JPH07177B2 - Method for producing catalyst for methanol steam reforming - Google Patents
Method for producing catalyst for methanol steam reformingInfo
- Publication number
- JPH07177B2 JPH07177B2 JP59209560A JP20956084A JPH07177B2 JP H07177 B2 JPH07177 B2 JP H07177B2 JP 59209560 A JP59209560 A JP 59209560A JP 20956084 A JP20956084 A JP 20956084A JP H07177 B2 JPH07177 B2 JP H07177B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- mol
- temperature
- steam reforming
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
Landscapes
- Hydrogen, Water And Hydrids (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、メタノールをスチームリフォーミングして水
素を得るための低温活性の高い触媒の製造方法に関する
ものである。TECHNICAL FIELD The present invention relates to a method for producing a catalyst having high low-temperature activity for steam reforming methanol to obtain hydrogen.
従来、市販されている触媒は、メタノール・スチームリ
フォーミング反応用の触媒として開発されたものは少な
く、メタノール合成（分解）、COシフト反応触媒として
発表されている。しかしこれらの触媒は、メタノール・
スチームリフォーミング反応機構の一部に有効に働くの
で、同反応用触媒としても転用が可能である。一般的に
はCu−Zu系、Cu−Cr系の触媒が知られている。Conventionally, few commercially available catalysts have been developed as catalysts for methanol / steam reforming reaction, and have been announced as catalysts for methanol synthesis (decomposition) and CO shift reaction. However, these catalysts
Since it works effectively in part of the steam reforming reaction mechanism, it can be used as a catalyst for the same reaction. Generally, Cu-Zu-based and Cu-Cr-based catalysts are known.
また、特開昭58-193738号公報には、CuO、ZnO、Al2O3か
らなる水素富化ガス製造用触媒が記載され、特開昭58-7
0839号公報には、CuO、ZnO、Al2O3からなる市販メタノ
ール合成触媒が記載され、特開昭58-17836号公報には、
CuO、ZnO、Al2O3からなるメタノール水蒸気改質触媒が
記載され、特開昭57-56302号公報には、ZnO、Cr2O3、Cu
O、Al2O3からなるメタノールリホーミング触媒が記載さ
れ、特開昭53-76991号公報には、Al2O3、CuO、ZnOから
なる水素製造用触媒が記載され、特開昭49-47281号公報
には、Cu、Zn、Alからなる水素製造用触媒が記載され、
特公昭56-95号公報には、Al2O3、Cr2O3、Cuからなる改
質用触媒が記載され、特開昭56-147633号公報には、Al2
O3、CuO、ZnO、Cr2O3からなるメタノール改質触媒が記
載されている。Further, JP-A-58-193738 describes a catalyst for producing a hydrogen-rich gas composed of CuO, ZnO, and Al 2 O 3 , which is disclosed in JP-A-58-7.
0839 publication describes CuO, ZnO, a commercial methanol synthesis catalyst consisting of Al 2 O 3 , JP-A-58-17836 discloses.
A methanol steam reforming catalyst consisting of CuO, ZnO, Al 2 O 3 is described, and JP-A-57-56302 discloses ZnO, Cr 2 O 3 , Cu.
O, a methanol reforming catalyst consisting of Al 2 O 3 is described, JP-A-53-76991 describes a hydrogen production catalyst consisting of Al 2 O 3 , CuO, ZnO, JP-A-49- Japanese Patent No. 47281 describes a catalyst for hydrogen production consisting of Cu, Zn and Al,
The Japanese Patent Publication 56-95, describes Al 2 O 3, Cr 2 O 3, reforming catalyst consisting of Cu, in JP-A-56-147633, Al 2
A methanol reforming catalyst consisting of O 3 , CuO, ZnO, Cr 2 O 3 is described.
しかし上記の従来の触媒では、低温（250℃以下）で高
活性を示すものが少なく、燃料電池用のH2発生装置など
の低レベルの熱エネルギーを利用した反応プロセスに適
用するには充分でなかった。また、上記の各公報には、
本発明における触媒成分含有量、製造条件は記載されて
いない。However, most of the above-mentioned conventional catalysts show high activity at low temperatures (250 ° C or lower), and are not enough to be applied to reaction processes using low-level thermal energy such as H 2 generators for fuel cells. There wasn't. Further, in each of the above publications,
The catalyst component content and manufacturing conditions in the present invention are not described.
本発明は上記の点に鑑みなされたもので、低温反応（25
0℃以下）においても高活性を示すメタノール・スチー
ムリフォーミング用触媒の製造方法を提供することを目
的とするものである。The present invention has been made in view of the above points, and a low temperature reaction (25
It is an object of the present invention to provide a method for producing a methanol / steam reforming catalyst that exhibits high activity even at 0 ° C or lower).
上記の目的を達成するために、本発明のメタノール・ス
チームリフォーミング用触媒の製造方法は、つぎの
（ａ）、（ｂ）の２工程、すなわち、 （ａ）CuO50〜90モル％、Al2O310〜50モル％およびZnO5
〜50モル％を含む硝酸塩混合水溶液と共沈剤とを30〜80
℃の温度で攪拌して一気に混合し沈殿を生じさせ、沈殿
物を水洗する工程、 （ｂ）水洗した沈殿物を150℃以下の温度で乾燥した
後、焼成し、ついで微粉砕し、微粉砕した粉末を成型す
る工程、 を包含することを特徴としている。In order to achieve the above object, a method for producing a catalyst for methanol / steam reforming of the present invention comprises the following two steps (a) and (b): (a) CuO 50 to 90 mol%, Al 2 O 3 10-50 mol% and ZnO 5
30-80% nitrate mixed aqueous solution containing -50 mol% and coprecipitating agent
A step of stirring at a temperature of ℃ and mixing at once to generate a precipitate, and washing the precipitate with water; And a step of molding the formed powder.
すなわち、本発明の触媒は、CuO50〜90モル％、Al2O310
〜50モル％およびZnO5〜50モル％からなる硝酸塩混合水
溶液とNa2CO3またはNaOHなどの共沈剤とを30〜80℃の温
度で攪拌し、沈殿が均一組成になるようにするために、
原料塩溶液と共沈剤とを一気に混合し、沈殿反応が終了
するまで強く攪拌を継続しながら、沈殿物を得、共沈さ
せた沈殿物を150℃以下で乾燥、焼成、粉砕、成型して
製造される。したがって本発明の方法により製造された
触媒は、CuO50〜90モル％、Al2O310〜50モル％およびZn
O5〜50モル％からなる。That is, the catalyst of the present invention is CuO 50-90 mol%, Al 2 O 3 10
~ 50 mol% and ZnO 5 ~ 50 mol% mixed nitrate aqueous solution and a coprecipitating agent such as Na 2 CO 3 or NaOH at a temperature of 30 ~ 80 ℃, in order to make the precipitation uniform composition ,
The raw salt solution and the coprecipitating agent are mixed at once, and the precipitate is obtained while continuously stirring strongly until the precipitation reaction is completed, and the coprecipitated precipitate is dried at 150 ° C. or lower, fired, crushed, and molded. Manufactured. Therefore, the catalyst produced by the method of the present invention comprises CuO 50-90 mol%, Al 2 O 3 10-50 mol% and ZnO.
O5 to 50 mol%.
本願明細書における「一気に混合」とは、「一方の容器
内の液を他方の容器内の液に一秒前後の短時間で注ぎ入
れて混合する」ことを言う。In the specification of the application, “mixing at once” means “pouring the liquid in one container into the liquid in the other container in a short time of about 1 second to mix”.
沈殿生成時の温度が30℃未満の場合は、原料塩の溶解度
が低いことと、沈殿反応が緩慢となることにより、一気
に沈殿反応を進行させることができず、均質で高性能な
触媒が得られない。一方、80℃を越える場合は、触媒原
料水溶液および沈殿剤水溶液の水分の蒸発損失が著し
く、そのため、沈殿反応操作前および反応中の濃度変化
が生じ、安定した操作が困難となる。If the temperature at which the precipitate is formed is less than 30 ° C, the solubility of the raw material salt is low and the precipitation reaction is slow, so that the precipitation reaction cannot proceed at once and a homogeneous and high-performance catalyst is obtained. I can't. On the other hand, when the temperature exceeds 80 ° C., the evaporation loss of water in the aqueous solution of the catalyst raw material and the aqueous solution of the precipitating agent is significant, so that the concentration changes before and during the precipitation reaction operation, and stable operation becomes difficult.
これらの点を考慮して、本発明では、30〜80℃という温
度範囲としている。In consideration of these points, in the present invention, the temperature range is 30 to 80 ° C.
つぎに本発明の実施例および比較例を説明する。 Next, examples and comparative examples of the present invention will be described.
実施例１ Cu(NO3)2・3H2O193.28g、Zn(NO3)2・6H2O29.748g、Al(N
O3)3・9H2O75.026gを秤量し、純水に溶解し、１の原
料塩水溶液を調整した。一方、Na2CO3・10H2O343.368g
を純水に溶解し、10wt％Na2CO3水溶液（沈殿剤水溶液）
を調整した。ついで原料塩水溶液および沈殿剤水溶液を
70℃（沸騰させない温度とする）として、原料塩水溶液
の中へ沈殿剤水溶液を強く攪拌しながら一気に投入し、
沈殿を生じさせた。しばらく静置し上澄み液を除去しpH
が7.0となるまで充分水洗した。ついで沈殿物をろ過し
固型物を採取した。Example 1 Cu (NO 3) 2 · 3H 2 O193.28g, Zn (NO 3) 2 · 6H 2 O29.748g, Al (N
O 3) were weighed 3 · 9H 2 O75.026g, it was dissolved in pure water and adjusted to 1 of the raw material salt aqueous solution. On the other hand, Na 2 CO 3 · 10H 2 O343.368g
Is dissolved in pure water to obtain a 10 wt% Na 2 CO 3 aqueous solution (precipitant aqueous solution)
Was adjusted. Then, the raw salt solution and the precipitant solution are added.
At 70 ° C (temperature not to boil), add the precipitant aqueous solution into the raw salt aqueous solution at once with strong stirring,
A precipitate formed. Let stand for a while and remove the supernatant liquid to
It was sufficiently washed with water until it reached 7.0. Then, the precipitate was filtered to collect a solid product.
この固型物を110℃で25時間乾燥した後、450℃で３時間
焼成しCuO-ZnO-Al2O3の結晶を得た。この焼成して得ら
れた結晶を微粉砕し、200メッシュ（74μｍ）以下とそ
れを越えるものとに分級した。200メッシュ（74μｍ）
以下の粉末をタブレット状に成型した後、触媒の活性試
験用のサンプルとして、均一な粒度に調整するため、粉
砕し分級して1mm平均径のものをサンプルとして採取し
た。このサンプルを10vol％H2−90vol％N2、300Ncc/min
（触媒平均粒径1mm、触媒充填量1cc）の気流中で、室温
から250℃まで昇温・還元し（昇温速度:5.5℃/min）、2
50℃で１時間保持して還元して、CuO80モル％ZnO10モル
％、Al2O310モル％の触媒を得た。This solid product was dried at 110 ° C. for 25 hours and then calcined at 450 ° C. for 3 hours to obtain CuO—ZnO—Al 2 O 3 crystals. The crystals obtained by this calcination were finely pulverized and classified into particles of 200 mesh (74 μm) or less and those of more than 200 mesh (74 μm). 200 mesh (74 μm)
The following powders were molded into tablets, and as a sample for a catalyst activity test, in order to adjust the particle size to be uniform, they were ground and classified, and a sample having an average diameter of 1 mm was taken as a sample. This sample is 10vol% H 2 −90vol% N 2 , 300Ncc / min
In a gas stream (catalyst average particle size 1 mm, catalyst filling amount 1 cc), the temperature is raised from room temperature to 250 ° C and reduced (heating rate: 5.5 ° C / min), 2
It was kept at 50 ° C. for 1 hour for reduction to obtain a catalyst containing 80 mol% CuO, 10 mol% ZnO and 10 mol% Al 2 O 3 .
ついでこの触媒を用いて以下のように活性試験を行っ
た。この触媒1ccを反応容器内に充填し、10vol％CH3OH
‐20vol％H2O‐70vol％N2を250Ncc/minの割合で供給し
て、反応温度とメタノール変換率との関係を試験した。
SVは1.5×10-4Hr-1、LHSV（メタノール基準）は2.7Hr-1
であった。結果は図面に示す如くであった。Then, using this catalyst, an activity test was conducted as follows. 1 cc of this catalyst was filled in the reaction vessel, and 10 vol% CH 3 OH
-20 vol% H 2 O-70 vol% N 2 was fed at a rate of 250 Ncc / min to test the relationship between reaction temperature and methanol conversion rate.
SV is 1.5 × 10 -4 Hr -1 , LHSV (methanol standard) is 2.7 Hr -1
Met. The results were as shown in the drawing.
比較例１ 共沈法により調整されたCu−Zn系の市販触媒を、実施例
１と同じ活性試験条件で反応温度とメタノール変換率と
の関係を試験した。結果は図面に示す如くであった。Comparative Example 1 A Cu—Zn-based commercial catalyst prepared by the coprecipitation method was tested for the relationship between the reaction temperature and the methanol conversion rate under the same activity test conditions as in Example 1. The results were as shown in the drawing.
比較例２ 共沈法により調整されたCu−ZnーCr系の市販触媒を、実
施例１と同じ活性試験条件で反応温度とメタノール変換
率との関係を試験した。結果は図面に示す如くであっ
た。Comparative Example 2 A Cu—Zn—Cr type commercial catalyst prepared by the coprecipitation method was tested for the relationship between the reaction temperature and the methanol conversion rate under the same activity test conditions as in Example 1. The results were as shown in the drawing.
以上説明したように、本発明の方法によれば、濃度変化
が生じず、安定した操作で沈殿反応を進行させることが
でき、このため、均質で高性能な触媒を得ることができ
る。また、本発明の方法により製造した触媒は、低温反
応（250℃以下）においても高活性を示すため、低温度
レベルの熱エネルギーを利用した反応プロセスが可能と
なり、燃料電池用のH2発生装置への利用、半導体製造時
の還元用H2の発生源など高温のH2を必要としない装置・
プロセスへの適用が可能であり、省エネルギー型のプロ
セス開発のための重要な要素技術として非常に有効であ
る。As described above, according to the method of the present invention, the concentration reaction does not occur, and the precipitation reaction can proceed in a stable operation. Therefore, a homogeneous and high-performance catalyst can be obtained. Further, the catalyst produced by the method of the present invention exhibits high activity even in low temperature reaction (250 ° C. or lower), which enables a reaction process utilizing heat energy at a low temperature level, and an H 2 generator for a fuel cell. Equipment that does not require high temperature H 2 such as H 2 generation source for reduction in semiconductor manufacturing
It can be applied to processes and is extremely effective as an important elemental technology for energy-saving process development.
図面は従来の触媒および本発明の方法により製造した触
媒の反応温度とメタノール変換率との関係を示すグラフ
である。The drawing is a graph showing the relationship between the reaction temperature and the methanol conversion rate of the conventional catalyst and the catalyst produced by the method of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−193738（ＪＰ，Ａ) 特開 昭58−70839（ＪＰ，Ａ) 特開 昭58−17836（ＪＰ，Ａ) 特開 昭56−147633（ＪＰ，Ａ) 特開 昭49−47281（ＪＰ，Ａ) 特開 昭57−56302（ＪＰ，Ａ) 特開 昭53−76991（ＪＰ，Ａ) 特公 昭56−95（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-193738 (JP, A) JP-A-58-70839 (JP, A) JP-A-58-17836 (JP, A) JP-A-56- 147633 (JP, A) JP-A-49-47281 (JP, A) JP-A-57-56302 (JP, A) JP-A-53-76991 (JP, A) JP-B-56-95 (JP, B2)
Claims (1)
ち、 （ａ）CuO 50〜90モル％、Al2O3 10〜50モル％およびZn
O 5〜50モル％を含む硝酸塩混合水溶液と共沈剤とを30
〜80℃の温度で攪拌して一気に混合し沈殿を生じさせ、
沈殿物を水洗する工程、 （ｂ）水洗した沈殿物を150℃以下の温度で乾燥した
後、焼成し、ついで微粉砕し、微粉砕した粉末を成型す
る工程、 を包含することを特徴とするメタノール・スチームリフ
ォーミング用触媒の製造方法。1. The following two steps (a) and (b): (a) CuO 50 to 90 mol%, Al 2 O 3 10 to 50 mol%, and Zn.
A nitrate mixed aqueous solution containing 5 to 50 mol% of O and a coprecipitating agent are added.
Stir at a temperature of ~ 80 ° C and mix all at once to form a precipitate,
A step of washing the precipitate with water, (b) a step of drying the washed precipitate at a temperature of 150 ° C. or lower, firing it, then pulverizing it, and molding a finely pulverized powder. A method for producing a catalyst for methanol steam reforming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59209560A JPH07177B2 (en) | 1984-10-05 | 1984-10-05 | Method for producing catalyst for methanol steam reforming |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59209560A JPH07177B2 (en) | 1984-10-05 | 1984-10-05 | Method for producing catalyst for methanol steam reforming |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6186946A JPS6186946A (en) | 1986-05-02 |
| JPH07177B2 true JPH07177B2 (en) | 1995-01-11 |
Family
ID=16574846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59209560A Expired - Lifetime JPH07177B2 (en) | 1984-10-05 | 1984-10-05 | Method for producing catalyst for methanol steam reforming |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07177B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63209753A (en) * | 1987-02-26 | 1988-08-31 | Agency Of Ind Science & Technol | Methanol reforming catalyst |
| JPH0427434A (en) * | 1990-05-23 | 1992-01-30 | Mitsubishi Heavy Ind Ltd | Catalyst for reforming methanol |
| DK173416B1 (en) * | 1995-07-21 | 2000-10-02 | Topsoe Haldor As | Process for producing hydrogen-rich gas |
| CN100457724C (en) * | 2003-11-17 | 2009-02-04 | 赫多特普索化工设备公司 | Process for the preparation of urea |
| CN100352544C (en) * | 2004-02-10 | 2007-12-05 | 中国科学院大连化学物理研究所 | Catalyst used for methanol oxidation oxidizing and reforming hydrogen production and preparation method thereof |
| JP6406629B2 (en) * | 2014-08-05 | 2018-10-17 | 東京瓦斯株式会社 | Hydrogen production system and hydrogen production method |
| CN115041174B (en) * | 2022-06-20 | 2023-09-29 | 西南化工研究设计院有限公司 | Preparation method of copper-based catalyst of large-scale methanol hydrogen production device |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2220617A1 (en) * | 1972-04-27 | 1973-11-15 | Metallgesellschaft Ag | METHOD FOR PRODUCTION OF HYDROGEN |
| US4091086A (en) * | 1976-12-20 | 1978-05-23 | Engelhard Minerals & Chemicals Corporation | Process for production of hydrogen |
| JPS5695A (en) * | 1979-06-15 | 1981-01-06 | Nippon Telegr & Teleph Corp <Ntt> | Signal rewriting system for circulation type memory |
| JPS56147633A (en) * | 1980-04-17 | 1981-11-16 | Mitsubishi Heavy Ind Ltd | Methanol reforming catalyst |
| BE884720A (en) * | 1980-08-11 | 1981-02-11 | Catalysts & Chem Europ | METHANOL REFORMING PROCESS AND DEVICE IMPLEMENTED |
| JPS5817836A (en) * | 1981-07-24 | 1983-02-02 | Fuji Electric Co Ltd | Reforming catalyst for methanol |
| JPS5870839A (en) * | 1981-10-26 | 1983-04-27 | Mitsui Toatsu Chem Inc | Catalyst for steam reforming of methanol |
| JPS58193738A (en) * | 1982-05-06 | 1983-11-11 | Mitsubishi Heavy Ind Ltd | Catalyst for production of gas enriched with hydrogen |
| JPS59189937A (en) * | 1983-04-13 | 1984-10-27 | Mitsubishi Gas Chem Co Inc | Preparation of steam reforming catalyst of methanol |
| JPS60110337A (en) * | 1983-11-18 | 1985-06-15 | Mitsubishi Heavy Ind Ltd | Catalyst for preparing hydrogen rich gas |
-
1984
- 1984-10-05 JP JP59209560A patent/JPH07177B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6186946A (en) | 1986-05-02 |
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