JPS6045537A - Production of oxygen-containing organic compound - Google Patents
Production of oxygen-containing organic compoundInfo
- Publication number
- JPS6045537A JPS6045537A JP58151633A JP15163383A JPS6045537A JP S6045537 A JPS6045537 A JP S6045537A JP 58151633 A JP58151633 A JP 58151633A JP 15163383 A JP15163383 A JP 15163383A JP S6045537 A JPS6045537 A JP S6045537A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- oxygen
- nitrate
- containing organic
- aqueous solution
- 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
【発明の詳細な説明】
本発明は含酸素有機化合物の製造方法に関し、詳しくは
特定の触媒を用いて一酸化炭素および水素から高い選択
率および転化率で効率良（含酸素有機化合物を製造する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an oxygen-containing organic compound, and more specifically, a method for producing an oxygen-containing organic compound from carbon monoxide and hydrogen with high selectivity and conversion rate using a specific catalyst. Regarding the method.
従来より、−酸化炭素および水素の混合ガスいわゆる合
成ガスを転化して工業上重要なメタノール、エタノール
、インブタノールなどのアルコールやジメチルエーテル
、ギ酸メチルなどの含酸素有機化合物を製造する方法は
種々知られている。Conventionally, various methods have been known for converting a mixed gas of carbon oxide and hydrogen, so-called synthesis gas, to produce industrially important alcohols such as methanol, ethanol, and inbutanol, and oxygen-containing organic compounds such as dimethyl ether and methyl formate. ing.
例ｔば、銅／コバルト／クロム、鉄、バナジウムあるい
はマンガン／アルカリ金属系の触媒を用いる方法（特開
昭５５−１４１４２０号公報）、ニッケル／アルカリ金
属アルコキシド系触媒を用いる方法（特開昭５６−１６
９３４号公報）、銀、金あるいはレニウム／コバルト系
触媒を用いる方法（特開昭５６−２５１２４号公報）、
銅／コバルトあるいは鉄／亜船、アルカリ金属あるいは
アルカリ土類金属系触媒を用いる方法（米国特許第４，
１２２，１１０号明細書）、ロジウム／マグネシウム系
触媒を用いる方法（特開昭５４−１４１７０５号公報）
等が挙げられる。For example, a method using a copper/cobalt/chromium, iron, vanadium or manganese/alkali metal catalyst (Japanese Unexamined Patent Publication No. 55-141420), a method using a nickel/alkali metal alkoxide catalyst (Japanese Unexamined Patent Application Publication No. 56/1986) -16
934), a method using a silver, gold or rhenium/cobalt catalyst (Japanese Unexamined Patent Publication No. 56-25124),
Methods using copper/cobalt or iron/submarine, alkali metal or alkaline earth metal catalysts (U.S. Pat. No. 4,
122,110), a method using a rhodium/magnesium catalyst (Japanese Unexamined Patent Publication No. 141705/1983)
etc.
しかしながら、これら従来の方法はいずれも転化率１選
択率、触媒の寿命、経済性、操作性等の全てＫわたって
、満足できるものではなく、実用上様々な問題があった
。However, none of these conventional methods are satisfactory in terms of conversion ratio, selectivity, catalyst life, economy, operability, etc., and have various practical problems.
そこで、本発明者らは、合成ガスから含酸素有機化合物
を製造するにあたって、転化率１選択率が高く、触媒の
寿命も長く、経済性、操作性等の良好な方法を開発すべ
く研究を行なった結果、特定の触媒を用いると目的が達
せられることを見い出し本発明を完成した。Therefore, the present inventors conducted research to develop a method with high conversion rate 1 selectivity, long catalyst life, and good economic efficiency and operability in producing oxygen-containing organic compounds from synthesis gas. As a result, they discovered that the purpose could be achieved by using a specific catalyst, and completed the present invention.
すなわち、本発明は（３）銅、亜鉛とより−ｘｉ−銀の
うちから選ばれた１種の元素（以下、（４）成分という
。）、（Ｉ３）周期律表第■族から選ばれた１ｆｉ４以
上の元素（以下、（］３）成分という。）および（ａ）
周期律表第１ＩＡ族から選ばれた１種以上の元素（以下
、（０）成分という。）を含有する触媒の存在下、−酸
化炭素および水素を反応させることを特徴とする含酸素
有機化合物の製造方法を提供するものである。That is, the present invention provides (3) one element selected from copper, zinc, and -xi-silver (hereinafter referred to as (4) component), and (I3) an element selected from Group Ⅰ of the periodic table. (hereinafter referred to as (]3) component) and (a)
An oxygen-containing organic compound characterized by reacting -carbon oxide and hydrogen in the presence of a catalyst containing one or more elements selected from Group 1IA of the Periodic Table (hereinafter referred to as component (0)). The present invention provides a method for manufacturing.
本発明に使用する触媒は（４）、■）および（Ｃ）成分
を含有する触媒である。The catalyst used in the present invention is a catalyst containing components (4), (2) and (C).
ここで（４）成分は銅、亜鉛あ゛よび〆銀から選ばれた
１種の元素であって、触媒の調製にあたってはこれらの
金属および金属の任意の化合物を用い得る。特に水溶性
の化合物が好ましく、例えば硝酸銅、硝酸亜鉛、硝酸銀
、硫酸銅、硫酸亜鉛、硫酸銀、塩化銅、酢酸銅、塩化亜
鉛、酢酸亜鉛などが挙げられる。Component (4) is one element selected from copper, zinc and silver, and any metal or compound of these metals may be used in preparing the catalyst. Particularly preferred are water-soluble compounds, such as copper nitrate, zinc nitrate, silver nitrate, copper sulfate, zinc sulfate, silver sulfate, copper chloride, copper acetate, zinc chloride, zinc acetate, and the like.
■）成分は周期律表第■族金属から選はれたｌ （Ｈｐ
以上の元素であって、具体的には鉄。ニッケル。■) Ingredients are selected from Group ■ metals of the periodic table (Hp
The above elements, specifically iron. nickel.
コバルト、ルテニウム、ロジウム、バラジウ１１あるい
は白金などであり、これらを単独であるいは混合して用
いる。触媒の調製にあたっては囚成分同様、上記金属お
よび金属の任意の化合物を用い得るが、とりわけ水溶性
の化合物が好ましく例えば硝酸ニッケル、硝酸コバルト
、硝酸鉄などが誉げられる。Cobalt, ruthenium, rhodium, baladium-11, platinum, etc. are used alone or in combination. In preparing the catalyst, any of the metals and metal compounds mentioned above can be used as well as the prisoner component, but water-soluble compounds are particularly preferred, such as nickel nitrate, cobalt nitrate, iron nitrate, and the like.
さらに（０）成分は周期律表第１１Ａ族の元素から選ば
れた１ｎｉ以上の元素であって、具体的にはベリリウム
、マグネシウム、カルシウム、ストロンチウム、バリウ
ムなどであり、これらを単独であるいは混合して用いる
。触媒の調製にあたって」二記金属および金属の化合物
であれば／ｌ寺に制限な（用いることができ、特に水溶
性化合物、例えば硝酸バリウム、硝酸カルシウム、硝酸
マグネシウム等が好ましい。Furthermore, component (0) is an element of 1ni or more selected from the elements of Group 11A of the periodic table, specifically beryllium, magnesium, calcium, strontium, barium, etc., and these may be used alone or in combination. used. In the preparation of the catalyst, any metal or metal compound may be used without any limitation, and water-soluble compounds such as barium nitrate, calcium nitrate, magnesium nitrate, etc. are particularly preferred.
本発明に用いる触媒の調製は各種の方法によることがで
きるが、一般にはまず上記（５）、φ）および（Ｃ）成
分を含有する化合物を混合し、焼成すればよい。The catalyst used in the present invention can be prepared by various methods, but in general, compounds containing the above components (5), φ) and (C) are mixed and calcined.
これら（４）、ω）および（Ｃ）成分の化合物を混合す
るには、各化合物を水に加えて水溶液あるいは水性懸濁
液として、室温あるいは加温しながら炭酸ナトリウム、
水酸化ナトリウムあるいは水酸化カリウム等の共沈剤を
加えて、ｐＨ調整して沈澱を生成せしめる共沈法が好ま
しい。共沈法で得られた沈澱物を必要に応じて熟成し、
水洗後８０〜１５０℃で２〜２４時間乾燥しさらに２０
０〜５００°Ｃ１好ましくは２５０〜３５０℃で１〜４
０時間、好ましくは２〜１０時間で焼成を行なう。冷却
後、グラファイトなどを添加して成形することにより、
目的とする触媒あるいはその前駆体が得られる。To mix the compounds of components (4), ω) and (C), add each compound to water to form an aqueous solution or suspension, add sodium carbonate,
A coprecipitation method in which a coprecipitant such as sodium hydroxide or potassium hydroxide is added to adjust the pH and form a precipitate is preferred. The precipitate obtained by the coprecipitation method is aged as necessary,
After washing with water, dry at 80-150℃ for 2-24 hours and then dry for 20 minutes.
0-500°C1 preferably 1-4 at 250-350°C
Firing is carried out for 0 hours, preferably 2 to 10 hours. After cooling, by adding graphite etc. and molding,
The desired catalyst or its precursor can be obtained.
なお、各化合物の混合方法としては共沈法のほかにｒ、
Ｐ￥！法などが適用でき、また合金を用いても良い。In addition to the coprecipitation method, methods for mixing each compound include r,
P¥! A method such as a method can be applied, and an alloy may also be used.
次いで、得られた触媒あるいはその前駆体は、そのまま
利用することもできるが、通常はこれらをさらに水素、
−酸化炭素あるいは水素および一酸化炭素などの還元雰
囲気下で２００〜５００’Ｃで２〜５０時間、好ましく
は５〜２０時間処理する。ここで還元雰囲気として水素
、−酸化炭素等に不活性ガスを加え希釈したものを用い
てもよい。Next, the obtained catalyst or its precursor can be used as it is, but it is usually further treated with hydrogen or hydrogen.
- Treatment under a reducing atmosphere such as carbon oxide or hydrogen and carbon monoxide at 200-500'C for 2-50 hours, preferably 5-20 hours. Here, hydrogen, carbon oxide, etc. diluted with an inert gas may be used as the reducing atmosphere.
以上のようにして、本発明の方法に用いる触媒が得られ
るが、この触媒における■、（Ｂ）および（Ｃ）成分の
含有量は特に制限はないが１通常（４）・（Ｂ）：（０
）＝０．０１〜０．７５ ： ０．０１〜０．７５ ：
０，０１〜０．７５ （モル比）、好ましくは０．２
〜０．６ ： ０．１〜０，４ ： Ｑ、１〜０．５（
モル比）とすべきである。In the manner described above, a catalyst used in the method of the present invention is obtained, and the contents of components (1), (B), and (C) in this catalyst are not particularly limited, but are usually (4) and (B): (0
)=0.01~0.75: 0.01~0.75:
0.01-0.75 (molar ratio), preferably 0.2
~0.6: 0.1~0,4: Q, 1~0.5(
molar ratio).
（４）成分の含有量が０．７５を越えると炭素数２以上
の含酸素化合物の側合が減少し、０．０１未満ではメタ
ンが増加する。Ｃｌ５）成分の含有量が０．７５を越え
るとメタンが増加し、０．０１未満ではメタノールが増
加して好ましくない。（０）成分の含有量が０．７５を
越えると含酸素有機化合物への転化率が低下し、また０
、０１未満では炭素数２以上の含酸素有機化合物の選択
率が低下する。When the content of the component (4) exceeds 0.75, the amount of oxygen-containing compounds having 2 or more carbon atoms decreases, and when it is less than 0.01, methane increases. If the content of the Cl5) component exceeds 0.75, methane will increase, and if it is less than 0.01, methanol will increase, which is not preferable. When the content of component (0) exceeds 0.75, the conversion rate to oxygen-containing organic compounds decreases, and
, less than 01, the selectivity of oxygen-containing organic compounds having 2 or more carbon atoms decreases.
本発明の方法はこのようにして得られた触媒を用いて、
−酸化炭素および水素より、含酵素有機化合物を製造す
ることである。ここで、原料として用いる合成ガスの組
成は特に制限はないが、一般に水素／−σ？化炭素のモ
ル比として１／１０〜１（１好ましくば１／３〜３の範
囲のガスが好適である。The method of the present invention uses the catalyst thus obtained,
-Producing enzyme-containing organic compounds from carbon oxide and hydrogen. Here, the composition of the synthesis gas used as a raw material is not particularly limited, but generally hydrogen/-σ? A gas having a molar ratio of 1/10 to 1 (1 preferably 1/3 to 3) is suitable.
また、本発明の方法の他の条件は、各種状況により適宜
選択すれば良く、特に制限はないが通常反応温度２００
〜５００℃、好ましくは２４０〜４００”Ｃ１反応圧力
１０−５００ ｋＦ！／ｃｎＬ２・Ｇ、好ましくは２０
〜２００ｋｇ＾２・Ｇ、ガス空間速度（ＧＪ（ＳＶ ）
５００〜１０００００ ｈｒ ’、好ましくは１００
０〜５００００ｈｒ、’の範囲とすべきである。Further, other conditions for the method of the present invention may be appropriately selected depending on various situations, and are not particularly limited, but usually the reaction temperature is 200 m
~500°C, preferably 240-400” C1 reaction pressure 10-500 kF!/cnL2·G, preferably 20
~200kg^2・G, gas space velocity (GJ(SV)
500-100000 hr', preferably 100
It should be in the range of 0 to 50,000 hr.
上記の如き本発明の方法によれば、メタノール。According to the method of the invention as described above, methanol.
エタノール、プロパツール、ブタノールなどのアルコー
ル、ジメチルエーテルあるいはギ酸メチルなどの各滑化
学製品の原料あるいは燃料などに有用な含酸素有機化合
物が効率良く得られる。竹に炭素数２以上のアルコール
の選択率が従来の方法より非常に高い。また、用いる触
媒の成分数が少なく、しかもアルカリ金属等を用いない
ため、触媒の製造工程も短縮され、触媒コストが安価で
ありそのうえ長寿命である。したがって、経済的にもき
わめて、有効な方法である。Oxygen-containing organic compounds useful as raw materials or fuels for various chemical products such as alcohols such as ethanol, propatool, and butanol, dimethyl ether, and methyl formate can be efficiently obtained. The selectivity of alcohols having 2 or more carbon atoms to bamboo is much higher than that of conventional methods. In addition, since the number of components of the catalyst used is small and no alkali metal or the like is used, the manufacturing process of the catalyst is shortened, the cost of the catalyst is low, and it has a long life. Therefore, it is an extremely effective method economically.
以上の如く、本発明は化学工業士きわめて有用である。As described above, the present invention is extremely useful to chemical engineers.
次に本発明を実施例によりさらに詳しく説明する。Next, the present invention will be explained in more detail with reference to Examples.
製造例１（触媒前１駆体の製造）
硝酸銅（３水塩） ３２．２９、硝酸ニッケル（６水塩
）９．７２および硝酸バリウム（無水） ３４．８９を
含む第２水溶液１．５１を９０°Ｃに加温し、これに９
０°Ｃに加温した炭酸ナトリウム（漁〔水）３７．１り
を含む第２水溶液１．５１を加え、激１． ＜攪拌しな
がら２時間９０℃に保った。Production Example 1 (Production of Catalyst Precursor 1) Second aqueous solution containing copper nitrate (trihydrate) 32.29, nickel nitrate (hexahydrate) 9.72 and barium nitrate (anhydrous) 34.89 1.51 Warm to 90°C and add 9
Add 1.5 l of a second aqueous solution containing 37.1 l of sodium carbonate (fish water) heated to 0°C, and add 1.5 l of a second aqueous solution containing 37.1 l of sodium carbonate (water). <Kept at 90°C for 2 hours while stirring.
次いでｐ過し共沈物のナトリウムが実質的に検知できな
くなるまで、すなわち酸化す） ＩＪウムとして０．１
重量％塀下となるまで水洗した。次いで、この沈澱物を
１２０°Ｃで５時間乾燥し、さらに４５０°Ｃで２時間
焼成した。冷却後、グラファイト２重量％を添加し、打
錠成形し、粉砕して１６メツシユは通過するが３２メツ
シユは通過しないようふるいわけることにより、触媒前
駆体が２３．０９得られた。これを触媒前駆体Ａとする
、製造例２
製造例１において、第１水溶液として硝酸銅（３水塩）
３２．２９、硝酸ニッケル（６水塩）２９．１９およ
び硝酸バリウム（無水） １７．４９を含む水溶液１．
５１を用いたこと以外は、製造例１と同様にして触媒前
駆体２４．２９を得た。これを触媒前駆体Ｂとする。It is then filtered until the sodium in the coprecipitate becomes virtually undetectable, i.e. oxidized) 0.1 as IJum.
It was washed with water until the weight percentage was below the wall. This precipitate was then dried at 120°C for 5 hours and further calcined at 450°C for 2 hours. After cooling, 2% by weight of graphite was added, the mixture was compressed into tablets, crushed, and sieved to allow 16 meshes to pass through but not 32 meshes, yielding 23.09 grams of a catalyst precursor. Production Example 2 This is used as catalyst precursor A. In Production Example 1, copper nitrate (trihydrate) is used as the first aqueous solution.
32.29, nickel nitrate (hexahydrate) 29.19 and barium nitrate (anhydrous) 17.49.
Catalyst precursor 24.29 was obtained in the same manner as in Production Example 1 except that 51 was used. This will be referred to as catalyst precursor B.
製造例３
製造例１において、第１水溶液として硝酸銅（３水塩）
２９．１９、硝酸ニッケル（６水塩）１７．５９およ
び硝酸カルシウム（４水塩） ２８．３を含む水溶液１
．５１を用いたこと以外は製造例１と同様にして触媒前
駆体２０．３９を得た。これを触媒前駆体Ｃとする。Production Example 3 In Production Example 1, copper nitrate (trihydrate) was used as the first aqueous solution.
Aqueous solution 1 containing 29.19, nickel nitrate (hexahydrate) 17.59 and calcium nitrate (tetrahydrate) 28.3
．． Catalyst precursor 20.39 was obtained in the same manner as in Production Example 1 except that 51 was used. This will be referred to as catalyst precursor C.
製造例４
製造例１において、第１水溶液として硝酸銅（３水塩）
２９．１９、硝酸ニッケル（６水塩）１７．５９およ
び硝酸マグネシウム（６水塩） ３０−９りを含む水溶
液１．５１を用いたことおよび第２水溶液とし゛Ｃ炭酸
ナトリウム（無水）３４，５りを含む水溶液１．５１を
用いたこと以外は、製造例１と同様にして触媒前駆体を
１９．５ｆｉ’得た。これを触媒前駆体りとする。Production Example 4 In Production Example 1, copper nitrate (trihydrate) was used as the first aqueous solution.
29.19, using an aqueous solution 1.51 containing nickel nitrate (hexahydrate) 17.59 and magnesium nitrate (hexahydrate) 30-9, and as the second aqueous solution {C sodium carbonate (anhydrous) 34.5 A catalyst precursor of 19.5 fi' was obtained in the same manner as in Production Example 1, except that 1.51 fi' of an aqueous solution containing 1. This is referred to as a catalyst precursor.
製造例５
製造例１において、第１水溶液として硝酸銅（３水塩）
２９．０ ｇ、硝酸コバルト（６水堵）１７．５９お
よび硝酸バリウム（無水） ３１．４りを含む水溶液１
．５４を用いたことおよび第２水溶液として炭酸ナトリ
ウム（無水） ３４．５りを含む水溶液１．５４を用い
たこと以外は製造例１と同様にして触媒前駆体２２’、
９９を得た。これを触媒前駆体Ｅとする。Production Example 5 In Production Example 1, copper nitrate (trihydrate) was used as the first aqueous solution.
An aqueous solution 1 containing 29.0 g, 17.59 g of cobalt nitrate (6 hydrate) and 31.4 g of barium nitrate (anhydrous)
．． Catalyst precursor 22',
I got 99. This will be referred to as catalyst precursor E.
製造例６
製造例１において、第１水溶液として硝酸亜鉛（６水塩
） ３５．８９、硝酸ニッケル（６水塩）１７．５９お
よび硝酸マグネシウム（６水塩）３０．９りを含む水溶
液１．５１を用いたことおよび第２水溶液として炭酸ナ
トリウム（無水） ３５．７りを庁む水溶液１．５１を
用いたこと以外は製造例１と同様にして触媒前駆体１９
．３りを得た。これを触媒前駆体Ｆとする。Production Example 6 In Production Example 1, an aqueous solution 1 containing 35.89% of zinc nitrate (hexahydrate), 17.59% of nickel nitrate (6hydrate), and 30.9% of magnesium nitrate (6hydrate) was used as the first aqueous solution. Catalyst precursor 19 was prepared in the same manner as in Production Example 1, except that 51 was used and an aqueous solution 1.51 containing sodium carbonate (anhydrous) 35.7 was used as the second aqueous solution.
．． I got 3 points. This will be referred to as catalyst precursor F.
製造例７
製造例Ｉにおいて、第１水溶液として硝酸亜鉛（６水塩
） ３５，８９、硝酸コバルト（６水塩）１７．５７お
よび硝酸カルシウム（４水塩） ２８．３りを含む水溶
液１．５１を用いたことおよび第２水溶液として炭酸ナ
トリウム（無水） ３６．９９を含む水溶７Ｉ’ｉ １
．５ Ａ’を用いたこと以外は製造例１と同様にして触
媒前１駆体１８．９９を得た。これを触媒前駆体Ｇとす
る。Production Example 7 In Production Example I, the first aqueous solution was an aqueous solution containing 35.89% of zinc nitrate (hexahydrate), 17.57% of cobalt nitrate (6hydrate), and 28.3% of calcium nitrate (tetrahydrate). Aqueous solution 7I'i 1 containing 51 and sodium carbonate (anhydrous) 36.99 as the second aqueous solution
．． 18.99 of a catalyst precursor 1 was obtained in the same manner as in Production Example 1 except that 5A' was used. This will be referred to as catalyst precursor G.
製造例８
製造例１において第１水溶液として硝酸銀（無水） ２
０．４９、硝酸ニッケル（６水塩） １７，５りおよび
硝酸バリウム（無水）３１．４りを含む水溶液１．５４
を用いたことおよび第２水溶液として炭酸す） ＩＪウ
ム（無水） ３４，８りを含む水溶液１．５１を用いた
こと以外は製造例１と同様にして触媒前駆体２４．６９
を得た。これを触媒前駆体Ｈとす実施例１〜８
（１１触媒の調製
第１表に示す触媒前駆体をステンレス製反応管にｌ ｍ
ｌ充填し、ＣＯ／／Ｎ２＝ｌ／９（モル比）のガスを０
月５Ｖ４０００ｈｒ−”で流しながら徐々に温度を上げ
、２４０℃にて第１表に示す反応時間処理して触媒を得
た。Production Example 8 Silver nitrate (anhydrous) 2 as the first aqueous solution in Production Example 1
An aqueous solution containing 0.49, 17.5 of nickel nitrate (hexahydrate) and 31.4 of barium nitrate (anhydrous) 1.54
Catalyst precursor 24.69 was prepared in the same manner as in Production Example 1, except that 1.51 aq.
I got it. This was used as catalyst precursor H. Examples 1 to 8 (11 Preparation of catalyst The catalyst precursor shown in Table 1 was placed in a stainless steel reaction tube.
1 filled with gas of CO//N2=l/9 (molar ratio)
The temperature was gradually raised while flowing at 5 V 4000 hr-'', and the reaction was carried out at 240° C. for the reaction time shown in Table 1 to obtain a catalyst.
（２）含酸素有機化合物の製造
（１）テ得られた触媒の充填されたステンレス製反応管
にｃｏ７′ｎ＝ ＝ １／’２ （モル比）の原料ガス
をＧＴＩＳＶ４０００ｈｒ’で流し、徐々に昇温して６
１ｋｇ／／ｃ了２・にとし、−酸化炭素転化率がほぼ２
０％とブよるように第１表に示す温度にて反応を行ブ、
「った。(2) Production of oxygen-containing organic compounds (1) A raw material gas of co7'n = = 1/'2 (mole ratio) was passed through a stainless steel reaction tube filled with the obtained catalyst at a GTISV of 4000 hr', and gradually Raise the temperature 6
1 kg//c to 2.0 kg, the carbon oxide conversion rate is approximately 2.
The reaction was carried out at the temperature shown in Table 1 so that the temperature was 0%,
“It was.
得られた生成物はガス状のまま活性炭、ボラパックＱお
よびボラパックＮ’４充填したガスクロマトグラフに導
入した。結果を第１表に示す。なお、含酸素有機化合物
以外の転化物は炭化水素であり、主としてメタンであっ
た。The obtained product was introduced in a gaseous state into a gas chromatograph filled with activated carbon, Vorapac Q, and Vorapac N'4. The results are shown in Table 1. The converted products other than the oxygen-containing organic compound were hydrocarbons, mainly methane.
Claims (1)
１種の元素、山）周期律表第■族から選ばれた１種以上
の元素および（０周期律表第［Ａ族から選ばれた１種以
上の元素を含有する触媒の存在下、−酸化炭素および水
素を反応させることを特徴とする含酸素有機化合物の製
造方法。(11 (A) One or more elements selected from copper, zinc, silver, and silver) One or more elements selected from group Ⅰ of the periodic table and (0) 1. A method for producing an oxygen-containing organic compound, which comprises reacting -carbon oxide and hydrogen in the presence of a catalyst containing one or more elements selected from Group A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58151633A JPS6045537A (en) | 1983-08-22 | 1983-08-22 | Production of oxygen-containing organic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58151633A JPS6045537A (en) | 1983-08-22 | 1983-08-22 | Production of oxygen-containing organic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6045537A true JPS6045537A (en) | 1985-03-12 |
| JPH0456015B2 JPH0456015B2 (en) | 1992-09-07 |
Family
ID=15522804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58151633A Granted JPS6045537A (en) | 1983-08-22 | 1983-08-22 | Production of oxygen-containing organic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6045537A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62226933A (en) * | 1986-03-17 | 1987-10-05 | アンステイテユ・フランセ・デユ・ペトロ−ル | Catalytic production of primary alcohol mixture from synthetic gas |
| JPH04121549U (en) * | 1991-04-19 | 1992-10-30 | トキコ株式会社 | disc brake |
| JPH07133465A (en) * | 1993-11-08 | 1995-05-23 | Fuji Capsule Kk | Method of recovering gelatin in producing soft capsule product |
| US6080269A (en) * | 1997-05-06 | 2000-06-27 | Ohzeki; Fumiaki | Gelatine recovery device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348570C (en) * | 2004-10-26 | 2007-11-14 | 中国科学院长春应用化学研究所 | Method for catalytic oxidation preparation of methyl formate from methanol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441291A (en) * | 1977-09-09 | 1979-04-02 | Sagami Chem Res Center | Cluster fixed substance, production thereof and catalyst |
| JPS5444605A (en) * | 1977-09-12 | 1979-04-09 | Sagami Chem Res Center | Preparation of methanol |
| JPS56104828A (en) * | 1980-01-24 | 1981-08-20 | British Petroleum Co | Manufacture of oxidated hydrocarbon from synthesizing gas |
| JPS56123925A (en) * | 1980-01-31 | 1981-09-29 | Ici Ltd | Manufacture of ethylene glycol |
| JPS57109728A (en) * | 1980-12-26 | 1982-07-08 | Showa Denko Kk | Preparation of oxygen-containing hydrocarbon compound from synthetic gas |
| JPS57126434A (en) * | 1981-01-27 | 1982-08-06 | Mitsui Toatsu Chem Inc | Synthesis of methanol |
-
1983
- 1983-08-22 JP JP58151633A patent/JPS6045537A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5441291A (en) * | 1977-09-09 | 1979-04-02 | Sagami Chem Res Center | Cluster fixed substance, production thereof and catalyst |
| JPS5444605A (en) * | 1977-09-12 | 1979-04-09 | Sagami Chem Res Center | Preparation of methanol |
| JPS56104828A (en) * | 1980-01-24 | 1981-08-20 | British Petroleum Co | Manufacture of oxidated hydrocarbon from synthesizing gas |
| JPS56123925A (en) * | 1980-01-31 | 1981-09-29 | Ici Ltd | Manufacture of ethylene glycol |
| JPS57109728A (en) * | 1980-12-26 | 1982-07-08 | Showa Denko Kk | Preparation of oxygen-containing hydrocarbon compound from synthetic gas |
| JPS57126434A (en) * | 1981-01-27 | 1982-08-06 | Mitsui Toatsu Chem Inc | Synthesis of methanol |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62226933A (en) * | 1986-03-17 | 1987-10-05 | アンステイテユ・フランセ・デユ・ペトロ−ル | Catalytic production of primary alcohol mixture from synthetic gas |
| JPH07108862B2 (en) * | 1986-03-17 | 1995-11-22 | アンステイテユ・フランセ・デユ・ペトロ−ル | Process for catalytic production of first alcohol mixture from synthesis gas |
| JPH04121549U (en) * | 1991-04-19 | 1992-10-30 | トキコ株式会社 | disc brake |
| JPH07133465A (en) * | 1993-11-08 | 1995-05-23 | Fuji Capsule Kk | Method of recovering gelatin in producing soft capsule product |
| US6080269A (en) * | 1997-05-06 | 2000-06-27 | Ohzeki; Fumiaki | Gelatine recovery device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0456015B2 (en) | 1992-09-07 |
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