JP7097948B2 - 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの生成方法 - Google Patents
不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの生成方法 Download PDFInfo
- Publication number
- JP7097948B2 JP7097948B2 JP2020504342A JP2020504342A JP7097948B2 JP 7097948 B2 JP7097948 B2 JP 7097948B2 JP 2020504342 A JP2020504342 A JP 2020504342A JP 2020504342 A JP2020504342 A JP 2020504342A JP 7097948 B2 JP7097948 B2 JP 7097948B2
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- catalyst
- less
- catalyst bed
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims description 19
- 239000002638 heterogeneous catalyst Substances 0.000 title claims description 4
- 238000006709 oxidative esterification reaction Methods 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000003054 catalyst Substances 0.000 claims description 52
- 238000002156 mixing Methods 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229910000510 noble metal Inorganic materials 0.000 claims description 17
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 12
- OBSHSWKHUYGFMF-UHFFFAOYSA-N 3,3-dimethoxy-2-methylprop-1-ene Chemical compound COC(OC)C(C)=C OBSHSWKHUYGFMF-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- -1 vanasia Chemical compound 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CQVDKGFMVXRRAI-UHFFFAOYSA-J Cl[Au](Cl)(Cl)Cl Chemical compound Cl[Au](Cl)(Cl)Cl CQVDKGFMVXRRAI-UHFFFAOYSA-J 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- AZMMUMQYPBKXHS-UHFFFAOYSA-N gold sodium Chemical compound [Na].[Au] AZMMUMQYPBKXHS-UHFFFAOYSA-N 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000007944 thiolates Chemical group 0.000 description 1
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0453—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being superimposed one above the other
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/065—Feeding reactive fluids
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00592—Controlling the pH
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
20重量%のメタクロレイン、200ppmの阻害剤、および残りのメタノールを混合し、炭化ケイ素の短い前部区分および10gの触媒を含む3/8インチ(9.5mm)のステンレス鋼管状反応器からなる触媒ゾーン、それに続くピッチドブレードタービンを備えた150mlの液量撹拌容器からなる混合ゾーン、それに続く炭化ケイ素の短い前部区分および10gの触媒を含む3/8インチのステンレス鋼管状反応器からなる第2の触媒ゾーンに供給する一連の作業を実施した。触媒は、Norproの直径1mmの高表面積アルミナ球状担体上の1.5重量%のAuからなっていた。出口ガスに約5%の酸素を有するのに十分な空気を第1の触媒ゾーンに供給し、出口ガスが4%~5%の酸素を有するのに十分な窒素中8%の酸素を含むガスを第2のゾーンに供給した。反応器を、60℃および160psig(1200kPa)で操作した。触媒ゾーン1の出口におけるpHは約6.3であった。反応器の生成物を、気液分離器に送り、蒸気を、液戻りを有する凝縮器に送った。結果を以下の表に記載する。いくつかの場合では、メタノール中のナトリウムメトキシドからなる塩基を混合ゾーンに添加した。いくつかの場合では、混合ゾーンを600RPMで撹拌し、他の場合には撹拌しなかった。MMAの生成物分布は、メタクロレイン反応物として生じる生成物中のMMAパーセントである。マイケル付加体の生成物分布は、メタクロレイン反応物として生じる生成物中の付加体パーセントである。空時収量(STY)は、Kg触媒時間あたりのMMA molである。
20重量%のメタクロレイン、200ppmの抑制剤、および残りのメタノールを、炭化ケイ素の短い前部区分およびそれに続く10gの触媒を含有する3/8インチのステンレス鋼管状反応器に供給する作業を実施した。触媒は、Norproの直径1mmの高表面積アルミナ球状担体上の1.5重量%のAuからなっていた。窒素中に8mol%の酸素を含むガスを、300sccmで反応器に供給し、ベントガスの酸素濃度は、4mol%~5mol%であった。反応器を、60℃および160psigで操作した。反応器の生成物を、気液分離器に送り、蒸気を、液戻りを有する凝縮器に送った。この分離器からの生成物流の一部分は、反応器の入口にリサイクルされ、反応器に入る供給物と混ぜ合わされた。結果を以下の表に記載する。生成物分布は、メタクロレイン反応物として生じる生成物中のMMAパーセントである。メタノール中の0.15重量%ナトリウムメトキシドからなる塩基を、混合目的のためにピッチドブレードインペラを含んだ気液分離器に添加した。
マルチゾーン反応器で得られたデータは、反応器への塩基の添加において、混合ゾーン(複数可)での混合が、本明細書でMMAへの生成物分布により測定されるように、マイケル付加体の形成を減少させ、一般的な選択性を増加させる重要なパラメータであることを示す。混合ゾーンでの不適切な混合を利用した場合、600RPMでのより典型的で適切な混合と比較して、マイケル付加体の形成は約2倍になった。
Claims (10)
- メタクロレインおよびメタノールからメタクリル酸メチルを調製する方法であって、前記方法が、少なくとも4つのゾーンを有する管状反応器内で、メタクロレイン、メタノール、酸素、および塩基を含む混合物を、担体および貴金属を含む不均一触媒の触媒床と接触させることを含み、触媒床を含む反応ゾーンが、触媒床を含まない混合ゾーンと交互になる、方法。
- 各反応ゾーンが、200ミクロン~10mmの平均直径を有する触媒粒子を含む触媒床を含む、請求項1に記載の方法。
- 前記反応器を通る液体の空塔速度が、2~30mm/秒である、請求項2に記載の方法。
- 各混合ゾーンが、熱交換装置と、(i)静的混合装置、(ii)ジェット混合装置、および(iii)0.1~10m/秒の先端速度を有する少なくとも1つのインペラのうちの少なくとも1つと、を含む、請求項3に記載の方法。
- 前記触媒床が、40~120℃の温度である、請求項4に記載の方法。
- 前記触媒床のpHが、4~8である、請求項5に記載の方法。
- 前記反応器が、4~10のゾーンを有する、請求項6に記載の方法。
- 前記塩基が、水酸化ナトリウムまたはナトリウムメトキシドである、請求項7に記載の方法。
- 前記触媒粒子が、400ミクロン~7mmの平均直径を有する、請求項8に記載の方法。
- 前記貴金属が、金およびパラジウムからなる群から選択される、請求項9に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201762538232P | 2017-07-28 | 2017-07-28 | |
US62/538,232 | 2017-07-28 | ||
PCT/US2018/039231 WO2019022886A1 (en) | 2017-07-28 | 2018-06-25 | PROCESS FOR THE PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIZATION USING A HETEROGENEOUS CATALYST |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2020528351A JP2020528351A (ja) | 2020-09-24 |
JP7097948B2 true JP7097948B2 (ja) | 2022-07-08 |
Family
ID=62948350
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2020504342A Active JP7097948B2 (ja) | 2017-07-28 | 2018-06-25 | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの生成方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US10745341B2 (ja) |
EP (1) | EP3658528B1 (ja) |
JP (1) | JP7097948B2 (ja) |
KR (1) | KR102563776B1 (ja) |
CN (1) | CN111433182B (ja) |
BR (1) | BR112020001722B1 (ja) |
CA (1) | CA3071437A1 (ja) |
SA (1) | SA520411167B1 (ja) |
SG (1) | SG11202000744UA (ja) |
WO (1) | WO2019022886A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024123526A1 (en) * | 2022-12-08 | 2024-06-13 | Dow Global Technologies Llc | Process for preparing alkyl methacrylates |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017504607A (ja) | 2013-12-20 | 2017-02-09 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | アルデヒドから出発する直接酸化エステル化による不飽和エステルの製造方法 |
JP2017507903A (ja) | 2013-12-20 | 2017-03-23 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | メチルメタクリレートの製造法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB761078A (en) * | 1953-02-20 | 1956-11-07 | Goodrich Co B F | Improvements in or relating to the preparation of alkyl acrylate esters |
DE2848369C3 (de) | 1977-11-17 | 1981-08-06 | Asahi Kasei Kogyo K.K., Osaka | Verfahren zur Herstellung von Carbonsäureestern |
DE3018071C2 (de) | 1979-05-17 | 1985-06-05 | Asahi Kasei Kogyo K.K., Osaka | Verfahren zur Herstellung von Carbonsäureestern |
JPS58185540A (ja) * | 1982-04-23 | 1983-10-29 | Asahi Chem Ind Co Ltd | 不飽和カルボン酸エステルの製造法 |
DE3306907A1 (de) | 1983-02-26 | 1984-08-30 | Basf Ag, 6700 Ludwigshafen | Katalysator und seine verwendung zur herstellung von methylmethacrylat |
NO300117B1 (no) * | 1994-12-22 | 1997-04-14 | Norske Stats Oljeselskap | Reaktor for dehydrogenering av hydrokarboner med selektiv oksidasjon av hydrogen |
JP3408662B2 (ja) * | 1995-06-14 | 2003-05-19 | 旭化成株式会社 | カルボン酸エステルの連続的製造法 |
USRE38283E1 (en) | 1995-07-18 | 2003-10-21 | Asahi Kasei Kabushiki Kaisha | 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 |
KR100438266B1 (ko) * | 1996-05-13 | 2004-09-13 | 레르 리뀌드, 소시에떼 아노님 아 디렉또와르 에 꽁세예 드 쉬르베양스 뿌르 레뛰드 에 렉스쁠로아따시옹 데 프로세데 죠르쥬 끌로드 | 기체상 화합물에 함유된 불순물을 제거하는 방법 |
TW377306B (en) | 1996-12-16 | 1999-12-21 | Asahi Chemical Ind | Noble metal support |
SG71815A1 (en) | 1997-07-08 | 2000-04-18 | Asahi Chemical Ind | Method of producing methyl methacrylate |
US7326806B2 (en) | 2001-06-04 | 2008-02-05 | Nippon Shokubai Co., Ltd. | Catalyst for the preparation of carboxylic esters and method for producing carboxylic esters |
JP4860064B2 (ja) | 2001-08-03 | 2012-01-25 | 旭化成ケミカルズ株式会社 | カルボン酸エステル合成反応器内のpH制御方法 |
ATE517856T1 (de) | 2004-11-17 | 2011-08-15 | Asahi Kasei Chemicals Corp | Oxidationskatalysator und oxidationsverfahren |
CN1931824A (zh) | 2006-09-18 | 2007-03-21 | 鲁东大学 | 一种由不饱和醛连续制备不饱和羧酸酯的方法及催化剂 |
WO2009022544A1 (ja) | 2007-08-13 | 2009-02-19 | Asahi Kasei Chemicals Corporation | カルボン酸エステル製造用触媒、その製造方法、並びにカルボン酸エステルの製造方法 |
GB201102502D0 (en) | 2011-02-14 | 2011-03-30 | Johnson Matthey Plc | Catalysts for use in reforming processes |
JP6501754B2 (ja) * | 2013-04-19 | 2019-04-17 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | メチルメタクリレートの製造方法 |
TW201509900A (zh) * | 2013-07-29 | 2015-03-16 | Rohm & Haas | 氧化酯化方法 |
EP3170558A1 (de) | 2015-11-19 | 2017-05-24 | Evonik Röhm GmbH | Gold-basierten katalysator für die oxidative veresterung von aldehyden zu carbonsäureestern |
EP3235560A1 (de) * | 2016-04-22 | 2017-10-25 | Evonik Röhm GmbH | Verfahren zur durchführung einer heterogen-katalysierten reaktion |
-
2018
- 2018-06-25 KR KR1020207004441A patent/KR102563776B1/ko active IP Right Grant
- 2018-06-25 BR BR112020001722-1A patent/BR112020001722B1/pt active IP Right Grant
- 2018-06-25 US US16/634,752 patent/US10745341B2/en active Active
- 2018-06-25 CA CA3071437A patent/CA3071437A1/en active Pending
- 2018-06-25 JP JP2020504342A patent/JP7097948B2/ja active Active
- 2018-06-25 CN CN201880056446.2A patent/CN111433182B/zh active Active
- 2018-06-25 EP EP18742643.2A patent/EP3658528B1/en active Active
- 2018-06-25 WO PCT/US2018/039231 patent/WO2019022886A1/en active Application Filing
- 2018-06-25 SG SG11202000744UA patent/SG11202000744UA/en unknown
-
2020
- 2020-01-28 SA SA520411167A patent/SA520411167B1/ar unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017504607A (ja) | 2013-12-20 | 2017-02-09 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | アルデヒドから出発する直接酸化エステル化による不飽和エステルの製造方法 |
JP2017507903A (ja) | 2013-12-20 | 2017-03-23 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツングEvonik Roehm GmbH | メチルメタクリレートの製造法 |
Also Published As
Publication number | Publication date |
---|---|
EP3658528A1 (en) | 2020-06-03 |
JP2020528351A (ja) | 2020-09-24 |
CN111433182A (zh) | 2020-07-17 |
KR20200033278A (ko) | 2020-03-27 |
KR102563776B1 (ko) | 2023-08-04 |
SG11202000744UA (en) | 2020-02-27 |
EP3658528B1 (en) | 2021-08-18 |
CN111433182B (zh) | 2023-04-04 |
BR112020001722B1 (pt) | 2023-03-14 |
US10745341B2 (en) | 2020-08-18 |
SA520411167B1 (ar) | 2022-06-12 |
CA3071437A1 (en) | 2019-01-31 |
US20200199059A1 (en) | 2020-06-25 |
BR112020001722A2 (pt) | 2020-07-21 |
WO2019022886A1 (en) | 2019-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7268007B2 (ja) | 不均一触媒を使用する酸化的エステル化によるメタクリル酸メチルを生成するための方法 | |
JP7212031B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7171697B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7457855B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7097948B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの生成方法 | |
JP7150816B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7150817B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7457859B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 | |
JP7189929B2 (ja) | 不均一触媒を使用した酸化的エステル化によるメタクリル酸メチルの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20200318 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20200512 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210615 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220608 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220608 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220628 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7097948 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S802 | Written request for registration of partial abandonment of right |
Free format text: JAPANESE INTERMEDIATE CODE: R311802 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |