JPH10174865A - Catalyst for producing synthetic gas, its production and production of synthetic gas - Google Patents
Catalyst for producing synthetic gas, its production and production of synthetic gasInfo
- Publication number
- JPH10174865A JPH10174865A JP8339757A JP33975796A JPH10174865A JP H10174865 A JPH10174865 A JP H10174865A JP 8339757 A JP8339757 A JP 8339757A JP 33975796 A JP33975796 A JP 33975796A JP H10174865 A JPH10174865 A JP H10174865A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- producing
- dimethyl ether
- synthetic gas
- carbon dioxide
- 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
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、ジメチルエーテル
と少なくとも水蒸気または二酸化炭素が含まれる混合ガ
スから合成ガスを生成させる触媒及びその製造方法なら
びにそれを用いた合成ガスの製造方法に関するものであ
る。The present invention relates to a catalyst for producing a synthesis gas from a mixed gas containing dimethyl ether and at least steam or carbon dioxide, a method for producing the same, and a method for producing a synthesis gas using the same.
【０００２】[0002]
【従来の技術】合成ガスは、一酸化炭素と水素からなる
ガスであり、直接、メタノール合成、オキソ合成、フィ
ッシャートロプシュ合成等の原料ガスに用いられるほ
か、アンモニア合成や各種化学製品の原料として広い用
途をもっている。2. Description of the Related Art Synthetic gas is a gas composed of carbon monoxide and hydrogen, and is directly used as a raw material gas for methanol synthesis, oxo synthesis, Fischer-Tropsch synthesis, etc., and is widely used as a raw material for ammonia synthesis and various chemical products. Has a use.
【０００３】従来、合成ガスを製造する方法はいくつか
知られている。Conventionally, several methods for producing synthesis gas are known.
【０００４】例えば、(１)石炭のガス化による方法、
(２)天然ガス、ＬＰＧ、ナフサなどを原料とする炭化水
素の水蒸気改質方法、(３)天然ガス、ＬＰＧ、ナフサ、
重質油などを原料とする炭化水素の部分酸化方法などが
ある。For example, (1) a method by gasification of coal,
(2) a method for steam reforming of hydrocarbons using natural gas, LPG, naphtha, etc. as raw materials; (3) a method for natural gas, LPG, naphtha,
There is a method of partially oxidizing hydrocarbons using heavy oil or the like as a raw material.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記
(１)の石炭ガス化法においては、極めて複雑でかつ高価
な石炭ガス化炉が必要であり、装置が大規模なプラント
となるなどの問題があった。また(２)の炭化水素の水蒸
気改質方法においては、反応が大きな吸熱であり、反応
の進行に７００〜１２００℃の高温を必要とするため、
特殊な改質炉が必要であり、また使用する触媒に高い耐
熱性が要求されるなどの問題があった。上記(３)の炭化
水素の部分酸化方法においても、１２００〜１５００℃
の高温を必要とするために特殊な部分酸化炉が必要であ
り、また反応に伴って大量のすすが生成するためその処
理が問題となり、さらに触媒を使用する場合には触媒表
面に炭素質物質が多量に析出して触媒が劣化するなどの
問題があった。SUMMARY OF THE INVENTION
In the coal gasification method (1), an extremely complicated and expensive coal gasification furnace is required, and there is a problem that the equipment becomes a large-scale plant. Further, in the hydrocarbon steam reforming method (2), since the reaction is a large endothermic and requires a high temperature of 700 to 1200 ° C. for the progress of the reaction,
There is a problem that a special reforming furnace is required, and that the catalyst used is required to have high heat resistance. Also in the method for partially oxidizing hydrocarbons of the above (3), 1200 to 1500 ° C.
Requires a special partial oxidation furnace because of the high temperature required, and a large amount of soot is generated during the reaction. However, there is a problem that a large amount of the catalyst precipitates to deteriorate the catalyst.
【０００６】本発明は、上記従来の問題点を解決し、低
温において高い収率で合成ガスを得ることができる触媒
及びその製造方法ならびに合成ガスの製造方法を提供す
ることを目的とする。An object of the present invention is to solve the above conventional problems and to provide a catalyst capable of obtaining a synthesis gas at a low temperature and a high yield, a method for producing the same, and a method for producing a synthesis gas.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記課題
を解決するべく鋭意検討の結果、原料ガスとしてジメチ
ルエーテルに着目するに至った。そして、ジメチルエー
テルと水蒸気または二酸化炭素を反応させて合成ガスを
生成させる触媒として、塩基性を有する金属酸化物にパ
ラジウムを担持させた触媒が極めて有効であり、低温で
効率よく合成ガスを生成させうること及びこの触媒は塩
基性水溶液で処理することによって触媒の高い活性を確
保することができることを見出して本発明を完成するこ
とができた。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have come to focus on dimethyl ether as a raw material gas. As a catalyst for generating synthesis gas by reacting dimethyl ether with water vapor or carbon dioxide, a catalyst in which palladium is supported on a basic metal oxide is extremely effective, and can efficiently generate synthesis gas at a low temperature. The present invention was completed by finding that the catalyst can be treated with a basic aqueous solution to ensure high activity of the catalyst.
【０００８】すなわち、本発明は、塩基性を有する金属
酸化物にパラジウムを担持させた、ジメチルエーテルと
水蒸気または二酸化炭素から合成ガスを生成させる触
媒、上記の触媒を製造するにあたり、塩基性を有する金
属酸化物にパラジウムを担持させた後、塩基性水溶液で
処理することを特徴とする合成ガス製造用触媒の製造方
法及びジメチルエーテルと少なくとも水蒸気または二酸
化炭素を含有する混合ガスに上記の触媒を接触させるこ
とを特徴とする合成ガスの製造方法に関するものであ
る。That is, the present invention provides a catalyst for producing a synthesis gas from dimethyl ether and water vapor or carbon dioxide in which palladium is supported on a basic metal oxide. After supporting palladium on the oxide, a method for producing a catalyst for syngas production, which comprises treating with a basic aqueous solution, and contacting the catalyst with a mixed gas containing dimethyl ether and at least steam or carbon dioxide And a method for producing a synthesis gas.
【０００９】本発明においては、塩基性を有する金属酸
化物を活性成分であるパラジウムの担体として用いるこ
とにより、メタンを主体とする炭化水素の生成を抑制し
て、高収率で合成ガスを生成させる。また、塩基性を有
する金属酸化物にパラジウムを担持する操作時におい
て、塩基性を有する金属酸化物はパラジウムを含む酸性
の強い水溶液と接触すると、塩基性が失われる。そこ
で、本発明の触媒の製造方法においては、金属酸化物の
塩基性を回復するために、金属酸化物にパラジウムを担
持した後、塩基性の水溶液で処理することを特徴とす
る。この処理操作により、高収率で合成ガスを得ること
ができる。In the present invention, by using a basic metal oxide as a carrier for palladium as an active component, the production of hydrocarbons mainly composed of methane is suppressed, and the synthesis gas is produced in high yield. Let it. In addition, during the operation of supporting palladium on a basic metal oxide, the basic metal oxide loses basicity when it comes into contact with a strongly acidic aqueous solution containing palladium. Therefore, the method for producing a catalyst of the present invention is characterized in that palladium is supported on a metal oxide and then treated with a basic aqueous solution in order to recover the basicity of the metal oxide. By this processing operation, a synthesis gas can be obtained with a high yield.
【００１０】[0010]
【発明の実施の形態】本発明の触媒は、塩基性を有する
金属酸化物にパラジウムを担持させたものである。塩基
性を有する金属酸化物は、Ｌi2Ｏ、Ｎａ2Ｏ、Ｋ2Ｏ、Ｒ
ｂ2Ｏ、Ｃｓ2Ｏ等のアルカリ金属の酸化物、ＢｅＯ、Ｍ
ｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ等のアルカリ土類金属の
酸化物、Ｙ2Ｏ3、Ｌａ2Ｏ3、ＣｅＯ2等の希土類元素の
酸化物、ＺｎＯ、ＳｎＯ2、ＺｒＯ2、Ａｌ2Ｏ3、ＴiＯ2
および前記の金属酸化物の２種以上の混合物である。ま
た前記の塩基性を有する金属酸化物を、塩基性を有しな
い他の金属酸化物、例えばシリカゲルなど、あるいは塩
基性を有しない他の化合物、例えば炭化珪素、活性炭な
どと組み合わせて用いることができる。パラジウムの担
持率は、塩基性を有する金属酸化物に対して約０．１〜
３０重量％、好ましくは０．２〜２０重量％である。パ
ラジウムの担持率が約０．１重量％未満および３０重量
％以上であると、合成ガスの収率が低下する。BEST MODE FOR CARRYING OUT THE INVENTION The catalyst of the present invention is obtained by supporting palladium on a basic metal oxide. Basic metal oxides are Li 2 O, Na 2 O, K 2 O, R
oxides of alkali metals such as b 2 O and Cs 2 O, BeO, M
gO, CaO, SrO, oxides of alkaline earth metals of BaO or the like, Y 2 O 3, La 2 O 3, oxides of rare earth elements such as CeO 2, ZnO, SnO 2, ZrO 2 , Al 2 O 3, TiO 2
And mixtures of two or more of the foregoing metal oxides. Further, the above-described basic metal oxide can be used in combination with another non-basic metal oxide, for example, silica gel, or another non-basic compound, for example, silicon carbide, activated carbon, or the like. . The loading ratio of palladium is about 0.1 to about a basic metal oxide.
It is 30% by weight, preferably 0.2 to 20% by weight. When the loading of palladium is less than about 0.1% by weight and 30% by weight or more, the yield of synthesis gas decreases.
【００１１】本発明の触媒の製造方法は、塩基性を有す
る金属酸化物にパラジウムを担持させた後、塩基性の水
溶液で処理することを特徴とする。この触媒の製造方法
としては、パラジウムの金属塩を含む水溶液、例えば塩
化パラジウムを含む水溶液に塩基性を有する金属酸化物
を投入して、蒸発乾固、乾燥の後、焼成する。焼成は、
窒素中または空気中において、３５０〜６００℃の温度
で１〜１０時間加熱して行うのが好ましい。ついでこの
ものを塩基性の水溶液で処理する。塩基性の水溶液とし
ては、アルカリ金属の水酸化物および炭酸塩ならびにア
ルカリ土類金属の水酸化物の水溶液があげられる。これ
らの塩基性化合物の濃度は０．５〜２０程度、通常１〜
１０程度が適当である。処理は触媒に塩基性水溶液を接
触させ、次いで塩基性水溶液を除去することによって行
う。この処理は常温〜８０℃の温度において、１〜５時
間行うのが好ましい。また、塩基性の水溶液で処理した
後、例えば上記の塩基性化合物を少量（例えば０．１〜
１．０程度）担持することもできる。触媒は調製の最終
段階において活性化処理を行うが、これは、水素雰囲気
下、３５０〜６００℃の温度で、１〜１０時間処理する
のが好ましい。The process for producing a catalyst according to the present invention is characterized in that palladium is supported on a basic metal oxide and then treated with a basic aqueous solution. As a method for producing this catalyst, a basic metal oxide is charged into an aqueous solution containing a metal salt of palladium, for example, an aqueous solution containing palladium chloride, and evaporated to dryness, dried, and then calcined. Firing
It is preferable to carry out the heating in nitrogen or air at a temperature of 350 to 600 ° C. for 1 to 10 hours. This is then treated with a basic aqueous solution. Examples of the basic aqueous solution include aqueous solutions of hydroxides and carbonates of alkali metals and hydroxides of alkaline earth metals. The concentration of these basic compounds is about 0.5 to 20, usually 1 to
About 10 is appropriate. The treatment is carried out by bringing a basic aqueous solution into contact with the catalyst and then removing the basic aqueous solution. This treatment is preferably performed at a temperature of normal temperature to 80 ° C. for 1 to 5 hours. After treatment with a basic aqueous solution, for example, a small amount of the above basic compound (for example, 0.1 to
1.0). The catalyst is subjected to an activation treatment at the final stage of preparation, which is preferably carried out in a hydrogen atmosphere at a temperature of 350 to 600 ° C. for 1 to 10 hours.
【００１２】このようにして調製された触媒にジメチル
エーテルと水蒸気および／または二酸化炭素の混合ガス
を流通させることにより、合成ガスが高収率で得られ
る。By passing a mixed gas of dimethyl ether, steam and / or carbon dioxide through the catalyst thus prepared, a synthesis gas can be obtained in high yield.
【００１３】本発明の合成ガスの製造方法では、原料の
ジメチルエーテルとともに水蒸気および／または二酸化
炭素を供給する。供給する水蒸気は原料のジメチルエー
テルに対し量論量以上あればよく、１〜２０モル倍、好
ましくは１〜１０モル倍である。水蒸気の供給が１モル
倍より少ないと、高いジメチルエーテル転化率が得られ
ず、また２０モル倍より多いと経済的でない。供給する
二酸化炭素は原料のジメチルエーテルに対して０．８〜
２．０モル倍、好ましくは０．９〜１．５モル倍であ
る。二酸化炭素の供給が０．８モル倍より少ないと、高
いジメチルエーテル転化率が得られず、また２．０モル
倍より多いと、合成ガスに多量の二酸化炭素が残存し
て、二酸化炭素を合成ガスから除去することが必要とな
り好ましくない。また水蒸気と二酸化炭素をともに供給
する場合には、水蒸気と二酸化炭素の合計がジメチルエ
ーテルに対して１〜１０モル倍、好ましくは１〜５モル
倍である。水蒸気と二酸化炭素の合計が１モル倍より少
ないと、高いジメチルエーテル転化率が得られず、また
１０モル倍より多いと経済的でなく、また合成ガスから
二酸化炭素の除去が必要となり好ましくない。この原料
ガスには、ジメチルエーテルと水蒸気、二酸化炭素以外
の成分も含むことができる。その他の成分として反応に
不活性なガス、例えば窒素、不活性ガス、ＣＯ、Ｈ2、
メタン等を含むことができる。これらの含有量は３０容
量％以下が適当であり、これより多くなると反応速度の
低下が問題になる。一方、空気（酸素）はジメチルエー
テルが燃焼してしまうのでなるべく排除したほうがよ
く、許容含有量は空気として５％以下である。In the method for producing a synthesis gas of the present invention, steam and / or carbon dioxide are supplied together with the raw material dimethyl ether. The supplied steam may be at least a stoichiometric amount with respect to the raw material dimethyl ether, and is 1 to 20 mole times, preferably 1 to 10 mole times. If the supply of steam is less than 1 mole, a high dimethyl ether conversion cannot be obtained, and if it is more than 20 moles, it is not economical. The supplied carbon dioxide is 0.8 to
The molar ratio is 2.0 times, preferably 0.9 to 1.5 times. If the supply of carbon dioxide is less than 0.8 mol times, a high conversion of dimethyl ether cannot be obtained, and if it is more than 2.0 mol times, a large amount of carbon dioxide remains in the synthesis gas, and the carbon dioxide is converted into synthesis gas. It is necessary to remove from the undesirably. When both steam and carbon dioxide are supplied, the sum of the steam and carbon dioxide is 1 to 10 times, preferably 1 to 5 times the molar amount of dimethyl ether. If the sum of water vapor and carbon dioxide is less than 1 mole, a high dimethyl ether conversion cannot be obtained, and if it is more than 10 moles, it is not economical, and carbon dioxide must be removed from the synthesis gas, which is not preferable. The raw material gas may contain components other than dimethyl ether, water vapor, and carbon dioxide. Gases inert to the reaction as other components, such as nitrogen, inert gas, CO, H 2 ,
It can contain methane and the like. The content of these is suitably not more than 30% by volume. If the content is more than 30% by volume, the reduction of the reaction rate becomes a problem. On the other hand, air (oxygen) burns dimethyl ether, so it is better to exclude it as much as possible, and the allowable content is 5% or less as air.
【００１４】反応温度は、ジメチルエーテルと水蒸気を
供給する場合、２００〜５００℃、好ましくは２５０〜
４００℃である。反応温度が２００℃より低いと高いジ
メチルエーテル転化率が得られず、かつ二酸化炭素の生
成割合が増加して合成ガスの収率を低下させ、また反応
温度が５００℃より高いとメタンを主体とする炭化水素
の生成が顕著となり、生成物中の合成ガスの割合が低下
して好ましくない。またジメチルエーテルと二酸化炭素
を供給する場合、２００〜６００℃、好ましくは３００
〜５００℃である。反応温度が２００℃より低いと高い
ジメチルエーテル転化率が得られず、また６００℃より
高いとメタンを主体とする炭化水素の生成が顕著とな
り、生成物中の合成ガスの割合が低下して好ましくな
い。When dimethyl ether and steam are supplied, the reaction temperature is 200 to 500 ° C., preferably 250 to 500 ° C.
400 ° C. If the reaction temperature is lower than 200 ° C., a high dimethyl ether conversion cannot be obtained, and the production ratio of carbon dioxide increases to decrease the yield of synthesis gas. If the reaction temperature is higher than 500 ° C., methane is mainly used. Hydrocarbon production becomes remarkable, and the ratio of synthesis gas in the product is undesirably reduced. When dimethyl ether and carbon dioxide are supplied, 200 to 600 ° C., preferably 300 to 200 ° C.
５００500 ° C. If the reaction temperature is lower than 200 ° C., a high conversion of dimethyl ether cannot be obtained, and if it is higher than 600 ° C., the generation of hydrocarbons mainly composed of methane becomes remarkable, and the ratio of synthesis gas in the product decreases, which is not preferable. .
【００１５】反応圧力は常圧〜１０ｋｇ／ｃｍ2が好ま
しい。反応圧力が１０ｋｇ／ｃｍ2より高いとジメチル
エーテル転化率が低下する。The reaction pressure is preferably normal pressure to 10 kg / cm 2 . If the reaction pressure is higher than 10 kg / cm 2 , the conversion of dimethyl ether decreases.
【００１６】空間速度（触媒１ｍ3あたりの標準状態に
おける混合ガスの供給速度ｍ3／ｈ）は、１０００〜２
００００ｍ3／ｍ3・ｈが好ましい。空間速度が２０００
０ｍ3／ｍ3・ｈより大きいとジメチルエーテル転化率が
低くなり、また１０００ｍ3／ｍ3・ｈより小さいと反応
器が極端に大きくなって経済的でない。The space velocity (supply rate m 3 / h of the mixed gas in a standard state per m 3 of the catalyst) is 1000 to 2
0000 m 3 / m 3 · h is preferred. Space velocity 2000
If it is greater than 0 m 3 / m 3 · h, the conversion of dimethyl ether is low, and if it is less than 1000 m 3 / m 3 · h, the reactor becomes extremely large and is not economical.
【００１７】なお、本発明の方法においては、固定床、
流動床のいずれの装置を用いてもよい。In the method of the present invention, a fixed bed,
Any apparatus of a fluidized bed may be used.
【００１８】こうして、ジメチルエーテル転化率６０〜
１００％程度、通常８０〜１００％程度で、合成ガスを
収率６０〜１００％程度、通常８０〜１００％程度で得
ることができる。得られた合成ガスのＨ2／ＣＯはモル
比で０．５〜４０程度、通常０．８〜３．０程度であ
る。副生物については、メタノールは１．０以下、通常
０．５以下、炭化水素は１０以下、通常５以下である。Thus, the conversion of dimethyl ether is 60 to
The synthesis gas can be obtained in about 100%, usually about 80 to 100%, and the yield of synthesis gas is about 60 to 100%, usually about 80 to 100%. The H 2 / CO of the obtained synthesis gas is about 0.5 to 40, usually about 0.8 to 3.0 in molar ratio. As for by-products, methanol is 1.0 or less, usually 0.5 or less, and hydrocarbon is 10 or less, usually 5 or less.
【００１９】[0019]
Ｉ．触媒の調製 実施例１、２ 塩酸６ｍｌおよび塩化パラジウム(ＰｄＣｌ2)８.３３ｇ
をイオン交換水約５００ｍｌに溶解させた水溶液に、酸
化亜鉛（関東化学製，試薬特級）１００ｇを投入して、
蒸発乾固した。これを、空気中１２０℃で２４時間乾燥
し、さらに空気中、５００℃で３時間焼成した。つい
で、このものを水酸化ナトリウム１０ｇをイオン交換水
約１０００ｍｌに溶解した水溶液中に投入し、５０℃に
加熱して、約１時間の処理を行った後、塩素イオンが検
出されなくなるまで洗浄し、１２０℃で２４時間乾燥し
た。さらに、このものを圧縮成型により、２０〜４０メ
ッシュに整粒した後、水素気流中、５００℃で３時間処
理を行って触媒を得た。I. Preparation of catalyst Examples 1, 2 6 ml of hydrochloric acid and 8.33 g of palladium chloride (PdCl 2 )
Was dissolved in about 500 ml of ion-exchanged water, and 100 g of zinc oxide (Kanto Chemical Co., Ltd., reagent grade) was added.
Evaporated to dryness. This was dried in air at 120 ° C. for 24 hours and fired in air at 500 ° C. for 3 hours. Then, this was put into an aqueous solution in which 10 g of sodium hydroxide was dissolved in about 1000 ml of ion-exchanged water, heated to 50 ° C., and treated for about 1 hour, and then washed until chlorine ions were not detected. And dried at 120 ° C. for 24 hours. Further, this was sized to 20 to 40 mesh by compression molding, and then treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.
【００２０】得られた触媒の組成は、Ｐｄ：ＺｎＯ＝
５：１００（重量比）であった。The composition of the obtained catalyst is Pd: ZnO =
5: 100 (weight ratio).
【００２１】実施例３、４ 実施例１、２の方法において、酸化亜鉛の代わりに酸化
セリウム(関東化学製,試薬特級）を用いる以外、実施例
１、２と同じ方法により触媒を調製した。Examples 3 and 4 Catalysts were prepared in the same manner as in Examples 1 and 2, except that cerium oxide (Kanto Chemical, special grade reagent) was used instead of zinc oxide.
【００２２】得られた触媒の組成は、Ｐｄ：ＣｅＯ2＝
５：１００（重量比）であった。The composition of the obtained catalyst is Pd: CeO 2 =
5: 100 (weight ratio).
【００２３】実施例５、６ 塩酸６ｍｌおよび塩化パラジウム（ＰｄＣｌ2）８．３
３ｇをイオン交換水約５００ｍｌに溶解させた水溶液
に、γ−アルミナ(日揮化学製，Ｎ６１２)１００ｇを投
入して、蒸発乾固した後、空気中１２０℃で２４時間乾
燥し、さらに空気中、５００℃で３時間焼成した。つい
でこのものを水酸化ナトリウム５０ｇをイオン交換水約
１０００ｍｌに溶解した水溶液中に投入し、５０℃に加
熱して、約１時間の処理を行った後、洗浄を行うことな
く、分離したのみで乾燥した。さらにこのものを圧縮成
型により、２０〜４０メッシュに整粒した後、水素気流
中、５００℃で３時間処理を行って触媒を得た。Examples 5 and 6 6 ml of hydrochloric acid and 8.3 of palladium chloride (PdCl 2 )
100 g of γ-alumina (manufactured by JGC Chemicals, N612) was added to an aqueous solution obtained by dissolving 3 g in about 500 ml of ion-exchanged water, evaporated to dryness, dried in air at 120 ° C. for 24 hours, It was baked at 500 ° C. for 3 hours. Then, this was put into an aqueous solution in which 50 g of sodium hydroxide was dissolved in about 1000 ml of ion-exchanged water, heated to 50 ° C., and treated for about 1 hour. Dried. This was further sized by compression molding to 20 to 40 mesh, and then treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.
【００２４】得られた触媒の組成は、Ｐｄ：Ｎａ2Ｏ：
Ａｌ2Ｏ3＝５：０．４：１００(重量比）であった。The composition of the obtained catalyst is Pd: Na 2 O:
Al 2 O 3 = 5: 0.4: 100 (weight ratio).
【００２５】実施例７、８ 塩酸６ｍｌおよび塩化パラジウム（ＰｄＣｌ2）８．３
３ｇをイオン交換水約５００ｍｌに溶解させた水溶液
に、シリカゲル（富士ディヴィソン化学，ＩＤ）１００
ｇを投入して、蒸発乾固した。これを、空気中１２０℃
で２４時間乾燥し、さらに空気中、５００℃で３時間焼
成した。ついで、このものを水酸化カルシウム１０ｇを
イオン交換水約１０００ｍｌに溶解した水溶液中に投入
し、５０℃に加熱して、約１時間の処理を行った後、洗
浄、乾燥を行った。さらにこのもの約８０ｇを、水酸化
カルシウム６．６ｇをイオン交換水約２００ｍｌに溶解
した水溶液に投入し、蒸発乾固した後、乾燥した。この
ものを圧縮成型により、２０〜４０メッシュに整粒した
後、水素気流中、５００℃で３時間処理を行って触媒を
得た。Examples 7 and 8 6 ml of hydrochloric acid and 8.3 of palladium chloride (PdCl 2 )
Silica gel (Fuji Divison Chemical, ID) 100 was added to an aqueous solution in which 3 g was dissolved in about 500 ml of ion-exchanged water.
g, and evaporated to dryness. This is 120 ° C in air
And calcined at 500 ° C. for 3 hours in the air. Then, this was put into an aqueous solution in which 10 g of calcium hydroxide was dissolved in about 1000 ml of ion-exchanged water, heated to 50 ° C., and treated for about 1 hour, followed by washing and drying. Further, about 80 g of this was put into an aqueous solution in which about 6.6 g of calcium hydroxide was dissolved in about 200 ml of ion-exchanged water, evaporated to dryness, and then dried. This was sized to 20 to 40 mesh by compression molding, and then treated in a hydrogen stream at 500 ° C. for 3 hours to obtain a catalyst.
【００２６】得られた触媒の組成は、Ｐｄ：ＣａＯ：Ｓ
ｉＯ2＝５：５：１００(重量比）であった。The composition of the obtained catalyst is Pd: CaO: S
iO 2 = 5: 5: 100 (weight ratio).
【００２７】II．反応方法 内径２０ｍｍのステンレス製反応管に所定量の上記触媒
を充填した。この反応管にジメチルエーテルと水蒸気お
よび／または二酸化炭素を所定量供給して、所定の温度
で反応させた。II. Reaction Method A predetermined amount of the above catalyst was charged into a stainless steel reaction tube having an inner diameter of 20 mm. A predetermined amount of dimethyl ether, steam and / or carbon dioxide was supplied to the reaction tube and reacted at a predetermined temperature.
【００２８】以上の操作により得られた反応生成物およ
び未反応物はガスクロマトグラフにより分析した。The reaction products and unreacted products obtained by the above operations were analyzed by gas chromatography.
【００２９】III．反応条件および実験結果 反応条件および実験結果を表１、２に示す。III. Reaction conditions and experimental results Reaction conditions and experimental results are shown in Tables 1 and 2.
【００３０】[0030]
【数１】 (Equation 1)
【００３１】[0031]
【数２】 (Equation 2)
【００３２】[0032]
【数３】 (Equation 3)
【００３３】[0033]
【数４】 各速度の単位は全て [ｍｏｌ／ｇ−ｃａｔ・ｈ](Equation 4) All units of each speed are [mol / g-cat · h]
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】本発明の合成ガス製造用触媒は、塩基性
を有する金属酸化物にパラジウムを担持させることによ
って、また本発明の合成ガス製造用触媒の製造方法は、
合成ガス製造用触媒を製造するにあたり、塩基性を有す
る金属酸化物にパラジウムを担持させた後、塩基性の水
溶液で処理することによって、高い合成ガス収率を得る
ことができる効果を有する。The catalyst for syngas production according to the present invention is obtained by supporting palladium on a basic metal oxide.
In producing a synthesis gas production catalyst, palladium is supported on a basic metal oxide and then treated with a basic aqueous solution, thereby providing an effect of obtaining a high synthesis gas yield.
【００３７】また、本発明の合成ガスの製造方法は、ジ
メチルエーテルと水蒸気および／または二酸化炭素の混
合ガスを、２００〜６００℃の低温で、塩基性を有する
金属酸化物にパラジウムを担持させた触媒と接触させる
ことによって、高い合成ガス収率を得ることができる効
果を有する。The method for producing a synthesis gas of the present invention is characterized in that a mixed gas of dimethyl ether and water vapor and / or carbon dioxide is used at a low temperature of 200 to 600 ° C. to support palladium on a basic metal oxide. By contacting with, there is an effect that a high synthesis gas yield can be obtained.
フロントページの続き (72)発明者 戸村 啓二 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内 (72)発明者 井上 紀夫 東京都千代田区丸の内一丁目１番２号 日 本鋼管株式会社内Continued on the front page (72) Inventor Keiji Tomura 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Inventor Norio Inoue 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Stock In company
Claims (3)
を担持させた、ジメチルエーテルと水蒸気または二酸化
炭素から合成ガスを生成させる触媒1. A catalyst in which palladium is supported on a basic metal oxide and which produces a synthesis gas from dimethyl ether and water vapor or carbon dioxide.
り、塩基性を有する金属酸化物にパラジウムを担持させ
た後、塩基性水溶液で処理することを特徴とする合成ガ
ス製造用触媒の製造方法2. A method for producing a catalyst for syngas production, comprising: producing palladium on a basic metal oxide and treating with a basic aqueous solution in producing the catalyst according to claim 1.
たは二酸化炭素を含有する混合ガスに請求項１記載の触
媒を接触させることを特徴とする合成ガスの製造方法3. A method for producing a synthesis gas, comprising contacting the catalyst according to claim 1 with a mixed gas containing dimethyl ether and at least water vapor or carbon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33975796A JP3613539B2 (en) | 1996-12-19 | 1996-12-19 | Catalyst for producing synthesis gas, method for producing the same, and method for producing synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33975796A JP3613539B2 (en) | 1996-12-19 | 1996-12-19 | Catalyst for producing synthesis gas, method for producing the same, and method for producing synthesis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10174865A true JPH10174865A (en) | 1998-06-30 |
| JP3613539B2 JP3613539B2 (en) | 2005-01-26 |
Family
ID=18330524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33975796A Expired - Fee Related JP3613539B2 (en) | 1996-12-19 | 1996-12-19 | Catalyst for producing synthesis gas, method for producing the same, and method for producing synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3613539B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999017875A1 (en) * | 1997-10-07 | 1999-04-15 | Nkk Corporation | Catalyst for producing hydrogen or synthesis gas and method of producing hydrogen or synthesis gas |
| JP2000000466A (en) * | 1998-04-17 | 2000-01-07 | Nkk Corp | Catalyst for production of synthetic gas and production of synthetic gas |
| JP2005510437A (en) * | 2001-11-29 | 2005-04-21 | ウィスコンシン アルムニ リサーチ ファウンデイション | Low temperature hydrogen production from oxidized hydrocarbons. |
| JP2006027949A (en) * | 2004-07-15 | 2006-02-02 | Electric Power Dev Co Ltd | Method of using carbon oxide-containing gas |
| JP2007091513A (en) * | 2005-09-28 | 2007-04-12 | Toshiba Corp | Hydrogen generator and fuel cell system |
| JP2008239485A (en) * | 2001-11-29 | 2008-10-09 | Wisconsin Alumni Research Foundation | Low-temperature hydrogen production from oxygenated hydrocarbons |
-
1996
- 1996-12-19 JP JP33975796A patent/JP3613539B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999017875A1 (en) * | 1997-10-07 | 1999-04-15 | Nkk Corporation | Catalyst for producing hydrogen or synthesis gas and method of producing hydrogen or synthesis gas |
| JP2000000466A (en) * | 1998-04-17 | 2000-01-07 | Nkk Corp | Catalyst for production of synthetic gas and production of synthetic gas |
| JP2005510437A (en) * | 2001-11-29 | 2005-04-21 | ウィスコンシン アルムニ リサーチ ファウンデイション | Low temperature hydrogen production from oxidized hydrocarbons. |
| JP2008239485A (en) * | 2001-11-29 | 2008-10-09 | Wisconsin Alumni Research Foundation | Low-temperature hydrogen production from oxygenated hydrocarbons |
| JP2006027949A (en) * | 2004-07-15 | 2006-02-02 | Electric Power Dev Co Ltd | Method of using carbon oxide-containing gas |
| JP2007091513A (en) * | 2005-09-28 | 2007-04-12 | Toshiba Corp | Hydrogen generator and fuel cell system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3613539B2 (en) | 2005-01-26 |
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