JPH0525546B2 - - Google Patents
Info
- Publication number
- JPH0525546B2 JPH0525546B2 JP60225976A JP22597685A JPH0525546B2 JP H0525546 B2 JPH0525546 B2 JP H0525546B2 JP 60225976 A JP60225976 A JP 60225976A JP 22597685 A JP22597685 A JP 22597685A JP H0525546 B2 JPH0525546 B2 JP H0525546B2
- Authority
- JP
- Japan
- Prior art keywords
- silver
- producing
- catalyst
- carrier
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 110
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 51
- 229910052709 silver Inorganic materials 0.000 claims description 51
- 239000004332 silver Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 25
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 17
- 230000001603 reducing effect Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000005658 halogenation reaction Methods 0.000 claims description 14
- 239000002683 reaction inhibitor Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229940100890 silver compound Drugs 0.000 claims description 10
- 150000003379 silver compounds Chemical class 0.000 claims description 10
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 9
- 241000534000 Berula erecta Species 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 239000010946 fine silver Substances 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 31
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 26
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- 229910001961 silver nitrate Inorganic materials 0.000 description 13
- 239000000969 carrier Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 description 6
- 150000001408 amides Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- -1 cesium metals Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- TZGPACAKMCUCKX-UHFFFAOYSA-N 2-hydroxyacetamide Chemical compound NC(=O)CO TZGPACAKMCUCKX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- RZESOXIJGKVAAX-UHFFFAOYSA-L [Ag++].[O-]C(=O)CCC([O-])=O Chemical compound [Ag++].[O-]C(=O)CCC([O-])=O RZESOXIJGKVAAX-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003152 propanolamines Chemical class 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- RUJQWQMCBPWFDO-UHFFFAOYSA-M silver;2-hydroxyacetate Chemical compound [Ag+].OCC([O-])=O RUJQWQMCBPWFDO-UHFFFAOYSA-M 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はエチレンと分子状酸素とをハロゲン化
反応抑制剤の存在下、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エチレン
オキシド製造用銀触媒の製造方法に関するもので
ある。
The present invention relates to a method for producing a silver catalyst for producing ethylene oxide, which is used in producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor.
工業的にエチエンと分子状酸素とをハロゲン化
反応抑制剤の存在下、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銀触媒に
は、その性能として高選択性、高活性触媒寿命の
耐久性および触媒層における低圧力損失が要求さ
れる。
これらの要求に対し、その性能を改善する目的
で今日迄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。銀の担持方法については種々の方法が提案さ
れている。たとえば、特公昭46−19606号、特公
昭55−22146号、特公昭59−29291号、米国特許第
4305844号、米国特許第4400308号の各公報明細書
などにおいて銀の担持方法の改良が試みられてい
る。
また反応促進剤については、主としてアルカリ
金属およびタリウムが有効とされ、元素の種類と
量および添加方法について、種々の提案がされて
いる。たとえば、特開昭49−30286号、特開昭50
−50307号、特開昭50−74589号、特開昭50−
95213号、特開昭50−160187号、特開昭52−
117293号、特公昭59−29293号、特開昭55−
127144号、特開昭56−5471号、特開昭57−107240
号の各公報明細書などである。
さらに担体に関する報告が多数提案されてい
る。たとえば、特公昭42−1412号、特公昭43−
13137号、特公昭45−21373号、特公昭45−22419
号、特公昭45−11217号、特開昭56−89843号、米
国特許第2766261号、米国特許第3172893号、米国
特許第3664970号、米国特許第4242235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。
The silver catalyst used industrially to produce ethylene oxide by catalytic gas-phase oxidation of ethene and molecular oxygen in the presence of a halogenation reaction inhibitor has the characteristics of high selectivity and long active catalyst life. Durability and low pressure drop in the catalyst layer are required. In response to these demands, various studies have been made to date to improve the performance, and much effort has been made to improve carriers, reaction accelerators, silver compounds, etc. Various methods have been proposed for supporting silver. For example, Japanese Patent Publication No. 46-19606, Japanese Patent Publication No. 55-22146, Japanese Patent Publication No. 59-29291, U.S. Patent No.
4,305,844 and US Pat. No. 4,400,308, attempts have been made to improve the method of supporting silver. As for reaction accelerators, alkali metals and thallium are mainly effective, and various proposals have been made regarding the types and amounts of the elements and methods of addition. For example, JP-A-49-30286, JP-A-50
−50307, Japanese Patent Application Publication No. 1983-74589, Japanese Patent Application Publication No. 1973-
No. 95213, JP-A No. 160187, JP-A No. 52-
No. 117293, Special Publication No. 1983-29293, Japanese Patent Publication No. 1983-
No. 127144, JP-A-56-5471, JP-A-57-107240
This includes the specifications of each publication of the issue. Furthermore, many reports regarding carriers have been proposed. For example, Special Publication No. 1412, Special Publication No. 1412, Special Publication No. 43-
No. 13137, Special Publication No. 1973-21373, Special Publication No. 1977-22419
No. 45-11217, JP-A-56-89843, U.S. Patent No. 2766261, U.S. Patent No. 3172893, U.S. Patent No. 3664970, U.S. Patent No. 4242235, etc. Much of it concerns the pore distribution and specific surface area of the carrier.
しかしこれらのいずれの方法においても担体の
形状による選択率および触媒層の圧力損失の改良
に関する記載はなく、これまでの工業的規模に大
部分採用されている形状であるペレツトか球かラ
シヒリングが開示されているにすぎない。
また、特公昭59−29293号明細書においては、
多孔性無機質耐火性担体に、還元性化合物を含有
した銀化合物溶液を含浸し、加熱還元処理せしめ
て担体外表面および細孔内壁面に金属銀を分散担
持した後、水および／または低級アルコールによ
り洗浄し、乾燥後さらにこれにアルカリ金属およ
び／またはアルカリ金属化合物含有溶液を含浸
し、液成分を蒸発乾燥せしめる方法が開示されて
いる。この方法は最も高い選択率、最も高い活
性、および触媒寿命の最も良い耐久性を合せもつ
た触媒性能を有する工業用銀触媒の製造方法の一
つであるがまだ選択性において十分満足できるも
のではない。
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、シリコンカーバイド、シリカル、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。
したがつて、本発明の目的は、エチレンと分子
状酸素とをハロゲン化反応抑制剤の存在下、接触
気相酸化してエチレンオキシドを製造するに際し
使用されるエチレンオキシド製造用銀触媒の製造
方法を提供することにある。
本発明の他の目的は、エチレンと分子状酸素と
をハロゲン化反応抑制剤の存在下、接触気相酸化
して高選択性でエチレンオキシドを製造する、触
媒層における低圧力損失の銀触媒の製造方法を提
供することにある。
本発明者等はエチエンオキシド製造用銀触媒に
用いるための好適な形状の担体を選択し、さらに
その担体に適した新規なエチレンオキシド製造用
銀触媒に関する研究を行なつた結果、これまでに
なく、高選択性でしかも触媒層の圧力損失が少な
い触媒の製造方法が得られることを見出して本発
明を完成した。
However, none of these methods discloses improvements in selectivity and pressure drop in the catalyst layer by changing the shape of the carrier, and only pellets, spheres, and Raschig rings, which are the shapes that have been mostly used on an industrial scale, have been disclosed. It's just that it's being done. In addition, in the specification of Japanese Patent Publication No. 59-29293,
A porous inorganic refractory carrier is impregnated with a silver compound solution containing a reducing compound, subjected to heat reduction treatment to disperse and support metallic silver on the outer surface of the carrier and the inner wall surface of the pores, and then impregnated with water and/or lower alcohol. A method is disclosed in which, after washing and drying, the material is further impregnated with a solution containing an alkali metal and/or an alkali metal compound, and the liquid components are evaporated to dryness. This method is one of the methods for producing industrial silver catalysts that have the highest selectivity, the highest activity, and the best durability of catalyst life, but it is still not fully satisfactory in terms of selectivity. do not have. There are still many unknown points regarding silver catalyst supports for ethylene oxide production, and there are many problems that need to be improved. For example, the components constituting the carrier, the specific surface area of the carrier, pore diameter, pore distribution, pore volume, porosity,
Examples include optimization of physical properties such as particle size and shape, and chemical properties of carrier materials such as α-alumina, silicon carbide, silica, and zirconia. Therefore, an object of the present invention is to provide a method for producing a silver catalyst for producing ethylene oxide, which is used in producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. It's about doing. Another object of the present invention is to produce a silver catalyst with low pressure loss in the catalyst layer, which produces ethylene oxide with high selectivity by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. The purpose is to provide a method. The present inventors selected a carrier with a suitable shape for use in a silver catalyst for producing ethylene oxide, and as a result of conducting research on a new silver catalyst for producing ethylene oxide that is suitable for that carrier, The inventors completed the present invention by discovering that a method for producing a catalyst with high selectivity and low pressure loss in the catalyst layer can be obtained.
本発明は、エチレンと分子状酸素とをハロゲン
化反応抑制剤の存在下、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多孔性無
機質耐火性担体の外表面および細孔内壁面に微細
銀粒子を分散付着せしめてなる銀接触の製造方法
において、インターロツクスサドルまたはベルル
サドルの形状を有する多孔性無機質耐火性担体
に、還元性化合物を含有した銀化合物溶液を含浸
し、加熱還元処理せしめて担体外表面および細孔
内壁面に金属銀を分散担持した後、水および／ま
たは低級アルコールにより洗浄し、乾燥後さらに
これにアルカリ金属および／またはアルカリ金属
化合物含有溶液を含浸し、液成分を蒸発乾燥せし
めてなることを特徴とするエチレンと分子状酸素
とをハロゲン化反応抑制剤の存在下、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
れるエチレンオキシド製造用銀触媒の製造方法に
関するものである。
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球あるいはラ
シヒリングの形状の担体よりもインターロツクス
サドルまたはベルルサドルの形状を有する多孔性
無機質耐火性担体に、還元性化合物を含有した銀
化合物溶液を含浸し、加熱還元処理せしめて担体
外表面および細孔内壁面に金属銀を分散担持した
後、水および／または低級アルコールにより洗浄
し、乾燥後さらにこれにアルカリ金属および／ま
たはアルカリ金属化合物含有溶液を含浸し、液成
分を蒸発乾燥せしめて得られたエチレンオキシド
製造用銀触媒は、これまでになく高選択性、触媒
相における低圧力損失の触媒が得られることを見
出したものである。
エチレンと分子状酸素とをハロゲン化反応抑制
剤の存在下、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。
しかしながら、単に多孔性粒状耐火物担体と言
つ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
コンカーバイド、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質が触媒
の性能に及ぼす影響は大きい。
したがつてどのような性質の担体を選ぶかは、
当業者にとつて大きな問題である。特に担体の形
状は触媒性能に大きく関係し、触媒製造時、銀と
アルカリ金属および／またはアルカリ金属化合物
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。また反応時触媒の粒子内でのガスの滞留
が起こりにくく反応熱の除去しやすい担体の形状
を選ぶことが選択性の優れた触媒を得る一つの方
法となる。この為には、担体の見かけの表面積と
見かけの体積（排除体積）との比が大きい方が有
利である。これまでの工業的規模に採用されてい
る大部分の担体の形状は球がラシヒリングである
が、この比を大きくするには、球においては粒径
を小さくすればよい。しかしあまり粒径を小さく
すると反応時の圧力損失が非常に大きくなり、装
置、ユーテイリテイー両面で不利となる、またラ
シヒリングにおいては、この比を大きくするのに
ラシヒリングの肉厚を減少するのが効果的である
が圧壊強度が減少し、また反応管の単位体積当り
の触媒表面積が減少する為不利となる。
したがつて必ずしも担体の見かけの表面積と見
かけの体積の比が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。
本発明者等は種々の形状の担体を検討した結
果、インターロツクスサドルまたはベルルサドル
の形状を有する多孔性無機質耐火性担体を使用し
た触媒が高選択率でしかも触媒層の圧力損失が低
いことを見出した。
インターロツクスサドルおよびベルルサドルの
形状を有する多孔性無機質耐火性担体は、ラシヒ
リングに比べ、粒径、肉厚が同じ場合、充填比重
が小さい、このことは反応管の単位体積当りの触
媒表面積が小さくなることになる。このような一
見不利とも考えられる形状にもかかわらず選択性
に優れ、しかも触媒層における低圧力損失の触媒
が得られたことは驚くべきことである。球やラシ
ヒリングの担体を用いた触媒において、見かけの
表面積と見かけの体積の比を、インターロツクス
サドルやベルルサドルの形状を有する多孔性無機
質耐火性担体を用いた触媒と同じようにしても、
インターロツクスサドルやベルルサドルの形状を
有する多孔性無機質耐火性担体を用いた触媒ほど
高選択性、低圧力損失とはならない。またインタ
ーロツクスサドルやベルルサドルの形状を有する
多孔性無機質耐火性担体を用いた触媒と同じ充填
比重の球やラシヒリングの担体を用いた触媒はイ
ンターロツクスサドルやベルルサドルの形状を有
する多孔性無機質耐火性担体を用いた触媒ほどの
高選択性および低圧力損失とはならない。
本発明のインターロツクスサドルまたはベルル
サドルの形状を有する多孔性無機質耐火性担体の
比表面積としては0.01m2／ｇ〜10m2／ｇ、特に
0.1〜５m2／ｇの範囲が有効である。0.01m2／ｇ
未満となるインターロツクスサドルやベルルサド
ルの形状を有する多孔性無機質耐火性担体は充填
比重が小さいため、反応管の単位体積当りの表面
積が非常に小さくなり活性の面で不利となる。ま
た10m2／ｇを超えた場合は担体内細孔径が小さく
なりすぎ反応時触媒の粒子内での反応ガスおよび
生成ガスの滞留が起こりやすくなる。また本発明
で使用されるインターロツクスサドルやベルルサ
ドルの形状を有する多孔性無機質耐火性担体の見
かけの体積に対する見かけの表面積の比は0.1〜
10mm-1である。見かけの体積に対する見かけの表
面積の比が0.1mm-1未満の場合、肉厚が厚くなり
選択率が低下する。また見かけの体積に対する見
かけの表面積の比が10mm-1を超えた場合、肉厚が
大変薄くなり工業用触媒として必要な強度を保て
なくなる。
インターロツクスサドルの形状を有する多孔性
無機質耐火性担体の物性は、見かけの気孔率20〜
80％、比気孔容積0.06〜1.0c.c.／ｇ、外周の長さ
(A)３〜70mm、特に3.5〜30mm、内周の長さ(C)1.5〜
68mm、特に1.8〜28mm、厚さ(W)0.1〜４mm、特に0.8
〜３mm、外径(D)0.5〜20mm、特に３〜15mm、長さ
(E)0.5〜65mm、特に３〜20mmの範囲が好ましい。
ベルルサドルの形状を有する多孔性無機質耐火
性担体の物性は、見かけの気孔率20〜80％、比気
孔容積0.06〜1.0c.c.／ｇ、外周の長さ(A)３〜70mm、
特に3.5〜30mm、内周の長さ(C)1.5〜68mm、特に1.8
〜28mm、厚さ(W)0.1〜４mm、特に0.8〜３mm、外径
(D)0.5〜20mm、特に３〜15mm、長さ(E)0.5〜65mm、
特に３〜20mmの範囲が好ましい。
また、担体材料としては、α−アルミナ、シリ
コンカーバイド、シリカ、ジルコニア、粘土が好
ましいが、得にα−アルミナが好適である。さら
にまた担体主成分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量が好ましい。
本発明に使用される担体の形状の例を図面に示
す。図−１〜３はインターロツクスサドルの形状
を有する多孔性無機質耐火性担体、図−４〜６は
ベルルサドルの形状を有する多孔性無機質耐火性
担体を示す。
まず、本発明にかかる触媒は、以下の如くにし
て製造される。
本発明に使用される還元性化合物を含有した銀
化合物溶液としては、これまで公知の全てのもの
が利用できるが、有効には低級酸アミドを還元成
分として含有した硝酸銀のモノエチレングリコー
ル溶液、アルカノールアミンを還元性化合物とし
て含有した、各種銀化合物をアルカノールアミン
または他のアミンに溶かした溶液、ホルマリンを
還元成分として含有した硝酸銀水溶液等が利用で
きる。
還元性化合物として用いられる低級酸アミドと
しては、ホルムアミド、アセトアミド、プロピオ
ン酸アミド、グリコ−ル酸アミド、ジメチルホル
ムアミドなどが挙げられる。アルカノールアミン
または他のアミンとしては、モノ−・ジ−・トリ
エタノ−ルアミン類、モノ−・ジ−・トリ−ｎ−
プロパノ−ルアミン類、モノ−・ジ−・トリ−イ
ソプロパノールアミン類、ｎ−ブタノールアミン
類、イソブタノールアミン類などが挙げられる。
これら還元性化合物は、常温〜200℃で還元作用
を有し、溶存する銀化合物を金属銀に還元する。
原料として用いられる銀化合物には、上記低級
酸アミドと反応して錯塩を形成する無機銀塩およ
び有機銀塩のいかなるものも用いうるが、一例を
挙げると、硝酸銀、炭酸銀、硫酸銀、酢酸銀、乳
酸銀、コハク酸銀、グリコール酸銀などが用いう
る。
銀担持率は触媒に対し５〜30重量％、好ましく
は５〜25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。
また、用いられる溶媒としては、アルコール性
水酸基を１分子中に１〜３個有する炭素数２〜６
の低級脂肪族化合物、たとえば、モノエチレング
リコール、ジエチレングリコール、トリエチレン
グリコール、トリメチレングリコール、モノプロ
ピレングリコール、メチルセロソルブ、エチルセ
ロソルブ、メチルカルビトール、エチルカルビト
ール、グリセリンなどが、とくに還元性化合物と
して低級酸アミド類を用いる場合に好適に使用さ
れる。またアルカノールアミン等のアミン類およ
び水も好適に溶媒として使用できる。
アルカリ金属またはアルカリ金属化合物はカリ
ウム、ルビジウム、セシウムの金属または化合物
の中から選ばれた１種あるいは２種以上を用いる
ことができる。たとえば硝酸塩、硫酸塩、水酸化
物、酸化物、酢酸塩等の各種化合物が挙げられ
る。これらの水溶液あるいはメタノール、エタノ
ール、プロパノールのごとき低級アルコール溶液
の形で用いられる。アルカリ金属またはアルカリ
金属化合物は完成触媒１キログラムあたり0.0001
〜0.03グラム当量、特に0.0008〜0.02グラム当量
の範囲内が好ましい。
次に具体的に本発明にかかる銀担持触媒の製造
方法について還元性化合物として低級酸アミドを
使用した方法について説明する。
硝酸銀を１〜20重量倍の溶媒、特に１〜10重量
倍の溶媒、たとえばエチレングリコール中に溶解
する。この溶液に銀成分に対し0.5〜５倍モル、
特に１〜３倍モルの還元性化合物、たとえばホル
ムアミドを加え、よく攪拌後所定量のインターロ
ツクスサドルまたはベルルサドルの形状を有する
多孔性無機質耐火性担体に含浸し、100〜150℃で
１〜10時間加熱処理して銀が微粒子となつて担体
外表面および細孔内壁面に還元担持される。
かくして活性銀を担体外表面および細孔内壁面
に分散付着せしめた後、水洗、好ましくは煮沸水
洗される。これは触媒中のホルムアミドおよびエ
チレングリコール等の有機物を除去せしめること
と共に生成した活性銀の表面を洗浄化してさらに
高活性化させる効果を有する。
洗浄後50〜150℃に加熱し乾燥する。ついでこ
の触媒を所定量の反応促進剤を含有する水溶液ま
たはメタノール、エタノール等低級アルコール溶
液を含浸しさらにこれら溶媒を50〜150℃で蒸発
させて除去する。これらの工程において注意すべ
きことは触媒を200℃以上に加熱しないことであ
る。
本発明の銀触媒を使用してエチレンと分子状態
素とを接触気相酸化してエチレンオキシドを製造
する方法において、ハロゲン化反応抑制剤の存在
は必須である。
ハロゲン化反応抑制剤としては二塩化エチレ
ン、塩化ビニール、塩化ジフエニル、モノクロロ
ベンゼン、ジクロロベンゼン等の塩素化物あるい
はフツソ化物、臭素化物、ヨウ素化物等のハロゲ
ン化物を挙げることができる。
エチレンと分子状酸素とを接触気相酸化してエ
チレンオキシドを製造する際に存在させるハロゲ
ン化反応抑制剤の濃度は0.1〜10ppm（容量）、好
ましくは0.5〜5ppm（容量）存在させることが必
須である。
本発明の銀触媒を使用してエチレンと分子状酸
素とを接触気相酸化してエチレンオキシドを製造
する方法において、ハロゲン化反応抑制剤の存在
させない場合エチレンオキシドの選択率は低くな
る。
本発明の銀触媒を使用してエチレンと分子状酸
素とをハロゲン化反応抑制剤の存在下、接触気相
酸化してエチレンオキシド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。工業的製造規
模における一般的な条件、すなわち反応温度150
〜300℃、好ましくは180〜280℃、反応圧力２〜
40Kg／cm2Ｇ、好ましくは10〜30Kg／cm2Ｇ、空間速
度1000〜30000Hr-1（STP）、好ましくは3000〜
8000Hr-1（STP）が採用される。そして触媒を通
過する原料ガス組成としては、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が好
適に採用できる。
The present invention provides fine particles on the outer surface and inner wall surface of pores of a porous inorganic refractory carrier used in the production of ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. In a method for producing a silver contact by dispersing and adhering silver particles, a porous inorganic refractory carrier having the shape of an interlocking saddle or a Berl saddle is impregnated with a silver compound solution containing a reducing compound and subjected to a heat reduction treatment. After dispersing and supporting metallic silver on the outer surface of the carrier and the inner wall surface of the pores, it is washed with water and/or lower alcohol, and after drying, it is further impregnated with a solution containing an alkali metal and/or an alkali metal compound to remove the liquid components. This invention relates to a method for producing a silver catalyst for producing ethylene oxide, which is characterized by being evaporated to dryness and used in producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. It is. Studies on suitable supports for use in silver catalysts for the production of ethylene oxide have shown that porous supports having the shape of interlocking saddles or Berl saddles are preferable to the sphere or Raschig ring shaped supports commonly used in the prior art on an industrial scale. A refractory inorganic carrier is impregnated with a silver compound solution containing a reducing compound, subjected to heat reduction treatment to disperse and support metallic silver on the outer surface of the carrier and the inner wall surface of the pores, and then washed with water and/or lower alcohol. After drying, the catalyst was further impregnated with a solution containing an alkali metal and/or an alkali metal compound, and the liquid component was evaporated to dryness. It was discovered that a catalyst with low pressure loss can be obtained. The catalyst used when producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor is a silver catalyst,
It goes without saying that most of them are supported catalysts using carriers. It is also well known that the carrier used is a porous particulate refractory. However, even though it is simply 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 material constituting the carrier, such as α- The physical and chemical properties of alumina, silica, silicon carbide, zirconia, clay, etc. have a large influence on the performance of the catalyst. Therefore, what kind of carrier should be selected?
This is a big problem for those skilled in the art. In particular, the shape of the carrier has a great relationship with the catalyst performance, and it is important to choose a carrier shape that allows easy and uniform support in the process of supporting silver, alkali metals, and/or alkali metal compounds during catalyst production to produce a catalyst with excellent selectivity. You will get it. In addition, one method of obtaining a catalyst with excellent selectivity is to select a carrier shape that prevents gas from remaining in the particles of the catalyst during the reaction and facilitates the removal of reaction heat. For this purpose, it is advantageous that the ratio between the apparent surface area and the apparent volume (excluded volume) of the carrier is large. Most carriers that have been used on an industrial scale so far have a spherical Raschig ring shape, but in order to increase this ratio, the particle size of the spheres can be made smaller. However, if the particle size is made too small, the pressure loss during the reaction will become very large, which is disadvantageous in both equipment and utility. Although effective, it is disadvantageous because the crushing strength is reduced and the catalyst surface area per unit volume of the reaction tube is reduced. Therefore, it cannot necessarily be said that it is better to have a larger ratio between the apparent surface area and the apparent volume of the carrier, and this naturally leads to limitations. As a result of examining carriers of various shapes, the present inventors found that a catalyst using a porous inorganic refractory carrier having an interlocking saddle or Berl saddle shape has high selectivity and low pressure loss in the catalyst layer. I found it. Compared to Raschig rings, porous inorganic refractory carriers with the shapes of interlox saddles and Berl saddles have a smaller filling specific gravity when the particle size and wall thickness are the same, which means that the catalyst surface area per unit volume of the reaction tube is smaller. It will become. It is surprising that despite such a seemingly disadvantageous shape, a catalyst with excellent selectivity and low pressure loss in the catalyst layer was obtained. Even if the ratio of the apparent surface area to the apparent volume of a catalyst using a sphere or Raschig ring support is the same as that of a catalyst using a porous inorganic refractory support having an interlocking saddle or Berl saddle shape,
Catalysts using porous inorganic refractory supports having the shape of interlocking saddles or Berl saddles do not have as high selectivity and low pressure loss. Catalysts using porous inorganic refractory carriers with the shape of interlox saddles or Berl saddles and catalysts using spheres or Raschig ring carriers with the same packing specific gravity are However, the selectivity and pressure drop are not as high as those using catalysts using neutral carriers. The specific surface area of the porous inorganic refractory carrier having the shape of an interlocked saddle or Berl saddle of the present invention is 0.01 m 2 /g to 10 m 2 /g, particularly
A range of 0.1 to 5 m 2 /g is effective. 0.01m 2 /g
Since the porous inorganic refractory carrier having the shape of an interlocked saddle or a Berl saddle has a small filling specific gravity, the surface area per unit volume of the reaction tube becomes extremely small, which is disadvantageous in terms of activity. If it exceeds 10 m 2 /g, the pore diameter within the carrier becomes too small and reaction gas and product gas tend to stagnate within the particles of the catalyst during reaction. Furthermore, the ratio of the apparent surface area to the apparent volume of the porous inorganic refractory carrier having the shape of an interlocking saddle or a Berl saddle used in the present invention is 0.1 to
10mm -1 . When the ratio of the apparent surface area to the apparent volume is less than 0.1 mm -1 , the wall thickness increases and the selectivity decreases. Furthermore, if the ratio of the apparent surface area to the apparent volume exceeds 10 mm -1 , the wall thickness will become very thin and the strength required for an industrial catalyst will not be maintained. The physical properties of the porous inorganic refractory carrier having the shape of an interlocking saddle have an apparent porosity of 20~
80%, specific pore volume 0.06-1.0cc/g, circumference length
(A) 3~70mm, especially 3.5~30mm, inner circumference length (C) 1.5~
68mm, especially 1.8~28mm, thickness (W) 0.1~4mm, especially 0.8
~3mm, outer diameter (D) 0.5~20mm, especially 3~15mm, length
(E) A range of 0.5 to 65 mm, particularly 3 to 20 mm is preferred. The physical properties of the porous inorganic refractory carrier having the shape of a Berl saddle are: apparent porosity 20-80%, specific pore volume 0.06-1.0 cc/g, circumference length (A) 3-70 mm,
Especially 3.5~30mm, inner circumference length (C) 1.5~68mm, especially 1.8
~28mm, thickness (W) 0.1~4mm, especially 0.8~3mm, outer diameter
(D) 0.5-20mm, especially 3-15mm, length (E) 0.5-65mm,
Particularly preferred is a range of 3 to 20 mm. Further, as the carrier material, α-alumina, silicon carbide, silica, zirconia, and clay are preferred, and α-alumina is particularly preferred. Furthermore, carrier components other than the main carrier component are preferably contained in carriers commonly used in this field. Examples of the shape of the carrier used in the present invention are shown in the drawings. Figures 1 to 3 show porous inorganic refractory carriers having the shape of interlocked saddles, and Figures 4 to 6 show porous inorganic refractory carriers having the shape of Berle saddles. First, the catalyst according to the present invention is manufactured as follows. As the silver compound solution containing the reducing compound used in the present invention, all known solutions can be used, but effective solutions include a monoethylene glycol solution of silver nitrate containing a lower acid amide as a reducing component, and an alkanol solution. Solutions of various silver compounds dissolved in alkanolamines or other amines containing amines as reducing compounds, silver nitrate aqueous solutions containing formalin as reducing components, etc. can be used. Examples of the lower acid amide used as the reducing compound include formamide, acetamide, propionic acid amide, glycolic acid amide, dimethylformamide, and the like. Alkanolamines or other amines include mono-, di-, and triethanolamines, mono-, di-, and tri-n-
Examples include propanolamines, mono-, di-, and tri-isopropanolamines, n-butanolamines, and isobutanolamines.
These reducing compounds have a reducing action at room temperature to 200°C and reduce dissolved silver compounds to metallic silver. As the silver compound used as a raw material, any of the inorganic and organic silver salts that react with the lower acid amide to form a complex salt can be used; examples include silver nitrate, silver carbonate, silver sulfate, and acetic acid. Silver, silver lactate, silver succinate, silver glycolate, etc. can be used. The silver supported ratio can be 5 to 30% by weight, preferably 5 to 25% by weight, based on the catalyst, and can be deposited in the form of fine particles on the inner and outer surfaces of the carrier. In addition, the solvent used is a carbon number 2-6 having 1-3 alcoholic hydroxyl groups in one molecule.
Lower aliphatic compounds, such as monoethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, monopropylene glycol, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, glycerin, etc., are especially lower reducing compounds. It is preferably used when acid amides are used. Furthermore, amines such as alkanolamines and water can also be suitably used as solvents. As the alkali metal or alkali metal compound, one or more selected from potassium, rubidium, and cesium metals or compounds can be used. Examples include various compounds such as nitrates, sulfates, hydroxides, oxides, and acetates. These are used in the form of aqueous solutions or solutions of lower alcohols such as methanol, ethanol, and propanol. Alkali metal or alkali metal compound: 0.0001 per kilogram of finished catalyst
A range of 0.03 to 0.03 gram equivalent, particularly 0.0008 to 0.02 gram equivalent is preferred. Next, a method for producing a silver-supported catalyst according to the present invention using a lower acid amide as a reducing compound will be specifically described. Silver nitrate is dissolved in 1 to 20 parts by weight of a solvent, especially 1 to 10 parts by weight of a solvent, such as ethylene glycol. Add 0.5 to 5 times the mole of silver to this solution,
In particular, 1 to 3 times the mole of a reducing compound, such as formamide, is added, stirred thoroughly, and then impregnated into a predetermined amount of a porous inorganic refractory carrier in the shape of an interlocking saddle or Berl saddle, and heated at 100 to 150°C for 1 to 10 hours. After the heat treatment for a period of time, silver becomes fine particles and is reduced and supported on the outer surface of the carrier and the inner wall surface of the pores. After the active silver is thus dispersed and adhered to the outer surface of the carrier and the inner wall surface of the pores, the carrier is washed with water, preferably with boiling water. This has the effect of removing organic substances such as formamide and ethylene glycol in the catalyst and cleaning the surface of the produced activated silver to further increase its activation. After washing, heat to 50-150℃ and dry. Next, this catalyst is impregnated with an aqueous solution or a lower alcohol solution such as methanol or ethanol containing a predetermined amount of a reaction accelerator, and these solvents are removed by evaporation at 50 to 150°C. In these steps, care must be taken not to heat the catalyst above 200°C. In the method of producing ethylene oxide by catalytic gas phase oxidation of ethylene and a molecular state element using the silver catalyst of the present invention, the presence of a halogenation reaction inhibitor is essential. Examples of the halogenation reaction inhibitor include chlorinated products such as ethylene dichloride, vinyl chloride, diphenyl chloride, monochlorobenzene, and dichlorobenzene, and halogenated products such as fluorinated products, brominated products, and iodized products. When producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen, the concentration of the halogenation reaction inhibitor to be present is 0.1 to 10 ppm (volume), preferably 0.5 to 5 ppm (volume). be. In the method of producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen using the silver catalyst of the present invention, the selectivity of ethylene oxide is low in the absence of a halogenation reaction inhibitor. The reaction conditions that can be employed in the method for producing ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor using the silver catalyst of the present invention are not known in the art. All conditions can be adopted. Typical conditions at industrial production scale, i.e. reaction temperature 150
~300℃, preferably 180~280℃, reaction pressure 2~
40Kg/ cm2G , preferably 10-30Kg/ cm2G , space velocity 1000-30000Hr -1 (STP), preferably 3000-
8000Hr -1 (STP) is adopted. The raw material gas composition passing through the catalyst is ethylene 0.5-40.
% by volume, 3 to 10 % by volume of oxygen, 5 to 30 % by volume of carbon dioxide, and the balance being an inert gas such as nitrogen, argon, or water vapor, and lower hydrocarbons such as methane or ethane.
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。
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。
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
実施例 １
硝酸銀1600ｇをモノエチレングリコール1.8
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)13.3mmおよび内周の長さ(C)5.8mm、長さ
(E)10.0mm、見かけの体積に対する見かけの表面積
の比が1.7mm-1のインターロツクスサドルの形状
をしたα−アルミナ担体（図−１〜３）9000mlに
含浸後、含浸混合物を徐々に130℃まで昇温しそ
の温度で２時間攪拌後160℃まで昇温し、さらに
２時間攪拌し還元銀を担体に分散付着せしめた。
得られた銀担持触媒を数回9000mlの水で沸騰洗浄
後90〜100℃で乾燥した。ついで、乾燥したこの
触媒に4.52ｇの炭酸セシウムを2400mlのエチルア
ルコールに溶解した液を加えて含浸し、得られた
銀担持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、炭酸ガス７容量％、残部
がメタン、窒素、アルゴン、エタンからなり、さ
らに二塩化エチレン3ppmからなる混合ガスを導
入し、反応圧力24Kg／m2Ｇ、空間速度5500Hr-1
にて30日間反応をおこなつた。30日後の結果を表
−１に示す。
実施例 ２
硝酸銀1600ｇをモノエチレングリコール1.7
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)15.4mmおよび内周の長さ(C)6.2mm、見か
けの体積に対する見かけの表面積の比が1.7mm-1
のベルルサドルの形状をしたα−アルミナ担体
（図−４〜６）9000mlに含浸後、含浸混合物を
徐々に130℃まで昇温しその温度で２時間攪拌後
160℃まで昇温し、さらに２時間攪拌し還元銀を
担体に分散付着せしめた。得られた銀担持触媒を
数回9000mlの水で沸騰洗浄後90〜100℃で乾燥し
た。ついで、乾燥したこの触媒に4.31ｇの炭酸セ
シウムを2300mlのエチルアルコールに溶解した液
を加えて含浸し、得られた銀担持触媒を80〜100
℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。
30日後の結果を表−１に示す。
実施例 ３
硝酸銀1600ｇをモノエチレングリコール1.8
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)13.3mmおよび内周の長さ(C)5.8mm、長さ
(E)10.0mm、見かけの体積に対する見かけの表面積
の比が1.7mm-1のインターロツクスサドルの形状
をしたα−アルミナ担体（図−１〜３）9000mlに
含浸後、含浸混合物を徐々に130℃まで昇温しそ
の温度で２時間攪拌後160℃まで昇温し、さらに
２時間攪拌し還元銀を担体に分散付着せしめた。
得られた銀担持触媒を数回9000mlの水で沸騰洗浄
後90〜100℃で乾燥した。ついで、乾燥したこの
触媒に9.61ｇの炭酸ルビジウムを2400mlのエチル
アルコールに溶解した液を加えて含浸し、得られ
た銀担持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。30日後の結果を表−１に示す。
実施例 ４
硝酸銀1600ｇをモノエチレングリコール1.8
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)13.3mmおよび内周の長さ(C)5.8mm、長さ
(E)10.0mm、見かけの体積に対する見かけの表面積
の比が1.7mm-1のインターロツクスサドルの形状
をしたα−アルミナ担体（図−１〜３）9000mlに
含浸後、含浸混合物を徐々に130℃まで昇温しそ
の温度で２時間攪拌後160℃まで昇温し、さらに
２時間攪拌し還元銀を担体に分散付着せしめた。
得られた銀担持触媒を数回9000mlの水で沸騰洗浄
後90〜100℃で乾燥した。ついで、乾燥したこの
触媒に4.51ｇの酢酸カリウムを2400mlのエチルア
ルコールに溶解した液を加えて含浸し、得られた
銀担持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。30日後の結果を表−１に示す。
比較例 １
硝酸銀1600ｇをモノエチレングリコール2.14
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。この含浸
溶液を見かけ気孔率60％、BET比表面積0.7m2／
ｇ、細孔容積0.40c.c.／ｇ、予め約100℃に加熱し
た、見かけの体積に対する見かけの表面積の比が
1.3mm-1、外径(D)7.0mm、内径(B)3.0mm、長さ(E)7.0
mm、のラシヒリングの形状をしたα−アルミナ担
体（図−７〜９）9000mlに含浸後、含浸混合物を
徐々に130℃まで昇温しその温度で２時間攪拌後
160℃まで昇温し、さらに２時間攪拌し還元銀を
担体に分散付着せしめた。得られた銀担持触媒を
数回9000mlの水で沸騰洗浄後90〜100℃で乾燥し
た。ついで、乾燥したこの触媒に5.13ｇの酢酸カ
リウムムを2700mlのエチルアルコールに溶解した
液を加えて含浸し、得られた銀担持触媒を80〜
100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。30日後の結果を表−１に示す。
比較例 ２
硝酸銀1600ｇをモノエチレングリコール3.14
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。この含浸
溶液を見かけ気孔率60％、BET比表面積0.7m2／
ｇ、細孔容積0.40c.c.／ｇ、予め約100℃に加熱し
た、見かけの体積に対する見かけの表面積の比が
1.7mm-1、直径3.5mmの球の形状をしたα−アルミ
ナ担体9000mlに含浸後、含浸混合物を徐々に130
℃まで昇温しその温度で２時間攪拌後160℃まで
昇温し、さらに２時間攪拌し還元銀を担体に分散
付着せしめた。得られた銀担持触媒を数回9000ml
の水で沸騰洗浄後90〜100℃で乾燥した。ついで、
乾燥したこの触媒に7.05ｇの炭酸セシウムを3700
mlのエチルアルコールに溶解した液を加えて含浸
し、得られた銀担持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。
30日後の結果を表−１に示す。
比較例 ３
硝酸銀1600ｇをモノエチレングリコール1.56
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、見かけの体積に対する見かけの表
面積の比が1.7mm-1、外径(D)7.0mm、内径(B)4.2mm、
長さ(E)7.0mm、のラシヒリングの形状をしたα−
アルミナ担体（図−１０〜１２）9000mlに含浸
後、含浸混合物を徐々に130℃まで昇温し、その
温度で２時間攪拌後160℃まで昇温し、さらに２
時間攪拌し還元銀を担体に分散付着せしめた。得
られた銀担持触媒を数回9000mlの水で沸騰洗浄後
90〜100℃で乾燥した。ついで乾燥したこの触媒
に4.04ｇの炭酸セシウムを2130mlのエチルアルコ
ールに溶解した液を加えて含浸し、得られた銀担
持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなり、さらに二塩化エチレン
3ppmからなる混合ガスを導入し、反応圧力24
Kg／m2Ｇ、空間速度5500Hr-1にて30日間反応を
おこなつた。30日後の結果を表−１に示す。
比較例 ４
硝酸銀1600ｇをモノエチレングリコール1.8
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)13.3mmおよび内周の長さ(C)5.8mm、長さ
(E)10.0mm、見かけの体積に対する見かけの表面積
の比が1.7mm-1のインターロツクスサドルの形状
をしたα−アルミナ担体（図−１〜３）9000mlに
含浸後、含浸混合物を徐々に130℃まで昇温しそ
の温度で２時間攪拌後160℃まで昇温し、さらに
２時間攪拌し還元銀を担体に分散付着せしめた。
得られた銀担持触媒を数回9000mlの水で沸騰洗浄
後90〜100℃で乾燥した。ついで、乾燥したこの
触媒に4.52ｇの炭酸セシウムを2400mlのエチルア
ルコールに溶解した液を加えて含浸し、得られた
銀担持触媒を80〜100℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなる混合ガスを導入し、反応
圧力24Kg／m2Ｇ、空間速度5500Hr-1にて30日間
反応をおこなつた。30日後の結果を表−１に示
す。
比較例 ５
硝酸銀1600ｇをモノエチレングリコール1.7
に溶解し、この溶液にホルムアミド636ｇを添加
しよく攪拌し、銀含浸溶液を調製した。
この含浸溶液を見かけ気孔率60％、BET比表
面積0.7m2／ｇ、細孔容積0.40c.c.／ｇ、予め約100
℃に加熱した、外径(D)6.0mm、厚さ(W)2.0mm、外周
の長さ(A)15.4mmおよび内周の長さ(C)6.2mm、見か
けの体積に対する見かけの表面積の比が1.7mm-1
のベルルサドルの形状をしたα−アルミナ担体
（図−４〜９）9000mlに含浸後、含浸混合物を
徐々に130℃まで昇温しその温度で２時間攪拌後
160℃まで昇温し、さらに２時間攪拌し還元銀を
担体に分散付着せしめた。得られた銀担持触媒を
数回9000mlの水で沸騰洗浄後90〜100℃で乾燥し
た。ついで、乾燥したこの触媒に4.31ｇの炭酸セ
シウムを2300mlのエチルアルコールに溶解した液
を加えて含浸し、得られた銀担持触媒を80〜100
℃で乾燥した。
この触媒を内径33mm、触媒層長10000mm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％、残部がメタン、窒素、ア
ルゴン、エタンからなる混合ガスを導入し、反応
圧力24Kg／m2Ｇ、空間速度5500Hr-1にて30日間
反応をおこなつた。30日後の結果を表−１に示
す。
In order to be more specific, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless it goes against the spirit thereof. Note that the rate of change and selectivity described in Examples and Comparative Examples were calculated using the following formula. Rate of change (%) = Number of moles of ethylene reacted/
Number of moles of ethylene in raw material gas x 100 Selectivity (%) = Number of moles of ethylene converted to ethylene oxide/Number of moles of reacted ethylene x 100 Example 1 1600g of silver nitrate was mixed with 1.8g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 13.3 mm, inner circumference length (C) 5.8 mm, length
(E) After impregnating 9000 ml of an α-alumina support in the form of an interlocked saddle (Figures 1 to 3) with a ratio of apparent surface area to apparent volume of 1.7 mm -1 , the impregnation mixture was gradually added. The temperature was raised to 130°C, and the mixture was stirred for 2 hours at that temperature, then the temperature was raised to 160°C, and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier.
The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 4.52 g of cesium carbonate dissolved in 2400 ml of ethyl alcohol, and the resulting silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into an externally heated double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm. A mixed gas consisting of 7% gas by volume, the balance consisting of methane, nitrogen, argon, and ethane, and 3 ppm of ethylene dichloride was introduced, the reaction pressure was 24 Kg/m 2 G, and the space velocity was 5500 Hr -1.
The reaction was carried out for 30 days. The results after 30 days are shown in Table-1. Example 2 1600g of silver nitrate was mixed with 1.7g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 15.4 mm and inner circumference length (C) 6.2 mm, apparent surface area relative to apparent volume. The ratio is 1.7mm -1
After impregnating 9000 ml of α-alumina carrier in the shape of a Berle saddle (Figures 4 to 6), the impregnation mixture was gradually heated to 130°C and stirred at that temperature for 2 hours.
The temperature was raised to 160°C and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier. The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 4.31 g of cesium carbonate dissolved in 2300 ml of ethyl alcohol, and the resulting silver-supported catalyst was
Dry at °C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Example 3 1600g of silver nitrate and 1.8g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 13.3 mm, inner circumference length (C) 5.8 mm, length
(E) After impregnating 9000 ml of an α-alumina support (Figs. 1 to 3) in the form of an interlocking saddle with a ratio of apparent surface area to apparent volume of 1.7 mm -1 , the impregnation mixture was gradually added. The temperature was raised to 130°C, and the mixture was stirred for 2 hours at that temperature, then the temperature was raised to 160°C, and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier.
The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 9.61 g of rubidium carbonate dissolved in 2400 ml of ethyl alcohol, and the obtained silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Example 4 1600g of silver nitrate and 1.8g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 13.3 mm, inner circumference length (C) 5.8 mm, length
(E) After impregnating 9000 ml of an α-alumina support in the form of an interlocked saddle (Figures 1 to 3) with a ratio of apparent surface area to apparent volume of 1.7 mm -1 , the impregnation mixture was gradually added. The temperature was raised to 130°C, and the mixture was stirred for 2 hours at that temperature, then the temperature was raised to 160°C, and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier.
The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Then, a solution prepared by dissolving 4.51 g of potassium acetate in 2400 ml of ethyl alcohol was added to impregnate the dried catalyst, and the resulting silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Comparative Example 1 1600g of silver nitrate was mixed with 2.14g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution has an apparent porosity of 60% and a BET specific surface area of 0.7 m 2 /
g, pore volume 0.40cc/g, preheated to about 100℃, ratio of apparent surface area to apparent volume
1.3mm -1 , outer diameter (D) 7.0mm, inner diameter (B) 3.0mm, length (E) 7.0
After impregnating 9000 ml of α-alumina carrier in the shape of a Raschig ring (Figures 7 to 9), the impregnation mixture was gradually heated to 130°C and stirred at that temperature for 2 hours.
The temperature was raised to 160°C and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier. The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 5.13 g of potassium acetate dissolved in 2700 ml of ethyl alcohol, and the resulting silver-supported catalyst was
Dry at 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Comparative Example 2 1600g of silver nitrate was mixed with 3.14g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution has an apparent porosity of 60% and a BET specific surface area of 0.7 m 2 /
g, pore volume 0.40cc/g, preheated to about 100℃, ratio of apparent surface area to apparent volume
After impregnating 9000 ml of α-alumina support in the shape of a sphere with a diameter of 3.5 mm and 1.7 mm -1 , the impregnation mixture was gradually added to 130 ml of α-alumina support.
The mixture was heated to 160° C. and stirred for 2 hours at that temperature, then heated to 160° C. and further stirred for 2 hours to disperse and adhere the reduced silver to the carrier. 9000 ml of the obtained silver-supported catalyst several times
After washing with boiling water, it was dried at 90-100℃. Then,
Add 7.05g of cesium carbonate to this dried catalyst at 3700g.
A solution dissolved in 1 ml of ethyl alcohol was added for impregnation, and the resulting silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Comparative example 3 1600g of silver nitrate was mixed with 1.56g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
heated to °C, the ratio of apparent surface area to apparent volume is 1.7 mm -1 , outer diameter (D) 7.0 mm, inner diameter (B) 4.2 mm,
α− in the shape of a Raschig ring with a length (E) of 7.0 mm.
After impregnating 9000 ml of alumina carrier (Figures 10 to 12), the temperature of the impregnated mixture was gradually raised to 130°C, and after stirring at that temperature for 2 hours, the temperature was raised to 160°C, and then
The mixture was stirred for a period of time to disperse and adhere the reduced silver to the carrier. After washing the obtained silver-supported catalyst several times with 9000 ml of water by boiling
Dry at 90-100℃. This dried catalyst was then impregnated with a solution of 4.04 g of cesium carbonate dissolved in 2130 ml of ethyl alcohol, and the resulting silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. consists of methane, nitrogen, argon, ethane, and ethylene dichloride.
A mixed gas consisting of 3 ppm was introduced, and the reaction pressure was 24
The reaction was carried out for 30 days at Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Comparative example 4 1600g of silver nitrate was mixed with 1.8g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 13.3 mm, inner circumference length (C) 5.8 mm, length
(E) After impregnating 9000 ml of an α-alumina support in the form of an interlocked saddle (Figures 1 to 3) with a ratio of apparent surface area to apparent volume of 1.7 mm -1 , the impregnation mixture was gradually added. The temperature was raised to 130°C, and the mixture was stirred for 2 hours at that temperature, then the temperature was raised to 160°C, and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier.
The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 4.52 g of cesium carbonate dissolved in 2400 ml of ethyl alcohol, and the resulting silver-supported catalyst was dried at 80 to 100°C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. A mixed gas consisting of methane, nitrogen, argon, and ethane was introduced, and the reaction was carried out for 30 days at a reaction pressure of 24 Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1. Comparative Example 5 1600g of silver nitrate was mixed with 1.7g of monoethylene glycol
636 g of formamide was added to this solution and stirred well to prepare a silver impregnation solution. This impregnating solution was prepared in advance with an apparent porosity of 60%, a BET specific surface area of 0.7 m 2 /g, a pore volume of 0.40 cc/g, and a
Heated to °C, outer diameter (D) 6.0 mm, thickness (W) 2.0 mm, outer circumference length (A) 15.4 mm and inner circumference length (C) 6.2 mm, apparent surface area relative to apparent volume. The ratio is 1.7mm -1
After impregnating 9000 ml of α-alumina carrier in the shape of a Berle saddle (Figures 4 to 9), the impregnation mixture was gradually heated to 130°C and stirred at that temperature for 2 hours.
The temperature was raised to 160°C and the mixture was further stirred for 2 hours to disperse and adhere the reduced silver to the carrier. The obtained silver-supported catalyst was boiled and washed several times with 9000 ml of water and then dried at 90-100°C. Next, this dried catalyst was impregnated with a solution of 4.31 g of cesium carbonate dissolved in 2300 ml of ethyl alcohol, and the resulting silver-supported catalyst was
Dry at °C. This catalyst was packed into a double-tube stainless steel reactor with an inner diameter of 33 mm and a catalyst layer length of 10,000 mm, heated on the outside. A mixed gas consisting of methane, nitrogen, argon, and ethane was introduced, and the reaction was carried out for 30 days at a reaction pressure of 24 Kg/m 2 G and a space velocity of 5500 Hr -1 . The results after 30 days are shown in Table-1.
【表】【table】
【表】【table】
エチレンと分子状酸素とをハロゲン化反応抑制
剤の存在下、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多孔性無機質耐火性
担体の外表面および細孔内壁面に微細銀粒子を分
散付着せしめてなる銀接触の製造方法において、
インターロツクスサドルまたはベルルサドルの形
状を有する多孔性無機質耐火性担体に、還元性化
合物を含有した銀化合物溶液を含浸し、加熱還元
処理せしめて担体外表面および細孔内壁面に金属
銀を分散担持した後、水および／または低級アル
コールにより洗浄し、乾燥後さらにこれにアルカ
リ金属および／またはアルカリ金属化合物含有溶
液を含浸し、液成分を蒸発乾燥せしめて製造され
たエチレンオキシド製造用銀触媒は、これまでに
なく、高選択性でしかも触媒層の圧力損失が少な
い触媒であり工業上大きな効果を発揮するもので
ある。
Fine silver particles are dispersed on the outer surface and inner wall surface of the pores of a porous inorganic refractory carrier used in the production of ethylene oxide through catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. In a method for producing a silver contact formed by adhering,
A porous inorganic refractory carrier having the shape of an interrox saddle or a berl saddle is impregnated with a silver compound solution containing a reducing compound, and subjected to heat reduction treatment to disperse and support metallic silver on the outer surface of the carrier and the inner wall surface of the pores. The silver catalyst for ethylene oxide production is manufactured by washing with water and/or lower alcohol, drying, impregnating this with an alkali metal and/or alkali metal compound-containing solution, and evaporating the liquid component to dryness. This is a catalyst with unprecedented high selectivity and low pressure loss in the catalyst layer, which is highly effective industrially.
図面は担体の形状を示すものである。図−１は
インターロツクスサドル担体斜視図、図−２はイ
ンターロツクスサドル担体正面図、図−３はイン
ターロツクスサドル担体側面図、図−４はベルル
サドル担体斜視図、図−５はベルルサドル担体正
面図、図−６はベルルサドル担体側面図、図−７
はラシヒリング担体斜視図、図−８はラシヒリン
グ担体正面図、図−９はラシヒリング担体側面
図、図−１０はラシヒリング担体斜視図、図−１
１はラシヒリング担体正面図、図−１２はラシヒ
リング担体側面図。
The drawing shows the shape of the carrier. Figure 1 is a perspective view of the Interlox saddle carrier, Figure 2 is a front view of the Interlox saddle carrier, Figure 3 is a side view of the Interlox saddle carrier, Figure 4 is a perspective view of the Berl saddle carrier, and Figure 5 is the Berl saddle. Front view of the carrier, Figure 6 is a side view of the Berl saddle carrier, Figure 7
is a perspective view of the Raschig ring carrier, Figure 8 is a front view of the Raschig ring carrier, Figure 9 is a side view of the Raschig ring carrier, Figure 10 is a perspective view of the Raschig ring carrier, Figure 1
1 is a front view of the Raschig ring carrier, and FIG. 12 is a side view of the Raschig ring carrier.
Claims (1)
制剤の存在下、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多孔性無機質耐火
性担体の外表面および細孔内壁面に微細銀粒子を
分散付着せしめてなる銀接触の製造方法におい
て、インターロツクサドルまたはベルルサドルの
形状を有する多孔性無機質耐火性担体に、還元性
化合物を含有した銀化合物溶液を含浸し、加熱還
元処理せしめて担体外表面および細孔内壁面に金
属銀を分散担持した後、水および／または低級ア
ルコールにより洗浄し、乾燥後さらにこれにアル
カリ金属および／またはアルカリ金属化合物含有
溶液を含浸し、液成分を蒸発乾燥せしめてなるこ
とを特徴とするエチレンオキシド製造用銀接触の
製造方法。 ２ インターロツクスサドルの形状を有する多孔
性無機質耐火性担体の比表面積が0.01〜10m2／ｇ
である特許請求の範囲第１項記載の触媒の製造方
法。 ３ ベルルサドルの形状を有する多孔性無機質耐
火性担体の比表面積が0.01〜10m2／ｇである特許
請求の範囲第１項記載の触媒の製造方法。 ４ インターロツクスサドルの形状を有する多孔
性無機質耐火性担体の見かけの体積に対する見か
けの表面積の比が0.1〜10mm-1である特許請求の
範囲第１〜２項のいずれかに記載の触媒の製造方
法。 ５ ベルルサドルの形状を有する多孔性無機質耐
火性担体を見かけの体積に対する見かけの表面積
の比が0.1〜10mm-1である特許請求の範囲第１ま
たは３項記載の触媒の製造方法。 ６ 比表面積が0.50〜２m2／ｇである特許請求の
範囲第１項記載の触媒の製造方法。 ７ 見掛気孔率が20〜80％の範囲である特許請求
の範囲第１項記載の触媒の製造方法。 ８ アルカリ金属およびアルカリ金属化合物より
なる群から選ばれた少なくとも１種の担持量が完
成触媒１キログラム当り0.0001〜0.03グラム当量
重量である特許請求の範囲第１項記載の触媒の製
造方法。 ９ アルカリ金属がセシウムである特許請求の範
囲第１項記載の触媒の製造方法。[Scope of Claims] 1. The outer surface and inside pores of a porous inorganic refractory carrier used in the production of ethylene oxide by catalytic gas phase oxidation of ethylene and molecular oxygen in the presence of a halogenation reaction inhibitor. In a method for producing a silver contact in which fine silver particles are dispersed and adhered to a wall surface, a porous inorganic refractory carrier having an interlock saddle or Berl saddle shape is impregnated with a silver compound solution containing a reducing compound, and then heated and reduced. After treatment to disperse and support metallic silver on the outer surface of the carrier and the inner wall surface of the pores, it is washed with water and/or lower alcohol, dried, and further impregnated with an alkali metal and/or alkali metal compound-containing solution. A method for producing a silver contact for producing ethylene oxide, which comprises evaporating and drying the components. 2. The specific surface area of the porous inorganic refractory carrier having the shape of an interlocking saddle is 0.01 to 10 m 2 /g
A method for producing a catalyst according to claim 1. 3. The method for producing a catalyst according to claim 1, wherein the porous inorganic refractory carrier having a Berle saddle shape has a specific surface area of 0.01 to 10 m 2 /g. 4. The catalyst according to any one of claims 1 to 2, wherein the porous inorganic refractory carrier having the shape of an interlocking saddle has a ratio of apparent surface area to apparent volume of 0.1 to 10 mm -1 . Production method. 5. The method for producing a catalyst according to claim 1 or 3, wherein the porous inorganic refractory carrier having a Berle saddle shape has a ratio of apparent surface area to apparent volume of 0.1 to 10 mm -1 . 6. The method for producing a catalyst according to claim 1, which has a specific surface area of 0.50 to 2 m 2 /g. 7. The method for producing a catalyst according to claim 1, wherein the apparent porosity is in the range of 20 to 80%. 8. The method for producing a catalyst according to claim 1, wherein the amount of at least one selected from the group consisting of alkali metals and alkali metal compounds supported is 0.0001 to 0.03 gram equivalent weight per kilogram of the finished catalyst. 9. The method for producing a catalyst according to claim 1, wherein the alkali metal is cesium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60225976A JPS6287246A (en) | 1985-10-12 | 1985-10-12 | Production of silver catalyst for producing ethylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60225976A JPS6287246A (en) | 1985-10-12 | 1985-10-12 | Production of silver catalyst for producing ethylene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6287246A JPS6287246A (en) | 1987-04-21 |
| JPH0525546B2 true JPH0525546B2 (en) | 1993-04-13 |
Family
ID=16837832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60225976A Granted JPS6287246A (en) | 1985-10-12 | 1985-10-12 | Production of silver catalyst for producing ethylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6287246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031601A (en) * | 1999-07-14 | 2001-02-06 | Nippon Shokubai Co Ltd | Production of highly pure monoethylene glycol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69919425T2 (en) * | 1998-02-20 | 2005-09-08 | Nippon Shokubai Co. Ltd. | Silver catalyst for the production of ethylene oxide, process for its preparation and process for the production of ethylene oxide |
-
1985
- 1985-10-12 JP JP60225976A patent/JPS6287246A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001031601A (en) * | 1999-07-14 | 2001-02-06 | Nippon Shokubai Co Ltd | Production of highly pure monoethylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6287246A (en) | 1987-04-21 |
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