JPH01228543A - Preparation of catalyst - Google Patents
Preparation of catalystInfo
- Publication number
- JPH01228543A JPH01228543A JP5375188A JP5375188A JPH01228543A JP H01228543 A JPH01228543 A JP H01228543A JP 5375188 A JP5375188 A JP 5375188A JP 5375188 A JP5375188 A JP 5375188A JP H01228543 A JPH01228543 A JP H01228543A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- value
- activated carbon
- aqueous ammonia
- less
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 6
- -1 silane compound Chemical class 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 21
- 229910001868 water Inorganic materials 0.000 description 18
- 229910052763 palladium Inorganic materials 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 230000005587 bubbling Effects 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 208000031212 Autoimmune polyendocrinopathy Diseases 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
仁発明の目的
の１
この発明は、各種産業部門、特に化学工業で使用される
活性炭に活性金属を担持させた触媒に関し、特に使用時
において安定したｐＨを維持する触媒の調製法に関する
ものである。Detailed Description of the Invention Object of the Invention 1 This invention relates to a catalyst in which an active metal is supported on activated carbon used in various industrial sectors, particularly in the chemical industry, and in particular to a catalyst that maintains a stable pH during use. It relates to a method for preparing.
【久立且ｊ
活性炭担持金属触媒の代表例である活性炭にパラジウム
を担持させたＰｄ−活性炭触媒は、活性炭を予め酸又は
塩基類で処理し、そのあとで塩化パラジウム、硝酸パラ
ジウム等の水溶性パラジウム塩の水溶液に浸漬した後蒸
発乾固させ、還元処理をすることにより調製されている
。還元処理としては、通常のＨ２還元のほか、ヒドラジ
ンや水素化ホウ素ナトリウム等の液相還元剤による還元
も行われている。[Kudachi Katsujj Pd-activated carbon catalyst, in which palladium is supported on activated carbon, is a typical example of activated carbon-supported metal catalyst.Activated carbon is treated with acid or base in advance, and then water-soluble palladium chloride, palladium nitrate, etc. It is prepared by immersing it in an aqueous solution of palladium salt, evaporating it to dryness, and then subjecting it to reduction treatment. As reduction treatment, in addition to normal H2 reduction, reduction using a liquid phase reducing agent such as hydrazine or sodium borohydride is also performed.
このような通常の調製法で得られるＰｄ−活性炭触媒は
、使用雰囲気によってはｐＨが大きく変動し安定なＰＨ
を維持することか出来ない。The Pd-activated carbon catalyst obtained by such a normal preparation method has a stable pH that fluctuates greatly depending on the atmosphere in which it is used.
It is not possible to maintain it.
ｐＨ変動の原因は触媒調製時に使用される酸又は塩基成
分の溶出にあると考えられる。しかし、触媒を使用前に
単に水洗浄するたけでは、使用雰囲気におけるｐＨ変動
を防止し安定化するためには不十分であることは、これ
までの使用実績から明らかである。The cause of pH fluctuation is thought to be the elution of acid or base components used during catalyst preparation. However, it is clear from past usage results that simply washing the catalyst with water before use is insufficient to prevent and stabilize pH fluctuations in the atmosphere in which it is used.
ＰＨを調整するため、塩酸、リン酸、硫酸などの酸又は
ＮａＯＨなどのアルカリを加えることも行われているが
、使用雰囲気によってはこれらが溶出するためＰＨの変
動は避けられない。In order to adjust the pH, acids such as hydrochloric acid, phosphoric acid, and sulfuric acid, or alkalis such as NaOH are added, but depending on the atmosphere in which they are used, these dissolve, so that fluctuations in the pH are unavoidable.
液相反応ではＰＨの影響か触媒活性、選択性の重要な支
配因子となる。ところが活性炭担持金属触媒を溶液／水
系又は懸濁系で各種ガスのバブリング下に使用するとｐ
Ｈが著しく変化し、これは水洗浄を繰り返し行ったもの
でも解消できないことかわかった。従ってどのようにし
てｐＨを安定化するかが重要な課題である。In liquid phase reactions, the influence of pH is an important controlling factor for catalyst activity and selectivity. However, when an activated carbon-supported metal catalyst is used in a solution/water system or suspension system under bubbling of various gases, p.
It was found that the H value changed significantly and that this could not be resolved even by repeated washing with water. Therefore, how to stabilize pH is an important issue.
特公昭４６−２２４４４号には、Ｐｄ−活性炭触媒の高
活性を得る目的で、陰イオンか実質的に認められなくな
るまで水洗する方法が開示されているか、これによるＰ
Ｈの安定化の問題には一切触れられていない。Japanese Patent Publication No. 46-22444 discloses a method of washing the Pd-activated carbon catalyst with water until substantially no anions are recognized, in order to obtain high activity of the Pd-activated carbon catalyst.
The issue of stabilizing H is not mentioned at all.
、 か じよ−と る■
本発明は、液相反応における触媒自体のＰＨを安定化し
、かつ任意のｐＨに制御し、触媒活性及びその選択性を
向上することかできる活性金属を担持した活性炭触媒の
調製法を提供することを目的とする。, Kajiyotoru ■ The present invention is an activated carbon supporting an active metal that can stabilize the pH of the catalyst itself in a liquid phase reaction, control it to an arbitrary pH, and improve the catalyst activity and selectivity. The purpose is to provide a method for preparing a catalyst.
口９発明の構成
４． 古な るだめの
本発明による触媒の調製法は、活性炭に活性金属な担持
させた後ｐＨ値１０以上のアンモニア水で洗浄処理する
ことを特徴とする。9. Structure of the invention 4. The method for preparing a catalyst according to the present invention by Rudame is characterized by supporting an active metal on activated carbon and then washing it with aqueous ammonia having a pH value of 10 or more.
ｐＨ値１０以上のアンモニア水での洗浄処理は回分方式
でも、流通方式でもよいか、通常室温〜５０℃の範囲で
、洗浄に使用したアンモニア水のｐＨが一定になるまで
行う０通常０．５〜１時間で定常化するが、更に０．５
〜１時間継続することが好ましい、この処理により触媒
のＰＨは各種の使用雰囲気、例えばＨ２Ｏ系、溶剤／Ｈ
２０系等において長時間使用しても一定値に維持される
。The cleaning treatment with ammonia water with a pH value of 10 or more may be carried out in a batch method or a distribution method, or it is usually carried out at a temperature ranging from room temperature to 50°C until the pH of the ammonia water used for cleaning becomes constant.0 Usually 0.5 It stabilizes in ~1 hour, but further increases by 0.5
This treatment, which is preferably continued for ~1 hour, changes the pH of the catalyst in various working atmospheres, such as H2O system, solvent/H2O system, etc.
20 series etc., it is maintained at a constant value even if it is used for a long time.
これに対して、ｐＨ値１０未満のアンモニア水を使用し
た場合は、洗浄時間を長くしても触媒のｐＨは安定化さ
れない。On the other hand, if ammonia water with a pH value of less than 10 is used, the pH of the catalyst will not be stabilized even if the washing time is increased.
このようにして調製された触媒は、各種の使用条件下で
一定のｐＨ値を維持するか、更に、これをアミノ基を有
するシラン化合物、好ましくは３−アミノプロビルトリ
エトキシシランて処理することにより、使用シラン化合
物量に応じて、その一定に維持されるｐＨを任意の値に
定めることができる。The catalyst prepared in this way can be maintained at a constant pH value under various conditions of use or can be further treated with a silane compound containing amino groups, preferably 3-aminopropyltriethoxysilane. Accordingly, the pH to be maintained constant can be set to an arbitrary value depending on the amount of the silane compound used.
また、前記アンモニア水で洗浄処理した触媒とざらにア
ミノ基を有するシラン化合物で処理した触媒又は担体を
混合して使用することにより、反応系のＰＨを調整する
こともできる。Furthermore, the pH of the reaction system can be adjusted by mixing and using the catalyst washed with ammonia water and the catalyst or carrier treated with a silane compound having roughly an amino group.
本発明はパラジウムのほか、白金、ルテニウム等の任意
の活性金属を担持した活性炭触媒に適用できる。The present invention can be applied to activated carbon catalysts supporting any active metal such as platinum or ruthenium in addition to palladium.
以下実施例により本発明を具体的に説明する。The present invention will be specifically explained below using Examples.
実施例１
重版の５％Ｐｄ−活性炭触媒（武田薬品輛製）５ｇをビ
ーカーに入れ、ｐｉ−ｉ値が１２，３のアンモニア水１
００ｍｆＬを添加し、室温にてＨ２流通下で約２時間攪
拌し、その後濾過、洗浄し、乾燥器で乾燥したものをサ
ンプルＡとした。Example 1 5 g of reprinted 5% Pd-activated carbon catalyst (manufactured by Takeda Pharmaceutical Co., Ltd.) was placed in a beaker, and 1 ammonia water with a pi-i value of 12.3 was added.
Sample A was obtained by adding 00 mfL and stirring at room temperature under H2 flow for about 2 hours, followed by filtration, washing, and drying in a drier.
同様にｐＨ値がそれぞれ１１．２．９．５又は７．８の
アンモニア水を使用した場合のサンプルをＢ、Ｃ，Ｄ、
未処理のサンプルをＥとした。Similarly, samples B, C, D, when using ammonia water with a pH value of 11.2, 9.5 or 7.8, respectively.
The untreated sample was designated as E.
これらサンプルＡ−Ｅ１ｇをＨ２Ｏ１００ｍＭに懸濁し
、Ｈ２バブリング（１００ｍ ｌ ／分）における使用
開始時と３００時間後のＰＨの差ΔｐＨを第１図に示す
、 第１図において横軸は使用したアンモニア水のｐＨ
１縦軸は上記使用条件下におけるΔＰＨを表す。1 g of these samples A-E were suspended in 100 mM H2O, and the difference ΔpH between the pH at the start of use and after 300 hours in H2 bubbling (100 ml/min) is shown in Figure 1. In Figure 1, the horizontal axis represents the ammonia water used. pH of
1 The vertical axis represents ΔPH under the above usage conditions.
この結果から、ｐＨ１０以上のアンモニア水で処理した
触媒のｐＨ値は全く変化せず、安定化していることがわ
かる。This result shows that the pH value of the catalyst treated with aqueous ammonia having a pH of 10 or more did not change at all and was stabilized.
実施例２
上記のサンプルＡ、Ｃ及びＥを各種の雰囲気下で実施例
１と同様に使用した時のｐＨの経時変化を第２図に示す
。Example 2 FIG. 2 shows changes in pH over time when the above samples A, C, and E were used in the same manner as in Example 1 under various atmospheres.
第２図において横軸は経過時間、縦軸は反応系のｐＨを
表し、Ｏ印はサンプルＡをＨ２０懸濁、Ｈ２バブリング
雰囲気で、・印はサンプルＡをテトラヒドロフラン（以
下ＴＨＦという）５０ｍＪ１とＨ２０５０ｍ ｌの混合
溶媒に懸濁、Ｈ２バブリング雰囲気で、Δ印はサンプル
ＣをＨ２０懸濁、Ｈ２バブリング雰囲気で、０印はサン
プルＥをＨ２０懸濁、Ｈ２バブリング雰囲気で使用した
場合な示す。In Fig. 2, the horizontal axis represents the elapsed time, and the vertical axis represents the pH of the reaction system. The O mark indicates sample A suspended in H20 in a H2 bubbling atmosphere, and the * mark indicates sample A mixed with 50 mJ1 of tetrahydrofuran (hereinafter referred to as THF) and H2050 mJ1. The Δ mark indicates sample C suspended in H20 in a H2 bubbling atmosphere, and the 0 mark indicates sample E suspended in H20 in an H2 bubbling atmosphere.
ＰＨ＝１２．３のアンモニア水で処理したサンプルＡで
は、Ｎ２０系でもＴＨＦ／Ｈ２０系でもＰＨ値は安定し
ていることかわかる。It can be seen that in sample A treated with ammonia water with pH=12.3, the pH value is stable in both the N20 system and the THF/H20 system.
実施例３
１０ｇのサンプルＡをビーカーに入れ、０．８％濃度の
３−アミノプロピルトリエトキシシラン（以下ＡＰＳと
いう）水溶液１００＋ｎＪＪを添加し、室温て２時間攪
拌混合した。次いで濾過、洗浄し、乾燥したものをサン
プルＦとした。Example 3 10 g of sample A was placed in a beaker, 100+nJJ of a 0.8% aqueous solution of 3-aminopropyltriethoxysilane (hereinafter referred to as APS) was added, and the mixture was stirred and mixed at room temperature for 2 hours. Sample F was then filtered, washed, and dried.
同様に、Ａ Ｐ Ｓ ｅＲＩｆｆを１．２５％、１．９
％、３．１５％とした場合のサンプルをそれぞれＧ、Ｈ
，にとした。これらのサンプルについて、実施例１と同
様な試験を行った時のｐＨ値とＡＰＳ５度との関係を第
３図に示す。Similarly, AP S eRIff is 1.25%, 1.9
% and 3.15%, the samples are G and H, respectively.
, I did it. FIG. 3 shows the relationship between pH value and APS 5 degrees when the same test as in Example 1 was conducted for these samples.
第３図において横軸はＡ Ｐ Ｓ Ｎ （ｇ ／ ｇ触
媒）、縦軸はＡＰＳ処理をしないものとのＰＨの差（Δ
ｐＨ）を表す。In Fig. 3, the horizontal axis is AP S N (g/g catalyst), and the vertical axis is the difference in pH (∆) from that without APS treatment.
pH).
この図より、ＡＰＳの濃度（添加量）により、ｐＨ値を
任意に制御できることかわかる。From this figure, it can be seen that the pH value can be arbitrarily controlled by adjusting the concentration (addition amount) of APS.
実施例４
実施例３で得たサンプルＦ、Ｇ、Ｈ，に各々について実
施例１と同じＮ２０懸濁、Ｎ２バブリング下でのＰＨ経
時変化を第４図に示す。Example 4 FIG. 4 shows the PH changes over time for samples F, G, and H obtained in Example 3 under the same N20 suspension and N2 bubbling as in Example 1.
第４図において、横軸は経過時間、縦軸は反応系のＰＨ
を表す、この図から各サンプルともそのｐＨか安定しい
ることかわかる。In Figure 4, the horizontal axis is the elapsed time, and the vertical axis is the PH of the reaction system.
It can be seen from this figure that the pH of each sample is stable.
比」し例」２
市販の５％Ｐｄ−活性炭触媒及び活性炭担体の各種雰囲
気下てのＰＨ経時変化を測定した。Comparison Example 2 Changes in pH over time of a commercially available 5% Pd-activated carbon catalyst and activated carbon carrier under various atmospheres were measured.
■Ｈ２０系（ｔ５５図口印）
実施例１で使用した市販の５％Ｐｄ−活性炭触媒１ｇと
Ｈ２Ｏ１００ｍ文をビーカー中で室温でスタラーで攪拌
懸濁させ、Ｎ２をｌｏｏｍｉ／分でバブリングさせなが
らｐＨの経時変化を測定した。■ H20 system (t55 figure mark) 1 g of the commercially available 5% Pd-activated carbon catalyst used in Example 1 and 100 m of H2O were stirred and suspended in a beaker at room temperature using a stirrer, and the pH was adjusted while bubbling N2 at a loomi/min. The changes over time were measured.
■ＴＨＦ／Ｈ２０系（第５図■印）
市販の５％Ｐｄ−活性炭触媒（武田薬品■製）１ｇをＴ
ＨＦ５０ｍｌとＨ２０５０ｍＪＬの混合溶液にＮ２０系
と同様な方法で懸濁し、Ｎ２を１００ｍ１／分てバブリ
ングさせながらｐＨを測定した。■THF/H20 system (marked ■ in Figure 5) 1 g of commercially available 5% Pd-activated carbon catalyst (manufactured by Takeda Pharmaceutical ■) was
It was suspended in a mixed solution of 50 ml of HF and 50 mJL of H2 in the same manner as the N20 system, and the pH was measured while bubbling N2 at 100 ml/min.
■Ｈ２０系（第５図ム印）
前記■で使用したと同じ５％Ｐｄ−活性炭触媒１ｇとＨ
２０１０Ｑｍｌをビーカー中で室温でスタラーで攪拌懸
濁させ、Ｎ２をｌｏｏｍｕ／分でバブリングさせなから
ＰＨの経時変化を測定した。■H20 system (marked by mu in Figure 5) 1 g of 5% Pd-activated carbon catalyst and H
2010Qml was stirred and suspended in a beaker at room temperature using a stirrer, and while N2 was bubbled at a rate of loomu/min, the change in pH over time was measured.
■Ｈ２０系（第５図Δ印）
市販の活性炭担体を、Ｐｄ−活性炭触媒の場合と同様に
して、）（２０系でｐＨＢ定を行った。(2) H20 system (Δ mark in Figure 5) pHB determination was carried out using a commercially available activated carbon carrier in the same manner as in the case of the Pd-activated carbon catalyst.
これらの測定結果を第５図に示した６
第５図において、横軸は経過時間、縦軸は反応系のｐＨ
を表す。いずれの場合にもＰＨ値は処理時間ともに低下
することがわかる。These measurement results are shown in Figure 5.6 In Figure 5, the horizontal axis is the elapsed time, and the vertical axis is the pH of the reaction system.
represents. It can be seen that in both cases, the PH value decreases with the processing time.
−五直ユ
比較例１の■の操作を繰り返し行った。即ち、実施例１
で使用した市販の５％Ｐｄ−活性炭触媒を１００ｍ１の
Ｎ２０に懸濁し、Ｎ２バブリングを２８０分行った後触
媒を濾過し、新たに１００ｍ１の８２０に懸濁し、Ｎ２
バブリングをする操作を鰻り返してｐＨの経時変化を測
定した。- Five Directions The operation (■) of Comparative Example 1 was repeated. That is, Example 1
The commercially available 5% Pd-activated carbon catalyst used in was suspended in 100 ml of N20, N2 bubbling was performed for 280 minutes, the catalyst was filtered, and newly suspended in 100 ml of 820, and N2
The bubbling operation was repeated to measure the change in pH over time.
結果を第６図に示す、第６図において、横軸は経過時間
、縦軸は反応系のｐＨを表す。The results are shown in FIG. 6, in which the horizontal axis represents the elapsed time and the vertical axis represents the pH of the reaction system.
この結果より単なる繰り反し使用だけではＰＨか安定し
ないことがわかる。This result shows that mere repeated use does not stabilize the pH.
さらに１作り反し初期のｐＨが元のｐＨ９，４付近まで
戻ることから、ｐＨ低下の原因は触媒から溶液中に酸性
物質が流出するためであるとする推定か裏付けられる。Furthermore, since the initial pH returned to around the original pH of 9.4 after one batch, the assumption that the cause of the pH drop was due to acidic substances flowing out from the catalyst into the solution is supported.
ハ１発明の効果
一般に液相の接触反応おいては、適正なｐＨ領域で行う
ことは触媒の活性及び選択性を向上させる上で極めて重
要である。このような見地から、本発明では次のような
効果が期待てきる。C1 Effects of the Invention In general, in liquid phase catalytic reactions, it is extremely important to carry out the reaction in an appropriate pH range in order to improve the activity and selectivity of the catalyst. From this standpoint, the following effects can be expected from the present invention.
（１）一定且つ最適のＰＨ値を有する触媒を調製するこ
とができ、反応収率、反応条件を著しく４片することか
できる。(1) It is possible to prepare a catalyst having a constant and optimal pH value, and the reaction yield and reaction conditions can be significantly changed.
（２）任意のｐＨで使用できるので、各種の反応に広範
に応用することができる。(2) Since it can be used at any pH, it can be widely applied to various reactions.
第１図は５％Ｐｄ−活性炭触媒を各種濃度のアンモニア
水で処理したもの及び未処理のものの使用開始時と３０
０時間後のＰＨの差ΔｐＨを示す図、第２図は５％Ｐｄ
−活性炭触媒を各Ｓ濃度のアンモニア水で処理したもの
及び未処理のものを各雰囲気下で使用した場合のＰＨの
経時変化を示す図、第３図はｐＨ１２，３のアンモニア
水で処理した５％Ｐｄ−活性炭触媒を更に異なる濃度の
ＡＰＳ液で処理したもののＰＨ値を示す図、第４図はＰ
Ｈ１２，３％のアンモニア水処理−ＡＳＰ処理５％Ｐｄ
活性炭触媒のＨ２０懸濁、Ｈ２バブリング雰囲気下での
ｐＨの経時変化を示す図、第５図は市販の５％Ｐｄ−活
性炭触媒及び活性炭担体の各種雰囲気下でのＰＨの経時
変化を示す図、第６図は市ｔ１５％Ｐｄ−活性炭触媒の
Ｈ２０懸濁、Ｈ２バブリング繰り返し使用におけるＰＨ
の経時変化を示す図である。Figure 1 shows the 5% Pd-activated carbon catalyst treated with aqueous ammonia at various concentrations and the untreated one at the beginning of use and after 30 minutes.
A diagram showing the pH difference ΔpH after 0 hours, Figure 2 is 5% Pd
- Diagrams showing changes in pH over time when activated carbon catalysts treated with aqueous ammonia at various S concentrations and untreated were used in various atmospheres. Figure 4 shows the pH values of %Pd-activated carbon catalysts treated with APS liquids of different concentrations.
H12, 3% ammonia water treatment - ASP treatment 5% Pd
FIG. 5 is a diagram showing changes in pH over time of activated carbon catalyst under H20 suspension and H2 bubbling atmosphere, FIG. 5 is a diagram showing changes in pH over time of commercially available 5% Pd-activated carbon catalyst and activated carbon carrier under various atmospheres, Figure 6 shows the pH of 15% Pd-activated carbon catalyst in H20 suspension and repeated use of H2 bubbling.
FIG. 3 is a diagram showing changes over time.
Claims (1)
アンモニア水で洗浄処理することを特徴とする触媒の調
製法。 ２ 活性炭に活性金属を担持させ、ｐＨ値１０以上のア
ンモニア水で洗浄処理した後、アミノ基を有するシラン
化合物で処理することを特徴とする触媒の調製法。[Scope of Claims] 1. A method for preparing a catalyst, which comprises supporting activated metal on activated carbon and then washing the activated carbon with aqueous ammonia having a pH value of 10 or more. 2. A method for preparing a catalyst, which comprises supporting activated metal on activated carbon, washing with aqueous ammonia having a pH value of 10 or more, and then treating with a silane compound having an amino group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5375188A JPH01228543A (en) | 1988-03-09 | 1988-03-09 | Preparation of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5375188A JPH01228543A (en) | 1988-03-09 | 1988-03-09 | Preparation of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01228543A true JPH01228543A (en) | 1989-09-12 |
| JPH0556184B2 JPH0556184B2 (en) | 1993-08-18 |
Family
ID=12951514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5375188A Granted JPH01228543A (en) | 1988-03-09 | 1988-03-09 | Preparation of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01228543A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032305A1 (en) * | 1999-10-29 | 2001-05-10 | Exxon Research And Engineering Company | Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions |
| JP2006198503A (en) * | 2005-01-19 | 2006-08-03 | Hiroshima Univ | Catalyst composition which carries inorganic catalytic component and organic compound, and its utilization |
| CN103861645A (en) * | 2014-04-11 | 2014-06-18 | 广州旺承能源科技有限公司 | Aluminium/water reaction controllable-hydrogen catalyst and preparation method thereof |
-
1988
- 1988-03-09 JP JP5375188A patent/JPH01228543A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001032305A1 (en) * | 1999-10-29 | 2001-05-10 | Exxon Research And Engineering Company | Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions |
| US6313062B1 (en) | 1999-10-29 | 2001-11-06 | Exxon Reserach And Engineering Company | Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst composition, use of the catalysts for conducting such reactions, and the products of such reactions |
| AU769483B2 (en) * | 1999-10-29 | 2004-01-29 | Exxonmobil Research And Engineering Company | Process for the preparation of high activity carbon monoxide hydrogenation catalysts; the catalyst compositions, use of the catalysts for conducting such reactions, and the products of such reactions |
| JP2006198503A (en) * | 2005-01-19 | 2006-08-03 | Hiroshima Univ | Catalyst composition which carries inorganic catalytic component and organic compound, and its utilization |
| CN103861645A (en) * | 2014-04-11 | 2014-06-18 | 广州旺承能源科技有限公司 | Aluminium/water reaction controllable-hydrogen catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0556184B2 (en) | 1993-08-18 |
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