JPH05329368A - Silver catalyst for ethylene oxide production and its preparation - Google Patents

Silver catalyst for ethylene oxide production and its preparation

Info

Publication number
JPH05329368A
JPH05329368A JP4330547A JP33054792A JPH05329368A JP H05329368 A JPH05329368 A JP H05329368A JP 4330547 A JP4330547 A JP 4330547A JP 33054792 A JP33054792 A JP 33054792A JP H05329368 A JPH05329368 A JP H05329368A
Authority
JP
Japan
Prior art keywords
carrier
alumina
catalyst
silver
ethylene oxide
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
Application number
JP4330547A
Other languages
Japanese (ja)
Other versions
JP3313164B2 (en
Inventor
Shinichi Nagase
慎一 長瀬
Hirohiko Tanabe
弘彦 田邉
Hideki Imai
秀樹 今井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Shokubai Co Ltd filed Critical Nippon Shokubai Co Ltd
Priority to JP33054792A priority Critical patent/JP3313164B2/en
Priority to CA002089510A priority patent/CA2089510C/en
Priority to AU33125/93A priority patent/AU659914B2/en
Priority to KR1019930002577A priority patent/KR0145749B1/en
Priority to MX9301029A priority patent/MX9301029A/en
Priority to TW082101362A priority patent/TW304891B/zh
Priority to US08/025,157 priority patent/US5395812A/en
Priority to EP93301492A priority patent/EP0558346B1/en
Priority to DE69300497T priority patent/DE69300497T2/en
Priority to BR9300692A priority patent/BR9300692A/en
Priority to CN93103580A priority patent/CN1050778C/en
Publication of JPH05329368A publication Critical patent/JPH05329368A/en
Application granted granted Critical
Publication of JP3313164B2 publication Critical patent/JP3313164B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66Silver or gold
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/04Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
    • C07D301/08Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
    • C07D301/10Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12Silica and alumina
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

PURPOSE:To provide a new silver catalyst for ethylene oxide production which has functions such as a high selectivity, activity, and durable catalystic life as a catalyst used in producting ethylene oxide by contact gas-phase oxidation of ethylene with molecular oxygen. CONSTITUTION:A silver catalyst for ethylene oxide production is composed of an alpha-alumina carrier and metal silver fine power particles in 5-25wt.% of the completed catalyst and cesium in 0.0001-0.05g-equivalent weight per 1kg of the completed catalyst which are carried on the carrier wherein the outer surface of the carrier and the surfaces of the pores of the carrier are coated with amorphous silica-alumina and the total amount of Si and Al in the amorphous silica-alumina is 3X10<-4> to 2X10<-1>g/g carrier and the Si/Al ratio of the amorphous material is 0.05-50.0g/g. Consequently, a new silver catalyst for ethylene oxide production which has an effect to maintain high selectivity and high activity for a long time is obtained.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明はエチレンを分子状酸素に
より接触気相酸化してエチレンオキシドを製造するに際
して使用される銀触媒およびその製造方法に関するもの
である。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver catalyst used in the catalytic vapor phase oxidation of ethylene with molecular oxygen to produce ethylene oxide and a method for producing the same.

【0002】[0002]

【従来の技術】工業的にエチレンを分子状酸素により接
触気相酸化してエチレンオキシドを製造するに際し使用
される触媒には、その性能として高選択性、高活性、お
よび触媒寿命の耐久性が要求される。
2. Description of the Related Art A catalyst used in the industrial production of ethylene oxide by catalytic gas-phase oxidation of ethylene with molecular oxygen is required to have high selectivity, high activity and durability of catalyst life. To be done.

【0003】これらの要求に対し、その性能を改善する
目的で触媒調製上、今日まで種々検討がなされており、
担体、反応促進剤、銀化合物等の改良に多くの努力が払
われてきた。担体に関する報告は多数提案されている。
たとえば、特公昭42−1412号、特公昭43−13
137号、特公昭45−21373号、特公昭45−2
2419号、特公昭45−11217号、特開昭57−
171435号、米国特許第2766261号、米国特
許第3172893号、米国特許第3664970号の
各公報明細書などであるが、その多くは、担体の細孔分
布と比表面積に関するものである。
In response to these requirements, various studies have been made to date on catalyst preparation for the purpose of improving the performance thereof.
Many efforts have been made to improve carriers, reaction accelerators, silver compounds and the like. Many reports on carriers have been proposed.
For example, Japanese Patent Publication No. 42-1412 and Japanese Patent Publication No. 43-13
No. 137, Japanese Patent Publication No. 45-21373, Japanese Patent Publication No. 45-2
No. 2419, Japanese Patent Publication No. 45-11217, and Japanese Patent Laid-Open No. 57-
No. 171435, US Pat. No. 2,766,261, US Pat. No. 3,172,893, US Pat. No. 3,664,970, and the like, most of which relate to the pore distribution and specific surface area of the carrier.

【0004】米国特許第2125333号明細書には、
ナトリウムまたはカリウムはおよびその金属塩を含有す
るアルカリ金属塩はエチレンオキシド製造用銀触媒の添
加剤として使用されることが記載されている。
US Pat. No. 2,125,333 describes
It is stated that alkali metal salts containing sodium or potassium and its metal salts are used as additives in silver catalysts for the production of ethylene oxide.

【0005】米国特許第2238474号明細書には、
水酸化ナトリウムはエチレンオキシド製造用銀触媒の活
性度を向上させるが、水酸化カリウムは触媒作用に悪影
響を及ぼすことが記載されている。
US Pat. No. 2,238,474 describes
While sodium hydroxide improves the activity of silver catalysts for the production of ethylene oxide, potassium hydroxide is described as having a detrimental effect on catalysis.

【0006】米国特許第2765283号明細書には、
担体に銀を担持する前に触媒担体に塩化ナトウムのごと
き無機塩素化物を1〜2000ppm重量添加すること
により触媒が改善される旨が記載されている。
US Pat. No. 2,765,283 describes
It is described that the catalyst is improved by adding 1 to 2000 ppm by weight of an inorganic chlorinated material such as sodium chloride to the catalyst carrier before supporting silver on the carrier.

【0007】米国特許第2799687号明細書には、
20〜16000ppm重量の塩化ナトリウム、塩化カ
リウムのごときハロゲン化物は抑制剤として作用し、触
媒の活性低下を起すことが記載されている。
US Pat. No. 2,799,687 discloses that
It is described that a halide such as sodium chloride or potassium chloride having a weight of 20 to 16000 ppm acts as an inhibitor and causes a decrease in the activity of the catalyst.

【0008】特開昭50−90591号明細書には、担
体中に不純物またはセメントとして存在するよりも過剰
量であって促進作用を有する量の銅、金、亜鉛、カドミ
ウム、水銀、ニオブ、タンタル、モリリブデン、タング
ステン、バナジウム、または好ましくはクロム、カルシ
ウム、マグネシウム、ストロンチウムおよび/またはさ
らに好ましくはバリウム、ならびに好ましくはさらに、
アルカリ金属を含有するアルキレンオキシド製造用触媒
が開示されている。
JP-A-50-90591 discloses that copper, gold, zinc, cadmium, mercury, niobium and tantalum are present in an amount that is in excess of and has a promoting action over impurities or cement present in the carrier. , Molylibden, tungsten, vanadium, or preferably chromium, calcium, magnesium, strontium and / or more preferably barium, and preferably further
A catalyst for producing an alkylene oxide containing an alkali metal is disclosed.

【0009】特開昭52−151690号明細書には、
比表面積0.05〜10m2 /gを有する多孔質の耐熱
性担体に担持された銀を含有しさらに担体中の不純物も
しくは結合剤としての存在量以外に、促進量のナトリウ
ムとカリウム、ルビジウムおよびセシウムより成る群か
ら選ばれた少なくとも1種の促進量の他のアルカリ金属
とを含有するアルキレンオキシド製造用触媒が開示され
ている。
Japanese Patent Application Laid-Open No. 52-151690 discloses
It contains silver supported on a porous heat-resistant carrier having a specific surface area of 0.05 to 10 m 2 / g, and further contains an accelerating amount of sodium and potassium, rubidium and A catalyst for the production of alkylene oxides is disclosed which contains at least one promoting amount of another alkali metal selected from the group consisting of cesium.

【0010】特開昭54−79193号明細書には、担
体上に先ず銀および場合によりナトリウムまたはリチウ
ムを該当する塩の形で施し、常法により加熱し、そして
後続の処理においてカリウム、ルビジウムおよびセシウ
ムのアルカリ金属の塩をアミンおよび/またはアンモニ
アと共に施すことによりアルキレンオキシド製造用触媒
が得られることが開示されている。
In JP 54-79193 A, silver and optionally sodium or lithium in the form of the corresponding salts are first applied to a support, heated in the usual manner, and in a subsequent treatment potassium, rubidium and It is disclosed that a catalyst for the production of alkylene oxides can be obtained by applying an alkali metal salt of cesium together with an amine and / or ammonia.

【0011】特開昭55−145677号明細書には、
酸化反応触媒としてアルミナ、シリカおよびチタニアの
合計含有量が99重量%以上であり、周期率表のVa、
VIa、VIIa、VIII、IbおよびIIbの各族
の金属の含有量が金属酸化物合計量として0.1重量%
未満であり、かつpKaが+4.8のメチルレッドによ
り酸性いろを呈しない非酸性担体に銀および必要に応じ
てさらにアルカリ金属成分又はアルカリ土類金属成分を
担持してなる銀触媒が開示されている。
Japanese Patent Laid-Open No. 55-145677 discloses that
The total content of alumina, silica and titania as an oxidation reaction catalyst is 99% by weight or more, and Va of the periodic table is
The content of the metal of each group of VIa, VIIa, VIII, Ib and IIb is 0.1% by weight as the total amount of metal oxides.
Disclosed is a silver catalyst in which silver and, if necessary, an alkali metal component or an alkaline earth metal component are further supported on a non-acidic carrier having a pKa of less than +4.8 and a methyl red having a pKa of +4.8 and which does not exhibit acid color. There is.

【0012】特開昭56−89843号明細書には、ナ
トリウム成分が0.07重量%以下、比表面積が0.5
〜5m2 /gのα―アルミナ担体に完成触媒に対し5〜
25重量%担持された金属銀粒子と、担体中の存在量以
外に完成触媒1キログラムあたり0.001〜0.05
グラム当量を担持されたアルカリ金属またはアルカリ金
属の化合物の少なくとも1種とを含有するエチレンオキ
シド製造用銀触媒が開示されている。
JP-A-56-89843 discloses that the sodium component is 0.07% by weight or less and the specific surface area is 0.5.
5 to 5 m 2 / g of α-alumina carrier for finished catalyst
25% by weight of metallic silver particles supported, and 0.001 to 0.05 per 1 kg of the finished catalyst in addition to the amount present in the carrier.
A silver catalyst for the production of ethylene oxide is disclosed containing gram equivalents of at least one alkali metal or alkali metal compound supported.

【0013】特開昭56−105750号明細書には、
ナトリウム成分が0.07重量%以下、比表面積が1〜
5m2 /gのα―アルミナ主成分担体を、完成触媒に対
し5〜25重量%の担持率となる如き分解性銀溶液に、
完成触媒1キログラムあたり0.001〜0.05グラ
ム当量のアルカリ金属とホウ素の錯合物、アルカリ金属
とモリブデンの錯合物および/またはアルカリ金属とタ
ングステンの錯合物含む含浸液で含浸処理をおこない、
加熱し還元または熱分解して製造されたエチレンオキシ
ド製造用銀触媒が開示されている。
Japanese Patent Application Laid-Open No. 56-105750 discloses that
Sodium component is 0.07 wt% or less, specific surface area is 1 to
5 m 2 / g of α-alumina main component carrier was added to a decomposable silver solution having a loading rate of 5 to 25% by weight based on the finished catalyst,
Impregnation treatment with an impregnating solution containing 0.001 to 0.05 gram equivalent of a complex of alkali metal and boron, a complex of alkali metal and molybdenum and / or a complex of alkali metal and tungsten per kilogram of the finished catalyst. Do
A silver catalyst for producing ethylene oxide produced by heating, reduction or thermal decomposition is disclosed.

【0014】特開昭57−107241号明細書には、
銀の他にカチオン成分としてナトリウム(Na)および
アニオン成分として塩素(CI)を少なくとも含有し、
かつCI/Naの原子比が1未満となるよう割合で加え
られているエチレンオキシド製造用銀触媒が開示されて
いる。
Japanese Patent Application Laid-Open No. 57-107241 discloses that
In addition to silver, it contains at least sodium (Na) as a cation component and chlorine (CI) as an anion component,
Further, a silver catalyst for producing ethylene oxide, which is added in a ratio such that the atomic ratio of CI / Na is less than 1, is disclosed.

【0015】特開昭57−140654号明細書には、
銀の他にカチオン成分としてナトリウムおよびセシウム
を、アニオン成分として塩素を少なくとも含有するエチ
レンオキシド製造用銀触媒が開示されている。
JP-A-57-140654 discloses that
A silver catalyst for producing ethylene oxide containing at least sodium and cesium as a cation component and chlorine as an anion component in addition to silver is disclosed.

【0016】特開昭63−116743号明細書には、
触媒成分として銀の他にカチオン成分として少くともナ
トリウム、カリウム、ルビジウム及び/又はセシウムを
含み、かつ担体が主としてα―アルミナよりなりその表
面積が0.6〜2m2 /g、吸水率が20〜50%、シ
リカ含量0.5〜12重量%、かつ表面積当りのシリカ
含量(重量%/m2 /g)が0.5〜12,好ましくは
1〜8であって、ナトリウム含量が0.08〜2重量%
であるエチレンオキシド製造用銀触媒が開示されてい
る。
Japanese Patent Application Laid-Open No. 63-116743 discloses that
In addition to silver as a catalyst component, at least sodium, potassium, rubidium and / or cesium as a cation component are contained, and the carrier is mainly α-alumina, and its surface area is 0.6 to 2 m 2 / g and the water absorption rate is 20 to 50%, silica content 0.5 to 12% by weight, silica content per surface area (% by weight / m 2 / g) 0.5 to 12, preferably 1 to 8 and sodium content 0.08. ~ 2% by weight
A silver catalyst for producing ethylene oxide is disclosed.

【0017】以上のように数多く出されているが、その
多くは限定された範囲内のアルカリ金属を銀触媒に添加
することにより触媒性能を向上させているものである。
しかしながら、これらの触媒は初期の触媒性能は良好で
あるがその後の触媒寿命の点で問題がある。
As described above, many are produced, but most of them improve the catalytic performance by adding an alkali metal within a limited range to the silver catalyst.
However, although these catalysts have good initial catalyst performance, they have a problem in terms of catalyst life after that.

【0018】[0018]

【発明が解決しようとする問題点】エチレンオキシド製
造用銀触媒の担体についてまだ不明な点も多く改良すべ
き問題が数多く存在する。たとえば、担体を構成する成
分、担体の比表面積、細孔径、細孔分布、細孔容積、気
孔率、粒径、形状等の物理的性質、また、α―アルミ
ナ、シリコンカ―バイド、シリカ、ジルコニア等の担体
材料の持つ化学的性質等の最適化への改良が挙げられ
る。
Problems to be Solved by the Invention There are many unclear points regarding the carrier of the silver catalyst for producing ethylene oxide, and there are many problems to be improved. For example, physical properties such as components constituting the carrier, specific surface area of the carrier, pore size, pore distribution, pore volume, porosity, particle size, shape, and α-alumina, silicon carbide, silica, zirconia And other improvements to the optimization of the chemical properties of the carrier material.

【0019】したがって、本発明の目的は、高選択性、
高活性および触媒寿命の耐久性の各性能を合せもった新
規なエチレンオキシド製造用銀触媒を提供することにあ
る。本発明の他の目的は、比表面積が0.75〜5m2
/g、見掛気孔率45〜70%よりなるα―アルミナ担
体を用いて触媒寿命を向上した新規なエチレンオキシド
製造用銀触媒を提供することにある。
Therefore, the object of the present invention is to achieve high selectivity,
It is an object of the present invention to provide a novel silver catalyst for producing ethylene oxide, which has both high activity and durability of catalyst life. Another object of the present invention is to have a specific surface area of 0.75-5 m 2
Another object of the present invention is to provide a novel silver catalyst for producing ethylene oxide, which has an improved catalyst life by using an α-alumina carrier having an apparent porosity of 45 to 70% / g.

【0020】本発明者等はエチレンオキシド製造用銀触
媒に用いる好適な担体を構成する成分および担体の比表
面積に関する研究を行なっており、すでに特開平2−1
94839号明細書において担体の外表面上および担体
の気孔の表面上が非晶質シリカで被覆されたα―アルミ
ナ担体を用いた銀触媒で、高選択性でしかも高選択性を
長期に渡って維持できる触媒が得られることを見出して
いる。しかしながら、さらに検討を重ねた結果、担体の
外表面上および担体の気孔の表面上を被覆する物質が非
晶質シリカである担体よりも、シリカとアルミナの混合
した非晶質シリカーアルミナで被覆されたα―アルミナ
担体を用いた銀触媒の方がエチレンオキシドを製造する
際にさらにより高選択性となり、しかもその高選択性を
長期に渡って維持することにおいても改善されることを
見出し本発明を完成した。
The present inventors have been conducting research on the components constituting a suitable carrier used for a silver catalyst for producing ethylene oxide and the specific surface area of the carrier, and have already disclosed JP-A 2-1.
No. 94839, a silver catalyst using an α-alumina carrier in which the outer surface of the carrier and the surface of the pores of the carrier are coated with amorphous silica, and has high selectivity and high selectivity over a long period of time. It has been found that a sustainable catalyst is obtained. However, as a result of further studies, the substance coated on the outer surface of the carrier and the surface of the pores of the carrier is amorphous silica-alumina mixed with silica and alumina rather than the carrier in which the substance is amorphous silica. It was found that the silver catalyst using the α-alumina carrier thus produced has a higher selectivity in producing ethylene oxide and is improved in maintaining the high selectivity for a long period of time. Was completed.

【0021】[0021]

【問題点を解決するための手段】上記諸目的は、担体の
外表面上および担体の気孔の表面上が非晶質シリカーア
ルミナで被覆されたα―アルミナ担体で、該非晶質シリ
カーアルミナ中のSiおよびAlの合計量が3×10-4
〜2×10-1g/g担体であり、かつ非晶質分のSi/
Al比が0.05〜50.0g/gであるα―アルミナ
担体に完成触媒当り5〜25重量%の金属銀微粒子およ
び完成触媒1キログラム当り0.0001〜0.05グ
ラム当量重量のセシウムを担持したことを特徴とするエ
チレンオキシド製造用銀触媒により達成される。
[Means for Solving the Problems] The above objects are to provide an α-alumina carrier in which the outer surface of the carrier and the surface of the pores of the carrier are coated with amorphous silica-alumina. The total amount of Si and Al is 3 × 10 −4
˜2 × 10 −1 g / g carrier and amorphous Si /
On an α-alumina carrier having an Al ratio of 0.05 to 50.0 g / g, 5 to 25% by weight of fine metal silver particles per finished catalyst and 0.0001 to 0.05 gram equivalent weight of cesium per kilogram of finished catalyst were added. It is achieved by a supported silver catalyst for producing ethylene oxide.

【0022】上記諸目的は、0.1〜10μmの径のα
―アルミナ一次粒子で構成された20〜200μmの2
次粒子径を有し、比表面積が0.1〜10m2 /gのア
ルミナ粉体を主原料とし、混合時にコロイド状であるア
ルミナおよびシリカを混合した後、成形、乾燥さらに1
000〜1600℃の温度で焼成し、担体の外表面上お
よび担体の気孔の表面上がSiおよびAlの合計量が3
×10-4〜2×10-1g/g担体であり、かつ非晶質分
のSi/Al比が0.05〜50.0g/gである非晶
質シリカーアルミナで被覆されたα―アルミナ担体を調
製し、該α―アルミナ担体に完成触媒当り5〜25重量
%の金属銀微粒子および完成触媒1キログラム当り0.
0001〜0.05グラム当量重量のセシウムを担持せ
しめた後、賦活化処理して、銀とセシウムとを多孔性無
機質耐火性担体に析出した後、不活性ガス中で400〜
950℃の範囲で高温加熱処理することを特徴とするエ
チレンオキシド製造用銀触媒の製造方法によっても達成
される。
[0021] The above-mentioned various purposes are based on α having a diameter of 0.1 to 10 µm.
20 to 200 μm 2 composed of alumina primary particles
Alumina powder having a secondary particle size and a specific surface area of 0.1 to 10 m 2 / g is used as a main raw material, and colloidal alumina and silica are mixed at the time of mixing, followed by molding and drying.
Calcination is performed at a temperature of 000 to 1600 ° C., and the total amount of Si and Al is 3 on the outer surface of the carrier and on the surface of the pores of the carrier.
Α coated with amorphous silica-alumina having a Si / Al ratio of 0.05 to 50.0 g / g, which is a carrier of × 10 -4 to 2 × 10 -1 g / g. -Alumina carrier was prepared, and 5 to 25% by weight of fine metal silver particles per finished catalyst and 0.
After supporting 0001 to 0.05 gram equivalent weight of cesium, activation treatment is performed to deposit silver and cesium on the porous inorganic refractory carrier, and then 400 to 400 in an inert gas.
It is also achieved by a method for producing a silver catalyst for producing ethylene oxide, which comprises performing high temperature heat treatment in the range of 950 ° C.

【0023】[0023]

【作用】エチレンオキシド製造用銀触媒に用いる好適な
担体に関する研究によれば、従来技術で一般的に工業的
規模において用いられている担体よりも比表面積が0.
75〜5m2 /g、見掛気孔率45〜70%よりなる担
体の外表面上および担体の気孔の表面上が非晶質シリカ
で被覆されたα―アルミナ担体を用いた場合、触媒にし
たときの選択率の低さのゆえに当該分野の工業的規模に
おいて一般的に用いられることのなかった比較的高比表
面績の担体をも有効に使用でき、これと特に反応促進剤
としてセシウムおよび/またはセシウム化合物を担持せ
しめた後、賦活化処理して、銀とセシウムおよび/また
はセシウム化合物とをα―アルミナ担体に析出した後、
不活性ガス中で400〜950℃の範囲で高温加熱処理
して得られた触媒はこれまでになく高活、高選択性、耐
久性の触媒が得られることを見い出したものである。
According to the research on a suitable carrier used for a silver catalyst for producing ethylene oxide, the specific surface area is less than that of the carrier generally used on the industrial scale in the prior art.
An α-alumina carrier having an outer surface of the carrier of 75 to 5 m 2 / g and an apparent porosity of 45 to 70% and the surface of the pores of the carrier coated with amorphous silica was used as a catalyst. A carrier having a relatively high specific surface area, which has not been generally used on the industrial scale of the field due to its low selectivity, can also be effectively used, and in particular, cesium and / or a reaction accelerator can be used. Alternatively, after supporting a cesium compound, an activation treatment is carried out to deposit silver and cesium and / or a cesium compound on an α-alumina carrier,
It has been found that a catalyst obtained by heating at a high temperature in the range of 400 to 950 ° C. in an inert gas can obtain a catalyst with high activity, high selectivity and durability as never before.

【0024】エチレンを分子状酸素により接触気相酸化
してエチレンオキシドを製造する際に用いられる触媒は
銀触媒であり、そのほとんどが担体を使用した担持触媒
であることは言うまでもないことである。また、用いら
れる担体が多孔性粒状耐火物であることも周知である。
Needless to say, the catalyst used for producing ethylene oxide by catalytic vapor-phase oxidation of ethylene with molecular oxygen is a silver catalyst, and most of them are supported catalysts using a carrier. It is also well known that the carrier used is a porous granular refractory.

【0025】しかしながら、単に多孔性粒状耐火物担体
と言っても千差万別で担体の比表面積、細孔分布、細孔
容積、粒径、形状等の物理的性質及び担体を構成する材
質、例えばα―アルミナ、シリカ、シリコンカ―バイ
ド、ジルコニア、粘土等のもつ化学的性質等、これらの
物理的および化学的性質が触媒の性能に及ぼす影響は大
きい。
However, even if it is simply referred to as a porous granular refractory carrier, the physical properties such as the specific surface area, pore distribution, pore volume, particle size, shape, etc. of the carrier and the materials constituting the carrier are various. For example, the physical and chemical properties of α-alumina, silica, silicon carbide, zirconia, clay, etc. have a great influence on the performance of the catalyst.

【0026】したがって、どのような性質の担体を選ぶ
かは、当業者にとって大きな問題である。担体の物性の
中でも比表面積は細孔径にも関係し、触媒性能に与える
影響は大きく大いに留意しなければならない。即ち、活
性、耐久性の面から考えると触媒比表面積は大きい方が
良く、そのためには担体比表面は大きい方が望ましい
が、担体比表面積を大きくするためには担体材料のアル
ミナ粒子は小さいものを選ぶ必要がある。そのことは必
然的に小さな細孔径の形成を意味する。このことはガス
の拡散滞留、反応熱の除去という点から考えると不利に
なる。また担体表面の露出面積が増大することからも不
利である。これ等のことはいずれも選択率の低下につな
がる。このような事実から、必ずしも比表面積は大きい
方が良いとばかりは言えず自ずと制限が出てくる。これ
までの工業的規模に採用されている大部分の担体の比表
面積は1m2 /g以下であり、さらには0.5m2 /g
以下である。例外的には1m2 /g以上の担体を使った
例もあるが、低表面積のものより選択率は低い。
Therefore, what kind of carrier should be selected is a big problem for those skilled in the art. Among the physical properties of the carrier, the specific surface area is also related to the pore size, and it has a great influence on the catalyst performance, and it must be noted that it is very important. That is, from the viewpoint of activity and durability, it is preferable that the catalyst specific surface area is large, and for that purpose, the carrier specific surface is preferably large, but in order to increase the carrier specific surface area, the alumina particles of the carrier material are small. Need to choose. That necessarily means the formation of small pore sizes. This is disadvantageous in terms of diffusion and retention of gas and removal of reaction heat. It is also disadvantageous because the exposed area of the carrier surface increases. All of these lead to a decrease in selectivity. From such a fact, it cannot always be said that the larger the specific surface area is, the better it is. The specific surface area of most of the carriers used on the industrial scale to date is 1 m 2 / g or less, and further 0.5 m 2 / g.
It is below. Exceptionally, there is an example in which a carrier of 1 m 2 / g or more is used, but the selectivity is lower than that of low surface area.

【0027】本願発明者等は、これ等の欠点を無くすべ
く検討した結果0.75m2 /g以上の大きな比表面積
の担体を用いても選択率の低下を招くことなく、さらに
向上させかつ高活性、耐久性を維持、促進させる方法を
発見した.すでに本願出願人は特開平2−194839
号明細書において開示した担体の外表面上および担体の
気孔の表面上が非晶質シリカで被覆されたα―アルミナ
担体よりも、本願発明の担体の外表面上および担体の気
孔の表面上をシリカとアルミナの混合した非晶質シリカ
ーアルミナで被覆されたα―アルミナ担体を用いた銀触
媒の方がエチレンオキシドを製造する際にさらにより高
選択性となり、しかもその高選択性を長期に渡って維持
することが可能となった。このことは、特に0.75m
2 /g以上の高比表面積担体に有効で、また増量された
セシウム化合物添加触媒に有効である。このような物性
面からの不利益を担体の化学的性質、特に担体の外表面
上および担体の気孔の表面上が非晶質シリカーアルミナ
で被覆されたα―アルミナ担体の使用によって、非晶質
シリカで被覆されたα―アルミナ担体よりも改善される
ことは驚くべきことである。なお、本明細書における比
表面積はBrunauer−Emmett−Telle
r(以下、BETという)法により測定される値であ
る。
The inventors of the present invention have conducted studies to eliminate these drawbacks, and as a result, even if a carrier having a large specific surface area of 0.75 m 2 / g or more is used, the selectivity is not lowered and the carrier is further improved and improved. We have discovered a method to maintain and promote activity and durability. The applicant of the present application has already filed JP-A-2-194839.
Than the α-alumina carrier in which the outer surface of the carrier and the surface of the pores of the carrier disclosed in the specification are coated with amorphous silica, A silver catalyst using an α-alumina carrier coated with amorphous silica-alumina, which is a mixture of silica and alumina, has even higher selectivity when producing ethylene oxide, and its high selectivity is maintained for a long time. It became possible to maintain. This is especially 0.75m
It is effective for a carrier having a high specific surface area of 2 / g or more and is effective for an increased amount of a cesium compound-added catalyst. These disadvantages from the aspect of physical properties are caused by the use of an α-alumina carrier in which the chemical properties of the carrier, particularly the outer surface of the carrier and the surface of the pores of the carrier are coated with amorphous silica-alumina. It is surprising that there is an improvement over the α-alumina support coated with porous silica. In addition, the specific surface area in this specification is Brunauer-Emmett-Telle.
It is a value measured by the r (hereinafter referred to as BET) method.

【0028】本発明によれば担体の外表面上および担体
の気孔の表面上は触媒性能に微妙に影響し、特に従来当
分野で通常使われている比表面積0.5m2 /g以下の
担体ではその悪い影響は、比表面積が小さくなる程小さ
いが、0.5m2 /g以上になるとだんだん大きくなり
0.75m2 /g以上になるとその影響は顕著になる。
本願発明者等が既に見い出した担体の外表面上および
担体の気孔の表面上が非晶質シリカで被覆されたα―ア
ルミナ担体により、これまで使用されなかった比表面積
0.75m2 /g以上の担体の使用が可能となった。こ
の担体の外表面上および担体の気孔の表面上が非晶質シ
リカで被覆されたα―アルミナ担体よりも、本願発明の
担体の外表面上および担体の気孔の表面上をシリカとア
ルミナの混合した非晶質シリカーアルミナで被覆された
α―アルミナ担体を用いた銀触媒の方がエチレンオキシ
ドを製造する際にさらにより活性および選択性において
さらに優位になることを見い出した。
According to the present invention, the outer surface of the carrier and the surface of the pores of the carrier have a delicate influence on the catalytic performance, and in particular, a carrier having a specific surface area of 0.5 m 2 / g or less, which is conventionally used in the art, is used. However, the adverse effect becomes smaller as the specific surface area becomes smaller, but becomes gradually larger when the specific surface area becomes 0.5 m 2 / g or more and becomes remarkable when the specific surface area becomes 0.75 m 2 / g or more.
The α-alumina carrier, on which the outer surface of the carrier and the surface of the pores of the carrier have been found by the inventors of the present application, is coated with amorphous silica, so that the specific surface area not used up to now is 0.75 m 2 / g or more. It became possible to use the carrier. Mixing silica and alumina on the outer surface of the carrier of the present invention and on the surface of the pores of the carrier is more preferable than the α-alumina carrier in which the outer surface of the carrier and the surface of the pores of the carrier are coated with amorphous silica. It has been found that the silver catalyst using the α-alumina support coated with the amorphous silica-alumina is more advantageous in the activity and selectivity in producing ethylene oxide.

【0029】このことは後述の実施例でも分るように、
担体の物性が多少関係あるにしても、セシウムを添加し
た触媒にした時の触媒の寿命に性能の差が出ることは驚
くべきことである。このことがどういう作用によるか、
我々には正確には分らない。ただ担体の外表面上および
担体の気孔の表面上を被覆する物質が非晶質シリカであ
るよりも非晶質シリカーアルミナであることが良いとい
うこと、またセシウムを担持せしめた後、賦活化処理し
て、銀とセシウムおよび/またはセシウム化合物とを多
孔性無機質耐火性担体に析出した後、不活性ガス中で4
00〜950℃の範囲で高温加熱処理することにより、
非晶質物質がシリカであるのものに比較して選択率の向
上が約1%であること、さらにまた文献に、アルミナや
シリカへの金属イオンの吸着がpHに強く依存すること
が記載されていること等を考慮に入れると、担体の外表
面上および担体の気孔の表面上の非晶質シリカであるよ
りも非晶質シリカーアルミナの方が銀およびセシウム含
有溶液を担体へ含浸する際に、担体内のpH分布との違
いから、銀あるいはそれ以上にセシウムの析出分布およ
び析出したときの担体との結合力に強く影響を与えるこ
とが考えられる。そのことが触媒性能に関係してくると
思える。
This can be seen in the examples described below.
Even if the physical properties of the carrier are somewhat related, it is surprising that there is a difference in the life of the catalyst when the catalyst containing cesium is used. How this works
We don't know exactly. However, it is preferable that the substance coating the outer surface of the carrier and the surface of the pores of the carrier is amorphous silica-alumina rather than amorphous silica, and that after cesium is loaded, activation is performed. After treatment, silver and cesium and / or cesium compound are deposited on the porous inorganic refractory carrier, and then 4 in an inert gas.
By high-temperature heat treatment in the range of 00 to 950 ° C,
It is noted that the selectivity improvement is about 1% compared to the one in which the amorphous substance is silica, and that the literature also strongly suggests that the adsorption of metal ions on alumina or silica strongly depends on pH. In consideration of the above, the amorphous silica-alumina impregnates the carrier with a solution containing silver and cesium rather than the amorphous silica on the outer surface of the carrier and the surface of the pores of the carrier. In this case, it is considered that the precipitation distribution of cesium on silver or more and the binding force with the carrier when precipitated are strongly influenced from the difference with the pH distribution in the carrier. That seems to be related to catalyst performance.

【0030】本発明の好適なセシウムおよび/またはセ
シウム化合物の添加量の範囲は、完成触媒1キログラム
当り0.0001〜0.05グラム当量重量、好ましく
は0.001〜0.03グラム当量重量であり、特に好
ましくは0.008グラム当量重量を越えかつ0.03
グラム当量重量以下である。
The preferred cesium and / or cesium compound addition amount range of the present invention is 0.0001 to 0.05 gram equivalent weight, preferably 0.001 to 0.03 gram equivalent weight per kilogram of the finished catalyst. Yes, particularly preferably greater than 0.008 gram equivalent weight and 0.03
Not more than gram equivalent weight.

【0031】本発明のα−アルミナ担体の比表面積とし
ては比表面積が0.75〜5m2 /gの範囲、さらに好
ましくは0.8〜2m2 /gのものが有効である。5m
2 /gを越えるものは実質的に良いものは得られておら
ず実際的でない。さらにまたα−アルミナ、ナトリウム
成分(主にNa2 O)以外の担体成分は当分野で慣用の
担体に含まれる程度の成分および量が好ましい。
As the specific surface area of the α-alumina carrier of the present invention, a specific surface area of 0.75 to 5 m 2 / g, more preferably 0.8 to 2 m 2 / g is effective. 5m
If the amount exceeds 2 / g, a substantially good product is not obtained and it is not practical. Furthermore, carrier components other than α-alumina and sodium components (mainly Na 2 O) are preferably components and amounts such that they are contained in carriers commonly used in this field.

【0032】本発明のα−アルミナ担体の見かけの気孔
率は45〜70%、特に50〜60%が好ましい。
The apparent porosity of the α-alumina carrier of the present invention is preferably 45 to 70%, particularly preferably 50 to 60%.

【0033】本発明のα−アルミナ担体の比気孔容積は
0.1〜0.8cc/g、特に0.2〜0.5cc/g
が好ましい。
The specific pore volume of the α-alumina carrier of the present invention is 0.1 to 0.8 cc / g, especially 0.2 to 0.5 cc / g.
Is preferred.

【0034】本発明のα−アルミナ担体は粒径3〜20
mmのα−アルミナ主成分、好ましくは90重量%以上
がα−アルミナ成分であり、0.1〜10μmの径のα
−アルミナ1次粒子で構成された20〜200μmの径
のα−アルミナ2次粒子を有し、比表面積0.1〜10
2 /gのアルミナ粉体を用いたα−アルミナ担体が使
用できる。本発明で使用される担体は球、ペレット、リ
ング等の粒状の耐火性担体であり、その平均相当直径は
3〜20mm、好ましくは5〜10mm、特に担体を構
成する成分、担体の比表面積は触媒性能に大きく関係
し、触媒製造時、銀とセシウムおよび/またはセシウム
化合物の担持工程において均一なる担持の容易な担体の
形状を選ぶことが選択性に優れた触媒を得ることにな
る。
The α-alumina carrier of the present invention has a particle size of 3 to 20.
mm α-alumina main component, preferably 90% by weight or more is the α-alumina component, and α having a diameter of 0.1 to 10 μm.
-Having α-alumina secondary particles having a diameter of 20 to 200 µm composed of alumina primary particles and having a specific surface area of 0.1 to 10
An α-alumina carrier using m 2 / g of alumina powder can be used. The carrier used in the present invention is a granular refractory carrier such as spheres, pellets, rings, etc., and the average equivalent diameter thereof is 3 to 20 mm, preferably 5 to 10 mm, especially the components constituting the carrier, and the specific surface area of the carrier. It is greatly related to the catalyst performance, and when a catalyst is manufactured, it is possible to obtain a catalyst having excellent selectivity by selecting a uniform carrier shape that is easily supported in the step of supporting silver and cesium and / or a cesium compound.

【0035】またα―アルミナ担体としては、例えば好
ましくはBET比表面積0.8〜2m2 /g、見掛気孔
率50〜60%、細孔容積0.2〜0.5cc/g、粒
径3〜20mmのα−アルミナ主成分、好ましくは90
重量%以上がα−アルミナ成分の担体である。このα−
アルミナ担体は0.1〜10μmの径のα−アルミナ1
次粒子で構成された20〜200μmの径のα−アルミ
ナ2次粒子を有し、比表面積0.1〜10m2 /g、好
ましくは1〜5m2 /gのアルミナ粉体を主原料とし、
これに1〜300nm、好ましくは1〜20nmの径を
有するアルミナおよびシリカ粒子をコロイド状にして混
合し、担体造粒時に通常用いられる有機結合剤、水をニ
ーダー等の混練機を用いて十分に混合したのち、押し出
し成形、造粒、乾燥し、1000〜1600℃、好まし
くは1200〜1500℃で1〜10時間、好ましくは
2〜10時間焼成し、得られた担体の外表面上および担
体の気孔の表面上が非晶質シリカーアルミナで被覆され
たα―アルミナ担体が好適である。
The α-alumina carrier is preferably, for example, a BET specific surface area of 0.8 to 2 m 2 / g, an apparent porosity of 50 to 60%, a pore volume of 0.2 to 0.5 cc / g, and a particle size. 3 to 20 mm α-alumina main component, preferably 90
The carrier of the α-alumina component accounts for at least wt%. This α-
The alumina carrier is α-alumina 1 having a diameter of 0.1 to 10 μm.
It has α- alumina secondary particle diameter of 20~200μm made up of the following particle, the specific surface area of 0.1 to 10 m 2 / g, preferably as a main raw material alumina powder of 1 to 5 m 2 / g,
Alumina and silica particles having a diameter of 1 to 300 nm, preferably 1 to 20 nm are made into a colloidal form and mixed, and an organic binder and water usually used at the time of carrier granulation are sufficiently mixed by using a kneader such as a kneader. After mixing, extrusion molding, granulation, drying and baking at 1000 to 1600 ° C., preferably 1200 to 1500 ° C. for 1 to 10 hours, preferably 2 to 10 hours, on the outer surface of the obtained carrier and An α-alumina carrier in which the surface of the pores is coated with amorphous silica-alumina is suitable.

【0036】1〜300nmの径を有するアルミナおよ
びシリカ粒子としては、一般的にはアルミナゾル、コロ
イダルシリカの水溶液として用いるのが分散の容易さか
ら好ましい。アルミナゾルおよびコロイダルシリカの調
製は「超微粒子開発応用ハンドブック」1989年4月
5日、(株)サイエンスフォーラムに記載されている。
アルミナゾルはアルミニウム塩を加水分解して得る方
法やアルミニウム塩水溶液をアルカリで中和して一旦ゲ
ルとしてた後、解膠して得る方法がある。
As the alumina and silica particles having a diameter of 1 to 300 nm, it is generally preferable to use them as an aqueous solution of alumina sol or colloidal silica because of easy dispersion. Preparation of alumina sol and colloidal silica is described in "Ultrafine Particle Development and Application Handbook", Science Forum Co., Ltd., April 5, 1989.
The alumina sol can be obtained by hydrolyzing an aluminum salt, or by neutralizing an aqueous solution of an aluminum salt with an alkali to once form a gel, and then peptizing it.

【0037】コロイダルシリカは珪酸ソーダ水溶液を酸
で中和して一旦ゲルとした後、解膠して得る方法や珪酸
ソーダ水溶液をイオン交換により脱ソーダ化して得る方
法がある。市販品としては、アルミナゾルとしては、日
産化学(株)より販売されている「アルミナゾル10
0、アルミナゾル200、アルミナゾル500」が使用
できる。また、コロイダルシリカとしては、、日産化学
(株)より販売されている「スノーテックス0」が使用
できる。
The colloidal silica can be obtained by neutralizing an aqueous solution of sodium silicate with an acid to form a gel and then deflocculating it, or by removing the aqueous solution of sodium silicate by de-sodating. As a commercially available product, as the alumina sol, “Alumina sol 10” sold by Nissan Chemical Industries, Ltd.
0, alumina sol 200, and alumina sol 500 "can be used. As the colloidal silica, "Snowtex 0" sold by Nissan Chemical Industries, Ltd. can be used.

【0038】本発明のα−アルミナ担体はα―アルミナ
担体に対して、担体1グラムあたりSiおよびAlの合
計量が3×10-4〜2×10-1g/g担体、特に5×1
-4〜1×10-1g/g担体になるように非晶質シリカ
ーアルミナを含有させることが好適である。α―アルミ
ナ担体の非晶質シリカーアルミナはSiとAlとして、
Si/Al比が0.05〜50.0、特に0.5〜1
0.0であるα―アルミナ担体が好適である。
The α-alumina carrier of the present invention has a total amount of Si and Al of 3 × 10 -4 to 2 × 10 -1 g / g, especially 5 × 1 per gram of the α-alumina carrier.
Amorphous silica-alumina is preferably contained so as to form a carrier of 0 −4 to 1 × 10 −1 g / g. Amorphous silica-alumina of α-alumina carrier is Si and Al,
Si / Al ratio of 0.05 to 50.0, especially 0.5 to 1
An α-alumina support having a value of 0.0 is preferred.

【0039】触媒の調製法は、分解性銀塩の水溶液域い
は有機溶媒溶液、例えば硝酸銀水溶液、無機、有機酸銀
のアンモニア錯体、域いは有機酸銀のアミン錯体、乳酸
銀水溶液等を前記のごとき担体に含浸する方法が採用さ
れる。セシウムおよび/またはセシウム化合物は担体に
先に析出させておいてもよく、また銀溶液に加えておい
て銀と同時に担体に折出させても良く、または銀の分解
還元過程とそれに続く分解除去過程の後、銀を担持した
担体に析出させても良い。ついでこの含浸担体を加熱
し、分解性銀塩を分解あるいは還元し続いて分解物を加
熱ガスにより分解除去する方法が採用できる。
The catalyst is prepared by using an aqueous solution of a decomposable silver salt in an organic solvent solution, for example, an aqueous solution of silver nitrate, an inorganic, silver complex of organic acid silver, an amine complex of organic acid silver, an aqueous solution of silver lactate and the like. The method of impregnating the carrier as described above is adopted. Cesium and / or cesium compound may be pre-deposited on the carrier, may be added to the silver solution and may be simultaneously projected on the carrier simultaneously with silver, or the decomposition and reduction process of silver and subsequent decomposition and removal thereof. After the process, it may be deposited on a carrier carrying silver. Then, a method of heating the impregnated carrier to decompose or reduce the decomposable silver salt and subsequently decompose and remove the decomposed product with a heating gas can be adopted.

【0040】本発明のα−アルミナ担体を用いた銀触媒
の調製方法としてはたとえばエチレンを分子状酸素によ
り気相接触酸化してエチレンオキシドを製造する際に使
用する銀触媒において、本発明のα−アルミナ担体を使
用し、これに有機酸銀のアミン錯体等の分解性銀溶液を
含浸後100〜300℃に加熱し、還元、あるいは熱分
解し、銀とセシウムおよび/またはセシウム化合物とを
多孔性無機質耐火性担体に担持せしめた後、最終的に、
含有酸素濃度が3容量%以下の不活性ガス中、好ましく
は不活性ガス中で、400〜950℃、好ましくは50
0〜800℃の範囲で高温加熱処理して得られるエチレ
ンオキシド製造用銀触媒の製造方法等を採用することが
できる。
The method for preparing a silver catalyst using the α-alumina carrier of the present invention includes, for example, a silver catalyst used in the production of ethylene oxide by vapor-phase catalytic oxidation of ethylene with molecular oxygen. Alumina carrier is used, impregnated with a decomposable silver solution such as an amine complex of organic acid silver, and then heated at 100 to 300 ° C. to reduce or thermally decompose the silver and cesium and / or cesium compound to make it porous. After loading it on the inorganic refractory carrier, finally,
400 to 950 ° C., preferably 50, in an inert gas having an oxygen content of 3% by volume or less, preferably in an inert gas.
A method for producing a silver catalyst for producing ethylene oxide, which is obtained by heating at a high temperature in the range of 0 to 800 ° C., or the like can be adopted.

【0041】本発明の銀触媒の銀は触媒に対し5〜25
重量%好ましくは5〜20重量%を微粒状に担体内外表
面に析出させることができる。セシウムまたはセシウム
化合物を水溶液あるいはアルコ―ル性溶液の形で完成触
媒1キログラムあたり0.0001〜0.05グラム当
量、特に0.003グラム当量を越え、かつ、0.03
グラム当量以下の範囲内を銀溶液に加えて銀と同時に析
出させるか、または銀の析出前の担体または銀担持後の
担体に析出させることができる。
The silver of the silver catalyst of the present invention is 5 to 25 with respect to the catalyst.
%, Preferably 5 to 20% by weight can be finely deposited on the inner and outer surfaces of the carrier. Cesium or a cesium compound in the form of an aqueous solution or an alcoholic solution is added in an amount of 0.0001 to 0.05 gram equivalent, particularly 0.003 gram equivalent per kilogram of the finished catalyst, and 0.03
A range of not more than gram equivalent can be added to the silver solution to cause simultaneous precipitation with silver, or the carrier can be precipitated before the precipitation of silver or after the support of silver.

【0042】本発明の銀触媒を使用してエチレンを分子
状酸素により酸化して酸化エチレンを製造する方法にお
いて採用できる反応条件は、これまで当分野で知られて
いる全ての条件が採用できるが、工業的製造規模におけ
る一般的な条件、すなわち原料ガス組成としてエチレン
0.5〜40容量%、酸素3〜10容量%、炭酸ガス5
〜30容量%、残部が窒素、アルゴン、水蒸気等の不活
性ガスおよびメタン、エタン等の低級炭化水素類さらに
また反応抑制剤としての二塩化エチレン、塩化ジフェニ
ル等のハロゲン化物、空間速度1000〜30000h
-1(STP)、好ましくは3000〜8000h
-1、圧力2〜40kg/cm2 G、好ましくは15〜
40kg/cm2 G等が好適に採用できる。
As the reaction conditions which can be adopted in the method of producing ethylene oxide by oxidizing ethylene with molecular oxygen using the silver catalyst of the present invention, all the conditions known in the art can be adopted. General conditions on an industrial production scale, that is, as a raw material gas composition, ethylene 0.5 to 40% by volume, oxygen 3 to 10% by volume, carbon dioxide gas 5
-30% by volume, the balance being inert gas such as nitrogen, argon, water vapor, etc. and lower hydrocarbons such as methane, ethane, etc. Further, halides such as ethylene dichloride, diphenyl chloride etc. as a reaction inhibitor, space velocity: 1000-30000 h
r -1 (STP), preferably 3000-8000h
r -1 , pressure 2 to 40 kg / cm 2 G, preferably 15 to
40 kg / cm 2 G or the like can be preferably adopted.

【0043】[0043]

【実施例】以下さらに具体的にするために実施例および
比較例をあげて詳細に説明するが、本発明はその主旨に
反しない限りこれらの実施例に限定されるものではな
い。
EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it goes against the gist of the invention.

【0044】なお、実施例および比較例に記載する変化
率および選択率は次式により算出されたものである。
The change rates and selectivities described in Examples and Comparative Examples are calculated by the following equations.

【0045】変化率(%)=(反応したエチレンのモル
数/原料ガス中のエチレンのモル数)×100 選択率(%)=(エチレンオキシドに変化したエチレン
のモル数/反応したエチレンのモル数)×100 [担体Aの製造方法]市販のアルミナ粉体(α−アルミ
ナ1次粒子径1〜2μm、平均2次粒子径50〜60μ
m、BET比表面積2.5〜3.5m2 /g)の93重
量部と有機結合剤5重量部をニーダに投入し、十分に混
合した後、粒径2〜20nmのアルミナゾル4重量部
(Al2 3 含有量として)と粒径2〜20nmのコロ
イド状シリカ3重量部(SiO2 含有量として)を加
え、これに水40重量部をニーダに投入し、十分に混合
したアルミナ混合物を押し出し成形した後、造粒、乾燥
し、1450℃で2時間乾燥し担体を得た。得られた担
体はBET比表面積1.26m2 /g、見掛気孔率5
5.7%、細孔容積0.40cc/gのα−アルミナ粉
体の担体の外表面上および担体の気孔の表面上の非晶質
シリカ−アルミナで被覆された外径7mm、内径3m
m、長さ7mmのリング形状のα−アルミナ担体を担体
Aとした。担体Aに担持した非晶質シリカ−アルミナ量
は以下の方法による測定によれば、各々1.2×10-2
Si g/g担体および1.0×10-2Al g/g
担体で、Si/Al比1.2g/gであった。
Change rate (%) = (mol number of reacted ethylene / mol number of ethylene in raw material gas) × 100 Selectivity (%) = (mol number of ethylene converted to ethylene oxide / mol number of reacted ethylene) ) × 100 [Production method of carrier A] Commercially available alumina powder (α-alumina primary particle diameter 1 to 2 μm, average secondary particle diameter 50 to 60 μm)
m, BET specific surface area of 2.5 to 3.5 m 2 / g) and 93 parts by weight of organic binder and 5 parts by weight of organic binder were put into a kneader and sufficiently mixed, and then 4 parts by weight of alumina sol having a particle size of 2 to 20 nm ( Al 2 O 3 content) and 3 parts by weight of colloidal silica having a particle size of 2 to 20 nm (as SiO 2 content) are added, and 40 parts by weight of water is added to a kneader to form a well-mixed alumina mixture. After extrusion molding, the mixture was granulated, dried, and dried at 1450 ° C. for 2 hours to obtain a carrier. The obtained carrier has a BET specific surface area of 1.26 m 2 / g and an apparent porosity of 5
Outer diameter 7 mm, inner diameter 3 m coated with amorphous silica-alumina on the outer surface of the carrier of 5.7% α-alumina powder with a pore volume of 0.40 cc / g and on the surface of the pores of the carrier.
The carrier A was a ring-shaped α-alumina carrier having m and a length of 7 mm. The amount of amorphous silica-alumina supported on the carrier A was 1.2 × 10 -2 when measured by the following method.
Si g / g carrier and 1.0 × 10 -2 Al g / g
The carrier had a Si / Al ratio of 1.2 g / g.

【0046】「得られたα―アルミナ担体Aの担体の外
表面上および担体の気孔の表面上の非晶質シリカ及びア
ルミナの量の測定方法]10gの担体を8〜10メッシ
ュにくだき46重量%フッ化水素酸水溶液20mlに1
時間室温で浸した後、濾過を行ない溶液中のSiイオン
およびAlイオンを原子吸光分析器で測定して求めた。
[Measurement Method of Amount of Amorphous Silica and Alumina on the Outer Surface of Carrier of A-Alumina Carrier A Obtained and on Surface of Pore of Carrier] 10 g of the carrier was put into 8 to 10 mesh and 46 wt. 1 to 20 ml of aqueous hydrofluoric acid solution
After soaking at room temperature for a period of time, filtration was performed and Si ion and Al ion in the solution were measured by an atomic absorption spectrometer to obtain the value.

【0047】実施例1 修酸銀830gを水200mlと泥状にしておき、これ
にエタノ―ルアミン700mlを加え、よく攪拌し、溶
解させ、さらに水100mlを加えよく攪拌後、これに
7.5gの硝酸セシウムを水200mlに溶解した液を
加えて攪拌し、含浸溶液を調製した。
Example 1 830 g of silver oxalate was made into a muddy state with 200 ml of water, 700 ml of ethanolamine was added thereto, and well stirred and dissolved, and 100 ml of water was further added and well stirred, and then 7.5 g of this was added. A solution prepared by dissolving cesium nitrate in Example 2 in 200 ml of water was added and stirred to prepare an impregnation solution.

【0048】この含浸溶液を予め約100℃に加熱した
α−アルミナ担体Aの3000gに含浸後、加熱濃縮乾
燥し、さらに、空気浴中で120℃で3時間加熱した
後、空気気流中で48時間280℃で賦活化した。
This impregnating solution was impregnated with 3000 g of α-alumina carrier A preheated to about 100 ° C., concentrated by heating and dried, and further heated in an air bath at 120 ° C. for 3 hours, and then in an air stream. Activation was carried out at 280 ° C for a time.

【0049】この触媒を外部から不活性ガスを導入でき
るステンレス製密閉容器に充填し、窒素ガスを送り込み
がら電気炉中で触媒層の温度530℃で3時間の高温加
熱処理して完成触媒とした。
This catalyst was filled in a stainless steel closed container into which an inert gas could be introduced from the outside, and heated at a catalyst layer temperature of 530 ° C. for 3 hours in an electric furnace while feeding nitrogen gas to obtain a completed catalyst. ..

【0050】得られた完成触媒中の全セシウムの量は1
1×10-3グラム当量重量/kg触媒であった。
The amount of total cesium in the obtained finished catalyst was 1
It was 1 × 10 −3 gram equivalent weight / kg catalyst.

【0051】[完成触媒中の全セシウムの量の測定方
法]サンプルの約20gを粉末にし、(20kg/cm
2 で)圧縮してテストシートにした;セシウム濃度既知
の触媒を同様に処理し、標準とした;テストシートを、
螢光X線分光分析装置で標準サンプルの記録データによ
り得られた計算グラフを使って評価した。その結果0.
15重量%のセシウムが測定された。この量は11×1
-3グラム当量重量/kg触媒と計算された。
[Method for measuring the amount of total cesium in the finished catalyst] About 20 g of the sample was made into powder and (20 kg / cm
2 ) Compressed into test sheets; catalysts of known cesium concentration were similarly treated to become standard;
Evaluation was carried out using a calculation graph obtained from the recorded data of a standard sample with a fluorescent X-ray spectrophotometer. As a result, 0.
15% by weight of cesium was measured. This amount is 11 x 1
0 -3 was calculated to gram equivalent weight / kg catalyst.

【0052】得られた完成触媒を内径25mm、管長1
1000mmの外部が加熱型の二重管式ステンレス製反
応器に充填し、該充填層に、エチレン20容量%、酸素
7容量%、炭酸ガス7容量%、残余がメタン、窒素、ア
ルゴンおよびエタンからなり、さらに二塩化エチレン1
ppmからなる混合ガスを導入し、反応圧力24kg/
cm2 G、空間速度5500hr-1、熱媒温度230℃
まで昇温し反応を行った。その10日後の結果および1
年後の結果を表1に示す。
The completed catalyst thus obtained had an inner diameter of 25 mm and a tube length of 1
A 1000 mm external heating type double tube type stainless steel reactor was filled, and the packed bed was filled with 20% by volume of ethylene, 7% by volume of oxygen, 7% by volume of carbon dioxide, and the balance from methane, nitrogen, argon and ethane. And 1 more ethylene dichloride
Introducing a mixed gas consisting of ppm, reaction pressure 24 kg /
cm 2 G, space velocity 5500 hr -1 , heat medium temperature 230 ° C
The temperature was raised up to the reaction. Results 10 days later and 1
The results after one year are shown in Table 1.

【0053】実施例2 実施例1において高温加熱処理を表−1に示す条件にし
た以外は実施例1と同様な方法で行なった。その10日
後の結果および1年後の結果を表1に示す。
Example 2 The same procedure as in Example 1 was carried out except that the high temperature heat treatment in Example 1 was carried out under the conditions shown in Table 1. The results after 10 days and after 1 year are shown in Table 1.

【0054】実施例3〜4 実施例1において担体として表−1に示す担体を用いる
以外は実施例1と同様な方法で行なった。その10日後
の結果および1年後の結果を表1に示す。
Examples 3 to 4 The same procedure as in Example 1 was carried out except that the carrier shown in Table 1 was used as the carrier in Example 1. The results after 10 days and after 1 year are shown in Table 1.

【0055】比較例1〜2 実施例1において高温加熱処理を表−1に示す条件にし
た以外は実施例1と同様な方法で行なった。その10日
後の結果および1年後の結果を表1に示す。
Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out except that the high temperature heat treatment in Example 1 was carried out under the conditions shown in Table 1. The results after 10 days and after 1 year are shown in Table 1.

【0056】比較例3 実施例1において担体として市販のノートン社製担体S
A−5205をそのまま用いる以外は実施例1と同様な
方法で行なった。その10日後の結果および1年後の結
果を表1に示す。
Comparative Example 3 Norton carrier S commercially available as a carrier in Example 1
The same procedure as in Example 1 was repeated except that A-5205 was used as it was. The results after 10 days and after 1 year are shown in Table 1.

【0057】比較例4 実施例1において担体として市販のノートン社製担体S
A−5102をそのまま用いる以外は実施例1と同様な
方法で行なった。その10日後の結果および1年後の結
果を表1に示す。
Comparative Example 4 Norton carrier S commercially available as a carrier in Example 1
The same procedure as in Example 1 was repeated except that A-5102 was used as it was. The results after 10 days and after 1 year are shown in Table 1.

【0058】比較例5〜6 実施例1において担体としてノートン社製担体SA−5
102にコロイダルシリカ(2〜50nm)を含浸、加
熱濃縮乾燥後、1000℃で時間焼成し、得られた担体
の外表面上および担体の気孔の表面上の非晶質シリカで
被覆された担体を用いる以外は実施例1と同様な方法で
行なった。その10日後の結果および1年後の結果を表
1に示す。
Comparative Examples 5 to 6 As a carrier in Example 1, Norton carrier SA-5 is used.
102 was impregnated with colloidal silica (2 to 50 nm), concentrated by heating and dried, and then calcined at 1000 ° C. for an hour to obtain a carrier coated with amorphous silica on the outer surface of the carrier and on the surface of the pores of the carrier. The same procedure as in Example 1 was carried out except that it was used. The results after 10 days and after 1 year are shown in Table 1.

【0059】比較例7 実施例1において担体としてノートン社製担体SA−5
102をそのまま用い、含有セシウム量を表1に示す
量、また高温処理を行わない以外は実施例1と同様な方
法で行なった。その10日後の結果および1年後の結果
を表1に示す。
Comparative Example 7 Norton carrier SA-5 as a carrier in Example 1
Example 102 was carried out in the same manner as in Example 1 except that 102 was used as it was, the amount of cesium contained was as shown in Table 1, and the high temperature treatment was not performed. The results after 10 days and after 1 year are shown in Table 1.

【0060】比較例8 実施例1において、含有セシウム量を表1に示す量、ま
た高温処理を行わない以外は実施例1と同様な方法で行
なった。その10日後の結果および1年後の結果を表1
に示す。
Comparative Example 8 The same procedure as in Example 1 was carried out except that the amount of cesium contained was the amount shown in Table 1 and the high temperature treatment was not performed. The results after 10 days and after 1 year are shown in Table 1.
Shown in.

【0061】[0061]

【表1】 [Table 1]

【0062】[0062]

【表2】 [Table 2]

【0063】[0063]

【発明の効果】本発明は、担体の外表面上および担体の
気孔の表面上が非晶質シリカ−アルミナで被覆されたα
―アルミナ担体の非晶質シリカーアルミナ中のSiおよ
びAlが特定の比率であるα―アルミナ担体を用いて完
成触媒当り5〜25重量%の金属銀微粒子および完成触
媒1キログラム当り0.0001〜0.05グラム当量
重量のセシウムを担持したことにより高選択性および高
活性を長期間に渡って維持できる効果をもった新規なエ
チレンオキシド製造用銀触媒が得られるものである。
INDUSTRIAL APPLICABILITY According to the present invention, the outer surface of the carrier and the surface of the pores of the carrier are coated with amorphous silica-alumina.
-Amorphous silica of alumina support-Using an α-alumina support having a specific ratio of Si and Al in alumina, 5 to 25% by weight of fine metal silver particles per finished catalyst and 0.0001 to 1 per kilogram of finished catalyst. By supporting 0.05 gram equivalent weight of cesium, a novel silver catalyst for producing ethylene oxide having the effect of maintaining high selectivity and high activity over a long period of time can be obtained.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 担体の外表面上および担体の気孔の表面
上が非晶質シリカーアルミナで被覆されたα―アルミナ
担体で、該非晶質シリカーアルミナ中のSiおよびAl
の合計量が3×10-4〜2×10-1g/g担体であり、
かつ非晶質分のSi/Al比が0.05〜50.0g/
gであるα―アルミナ担体に完成触媒当り5〜25重量
%の金属銀微粒子および完成触媒1キログラム当り0.
0001〜0.05グラム当量重量のセシウムを担持し
たことを特徴とするエチレンオキシド製造用銀触媒。
1. An α-alumina carrier in which the outer surface of the carrier and the surface of pores of the carrier are coated with amorphous silica-alumina, wherein Si and Al in the amorphous silica-alumina are used.
Is 3 × 10 −4 to 2 × 10 −1 g / g carrier,
And the Si / Al ratio of the amorphous component is 0.05 to 50.0 g /
5 to 25% by weight of metal silver fine particles per finished catalyst on an α-alumina support of 0.1 g and 0.1 per kilogram of finished catalyst.
A silver catalyst for producing ethylene oxide, which carries cesium in an amount of 0001 to 0.05 gram equivalent.
【請求項2】 0.1〜10μmの径のα―アルミナ一
次粒子で構成された20〜200μmの2次粒子径を有
し、比表面積が0.1〜10m2 /gのアルミナ粉体を
主原料とし、混合時にコロイド状であるアルミナおよび
シリカを混合した後、成形、乾燥さらに1000〜16
00℃の温度で焼成し、担体の外表面上および担体の気
孔の表面上がSiおよびAlの合計量が3×10-4〜2
×10-1g/g担体であり、かつ非晶質分のSi/Al
比が0.05〜50.0g/gである非晶質シリカーア
ルミナで被覆されたα―アルミナ担体を調製し、該α―
アルミナ担体に完成触媒当り5〜25重量%の金属銀微
粒子および完成触媒1キログラム当り0.0001〜
0.05グラム当量重量のセシウムを担持せしめた後、
賦活化処理して、銀とセシウムとを多孔性無機質耐火性
担体に析出した後、不活性ガス中で400〜950℃の
範囲で高温加熱処理することを特徴とするエチレンオキ
シド製造用銀触媒の製造方法。
2. An alumina powder having a secondary particle size of 20 to 200 μm and a specific surface area of 0.1 to 10 m 2 / g, which is composed of α-alumina primary particles having a diameter of 0.1 to 10 μm. After mixing alumina and silica, which are the main raw materials and are in a colloidal state at the time of mixing, molding and drying, and further 1000 to 16
Calcination was performed at a temperature of 00 ° C., and the total amount of Si and Al on the outer surface of the carrier and on the surface of the pores of the carrier was 3 × 10 −4 to 2
× 10 -1 g / g carrier and amorphous Si / Al
An α-alumina carrier coated with amorphous silica-alumina having a ratio of 0.05 to 50.0 g / g was prepared.
Alumina carrier, 5 to 25% by weight of metal silver fine particles per finished catalyst, and 0.0001 to 1 per kilogram of finished catalyst.
After supporting 0.05 gram equivalent weight of cesium,
Production of silver catalyst for ethylene oxide production, characterized by activating and precipitating silver and cesium on a porous inorganic refractory carrier, and then heat-treating at high temperature in the range of 400 to 950 ° C in an inert gas. Method.
JP33054792A 1992-02-27 1992-12-10 Silver catalyst for producing ethylene oxide and method for producing the same Expired - Fee Related JP3313164B2 (en)

Priority Applications (11)

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JP33054792A JP3313164B2 (en) 1992-02-27 1992-12-10 Silver catalyst for producing ethylene oxide and method for producing the same
CA002089510A CA2089510C (en) 1992-02-27 1993-02-15 Silver catalyst for production of ethylene oxide and method for production of the catalyst
AU33125/93A AU659914B2 (en) 1992-02-27 1993-02-17 Silver catalyst for production of ethylene oxide and method for production of the catalyst
KR1019930002577A KR0145749B1 (en) 1992-02-27 1993-02-24 Silver catalyst for production of ethylene oxide and method for production of the catalyst
TW082101362A TW304891B (en) 1992-02-27 1993-02-25
US08/025,157 US5395812A (en) 1992-02-27 1993-02-25 Silver catalyst for production of ethylene oxide and method for production of the catalyst
MX9301029A MX9301029A (en) 1992-02-27 1993-02-25 SILVER CATALYST FOR THE PRODUCTION OF ETHYLENE OXIDE AND METHOD FOR OBTAINING THE CATALYST.
EP93301492A EP0558346B1 (en) 1992-02-27 1993-02-26 Silver catalyst for production of ethylene oxide
DE69300497T DE69300497T2 (en) 1992-02-27 1993-02-26 Silver catalyst for the production of ethylene oxide.
BR9300692A BR9300692A (en) 1992-02-27 1993-02-26 SILVER CATALYST FOR PRODUCTION OF ETHYLENE OXIDE AND PROCESS FOR THE PRODUCTION OF CATALYST
CN93103580A CN1050778C (en) 1992-02-27 1993-02-27 Silver catalyst for production of ethylene oxides and method for production of the catalyst

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP4130392 1992-02-27
JP4-41303 1992-02-27
JP33054792A JP3313164B2 (en) 1992-02-27 1992-12-10 Silver catalyst for producing ethylene oxide and method for producing the same

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US6908879B1 (en) 1999-09-06 2005-06-21 Nippon Shokubai Co., Ltd. Ceramic article, carrier for catalyst, methods for production thereof, catalyst for producing ethylene oxide using the carrier, and method for producing ethylene oxide
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KR930017618A (en) 1993-09-20
KR0145749B1 (en) 1998-08-17
TW304891B (en) 1997-05-11
JP3313164B2 (en) 2002-08-12

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