TWI471299B - Hydroxylation of phenol - Google Patents
Hydroxylation of phenol Download PDFInfo
- Publication number
- TWI471299B TWI471299B TW101136641A TW101136641A TWI471299B TW I471299 B TWI471299 B TW I471299B TW 101136641 A TW101136641 A TW 101136641A TW 101136641 A TW101136641 A TW 101136641A TW I471299 B TWI471299 B TW I471299B
- Authority
- TW
- Taiwan
- Prior art keywords
- cobalt
- solid catalyst
- phenol
- source
- cerium
- Prior art date
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 34
- 238000005805 hydroxylation reaction Methods 0.000 title description 16
- 230000033444 hydroxylation Effects 0.000 title description 9
- 239000011949 solid catalyst Substances 0.000 claims description 48
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 44
- 239000010941 cobalt Substances 0.000 claims description 40
- 229910017052 cobalt Inorganic materials 0.000 claims description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 230000000640 hydroxylating effect Effects 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 phthalic acid ester Chemical class 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000002083 X-ray spectrum Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XZXAIFLKPKVPLO-UHFFFAOYSA-N cobalt(2+);dinitrate;hydrate Chemical compound O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XZXAIFLKPKVPLO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RKMUSWVGFJPTQI-UHFFFAOYSA-N COCCO[Co] Chemical compound COCCO[Co] RKMUSWVGFJPTQI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Chemical group 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Polymers CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Polymers CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- KYGISWNEHOVNRN-UHFFFAOYSA-N decane Polymers CCCCCCCCCC.CCCCCCCCCC.CCCCCCCCCC.CCCCCCCCCC KYGISWNEHOVNRN-UHFFFAOYSA-N 0.000 description 1
- MXIRHCBUSWBUKI-UHFFFAOYSA-N decane Polymers CCCCCCCCC[CH2+] MXIRHCBUSWBUKI-UHFFFAOYSA-N 0.000 description 1
- OWCFCPLYQPPJPH-UHFFFAOYSA-N decane Polymers CCCCCCCCCC.CCCCCCCCCC OWCFCPLYQPPJPH-UHFFFAOYSA-N 0.000 description 1
- YBPJNJSKPUAMKZ-UHFFFAOYSA-N decane Polymers CCCCCCCCC[CH2-] YBPJNJSKPUAMKZ-UHFFFAOYSA-N 0.000 description 1
- 239000007854 depigmenting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229910052733 gallium 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 229910052720 vanadium Chemical group 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本發明係關於一種苯酚羥基化之方法,更詳而言,係關於一種利用含鈷之固體觸媒催化苯酚羥基化之方法。
間苯二酚、對苯二酚及鄰苯二酚依其性質不同,可應用於電子、醫藥、化學各產業是重要的化工產品,其廣泛應用於顯影劑、阻聚劑、皮膚美白劑、抗氧劑、殺菌劑、橡膠助劑、電鍍添加劑、光穩定劑、染料、香料還原劑、特種墨水等有機合成工業。
通常,對苯二酚及鄰苯二酚之製造係以過氧化氫作為氧化劑使苯酚羥基化而得,反應過程中通常添加催化劑以促進羥基化反應之進行。目前苯酚羥基化反應多使用沸石作為催化劑,其具有反應後催化劑與產物易分離之優點。較常使用之沸石包括TS-1、ZSM-5、β以及Y型分子篩,其中又以市售TS-1型分子篩效果較佳。
第4,396,783號美國專利揭露在鈦-矽固體觸媒中加入改質金屬,以用於苯酚羥基化,惟,該專利實際上係使用鐵、鉻或釩進行改質,進行苯酚羥基化反應之二酚產率為8.58%,對苯二酚/鄰苯二酚(對/鄰)比最高為0.6。
第5,399,336號美國專利則揭露合成具有錫與鋯的矽觸媒(S-1),再以70重量%(wt%)之過氧化氫進行苯酚羥基化反應。於含錫之S-1催化下之反應之苯二酚產率27.5%,以含鋯之S-1催化下之反應之苯二酚產率為28%,兩者均
不僅有安全上的疑慮且皆未顯著提升苯二酚之產率。
第2116974號英國專利揭露一種以具MFI構造之TS-1固體觸媒作為苯酚羥基化之催化劑,所得之對/鄰比為1,過氧化氫選擇率為73.9%。同樣的,第0266825號歐洲專利揭露以含鎵之TS-1固體觸媒進行苯酚羥基化反應,過氧化氫固體觸媒率為74.7%,對/鄰比則為0.79。
由上可知,習知技術使用之固體觸媒在苯酚羥基化反應的應用上,仍存在二酚產物之對/鄰比值低、過氧化氫選擇率低之問題,且習知技術未有使用含有鈷之固體觸媒於苯酚羥基化上。
因此,開發一種提高產物的對/鄰比以、二酚選擇率及過氧化氫選擇率之固體觸媒,實已為迫切待解之課題。
本發明提供一種苯酚羥基化之方法,係於溶劑和具有沸石骨架之固體觸媒存在下,使苯酚與過氧化氫反應形成二酚,其中,該固體觸媒包括氧化矽、氧化鈦以及氧化鈷。於一具體實例中,本發明之方法所使用之固體觸媒具有MFI沸石骨架。
於較佳實施例中,本發明之方法所使用之固體觸媒係由鈦源、矽源及鈷源經水熱反應而得,其中,鈦源與矽源之鈦與矽之莫耳比為0.01至0.05,鈷源與矽源之鈷與矽莫耳比為0.00001至0.002。
本發明之方法中,反應的溫度範圍為20至100℃,較佳為30至80℃,更佳為50至70℃。於本發明之方法,該
過氧化氫與苯酚之莫耳比係介於0.2至1,較佳為0.25至0.8,更佳為0.33至0.6。
於本發明之方法,以苯酚與過氧化氫之總重量計,本發明之固體觸媒含量係介於0.5至10%,較佳為1至8%,更佳為1.5至6.5%。溶劑則無特殊限制,通常係選自醇類、酮類、腈類、有機酸及水所組成群組之一種或多種溶劑。
本發明之製備二酚之方法具有高過氧化氫利用率、高苯酚轉化率、提高產物的對/鄰比以及二酚選擇率,適用於工業上之大量生產。
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容輕易地瞭解本發明之優點及功效。本發明亦可藉由其它不同之實施方式加以施行或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本發明所揭示之精神下賦予不同之修飾與變更。
於一較佳實施例中,本發明之固體觸媒係由下述之製法製得,該製法包括:於5℃下將矽源、鈦源及模版劑混合均勻為一混合膠體後;加入含鈷化合物至該混合膠體以得到含鈷混合膠體;將該含鈷混合膠體進行水熱處理;以及煅燒該經水熱處理之含鈷混合膠體以得到本發明之固體觸媒。於本發明之固體觸媒之製法中,該矽源和鈦源之鈦與矽莫耳比係0.01至0.05,該含鈷化合物和矽源之鈷與矽莫耳比係0.00001至0.002。並可控制固體觸媒之鈦與
矽莫耳比為0.01至0.05,鈷與矽莫耳比為0.00001至0.002。
此外,本發明之固體觸媒之製法復可包括於形成含鈷混合膠體後,在該含鈷混合膠體中混入水或矽溶膠,再對混入水或矽溶膠之膠體混合物進行水熱步驟。
本發明之固體觸媒之製法中所使用之矽源,包括,但不限制於:矽酸酯或具下式(I)之化合物,其中,n獨立表示為1至5之整數。
於一實施例中,所使用之矽源,包括,但不限制於:四甲基矽酸酯、四乙基矽酸酯、四丙基矽酸酯、四丁基矽酸酯或其組成。矽源亦可使用聚乙氧基矽烷,例如,ES-28(n=1~2)、ES-32(n=3~4)及ES-40(n=4~5)(製造廠商為Colcoat株式會社)。
本發明之固體觸媒之製法中所使用之鈦源,包括,但不限制於:四烷基鈦酸酯。於較佳實施例中所使用之鈦源,但不限制於:四乙基鈦酸酯、四正丙基鈦酸酯、四異丙基鈦酸酯、四正丁基鈦酸酯或其組成。
本發明之固體觸媒之製法中所使用之模板劑,包括,但不限制於:四正丙基氫氧化銨、四正丁基氫氧化銨、四正丙基溴化銨、四正丁基溴化銨之水溶液或醇溶液,其中,
該醇溶液包括具有1至5個碳原子之醇,例如,甲醇、乙醇、異丙醇、正丁醇及第三丁醇所組成之群組之一種或多種溶劑。
本發明之固體觸媒之製法中所使用之含鈷化合物包括,但不限制於:鈷之烷氧化物、鹵化鹽或酸根鹽。例如,該鈷之烷氧化物包括,但不限制於:甲氧乙氧基鈷;該鈷之鹵化鹽包括,但不限制於:氯化鈷、溴化鈷或其組成;該鈷之酸根鹽包括,但不限制於:硝酸鈷、碳酸鈷、醋酸鈷、乙醯丙酮酸鈷或其組成。
以下係藉由特定之具體實施例進一步說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。本發明之實施例如下所示,但本發明並不限於這些實施例。
此實例係製備習知技術之鈦-矽固體觸媒,以作為比較例。
將250毫升(mL)之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00克(g)之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.46 g之四正丁基鈦酸酯至圓底燒瓶中,並且攪拌1小時,而後取44 g之水逐滴加入攪拌1小時,接著再於室溫下攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。
將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得比較觸媒(TS-1A)。
此實例係製備習知技術之鈦-矽固體觸媒,以作為比較例。
將250 mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.90 g之四正丁基鈦酸酯至圓底燒瓶中,並且攪拌1小時,而後取44 g之水逐滴加入攪拌1小時,接著再於室溫下攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得比較觸媒(TS-1B)。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃
溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.46 g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0626 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得本發明之固體觸媒(觸媒A),其中,該固體觸媒中鈦與矽的莫耳比為0.02,鈷與矽的莫耳比為0.001。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.46 g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0313 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入
鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得固體觸媒(觸媒B),其中,該固體觸媒中鈦與矽的莫耳比為0.02,鈷與矽的莫耳比為0.0005,其X-Ray圖譜係如第1圖所示,經PDF(Powder Diffraction File)資料庫比對,該觸媒B具有MFI結構。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.46 g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0063 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得固體觸媒(觸媒C),其中,該固體觸媒中鈦與矽的莫耳比為0.02,鈷與矽的莫耳比為0.0001。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.90g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0626 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得固體觸媒(觸媒D),其中,該固體觸媒中鈦與矽的莫耳比為0.026,鈷與矽的莫耳比為0.001。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.90 g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0313 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽
溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得本發明之固體觸媒(觸媒E),其中,該固體觸媒中鈦與矽的莫耳比為0.026,鈷與矽的莫耳比為0.0005,其X-Ray圖譜係如第2圖所示,經PDF資料庫比對,該觸媒E具有MFI結構。
將250mL之圓底燒瓶於真空系統中進行氮封,於5℃溫度下加入30.00 g之四乙基矽酸酯、56.00 g之四正丙基氫氧化銨(含量20wt%)、1.90 g之四正丁基鈦酸酯置於圓底燒瓶中,並且攪拌1小時,接著將0.0063 g之水合硝酸鈷溶於44.00 g之水中形成鈷源溶液,並將此鈷源溶液逐滴加入圓底燒瓶中攪拌1小時,接著於室溫下再攪拌1小時,最後於80℃下除醇2小時。取10.80 g之AS-40矽溶膠溶液分散於73 g水中,形成分散液,並加入圓底燒瓶中攪拌1小時。將此經除醇之含分散液之膠體混合物封入鐵氟龍內襯之不鏽鋼耐壓罐中,於180℃進行水熱處理120小時,將固體與液體分離後,固體部份以水洗至中性,於100℃乾燥及550℃煅燒8小時,以獲得本發明之固體觸媒(觸媒F),其中,該固體觸媒中鈦與矽的莫耳比為0.026,鈷與矽的莫耳比為0.0001。
使用比較例1與實施例1至6製得之固體觸媒,進行苯酚羥基化反應,反應步驟如下:取0.178莫耳(mol)苯酚、1.066 mol純水、1.844 g之觸媒於氮氣下置入250mL三頸瓶中,溫度升溫至60℃,加入0.089 mol之35%過氧化氫以幫浦進料共3小時,接著反應滯留3小時,待溫度降至室溫,分離反應液與觸媒,以氣相層析法分析反應液,結果顯示於表1。
使用比較例2與實施例5製得之鈦與矽莫耳比相同之固體觸媒,於不同溫度下進行苯酚羥基化反應,反應步驟如下:取0.178莫耳(mol)苯酚、1.066 mol純水、1.844 g之觸媒於氮氣下置入250mL三頸瓶中,分別在溫度55、65、70℃,加入0.089 mol之35%過氧化氫以幫浦進料共3小時,接著反應滯留3小時,待溫度降至室溫,分離反應液與觸媒,以氣相層析法分析反應液,結果顯示於表2。
由上述實施例所示,本發明之固體觸媒,用於苯酚羥基化之方法,不需高濃度之過氧化氫,即可達到高苯酚轉化率,並進一步提升二酚選擇率及產物之對/鄰比。本發明之含鈷固體觸媒不僅降低使用高濃度過氧化氫之安全性疑慮,且具有更廣的活性溫度範圍,俾達到提升生產效益之目的。
上述實施例僅例示說明本發明之原理及其功效,而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下,對上述實施例進行修飾與改變。因此,本發明之權利保護範圍,應如後述之申請專利範圍所列。
第1圖係實施例2之固體觸媒之X-Ray圖譜;以及第2圖係實施例5之固體觸媒之X-Ray圖譜。
Claims (7)
- 一種苯酚羥基化之方法,係於溶劑和固體觸媒存在下,使苯酚與過氧化氫反應形成二酚,其中,該固體觸媒係具有沸石骨架,且該固體觸媒係由鈦源、矽源及鈷源經水熱反應而得形成包括氧化矽、氧化鈦以及氧化鈷於該固體觸媒沸石骨架中。
- 如申請專利範圍第1項所述之方法,其中,該固體觸媒具有MFI沸石骨架。
- 如申請專利範圍第2項所述之方法,其中,鈦源與矽源之鈦與矽莫耳比為0.01至0.05,鈷源與矽源之鈷與矽莫耳比為0.00001至0.002。
- 如申請專利範圍第1項所述之方法,其中,該過氧化氫與苯酚之莫耳比係0.2至1。
- 如申請專利範圍第1項所述之方法,其中,以該苯酚與過氧化氫之總重量計,該觸媒之含量為0.5%至10%。
- 如申請專利範圍第1項所述之方法,其中,該反應溫度為20℃至100℃。
- 如申請專利範圍第1項所述之方法,其中,該溶劑係選自醇類、酮類、腈類、有機酸及水所組成群組之一種或多種溶劑。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW101136641A TWI471299B (zh) | 2012-10-04 | 2012-10-04 | Hydroxylation of phenol |
CN201210482934.4A CN103709011B (zh) | 2012-10-04 | 2012-11-23 | 苯酚羟基化的方法 |
US14/044,108 US9206101B2 (en) | 2012-10-04 | 2013-10-02 | Method for hydroxylation of phenol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW101136641A TWI471299B (zh) | 2012-10-04 | 2012-10-04 | Hydroxylation of phenol |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201414711A TW201414711A (zh) | 2014-04-16 |
TWI471299B true TWI471299B (zh) | 2015-02-01 |
Family
ID=50402404
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101136641A TWI471299B (zh) | 2012-10-04 | 2012-10-04 | Hydroxylation of phenol |
Country Status (3)
Country | Link |
---|---|
US (1) | US9206101B2 (zh) |
CN (1) | CN103709011B (zh) |
TW (1) | TWI471299B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9133088B1 (en) * | 2014-04-30 | 2015-09-15 | Yuan-Zhang Han | Process for hydroxylating phenolic substrate |
CN114057549B (zh) * | 2020-07-30 | 2024-02-09 | 中国石油化工股份有限公司 | 一种同时制备苯酚和苯二酚的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0314582A1 (fr) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Procédé d'hydroxylation de phénols et d'éthers de phénols |
CN1324269A (zh) * | 1998-10-19 | 2001-11-28 | 罗狄亚化学公司 | 制备mfi型钛硅沸石的方法,所获得的产品和它在催化中的应用 |
CN101264453A (zh) * | 2008-03-10 | 2008-09-17 | 华东理工大学 | 一种钛硅分子筛/硅藻土复合催化剂及制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1195029B (it) * | 1980-09-09 | 1988-09-28 | Anic Spa | Procedimento per la ossidrilazione di idrocarburi aromatici |
IT1150699B (it) * | 1982-03-19 | 1986-12-17 | Anic Spa | Procedimento per la ossidrilazione di idrocarburi aromatici |
IT1213363B (it) | 1986-10-22 | 1989-12-20 | Eniricerche Spa | Materiale sintetico cristallino poroso contenente ossidi di silicio titanio e gallio. |
EP0466545A1 (fr) | 1990-06-29 | 1992-01-15 | Rhone-Poulenc Chimie | Zéolithes à base de silice et d'oxydes d'éléments tétravalents, leur procédé de synthèse et leur application |
CN1510020A (zh) * | 2002-12-26 | 2004-07-07 | 中国石油化工股份有限公司北京燕山分 | 一种苯酚羟基化制备苯二酚的方法 |
CN101204667B (zh) * | 2006-12-22 | 2011-06-01 | 中国科学院大连化学物理研究所 | 一种分子筛催化剂及其在苯酚与过氧化氢合成苯二酚中的应用 |
-
2012
- 2012-10-04 TW TW101136641A patent/TWI471299B/zh not_active IP Right Cessation
- 2012-11-23 CN CN201210482934.4A patent/CN103709011B/zh not_active Expired - Fee Related
-
2013
- 2013-10-02 US US14/044,108 patent/US9206101B2/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0314582A1 (fr) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Procédé d'hydroxylation de phénols et d'éthers de phénols |
CN1324269A (zh) * | 1998-10-19 | 2001-11-28 | 罗狄亚化学公司 | 制备mfi型钛硅沸石的方法,所获得的产品和它在催化中的应用 |
CN101264453A (zh) * | 2008-03-10 | 2008-09-17 | 华东理工大学 | 一种钛硅分子筛/硅藻土复合催化剂及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20140100392A1 (en) | 2014-04-10 |
CN103709011B (zh) | 2015-12-23 |
CN103709011A (zh) | 2014-04-09 |
US9206101B2 (en) | 2015-12-08 |
TW201414711A (zh) | 2014-04-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10214483B2 (en) | Titanium-silicalite molecular sieve, method for preparing the same and method for preparing cyclohexanone oxime using the molecular sieve | |
US9371238B2 (en) | Titanium-silicalite molecular sieve, method for preparing the same and method for preparing cyclohexanone oxime using the molecular sieve | |
US9433932B2 (en) | Hydrogenation catalyst and method of manufacturing the same | |
TW201404464A (zh) | 製備丙酮酸酯的方法 | |
TW201425288A (zh) | 苯二酚之製備方法 | |
TWI471299B (zh) | Hydroxylation of phenol | |
US20120271066A1 (en) | Method for preparing titanium-silicalite molecular sieve and method for preparing cyclohexanone oxime using the molecular sieve | |
TWI466875B (zh) | Method for making epoxides | |
JPWO2005033060A1 (ja) | エステル縮合物の製造方法 | |
WO2010032770A1 (ja) | アルコールの水素移動反応に用いる触媒、その製造方法、及びカルボニル基含有化合物の製造方法 | |
CN1123390C (zh) | 钛硅分子筛的合成方法 | |
JP7284990B2 (ja) | チタノシリケートとその製造方法 | |
CN107986293A (zh) | 一种钛硅分子筛及其合成方法和应用 | |
EP3323801B1 (en) | Methods of preparing cyclohexanone and derivatives | |
KR101964275B1 (ko) | 아크릴산 제조용 촉매 제조방법 및 이로부터 제조되는 촉매 | |
JP2866715B2 (ja) | 芳香族ヒドロキシ化合物の製造法 | |
TW201425280A (zh) | 製造酮肟之方法 | |
WO2009079713A1 (en) | Method of oxidising organic compounds | |
CN108654587B (zh) | 制备卤代烃的方法 | |
TW201406456A (zh) | 製造環氧化物之方法 | |
JP5655483B2 (ja) | エポキシ化合物の製造法 | |
WO2013022095A1 (ja) | メタクリル酸化合物の製造方法及び触媒 | |
JP5655476B2 (ja) | エポキシ化合物の製造方法 | |
CN101670297B (zh) | 一种含贵金属钛硅材料的合成方法 | |
JP3663687B2 (ja) | 担体への金属水酸化物及び/又は酸化物の担持方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |