JPH03217227A - Membrane reactor for dehydrogenation reaction - Google Patents
Membrane reactor for dehydrogenation reactionInfo
- Publication number
- JPH03217227A JPH03217227A JP2012645A JP1264590A JPH03217227A JP H03217227 A JPH03217227 A JP H03217227A JP 2012645 A JP2012645 A JP 2012645A JP 1264590 A JP1264590 A JP 1264590A JP H03217227 A JPH03217227 A JP H03217227A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- membrane
- hydrogen
- separation membrane
- reactor
- 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 35
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- 239000007789 gas Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 9
- 238000010030 laminating Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000005373 porous glass Substances 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000007738 vacuum evaporation Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2475—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は脱水素反応に用いる反応器に関し、更に詳しく
は水素分離膜を反応管内に設置し、反応生成物の水素の
一部を除外しながら脱水素反応を行わせるメンブレンリ
アクタに関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a reactor used for dehydrogenation reaction, and more specifically, a hydrogen separation membrane is installed in the reaction tube to exclude a part of the hydrogen of the reaction product. This invention relates to a membrane reactor that allows a dehydrogenation reaction to occur.
水素を生成する脱水素反応は一般に次のように表わされ
る。The dehydrogenation reaction that produces hydrogen is generally expressed as follows.
Ｃｒ，Ｈ． → ＣｎＬ−２＋ Ｌ
（ｔ）ＣｎＨ＋ａ ＋ ｎＬＯ →
ｎｃＯ ＋ （ｎ＋ ｍ／２）Ｈｚ （
２）ＣｎＬ ＋ ２ｎＨ２０− ｎｃＯ２＋ （２
ｎ＋ｍ／２）Ｈｚ （３）上記反応は大きな吸熱を伴
う反応で、熱力学平衡上転化率を高くするためには高温
にする必要があり、通常６００℃以上の高温で実施され
ている。Cr, H. → CnL-2+ L
(t)CnH+a+nLO →
ncO + (n+ m/2)Hz (
2) CnL + 2nH20- ncO2+ (2
n+m/2)Hz (3) The above reaction is a reaction accompanied by a large endotherm, and in order to increase the conversion rate above thermodynamic equilibrium, it is necessary to raise the temperature to a high temperature, and it is usually carried out at a high temperature of 600° C. or higher.
上記反応（１）の炭化水素の脱水素反応における各平衡
転化率を得るだめの反応温度を下北の表１に示す。Table 1 of Shimokita shows the reaction temperatures required to obtain each equilibrium conversion rate in the hydrocarbon dehydrogenation reaction of reaction (1) above.
また、上記反応（２）及び（３）の代表例として、メタ
ンの水蒸気改質反応における平衡転化率を下記の表２に
示す。Further, as a representative example of the above reactions (2) and (3), the equilibrium conversion rates in the steam reforming reaction of methane are shown in Table 2 below.
表 ２
メタンの水蒸気改質反応における平衡
転化率（ ＬＤ／ＣＨ４＝ ３ ｍｏｌ／ｍｏｌ）また
、脱水素反応を促進させる方法として、多孔質ガラス、
パラジウムメッキした多孔質ガラスなどの水素分離膜を
反応器内に設置し、反応生成物の水素の一部を反応器外
に取出しながら脱水素反応を行わせるメンブレンリアク
タを用いることが提案されている。Table 2 Equilibrium conversion rate in methane steam reforming reaction (LD/CH4 = 3 mol/mol) In addition, porous glass,
It has been proposed to use a membrane reactor in which a hydrogen separation membrane such as palladium-plated porous glass is installed inside the reactor, and a portion of the hydrogen produced by the reaction is taken out of the reactor while the dehydrogenation reaction takes place. .
前述したように、従来の脱水素反応は所定の転化率を得
るために非常に高温にする必要がある。そのため、高温
でも使用可能な高級な材料を使う必要がある。また、転
化率が低いため、リアクタ出口ガスを冷却゜して原料と
反応生成物を分離し、原料をリサイクルして使用してい
るが、リサイクルガスコンプレッサが必要であり、また
、加熱、冷却を繰返すため熱効率が低いなどの問題があ
る。さらには、反応温度が高いため、副反応が多く触媒
の活性低下が大きいという問題がある。As previously mentioned, conventional dehydrogenation reactions require very high temperatures to achieve a given conversion. Therefore, it is necessary to use high-grade materials that can be used even at high temperatures. In addition, because the conversion rate is low, the reactor outlet gas is cooled to separate the raw material and the reaction product, and the raw material is recycled for use, but a recycling gas compressor is required, and heating and cooling are required. Because it is repeated, there are problems such as low thermal efficiency. Furthermore, since the reaction temperature is high, there is a problem in that there are many side reactions and the activity of the catalyst is greatly reduced.
さらに、また、多孔質ガラス，パラジウムメッキした多
孔質ガラスを用いるメンブレンリアクタでは、強度が弱
く、かつ、５０ｃｍ長さ以上のパイプを製作するのが難
しく、実用上に問題がある。Furthermore, membrane reactors using porous glass or palladium-plated porous glass have low strength and are difficult to manufacture into pipes with a length of 50 cm or more, which poses practical problems.
本発明は原料供給口、生成物取出口を有し、内部に触媒
が充填され、外部に加熱手段を備えた反応器、該反応器
の触媒充填層に設けられた０． １〜２０μの細孔を有
する多孔質金属体の少なくとも一表面に５０μ以下の膜
厚のＰｄ含有薄膜を形成された水素分離膜で構成された
水素除去手段よりなることを特徴とする脱水素反応用メ
ンブレンリアクタである。The present invention includes a reactor having a raw material supply port and a product discharge port, the inside of which is filled with a catalyst, and the outside of which is equipped with a heating means. A dehydrogenation reaction characterized by comprising a hydrogen removal means constituted by a hydrogen separation membrane in which a Pd-containing thin film with a thickness of 50μ or less is formed on at least one surface of a porous metal body having pores of 1 to 20μ. It is a membrane reactor for
すなわち、本発明は前述の問題点を解決すべくなされた
ものであり、０．１〜２０μの細孔を有する多孔質金属
体の少なくとも一方の表面に膜厚が５０μ以下のＰｄを
含有する薄膜を形成せしめた水素分離膜を反応器内に設
置し、反応生成物の水素の一部を除外しながら脱水素反
応を行わせるようにしたメンブレンリアクタである。That is, the present invention was made to solve the above-mentioned problems, and includes a thin film containing Pd with a thickness of 50 μm or less on at least one surface of a porous metal body having pores of 0.1 to 20 μm. This is a membrane reactor in which a hydrogen separation membrane formed with hydrogen is installed in the reactor, and a dehydrogenation reaction is carried out while excluding a part of the hydrogen of the reaction product.
本発明において、細孔を有する多孔質金属としては、３
００℃以上の温度に耐える耐熱性を有し、処理すべき気
体と反応性を有せず、かつ、０．１〜１０μの範囲の中
で、できるだけ均一な細孔を有する多孔質金属体を使用
するのが適当である。細孔径を０．１μ以上としたのは
、ガス拡散の妨害にならないようにするためであり、１
０μ以下としたのはＰｄを含有する薄膜を膜厚５０μ以
下にコーティングした場合、ピンホールが生じ易くなる
からである。なお、多孔質金属体としては、円筒状、又
は板状のものを使用するのが適当であり、支持体として
の強度及び加工性などから、０．２〜２鵬の厚みのもの
が好ましい。In the present invention, the porous metal having pores includes 3
A porous metal body that has heat resistance that can withstand temperatures of 00°C or higher, has no reactivity with the gas to be treated, and has pores as uniform as possible within the range of 0.1 to 10μ. It is appropriate to use. The reason why the pore diameter is set to 0.1μ or more is to prevent gas diffusion from being obstructed.
The reason why the thickness is set to 0μ or less is that pinholes are likely to occur when a thin film containing Pd is coated to a thickness of 50μ or less. Note that it is appropriate to use a cylindrical or plate-shaped porous metal body, and preferably one having a thickness of 0.2 to 2 mm from the viewpoint of strength as a support and workability.
本発明において多孔質金属体の一例としては以下のもの
があげられる。Examples of porous metal bodies in the present invention include the following.
（１）発泡（多孔質）金属をプレス成型し細孔径を制御
したもの、さらにこれに溶射又はメッキなどにより細孔
を小さくしたもの。(1) Foamed (porous) metal is press-molded to control the pore diameter, and the pores are further made smaller by thermal spraying or plating.
（２）粒径の小さい金属微粉末（５０μ以下）を成型し
たもの。(2) Molded metal fine powder with small particle size (50μ or less).
（３）化学反応により除去可能な粉末（例えば、燃焼除
去が可能なグラファイト）を金属粉末に混合又は溶融し
た金属に添加した後、粉末を化学反応により除去し細孔
を生成させたもの。(3) Powder that can be removed by chemical reaction (for example, graphite that can be removed by combustion) is mixed with metal powder or added to molten metal, and then the powder is removed by chemical reaction to generate pores.
（４）金属繊維。(4) Metal fiber.
本発明において、Ｐｃｔを含有する薄膜としては、Ｐｄ
ｌ００％又はＰｄを１０重量％以上含有する合金からな
り、膜厚が５０μ以下、特に２〜２０μのものが適当で
ある。Ｐｄを１０重量％以上含有する合金としては、Ｐ
ｄ以外にＰｔ ， Ｒｈ ，Ｒｕ，Ｉｒなどの■族元素
、Ｃｕ ， Ａｇ ， ＡｕなどのＩｂ族元素を含有す
るものをさす。In the present invention, the thin film containing Pct is Pd
It is suitably made of an alloy containing 100% Pd or 10% by weight or more of Pd, and has a film thickness of 50 μm or less, particularly 2 to 20 μm. As an alloy containing 10% by weight or more of Pd, P
Refers to those containing, in addition to d, group Ⅰ elements such as Pt, Rh, Ru, and Ir, and group Ib elements such as Cu, Ag, and Au.
多孔質金属体の少なくとも一方の表面に膜厚が５０μ以
下のＰｄを含有する薄膜を形成させる方法の一例として
は、下記の方法が用いられる。As an example of a method for forming a Pd-containing thin film having a thickness of 50 μm or less on at least one surface of a porous metal body, the following method is used.
（１） メッキなどの液相法
表面活性化処理（塩化スズの水溶液と塩化パラジウムの
各液に交互に浸漬）後、無電解メッキ（パラジウムの化
合物と還元剣を含有する液に浸漬）
さらには、無電解メッキ後に電気メッキしたもの。(1) After liquid-phase surface activation treatment such as plating (immersion alternately in an aqueous solution of tin chloride and palladium chloride), electroless plating (immersion in a solution containing a palladium compound and a reducing sword), and , electroplated after electroless plating.
（２）真空蒸着法、イオンプレーティング法、気相化学
反応法（ＣＶＤ）などの気相法。(2) Gas phase methods such as vacuum evaporation, ion plating, and vapor phase chemical reaction (CVD).
以上のようにしてＰａｌ又はＰｄ合金の薄膜を形成させ
た多孔質金属体は水素のみを選択的に透過する水素分離
膜として使用できる。A porous metal body on which a thin film of Pal or Pd alloy is formed as described above can be used as a hydrogen separation membrane that selectively permeates only hydrogen.
上記のようにして調製したＰｄを含有する薄膜を形成せ
しめた水素分離膜を反応管内に設置したメンブレンリア
クタは、次のような作用を有する。A membrane reactor in which a hydrogen separation membrane having a Pd-containing thin film prepared as described above is installed in a reaction tube has the following effects.
（１）反応管内から反応生成物の一部である水素を除去
しながら同時に反応を行わせることにより、反応を熱力
学平衡の制約を受けずに進行させることができる。即ち
、平衡転化率以上の転化率が得られる。(1) By simultaneously carrying out the reaction while removing hydrogen, which is a part of the reaction product, from inside the reaction tube, the reaction can proceed without being constrained by thermodynamic equilibrium. That is, a conversion rate higher than the equilibrium conversion rate can be obtained.
この作用により、反応温度を従来法より低くすることが
できる。This effect allows the reaction temperature to be lower than in conventional methods.
（２）多孔質金属傳を用いることにより、強度、加工性
などの問題なく反応管内に設置することができる。(2) By using a porous metal membrane, it can be installed in a reaction tube without problems with strength, workability, etc.
以下、本発明方法を実施する装置の概要を説明する。The outline of the apparatus for carrying out the method of the present invention will be explained below.
第１図は本発明方法を実施する装置の要部の概略図で、
１は反応管（外管）、２は水素分離膜、３は触媒層、４
は原料ガス導入口、５は生成ガス排出口、６は水素排出
口、７は触媒支持板である。FIG. 1 is a schematic diagram of the main parts of an apparatus for carrying out the method of the present invention.
1 is a reaction tube (outer tube), 2 is a hydrogen separation membrane, 3 is a catalyst layer, 4
5 is a raw material gas inlet, 5 is a generated gas outlet, 6 is a hydrogen outlet, and 7 is a catalyst support plate.
反応管の外管１と水素分離膜２との間には、脱水素反応
用触媒３が充填されており触媒支持板７に保持されてい
る。触媒層３には原料ガスが導入口４より供給され、脱
水素反応が進行する。反応の進行に伴ない、発生した水
素は水素分離膜２を透過し、水素排出口６より排出され
る。未反応ガス及び生成ガスはガスが透過しやすいよう
に多孔板で形成されている触媒支持板７を通過し、生成
ガス排出口５より排出される。A dehydrogenation reaction catalyst 3 is filled between the outer tube 1 of the reaction tube and the hydrogen separation membrane 2, and is held on a catalyst support plate 7. A raw material gas is supplied to the catalyst layer 3 through an inlet 4, and the dehydrogenation reaction proceeds. As the reaction progresses, generated hydrogen passes through the hydrogen separation membrane 2 and is discharged from the hydrogen outlet 6. The unreacted gas and the produced gas pass through the catalyst support plate 7, which is made of a perforated plate so that the gas can easily pass therethrough, and are discharged from the produced gas outlet 5.
反応管の外管１の外側からは、反応温度を維持し、反応
に必要な熱を補うための熱が供給される。水素分離膜２
は反応管１内に複数個設置される。また水素分離膜２に
右いては、水素透過速度を大きくするためにイナートガ
ス（スイープガス）を流すこともできる。Heat is supplied from the outside of the outer tube 1 of the reaction tube to maintain the reaction temperature and supplement the heat necessary for the reaction. Hydrogen separation membrane 2
A plurality of are installed in the reaction tube 1. Furthermore, inert gas (sweep gas) can be passed through the hydrogen separation membrane 2 in order to increase the hydrogen permeation rate.
〔実施例１〕
平均粒子径１μのＳＵＳ ３０４の金属微粉末を用い、
平均細孔径が０．５μの多孔質金属パイプ（１０°”Ｘ
８”Ｘ５ ０ ０Ｌｍｍ）を成型した。このバイブの外
側の面にパラジウムのみを蒸着したサンプル１、パラジ
ウムと銀の合金（Ｐｄ ： Ａｇ＝８５：１５重量比）
を蒸着したサンプル２またパラジウムと銅の合金（Ｐｄ
：Ｃｕ＝９ ０ ： １ ０重量比）を蒸着したサンプ
ル３を調製した。[Example 1] Using fine SUS 304 metal powder with an average particle size of 1μ,
Porous metal pipe with an average pore diameter of 0.5μ (10°”
Sample 1, in which only palladium was deposited on the outer surface of the vibrator, was an alloy of palladium and silver (Pd:Ag=85:15 weight ratio).
Sample 2 was also deposited with palladium and copper alloy (Pd
:Cu=90:10 weight ratio) was prepared.
パラジウム又はパラジウム合金をコーティングした多孔
質金属パイプ（サンプル１〜３）を水素分離膜として使
用し、第２図に示す装置で試験を行った。水素分離膜１
１を０リング１２でステンレス鋼製外管ｌ３に同定し、
その外側を電気炉で加熱する。温度はサーモカップル１
８を使用し内管の中心部で測定した。触媒は外管１３と
内管である水素分離膜１１の間１９に充填した。Porous metal pipes coated with palladium or palladium alloy (samples 1 to 3) were used as hydrogen separation membranes, and tests were conducted using the apparatus shown in FIG. 2. Hydrogen separation membrane 1
1 to the stainless steel outer tube l3 with an O ring 12,
The outside is heated in an electric furnace. Temperature is thermocouple 1
8 was used to measure the center of the inner tube. The catalyst was filled in the space 19 between the outer tube 13 and the hydrogen separation membrane 11, which is the inner tube.
Ｎｉ０２０ｗｔ％、Ａｌ２ａ３８ ０ｗｔ％の組成を有
する触媒（平均粒径１ｍｍ＞５ｇを充填した後、５００
℃で水素還元した。After filling the catalyst with the composition of Ni020wt% and Al2a380wt% (average particle size 1mm>5g, 500wt%
Hydrogen reduction was carried out at ℃.
メタンと水蒸気の混合ガスを供給孔１４から連続的に供
給し、排出孔１５から透過水素以外の生成ガスを排出し
た。また上部の供給孔１７からスイーブガスとしてアル
ゴンを供給し、水素分離膜１ｌを透過した水素と一緒に
取出孔１６から水素含有ガスを得た。A mixed gas of methane and water vapor was continuously supplied from the supply hole 14, and generated gas other than permeated hydrogen was discharged from the discharge hole 15. Further, argon was supplied as a sweep gas from the upper supply hole 17, and a hydrogen-containing gas was obtained from the take-out hole 16 together with the hydrogen that had permeated through 1 liter of the hydrogen separation membrane.
反応条件は次のとおりである。The reaction conditions are as follows.
試験結果を表２に示す。The test results are shown in Table 2.
表
２
〔比較例１〕
水素分離膜を用いない（スイープガスも流さない）こと
以外は、実施例１と同じ方法でメタン改質反応の実験を
行った結果メタン転化率は２４％であった。Table 2 [Comparative Example 1] A methane reforming reaction experiment was conducted in the same manner as in Example 1, except that a hydrogen separation membrane was not used (no sweep gas was flowed), and the methane conversion rate was 24%. .
〔実施例２〕
実施例１における多孔質金属パイプ（サンプル３）を用
いた試験において反応圧力、温度を変えて試験を行った
結果、以下の通りであった。[Example 2] In the test using the porous metal pipe (sample 3) in Example 1, the reaction pressure and temperature were changed and the results were as follows.
〔実施例３〕
平均細孔径が２μの多孔質金属パイプ（ニチダイ■製積
層焼結金網フィルタ：１０°Ｄ Ｘ ８ ２０Ｘ５００
Ｌ［［ｌｆｆｌ）を用いて、無電解メッキ後、電気メッ
キし、Ｐｄを２０μコーティングし、実施例１と同じ装
置、方法でプロパン，ブタン及びエチルベンゼンの脱水
素反応を行った。[Example 3] Porous metal pipe with an average pore diameter of 2μ (laminated sintered wire mesh filter manufactured by Nichidai ■: 10°D x 8 20X500
After electroless plating using L[[lffl], electroplating was performed to coat with 20μ of Pd, and a dehydrogenation reaction of propane, butane and ethylbenzene was performed using the same apparatus and method as in Example 1.
共通の反応条件は次の通りである。Common reaction conditions are as follows.
試験結果１１表３のとおりである。Test results 11 are as shown in Table 3.
表
３
〔比較例２〕
水素分離膜を用いない
（スイーブガスも流さ
ない）
こと以外は、
実施例３と同じ方法でプロ
バン，ブタン及びエチルベンゼンの脱水素反応を行った
結果を表４に示す。Table 3 [Comparative Example 2] Table 4 shows the results of a dehydrogenation reaction of propane, butane, and ethylbenzene performed in the same manner as in Example 3, except that a hydrogen separation membrane was not used (no sweep gas was flowed).
表 ４
〔発明の効果〕
本発明は脱水素反応において、多孔質金属体にＰｄを含
有する薄膜を形成せしめた水素分離膜を反応管内に設置
し、反応生成物中の水素の一部を反応系から除外するこ
とにより、従来法より低い温度で高い転化率を得ること
ができた。Table 4 [Effects of the Invention] In the dehydrogenation reaction of the present invention, a hydrogen separation membrane in which a thin film containing Pd is formed on a porous metal body is installed in a reaction tube, and a part of the hydrogen in the reaction product is removed by the reaction. By excluding it from the system, a high conversion rate could be obtained at a lower temperature than in the conventional method.
第１図は本発明方法を実施する装置の概要を説明する概
略図、第２図は本発明方法の実施例において使用した試
験反応装置の概略図である。
轍・１図FIG. 1 is a schematic diagram illustrating the outline of an apparatus for carrying out the method of the present invention, and FIG. 2 is a schematic diagram of a test reaction apparatus used in an example of the method of the present invention. Rut・1 diagram
Claims (1)
れ、外部に加熱手段を備えた反応器、該反応器の触媒充
填層に設けられた０．１〜２０μの細孔を有する多孔質
金属体の少なくとも一表面に５０μ以下の膜厚のＰｄ含
有薄膜を形成された水素分離膜で構成された水素除去手
段よりなることを特徴とする脱水素反応用メンブレンリ
アクタ。A reactor having a raw material supply inlet and a product outlet, filled with a catalyst inside and equipped with heating means on the outside, and having pores of 0.1 to 20μ provided in the catalyst packed bed of the reactor. 1. A membrane reactor for dehydrogenation reaction comprising a hydrogen removal means constituted by a hydrogen separation membrane in which a Pd-containing thin film with a thickness of 50 μm or less is formed on at least one surface of a porous metal body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012645A JPH03217227A (en) | 1990-01-24 | 1990-01-24 | Membrane reactor for dehydrogenation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012645A JPH03217227A (en) | 1990-01-24 | 1990-01-24 | Membrane reactor for dehydrogenation reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03217227A true JPH03217227A (en) | 1991-09-25 |
Family
ID=11811104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012645A Pending JPH03217227A (en) | 1990-01-24 | 1990-01-24 | Membrane reactor for dehydrogenation reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03217227A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998019960A1 (en) * | 1996-11-07 | 1998-05-14 | Toyota Jidosha Kabushiki Kaisha | Hydrogen manufacturing and supplying apparatus and electric motorcar |
| JP2007076992A (en) * | 2005-09-16 | 2007-03-29 | Nippon Oil Corp | Apparatus for producing hydrogen and fuel cell system using the same |
| JP2007084378A (en) * | 2005-09-21 | 2007-04-05 | Nippon Oil Corp | Method for producing hydrogen and apparatus used in the same |
| WO2011083653A1 (en) * | 2010-01-06 | 2011-07-14 | Ｊｘ日鉱日石エネルギー株式会社 | Reactor for dehydrogenation of organic compound, hydrogen production apparatus, and hydrogen production process |
| JP2011140411A (en) * | 2010-01-06 | 2011-07-21 | Jx Nippon Oil & Energy Corp | Organic compound dehydrogenation reactor and hydrogen production method |
| JP2011195418A (en) * | 2010-03-23 | 2011-10-06 | Jx Nippon Oil & Energy Corp | Apparatus for producing hydrogen, and method for producing hydrogen |
| KR20120039508A (en) * | 2009-02-17 | 2012-04-25 | 아셈블론, 인크. | Hydrogen release and recovery from aliphatic primary amines or di-amines |
| JP2017043552A (en) * | 2015-08-25 | 2017-03-02 | 株式会社東芝 | Manufacturing method of hydrogen carrier and manufacturing system of hydrogen carrier |
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| JPS51131473A (en) * | 1975-05-12 | 1976-11-15 | Masao Okubo | A process for manufacturing hydrogen permeable film |
| JPS6272502A (en) * | 1985-09-25 | 1987-04-03 | Yazaki Corp | Hydrogen separator |
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| JPS51131473A (en) * | 1975-05-12 | 1976-11-15 | Masao Okubo | A process for manufacturing hydrogen permeable film |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998019960A1 (en) * | 1996-11-07 | 1998-05-14 | Toyota Jidosha Kabushiki Kaisha | Hydrogen manufacturing and supplying apparatus and electric motorcar |
| US6294276B1 (en) | 1996-11-07 | 2001-09-25 | Toyota Jidosha Kabushiki Kaisha | Hydrogen manufacturing and supplying apparatus and electric motorcar |
| JP2007076992A (en) * | 2005-09-16 | 2007-03-29 | Nippon Oil Corp | Apparatus for producing hydrogen and fuel cell system using the same |
| JP2007084378A (en) * | 2005-09-21 | 2007-04-05 | Nippon Oil Corp | Method for producing hydrogen and apparatus used in the same |
| KR20120039508A (en) * | 2009-02-17 | 2012-04-25 | 아셈블론, 인크. | Hydrogen release and recovery from aliphatic primary amines or di-amines |
| JP2012519658A (en) * | 2009-02-17 | 2012-08-30 | アセンブロン インコーポレイテッド | Release and recovery of hydrogen from aliphatic primary amines or diamines |
| WO2011083653A1 (en) * | 2010-01-06 | 2011-07-14 | Ｊｘ日鉱日石エネルギー株式会社 | Reactor for dehydrogenation of organic compound, hydrogen production apparatus, and hydrogen production process |
| JP2011140411A (en) * | 2010-01-06 | 2011-07-21 | Jx Nippon Oil & Energy Corp | Organic compound dehydrogenation reactor and hydrogen production method |
| US9206046B2 (en) | 2010-01-06 | 2015-12-08 | Jx Nippon Oil & Energy Corporation | Reactor for dehydrogenation of organic compound, hydrogen production apparatus, and hydrogen production process |
| JP2011195418A (en) * | 2010-03-23 | 2011-10-06 | Jx Nippon Oil & Energy Corp | Apparatus for producing hydrogen, and method for producing hydrogen |
| JP2017043552A (en) * | 2015-08-25 | 2017-03-02 | 株式会社東芝 | Manufacturing method of hydrogen carrier and manufacturing system of hydrogen carrier |
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