JPH0889784A - Method of forming activated carbon-supported catalyst bed - Google Patents
Method of forming activated carbon-supported catalyst bedInfo
- Publication number
- JPH0889784A JPH0889784A JP23175094A JP23175094A JPH0889784A JP H0889784 A JPH0889784 A JP H0889784A JP 23175094 A JP23175094 A JP 23175094A JP 23175094 A JP23175094 A JP 23175094A JP H0889784 A JPH0889784 A JP H0889784A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- tank
- slurry
- activated carbon
- solvent
- 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 107
- 238000000034 method Methods 0.000 title claims description 11
- 239000002002 slurry Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims description 34
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【目的】 反応器に粒状活性炭担持触媒を充填して固定
触媒床を形成する際に、触媒が摩擦や衝撃により破砕し
て微粉が発生するのを回避し、且つ触媒に付着している
微粉も除去して、微粉を含まない触媒床を形成する。
【構成】 スラリー化槽に上部から触媒、下部から水を
導入し、水の一部は槽内を触媒と向流接触しつつ上昇さ
せて槽上部から触媒の微粉を含んで溢流させ、触媒は槽
内を下降させて槽底から水の残部と共にスラリーとして
反応器に流入させる。流入したスラリーからは触媒を沈
降させて触媒床を形成させ、水は器外に排出する。
(57) [Abstract] [Purpose] When a reactor is packed with a granular activated carbon-supported catalyst to form a fixed catalyst bed, the catalyst is prevented from being crushed by friction or impact to generate fine powder, and Adhering fines are also removed to form a fines-free catalyst bed. [Composition] A catalyst is introduced into the slurry tank from the upper part, and water is introduced from the lower part, and a part of the water is raised while making countercurrent contact with the catalyst in the tank and overflowed from the upper part of the tank containing the fine powder of the catalyst. Moves down the inside of the tank and flows into the reactor from the bottom of the tank as a slurry together with the rest of the water. The catalyst is settled from the inflowing slurry to form a catalyst bed, and water is discharged out of the vessel.
Description
【０００１】[0001]
【産業上の利用分野】本発明は触媒槽に粒状活性炭担持
触媒を充填して触媒床を形成する方法に関するものであ
る。本発明方法で形成された触媒床は各種の反応に有利
に用いることができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a catalyst bed by filling a catalyst tank with a granular activated carbon-supported catalyst. The catalyst bed formed by the method of the present invention can be advantageously used for various reactions.
【０００２】[0002]
【従来の技術】粒状活性炭担持触媒は各種の反応に広く
利用されている。その代表的な例の一つは粗テレフタル
酸の水添精製である。この方法では、粒状活性炭にパラ
ジウムなどの貴金属を担持した触媒で形成した触媒床に
高温下で調製した粗テレフタル酸水溶液と水素とを流通
させ、粗テレフタル酸中の４−カルボキシベンツアルデ
ヒドなどの不純物を水添して除去する。触媒床から流出
したテレフタル酸水溶液は直列に接続された数個の晶析
槽から成る晶析装置に導入し、順次に温度を低下させな
がらテレフタル酸結晶を析出させる。最後の晶析槽から
流出するテレフタル酸結晶スラリーからは、濾過又は遠
心分離によりテレフタル酸結晶を回収する。2. Description of the Related Art Granular activated carbon-supported catalysts are widely used for various reactions. One of the typical examples is hydrorefining of crude terephthalic acid. In this method, a crude terephthalic acid aqueous solution prepared under high temperature and hydrogen are circulated through a catalyst bed formed of a catalyst in which a precious metal such as palladium is supported on granular activated carbon, and impurities such as 4-carboxybenzaldehyde in the crude terephthalic acid are circulated. Is removed by hydrogenation. The terephthalic acid aqueous solution flowing out from the catalyst bed is introduced into a crystallizer comprising several crystallizers connected in series, and terephthalic acid crystals are precipitated while sequentially lowering the temperature. From the terephthalic acid crystal slurry flowing out from the last crystallization tank, terephthalic acid crystals are recovered by filtration or centrifugation.
【０００３】[0003]
【発明が解決しようとする課題】この方法における問題
点の一つは、粒状活性炭担持触媒は強度が比較的弱いの
で、運搬や触媒槽への充填に際し衝撃や摩擦により容易
に破砕して微粉を生ずることである。触媒床中の微粉
は、触媒床を流通するテレフタル酸水溶液と共に少しづ
つ触媒床から流出してくる。この微粉が晶析槽に流入す
るとテレフタル酸結晶の品位を著しく低下させるので、
晶析装置への流路の途中にフィルターを設けて微粉を完
全に捕集しなければならない。しかし微粉によりフィル
ターが目詰まりを起こすので、ときどきフィルターを交
換する必要がある。また、微粉中には貴金属が触媒本体
中よりも高濃度に含有されているので、微粉の生成・流
失は触媒活性の低下と貴金属の損失をもたらす。従って
本発明は、触媒槽に粒状活性炭担持触媒を充填するに際
し、触媒が破砕して微粉を生じないような充填方法を提
供せんとするものである。また本発明は触媒槽に粒状活
性炭担持触媒を充填するに際し、触媒に付着している微
粉を除去して、形成された触媒床中に極く少量の微粉し
か存在しないようにする方法を提供せんとするものであ
る。One of the problems in this method is that since the granular activated carbon-supported catalyst has a relatively low strength, it is easily crushed by impact or friction during transportation or filling into the catalyst tank to form fine powder. It will happen. The fine powder in the catalyst bed gradually flows out of the catalyst bed together with the aqueous terephthalic acid solution flowing through the catalyst bed. When this fine powder flows into the crystallization tank, the quality of terephthalic acid crystals is significantly reduced,
A fine powder must be completely collected by providing a filter on the way to the crystallizer. However, it is necessary to change the filter from time to time, because the fine particles cause the filter to become clogged. Further, since the noble metal is contained in the fine powder in a higher concentration than that in the catalyst body, the generation / flow-out of the fine powder causes a decrease in catalytic activity and loss of the noble metal. Accordingly, the present invention is to provide a filling method in which the catalyst is not crushed to form fine powder when the catalyst-supported granular catalyst is filled in the catalyst tank. Further, the present invention does not provide a method for removing the fine powder adhering to the catalyst when filling the catalyst tank with the granular activated carbon-supported catalyst so that only a very small amount of fine powder is present in the formed catalyst bed. It is what
【０００４】[0004]
【課題を解決するための手段】本発明によれば、上部に
触媒供給口と溢流液抜出口とを有し、下部にスラリー抜
出口と溶媒供給口とを有するスラリー化槽と、触媒床を
収容する触媒槽とを配管で連結してなる装置を用いて触
媒床の形成が行なわれる。粒状活性炭担持触媒はスラリ
ー化槽でスラリー化して触媒槽に流入させる。粒状活性
炭担持触媒のスラリー化は、溶媒供給口から溶媒を供給
してその一部を溶媒溢流口から溢流させながら、触媒供
給口から触媒を供給することにより行なわれる。スラリ
ー化槽内で下降する触媒と溢流しようと上昇する溶媒と
が向流接触するので、触媒に付着していた微粉は触媒か
ら剥離して上昇する溶媒により持去られ、槽外に溢流す
る。一方、微粉を除去された触媒は溶媒の一部と共にス
ラリー化槽から配管を経て触媒槽に流入する。流入した
スラリーから触媒を沈降させ溶媒を槽外に流出させる
と、密に充填された触媒床が形成される。According to the present invention, there is provided a slurry tank having a catalyst supply port and an overflow liquid outlet at the upper portion and a slurry outlet and a solvent inlet at the lower portion, and a catalyst bed. A catalyst bed is formed by using a device in which a catalyst tank for housing is connected by a pipe. The granular activated carbon-supported catalyst is slurried in a slurry tank and allowed to flow into the catalyst tank. Slurrying of the granular activated carbon-supported catalyst is performed by supplying the solvent from the solvent supply port and causing a part of the solvent to overflow from the solvent overflow port while supplying the catalyst from the catalyst supply port. In the slurry tank, the descending catalyst comes into countercurrent contact with the rising solvent to overflow, so the fine powder adhering to the catalyst separates from the catalyst and is carried away by the rising solvent to overflow outside the tank. To do. On the other hand, the catalyst from which the fine powder has been removed flows into the catalyst tank together with a part of the solvent from the slurry tank through the pipe. When the catalyst is allowed to settle from the inflowing slurry and the solvent is allowed to flow out of the tank, a densely packed catalyst bed is formed.
【０００５】本発明を図面に基づいて更に具体的に説明
すると、図中、１は触媒槽であり、２は触媒槽への反応
原料液の供給管、３は触媒槽からの反応生成液の流出
管、４は触媒床の支持材である。触媒槽１には予め溶媒
を充満させておくのが好ましい。５はスラリー化槽であ
り、６はスラリー化槽への触媒の供給口、７はスラリー
化槽から溢流する溶媒の抜出口である。図示の如く、通
常、触媒供給口はスラリー化槽の頭部に、溢流液抜出口
は上部側面に設けるのが好ましい。８はスラリー化槽へ
の溶媒の供給口であり、９はスラリー化槽からのスラリ
ーの抜出口である。溶媒がスラリー化槽内を全断面に亘
って上昇するように、溶媒供給口はスラリー化槽の周壁
にほぼ均等に数ヶ所に配置するのが好ましい。溶媒供給
口から供給された溶媒は、一部は触媒供給口から供給さ
れた触媒と向流接触しつつ上昇させ、残部は触媒と共に
スラリーを形成させて触媒槽に流入させる。本発明では
上昇する溶媒により触媒に付着している微粉を除去する
ので、触媒の粒径や微粉の付着状況にもよるが触媒１ｋ
ｇ当り少くとも０．０１ｍ3 の溶媒が上昇するようにす
るのが好ましい。上昇する溶媒量が多いほど微粉の除去
は良好に行なわれるので、通常は触媒１ｋｇ当り０．０
３〜０．０５ｍ3 の溶媒が上昇するようにする。粒状活
性炭担持触媒は比重が比較的小さいので、上昇流の流速
は通常１〜５ｍ／分、好ましくは１．５〜３ｍ／分程度
である。微粉を含んでスラリー化槽から溢流した溶媒
は、フィルター１０で濾過して微粉を回収する。微粉中
には一般に触媒本体よりも高濃度で触媒金属成分が含ま
れているので、捕集した微粉からは常法により効率よく
金属成分を回収することができる。The present invention will be described in more detail with reference to the drawings. In the figure, 1 is a catalyst tank, 2 is a reaction material liquid supply pipe to the catalyst tank, and 3 is a reaction product liquid from the catalyst tank. Outflow pipe 4 is a support for the catalyst bed. The catalyst tank 1 is preferably filled with a solvent in advance. Reference numeral 5 is a slurry forming tank, 6 is a catalyst supply port to the slurry forming tank, and 7 is a solvent outlet for overflowing the solvent from the slurry forming tank. As shown in the figure, it is usually preferable to provide the catalyst supply port at the head of the slurry tank and the overflow liquid outlet at the upper side surface. Reference numeral 8 is a solvent supply port to the slurry forming tank, and 9 is a slurry outlet from the slurry forming tank. It is preferable that the solvent supply ports are arranged at several positions substantially evenly on the peripheral wall of the slurry-forming tank so that the solvent rises in the slurry-forming tank over the entire cross section. A part of the solvent supplied from the solvent supply port rises while making countercurrent contact with the catalyst supplied from the catalyst supply port, and the rest forms a slurry with the catalyst and flows into the catalyst tank. In the present invention, the fine particles adhering to the catalyst are removed by the ascending solvent.
It is preferred that at least 0.01 m 3 of solvent be raised per gram. The larger the amount of solvent that rises, the better the fine powder can be removed.
Allow 3 to 0.05 m 3 of solvent to rise. Since the granular activated carbon-supported catalyst has a relatively low specific gravity, the flow rate of the upward flow is usually 1 to 5 m / min, preferably about 1.5 to 3 m / min. The solvent containing the fine powder and overflowing from the slurry forming tank is filtered by the filter 10 to collect the fine powder. Since the fine metal powder generally contains the catalyst metal component in a higher concentration than the catalyst body, the metal component can be efficiently recovered from the collected fine powder by a conventional method.
【０００６】一方、スラリー化槽で微粉を除去された触
媒は溶媒と共にスラリーとなって触媒槽に流入するの
で、衝撃、摩擦による触媒の粉化は、触媒を乾燥状態で
充填する場合に比して大幅に減少する。特に前述の如く
触媒槽に予め溶媒を充満させておき、触媒スラリーをこ
の溶媒中に流入させるようにすると、スラリー流入時の
衝撃をさらに軽減させることができる。流入したスラリ
ー中の触媒は沈降して支持材４上に堆積し、溶媒は支持
材を通過して導管３に流入する。このように本発明によ
れば、スラリー中から触媒が沈降・堆積して触媒床か形
成されるので、触媒床が緻密に構成され、使用中に触媒
床の圧密化が起こらない。On the other hand, since the catalyst from which fine powder has been removed in the slurry tank flows into the catalyst tank as a slurry together with the solvent, powdering of the catalyst by impact and friction is more difficult than when the catalyst is packed in a dry state. Greatly reduced. Particularly, when the catalyst tank is filled with the solvent in advance and the catalyst slurry is allowed to flow into the solvent as described above, the impact at the time of inflow of the slurry can be further reduced. The catalyst in the inflowing slurry settles and deposits on the support material 4, and the solvent passes through the support material and flows into the conduit 3. As described above, according to the present invention, the catalyst is settled and deposited from the slurry to form the catalyst bed, so that the catalyst bed is densely formed and the catalyst bed is not consolidated during use.
【０００７】本発明の実施の態様の１例を示すと、直径
５００ｍｍ、高さ１５００ｍｍで、底部が若干円錐形と
なっておりその中心にスラリー抜出管が設けられている
スラリー化槽に上部から粒状活性炭担持パラジウム触媒
（粒径２〜５ｍｍ、パラジウム担持量０．５％）を６０
０ｋｇ／時間で供給し、同時にスラリー化槽の下部から
水を２５ｍ3 ／時間で供給した。水はほぼ上方に９０
％、下方に１０％の比率で分配されるようにスラリー抜
出管のバルブを調節した。スラリー化槽の上部から微粉
を含んで溢流した水はフィルターで濾過して微粉を回収
した。As an example of the embodiment of the present invention, the diameter is 500 mm, the height is 1500 mm, the bottom is slightly conical, and the upper part of the slurry forming tank is provided with the slurry discharge pipe at the center thereof. Granular activated carbon-supported palladium catalyst (particle size 2-5 mm, palladium loading 0.5%)
It was supplied at 0 kg / hour, and at the same time, water was supplied at 25 m 3 / hour from the lower portion of the slurry forming tank. Water is almost 90 up
%, And the valve of the slurry withdrawal pipe was adjusted so as to be distributed at a ratio of 10% downward. The water containing the fine powder and overflowing from the upper part of the slurry forming tank was filtered with a filter to collect the fine powder.
【０００８】スラリー抜出管を経て抜出されたスラリー
は水を充満させた触媒槽に流入させた。触媒槽の下部に
は、金網の中底があり、触媒は金網上に堆積し、水は金
網を抜け槽底の流出管を経て槽外に流出するようになっ
ている。流出管のバルブを調節して触媒槽内には常に水
が充満しているようにした。このようにして触媒床の形
成を行なったところ、触媒１ｋｇ当り１ｇの微粉が捕集
され、微粉のパラジムウ含有量は１３％であった。ま
た、この触媒系にテレフタル酸水溶液と水素とを並流で
導入してテレフタル酸の精製を行なったところ、フィル
ターの目詰まりもなく長期間に亘り安定して運転を行な
うことができた。The slurry withdrawn through the slurry withdrawal pipe was allowed to flow into a catalyst tank filled with water. The bottom of the catalyst tank has an inner bottom of the wire net, the catalyst is deposited on the wire net, and water passes through the wire net and flows out of the tank through the outflow pipe at the bottom of the tank. The valve of the outflow pipe was adjusted so that the catalyst tank was always filled with water. When the catalyst bed was formed in this manner, 1 g of fine powder was collected per 1 kg of the catalyst, and the content of paradigm in the fine powder was 13%. Further, when terephthalic acid was purified by introducing an aqueous solution of terephthalic acid and hydrogen into this catalyst system in parallel flow, the filter was not clogged, and stable operation was possible for a long period of time.
【０００９】[0009]
【発明の効果】本発明によれば衝撃や摩擦により微粉化
しやすい粒状活性炭担持触媒から、微粉を含まない触媒
床を構成することができる。EFFECTS OF THE INVENTION According to the present invention, a catalyst bed containing no fine powder can be constructed from a granular activated carbon-supported catalyst which is easily pulverized by impact or friction.
【図１】本発明に従い触媒床を形成する為の装置の１例
である。1 is an example of an apparatus for forming a catalyst bed according to the present invention.
１ 触媒槽 ２ 反応原料液供給管 ３ 反応生成液抜出管 ４ 触媒支持部材 ５ スラリー化槽 ６ 触媒供給口 ７ 溢流液抜出口 ８ 溶媒供給口 ９ スラリー抜出管 １０ フィルター 1 Catalyst Tank 2 Reaction Raw Material Liquid Supply Pipe 3 Reaction Product Liquid Extraction Pipe 4 Catalyst Support Member 5 Slurrying Tank 6 Catalyst Supply Port 7 Overflow Liquid Extraction Port 8 Solvent Supply Port 9 Slurry Extraction Pipe 10 Filter
Claims (5)
し、下部にスラリー抜出口と溶媒供給口とを有するスラ
リー化槽と触媒床を収容する触媒槽とを配管で連結する
こと、スラリー化槽に溶媒を供給しながら粒状活性炭担
持触媒を供給して溶媒の一部を触媒中の微粉と共にスラ
リー化槽から溢流させ残部は触媒の残部と共にスラリー
を形成させ配管を経て触媒槽に流入させること、及び触
媒槽に流入した触媒スラリーのうち、触媒は槽内に堆積
させ溶媒は槽外に排出することの各工程から成ることを
特徴とする活性炭担持触媒床の形成方法。1. A pipe for connecting a slurry tank having a catalyst supply port and an overflow liquid outlet at the upper portion and a slurry outlet having a slurry outlet and a solvent inlet at the lower portion to a catalyst tank containing a catalyst bed. That is, while supplying the solvent to the slurry forming tank, the granular activated carbon-supported catalyst is supplied to cause a part of the solvent to overflow from the slurry forming tank together with the fine powder in the catalyst, and the remaining part forms a slurry with the rest of the catalyst to form a catalyst through a pipe A method for forming an activated carbon-supported catalyst bed, which comprises the steps of flowing into a tank and, of the catalyst slurry flowing into the catalyst tank, depositing a catalyst inside the tank and discharging a solvent outside the tank.
溶媒の中に触媒スラリーを流入させることを特徴とする
請求項１記載の活性炭担持触媒床の形成方法。2. The method for forming an activated carbon-supported catalyst bed according to claim 1, wherein the catalyst tank contains a solvent, and the catalyst slurry is caused to flow into the solvent.
属を担持させたものであることを特徴とする請求項１又
は２記載の活性炭担持触媒床の形成方法。3. The method for forming an activated carbon-supported catalyst bed according to claim 1, wherein the granular activated carbon-supported catalyst is a granular activated carbon on which a noble metal is supported.
の微粉を回収することを特徴とする請求項３記載の活性
炭担持触媒床の形成方法。4. The method for forming an activated carbon-supported catalyst bed according to claim 3, wherein fine catalyst powder is recovered from the solvent overflowing from the slurry tank.
ル酸水溶液を水素と共に接触させて粗テレフタル酸の精
製を行うためのものであることを特徴とする請求項３又
は４記載の活性炭担持触媒床の形成方法。5. The activated carbon-supported catalyst according to claim 3 or 4, wherein the activated carbon-supported catalyst bed is for purifying the crude terephthalic acid by bringing it into contact with an aqueous crude terephthalic acid solution. How to form a floor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23175094A JP3620072B2 (en) | 1994-09-27 | 1994-09-27 | Method for forming an activated carbon-supported catalyst bed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23175094A JP3620072B2 (en) | 1994-09-27 | 1994-09-27 | Method for forming an activated carbon-supported catalyst bed |
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| Publication Number | Publication Date |
|---|---|
| JPH0889784A true JPH0889784A (en) | 1996-04-09 |
| JP3620072B2 JP3620072B2 (en) | 2005-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP23175094A Expired - Lifetime JP3620072B2 (en) | 1994-09-27 | 1994-09-27 | Method for forming an activated carbon-supported catalyst bed |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008535646A (en) * | 2005-03-08 | 2008-09-04 | ビーエーエスエフ ソシエタス・ヨーロピア | How to charge the reactor |
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1994
- 1994-09-27 JP JP23175094A patent/JP3620072B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008535646A (en) * | 2005-03-08 | 2008-09-04 | ビーエーエスエフ ソシエタス・ヨーロピア | How to charge the reactor |
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|---|---|
| JP3620072B2 (en) | 2005-02-16 |
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