JP3789261B2 - Catalyst for producing ethylene oxide and method for producing ethylene oxide - Google Patents
Catalyst for producing ethylene oxide and method for producing ethylene oxide Download PDFInfo
- Publication number
- JP3789261B2 JP3789261B2 JP28389799A JP28389799A JP3789261B2 JP 3789261 B2 JP3789261 B2 JP 3789261B2 JP 28389799 A JP28389799 A JP 28389799A JP 28389799 A JP28389799 A JP 28389799A JP 3789261 B2 JP3789261 B2 JP 3789261B2
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- Prior art keywords
- alkali metal
- catalyst
- silver
- tin
- supported
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims description 62
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 35
- 150000001340 alkali metals Chemical class 0.000 claims description 35
- 229910052709 silver Inorganic materials 0.000 claims description 35
- 239000004332 silver Substances 0.000 claims description 34
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 14
- -1 amine compound Chemical class 0.000 claims description 14
- 229910052792 caesium Inorganic materials 0.000 claims description 14
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 14
- 229940100890 silver compound Drugs 0.000 claims description 9
- 150000003379 silver compounds Chemical class 0.000 claims description 9
- 150000003606 tin compounds Chemical class 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229940071182 stannate Drugs 0.000 description 2
- 239000012808 vapor phase Substances 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
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Description
【０００１】
【発明の属する技術分野】
本発明は、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ための改良された銀触媒及びエチレンオキシドの製造方法に関する。
エチレンオキシドは活性水素化合物に付加重合させて非イオン系界面活性剤の製造に向けられる他、水を付加させてエチレングリコールとなし、ポリエステルやポリウレタン系高分子の原料、エンジン用不凍液等に使用される。
【０００２】
【従来の技術】
エチレンを分子状酸素により気相接触酸化して工業的にエチレンオキシドを製造する際に使用される触媒は銀触媒である。エチレンオキシドを効率よく生産するために、触媒の改良の要請が強く、より高選択性、長寿命の触媒の出現が望まれている。このため、従来から種々の方法が提案されているが、主活性成分である銀と反応促進剤であるアルカリ金属等との組合せ、その配合比の最適化、これらを担持する担体の改良等がその主なものである。
【０００３】
例えば、ＵＳＰ４，９０８，３４３号および５，０５７，４８１号には、反応促進剤の一つとしてアルカリ金属，アルカリ土類金属をカチオンとし原子番号が７もしくは１５から８３である１３族から１７族の元素のオキシアニオンをアニオンとする種々の塩を担持させた触媒が開示されている。また、特開平４−２９８２４１号には、レッドックス半反応対である少なくとも１種の効率向上性気体状構成員の存在下に気相中のアルケンをエポキシ化することによるアルキレンオキシド製造用触媒であって、効率向上量のレドックス半反応対の一員である少なくとも１種の効率向上性塩、および、鉄、ニッケル、銅、ルテニウム、ロジウム、オスミウム、イリジウム、希土類金属、レニウム、アンチモン、金、亜鉛、タリウム、鉛、スズおよびカドミウムから成る群から選択される少なくとも１種の金属を担持させた触媒が開示されている。更に、ＵＳＰ５，８５４，１６７号には、レニウムを含まず３０００ｐｐｍ以下のアルカリ金属、５〜３００ｐｐｍの硫黄、１０〜１０００ｐｐｍのゲルマニウムもしくはスズ、１０〜１０００ｐｐｍのフッ素を含む触媒が開示されている。他方、アルカリ金属を担体に前含浸させた触媒も提案されている（特開昭５５−１２７１４４号、特開平４−３４６８３５号及び特開平８−２４４４７７号等参照）。
【０００４】
【発明が解決しようとする課題】
以上のように、エチレンオキシド製造用触媒については、反応促進剤などにスズを使用すること、また、アルカリ金属を使用する場合でも、いろいろな提案がなされている。しかしながら、未だ十分に満足すべきレベルに達しているとは言えず、触媒性能改善のための努力が、継続して行われている状況にある。
本発明の目的は、従来の触媒に比較してより高い選択率と優れた活性を合わせ持つエチレンオキシド製造用触媒を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、多孔性担体に前処理としてアルカリ金属の少なくとも１種とスズとを担持させ、次いで、銀とアルカリ金属の少なくとも１種とを担持させてなり、前処理が、多孔性担体にアルカリ金属化合物を含有する溶液とスズ化合物を含有する溶液とで含浸後、加熱処理して担持させる方法でおこなわれ、その際、多孔性担体に前処理として担持させるスズが全触媒重量当たり１０〜１５００ｐｐｍであり、加熱処理温度が１００〜３００℃である、ことを特徴とするエチレンを酸化してエチレンオキシドを製造するための触媒、及び該触媒の存在下でのエチレンオキシドの製造方法に関する。
【０００６】
【発明の実施の形態】
以下、本発明の触媒について詳細に説明する。
（多孔性担体）
本発明の触媒は多孔性担体に触媒主成分として銀を担持させた触媒である。多孔性担体としては、アルミナ、炭化珪素、チタニア、ジルコニア及びマグネシア等の多孔性耐火物が挙げられるが、主成分がα−アルミナであるものが特に好適である。また、多孔性担体には通常１０％程度を上限としてシリカ成分を含有させたものであってもよい。
【０００７】
本発明においては多孔性担体の諸物性がその触媒活性に大きな影響を与える場合があり、多孔性担体の表面積は、通常０．１〜１０ｍ2 ／ｇ、好ましくは０．６〜５ｍ2 ／ｇ、更に好ましくは０．８〜２ｍ2 ／ｇであるものが望ましい。また、かかる表面積を保持して触媒成分の含浸操作を容易にするという点で、担体の吸水率が好ましくは２０〜５０％、更に好ましくは２５〜４５％であるものが望ましい。
【０００８】
（触媒の調製）
本発明の触媒は、多孔性担体にアルカリ金属とスズとを担持させ、次いで、銀とアルカリ金属とを担持させて調製されるものである。この２段の担持処理の内、初めの多孔性担体にアルカリ金属とスズとを担持する工程を「前処理工程」といい、また、前処理後に銀とアルカリ金属とを担持する工程を「本処理工程」と定義して説明する。
【０００９】
（前処理工程）前処理工程で多孔性担体に担持する金属は、アルカリ金属とスズである。アルカリ金属としては、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム等のいずれでもよいが、セシウムが好ましい。これらは１種又は２種以上で使用される。アルカリ金属の担持量は、全触媒重量当たり好ましくは、５０〜２０００ｐｐｍ、より好ましくは１００〜１０００ｐｐｍである。スズの担持量は、１０〜１５００ｐｐｍ、好ましくは１０〜１０００ｐｐｍである。
【００１０】
前処理工程で使用されるアルカリ金属化合物の種類は特に限定はなく、例えば硝酸塩、水酸化物、ハロゲン化物、炭酸塩、重炭酸塩、シュウ酸塩、カルボン酸塩等が挙げられる。また、スズ化合物の種類も特に限定はなく、例えばハロゲン化物、硫酸塩、ハロゲン化スズ酸アンモニウム塩等が挙げられる。
前処理工程において、アルカリ金属とスズとを担持させる方法は、従来公知の方法が採用できるが、例えば、多孔性担体にアルカリ金属を含有する溶液とスズを含有する溶液とを含浸後、乾燥処理することにより担持することができる。
【００１１】
含浸させる方法としてはアルカリ金属化合物を含有する溶液中、およびスズ化合物を含有する溶液中に多孔性担体を浸漬する方法を用いる。なお、該処理は、アルカリ金属化合物を含有する溶液での処理とスズ化合物を含有する溶液での処理とを別々に行ってもよいし、アルカリ金属化合物を含有する溶液とスズ化合物を含有する溶液との両方を含有する溶液で行ってもよい。
【００１２】
前処理工程で、担体にアルカリ金属化合物とスズ化合物とを担持するために使用する溶液の溶媒としては、使用するアルカリ金属化合物及びスズ化合物に対して溶解性があれば、特に限定なく使用でき、水、低沸点の有機溶媒、および水と低沸点の有機溶媒の混合物等が使用できる。乾燥処理としては、含浸処理後、多孔性担体と余剰のアルカリ金属化合物とスズ化合物の含有溶液を分離後、減圧乾燥または加熱処理による乾燥等が挙げられる。本発明でおこなう加熱処理としては、１００〜３００℃、好ましくは１３０〜２７０℃での空気、窒素等の不活性ガス、過熱水蒸気を利用する方法がある。特に好ましいのは過熱水蒸気を利用する方法である。
【００１３】
（本処理工程）
本発明の本処理工程とは、前記の前処理工程でアルカリ金属とスズとを担持させた多孔性担体に、銀とアルカリ金属とを担持させる処理である。
本処理工程に用いるアルカリ金属も前処理と同様、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム等のいずれでもよい。これらは１種又は２種以上で担持されうる。
銀の担持量は、全触媒重量当たり好ましくは、５〜３０重量％、より好ましくは８〜２０重量％である。担持された銀は担体上で通常、金属銀の形態で存在する。また、アルカリ金属の担持量は、全触媒重量当たり好ましくは１０〜１００００ｐｐｍ、より好ましくは５０〜５０００ｐｐｍである。
【００１４】
アルカリ金属がセシウムである場合には、特に２００〜２０００ｐｐｍが好ましい。本発明の触媒に含まれるアルカリ金属の総量は、前処理工程で担持された量と本処理工程で担持された量との和となる。
本処理工程で、銀を担体に担持させるために有利に使用される銀化合物としては、酸化銀、硝酸銀、炭酸銀、あるいは、酢酸銀、シュウ酸銀などの各種カルボン酸銀を挙げられ、例えば、アミン化合物と溶媒中で可溶な錯体を形成し、そして５００℃以下、好ましくは３００℃以下、より好ましくは２６０℃以下の温度で分解して銀を析出するものである。この内、シュウ酸銀が特に好ましい。錯体形成剤としてのアミン化合物は、上記銀化合物を溶媒中で可溶化し得るものが用いられる。かかるアミン化合物としては、例えばピリジン、アンモニア、１〜６個の炭素を有するアミン類などが挙げられる。中でもアンモニア、ピリジン、ブチルアミンなどのモノアミン、エタノールアミンなどのアルカノールアミン、エチレンジアミン、１，３−プロパンジアミンの如きポリアミンが好ましい。特にエチレンジアミン及び／又は１，３−プロパンジアミンの使用、特にその混合使用が最適である。
【００１５】
また、本処理工程で使用されるアルカリ金属化合物の種類は特に限定はなく、例えば硝酸塩、水酸化物、ハロゲン化物、炭酸塩、重炭酸塩、シュウ酸塩、カルボン酸塩等が挙げられる。
本処理工程で、銀化合物及びアルカリ金属化合物を担持させる方法は、従来公知の方法が採用でき、例えば、前処理を施した多孔性担体に銀化合物及びアルカリ金属化合物を含有する溶液を含浸させ、次いで加熱処理することにより、担持することができる。
銀化合物の含浸方法としては、銀化合物をアミン化合物との水溶液の形として用いることが最も現実的であるが、アルコールなどを加えた水溶液としても用い得る。最終的には触媒成分として５〜３０重量％の銀が担持されるように含浸液中の銀濃度は決定される。また、含浸の後、要すれば減圧、加熱、スプレー吹き付けなどを併せて行うこともできる。アミン化合物は銀化合物を錯化するに必要な量（通常アミノ基２個が銀１原子に対応する）で加えられる。この場合アミン化合物は、上記必要量より５〜３０％過剰に加えるのが、反応性の面から好ましい。
【００１６】
また、アルカリ金属化合物は銀化合物水溶液中に溶解し、銀と同時に担体上に担持すればよい。含浸後の加熱処理は、銀が担体上に析出するのに必要な温度と時間を測定して実施する。担体上に銀ができるだけ均一に、微細な粒子で存在するように析出する条件を選ぶことが最も好ましい。一般的に加熱処理は、高温、長時間となるほど、析出した銀粒子の凝集を促進するので好ましくない。好ましい加熱処理は、１３０℃〜３００℃で、加熱した空気（又は窒素などの不活性ガス）又は、過熱水蒸気を使用して、５分から３０分の短時間行われる。好ましい上記熱処理は、触媒調製工程の時間短縮という観点からも望ましく、他に過熱水蒸気を使用すると、担体上の銀の分布が均一になり触媒性能も向上するので特に好ましい。
【００１７】
（反応方法）
本発明の触媒を用いてエチレンをエチレンオキシドに転換する反応は、慣用操作で実施できる。反応圧力は通常０．１〜３．６ＭＰａ（０〜３５ｋｇ／ｃｍ2 Ｇ）であり、反応温度は通常１８０〜３５０℃、好ましくは２００〜３００℃である。反応原料ガスの組成は、一般に、エチレンが１〜４０容量％、分子状酸素が１〜２０容量％の混合ガスが用いられ、また、一般に希釈剤、例えばメタンや窒素等の不活性ガスを一定割合、例えば１〜７０容量％で存在させることができる。分子状酸素含有ガスとしては、通常、空気あるいは工業用酸素が用いられる。更に、反応改変剤として、例えばハロゲン化炭化水素を０．１〜５０ｐｐｍ程度、反応原料ガスに加えることにより触媒中のホットスポットの形成を防止でき、且つ触媒の性能、殊に触媒選択性を大幅に改善させることができる。
【００１８】
【実施例】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
実施例１
（１）前処理工程
担体としてα−アルミナ担体（表面積１．０４ｍ2 ／ｇ、吸水率３２．３％、平均細孔径１．４μｍ、シリカ３％、８φ×３φ×８ｍｍのリング状）３０ｇを炭酸セシウム（Ｃｓ2 ＣＯ3 ）０．０４３ｇが溶解した水溶液５０ｍｌに浸漬させ、余分な液を切り、次いでこれを１５０℃の過熱水蒸気にて１５分間、２ｍ／秒の流速で加熱し、セシウムを含浸させた担体を調製した。次いで、フッ化スズ酸アンモニウム（（ＮＨ4 ）2 ＳｎＦ6 ）０．０１２ｇが溶解した水溶液９．７ｍｌをセシウムが含浸されたα−アルミナ担体３０ｇにエバポレーター中で減圧下、４０℃の加温中で含浸した。この含浸担体を２００℃の過熱水蒸気にて１５分間、２ｍ／秒の流速で加熱し、セシウムとスズを含浸させた担体を調製した。
【００１９】
（２）シュウ酸銀の調製
硝酸銀（ＡｇＮＯ3 ）２２８ｇとシュウ酸カリウム（Ｋ2 Ｃ2 Ｏ4 ・Ｈ2 Ｏ）１３５ｇを各々１リットルの水に溶解した後、水溶液中で６０℃に加温しながら徐々に混合し、シュウ酸銀の白色沈殿を得た。濾過後蒸留水により沈殿を洗浄して、沈殿物中のカリウムを除いた。
【００２０】
（３）銀アミン錯体溶液の調製
（２）で得られたシュウ酸銀（Ａｇ2 Ｃ2 Ｏ4 、含水率１７．０９％）の一部（６．９５ｇ）をエチレンジアミン２．０５ｇ、プロパンジアミン０．５６ｇ、及び水２．６５ｇよりなるアミン混合水溶液に徐々に溶解して、銀アミン錯体溶液を調製した。この銀アミン錯体溶液に、水０．７２ｍｌを添加し、更に、攪拌しながら塩化セシウム（ＣｓＣｌ）１．１４重量％と硝酸セシウム（ＣｓＮＯ3 ）１．９８重量％を含有する混合水溶液０．６ｍｌを添加した。
【００２１】
（４）本処理工程
セシウムを含有するこの銀アミン錯体溶液を（１）で調製したセシウムとスズが含浸されたα−アルミナ担体３０ｇにエバポレーター中で減圧下、４０℃の加温中で含浸した。この含浸担体を２００℃の過熱水蒸気にて１５分間、２ｍ／秒の流速で加熱し、触媒を得た。該触媒における銀（Ａｇ）、セシウム（Ｃｓ）およびスズ（Ｓｎ）の担持量は１２％、７５３ｐｐｍ、１５０ｐｐｍであった。
【００２２】
（５）エチレンオキシドの製造
上記方法で調製した触媒を、６〜１０メッシュに砕き、その３ｍｌを内径７．５ｍｍのＳＵＳ製反応管に充填し、反応ガス（エチレン３０％、酸素８．５％、塩化ビニル１．５ｐｐｍ、二酸化炭素６．０％、残り窒素）を、ＧＨＳＶ４３００ｈ-1、圧力０．８ＭＰａ（７ｋｇ／ｃｍ2 Ｇ）で流し、反応を行った。反応を開始して１週間経過後の、酸素転化率が４０％になるときの反応温度Ｔ４０（℃）と酸素転化率が４０％となるときのエチレン基準の酸化エチレンの選択率Ｓ４０（％）を表１に示す。
【００２３】
実施例２
実施例１において、前処理工程のスズの担持量が３００ｐｐｍとなるように溶液の濃度を代え、本処理工程で担持させるセシウムの量が６３２ｐｐｍとなるように溶液の濃度を代えた他は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
【００２４】
実施例３
実施例１において、前処理工程のスズの担持量が５０ｐｐｍとなるように溶液の濃度を代え、本処理工程で担持させるセシウムの量が３９５ｐｐｍとなるように溶液の濃度を代えた他は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
【００２５】
実施例４
実施例２において、前処理工程のスズの担持量が４００ｐｐｍとなるように溶液の濃度を代えた他は実施例２と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
【００２６】
比較例１
実施例３において、前処理工程で担体にスズを担持しない他は実施例３と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
比較例２
実施例１において、前処理工程で担体にスズを担持せず、また本処理工程でフッ化スズ酸アンモニウムの３．８６重量％水溶液０．３ｍｌをスズの担持量が１５０ｐｐｍとなるようにセシウムを含有する銀アミン錯体溶液に更に添加した溶液をセシウムが含浸された担体に含浸させた他は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
【００２７】
比較例３
実施例２において、前処理工程で担体にスズを担持せず、本処理工程でフッ化スズ酸アンモニウムの３．８６重量％水溶液０．６ｍｌをスズの担持量が３００ｐｐｍとなるようにセシウムを含有する銀アミン錯体溶液に更に添加した溶液をセシウムが含浸された担体に含浸させた他は実施例２と同様の方法で触媒を調製し反応を行った。反応結果を表１に示す。
【００２８】
【表１】
【発明の効果】
本発明によれば、多孔性担体にアルカリ金属の少なくとも１種とスズとを担持させ、次いで、銀とアルカリ金属の少なくとも１種とを担持させてなる触媒を用いることにより、従来の触媒と比較して温和な条件下で高い選択率でエチレンオキシドを製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved silver catalyst for producing ethylene oxide by vapor phase catalytic oxidation of ethylene with molecular oxygen and a method for producing ethylene oxide.
Ethylene oxide is added to active hydrogen compounds for production of nonionic surfactants, and water is added to form ethylene glycol, which is used for polyester and polyurethane polymer raw materials, engine antifreeze, etc. .
[0002]
[Prior art]
A catalyst used when industrially producing ethylene oxide by vapor-phase catalytic oxidation of ethylene with molecular oxygen is a silver catalyst. In order to efficiently produce ethylene oxide, there is a strong demand for improvement of the catalyst, and the appearance of a catalyst with higher selectivity and longer life is desired. For this reason, various methods have been proposed in the past, but the combination of silver as the main active ingredient and alkali metal as the reaction accelerator, optimization of the blending ratio, improvement of the carrier supporting these, etc. The main thing.
[0003]
For example, US Pat. Nos. 4,908,343 and 5,057,481 disclose a group 13 to group 17 having an alkali metal or alkaline earth metal as a cation as one of the reaction accelerators and an atomic number of 7 or 15 to 83. Catalysts on which various salts having an oxyanion as an anion are supported are disclosed. JP-A-4-298241 discloses a catalyst for producing an alkylene oxide by epoxidizing an alkene in the gas phase in the presence of at least one efficiency-enhancing gaseous member which is a Redox half-reaction pair. At least one efficiency-improving salt that is a member of an efficiency-improving amount of a redox half-reaction pair, and iron, nickel, copper, ruthenium, rhodium, osmium, iridium, rare earth metals, rhenium, antimony, gold, zinc, A catalyst supporting at least one metal selected from the group consisting of thallium, lead, tin and cadmium is disclosed. Further, USP 5,854,167 discloses a catalyst which does not contain rhenium and contains no more than 3000 ppm alkali metal, 5 to 300 ppm sulfur, 10 to 1000 ppm germanium or tin, and 10 to 1000 ppm fluorine. On the other hand, the alkali metal has been proposed a catalyst obtained by pre-impregnating the support (see JP-55-127144, JP-A-4-346835 and JP-A-8-244477, etc.).
[0004]
[Problems to be solved by the invention]
As described above, various proposals have been made on ethylene oxide production catalysts even when tin is used as a reaction accelerator or when an alkali metal is used. However, it cannot be said that a satisfactory level has been reached yet, and efforts to improve catalyst performance are ongoing.
An object of the present invention is to provide a catalyst for producing ethylene oxide, which has higher selectivity and superior activity compared to conventional catalysts.
[0005]
[Means for Solving the Problems]
The present invention, by supporting at least one and the tin of an alkali metal as a pretreatment to the porous carrier, then Ri Na by supporting the at least one silver and alkali metal, pretreatment, the porous carrier After impregnation with a solution containing an alkali metal compound and a solution containing a tin compound, it is carried out by a method of carrying by heat treatment, and at that time, the tin carried on the porous carrier as a pretreatment is 10 to 10 per weight of the total catalyst. The present invention relates to a catalyst for oxidizing ethylene to produce ethylene oxide , which is 1500 ppm and having a heat treatment temperature of 100 to 300 ° C., and a method for producing ethylene oxide in the presence of the catalyst.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the catalyst of the present invention will be described in detail.
(Porous carrier)
The catalyst of the present invention is a catalyst in which silver is supported as a catalyst main component on a porous carrier. Examples of the porous carrier include porous refractories such as alumina, silicon carbide, titania, zirconia, and magnesia, and those having a main component of α-alumina are particularly suitable. In addition, the porous carrier may contain a silica component with an upper limit of usually about 10%.
[0007]
In the present invention, various physical properties of the porous carrier may greatly affect the catalytic activity, and the surface area of the porous carrier is usually 0.1 to 10 m 2 / g, preferably 0.6 to 5 m 2 / g. More preferably, it is 0.8 to 2 m 2 / g. Further, in view of facilitating the impregnation operation of the catalyst component while maintaining the surface area, the carrier preferably has a water absorption rate of 20 to 50%, more preferably 25 to 45%.
[0008]
(Preparation of catalyst)
The catalyst of the present invention is prepared by supporting an alkali metal and tin on a porous carrier and then supporting silver and an alkali metal. Of these two stages of supporting treatment, the step of supporting alkali metal and tin on the first porous carrier is called “pretreatment step”, and the step of supporting silver and alkali metal after pretreatment is called “main step”. It is defined as “processing step”.
[0009]
(Pretreatment step) The metal supported on the porous carrier in the pretreatment step is an alkali metal and tin. As the alkali metal, for example, any of lithium, sodium, potassium, rubidium, cesium and the like may be used, but cesium is preferable. These are used alone or in combination of two or more. The supported amount of alkali metal is preferably 50 to 2000 ppm, more preferably 100 to 1000 ppm, based on the total catalyst weight. Loading amount of tin, 1 0~1500ppm, is good Mashiku is 10-1000 ppm.
[0010]
The kind of alkali metal compound used in the pretreatment step is not particularly limited, and examples thereof include nitrates, hydroxides, halides, carbonates, bicarbonates, oxalates, and carboxylates. Moreover, the kind of tin compound is not particularly limited, and examples thereof include halides, sulfates, and halogenated ammonium stannates.
In the pretreatment step, a conventionally known method can be adopted as a method of supporting alkali metal and tin. For example, after impregnating a porous carrier with a solution containing an alkali metal and a solution containing tin, a drying treatment is performed. It can carry | support by doing.
[0011]
As the impregnation method, a method of immersing a porous carrier in a solution containing an alkali metal compound and a solution containing a tin compound is used. The treatment may be performed separately with a solution containing an alkali metal compound and a solution containing a tin compound, or a solution containing an alkali metal compound and a solution containing a tin compound. And a solution containing both.
[0012]
In the pretreatment step, the solvent of the solution used for supporting the alkali metal compound and the tin compound on the carrier can be used without particular limitation as long as it is soluble in the alkali metal compound and tin compound to be used. Water, a low-boiling organic solvent, a mixture of water and a low-boiling organic solvent, or the like can be used. Examples of the drying treatment include, after the impregnation treatment, separation of the porous carrier, excess alkali metal compound, and tin compound-containing solution, followed by drying under reduced pressure or heat treatment. The heating process performed in the present invention, 1 from 00 to 300 ° C., the good Mashiku there is a method of utilizing air at one hundred thirty to two hundred seventy ° C., an inert gas such as nitrogen, superheated steam. Particularly preferred is a method using superheated steam.
[0013]
(Main treatment process)
The main treatment step of the present invention is a treatment in which silver and alkali metal are supported on the porous carrier in which alkali metal and tin are supported in the pretreatment step.
The alkali metal used in this treatment step may be any of lithium, sodium, potassium, rubidium, cesium, etc., as in the pretreatment. These can be supported by one or more kinds.
The supported amount of silver is preferably 5 to 30% by weight, more preferably 8 to 20% by weight, based on the total catalyst weight. The supported silver is usually present in the form of metallic silver on the support. The supported amount of alkali metal is preferably 10 to 10,000 ppm, more preferably 50 to 5000 ppm, based on the total catalyst weight.
[0014]
When the alkali metal is cesium, 200 to 2000 ppm is particularly preferable. The total amount of alkali metal contained in the catalyst of the present invention is the sum of the amount carried in the pretreatment step and the amount carried in the treatment step.
Examples of the silver compound that is advantageously used for supporting silver on a carrier in this treatment step include silver oxide, silver nitrate, silver carbonate, or various silver carboxylates such as silver acetate and silver oxalate. , A complex soluble in the solvent with the amine compound is formed, and silver is precipitated by decomposition at a temperature of 500 ° C. or lower, preferably 300 ° C. or lower, more preferably 260 ° C. or lower. Of these, silver oxalate is particularly preferred. As the amine compound as the complex forming agent, those capable of solubilizing the silver compound in a solvent are used. Examples of such amine compounds include pyridine, ammonia, and amines having 1 to 6 carbons. Of these, monoamines such as ammonia, pyridine and butylamine, alkanolamines such as ethanolamine, and polyamines such as ethylenediamine and 1,3-propanediamine are preferred. In particular, the use of ethylenediamine and / or 1,3-propanediamine, especially the mixed use thereof, is optimal.
[0015]
Moreover, the kind of alkali metal compound used in this treatment step is not particularly limited, and examples thereof include nitrates, hydroxides, halides, carbonates, bicarbonates, oxalates, and carboxylates.
In this treatment step, the silver compound and the alkali metal compound can be supported by a conventionally known method, for example, a pre-treated porous carrier is impregnated with a solution containing the silver compound and the alkali metal compound, Subsequently, it can carry | support by heat-processing.
As the impregnation method of the silver compound, it is most realistic to use the silver compound in the form of an aqueous solution with an amine compound, but it can also be used as an aqueous solution to which alcohol or the like is added. Finally, the silver concentration in the impregnating solution is determined so that 5 to 30% by weight of silver is supported as a catalyst component. Further, after impregnation, if necessary, decompression, heating, spraying, etc. can be performed together. The amine compound is added in an amount necessary to complex the silver compound (usually two amino groups correspond to one silver atom). In this case, the amine compound is preferably added in an amount of 5 to 30% in excess of the above required amount from the viewpoint of reactivity.
[0016]
The alkali metal compound may be dissolved in the aqueous silver compound solution and supported on the carrier simultaneously with silver. The heat treatment after impregnation is carried out by measuring the temperature and time required for silver to deposit on the support. Most preferably, conditions are selected so that silver is present on the support as uniformly as possible and in fine particles. In general, the heat treatment is not preferable as the temperature and the time are increased, since the aggregation of the precipitated silver particles is promoted. Preferable heat treatment is performed at 130 ° C. to 300 ° C. for a short time of 5 to 30 minutes using heated air (or an inert gas such as nitrogen) or superheated steam. The preferable heat treatment is also desirable from the viewpoint of shortening the time of the catalyst preparation step, and the use of superheated steam is particularly preferable because the distribution of silver on the support becomes uniform and the catalyst performance is improved.
[0017]
(Reaction method)
The reaction for converting ethylene to ethylene oxide using the catalyst of the present invention can be carried out by a conventional operation. The reaction pressure is usually 0.1 to 3.6 MPa (0 to 35 kg / cm 2 G), and the reaction temperature is usually 180 to 350 ° C., preferably 200 to 300 ° C. The composition of the reaction raw material gas is generally a mixed gas of 1 to 40% by volume of ethylene and 1 to 20% by volume of molecular oxygen. In general, a diluent, for example, an inert gas such as methane or nitrogen is constant. It can be present in proportions, for example 1 to 70% by volume. As the molecular oxygen-containing gas, air or industrial oxygen is usually used. Furthermore, as a reaction modifier, for example, by adding about 0.1 to 50 ppm of halogenated hydrocarbon to the reaction raw material gas, the formation of hot spots in the catalyst can be prevented, and the performance of the catalyst, especially the catalyst selectivity is greatly increased. Can be improved.
[0018]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
(1) 30 g of α-alumina carrier (surface area 1.04 m 2 / g, water absorption 32.3%, average pore diameter 1.4 μm, silica 3%, 8φ × 3φ × 8 mm ring shape) as a pretreatment process carrier Immerse it in 50 ml of an aqueous solution in which 0.043 g of cesium carbonate (Cs 2 CO 3 ) is dissolved, drain the excess liquid, and then heat it with superheated steam at 150 ° C. for 15 minutes at a flow rate of 2 m / sec. An impregnated support was prepared. Next, 9.7 ml of an aqueous solution in which 0.012 g of ammonium fluostonate ((NH 4 ) 2 SnF 6 ) was dissolved was added to 30 g of an α-alumina carrier impregnated with cesium under reduced pressure in an evaporator at 40 ° C. Impregnated with. This impregnated support was heated with superheated steam at 200 ° C. for 15 minutes at a flow rate of 2 m / second to prepare a support impregnated with cesium and tin.
[0019]
(2) Preparation of silver oxalate 228 g of silver nitrate (AgNO 3 ) and 135 g of potassium oxalate (K 2 C 2 O 4 .H 2 O) were each dissolved in 1 liter of water and heated to 60 ° C. in an aqueous solution. The mixture was gradually mixed to obtain a white precipitate of silver oxalate. After filtration, the precipitate was washed with distilled water to remove potassium in the precipitate.
[0020]
(3) Preparation of silver amine complex solution A part (6.95 g) of silver oxalate (Ag 2 C 2 O 4 , water content 17.09%) obtained in (2) was obtained by using 2.05 g of ethylenediamine and propanediamine. A silver amine complex solution was prepared by gradually dissolving in an amine mixed aqueous solution consisting of 0.56 g and 2.65 g of water. 0.72 ml of water was added to this silver amine complex solution, and further 0.6 ml of a mixed aqueous solution containing 1.14% by weight of cesium chloride (CsCl) and 1.98% by weight of cesium nitrate (CsNO 3 ) with stirring. Was added.
[0021]
(4) This treatment step This silver amine complex solution containing cesium was impregnated into 30 g of α-alumina carrier impregnated with cesium and tin prepared in (1) in an evaporator under reduced pressure and at 40 ° C. under heating. . The impregnated support was heated with superheated steam at 200 ° C. for 15 minutes at a flow rate of 2 m / second to obtain a catalyst. The supported amounts of silver (Ag), cesium (Cs) and tin (Sn) in the catalyst were 12%, 753 ppm and 150 ppm.
[0022]
(5) Production of ethylene oxide The catalyst prepared by the above method is crushed into 6 to 10 mesh, 3 ml of the catalyst is filled into a SUS reaction tube having an inner diameter of 7.5 mm, and reaction gas (ethylene 30%, oxygen 8.5%, A reaction was performed by flowing 1.5 ppm of vinyl chloride, 6.0% carbon dioxide, and the remaining nitrogen) at GHSV 4300 h −1 and a pressure of 0.8 MPa (7 kg / cm 2 G). One week after starting the reaction, the reaction temperature T40 (° C.) when the oxygen conversion rate becomes 40% and the ethylene oxide selectivity S40 (%) when the oxygen conversion rate becomes 40% Is shown in Table 1.
[0023]
Example 2
In Example 1, the concentration of the solution was changed so that the amount of tin supported in the pretreatment step was 300 ppm, and the concentration of the solution was changed so that the amount of cesium supported in this treatment step was 632 ppm. A catalyst was prepared and reacted in the same manner as in 1. The reaction results are shown in Table 1.
[0024]
Example 3
In Example 1, the concentration of the solution was changed so that the amount of tin supported in the pretreatment step was 50 ppm, and the concentration of the solution was changed so that the amount of cesium supported in this treatment step was 395 ppm. A catalyst was prepared and reacted in the same manner as in 1. The reaction results are shown in Table 1.
[0025]
Example 4
In Example 2, a catalyst was prepared and reacted in the same manner as in Example 2 except that the concentration of the solution was changed so that the amount of tin supported in the pretreatment step was 400 ppm. The reaction results are shown in Table 1.
[0026]
Comparative Example 1
In Example 3, a catalyst was prepared and reacted in the same manner as in Example 3 except that tin was not supported on the support in the pretreatment step. The reaction results are shown in Table 1.
Comparative Example 2
In Example 1, tin was not supported on the support in the pretreatment step, and 0.3 ml of a 3.86% by weight aqueous solution of ammonium fluoride stannate was added in this treatment step so that the supported amount of tin was 150 ppm. A catalyst was prepared and reacted in the same manner as in Example 1 except that the carrier further impregnated with the silver amine complex solution contained was impregnated into a carrier impregnated with cesium. The reaction results are shown in Table 1.
[0027]
Comparative Example 3
In Example 2, tin is not supported on the support in the pretreatment step, and 0.6 ml of a 3.86 wt% aqueous solution of ammonium fluoride stannate is contained in this treatment step so that the supported amount of tin is 300 ppm. A catalyst was prepared and reacted in the same manner as in Example 2 except that the carrier further impregnated with the silver amine complex solution was impregnated with the carrier impregnated with cesium. The reaction results are shown in Table 1.
[0028]
[Table 1]
【The invention's effect】
According to the present invention, by using a catalyst in which at least one alkali metal and tin are supported on a porous carrier, and then at least one of silver and an alkali metal is supported, compared with a conventional catalyst. Thus, ethylene oxide can be produced with high selectivity under mild conditions.
Claims (11)
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| JP28389799A JP3789261B2 (en) | 1999-10-05 | 1999-10-05 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
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