TWI228433B - Catalyst carriers - Google Patents
Catalyst carriers Download PDFInfo
- Publication number
- TWI228433B TWI228433B TW092102533A TW92102533A TWI228433B TW I228433 B TWI228433 B TW I228433B TW 092102533 A TW092102533 A TW 092102533A TW 92102533 A TW92102533 A TW 92102533A TW I228433 B TWI228433 B TW I228433B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 239000000969 carrier Substances 0.000 title abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000002245 particle Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 238000001125 extrusion Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001679 gibbsite Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 6
- -1 thallium hydrocarbons Chemical class 0.000 description 5
- 239000013598 vector Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000019271 petrolatum Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 241000758789 Juglans Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004264 Petrolatum Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 210000002257 embryonic structure Anatomy 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229940066842 petrolatum Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Epoxy Compounds (AREA)
Description
^228433 玖、發明說明 (發明說明應敘明:發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 【技術領域】 本發明係關陶瓷觸媒載體,特別有關埽烴類環氧化作用 諸如乙烯氧化成環氧乙烷("E0”)中適用的觸媒載體。為簡 化計將就此反應之背景說明,但需了解有較廣應用性。 【先前技術】 觸媒性能係根據選擇性與反應溫度來評價。選擇性為在 標準流動條件下以轉化進料流内固定埽烴百分比目伊轉 化進料流中婦烴之百分率,環氧乙烷的工業生產中此—、 字一般在80上下。缔烴反應之百分率隨時間減低,欲維 懷定私度須提升反應溫度。但如此將不利影塑 '、曰 Ά屋物的 轉化選擇性。此外,所用設備僅能耐受至一定程度,、 當溫度到達不適於反應器水準時必要終止反應。因此=致 高度選擇性及可接受之低溫維持愈久,反應器 此在 體加料時間愈長,可得產物愈多。維持長期間選擇性載 當適度之改良使得在製法效率上產生 、相 環氧化作用一般包含一種銀組分,常在一陶;^ 共同沉積^文良劑。經發現載體之性質對其所帶觸=上帶 能有極大影t,但其影響的⑨因不全了解。載體典刑〈性 熱陶毫氧化物諸氧化铭製作,並發現通常純=耐 與性能愈佳相關。但已發現例如載體中存在最小量^愈高 質如鹼金屬及某些形式之氧化矽能具有益影響。里70素雜 亦可能直覺地認為載體表面積愈高、觸媒㈣ 1228433 (2)
和思大’因而其上澱積之觸媒更有效。不過經 ^ 兄此點並 非常情’現代載體/觸媒組合内趨向用一種表面 2 /、他於1 . 〇 m /g的載體,因為此等維持可接受之活性與選擇性水、隹· 同時保持必要的抗碎強度在工業反應器内經得卞 ^ 笔長期使 用而供損其物體完整。此外,經發現高表面積之 ^ 、我隨常有 咼活性,但選擇性較遜。 惟現經發現有關載體表面積的情況比起先認 7寄更為 複雜’因已發現載體孔率之本性所負任務最重 ^ 此一發
現為本發明的基礎,其導使觸媒/載體組合之 式 私展有卓越 活性且在適當溫度下具異常延長持留性之極高選擇率。 【發明内容】
本發明提供一種晞烴環氧化觸媒的載體,包含至少95% α-氧化鋁,其表面積為1 ·〇至2.6 m2/g,較佳為至少1 6至2 2 m/g及自35至55%之吸水率,其中微孔分佈使至少7〇%、 較佳至少80%的孔隙度由具0.2至10微米孔徑之微孔產 生,並供應至少0.27 mL/g的載體孔隙度。在根據本發明較 佳載體内孔徑大於1 0微米之微孔佔總孔隙率的0至20%, 較佳0至15%。更佳其餘孔徑小於0.2微米之微孔佔〇至1〇% 的總孔隙率。果孔隙度典型最高至0.56 mL/g,較普通自0.35 至 0·45 mL/g。 文内用辭’f表面積”已知係指由美國化學會刊60 (1938)第 309-3 16 頁所述之 BET (Brunauer,Emmett & Teller)法測定的表 面積。由於表面積與微孔之數目及大小以及孔隙度相關, 應注意實際上載體須具一定最小抗碎強度,其係與微孔周 發明說明績頁 1228433 (3) 圍的壁厚有關。縮減此厚度使孔壁於正常負荷情況下更易 破裂,以致對工業上相關之載體表面積有實際限制,至少 當用現行技術設計併入觸媒組合時係如此。 孔隙率與孔大小分佈係由傳統汞侵入裝置測量,其係將 液態汞強制壓入載體之孔中。強制汞進入較小之孔必需更 大壓力,壓力增量的測量相當於滲入微孔之體積增量,因 此相當於增量體積内之孔大小。以下說明内,孔隙率係用 一 Micromeritics Autopore 9200 型(1300 接觸角及表面張力 0.473 N/m的汞)於逐漸增壓至3.0 X 108 Pa之壓力下藉汞侵入 而測得。 根據本發明載體的孔隙度雖至少為0.27 mL/g,較佳為孔 具有自0.2至10微米之孔徑而提供在0.30至0.56 mL/g之間 的孔隙度,以確保載體具備工業上合格的物理性質。 吸水性係藉能吸進載體微孔内水重為載體總重之百分 比量得。前文指出此量可在3 5至5 5 %範圍内,但較佳載體 有吸水性3 8至5 0 %,最適宜4 0至4 5 %。 本發明亦包括一種晞烴環氧化觸媒用載體製法,含有作 一混合物包含: a) 自50至90%重量的第一細粒α-氧化鋁,有平均粒子 大小(d5〇)自10至90,較佳自10至60,最宜自20至40 微米;與 b) 有根據α-氧化鋁總重自10至50%重量之第二微粒α -氧化鋁,具平均粒子大小(d5G)自2,0至6.0微米; c) 自2至5 %重量比的水合氧化鋁; 顯_歉 ·;ϋ·:·:·:·ί<:ί;·>.·-:·:ί^·:·:·.':·;ί:·;·:·>:·;·ί·:·>:·:·.·:·ίί:'·;ϊ·Λ'.··>:·Ν·<·:·:· Λ·:· :.:·¾·>^;·^;· Is·;·:-:·:··:·:·::·: ·.·;·;·.·* 1228433 (4) d) 按氧化矽計量自0.2至0.8%之非晶矽氧化合物;及 e) 按鹼金屬氧化物計量自0.05至0.3%的一種鹼金屬 化合物; 全部百分比以混合物之α-氧化鋁總含量為基礎,隨後將 混合物製成粒子,並於自1250至1470 °C的溫度燒成載體。 載體粒子能用任何便利傳統措施諸如擠壓或模塑形 成。要求較細粒子時能藉例如噴霧乾燥法獲得。 若用擠壓製粒可望包含習用擠壓助劑、視情況包含烺燒 材料及水。此等組分之用量多少互相關聯,將視有關用具 的許多因素而定。不過此等問題大都在擠壓陶瓷材料技術 熟練人士之常識内。 平均粒子大小文内以’’d50’’指示者為用一 Horiba(或其相 仿者)粒子大小分析儀於五分鐘的超音波處理後測得值, 其代表在與所述平均粒子大小相比時較大及較小粒子具 有相等體積比時之粒子直徑。 本發明方法在謹慎配合氧化鋁組份的粒子大小方面極 適合製造本發明載劑。併合傳統燒過材料能達到吸水率調 整,材料典型為細碎有機化合物諸如細粒聚婦烴類,特別 聚乙晞與聚丙婦及核桃穀粒。不過,燒過材料主要用以在 生料(或未烺燒相)内混合物可藉模塑或擠壓程序型成粒 子期間確實保存多孔結構。在燃燒期間全部脫除而得成品 載劑。實際上以上孔徑限制意謂根據本發明之載體並無過 多數大孔隙(即大於約1 0微米的孔),且有比通常情況較少 0.2微米之孔。 發明說明績頁 1228433
本發明載體宜含一結合材料製作包括足量的氧化矽與 鹼金屬化合物以實質地防止生成結晶矽氧化合物。結合劑 典型亦含一種水合之鋁氧組份如二水鋁礦或三水鋁礦。矽 氧組份可係一珍膠、一沉殿珍石、一非晶碎石或一非晶驗 金屬石夕酸鹽或铭碎酸鹽。驗金屬化合物舉例可係一鹽如鈉 或鉀鹽。摻合氧化鋁粒子製作載體用的合宜結合材料為二 水銘癌、一種氨穩定之碎膠與一可溶性#3鹽的混合物。掺 併習用陶瓷結合物配方使含鋁矽酸鹽與一鹼金屬組份能 獲得相同效果。進一步發現載體/觸媒組合之性能若洗脫 載體中可溶性殘餘物然後殿積觸媒將大為增高。 【實施方式】
氧化鋁基載體能以多種不同方法製作,各可影響孔徑分 佈。一般係將微粒礦物組份於升溫燃燒直到粒子燒結一起 而得。孔率能受一起燒結粒子的大小與燒結時間影響。本 發明一較佳具體例中用二種不同中點粒子大小分佈之氧 化铭粒子:大粒子與小粒子。此等可作配方的各別組份加 入從而形成載體或就地碾磨易碎燒結塊直至所得粒子大 小掺合物有要求之兩型分佈。因此理論上由單一分佈模式 的氧化鋁粒子起始亦可能完成本發明載體。預定全部此等 方式將屬於文内申請之製法範圍。 若繼續燒結直到粒子結合一起,隨意自任何添加結合材 料形成結合地位或經由燒結,但不到因粒子群集產生孔率 大為減縮的地步,較大粒子會導致較大孔洞,較小粒子則 得孔洞較細。如前指示,吸水性亦受使用燒過材料影響, -10-
1228433 (6) 因該材料容許更完全之燒結而不會使載體表面積大量縮 減。 使用結合材料縮短粒子結合一起所須燒結之時間,由於 燒結常連帶降低孔隙度,此結合劑的使用為本發明特色。 選擇結合劑作用亦在製造一更易接納之載體表面。前文已 指出,結合材料含二氧化矽與鹼金屬組份一起的某種形式 確保二氧化矽為非晶式。
較佳鋁氧水合物為二水鋁礦,惟亦能用三水鋁礦、拜耳 礬土或水礬石。亦宜將載體製成丸片式,其大小通常由其 將澱積之反應器維度決定。不過一般發現頗便利採用空心 圓筒式丸片,長度與截面尺寸自5至10 mm,大約相等。丸 片能由混合物以任何方便模塑法形成,惟較佳由混合物擠 壓形成。為繫助擠壓該混合物,通常與以混合物重量計最 多約2 5 %、較佳自1 0至2 0 %擠壓助劑及燒過物之混合,隨 後加足夠水作成能擠壓的混合物。擠壓助劑為技術上所週 知,包括物料如凡士林、聚氧化婦烴及聚乙二醇等。技術 上同樣週知有機燒過物,包括材料如微粒聚婦烴類,粉碎 核桃殼及其他細有機微粒等。 擠壓助劑之添加量為必要促進特定配方擠壓之量,且其 受粒子大小、結合材料(如有加入)的量與含水量及擠壓機 設計而影響。擠壓助劑實際用量對最後產物並不關键,業 界技術人士將易顯知其適當量。燃燒後完全除去。燒過物 質亦按根據本發明製備產物要求提升吸水率所需量增 加。在適當的情況下,擠壓助劑或燒過物質都有可能提供該 -11- 1228433⑺ [w說明續頁| 添加劑(如上所述)可被加入該配方之混合總重量。 已成形丸片然後經乾燥並於足夠保證氧化鋁粒子受燒 結作用或經混合物内摻合結合材料成結合位置或兩種機 制之混合聯合一起的溫度燃燒。燃燒一般在約1250與1470 °C間進行’較佳於約1300至1440進行最多約5小時,較 佳自2至4小時。 選擇材料與結合劑對孔徑分佈之影響藉本發明載體 (INV-1,INV-2及INV-3)與一對照载體(c〇Mp-A)比較例證。 下表1顯現根據本發明載體與諸對照載體的各種重要物理 特性。
0.2-10 μ P.V.mL/g (ρ·ν·係指孔隙度) 戴體之製法 如前指示本發明载體能用業 w <夜術人士瞭解的許多7 式製備。生產較佳载體(ΙΝλΜ) L 人、u n J f用以組成分作一混^ 物,全邵比例為燒成载體内存 <組分重量: -12- 1228433 “ 厂__ (8) 漫麵_7 • 67·4/。氧化鋁,平均粒子大小㈨⑼)29微米; • 29/° α''氧化銘,平均粒子大小(d5G) 3微米; 3 · 3 %二水鋁礦; 〇·5 /〇 一氧化矽(呈氨穩定化矽膠式);及 5 · 0 · 1 /〇氧化鈉(呈醋酸鈉式)。 氧化石夕及贈酸鈉與二水鋁礦一起用以提供賦於生胚強 度的結合。此、、日入^丄 G此合物中加5%重量凡士林、9%微粒有機燒 過物此合物及0 · 1 %重量硼酸混合物。然後加水使混合物 能經擠壓,於e t十疏、, 、疋私壓此混合物作成約8 mm直徑與8 mm長 炙工〜圓同。乾燥後在1425 °C富内燃燒產生本發明多孔鋁 氧載體。 以1ΝλΜ完全同一方式製備INV-2載體,惟混合物含14% 而非9 %的微粒有機燒過混合物。INV_3載體以丨4 %凡士林 與8%細有機燒過物製備。
COMP-A載體係根據USP 5,100,859實例1内所述製程製 得。評價之載體皆由氧化鋁作成,諸組份的比例與粒子大 小dw顯示於下表2。補足i〇〇%之比例餘額為結合材料。 表2
Al2〇3 COMP-A L INV-1 INV-2 INV-3 1 98.8% 3 μ 29% 3 μ 29% 3 μ 20% 3 μ 2 67.4% 29 μ 67.4% 29 μ 3* 3% 3% 3% 4 76.4% 16 μ *指示二水鋁礦按AU〇3計量 -13- 發明說明績頁 1228433 (9) 載體的評估 對照載體對本發明之INV-1載體進行評估。以USP 5,3 80,697内所概述方法用載體製備環氧乙烷觸媒。根據本 發明載劑之性能隨後於相等條件下對照載體評價。 用觸媒自乙烯與氧製造環氧乙烷。製造時將1.5至2 g磨 碎觸媒填裝入内徑6.35 mm的U-形不銹鋼管内。浸管於熔 融金屬浴(載熱體)中,兩端聯接至氣體流動系統。調整觸 媒用重量與進氣流速至6800 cc/cc觸媒/小時之氣體時空間 速度。進氣壓力為210 psig。 在一”單程作業”中包括起動的整個試驗運轉期間,通過 觸媒之氣體混合物含25%乙婦、7%氧、5%二氧化碳、63% 氮及2 · 0至6.0 ppmv氯乙燒。 起始反應器溫度180°C,以每小時l〇°C之速率猛升至225 °C後調整致達到在2.5 ppmv氯乙烷濃度的出口氣流中1.5 vol%之恆定含量之環氧乙烷。當觸媒已運轉總共至少1 -2 日時通常可獲得此轉化量之成果數據。 選擇性與溫度的起始性能值報告於下表3。 表3 載體 選擇性(%) 溫度(°C) 本發明-1 82.5 224 本發明-2 81.9 232 對照-a 81.9 240 根據載體COMP-A之觸媒有比根據INV-1載體者相當低的 選擇性而必須更高溫度。在如此低溫、反應保持優越選擇 性水準之事實強烈指出根據本發明載體的配方比對照載 -14- 發明:¾:明續:頁 、'、'、、、 、、、'、;、、 s ' 1228433 ⑽ 體(A)之配方可有更長壽命。 此等改進在商業上價值極高,因為反應愈長久在高活性 及選擇性水準運轉而不更換極高價觸媒/載體加料,製法 愈經濟。
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Claims (1)
- 申請專利範圍續頁 1228433 d) 自0 · 2至0.8 %之非晶二氧化矽化合物,以二氧化 矽測計;及 e) 自0.05至0.3%的鹼金屬化合物,以鹼金屬氧化物 涓,J計; 全部百分率以混合物總α -氧化鋁含量為基礎,然後 使混合物形成粒子,於1250至1470°C之溫度燃燒作 成載體。8. 根據申請專利範圍第7項之方法,其中氧化鋁水合物 係二水鋁礦。 9. 根據申請專利範圍第7項之方法,其中混合物包含 多達2 0 %重量比之有機燒過物。 10. 根據申請專利範圍第7項之方法,其中混合物與基 於混合物重量計自1 0至2 5 %的擠壓助劑及有機燒 過物與充分水調合俾使混合物能擠壓,隨後擠壓成 丸片,再乾燥並燃燒產生載體。 11.根據申請專利範圍第7項之方法,其中烯烴為乙錦Γ。払;V、 Ί發明、利說明書 1228433 ,中文說明書替換本(93年5月) (填寫本書件時請先行詳閱申請書後之申請須知,作※記號部分請勿填寫) ※申請案號: ※申請曰期: ^PC分類:β〇η^/〇ο 壹、發明名稱 (中文L催化劑盤體_ (英文I£ATALYST CARRTRRS 貳、發明人(共5人) 發明人《»1_ (如發明人超過一人,請填說明書發明人續頁) 姓名··(中文)湯馬士西罾斯某_______ 淺文)THOMAS SZYMANSKT — _ 住居所地址:(中文)美國俄玄俄州胡寿市葭哈尊道2705號_ ί^χ) 2705 BLUE HERON DRIVE. HUDSON. OH 44236. U.S.A.________ 國籍:比文)美國___(^x)U.S.A.__ 參、申請人(共1人) 申請人一1—(如中請人超過-人,請填說明書申請人績頁) 姓名或名稱:[中文)美商聖高祥諾普公司 ___ SAINT-GOBAIN NORPRQ CORPORATION__ 住居所或營業所地址:技文)美國俄玄俄州屮導市費許奋克路3840號一^ ί^Χ) 3840 FISHCREEKRQAD, STOW. OH__ 44224· U.S.A-_____ 國籍:文)美國____(英文_ ___ 代表人:(中文)弗券,R.俄亦里奇_ _ (英文)VOLKER R. UT;RRT「fT1228433 ^ , Γ 拾、申請專利範圍 1 . 一種供婦烴環氧化作用觸媒用之載體,其包含至少9 5 % 具有表面積自1.0至2.6 m2/g的α-氧化鋁及自35至55%之 吸水率,其中孔之分佈使至少7 0 %之孔隙度為具有0.2 至1 0微米微孔徑的孔形式,且直徑在0.2至1 0微米間之 孔提供至少0.27 mL/g的載體體積。 2. 根據申請專利範圍第1項之載體,其中直徑小於0.2 微米的孔佔0至1 0 %之總孔隙度。 3. 根據申請專利範圍第1項之載體,其中汞孔隙度高 達 0.56 mL/g 〇 4. 根據申請專利範圍第1項之載體,其中表面積係自 1 · 6 至 2.2 m2/g。 5. 根據申請專利範圍第1項之載體,其中孔之分佈使 孔徑大於1 0微米的孔佔2 0 %以下之總孔率。 6. 根據申請專利範圍第1項之載體,其中另包含0.2至0.8% 的非晶二氧化矽化合物。 7. —種製造晞烴環氧化觸媒載體之方法,其中包括形成 包含下列的混合物: a) 50至9 0%重量比,具有平均粒子大小(d5〇)自10至 90微米之第一粒狀α-氧化鋁; b) 基於α -氧化鋁總重量計1 0至5 0 %重量比,具有平 均粒子大小(d5G)自2至6微米之第二粒狀α-氧化 銘, c) 重量比2至5 %的氧化銘水合物;
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JP2000044331A (ja) | 1998-05-22 | 2000-02-15 | Sumitomo Chem Co Ltd | α―アルミナ触媒担体、その製造方法、該触媒担体を用いた触媒 |
BR9913602A (pt) | 1998-09-14 | 2001-05-22 | Shell Int Research | Transportador de catalisador de epoxidação, preparação e uso do mesmo |
CN1167500C (zh) | 1998-09-14 | 2004-09-22 | 国际壳牌研究有限公司 | 用于由催化剂表面除去可离子化物质以提高催化性能的方法 |
EP1115486B1 (en) | 1998-09-14 | 2008-04-09 | Shell Internationale Researchmaatschappij B.V. | Process for preparing catalysts with improved catalytic properties |
EP1201301B1 (en) * | 2000-10-25 | 2005-03-30 | Mitsubishi Chemical Corporation | Process of olefins oxidation using a catalyst comprising silver and alkali metal(s) |
US6831037B2 (en) * | 2002-02-25 | 2004-12-14 | Saint-Gobain Norpro Corporation | Catalyst carriers |
-
2002
- 2002-02-25 US US10/082,761 patent/US6831037B2/en not_active Expired - Lifetime
-
2003
- 2003-01-27 MY MYPI20030266A patent/MY130801A/en unknown
- 2003-02-07 TW TW092102533A patent/TWI228433B/zh not_active IP Right Cessation
- 2003-02-25 CA CA002477067A patent/CA2477067C/en not_active Expired - Lifetime
- 2003-02-25 EP EP03743238.2A patent/EP1478458B1/en not_active Expired - Lifetime
- 2003-02-25 EP EP17164712.6A patent/EP3254756A1/en not_active Withdrawn
- 2003-02-25 WO PCT/US2003/005719 patent/WO2003072244A1/en active IP Right Grant
- 2003-02-25 MX MXPA04008258A patent/MXPA04008258A/es active IP Right Grant
- 2003-02-25 CN CNB038079399A patent/CN100531897C/zh not_active Expired - Lifetime
- 2003-02-25 AU AU2003216412A patent/AU2003216412A1/en not_active Abandoned
- 2003-02-25 DK DK03743238.2T patent/DK1478458T3/en active
- 2003-02-25 RU RU2004126091/04A patent/RU2282497C2/ru not_active IP Right Cessation
- 2003-02-25 JP JP2003570979A patent/JP5139622B2/ja not_active Expired - Lifetime
- 2003-02-25 KR KR1020047013272A patent/KR100591031B1/ko active IP Right Grant
- 2003-02-25 BR BRPI0307963-5B1A patent/BR0307963B1/pt active IP Right Grant
-
2004
- 2004-03-08 US US10/795,627 patent/US20040170556A1/en not_active Abandoned
- 2004-08-24 IN IN1883CH2004 patent/IN2004CH01883A/en unknown
- 2004-12-13 US US11/010,488 patent/US20050096219A1/en not_active Abandoned
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2008
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Also Published As
Publication number | Publication date |
---|---|
MY130801A (en) | 2007-07-31 |
MXPA04008258A (es) | 2005-07-13 |
TW200400083A (en) | 2004-01-01 |
CA2477067C (en) | 2007-07-17 |
DK1478458T3 (en) | 2017-07-24 |
US20050096219A1 (en) | 2005-05-05 |
AU2003216412A1 (en) | 2003-09-09 |
BR0307963A (pt) | 2004-12-21 |
EP3254756A1 (en) | 2017-12-13 |
WO2003072244A1 (en) | 2003-09-04 |
KR100591031B1 (ko) | 2006-06-22 |
CN1646219A (zh) | 2005-07-27 |
IN2004CH01883A (zh) | 2006-06-23 |
CN100531897C (zh) | 2009-08-26 |
CA2477067A1 (en) | 2003-09-04 |
RU2282497C2 (ru) | 2006-08-27 |
EP1478458B1 (en) | 2017-04-05 |
US20040170556A1 (en) | 2004-09-02 |
JP5139622B2 (ja) | 2013-02-06 |
BR0307963B1 (pt) | 2013-07-09 |
EP1478458A1 (en) | 2004-11-24 |
KR20040095231A (ko) | 2004-11-12 |
US20030162655A1 (en) | 2003-08-28 |
JP2005518275A (ja) | 2005-06-23 |
RU2004126091A (ru) | 2005-05-27 |
US6831037B2 (en) | 2004-12-14 |
JP2009072787A (ja) | 2009-04-09 |
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