TW201512168A - 氧化酯化方法 - Google Patents
氧化酯化方法 Download PDFInfo
- Publication number
- TW201512168A TW201512168A TW103125653A TW103125653A TW201512168A TW 201512168 A TW201512168 A TW 201512168A TW 103125653 A TW103125653 A TW 103125653A TW 103125653 A TW103125653 A TW 103125653A TW 201512168 A TW201512168 A TW 201512168A
- Authority
- TW
- Taiwan
- Prior art keywords
- catalyst
- alumina
- group
- methacrolein
- support
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title abstract description 9
- 238000006709 oxidative esterification reaction Methods 0.000 title description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000011949 solid catalyst Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 49
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical group 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- -1 1:10 to 1 Chemical compound 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- SEBZSCZCDFOSIE-UHFFFAOYSA-N cerium(3+) trinitrate pentahydrate Chemical compound O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SEBZSCZCDFOSIE-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- NTWUDWUVKKRQRK-UHFFFAOYSA-N aluminum;cerium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Ce+3] NTWUDWUVKKRQRK-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 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 description 1
- BBLKWSIOIYLDHV-UHFFFAOYSA-J cerium(4+);tetrachloride Chemical compound Cl[Ce](Cl)(Cl)Cl BBLKWSIOIYLDHV-UHFFFAOYSA-J 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/624—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with germanium
-
- 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
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
-
- 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
- B01J37/0201—Impregnation
-
- 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
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本發明提供一種用於生產甲基丙烯酸甲酯之方法,該方法包含在存在固體催化劑之反應條件下,使包含甲基丙烯醛、甲醇及含氧氣體之反應物接觸,該固體催化劑包含鈀、鉍及至少一種選自由Fe、Zn、Ge及Pb組成之群之第三元素X,其中該固體催化劑進一步包含選自至少一個由二氧化矽及氧化鋁組成之群之成員的載體。
Description
本發明係關於經由氧化酯化來催化製備羧酸酯。
由甲基丙烯醛(MAC)、甲醇及氧氣生產甲基丙烯酸甲酯(MMA)為已知的。舉例而言,美國專利6,040,472揭示於具有微量氧化鋁及氧化鎂組分之二氧化矽載體上使用鈀(Pd)-鉛(Pb)晶體結構(Pd3Pb1)之此反應。然而,Pd-Pb催化劑能夠產生非所需的大量副產物甲酸甲酯。美國專利4,518,796揭示Pd-鉍(Bi)催化劑之用途。然而,該催化劑未產生此反應所需之高MMA選擇率。
美國專利5,892,102揭示於ZnO或CaCO3上包括Pd-Bi-X金屬互化物之MA氧化酯化催化劑,其中X可為各種元素。此等載體自機械穩定性、可能抗酸性及長期催化劑壽命之觀點來看為非所需的。
需要一種於穩定載體上使用非鉛催化劑(藉此避免產生與含鉛廢料流有關之問題)選擇性生產MMA而產生之甲酸甲酯副產物極少的方法。
本發明之方法為用於生產甲基丙烯酸甲酯之此類方法,該方法包含在存在固體催化劑之反應條件下,使包含甲基丙烯醛、甲醇及含氧
氣體之反應物接觸,該固體催化劑包含鈀、鉍及至少一種選自由Fe、Zn、Ge及Pb組成之群之第三元素X,其中該固體催化劑進一步包含選自至少一個由二氧化矽及氧化鋁組成之群之成員的載體。
令人驚訝的是,本發明之方法當用於經由氧化酯化自MAC生產MMA中時提供高MMA產率,且在該方法中可使甲酸甲酯副產物之含量降低。
如本文所用,「一(a或an)」、「該(the)」、「至少一種(at least one)」及「一或多種(one or more)」可互換使用。術語「包含(comprises)」、「包括(includes)」及其變化形式當此等術語出現在說明書及申請專利範圍中時不具有限制性含義。因此,例如,包括「一種」疏水性聚合物之粒子的水性組成物可解釋為意謂該組成物包括「一或多種」疏水性聚合物之粒子。
亦在本文中,藉由端點對數值範圍進行之敍述包括該範圍內所包含之所有數字(例如1至5包括1、1.5、2、2.75、3、3.80、4、5等)。出於本發明之目的,與一般熟習此項技術者應瞭解一致,應理解數值範圍意欲包括且支持該範圍內所包括之所有可能子範圍。舉例而言,1至100之範圍意欲傳達1.01至100、1至99.99、1.01至99.99、40至60、1至55等。
亦在本文中,數值範圍及/或數值之敍述(包括申請專利範圍中之該等敍述)可解讀為包括術語「約(about)」。在該等情況下,術語
「約(about)」係指與本文所述之彼等數值範圍及/或數值實質上相同之數值範圍及/或數值。
如本文所用,使用術語「(甲基(meth))」後接諸如丙烯酸酯之另一術語係指丙烯酸酯及甲基丙烯酸酯。舉例而言,術語「(甲基)丙烯酸酯((meth)acrylate)」係指丙烯酸酯或甲基丙烯酸酯;術語「(甲基)丙烯酸系((meth)acrylic)」係指丙烯酸系或甲基丙烯酸系;且術語「(甲基)丙烯酸((meth)acrylic acid)」係指丙烯酸或甲基丙烯酸。
除非相反說明或上下文暗示,否則所有份數及百分比均以重量計且所有測試方法為截至本申請案申請日期之現行方法。出於美國專利實務之目的,任何所參考專利、專利申請案或公開案之內容均以全文引用的方式併入(或其等效美國版本如此以引用的方式併入),尤其對此項技術中之定義(直至與本發明特定提供之任何定義無不一致的程度)及一般性知識之揭示。
本發明之方法採用MAC、甲醇、含氧氣體及催化劑。
甲醇可廣泛購得。甲基丙烯醛可藉由如熟習此項技術者所知之各種工業規模方法製得。參見例如美國專利4,329,513及5,969,178。
在本發明之反應中,所饋入之甲醇與所饋入之甲基丙烯醛之量的比率不受特定限制,且該反應可在甲醇與甲基丙烯醛之莫耳比的大範圍(諸如1:10至1,000:1,較佳1:1至10:1)內進行。
含氧氣體可為氧氣或包含氧氣及對於反應呈惰性之稀釋劑(諸如氮氣、二氧化碳或其類似物)之混合氣體。可將空氣用作含氧氣體。反應系統中所存在之氧氣的量有利地不小於反應所需之化學計算量,且較
佳不小於該化學計算量之1.2倍。在本發明之一個具體實例中,反應系統中所存在之氧氣的量為所需化學計算量之1.2倍至2倍。可將過氧化氫作為氧化劑引入反應系統中。可藉由如熟習此項技術者所知之適合方法將含氧氣體引入反應系統中。舉例而言,可經由噴布器或管道將含氧氣體引入反應器中。可採用簡單之將含氧氣體吹入反應系統中之方法。
催化劑為非均質、多孔催化劑。該催化劑包含鈀、鉍及至少一種選自由Fe、Zn、Ge及Pb組成之群之第三元素X。X較佳為Fe或Pb。可採用X之組合。
較佳地,任一催化金屬係呈還原態,即零價,且不呈陽離子態且可以還原態或化合物形式存在。催化元素以使得其彼此可具有一些相互作用之形式存在於反應系統中。舉例而言,鈀、鉍及X可形成合金或具有一些其他相互作用,諸如金屬間化合物。在本發明之一個具體實例中,催化劑實質上不含第1族至第3族之元素。
催化元素可負載於諸如二氧化矽或氧化鋁之載體上,且負載於該載體上之催化成分之量以載體之重量可有利地為0.1wt%至20wt%,較佳為1wt%至10wt%。在本發明之一個具體實例中,載體包含二氧化矽、氧化鋁及二氧化矽-氧化鋁中之至少一者。載體之實例包括熱解二氧化矽、矽膠、α氧化鋁及γ氧化鋁。催化劑成分亦可以金屬形式或以化合物形式使用而無需負載於載體上。催化劑中之鈀與鉍比率較佳為1:0.05至1:10(原子比)以達成上述目的。X與鉍之比率有利地為1:01至1:10,且在本發明之一個具體實例中為約1:1。如熟習此項技術者所知,載體可經改質。舉例而言,二氧化矽載體可經氧化鋁及/或氧化鎂改質。可採用載體之組合。
可以習知方式製備催化劑。舉例而言,可用諸如福馬林(formalin)水溶液之還原劑還原諸如氯化鈀之可溶性鹽以沈積金屬鈀且可過濾所沈積之金屬鈀以製備金屬鈀催化劑,或可用可溶性鈀鹽之酸性水溶液浸漬適合載體且用還原劑對經浸漬之載體進行還原以製備負載型鈀催化劑。在本發明之一個具體實例中,當希望製備其中鈀、鉍化合物及至少一種第三化合物(其為X之化合物)負載於載體上之催化劑時,用可溶性鈀鹽之水溶液浸漬適合載體,且用適合還原劑還原經浸漬之載體,隨後將經還原之載體浸沒於鉍化合物及第三化合物之水溶液中,且蒸乾且乾燥。或者,可藉由首先將鉍化合物負載於載體上,接著用鈀及第三化合物浸漬該載體及其後添加諸如肼之還原劑來製備該催化劑。
作為用於製備以上催化劑之鉍化合物,可使用任何含鉍化合物。舉例而言,可採用鉍之脂肪酸鹽,諸如乙酸鉍、硬脂酸鉍及其類似物。其他適合化合物包括氧化鉍;氫氧化鉍及硝酸鉍。此等鉍化合物可為無水或可呈水合物形式。作為用於製備以上催化劑之第三化合物,可使用任何適合的含有X之化合物。舉例而言,硝酸鐵或乙酸鉛可分別用作鐵或鉛之來源。
如熟習此項技術者所知,可對催化劑進行活化及/或再生。舉例而言,美國專利6,040,472揭示各種催化劑活化技術。
以催化量使用催化劑。儘管催化劑與起始醛之重量比一般為1:1000至20:1,但催化劑(亦即催化元素及視情況選用之載體)之量可視起始材料之種類及量、製備催化劑之方法、製程操作條件及其類似因素而自由改變。有利地,催化劑與醛之比率為1:100至2:1。然而,可以此等範圍
外之量使用催化劑。
用於生產甲基丙烯酸甲酯之方法包含在存在催化劑之氧化酯化條件下,使包含甲基丙烯醛、甲醇及含氧氣體之反應物接觸。在本發明之一個具體實例中,可在反應區中使用呈液相之催化劑漿液進行反應。可在0℃至120℃,較佳40℃至90℃之溫度下進行反應。可在減壓下、在大氣壓下或在超大氣壓下進行反應。可在0.5至20個絕對大氣壓,較佳1至10個絕對大氣壓之壓力下進行反應。可以分批、半分批或連續方式進行反應。反應在液相中進行有利。
當產物為可聚合化合物時,在該方法中可採用聚合抑制劑。多種抑制劑為已知且可市購而得。抑制劑之實例包括對苯二酚、啡噻嗪、對苯二酚之甲酯(MEHQ)、4-羥基-2266-四甲基哌啶-N-氧基(4-羥基TEMPO)及其類似物。
在MAC氧化酯化以形成MMA時,甲酸甲酯之非所需形成消耗反應物甲醇及氧氣且每莫耳甲酸甲酯產生兩莫耳水。因為水難以自反應混合物移除,可促使在催化劑表面上形成非所需氧化物且可促使形成非所需副產物甲基丙烯酸,所以水為非所需的。甲基丙烯酸之形成消耗反應物甲基丙烯醛及反應物氧氣且可引起催化劑去活化。
令人驚訝的是,在各種具體實例中,該方法產生含有每莫耳甲基丙烯酸甲酯小於2莫耳、小於1莫耳、小於0.8莫耳、小於0.6莫耳、小於0.4莫耳、小於0.2莫耳、小於0.1莫耳、小於0.05莫耳或小於0.01莫耳之甲酸甲酯的MMA。在本發明之各種具體實例中,以甲基丙烯醛計,該方法提供至少90%或至少95%之MMA產率,其中產率依轉化率乘以選擇率
之數學乘積計算。
提供以下實施例以說明本發明且不應理解為限制其範疇。對於其中計算之實施例,忽略6小時活化時間段(在此期間選擇率相對不佳)計算轉化率及選擇率。
使用Sigma Aldrich 5wt% Pd/氧化鋁作為起點製備氧化鋁載體上具有5wt% Pd、2wt% Bi及1wt% Fe的催化劑。藉由將0.90公克五水合硝酸鉍溶解在100ml去離子水中,接著添加1.4公克硝酸鐵且接著添加20.0公克Aldrich Pd/氧化鋁來製備漿液。在60℃下攪拌漿液1小時,隨後緩慢、逐滴添加10.0公克水合肼,且在90℃下再攪拌1小時。接著經由真空過濾分離所得固體,用500ml去離子水洗滌且在45℃下真空乾燥10小時。
將5公克實施例1之催化劑樣品置放於含有100g含4.0wt%甲基丙烯醛之甲醇溶液的玻璃反應器中。溶液亦含有抑制劑以防止聚合。溶液在大氣壓下,在攪拌下,在35cc/min 8% O2/N2鼓泡通過其的情況下加熱至40℃維持22小時。反應器配備有葉輪及乾冰冷凝器。
MAC之轉化率為100%。甲基丙烯酸甲酯之選擇率以MAC計為88.3%。因此產率依100%×88.3%=88.3%計算。令人驚訝的是,所得產物中量測到的甲酸甲酯及甲基丙烯酸極少。
使用Sigma Aldrich 5wt% Pd/氧化鋁作為起點製備氧化鋁載
體上具有5wt% Pd、2wt% Bi及1wt% Zn的催化劑。藉由將0.90公克五水合硝酸鉍溶解於100ml去離子水中,接著添加0.64g二水合乙酸鋅以提供以載體計1wt%之Zn,且接著添加20.0公克Pd/氧化鋁來製備漿液。在60℃下攪拌漿液1小時,接著緩慢、逐滴添加10.0公克水合肼,且在90℃下再攪拌1小時。接著經由真空過濾分離所得固體,用500ml去離子水洗滌且在45℃下真空乾燥10小時。
重複實施例2之程序,但其中採用實施例3之催化劑。
MAC之轉化率為100%。甲基丙烯酸甲酯之選擇率以MAC計為83.7%。
使用Sigma Aldrich 5wt% Pd/氧化鋁作為起點製備氧化鋁載體上具有5wt% Pd、2wt% Bi及1wt% Ge的催化劑。藉由將0.90公克五水合硝酸鉍溶解於100ml去離子水中,接著添加0.56g氯化鍺(IV)以提供以載體計1wt%之Ge,且接著添加20.0公克Aldrich Pd/氧化鋁來製備漿液。在60℃下攪拌漿液1小時,接著緩慢、逐滴添加10.0公克水合肼,且在90℃下再攪拌1小時。接著經由真空過濾分離所得固體,用500ml去離子水洗滌且在45℃下真空乾燥10小時。
將5公克實施例5之催化劑樣品置放於含有100g含5.1wt%甲基丙烯醛之甲醇溶液的玻璃反應器中。溶液亦含有抑制劑以防止聚合。溶液在大氣壓下,在攪拌下,在35cc/min 8% O2/N2鼓泡通過其的情況下加
熱至40℃維持22小時。反應器配備有乾冰冷凝器及葉輪。
MAC之轉化率為100%。甲基丙烯酸甲酯之選擇率以MAC計為66.3%。
Claims (11)
- 一種用於生產甲基丙烯酸甲酯之方法,該方法包含在存在固體催化劑之反應條件下,使包含甲基丙烯醛、甲醇及含氧氣體之反應物接觸,該固體催化劑包含鈀、鉍及至少一種選自由Fe、Zn、Ge及Pb組成之群之第三元素X,其中該固體催化劑進一步包含選自至少一個由二氧化矽及氧化鋁組成之群之成員的載體。
- 如申請專利範圍第1項中任一項之催化劑,其中X係選自由Fe、Pb及其組合組成之群。
- 如申請專利範圍中前述任一項之催化劑,其中該載體包含氧化鋁及二氧化矽中之至少一者。
- 如申請專利範圍中前述任一項之催化劑,其中該載體主要包含氧化鋁。
- 如申請專利範圍中前述任一項之方法,其中該載體係選自至少一個由α氧化鋁及γ氧化鋁組成之群之成員。
- 如申請專利範圍中前述任一項之之方法,其中該載體包含γ氧化鋁。
- 如申請專利範圍中前述任一項之方法,其中甲醇與甲基丙烯醛之比率為1:1至10:1莫耳百分比。
- 如申請專利範圍中前述任一項之方法,其中該反應在聚合抑制劑存在下進行。
- 如申請專利範圍中前述任一項之催化劑,其中X為Fe。
- 如申請專利範圍中前述任一項之方法,其中該催化劑實質上不含第1族至第3族之元素。
- 如申請專利範圍第1項之方法,其中X包含Fe、Zn及/或Ge中之至少 一者。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361859544P | 2013-07-29 | 2013-07-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW201512168A true TW201512168A (zh) | 2015-04-01 |
Family
ID=51303129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103125653A TW201512168A (zh) | 2013-07-29 | 2014-07-28 | 氧化酯化方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20160207870A1 (zh) |
EP (1) | EP2989076A1 (zh) |
JP (1) | JP2016527267A (zh) |
KR (1) | KR20160035591A (zh) |
CN (1) | CN105377805A (zh) |
CA (1) | CA2918402A1 (zh) |
MX (1) | MX2016000765A (zh) |
TW (1) | TW201512168A (zh) |
WO (1) | WO2015017436A1 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG11201601819WA (en) | 2013-10-28 | 2016-05-30 | Rohm & Haas | Process for separating methacrolein |
EP3630711B1 (en) * | 2017-05-25 | 2021-03-17 | Rohm and Haas Company | Process for preparing methacrolein |
CN109694946B (zh) | 2017-10-24 | 2020-06-23 | 宝山钢铁股份有限公司 | 快速加热冷轧带钢的装置与方法 |
GB201721527D0 (en) * | 2017-12-21 | 2018-02-07 | Johnson Matthey Japan Godo Kaisha | Oxidation catalyst for a diesel engine exhaust |
KR20200105854A (ko) * | 2018-01-10 | 2020-09-09 | 다우 글로벌 테크놀로지스 엘엘씨 | 산화적 에스터화에 의한 메틸 메타크릴레이트 생산용 불균일 촉매 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY119415A (en) * | 1995-07-18 | 2005-05-31 | Asahi Chemical Ind | Catalyst for use in producing carboxylic esters |
JPH09216850A (ja) * | 1996-02-09 | 1997-08-19 | Mitsubishi Rayon Co Ltd | カルボン酸エステルの製造方法 |
JP3103500B2 (ja) * | 1996-02-14 | 2000-10-30 | 三菱レイヨン株式会社 | カルボン酸エステルの製造方法 |
TW385304B (en) * | 1996-09-10 | 2000-03-21 | Asahi Chemical Ind | Process for producing methacrylic acid ester or acrylic acid ester |
JPH10158124A (ja) * | 1996-11-25 | 1998-06-16 | Pola Chem Ind Inc | 発毛・育毛料 |
JP3313993B2 (ja) * | 1996-11-29 | 2002-08-12 | 三菱レイヨン株式会社 | カルボン酸エステルの製造法 |
JP3297342B2 (ja) * | 1997-03-24 | 2002-07-02 | 三菱レイヨン株式会社 | カルボン酸エステルの製造法 |
JP2002241345A (ja) * | 2001-02-13 | 2002-08-28 | Asahi Kasei Corp | カルボン酸エステルの製造方法 |
CN101074192A (zh) * | 2007-06-20 | 2007-11-21 | 天津大学 | 以甲醛为原料制备甲基丙烯酸甲酯的方法 |
ES2431791T3 (es) * | 2007-08-13 | 2013-11-28 | Asahi Kasei Chemicals Corporation | Catalizador para la producción de éster del ácido carboxílico, procedimiento de producción del mismo y procedimiento para la producción de éster del ácido carboxílico |
-
2014
- 2014-07-28 TW TW103125653A patent/TW201512168A/zh unknown
- 2014-07-29 KR KR1020167003922A patent/KR20160035591A/ko not_active Application Discontinuation
- 2014-07-29 CA CA2918402A patent/CA2918402A1/en not_active Abandoned
- 2014-07-29 MX MX2016000765A patent/MX2016000765A/es unknown
- 2014-07-29 CN CN201480040170.0A patent/CN105377805A/zh active Pending
- 2014-07-29 EP EP14750668.7A patent/EP2989076A1/en not_active Withdrawn
- 2014-07-29 JP JP2016531828A patent/JP2016527267A/ja active Pending
- 2014-07-29 US US14/907,452 patent/US20160207870A1/en not_active Abandoned
- 2014-07-29 WO PCT/US2014/048665 patent/WO2015017436A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
EP2989076A1 (en) | 2016-03-02 |
KR20160035591A (ko) | 2016-03-31 |
CN105377805A (zh) | 2016-03-02 |
CA2918402A1 (en) | 2015-02-05 |
US20160207870A1 (en) | 2016-07-21 |
WO2015017436A1 (en) | 2015-02-05 |
JP2016527267A (ja) | 2016-09-08 |
MX2016000765A (es) | 2016-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW201512168A (zh) | 氧化酯化方法 | |
JP6506281B2 (ja) | 酸化的エステル化方法を介するメチルアクリレートの調製 | |
TWI577659B (zh) | 氧化酯化方法 | |
TW201509900A (zh) | 氧化酯化方法 | |
CA2918239C (en) | Oxidative esterification catalyst |