TWI436824B - 供甲醛製備用之銀觸媒 - Google Patents
供甲醛製備用之銀觸媒 Download PDFInfo
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- TWI436824B TWI436824B TW098127604A TW98127604A TWI436824B TW I436824 B TWI436824 B TW I436824B TW 098127604 A TW098127604 A TW 098127604A TW 98127604 A TW98127604 A TW 98127604A TW I436824 B TWI436824 B TW I436824B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims description 99
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 51
- 229910052709 silver Inorganic materials 0.000 title claims description 51
- 239000004332 silver Substances 0.000 title claims description 51
- 239000003054 catalyst Substances 0.000 title claims description 42
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000013078 crystal Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- -1 ethoxylate Chemical compound 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 2
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 claims description 2
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 71
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001915 proofreading effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 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
- 239000000344 soap Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/398—Egg yolk like
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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
- B01J37/02—Impregnation, coating or precipitation
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/04—Formaldehyde
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Powder Metallurgy (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本發明有關一種製造經塗覆之銀觸媒的方法。本發明另外針對該等銀觸媒本身及其在甲醛合成中之有利用途。
甲醛(FA)係最重要的大宗化學品之一；2002年歐盟區的產量高於300萬噸，過去全球的生產量約為此數量的2倍(1989年530萬噸)[K. Weissermel、H.-J. Arpe，Industrielle Organische Chemie，VCH，1994]。各種樹脂(酚、三聚氰胺等)以及聚合物之製造尤其需要FA。該合成實際上只用甲醇進行[K. Weissermel、H.-J. Arpe，Industrielle Organische Chemie，VCH，1994年；M. Qian、M.A. Liauw、G. Emig，Appl. Catal. A:General，238(2003年)211]，不過從甲烷的直接合成亦已經被研究[H. Berndt、A. Martin、A.、E. Schreier、D.、H. Kosslick、G.-U. Wolf、B.，J. Catal.，191(2000年)384]。從甲醇的合成係藉由脫氫作用或部分氧化作用進行。雖然該脫氫作用(反應式1)係吸熱進行(+84kJ/mol)，但該部分氧化作用(反應式2)則為劇烈放熱反應(-159kJ/mol)。
該部分氧化作用係以兩種不同方法使用不同觸媒進行。主要區分特徵首先是不同觸媒，其次是觀察到MeOH在空氣中之爆炸限制。
在空氣不足或銀接觸製法(BASF、Borden、Bayer、Degussa、ICI、Celanese、DuPont、Mitsubishi、Mitsui，廠房大小：80-135kt/a之FA)中，使用>37.5體積%之MeOH含量。在空氣過量、鉬酸鹽或FORMOX製法(Lummus、Montecatini、Hiag/Lurgi、Perstorp/Reichsdorf，廠房大小：20-30kt/a之FA)中，該方法係在MeOH含量<7體積%情況進行。所有廠房的約80%係藉由空氣不足或銀接觸製法操作；西歐約55%之FA產量係根據銀接觸製法進行[M. Qian、M.A. Liauw、G. Emig，Appl. Catal. A:General，238(2003)211；Catalysis from A to Z，VCH Wiley，2000年，第224頁]。
藉由空氣不足的部分氧化方法主要係以兩種變體進行：(i)MeOH壓載法(例如Degussa、ICI)及(ii)水壓載法(BASF)。然而在僅使用MeOH與空氣的第一種方法中獲致不完全轉化，且在額外加入蒸氣的第二種方法可獲致實質上完全轉化。以60/40之MeOH/H2
O混合物操作是相當常見。
然而現有方法全部受到銀觸媒在反應溫度下迅速結塊而使得待導入氣體更難流經該觸媒床的事實所影響。當此時的耗損過大時，甲醛廠房必須停止運轉並更換觸媒，此會導致高成本之生產停止運轉。水的高熱容量在水壓載法中獲致熱均勻分佈且保護觸媒以免過快「燒結」。此外，蒸氣有助於避免或最小化焦炭形成。因此，水壓載法中之銀觸媒的使用期限明顯高於甲醇壓載法，惟可能需要進一步提高服務期限(WO 0130492)。
原則上已知製造具有多孔矽膠塗層之奈米微粒銀鉑合金(作為新穎觸媒前驅體之塗覆有超薄多孔氧化矽的銀鉑合金奈米粒子，Kai Man K. Yu、David Thompsett、Shik Chi Tsang，Chem. Commun. ，2003年，(13)，1522-1523)。不過，由於此等奈米粒子的體密度太大，當其用於觸媒床時待轉化之氣體因而極難流經該等奈米粒子，故其不適於甲醛合成。
因此，本發明目的係詳細說明一種製造銀結晶之方法以及詳細說明該等銀結晶本身，該銀結晶的服務期限較先前技術的結晶在利用水壓載法之甲醛合成作用中的服務期限獲得改善。同時，諸如空間-時間產率、觸媒交換速度與活性等其他參數不應受到負面影響。
根據申請專利範圍而達到本發明的目的。
由此，可藉由以下述的方式進行下列的方法而以簡單但不會較不利之方式獲得所述問題的解決方法，所述之方法係為一種用於製造具有氧化材料之多孔薄塗層的銀結晶之方法，而該等氧化材料含有選自鋁、矽、鋯、鈦與其混合物的元素：
a) 該銀結晶係與所述元素的溶膠-凝膠溶液接觸，且
b) 收集所得之銀結晶，
c) 去除有機溶劑，及
d) 然後在50℃與銀熔點之間的溫度下熱處理。儘管含有該塗層，所得之銀觸媒具有與無對應塗層之原本使用銀結晶同等的活性以及選擇性，且得到一樣良好的空間-時間產率。同時，該塗層卻有助於阻礙銀結晶燒結，此顯著增長該觸媒的服務期限，因而由於不必進行無觸媒交換而大幅降低成本。此外，十分令人意外的是因待交換材料未結塊且比習用材料更能輕易地從反應器移出之故，該觸媒交換本身可以更容易控制。
在本方法之步驟a)中，該銀結晶係與所述元素的溶膠-凝膠溶液接觸。此較佳係僅以適當溶液濕潤該銀結晶而完成。較有利地，步驟a)係在包含有機溶劑之溶劑中進行。該結晶較佳亦可導入容納溶膠-凝膠溶液的容器/反應器，隨意地加以攪拌。該添加作用亦可逆向進行。有利地，該溶膠-凝膠溶液係所述元素之烷氧化物溶解於有機基質中之溶膠-凝膠溶液。由於水解的緣故，該烷氧化物可能已部分交聯，因此可能以膠態溶解形式存在。為了安定該溶液，可添加特定添加劑。
如本文所指示，該溶膠-凝膠溶液較佳係以有機介質之形式使用。熟悉本技術之人士明白此處以何種溶液為佳。不過，特佳之具體實例係所使用溶劑為醇類。尤佳之溶劑可為選自甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、正戊醇、及與其鍵結異構物及其混合物。可將其他有機溶劑添加於該溶膠-凝膠溶液，例如醚類。
特佳之具體實例係所選擇之溶膠-凝膠溶液係所述元素之烷氧化物於作為該有機溶劑之對應的醇中。因此，所述元素非常特別佳的烷氧化物係選自由甲氧化物、乙氧化物、丙氧化物、異丙氧化物、正丁氧化物、第二丁氧化物、異丁氧化物、第三丁氧化物、正丙氧化物或其鍵結異構物或其混合物。
其次，收集該銀結晶並去除過量溶膠-凝膠溶液。該收集作用可藉由簡單過濾、傾析或類似方法進行。然後，去除仍附著於該銀結晶的過量溶劑。此可藉由在周圍條件下蒸發溶劑而從所得之銀結晶去除該溶劑的簡單方法完成。其他方法亦為熟悉本技術之人士所通曉。特別是，該溶劑亦可藉由額外措施，例如施加真空、曝於氣流(空氣、氮)等而以加速方式去除。
在隨意的最終步驟中，所得銀結晶係在50℃與銀熔點之間的溫度下熱處理。此較佳係在300℃與700℃之間的溫度下進行，最佳係在400℃至600℃的溫度下進行。該熱處理可藉由施加真空或在氧化氣氛(較有利為空氣)的存在下進行。
如此獲得的銀結晶可以此形式供甲醛製造，或隨意地在如上述的進一步處理措施之後供甲醛製造。
本發明另一形態中，本發明因而有關氧化材料的多孔薄塗層之銀結晶，該等氧化材料含有選自鋁、矽、鋯、錫、鈦與其混合物的元素，該銀結晶可由本發明之方法製得。
供甲醛合成之銀結晶必須具有特定形狀以便能順利地用作為觸媒。該銀結晶不可太小，否則留在個別銀結晶之間的孔腔太小無法供待轉化氣體流過。觸媒床會因此而阻塞。另一方面，該結晶之粒子大小不應太大，否則其結果係昂貴觸媒材料與表面積之間的比率不佳。已發現當平均粒子大小分佈為0.15至2.5mm較有利，更佳為0.5至2.0mm，最佳為0.5至1.0mm。
該銀結晶之塗層係如前述用以防止銀結晶在甲醛合成作用中於觸媒床中燒結在一起。該塗層必須具有適當厚度以便能充分確保此效果。因此，該塗層所具有之厚度應儘可能不小於0.3μm。另一方面，從黏著性與磨耗觀點來看，可推論該塗層厚度太大並未顯得較有利。因此該塗層厚度應在0.3μm至10μm之間。較佳厚度為1.0至5.0μm，更佳為2.0至4.0μm，最佳為約3.0μm。
該塗層係由預期之元素的氧化材料所組成。根據本發明，此種材料被視為包含所提之元素的無機化合物，該等元素係經由氧原子彼此鍵結存在整體材料內或在至少主要部分內。因此該氧化材料較佳包含各種類型之SiO2
、鋁氧化物(例如，α-、β-、γ-Al2
O3
、水軟鋁石等)、TiO2
、ZrO2
、該等化合物之氧化物或混合氧化物的混合物，例如各種沸石、SAPO、鈣鈦礦、尖晶石等。該塗層亦可以陶瓷形式存在。
本發明觸媒應較有利地具有特定的體密度。其應在>1700與<3800g/l之間，較佳係>1700與<2400g/l，最佳係在>1700與<2000g/l之間。
本發明亦另外有關使用根據本發明之經塗覆的銀結晶作為供甲醛製備用之觸媒的用途。
就該應用(例如甲醛合成)而言，該銀結晶應具有之純度為>99.9%，較佳為>99.99%。已發現存在該銀結晶中之超小量元素係選自金、鉍、銅、鐵、鉛、鈀與鉑之元素。該等元素之量小於100ppm，較佳為<50ppm，更佳為<30ppm。
該銀結晶之塗層至少關鍵性地延遲在甲醛合成期間之該結晶的燒結結塊。當計畫交換觸媒時，由於結晶的結塊較不顯著，亦可顯著地更迅速從反應器移除該結晶。該塗層有效地賦予該銀結晶外骨架，其顯著地延長甲醛合成中該觸媒床的服務期限，因此抵消頻繁之觸媒交換。由於該觸媒交換與該觸媒交換所造成的生產停止運轉關係到甲醛製造的一大部分成本，故本發明有助於進行明顯較便宜之甲醛合成作用。
許多測試已證實使用本發明新穎觸媒之產率令人意外地並未明顯比採用原本使用之銀觸媒差。(圖1、圖2)。
觸媒之製造
利用膠態水軟鋁石(AlOOH)溶膠或聚合Al2
O3
溶膠對該Ag觸媒塗覆以陶瓷γ-Al2
O3
層。
膠態溶膠之特徵係將超小粒子分散在1nm之區域中，該等超小粒子因表面電荷而彼此靜電互斥。為製備該膠態水軟鋁石溶膠，三第二丁氧化鋁(ATSB)係經2-丁醇稀釋並逐滴加入經硝酸酸化的水中。所發生的水解係以過量水進行。形成之2-丁醇隨後被蒸餾去除。由於在120℃回流下沸騰，轉化成水軟鋁石且同時安定該溶膠。獲得發出淡藍色微光之清澈溶膠。
就聚合溶膠而言，金屬烷氧化物同樣供作為前驅體材料。因此，同樣從經異丙醇稀釋之三丁氧化鋁(ATSB)製備該聚合氧化鋁溶膠。不同於與該膠態溶膠之製備，此處只供應少量水，其導致部分水解且避免該氫氧化物沉澱。該經部分水解之烷氧化物隨著水的消除而縮合，形成聚合物。藉由添加錯合劑(諸如乙醯丙酮)避免完全水解。攪拌排除空氣及添加硝酸使該溶膠安定。形成清澈溶膠。
所獲得之溶膠係用以藉由浸漬或噴霧而塗覆該Ag結晶。然後在網狀基板上以濕氣含量>50%且在25與100℃之間的溫度下乾燥該結晶。如此將溶膠轉化成凝膠；該奈米粒子係立體交聯。藉由在陶瓷坩堝中於500℃下保持3小時燒結該經塗覆結晶，在該Ag結晶上從該凝膠層製成陶瓷塗層。
活性測試
圖3所示之裝置係用以進行活性測試。
N2
與空氣/O2
係以MFC(多流控制器)計量，MFC係藉由皂膜計事先校正。為了校對，亦測量通過未經加熱反應器之後的氣流。藉由具有上游除氣器之HPLC泵計量該液體。該H2
O/MeOH混合物經由初重確立。為了計算待量入之液體體積(ml/min)，組份之密度的相加行為最初假設為該混合物之密度。在測試完成之後，參考液體貯存器之重量變化以核對所注射之液體量。因此，對所量入之MeOH量進行校正係為了計算MeOH轉化率(X-MeOH)，但亦針對所有進料組份的體積百分比和GHSV(氣體每小時空間速度)進行校正。
所使用之反應器為ALSINT 99.7陶瓷管；外徑15mm，內徑10mm，長度500mm(得自Haldenwanger Berlin(BTK-Technische Keramik,Neuss))。藉由水冷卻(冷卻盤管)將反應器入口與出口保持在約120℃。該恆溫箱(120℃)確保甲醛不會在該產物流被導入冷凝器以及導入產物樣本收集容器之前聚合。該液態反應物係在連接該反應器上游的蒸發器中以120℃蒸發。該反應器溫度係調節至觸媒床中所希望之溫度，該溫度係在觸媒床中間測得。當該液態進料速率與組成改變時，必須再調整該溫度。離開該反應器與熱箱之後，在螺旋狀冷卻器中將該產物冷卻至約5℃，並輸送至同樣經冷卻之樣本取出點。
各例中之觸媒床係由0.1g之粒子分率為0.5至1mm的Ag觸媒所組成，且混有3g之1至1.4mm白色高級金剛砂(類似[M. Qian,M.A. Liauw,G. Emig,Appl. Catal. A:General,238(2003)211]。該床之容積為2.3ml(根據GHSV計算)。為了預熱入口側之進料，在該觸媒床上鋪上一層額外高級金剛砂床。
測試三個觸媒試樣：觸媒1："純銀"(Ag)，觸媒2：經聚合物為底質之氧化鋁改質的Ag(本發明之氫氧化鋁前驅體)(Ag-P)，觸媒3：經膠體為底質之氧化鋁改質的Ag(本發明之鋁溶膠前驅體)(Ag-K)。
氣體層析術分析係以Shimadzu GC 17A使用AT-Q 30m x 0.32mm毛細管柱以及具有上游甲烷化的FID器進行。更明確地說，使用下列條件：注射體積0.9μl，分流40，線性速度30.9cm/s，溫度計劃係於120℃恆溫6min，以10K/min升至200℃，保持1min，每個樣本注射5次。該毛細管GC柱係在起始溫度120℃操作，以避免甲醛聚合或與MeOH形成甲縮醛。
在500至600℃且空氣速度為6000至20 000h-1
下進行測試；MeOH：水比率為0.67或1.2。MeOH轉化率在600℃下達到約70%；FA產率為35至40%。在低度裝料或長滯留時間下，觀察到FA分解速率高；CO為主要產物。
測試之細節示於以下表格：
在所有使用的反應條件下，令人意外的是以表面經氧化鋁沉積物改質之Ag觸媒(Ag-P和Ag-K)並未獲得顯著較差的產率與甲醇轉化率。
圖1與2顯示反應溫度和空間速度與MeOH轉化率和FA產率之函數關係。
圖1：MeOH轉化率與FA選擇性或產率相對於反應溫度。
圖2：MeOH轉化率與FA選擇性或產率相對於裝料。
X-MeOH：MeOH轉化率[%]
S-FA：甲醛選擇性[%]
Y-FA：甲醛產率[%]
圖1顯示MeOH轉化率和FA選擇性或產率與反應溫度的函數關係。
圖2顯示MeOH轉化率和FA選擇性或產率與空間速度之函數關係。
圖3顯示進行活性測試之裝置。
Claims (12)
- 一種用於製造具有氧化材料之多孔薄塗層的銀結晶之方法，而該等氧化材料含有選自鋁、矽、鋯、鈦與其混合物的元素，該方法的特徵在於：a) 該銀結晶係與所述元素的溶膠-凝膠溶液接觸，且b) 收集所得之銀結晶，c) 去除有機溶劑，及d) 然後在50℃與銀熔點之間的溫度下熱處理。
- 如申請專利範圍第1項之方法，其中步驟a)係在包含有機溶劑的溶劑中進行。
- 如申請專利範圍第1或2項之方法，其中所選擇之溶膠-凝膠溶液係所述元素之烷氧化物於作為該有機溶劑之對應的醇中。
- 如申請專利範圍第3項之方法，其中所選擇之所述元素的烷氧化物係選自由甲氧化物、乙氧化物、丙氧化物、異丙氧化物、正丁氧化物、第二丁氧化物、異丁氧化物、第三丁氧化物、正丙氧化物或其結構異構物之群組其中一者。
- 如申請專利範圍第1項之方法，其中藉由在周圍條件下令該溶劑蒸發而去除所得之銀結晶的溶劑。
- 如申請專利範圍第1項之方法，其中該熱處理係在400℃與800℃之間的溫度下進行。
- 一種具有氧化材料的多孔薄塗層之銀結晶，該等氧化材料含有選自鋁、矽、鋯、錫、鈦與其混合物的元素，該銀結晶可由申請專利範圍第1至6項中任一項之方法製得。
- 如申請專利範圍第7項之銀結晶，其中該銀結晶的平均粒子大小分布為0.15mm至2.5mm。
- 如申請專利範圍第7項之銀結晶，其中該塗層之厚度為0.3μm至10μm。
- 如申請專利範圍第7項之銀結晶，其中該氧化材料係選自SiO2 、各種鋁氧化物、TiO2 、ZrO2 、該等化合物之氧化物或混合氧化物的混合物，其可隨意地為陶瓷形式。
- 如申請專利範圍第7項之銀觸媒，其體密度介於>1700g/l與<3800g/l之間。
- 一種使用如申請專利範圍第7至10項中任一項之銀結晶作為供甲醛製備用之觸媒的用途。
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| DE102008045148A DE102008045148A1 (de) | 2008-09-01 | 2008-09-01 | Silberkatalysator zur Formaldehyd-Herstellung |
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| TWI436824B true TWI436824B (zh) | 2014-05-11 |
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| EP (2) | EP3685915A1 (zh) |
| JP (1) | JP5528450B2 (zh) |
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| MY (1) | MY153887A (zh) |
| RU (1) | RU2503497C2 (zh) |
| TW (1) | TWI436824B (zh) |
| WO (1) | WO2010022923A1 (zh) |
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| DE102010040921A1 (de) | 2010-09-16 | 2012-03-22 | Basf Se | Verfahren zur Herstellung von Acrylsäure aus Methanol und Essigsäure |
| DE102010040923A1 (de) | 2010-09-16 | 2012-03-22 | Basf Se | Verfahren zur Herstellung von Acrylsäure aus Ethanol und Formaldehyd |
| US10035136B2 (en) | 2014-03-25 | 2018-07-31 | Tpc Group Llc | Catalyst for reduced nitrogen oxide (NOx) emissions in an oxodehydrogenation process |
| CN105363320B (zh) * | 2015-11-10 | 2018-05-01 | 沭阳县金辉化工有限公司 | 一种新型高效脱醇甲醛吸收塔 |
| US10392333B2 (en) * | 2017-12-21 | 2019-08-27 | Purdue Research Foundation | Method of producing formaldehyde from methanol |
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| JPS5630064B2 (zh) * | 1974-06-04 | 1981-07-13 | ||
| JPS5759637A (en) * | 1980-09-22 | 1982-04-10 | Suredoneajiatsuki Nii Nefutepe | Manufacture of carbonyl compound |
| US4330437A (en) * | 1980-11-05 | 1982-05-18 | Borden, Inc. | Supported silver catalyst and a process of preparing it |
| NL8502993A (nl) * | 1985-11-01 | 1987-06-01 | Dow Chemical Nederland | Zilverkatalysator, alsmede werkwijze voor de bereiding daarvan. |
| JP2508847B2 (ja) * | 1989-07-20 | 1996-06-19 | 株式会社ハイミラー | ＳｉＯ２被膜が形成された銀コ―トガラスフレ―クの製造法 |
| US5948726A (en) * | 1994-12-07 | 1999-09-07 | Project Earth Industries, Inc. | Adsorbent and/or catalyst and binder system and method of making therefor |
| EP0818561B1 (en) * | 1995-12-28 | 2000-05-03 | Consejo Superior De Investigaciones Cientificas | Protection coatings produced by sol-gel on silver reflectors |
| AUPQ364699A0 (en) | 1999-10-25 | 1999-11-18 | University Of Queensland, The | Polycrystalline silver catalysts for methanol oxidation to formal dehyde |
| EP1110647A3 (en) * | 1999-12-22 | 2004-02-11 | Mitsui Mining and Smelting Co., Ltd | Paste to be fired for forming circuit board and method for preparing surface-modified silver powder |
| US6994948B2 (en) * | 2001-10-12 | 2006-02-07 | E.I. Du Pont De Nemours And Company, Inc. | Aqueous developable photoimageable thick film compositions |
| US20030166972A1 (en) * | 2002-02-20 | 2003-09-04 | Regents Of The University Of California Office Of Technology Licensing | Process for production of formaldehyde from dimethyl ether |
| US7226953B1 (en) * | 2003-11-17 | 2007-06-05 | Los Alamos National Security, Llc | Nanocrystal/sol-gel nanocomposites |
| JP4149385B2 (ja) * | 2004-01-27 | 2008-09-10 | 三井金属鉱業株式会社 | 酸化アルミニウム被覆微粒銀粉およびその製造方法 |
| JP4478526B2 (ja) * | 2004-07-20 | 2010-06-09 | 大研化学工業株式会社 | 非合金金属粉末及び合金金属粉末の製造方法 |
| EP1676625A1 (en) * | 2004-12-28 | 2006-07-05 | Mitsubishi Denki Kabushiki Kaisha | Method and catalyst for the oxidative decomposition of formaldehyde gas |
| JP2008528722A (ja) * | 2005-01-24 | 2008-07-31 | シンベンション アーゲー | 金属含有コンポジット材料 |
| EP1696006B1 (en) * | 2005-02-28 | 2009-06-17 | Samsung SDI Germany GmbH | metal ink and substrate for a display and method for manufacturing the same |
| US20060192183A1 (en) * | 2005-02-28 | 2006-08-31 | Andreas Klyszcz | Metal ink, method of preparing the metal ink, substrate for display, and method of manufacturing the substrate |
| FR2882746B1 (fr) * | 2005-03-01 | 2007-04-27 | Commissariat Energie Atomique | Procede de preparation d'une solution sol-gel et utilisation de cette solution pour constituer un revetement pour proteger un substrat a surface metallique |
| KR20070095497A (ko) * | 2005-09-30 | 2007-10-01 | 삼성에스디아이 주식회사 | 전극 형성용 전도성 분체, 이의 제조방법, 이를 이용한플라즈마 디스플레이 패널의 전극 형성방법, 및 이를포함하는 플라즈마 디스플레이 패널 |
| WO2007149881A2 (en) | 2006-06-19 | 2007-12-27 | Cabot Corporation | Metal-containing nanoparticles, their synthesis and use |
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- 2009-08-26 EP EP09778113.2A patent/EP2321044B1/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0918277A2 (pt) | 2015-12-15 |
| CA2735745A1 (en) | 2010-03-04 |
| BRPI0918277B1 (pt) | 2018-01-16 |
| ES2787550T3 (es) | 2020-10-16 |
| RU2503497C2 (ru) | 2014-01-10 |
| MY153887A (en) | 2015-04-15 |
| KR20110055705A (ko) | 2011-05-25 |
| DE102008045148A1 (de) | 2010-03-04 |
| EP2321044A1 (en) | 2011-05-18 |
| AU2009287008B2 (en) | 2014-10-02 |
| TW201012543A (en) | 2010-04-01 |
| BRPI0918277B8 (pt) | 2023-05-09 |
| EP3685915A1 (en) | 2020-07-29 |
| AU2009287008A1 (en) | 2010-03-04 |
| WO2010022923A1 (en) | 2010-03-04 |
| EP2321044B1 (en) | 2020-02-26 |
| CN102137716A (zh) | 2011-07-27 |
| US20110201843A1 (en) | 2011-08-18 |
| US8471071B2 (en) | 2013-06-25 |
| JP5528450B2 (ja) | 2014-06-25 |
| CA2735745C (en) | 2016-11-01 |
| CN102137716B (zh) | 2013-07-24 |
| KR101634082B1 (ko) | 2016-06-28 |
| RU2011112015A (ru) | 2012-10-10 |
| JP2012501241A (ja) | 2012-01-19 |
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