JP2001348205A - Membrane reactor - Google Patents
Membrane reactorInfo
- Publication number
- JP2001348205A JP2001348205A JP2000165289A JP2000165289A JP2001348205A JP 2001348205 A JP2001348205 A JP 2001348205A JP 2000165289 A JP2000165289 A JP 2000165289A JP 2000165289 A JP2000165289 A JP 2000165289A JP 2001348205 A JP2001348205 A JP 2001348205A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen
- membrane
- catalyst
- separation membrane
- hydrogen separation
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 95
- 239000001257 hydrogen Substances 0.000 claims abstract description 102
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 102
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 8
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000000629 steam reforming Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006057 reforming reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水蒸気改質反応や
脱水素反応などの触媒による水素生成反応を、水素分離
膜を利用して行うメンブレンリアクタに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a membrane reactor for performing a hydrogen generation reaction using a catalyst such as a steam reforming reaction or a dehydrogenation reaction by using a hydrogen separation membrane.
【０００２】[0002]
【従来の技術】従来、メタンやメタノ−ルなどの炭化水
素を、ニッケル触媒やルテニウム触媒を用いて水蒸気改
質し、水素含有ガスを製造する炭化水素類の水蒸気改質
反応やプロパンやｎ−ブタンなどを、白金触媒を用いて
脱水素反応し、プロピレンやｎ−ブチレンなどを製造す
る炭化水素類の脱水素反応などに、前記触媒と水素を選
択的に透過する無機水素分離膜とを組み合わせて設けた
メンブレンリアクタが発明されている。2. Description of the Related Art Conventionally, steam reforming of hydrocarbons such as methane and methanol using a nickel catalyst or a ruthenium catalyst to produce a hydrogen-containing gas is carried out by steam reforming of hydrocarbons, propane or n-type. Butane and the like are subjected to a dehydrogenation reaction using a platinum catalyst, and the dehydrogenation reaction of hydrocarbons producing propylene, n-butylene and the like is performed by combining the catalyst with an inorganic hydrogen separation membrane that selectively permeates hydrogen. A membrane reactor provided with the above has been invented.
【０００３】特開平５−１９４２８１号公報及び特開平
５−３１７７０８号公報などには炭化水素の脱水素反応
用のメンブレンリアクタが開示されており、また、特開
平１−２１９００１号公報及び特開平６−４０７０２号
公報などには炭化水素の水蒸気改質反応用のメンブレン
リアクタが開発されている。Japanese Patent Application Laid-Open Nos. 5-194281 and 5-317708 disclose membrane reactors for hydrocarbon dehydrogenation reactions. Japanese Patent Publication No. -40702 and the like have developed a membrane reactor for a steam reforming reaction of hydrocarbons.
【０００４】前記各公報に記載されたメンブレンリアク
タは、いずれも無機多孔質担体の少なくとも一方の表面
にパラジウム膜又はパラジウムを主体としたパラジウム
合金膜を被着してなる水素分離膜の周囲に夫々の触媒を
充填してなり、炭化水素類を触媒反応で、改質反応又は
脱水素反応させ、反応により生成した水素が直ちに水素
分離膜を透過して排出される構造となっている。前記の
反応はいずれも熱力学的平衡反応であり、温度又は原料
濃度を高くするか、生成物濃度を低くすることにより反
応が促進されるため、メンブレンリアクタでは、反応効
率を高く維持することができる。In each of the membrane reactors described in each of the above publications, a palladium membrane or a palladium alloy membrane mainly composed of palladium is coated on at least one surface of an inorganic porous carrier. And the hydrocarbons are subjected to a reforming reaction or a dehydrogenation reaction by a catalytic reaction, and the hydrogen generated by the reaction is immediately transmitted through the hydrogen separation membrane and discharged. All of the above reactions are thermodynamic equilibrium reactions, and the reaction is promoted by increasing the temperature or the raw material concentration or lowering the product concentration.Therefore, in the membrane reactor, the reaction efficiency can be maintained high. it can.
【０００５】[0005]
【発明が解決しようとする課題】前記従来のメンブレン
リアクタでは、触媒と１〜５０μｍの極めて薄い膜であ
る水素分離膜が直接接触しているため、水素分離膜に傷
が付きピンホ−ルが生じ易く、また、触媒に担持されて
いる金属が水素分離膜を形成するパラジウムなどと金属
拡散を起こして合金化し、水素分離性能を低下させる問
題がある。更に従来のメンブレンリアクタにおいては、
触媒の充填、水素分離膜や触媒の取り出しなども複雑で
あり、メンテナンスに手数がかかる問題もある。In the conventional membrane reactor, since the catalyst is in direct contact with the hydrogen separation membrane, which is an extremely thin membrane of 1 to 50 μm, the hydrogen separation membrane is damaged and pinholes are formed. Further, there is a problem that the metal supported on the catalyst easily diffuses with the palladium or the like forming the hydrogen separation membrane and alloys with the metal, thereby deteriorating the hydrogen separation performance. Furthermore, in a conventional membrane reactor,
The charging of the catalyst, the removal of the hydrogen separation membrane and the catalyst, and the like are complicated, and there is a problem that the maintenance is troublesome.
【０００６】また、触媒と水素分離膜が直接接触しない
ように、水素分離膜の周囲に多孔質の金属或いはセラミ
ックス製のシ−トや管を設け、分離膜を保護するメンブ
レンリアクタもある（特開平８−７３２０１号）が、シ
−ト状の保護部材では、強度的に弱いため、完全には水
素分離膜のピンホ−ル発生を防止することは困難であ
り、メンテナンス性も改善されない。更に、金属製のシ
−トを使用する場合は、材質や使用条件によって、水素
分離膜を形成するパラジウムなどと金属拡散を起こして
合金化し、水素分離性能を低下させる問題がある。ま
た、管状の保護部材では、構造が複雑となると共に、保
護部材が水素の透過性を阻害してメンブレンリアクタの
利点を少なくする問題がある。There is also a membrane reactor provided with a porous metal or ceramic sheet or tube around the hydrogen separation membrane to protect the separation membrane so that the catalyst does not come into direct contact with the hydrogen separation membrane. However, since the strength of the sheet-shaped protective member is weak, it is difficult to completely prevent the occurrence of pinholes in the hydrogen separation membrane, and the maintenance is not improved. Further, when a metal sheet is used, there is a problem that, depending on the material and use conditions, palladium or the like forming a hydrogen separation membrane is diffused and alloyed with the metal to deteriorate the hydrogen separation performance. Further, the tubular protective member has a problem that the structure becomes complicated and the protective member impairs the permeability of hydrogen, thereby reducing the advantage of the membrane reactor.
【０００７】本発明は、前記の問題に鑑みてなされたも
のであり、水素分離膜と触媒が直接接触すること無く、
それらの装着及び脱着が容易で、メンテナンス性がよい
ため、水素分離膜のピンホ−ル発生を防止することがで
き、耐久性が向上するメンブレンリアクタを提供する目
的で成されたものである。[0007] The present invention has been made in view of the above-mentioned problem, and the hydrogen separation membrane and the catalyst do not come into direct contact with each other.
The object of the present invention is to provide a membrane reactor which can be easily attached and detached and has good maintenance properties, thereby preventing generation of pinholes in the hydrogen separation membrane and improving durability.
【０００８】[0008]
【課題を解決するための手段】前記目的を達成するため
の本発明の要旨は、請求項１に記載の発明においては、
ハニカム状多孔質担体に触媒を担持したハニカム触媒
と、ハニカム触媒の空洞内に挿通された水素を選択的に
透過する筒状水素分離膜とからなるメンブレンユニット
を反応室内に設けたことを特徴とするメンブレンリアク
タである。前記の構成により、水素分離膜と触媒が直接
接触することが無いため、触媒により、水素分離膜に傷
が付きピンホ−ルを生じる恐れがなく、また、触媒に担
持されている金属が水素分離膜を形成するパラジウムな
どと金属拡散を起こして合金化し、水素分離性能を低下
させる恐れもない。更に、それらの装着及び脱着が容易
で、メンテナンス性がよいため、水素分離膜のピンホ−
ル発生を防止することができ、耐久性が向上する。The gist of the present invention for achieving the above object is as follows.
A membrane unit comprising a honeycomb catalyst in which a catalyst is supported on a honeycomb-shaped porous carrier and a tubular hydrogen separation membrane selectively permeating hydrogen inserted into the cavity of the honeycomb catalyst is provided in a reaction chamber. This is a membrane reactor. According to the above configuration, the hydrogen separation membrane and the catalyst do not come into direct contact with each other, so that the hydrogen separation membrane is not damaged by the catalyst and a pinhole is not generated, and the metal supported on the catalyst is separated by hydrogen. There is no danger of causing metal diffusion and alloying with palladium or the like that forms the membrane, thereby lowering the hydrogen separation performance. Further, since they can be easily attached and detached and maintenance is easy, the hydrogen separation membrane
Can be prevented, and the durability is improved.
【０００９】また、請求項２に記載の発明においては、
水素排出口を具備する水素室と被反応ガス入口及び反応
ガス出口を具備する反応室を隣設して設け、反応室内に
ハニカム状多孔質担体に触媒を担持したハニカム触媒
と、ハニカム触媒の空洞内に挿通された水素を選択的に
透過する筒状水素分離膜とからなるメンブレンユニット
を設け、筒状水素分離膜の水素透過側が水素室と連通し
たことを特徴とするメンブレンリアクタである。前記の
構成により、水素分離膜と触媒が直接接触することが無
いため、触媒により、水素分離膜に傷が付きピンホ−ル
を生じる恐れがなく、また、触媒に担持されている金属
が水素分離膜を形成するパラジウムなどと金属拡散を起
こして合金化し、水素分離性能を低下させる恐れもな
い。更に、それらの装着及び脱着が容易で、メンテナン
ス性がよいため、水素分離膜のピンホ−ル発生を防止す
ることができ、耐久性が向上すると共に、高純度水素を
効率的且つ容易に分離することができる。Further, in the invention according to claim 2,
A hydrogen chamber having a hydrogen outlet and a reaction chamber having a reactant gas inlet and a reaction gas outlet are provided adjacent to each other, and a honeycomb catalyst in which a catalyst is supported on a honeycomb-shaped porous carrier in the reaction chamber; and a cavity of the honeycomb catalyst A membrane reactor comprising: a tubular hydrogen separation membrane that selectively permeates hydrogen inserted therein; and a membrane unit, wherein a hydrogen permeable side of the tubular hydrogen separation membrane communicates with a hydrogen chamber. According to the above configuration, the hydrogen separation membrane and the catalyst do not come into direct contact with each other, so that the hydrogen separation membrane is not damaged by the catalyst and a pinhole is not generated, and the metal supported on the catalyst is separated by hydrogen. There is no danger of causing metal diffusion and alloying with palladium or the like that forms the membrane, thereby lowering the hydrogen separation performance. Furthermore, since they can be easily attached and detached and maintenance is good, the occurrence of pinholes in the hydrogen separation membrane can be prevented, the durability can be improved, and high-purity hydrogen can be efficiently and easily separated. be able to.
【００１０】請求項３に記載の発明においては、請求項
１又は請求項２のいずれか１項に記載のメンブレンリア
クタが、筒状水素分離膜が無機多孔質担体の少なくとも
一方の表面にパラジウム膜又はパラジウムを主体とした
パラジウム合金膜を被着してなることを特徴とする。前
記の構成により、請求項１〜請求項４のいずれか１項に
記載のメンブレンリアクタの効果と共に、耐熱性、耐食
性及び水素透過性の極めて高い水素分離膜に限定したこ
とにより、膜の寿命を延ばし、長期間効率的に水素分離
を行うことかできる。According to a third aspect of the present invention, in the membrane reactor according to any one of the first to second aspects, the tubular hydrogen separation membrane has a palladium membrane on at least one surface of the inorganic porous carrier. Alternatively, a palladium alloy film mainly composed of palladium is applied. According to the above configuration, the effect of the membrane reactor according to any one of claims 1 to 4, together with the heat resistance, the corrosion resistance and the hydrogen permeability, are limited to an extremely high hydrogen separation membrane. Prolonged, efficient hydrogen separation can be performed for a long period of time.
【００１１】[0011]
【発明の実施の形態】本発明の実施の形態を図面に基づ
いて説明する。図１は本発明の一実施の形態のメンブレ
ンリアクタの縦断面図、図２は図１のＡ−Ａ視のメンブ
レンユニットの断面図である。Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a vertical cross-sectional view of a membrane reactor according to an embodiment of the present invention, and FIG. 2 is a cross-sectional view of a membrane unit taken along line AA in FIG.
【００１２】符号１はハニカム状多孔質担体に触媒を担
持したハニカム触媒３と、ハニカム触媒３の空洞３ａ内
に挿通された、水素を選択的に透過する筒状水素分離膜
４とからなるメンブレンユニット２が、反応室５内に設
けられたメンブレンリアクタであり、両端にフランジ１
４、１５を具備するケ−シング７及び両端面を夫々覆蓋
する端板１７、１８により反応室５が形成され、反応室
５の一端側に装着される端部にフランジ１６を具備する
蓋体８と端板１８により水素室９が形成されている。Reference numeral 1 denotes a membrane comprising a honeycomb catalyst 3 having a catalyst supported on a honeycomb-shaped porous carrier, and a cylindrical hydrogen separation membrane 4 which is inserted into a cavity 3a of the honeycomb catalyst 3 and selectively transmits hydrogen. The unit 2 is a membrane reactor provided in the reaction chamber 5 and has flanges 1 at both ends.
A reaction chamber 5 is formed by a casing 7 provided with 4 and 15 and end plates 17 and 18 respectively covering both end faces, and a lid body provided with a flange 16 at an end attached to one end of the reaction chamber 5. A hydrogen chamber 9 is formed by the end plate 8 and the end plate 18.
【００１３】また、反応室５及び水素室９は、フランジ
１４、端板１８とフランジ１６及びフランジ１５と端板
１７を夫々ボルト、ナット又はクランプなどの適宜な締
着部材で締着することにより形成され、反応室５には被
反応ガス入口１０及び反応ガス出口１１が具備され、水
素室９には水素排出口１２が具備されている。更に、反
応室５に内設されたハニカム触媒３は、端板１７に具備
された固定部材１３により固定されている。The reaction chamber 5 and the hydrogen chamber 9 are formed by fastening the flange 14, the end plate 18 and the flange 16 and the flange 15 and the end plate 17 with appropriate fastening members such as bolts, nuts or clamps, respectively. The reaction chamber 5 is provided with a reaction gas inlet 10 and a reaction gas outlet 11, and the hydrogen chamber 9 is provided with a hydrogen outlet 12. Further, the honeycomb catalyst 3 provided in the reaction chamber 5 is fixed by a fixing member 13 provided on the end plate 17.
【００１４】前記ハニカム触媒３は、円柱体の両端面に
渡って貫通して穿孔された、断面が六角形の空洞３ａ
が、周方向に一定間隔で多数併設されてなるが、その形
状は、円柱体以外にも矩形体や多角体でもよく、また、
空洞３ａも断面が円形や矩形などであってもよい。な
お、ハニカム触媒３は、製造目的とする反応物などによ
って適宜な材料が使用されるが、例えば、脱水素反応で
は、セラミックス、活性炭又は金属をハニカム担体と
し、白金、ニッケル又は銅などが触媒成分として担持さ
れたハニカム触媒３が用いられ、また、水蒸気改質反応
では、セラミックス、活性炭又は金属をハニカム担体と
し、ニッケル又はルテニウムなどが触媒成分として担持
されたハニカム触媒３が用いられる。なお、担体への触
媒担持方法は、含浸法、イオン交換法又はＣＶＤ法など
が適宜に適用される。The above-mentioned honeycomb catalyst 3 has a hollow section 3a having a hexagonal cross section which is perforated through both end faces of the cylindrical body.
However, a large number of them are provided side by side at regular intervals in the circumferential direction, but the shape may be a rectangular or polygonal body other than the cylindrical body.
The cavity 3a may also have a circular or rectangular cross section. As the honeycomb catalyst 3, an appropriate material is used depending on a reactant or the like to be produced. For example, in a dehydrogenation reaction, ceramic, activated carbon or metal is used as a honeycomb carrier, and platinum, nickel or copper is used as a catalyst component. In the steam reforming reaction, a honeycomb catalyst 3 carrying ceramics, activated carbon or metal as a honeycomb carrier and nickel or ruthenium as a catalyst component is used. In addition, as a method of supporting the catalyst on the carrier, an impregnation method, an ion exchange method, a CVD method, or the like is appropriately applied.
【００１５】水素分離膜４は、一方端が閉塞された円筒
体であり、水素分離膜４はハニカム触媒３の空洞３ａの
長さよりも短く設定され、反応ガス出口１１側に位置し
て設けられ、被反応ガス入口１０側の開放端部には、水
素分離膜を形成しない金属管やセラミックス管などの接
合管６が接続され、接合管６は、端板１８を貫通して水
素室９と連通し、ハニカム触媒３の空洞３ａ部の間隔を
考慮して多数が端板１８に併設固定されている。なお、
水素分離膜４は、セラミックス、ガラス又は金属などの
無機多孔質担体の、少なくとも一方の表面にパラジウム
膜又はパラジウムを主体としたパラジウム合金膜が被着
されて形成されているが、無機多孔質担体の孔径を水素
選択透過するように調整した水素分離膜４であってもよ
い。また、水素分離膜４の長さは、ハニカム触媒３の空
洞３ａの長さよりも短く設定するのが、水素分圧が高い
状態で分離するため、水素分離効率がよくなり好ましい
が、本発明はその構造には限定されない。なお、水素分
離膜の製造方法は、化学メッキ法、電気メッキ法又は気
相法などが適宜に適用され、製造される水素分離膜の膜
厚は、１〜５０ｍμが好ましい。The hydrogen separation membrane 4 is a cylindrical body having one end closed. The hydrogen separation membrane 4 is set to be shorter than the length of the cavity 3 a of the honeycomb catalyst 3 and is provided at the reaction gas outlet 11 side. A joining pipe 6 such as a metal pipe or a ceramic pipe, on which a hydrogen separation membrane is not formed, is connected to the open end on the side of the reactant gas inlet 10, and the joining pipe 6 penetrates the end plate 18 and connects to the hydrogen chamber 9. Many are fixed to the end plate 18 in communication with each other in consideration of the interval between the cavities 3 a of the honeycomb catalyst 3. In addition,
The hydrogen separation membrane 4 is formed by coating a palladium film or a palladium alloy film mainly composed of palladium on at least one surface of an inorganic porous carrier such as ceramics, glass or metal. May be a hydrogen separation membrane 4 in which the pore diameter is adjusted to selectively permeate hydrogen. Further, it is preferable that the length of the hydrogen separation membrane 4 is set shorter than the length of the cavity 3a of the honeycomb catalyst 3 because the separation is performed at a high hydrogen partial pressure, so that the hydrogen separation efficiency is improved. The structure is not limited. As a method for producing the hydrogen separation membrane, a chemical plating method, an electroplating method, a vapor phase method, or the like is appropriately applied, and the thickness of the produced hydrogen separation membrane is preferably 1 to 50 μm.
【００１６】次に、前記構成のメンブレンリアクタの組
み立てについて述べる。ケ−シング７内にハニカム触媒
３を内設して、端板１７に具備された固定部材１３によ
り固定し、フランジ１５及び端板１７をボルト、ナット
又はクランプなどの適宜な締着部材で締着する。端板１
７の反対側のケ−シング７開口から、接合管６を介して
端板１８に併設固定された筒状水素分離膜４群を、ハニ
カム触媒３の空洞３ａ内に、ハニカム触媒３に接触しな
いように挿通してメンブレンユニット２を形成する。蓋
体８を端板１８に被せ、フランジ１４、端板１８及びフ
ランジ１６をボルト、ナット又はクランプなどの適宜な
締着部材で締着することにより、触媒反応で生成した水
素が水素分離膜を透過し、接合管６を経て水素室９に流
入する構造の反応室５及び水素室９からなるメンブレン
リアクタ１が組み立てられる。Next, the assembly of the membrane reactor having the above configuration will be described. The honeycomb catalyst 3 is provided inside the casing 7 and fixed by a fixing member 13 provided on an end plate 17, and the flange 15 and the end plate 17 are tightened by a suitable fastening member such as a bolt, a nut or a clamp. To wear. End plate 1
The cylindrical hydrogen separation membrane group 4 attached to and fixed to the end plate 18 via the joining pipe 6 is not brought into contact with the honeycomb catalyst 3 in the cavity 3 a of the honeycomb catalyst 3 from the opening of the casing 7 opposite to the casing 7. To form the membrane unit 2. The cover 8 is placed on the end plate 18, and the flange 14, the end plate 18, and the flange 16 are fastened with an appropriate fastening member such as a bolt, a nut, or a clamp. The membrane reactor 1 composed of the reaction chamber 5 and the hydrogen chamber 9 having a structure of permeating and flowing into the hydrogen chamber 9 through the joining pipe 6 is assembled.
【００１７】前記のように極めて容易にメンブレンリア
クタ１が組み立てられると共に、水素分離膜４とハニカ
ム触媒３が直接接触することが無いため、ハニカム触媒
３により、水素分離膜４に傷が付きピンホ−ルを生じる
恐れがなく、また、ハニカム触媒３に担持されている金
属が水素分離膜４を形成するパラジウムなどと金属拡散
を起こして合金化し、水素分離性能を低下させる恐れも
ない。As described above, the membrane reactor 1 is extremely easily assembled, and the hydrogen separation membrane 4 and the honeycomb catalyst 3 do not come into direct contact with each other. In addition, there is no danger that the metal supported on the honeycomb catalyst 3 will cause metal diffusion and alloy with palladium or the like forming the hydrogen separation membrane 4 to deteriorate the hydrogen separation performance.
【００１８】次に、前記構成のメンブレンリアクタによ
り炭化水素を水蒸気改質して高純度水素を回収する方法
ついて述べる。水蒸気が混合された炭化水素の被反応ガ
スを被反応ガス入口１０から反応室５内に供給し、所定
の改質反応温度でハニカム触媒３と接触させて改質し、
水素含有ガスを製造すると共に、生成した水素を直ちに
水素分離膜４から透過させ、接合管６を介して水素室９
に導入し、水素排出口１２から系外に排出して高純度水
素として回収する。また、反応ガスは、反応ガス出口１
１から系外に排出して燃料ガスなどとして使用される。Next, a method of recovering high-purity hydrogen by steam-reforming hydrocarbons using the membrane reactor having the above-described structure will be described. A reactant gas of a hydrocarbon mixed with water vapor is supplied from the reactant gas inlet 10 into the reaction chamber 5 and reformed by being brought into contact with the honeycomb catalyst 3 at a predetermined reforming reaction temperature.
In addition to producing the hydrogen-containing gas, the generated hydrogen is immediately permeated from the hydrogen separation membrane 4, and is passed through the joining pipe 6 to the hydrogen chamber 9.
And discharged out of the system through the hydrogen discharge port 12 to recover as high-purity hydrogen. The reaction gas is supplied to the reaction gas outlet 1
It is discharged out of the system from 1 and used as fuel gas and the like.
【００１９】前記において、反応により生成した水素を
直ちに水素分離膜を透過させて分離し、生成物濃度を低
くするため、熱力学的平衡反応である水蒸気改質反応が
促進されることになる。このことは、脱水素反応におい
ても同様の作用を有する。また、水素分離膜４部がハニ
カム触媒３の長さよりも短く設定され、反応ガス出口１
１側に位置して設けられ、あらかじめ触媒反応により水
素が生成され、水素分圧が高められてから水素が分離さ
れるため、水素を効率的に分離することができる効果も
ある。In the above, the hydrogen generated by the reaction is immediately passed through the hydrogen separation membrane to be separated to lower the product concentration, so that the steam reforming reaction, which is a thermodynamic equilibrium reaction, is promoted. This has a similar effect in the dehydrogenation reaction. Further, the hydrogen separation membrane 4 is set to be shorter than the length of the honeycomb catalyst 3, and the reaction gas outlet 1
Since it is provided on one side and hydrogen is generated in advance by a catalytic reaction and hydrogen is separated after the hydrogen partial pressure is increased, there is also an effect that hydrogen can be efficiently separated.
【００２０】[0020]
【発明の効果】本発明は、水素分離膜と触媒が直接接触
すること無く、それらの装着及び脱着が容易で、メンテ
ナンス性がよいため、水素分離膜のピンホ−ル発生を防
止することができ、耐久性が向上したメンブレンリアク
タである。According to the present invention, since the hydrogen separation membrane and the catalyst do not come into direct contact with each other, they can be easily attached and detached, and the maintenance property is good, so that the occurrence of pinholes in the hydrogen separation membrane can be prevented. And a membrane reactor with improved durability.
【図１】本発明の一実施の形態のメンブレンリアクタの
縦断面図FIG. 1 is a longitudinal sectional view of a membrane reactor according to an embodiment of the present invention.
【図２】図１のＡ−Ａ視のメンブレンユニットの断面図FIG. 2 is a cross-sectional view of the membrane unit taken along line AA of FIG.
１：メンブレンリアクタ ２：メンブレンユニット ３：ハニカム触媒筒状水素分離膜 ３ａ：空洞 ４：筒状水素分離膜 ５：反応室 ６：金属管 ７：ケ−シング ８：蓋体 ９：水素室 １０：被反応ガス入口 １１：反応ガス出口 １２：水素排出口 １３：固定部材 １４、１５，１６：フランジ １７，１８：端板 1: Membrane reactor 2: Membrane unit 3: Honeycomb catalyst cylindrical hydrogen separation membrane 3a: Cavity 4: Cylindrical hydrogen separation membrane 5: Reaction chamber 6: Metal tube 7: Casing 8: Lid 9: Hydrogen chamber 10: Reacted gas inlet 11: Reacted gas outlet 12: Hydrogen outlet 13: Fixing member 14, 15, 16: Flange 17, 18: End plate
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｃ０７Ｃ 5/333 Ｃ０７Ｃ 5/333 11/06 11/06 11/08 11/08 Ｆターム(参考） 4D006 GA41 HA21 JA10A JA14A JA18A JA27A JA70A MA02 MB04 PB18 PB66 PC69 4G040 DA03 DB05 EA02 EA03 EA06 EB33 EC03 FA02 FB09 FC01 FE01 4G069 AA03 AA11 BA08A BA13A BA17 BC31A BC68A BC75A CB07 CC17 CC25 EA18 EA28 EB10 4H006 AA04 AC12 BA26 BD81 Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) // C07C 5/333 C07C 5/333 11/06 11/06 11/08 11/08 F term (reference) 4D006 GA41 HA21 JA10A JA14A JA18A JA27A JA70A MA02 MB04 PB18 PB66 PC69 4G040 DA03 DB05 EA02 EA03 EA06 EB33 EC03 FA02 FB09 FC01 FE01 4G069 AA03 AA11 BA08A BA13A BA17 BC31A BC68A BC75A CB07 CC17 CC25 EA18A26 BA26
Claims (3)
ニカム触媒と、ハニカム触媒の空洞内に挿通された水素
を選択的に透過する筒状水素分離膜とからなるメンブレ
ンユニットを反応室内に設けたことを特徴とするメンブ
レンリアクタ。1. A membrane unit comprising a honeycomb catalyst having a catalyst supported on a honeycomb-shaped porous carrier and a tubular hydrogen separation membrane selectively permeating hydrogen inserted into a cavity of the honeycomb catalyst is provided in a reaction chamber. A membrane reactor.
入口及び反応ガス出口を具備する反応室を隣設して設
け、反応室内にハニカム状多孔質担体に触媒を担持した
ハニカム触媒と、ハニカム触媒の空洞内に挿通された水
素を選択的に透過する筒状水素分離膜とからなるメンブ
レンユニットを設け、筒状水素分離膜の水素透過側が水
素室と連通したことを特徴とするメンブレンリアクタ。2. A honeycomb catalyst having a hydrogen chamber having a hydrogen discharge port and a reaction chamber having a gas-to-be-reacted gas inlet and a reaction gas outlet provided adjacent to each other, and having a honeycomb-shaped porous carrier carrying a catalyst in the reaction chamber. A membrane unit comprising a tubular hydrogen separation membrane that selectively permeates hydrogen inserted into the cavity of the honeycomb catalyst, wherein the hydrogen permeable side of the tubular hydrogen separation membrane communicates with the hydrogen chamber. Reactor.
とも一方の表面にパラジウム膜又はパラジウムを主体と
したパラジウム合金膜を被着してなることを特徴とする
請求項１又は請求項２のいずれか１項に記載のメンブレ
ンリアクタ。3. A cylindrical hydrogen separation membrane comprising at least one surface of an inorganic porous carrier and a palladium film or a palladium alloy film mainly composed of palladium adhered thereto. The membrane reactor according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000165289A JP2001348205A (en) | 2000-06-02 | 2000-06-02 | Membrane reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000165289A JP2001348205A (en) | 2000-06-02 | 2000-06-02 | Membrane reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001348205A true JP2001348205A (en) | 2001-12-18 |
Family
ID=18668783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000165289A Pending JP2001348205A (en) | 2000-06-02 | 2000-06-02 | Membrane reactor |
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| Country | Link |
|---|---|
| JP (1) | JP2001348205A (en) |
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| JP5015766B2 (en) * | 2005-02-04 | 2012-08-29 | 日本碍子株式会社 | Permselective membrane reactor |
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