JPS61103545A - Silver catalyst for preparing ethylene oxide - Google Patents
Silver catalyst for preparing ethylene oxideInfo
- Publication number
- JPS61103545A JPS61103545A JP59224877A JP22487784A JPS61103545A JP S61103545 A JPS61103545 A JP S61103545A JP 59224877 A JP59224877 A JP 59224877A JP 22487784 A JP22487784 A JP 22487784A JP S61103545 A JPS61103545 A JP S61103545A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- silver
- ethylene oxide
- barium
- sodium
- 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】
〔産業上の利用分野〕
本発明は、エチレンを分子状酸素で酸化してエチレンオ
キシドを製造する方法に用いられる新規な銀触媒に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel silver catalyst used in a method for producing ethylene oxide by oxidizing ethylene with molecular oxygen.
エチレンを分子状酸素によ！７酸化してエチレンオキシ
ドを工業的に製造するのに用いられる実質上唯一の触媒
は銀触媒である。しかしながら、銀単独では必ずしも工
業触媒として完全ではなく種々の添加物を加えることに
より性能を向上させる努力がなされて−る。その中では
アルカリ金属を加えて性能を向上させている例が多い（
例えば特公昭５７−４８５５４号公告公報、特開昭５２
−１０８３９１号公開公報、特開昭５３−１１９１号公
開公報）が、その対イオンに特別の効果を認めているも
のは少なく、臭素などのハロゲンはむしろ銀の被毒物と
して除外されている例も多い。Convert ethylene to molecular oxygen! Virtually the only catalyst used to industrially produce ethylene oxide by oxidation is a silver catalyst. However, silver alone is not necessarily perfect as an industrial catalyst, and efforts are being made to improve its performance by adding various additives. Among them, there are many examples of adding alkali metals to improve performance (
For example, Japanese Patent Publication No. 57-48554, Japanese Patent Application Publication No. 52
-108391, Japanese Patent Application Laid-Open No. 1191/1983), there are few cases in which the counterions have a special effect, and in some cases halogens such as bromine are excluded as poisonous substances of silver. many.
しかるに、アニオン成分について特別な効果を認める考
え方が最近現われたう
例えば、特開昭５７−１４０６５４号及び同５７−１８
０４３４号公開公報には、従来被毒物と考えられてｈた
塩素、臭素等のアニオンも、適当なカチオンと組合せる
ことによシ、即ち、特定のカチオンとアニオンとの組合
せを選ぶことにより予期に反して触媒の性能が大巾に向
上することが述べられてｈる。However, a concept that recognizes special effects for anion components has recently appeared, for example, in JP-A-57-140654 and JP-A-57-18.
Publication No. 0434 states that anions such as chlorine and bromine, which were conventionally considered to be poisonous substances, can also be treated by combining them with appropriate cations, that is, by selecting a combination of a specific cation and anion. On the contrary, it has been stated that the performance of the catalyst is greatly improved.
しかしながら、か＼る触媒系についてもより一層の性能
向上が望まれており、また、頁料ガス中に含まれる硫黄
による触媒の被毒の問題も残されている。However, further improvement in the performance of such catalyst systems is desired, and the problem of poisoning of the catalyst by sulfur contained in the paging gas remains.
本発明者等は、先に出願した、銀の他に、カチオン成分
としてナトリウム及びセシウムを、アニオン成分として
塩素及び／又は臭素及び／又は弗素を含有する触媒に対
して、釘にアルカリ土類金属のバリウムを組合せること
により、触媒ｏ性能が著しく向上し、且つ実用上問題と
なる原料ガス中に含まれる硫黄による触媒の被毒が回避
されることを見り出し、本発明を完成するに至った。The present inventors have previously applied for a catalyst containing sodium and cesium as cationic components and chlorine and/or bromine and/or fluorine as anionic components in addition to silver. It was discovered that the catalyst o performance was significantly improved and the poisoning of the catalyst caused by sulfur contained in the raw material gas, which was a practical problem, was avoided by combining barium. It's arrived.
即ち、本発明は、
＋１１！＋レンを分子状酸素で酸化してエチレンオキシ
ドを製造するための触媒であって、該触媒は銀ノ他’Ｉ
Ｃ、カチオン成分としてナトリウム、セシウム及びバリ
ウムを、アニオン成分として塩素及び／又は臭素及び／
又は弗素を、少なくとも含有することを特徴とする触媒
である。That is, the present invention has +11! A catalyst for producing ethylene oxide by oxidizing ethylene with molecular oxygen, the catalyst comprising silver, etc.
C, sodium, cesium and barium as cationic components, chlorine and/or bromine and/or as anionic components;
Or a catalyst characterized by containing at least fluorine.
本発明の実施の態様を以下に説明する。ナトリウム化合
物は炭酸ナトリウム又は重炭酸ナトリウムの形で加える
ことが好ましい。もちろん水酸化物、硝酸塩、咀硝酸省
、カルボン酸塩又はハロゲン化物などの形で加えて４又
はこれらを炭酸ナトリウム、重炭酸ナトリウムと併用し
ても構わない。Embodiments of the present invention will be described below. Preferably, the sodium compound is added in the form of sodium carbonate or sodium bicarbonate. Of course, it may be added in the form of hydroxide, nitrate, nitrate, carboxylate, or halide, or these may be used in combination with sodium carbonate or sodium bicarbonate.
セシウム化合物としてはハロゲン化物が好ましいが、硝
酸塩、亜硝酸塩、炭酸塩、硫酸塩などの塩類、水酸化物
などの形で加えることも出来る。バリウム化合物として
は硝酸塩が好ましｂが、添加時に不溶性化合物を生成し
ないならば、炭酸塩、水酸化物、カルボン酸塩と）ロゲ
ン化物などの形で使用することも出来る。ハロゲン源と
しては上記ナトリウム、セシウム、バリウムとの塩の形
でも、他のリチウム、カリウム、ルビジウム、アンモニ
ウムなどの塩の形で加えてもよい。いずれにしても銀線
外にナトリウム、セシウム、バリウム及ヒハロゲンの添
加が必要でこれらを組合せた場合に触媒の性能が大巾に
向上する。The cesium compound is preferably a halide, but it can also be added in the form of salts such as nitrates, nitrites, carbonates, and sulfates, and hydroxides. As the barium compound, a nitrate is preferred, but it can also be used in the form of a carbonate, hydroxide, carboxylate, or logenide, provided that no insoluble compounds are formed during addition. The halogen source may be added in the form of a salt with the above-mentioned sodium, cesium, or barium, or in the form of another salt such as lithium, potassium, rubidium, or ammonium. In any case, it is necessary to add sodium, cesium, barium, and halogen in addition to the silver wire, and when these are combined, the performance of the catalyst is greatly improved.
ナトリウムの添加量は触媒に対して５０ｐｐｍ（キ／Ｋ
Ｉ！触媒）を越える量が好ましい。特に１１０００ｐｐ
以上１ ｗｔｌ 以下の範囲が好ましい。The amount of sodium added is 50 ppm (K/K) relative to the catalyst.
I! (catalyst) is preferred. Especially 11000pp
A range of 1 wtl or more is preferable.
ナトリウムが多すぎると活性、選択性共に低下し、少な
すぎる場合には本発明の触媒に比較］、て担体上のＡＰ
粒子の分散が悪くなることが走査型電子顕微鏡観察で認
められる触媒活性が低く、かつハロゲンを加えた効果が
充分に発現しない。If the sodium content is too large, both activity and selectivity will decrease; if the sodium content is too small, the AP on the carrier will decrease.
The catalytic activity is low as observed by scanning electron microscopy due to poor particle dispersion, and the effect of adding halogen is not fully expressed.
セシウムの添加量はナトリウムよりも少々−範囲が好適
で、触媒に対し１０ｐｐｍ以上０．５ ｗｔｅｌｒ以下
が好ましく、より好ましくけｉｓｐｐｍ以上、０．１ｗ
ｔ１以下である。多すぎると活性が順著に低下し、少な
すぎる場合にはハロゲンの効果が十分に現われない。The amount of cesium added is preferably a little more than that of sodium, preferably 10 ppm or more and 0.5 wtelr or less, and more preferably 10 ppm or more and 0.1 wtelr or more relative to the catalyst.
It is below t1. If the amount is too large, the activity will gradually decrease, and if it is too small, the effect of the halogen will not be sufficiently exhibited.
バリウムの添加量は１０ｐｐｍを越える量が好ましく
ｌ ｗｔ４以下である。特に好ましくは２０ｐｐｍ以上
、３０００ｐｐｍ以下である。少なすぎるとその効果が
なく、多すぎると含浸液中に沈殿物を生じたり、含浸工
穆が複雑になるなど実用面で問題がちや且つ活性が低く
なる。The amount of barium added is preferably over 10 ppm.
l wt4 or less. Particularly preferably, it is 20 ppm or more and 3000 ppm or less. If it is too small, it will not be effective, and if it is too large, it will tend to cause practical problems such as precipitation in the impregnation solution and complicate the impregnation process, and the activity will be low.
ハロゲンの添加量は触媒に対しｓｐｐｍ以上、ｏ、ｉ
ｗｔｃｓ以下が好適であ抄、より好ましくは７ｐｐｍ以
上、０．０７ ｗｔ４以下である。多く加えすぎると毒
作用を示し大巾な性能の低下を招く。すなわち本発明の
特竜は多量に加えると毒作用を示すハロゲンを、ナトリ
ウム、セシウム及びバリウムというカチオン成分と組合
せて微量加えることにより性能向上剤としての作用を見
出したことにある。The amount of halogen added is at least sppm to the catalyst, o, i
The content is preferably 7 ppm or more and 0.07 wt4 or less. If too much is added, it exhibits a toxic effect and results in a significant drop in performance. That is, the special feature of the present invention is that halogen, which is toxic when added in large amounts, has been found to act as a performance-improving agent by adding a small amount of halogen in combination with cationic components such as sodium, cesium, and barium.
また本発明の触媒においては、銀の他に添加されるカチ
オン成分は上記ナトリウム、セシウム及びバリウムのみ
に限定されるものではなく例えばリチウム、ルビジウム
、カリウム、タリウムなどが少竜添加されてもよい。Furthermore, in the catalyst of the present invention, the cationic components added in addition to silver are not limited to the above-mentioned sodium, cesium, and barium, and for example, lithium, rubidium, potassium, thallium, etc. may also be added.
上記触媒成分は、主として経済的及び触媒寿命の観点か
ら、担持触媒として使用される。担体としては多孔質耐
火物が用いられＢＢ’ｌ’表面積が０．１〜５−７２、
細孔容積が０．２ ｙｄ ／ ９以上のものが望まし１
．Ａが、特にａ−アルミナを主成分とするものが好まし
ｂｏ
ナトリウム、セシウム、バリウム及ヒハロゲンの担持は
前記した化合物を水性溶媒に溶解し、上記担体に含浸し
たあと窒素、空気、過熱スチームなどにより又はその存
在下加熱乾燥することにょり行なうのが好ましく減圧乾
燥も勿論採用できる。The abovementioned catalyst components are used as supported catalysts, primarily from the economic and catalyst life point of view. A porous refractory is used as the carrier, and the BB'l' surface area is 0.1 to 5-72,
It is desirable that the pore volume is 0.2 yd/9 or more1
．． A is particularly preferably one whose main component is a-alumina.Bo Sodium, cesium, barium, and hyhalogen are supported by dissolving the above-mentioned compounds in an aqueous solvent and impregnating the above-mentioned carrier with nitrogen, air, superheated steam, etc. It is preferable to carry out the drying by heating with or in the presence of a drying agent, and of course drying under reduced pressure can also be employed.
ナトリウム、セシウム、バリウム及びノーロゲンの担持
は同時でも別々に行なってもよく、かつ触媒調製の任意
の段階において種々の態様で行なうことが出来る。たと
えば銀化合物の含浸の前、同時又は後のいずれの時期の
ｂずれを採用しても差支えない。但し含浸液の均一性、
触媒の性能、工程の簡略化のために者も好ましいのけ、
ナ） １１ウム成分を前含浸し、バリウム、セシウム及
ヒハロゲンを銀化合物と同時に含浸するものである。The loading of sodium, cesium, barium and norogen may be carried out simultaneously or separately, and may be carried out in various manners at any stage of catalyst preparation. For example, the shift b may be adopted before, at the same time, or after the impregnation with the silver compound. However, the uniformity of the impregnating liquid,
Although it is preferable for the performance of the catalyst and the simplification of the process,
n) Pre-impregnation with the 11um component, and impregnation with barium, cesium and hyhalogen simultaneously with the silver compound.
担体に銀を担持せしめるには適当な形状、たとえば球状
、ペレット状、リング状に成型された担体を、銀の化合
物たとえば酸化銀、シュウ酸銀、又は乳酸銀などをアミ
ン類たとえば１．３−プロパンジアミン、エチレンジア
ミンなどの可溶化剤の存在下に溶解した水性溶液又は水
分散液に浸漬し、直接又は乾燥してから、過熱スチーム
、空気又は窒素などの不活性ガスにより又はその気流下
で加熱することによし行なうことが出来る。焼成温度は
通常１００〜１０００℃好ましくは１００〜３５０℃の
範囲である。触媒の銀担持ｔは通常１〜２５ ｗｔｌ、
好ましくは５〜１８ ｗｔチである。To support silver on a carrier, a carrier formed into an appropriate shape, such as a sphere, a pellet, or a ring, is mixed with a silver compound such as silver oxide, silver oxalate, or silver lactate, and an amine such as 1.3- Immersion in an aqueous solution or dispersion in the presence of a solubilizing agent such as propanediamine, ethylenediamine, etc., directly or after drying, and heating with or under a stream of superheated steam, air or an inert gas such as nitrogen. You can do good by doing. The firing temperature is usually in the range of 100 to 1000°C, preferably 100 to 350°C. The silver support t of the catalyst is usually 1 to 25 wtl,
Preferably it is 5 to 18 wt.
本発明の触媒を用いてエチレンをエチレンオキシドに転
喚する反応は慣用操作法で実施できる。The reaction of converting ethylene to ethylene oxide using the catalyst of the present invention can be carried out using conventional procedures.
例えば圧力は１〜３５Ｋｇ／、ｉ、温度は１８０〜３０
０℃、好ましくは２００〜２６０℃である。For example, the pressure is 1-35Kg/, i, the temperature is 180-30
The temperature is 0°C, preferably 200-260°C.
エチレンは１〜４０ ｖｏ１％、酸素は１〜２０ｖｏ７
憾で一般に希釈剤例えばメタンを一定割合例えば２０〜
７０ ｖｏＬ％で存在させることが好ましい。Ethylene is 1-40 vo1%, oxygen is 1-20 vo7
Unfortunately, it is common to use a diluent such as methane in a certain proportion, e.g.
Preferably it is present at 70 vol%.
酸素は空気の形態でまたは工業用酸素として供給してよ
い。反応改質剤として例えば塩化ビニルまたは２塩化エ
チレンを加えることにより触媒中にホットスポットの形
成が防止できかつ触媒の性能殊に選択性を大巾に改善で
きる。添加量としては数ｐｐｍ〜数ｔｏｐｐｍ程度が好
ましい。Oxygen may be supplied in the form of air or as industrial oxygen. By adding, for example, vinyl chloride or ethylene dichloride as reaction modifiers, the formation of hot spots in the catalyst can be prevented and the performance, particularly the selectivity, of the catalyst can be greatly improved. The amount added is preferably from several ppm to several top per million.
本発明の触媒は特に高活性であることが量大の〜
特徴であり、このため、例えば特開昭５２−１０８３９
１号公報の触媒に比べて約３０℃以上の低温で同一のエ
チレンオキシド生成速度を達成出来る。The catalyst of the present invention is characterized in large quantities by being particularly highly active.
Compared to the catalyst of Publication No. 1, the same ethylene oxide production rate can be achieved at a lower temperature of about 30° C. or higher.
従って、本発明の触媒については、使甲中の経時変化も
非常に少なく、その寿命も長くなっている。更に経時変
化のもう一つの要因である硫黄による被毒もバリウムの
添加により防止される。Therefore, the catalyst of the present invention undergoes very little change over time during use and has a long lifespan. Furthermore, poisoning by sulfur, which is another cause of deterioration over time, is also prevented by adding barium.
実施例Ｉ
ＮａｚＣＯ３２６，９ｆを水１０００ｔｄ！に溶解し、
α−アルミナ担体（８１？Ｘ３ｇＸ８のリング状。表面
積０．５Ｗ？／？、細孔容積０．４ｍＪ／ ｆ ｌ １
０００？を浸漬した。余分の液を切った後１４０℃の過
熱スチームで１５分轄燥した。Example I NazCO326,9f water 1000td! dissolved in
α-Alumina carrier (ring shape of 81?X3gX8.Surface area 0.5W?/?, pore volume 0.4mJ/f l 1
000? Soaked. After draining off the excess liquid, it was dried with superheated steam at 140°C for 15 minutes.
一方ＡｒＮ０ａ ２４８ ｆと修酸カリウム（ＫｚＣｚ
Ｏ＋。On the other hand, ArN0a 248 f and potassium oxalate (KzCz
O+.
ＨｚＯｌ １４ｓ ｆを各々ｌ ０００ｒｔｌの水に溶
解したき
後混合し水溶中６０℃に加熱して修酸銀の白色沈殿を得
た。涙過後蒸留水により沈殿を洗浄して沈殿物中のカリ
ウムを除いた。別に１，３−プロパンジアミン２１．７
ｆとエチレンジアミン７９．１９を水に溶解して水溶液
２００ｍ１を調製し、氷冷しながら上記修酸銀沈殿に少
量ずつ添加して銀−アミン溶液を調製した。これに硝酸
バリウム３．７８１？、塩化セシウム０．２３４ ｆを
加えた水溶液４０ｄを加えた後ロータリーエバポレータ
ー中に移し、ＮａｚＣＯ３を含浸後乾燥した前記の担体
を加えて回転下５０℃にて含浸操作を実施した。初期に
減圧し常圧に戻して５分後に取出し、２００℃の過熱ス
チームにて１０分間、２→ｍ／秒の流速で加熱し、触媒
を調製した。Ａｔの担持率は１３．５ ｗｔ憾であり、
Ｎａ Ｂａ％Ｃｓ及びＣｔの担持量はそれぞれ０．４
ｗｔ４．１７００１）ｐｍ、１５８１）ｐｍ及び４２ｐ
ｐｍであった。14s f of HzOl were each dissolved in 1,000 rtl of water, mixed, and heated to 60° C. in water to obtain a white precipitate of silver oxalate. After filtration, the precipitate was washed with distilled water to remove potassium in the precipitate. Separately 1,3-propanediamine 21.7
f and 79.19 ml of ethylenediamine were dissolved in water to prepare 200 ml of an aqueous solution, which was added little by little to the above silver oxalate precipitate while cooling on ice to prepare a silver-amine solution. Barium nitrate 3.781 for this? After adding 40 d of an aqueous solution containing 0.234 f of cesium chloride, the carrier was transferred to a rotary evaporator, and the above-mentioned carrier, which had been impregnated with NazCO3 and dried, was added thereto, and an impregnation operation was carried out at 50° C. under rotation. Initially, the pressure was reduced and returned to normal pressure, and after 5 minutes it was taken out and heated with superheated steam at 200°C for 10 minutes at a flow rate of 2→m/sec to prepare a catalyst. The loading rate of At is 13.5 wt,
The supported amounts of NaBa%Cs and Ct are each 0.4
wt4.17001)pm, 1581)pm and 42p
It was pm.
上記触媒を４〜９メツシユに砕き５ゴを内径２０醜の鋼
製反応間に充填し反応ガス（エチレン３０ｖｏｌ、 ％
、酸素Ｂｖｏｌｑ６、塩化ビニル２ ｐ９ｍｓ残り窒素
）ヲ１８Ｋｇ／ｃｎＧｃ７）加圧化８Ｖａ ｏ ｏ ｏ
ｈで通過させた。通過開始直後に活性が発現する。The above catalyst was crushed into 4 to 9 meshes, and 5 meshes were filled into a steel reaction chamber with an inner diameter of 20 mm, and the reaction gas (ethylene 30 vol, %
, oxygen Bvolq6, vinyl chloride 2p9ms remaining nitrogen) 18Kg/cnGc7) pressurization 8Va o o o
It passed at h. Activity is expressed immediately after passage begins.
浴温２１３℃で１週間反応後酸素転化率４０壬、エチレ
ンオキシドの選択率８１．６１を得た。反応後の触媒の
ＢＥＴ表面積は０．８０ｍ”／Ｓ’であった。After one week of reaction at a bath temperature of 213° C., an oxygen conversion rate of 40 gu and an ethylene oxide selectivity of 81.61 were obtained. The BET surface area of the catalyst after reaction was 0.80 m''/S'.
１．５ケ月の連続運転中に酸素転化率４０壬を保持する
ために浴温を２℃上昇させたが、選択率には資化は無か
った。During 1.5 months of continuous operation, the bath temperature was increased by 2° C. to maintain an oxygen conversion rate of 40 mm, but there was no assimilation of the selectivity.
実施例２
実施例１と同様な方法で、大型の装置を用いてｋＷ
１３．５ ｗｔ％、 ＮａＯ，４ｗｔ４、Ｂａ６７０
ｐ ｐ ｍ。Example 2 The same method as in Example 1 was used to generate kW using a large device.
13.5 wt%, NaO, 4wt4, Ba670
p p m.
ＣｓＣ５１５８１）ｐ及びＣＡ４０ｐｐｍを含有する触
媒１５に９を調製した。このうち１１Ｋｐを径３９．５
１、長さ１２ＦＦｌの鋼製反応器に充填し、反応ガス（
エチレン２４ ｖｏＬ％、酸素７，５ ｖｏｔ４、Ｈｚ
ｏｏ、５ｖｏｌ １４、ＣＯｚ １．８ ｖｏＬ％、２
塩化エチレン３ｐｐｍ残りＣＨ４）をｔａＫｐ／ｉＧの
加圧下５Ｖ４ｏｏｏｈ ”で通過させた。酸素転化率３
０係を得るように反応温度を制御して５ケ月運転した。Catalysts 15 to 9 containing CsC51581)p and 40 ppm CA were prepared. Of these, 11Kp has a diameter of 39.5
1. A steel reactor with a length of 12FFl is filled with a reaction gas (
Ethylene 24 voL%, oxygen 7.5 vot4, Hz
oo, 5vol 14, COz 1.8 vol%, 2
Ethylene chloride (3 ppm remaining CH4) was passed under the pressure of taKp/iG at 5V4oooh''.Oxygen conversion rate 3
The reaction temperature was controlled to obtain a zero coefficient, and the operation was continued for 5 months.
初期の反応温度は２１９℃、エチレンオキシド選択率は
８１．８係で５ケ月間で温度は数℃上昇したが選択率は
ほとんど資化がなかった。この触媒の一部を抜き出し硫
黄の蓄積量を測定したがａｓｐｐｍであり、水溶性テス
トなどの結果からこの硫黄はＢａＳＯ４を形成している
ものと推察される。本触媒が高い選択率を保持している
理由の一つは硫黄による銀の被毒がバリウムの添加によ
り阻止されていることにあると思われる。The initial reaction temperature was 219°C, and the ethylene oxide selectivity was 81.8 degrees.Although the temperature rose several degrees over 5 months, the selectivity was hardly assimilated. A portion of this catalyst was extracted and the amount of sulfur accumulated was measured, and it was found to be asppm, and from the results of water solubility tests, etc., it is inferred that this sulfur forms BaSO4. One of the reasons why this catalyst maintains a high selectivity is thought to be that poisoning of silver by sulfur is prevented by the addition of barium.
実施例３〜４
実施例１と同様な方法で、Ｂａ 添加量及びＢａ原料を
変えた触媒を調製した。実施例１と同じ方法で反応させ
た。その結果を第１表に示す。表中Ｔ４Ｇ 、 ８４Ｇ
は酸素転化率４０％のときの浴温（℃ｌと選択率（優）
である。Examples 3 to 4 Catalysts were prepared in the same manner as in Example 1, except that the amount of Ba added and the Ba raw material were changed. The reaction was carried out in the same manner as in Example 1. The results are shown in Table 1. T4G, 84G in the table
is the bath temperature (°Cl and selectivity (excellent) when the oxygen conversion rate is 40%)
It is.
第１表
この系でけＢａを少量添加しても活性、選択性が明らか
に向上する。Table 1 In this system, even if a small amount of Ba is added, the activity and selectivity are clearly improved.
実施例５
実施例１と同様の方法と装置を用いて実施例２と同一の
組成の触媒を調製した。この触媒を実施例１と同じ方法
で反応させた。その結果は第２表に示す。Example 5 A catalyst having the same composition as in Example 2 was prepared using the same method and apparatus as in Example 1. This catalyst was reacted in the same manner as in Example 1. The results are shown in Table 2.
比較例１〜５ 実施例１と同様な方法で各種の触媒を調製した。Comparative examples 1 to 5 Various catalysts were prepared in the same manner as in Example 1.
但し触媒加熱のための過熱スチームの温度は２２０℃で
あった。反応の結果を表２に示す。表中Ｔ４０゜８４０
は酸素転化率４０％のときの浴温但と選択率（チ）であ
る。However, the temperature of superheated steam for heating the catalyst was 220°C. The results of the reaction are shown in Table 2. T40°840 in the table
are the bath temperature and selectivity (h) when the oxygen conversion rate is 40%.
比較例６〜７
ハＩＪウム多量系触媒を調製した。バリウム量が多いと
銀−アミン溶液中に沈殿が生じるので同時含浸が不可能
である。比較例６では硝酸バリウムを、銀−アミン溶液
と同時ではなくそれ以前に、ＮａｚＣＯａ前含浸・乾燥
担体に浸漬し、１５０℃の過熱スチームで乾燥した点が
実施例１と異なる。Comparative Examples 6-7 High-IJium-rich catalysts were prepared. If the amount of barium is large, precipitation will occur in the silver-amine solution, making simultaneous impregnation impossible. Comparative Example 6 differs from Example 1 in that barium nitrate was immersed in the NazCOa pre-impregnated and dried carrier not simultaneously with the silver-amine solution, but before that, and dried with superheated steam at 150°C.
比較例７は、酢酸ナトリウムと硝酸バリウムをα−アル
ミナ担体に含浸乾燥した後に、銀−アミン溶液とＣｓＣ
１を同時含浸したものである。共に、上記以外は実施例
１と同様にして触媒を調製した。。In Comparative Example 7, after impregnating and drying an α-alumina support with sodium acetate and barium nitrate, a silver-amine solution and CsC
1 was impregnated at the same time. Both catalysts were prepared in the same manner as in Example 1 except for the above. .
反応結果と共に第３表に示す。The reaction results are shown in Table 3.
活性が非常に低いことがわかる。It can be seen that the activity is very low.
Claims (1)
ドを製造するための触媒であつて、該触媒は銀の他に、
カチオン成分としてナトリウム、セシウム及びバリウム
を、アニオン成分として塩素及び／又は臭素及び／又は
弗素を、少なくとも含有することを特徴とする触媒。(1) A catalyst for producing ethylene oxide by oxidizing ethylene with molecular oxygen, which catalyst includes, in addition to silver,
A catalyst characterized in that it contains at least sodium, cesium, and barium as cationic components, and chlorine and/or bromine and/or fluorine as anionic components.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59224877A JPS61103545A (en) | 1984-10-25 | 1984-10-25 | Silver catalyst for preparing ethylene oxide |
| US06/767,831 US4690913A (en) | 1984-08-21 | 1985-08-20 | Silver catalyst for production of ethylene oxide from ethylene and process for producing the catalyst |
| EP85110458A EP0172565B1 (en) | 1984-08-21 | 1985-08-20 | Silver catalyst for production of ethylene oxide from ethylene, and process for production thereof |
| DE8585110458T DE3582097D1 (en) | 1984-08-21 | 1985-08-20 | SILVER CATALYST FOR THE PRODUCTION OF ETHYLENE OXIDE FROM ETHYLENE AND METHOD FOR THE PRODUCTION THEREOF. |
| US07/017,686 US4786624A (en) | 1984-08-21 | 1987-02-24 | Silver catalyst for production of ethylene oxide from ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59224877A JPS61103545A (en) | 1984-10-25 | 1984-10-25 | Silver catalyst for preparing ethylene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61103545A true JPS61103545A (en) | 1986-05-22 |
| JPH0516903B2 JPH0516903B2 (en) | 1993-03-05 |
Family
ID=16820568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59224877A Granted JPS61103545A (en) | 1984-08-21 | 1984-10-25 | Silver catalyst for preparing ethylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61103545A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007510740A (en) * | 2003-11-10 | 2007-04-26 | エスディー リーツェンツ フェアベルツングス ゲセルシャフト エムベーハー ウント ツェーオー． カーゲー | Oxidation method and catalyst |
-
1984
- 1984-10-25 JP JP59224877A patent/JPS61103545A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007510740A (en) * | 2003-11-10 | 2007-04-26 | エスディー リーツェンツ フェアベルツングス ゲセルシャフト エムベーハー ウント ツェーオー． カーゲー | Oxidation method and catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0516903B2 (en) | 1993-03-05 |
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