は２２．５分であ
った。 Comparative Example 3 A powder having a volume particle size distribution of 2.8 to 125 μm and a cumulative 90%
Activated carbon whose particle size is adjusted so that the particle size of the particles is 44.16 μm or less and the volume-weighted average particle size is 22.97 μm or 3.3 μm or less has a cumulative value of 44.05% in the number particle size distribution. A 5% palladium-carbon catalyst was prepared in the same manner as in Example 1 except for the fact that the catalyst was used. When a filtration test was performed in the same manner as in Example 1, the filtration time was 22.5 minutes.
【００２７】比較例４ ３．９〜１２５μｍの体積粒度分布を有し、累積９０％
の粒子径が６６．４７μｍ以下、体積加重平均粒子径が
３３．０４μｍ、３．３μｍ以下の微粒子の累積値が個
数粒度分布で１３．４０％になるように粒度調整された
活性炭を用いたことを除き実施例１と同様にして５％パ
ラジウム炭素触媒を調製した。実施例１と同様に濾過試
験を行ったところ濾過時間は４．８分であった。またジ
ニトロトルエンによる触媒活性試験における水素吸収量
は３７５mlであった。 Comparative Example 4 having a volume particle size distribution of 3.9 to 125 μm and a cumulative 90%
Activated carbon whose particle size was adjusted so that the particle size of 66.47 μm or less, the volume-weighted average particle size was 33.04 μm, and the cumulative value of the fine particles having a size of 3.3 μm or less was 13.40% in the number particle size distribution. A 5% palladium carbon catalyst was prepared in the same manner as in Example 1 except for the above. When a filtration test was performed in the same manner as in Example 1, the filtration time was 4.8 minutes. The hydrogen absorption in the catalytic activity test with dinitrotoluene was 375 ml.
【００２８】実施例１および２に用いられた活性炭素担
体の体積粒度分布を表１に示す。Table 1 shows the volume particle size distribution of the activated carbon carrier used in Examples 1 and 2.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例１、および２に用いられた活性炭素
担体の個数粒度分布を表２に示す。Table 2 shows the number and particle size distribution of the activated carbon carriers used in Examples 1 and 2.
【００３１】[0031]
【表２】 [Table 2]
【００３２】比較例１および２に用いられた、活性炭素
担体の体積粒度分布を表３に示す。Table 3 shows the volume particle size distribution of the activated carbon carrier used in Comparative Examples 1 and 2.
【００３３】[0033]
【表３】 [Table 3]
【００３４】比較例１および２に用いられた活性炭素担
体の個数粒度分布を表４に示す。Table 4 shows the number particle size distribution of the activated carbon carriers used in Comparative Examples 1 and 2.
【００３５】[0035]
【表４】 [Table 4]
【００３６】実施例３ 白金３．９ｇを王水に溶解した後、濃縮して１５wt％塩
化白金酸溶液を得た。実施例１で用いた粒度調整活性炭
１２０ｇと炭酸ソーダ２３ｇを１２００mlの水に入れて
懸濁させ、この中に前記の塩化白金酸溶液を滴下した。
２時間後、過剰の水素化ホウ素ナトリウムの水溶液を滴
下して前記白金化合物の還元を行った。濾過水洗乾燥し
て３％白金炭素触媒を調製した。実施例１と同様にし
て、ジニトロトルエンによる触媒活性試験を行ったとこ
ろ、水素吸収量は４９６mlであった。 Example 3 3.9 g of platinum was dissolved in aqua regia and concentrated to obtain a 15 wt% chloroplatinic acid solution. 120 g of the particle-size-adjusted activated carbon and 23 g of sodium carbonate used in Example 1 were suspended in 1200 ml of water, and the above chloroplatinic acid solution was dropped therein.
Two hours later, an excess aqueous solution of sodium borohydride was added dropwise to reduce the platinum compound. After filtration, washing with water and drying, a 3% platinum carbon catalyst was prepared. When a catalytic activity test using dinitrotoluene was performed in the same manner as in Example 1, the amount of hydrogen absorbed was 496 ml.
【００３７】比較例５ 比較例１の活性炭を用いたことを除き、実施例３と同様
にして３％白金炭素触媒を調製した。実施例１と同様に
して、ジニトロトルエンによる触媒活性試験を行ったと
ころ、水素吸収量は４４６mlであった。 Comparative Example 5 A 3% platinum carbon catalyst was prepared in the same manner as in Example 3 except that the activated carbon of Comparative Example 1 was used. When a catalytic activity test using dinitrotoluene was performed in the same manner as in Example 1, the amount of hydrogen absorbed was 446 ml.
【００３８】[0038]
【発明の効果】本発明により触媒活性が高く、しかも濾
過分離にすぐれ、実用上反応効率および生産性が高く、
しかも再使用可能な貴金属炭素触媒が提供される。According to the present invention, the catalyst activity is high, the filtration efficiency is excellent, and the reaction efficiency and productivity are practically high.
Moreover, a reusable noble metal carbon catalyst is provided.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭54−19493（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 37/36 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-19493 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-37/36
Claims (2)
されている貴金属触媒成分とを含み、 前記活性炭粒子が、その体積粒度分布における累積９０
％が、６０μｍ以下の粒子サイズを有し、かつその個数
粒度分布において、３．３μｍ以下の粒子サイズを有す
る微粒子の累積値が４０％未満であるように粒度調整さ
れていることを特徴とする貴金属炭素触媒。1. A carrier comprising activated carbon particles and a noble metal catalyst component supported thereon, wherein said activated carbon particles have a cumulative 90% in the volume particle size distribution.
% Has a particle size of 60 μm or less, and the particle size is adjusted such that the cumulative value of the fine particles having a particle size of 3.3 μm or less in the number particle size distribution is less than 40%. Noble metal carbon catalyst.
白金を含有する請求項１に記載の貴金属炭素触媒。2. The noble metal carbon catalyst according to claim 1, wherein the noble metal catalyst component contains palladium or platinum.
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|---|---|---|---|
| JP00824595A JP3244605B2 (en) | 1995-01-23 | 1995-01-23 | Precious metal carbon catalyst with adjusted particle size |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00824595A JP3244605B2 (en) | 1995-01-23 | 1995-01-23 | Precious metal carbon catalyst with adjusted particle size |
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| Publication Number | Publication Date |
|---|---|
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| JP3244605B2 true JP3244605B2 (en) | 2002-01-07 |
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