JP2021038231A - メチルメタクリレートの製造法 - Google Patents
メチルメタクリレートの製造法 Download PDFInfo
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- JP2021038231A JP2021038231A JP2020181637A JP2020181637A JP2021038231A JP 2021038231 A JP2021038231 A JP 2021038231A JP 2020181637 A JP2020181637 A JP 2020181637A JP 2020181637 A JP2020181637 A JP 2020181637A JP 2021038231 A JP2021038231 A JP 2021038231A
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title abstract description 27
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- 238000006709 oxidative esterification reaction Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
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- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
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- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 12
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- 238000004519 manufacturing process Methods 0.000 claims description 27
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- 239000002638 heterogeneous catalyst Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910052737 gold Inorganic materials 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 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
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 tallium Chemical compound 0.000 claims description 4
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- 239000002184 metal Substances 0.000 claims description 3
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010949 copper Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
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- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
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- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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Images
Classifications
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- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/892—Nickel and noble metals
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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Abstract
Description
(a)製造プロセス系の反応器におけるMAL定常濃度は、反応器内の反応混合物の総質量の15質量%以下であり、かつ
(b)リットルで示される反応器内の反応混合物の液体総体積を、キログラムで示される反応器内の触媒の総質量で除したものに相当する比Fは4以下である
ことを特徴とする触媒連続法を提供する。
前述の通り、本願記載の1つの考えられる実施態様は図1に示される。この方法では、酸素または酸素含有ガス(好ましくは、不活性成分、例えばN2との混合物)は、導管1を通って供給される一方、MAL/メタノール混合物は、導管2を通って反応器Aに供給される。それらの成分が混合されて、結果として生じた不均一なガス/液体混合物は、導管3を通って外部熱交換器を備える固定床反応器Aに供給され、それに関して、ガス/液体混合物もそれらの個々の成分も、反応器の上部から供給されても、下部から供給されてもよい。
さらに、本発明を以下の非限定例1から3まで、および比較例1から2までにおいて説明する。以下の例1から3までは、本発明による好ましい実施態様をさらに説明するために用いるが、本発明を制限することを意図するものではない。すべての結果は、第1表に示されている。
水100mL中の硝酸マグネシウム六水和物51.2gおよび60%硝酸5.4gの溶液を20℃でSiO2担体(Fuji Silicia、Cariact Q−10、0.85mmから1.75mmまで)108gに添加した。この混合物を50℃で24時間撹拌し、その後、室温まで冷却し、乾燥して焼成させた。このSiO2−MgO担体30gを水100mLに懸濁させて、90℃に加熱した。15分後に90℃で、水100mL中の硝酸ニッケル六水和物1.64gおよび金酸(HAuCl4)530mgを滴下しながら30分の間、上述の懸濁液に添加した。さらに90℃で30分間撹拌した後、この混合物を冷却して固体を取り除き、その後、新鮮な水100mLで3分間洗浄して、いずれの場合も20℃で5分間撹拌してろ別した。触媒を105℃で10時間にわたって乾燥して、450℃で5時間にわたって焼成させた。ICP分析(inductively coupled plasma mass spectrometry(誘導結合プラズマ質量分析装置))は、結果として得られた紫色粉末が、Ni 1.1%およびAu 0.9%を含むことを示した。金のナノ粒子の平均径(TEM)は、5nm未満であった。
MAL 30.9質量%およびメタノール69.1質量%の混合物に、メタノール中の1%水酸化ナトリウム溶液を添加してpHを7にした。次に、この中和した混合物を20.9g/hの流量で、O2/N2ガス混合物(O2 7体積%)と一緒に6barで外部熱交換器を備える管型反応器に供給した(80℃)。排ガス中のO2残留含有率は4体積%に調整した。反応器は、触媒1を15g含んでいた。メタノール中の1%水酸化ナトリウム溶液を中和槽に連続的に添加して、pHを系内でpH7に保った。導管12を通って再循環される混合物の生成物産出量(product output)11に対する比R/Pは10であった。生成混合物をガスクロマトグラフィで分析した。第1表は、MMA製造法を運転して73時間後、および512時間後に得られた結果を示している。
例3は、例2と同じ運転条件下で実施したが、供給流量は15.1g/h、供給濃度はMAL 45.3質量%およびメタノール54.7質量%で実施した。
比較例1は、例2と同じ運転条件下で実施したが、供給流量は10.3g/h、供給濃度はMAL 63質量%およびメタノール27質量%で実施した。反応器内のMAL定常濃度は、15質量%よりも高かった。
比較例2は、例2と同じ運転条件下で実施したが、供給流量は21g/h、触媒1 5g、および供給濃度はMAL 33.3質量%およびメタノール66.7質量%で実施した。MAL定常濃度は、15質量%より高く、上に定義した比Fは4より高かった。
(B) 熱交換器
(C) ガス/液体分離器
(D) 中和槽、ここで、pHは5から9までに調整される
(E) 代替物または追加の熱交換器
(1) 酸素を含む気相(11)のための供給管
(2) 液体反応物(メタノールおよびMAL)(13)のための供給管
(3) 気相(11)と液体反応物(13)を混合するための供給管
(4) 反応器(A)からガス/液体分離器(C)および熱交換器(B)までの導管
(5) ガス/液体分離器(C)からの排ガス(14)のためのアウトプット導管
(6) ガス/液体分離器(C)から中和槽(D)までの導管
(7) 塩基性溶液(12)を中和槽(D)に供給するための供給管
(8) pHが調整された反応混合物の一部を、導管(1)を通って供給される気相(11)と混合しながら導管(3)を通して反応器(A)に返送するための再循環管
(9) MMAを含む液相(15)の精製のためのアウトプット導管
(10) 酸素を含む気相
(11) 塩基性溶液
(12) 液体反応物(メタノールおよびMAL)
(13) 排ガス
(14) MMAを含む液相
(15) 酸素含有ガスの一部を酸素含有ガス供給に返送するための再循環管
Claims (15)
- メタクロレインを酸素およびメタノールと、貴金属を含有する不均一系触媒の存在下で酸化エステル化反応において反応させる段階を含むメチルメタクリレートを製造するための触媒連続法であって、
(a)メタクロレインの定常濃度は、反応器内の反応混合物の総質量を基準として15質量%以下であり、かつ
(b)リットルで示される反応器内の液体総体積を、キログラムで示される反応器内の触媒の総質量で除した比Fは、4L/kg以下である
ことを特徴とする前記触媒連続法。 - 製造プロセス系におけるメタクロレインの定常濃度は、反応器内の反応混合物の総質量を基準として12質量%未満であることを特徴とする、請求項1に記載の触媒連続法。
- 製造プロセス系におけるメタクロレインの定常濃度は、反応器内の反応混合物の総質量を基準として8質量%未満であることを特徴とする、請求項2に記載の触媒連続法。
- 反応器での滞留時間は10時間未満であることを特徴とする、請求項1から3までのいずれか1項に記載の触媒連続法。
- 反応器での滞留時間は3時間未満であることを特徴とする、請求項4に記載の触媒連続法。
- 酸化エステル化を、120℃未満、好ましくは60℃から90℃までの反応器内温度で実施することを特徴とする、請求項1から5までのいずれか1項に記載の触媒連続法。
- 酸化エステル化反応を、2barから50barまでの圧力で実施することを特徴とする、請求項1から6までのいずれか1項に記載の触媒連続法。
- 反応器は固定床反応器であることを特徴とする、請求項1から7までのいずれか1項に記載の触媒連続法。
- 反応器は流動床反応器であることを特徴とする、請求項1から7までのいずれか1項に記載の触媒連続法。
- 酸化エステル化反応を、メタノール対メタクロレインのモル比が1:1から50:1までの範囲で行うことを特徴とする、請求項1から9までのいずれか1項に記載の触媒連続法。
- 酸化エステル化反応のために使用する貴金属を含有する不均一系触媒は、金、パラジウム、ルテニウム、ロジウムおよび銀からなる群から選択される平均粒径20nm未満の1つまたは複数の超微細分散した金属を含むことを特徴とする、請求項1から10までのいずれか1項に記載の触媒連続法。
- 酸化エステル化反応のために使用する貴金属を含有する不均一系触媒は、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、スカンジウム、イットリウム、ランタンおよび原子番号58から71までの別のランタノイド、ケイ素、チタン、ジルコニウム、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、レニウム、鉄、ルテニウム、オスミウム、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、白金、銅、銀、金、亜鉛、カドミウム、ホウ素、アルミニウム、ガリウム、インジウム、タリウム、ゲルマニウム、錫、鉛、アンチモン、ビスマス、テルルからなる群の、それぞれ金属および/または酸化形態で存在している1つまたは複数の要素を含むことを特徴とする、請求項1から11までのいずれか1項に記載の触媒連続法。
- 酸化エステル化反応のために使用する貴金属を含有する不均一系触媒は、200μm以下の平均径を有することを特徴とする、請求項9または11に記載の触媒連続法。
- 酸化エステル化反応のために使用する貴金属を含有する不均一系触媒は、200μm超の平均径を有することを特徴とする、請求項8または11に記載の触媒連続法。
- メタクロレインを、有機塩基である第二級アミンおよび少なくとも1つの有機酸の存在下で、プロパナールとホルムアルデヒドとのマンニッヒ縮合反応における反応により製造することを特徴とする、請求項1から14までのいずれか1項に記載の触媒連続法。
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Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN108126762B (zh) * | 2016-12-01 | 2021-06-08 | 中国科学院大连化学物理研究所 | 一种用于生产不饱和羧酸酯的钴基催化剂及制备和羧酸酯制造 |
BR112019023486A2 (pt) * | 2017-05-09 | 2020-06-30 | Röhm Gmbh | processo para esterificação oxidativa de aldeídos a ésteres de ácido carboxílico |
CN110997615A (zh) * | 2017-07-28 | 2020-04-10 | 罗门哈斯公司 | 通过使用非均相催化剂进行氧化酯化来生产甲基丙烯酸甲酯的方法 |
EP3658528B1 (en) * | 2017-07-28 | 2021-08-18 | Rohm and Haas Company | A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
KR102639247B1 (ko) | 2017-07-28 | 2024-02-21 | 다우 글로벌 테크놀로지스 엘엘씨 | 불균일 촉매를 사용하여 산화적 에스터화에 의해 메틸 메타크릴레이트를 제조하는 방법 |
CA3071242A1 (en) | 2017-07-28 | 2019-01-31 | Rohm And Haas Company | A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
KR102644577B1 (ko) * | 2017-07-28 | 2024-03-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 불균일 촉매를 사용하여 산화적 에스터화에 의해 메틸 메타크릴레이트를 제조하는 방법 |
BR112020001738A2 (pt) * | 2017-07-28 | 2020-07-21 | Dow Global Technologies Llc | método para preparar um catalisador heterogêneo. |
SG11202000745YA (en) * | 2017-07-28 | 2020-02-27 | Rohm & Haas | A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
SG11202000742QA (en) | 2017-07-28 | 2020-02-27 | Dow Global Technologies Llc | A method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
US10829434B2 (en) | 2017-07-28 | 2020-11-10 | Dow Global Technologies Llc | Method for production of methyl methacrylate by oxidative esterification using a heterogeneous catalyst |
WO2019022884A1 (en) * | 2017-07-28 | 2019-01-31 | Rohm And Haas Company | PROCESS FOR THE PRODUCTION OF METHYL METHACRYLATE BY OXIDATIVE ESTERIZATION USING A HETEROGENEOUS CATALYST |
CN111050909B (zh) * | 2017-07-28 | 2024-06-04 | 罗门哈斯公司 | 非均相催化剂 |
EP3450422A1 (de) | 2017-08-29 | 2019-03-06 | Evonik Röhm GmbH | Verfahren zur herstellung optischer formmassen |
EP3456704A1 (de) | 2017-09-19 | 2019-03-20 | Evonik Röhm GmbH | Katalysator für die oxidative veresterung von aldehyden zu carbonsäureestern |
JP7268007B2 (ja) * | 2017-09-19 | 2023-05-02 | ダウ グローバル テクノロジーズ エルエルシー | 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 |
CA3085928A1 (en) * | 2018-01-10 | 2019-07-18 | Dow Global Technologies Llc | Heterogeneous catalyst for the production of methyl methacrylate by oxidative esterification |
EP3587390A1 (de) | 2018-06-26 | 2020-01-01 | Röhm GmbH | Verfahren zur herstellung von mma in hohen ausbeuten |
US11498057B2 (en) | 2018-06-28 | 2022-11-15 | Rohm And Haas Company | Heterogeneous catalyst |
US11813593B2 (en) | 2018-06-28 | 2023-11-14 | Rohm And Haas Company | Heterogeneous catalyst |
EP3608305A1 (en) | 2018-08-10 | 2020-02-12 | Röhm GmbH | Process for producing methacrylic acid or methacrylic acid esters |
CN110981728B (zh) * | 2019-12-06 | 2022-09-02 | 潍坊三力本诺化学工业有限公司 | 一种甲基丙烯酸甲酯的制备方法 |
US20230113685A1 (en) * | 2020-03-17 | 2023-04-13 | Dow Global Technologies Llc | Process and catalyst for oxidative esterification with long-life catalyst |
CA3208372A1 (en) | 2021-02-17 | 2022-08-25 | Evonik Operations Gmbh | Process for separation of methanol and methyl (meth)acrylate |
WO2022248321A1 (en) | 2021-05-28 | 2022-12-01 | Röhm Gmbh | Reactor and process for producing alkyl methacrylates |
EP4347548A1 (en) | 2021-05-28 | 2024-04-10 | Röhm GmbH | Reactor and process for producing alkyl (meth)acrylates |
WO2023059674A1 (en) | 2021-10-08 | 2023-04-13 | Dow Global Technologies Llc | Process for low byproduct formation from an oxidative esterification reactor with base addition |
CA3233803A1 (en) | 2021-10-08 | 2023-04-13 | Kirk W. Limbach | Process for low byproduct formation of methyl methacrylate from an oxidative esterification reactor |
WO2023059675A1 (en) | 2021-10-08 | 2023-04-13 | Rohm And Haas Company | Process for methyl methacrylate production |
WO2023059679A1 (en) | 2021-10-08 | 2023-04-13 | Rohm And Haas Company | Process for methyl methacrylate production from ethanol |
CN118055921A (zh) | 2021-10-08 | 2024-05-17 | 罗门哈斯公司 | 用于产生甲基丙烯酸烷基酯的方法 |
CN118076575A (zh) | 2021-10-08 | 2024-05-24 | 罗门哈斯公司 | 用于产生甲基丙烯酸甲酯的方法 |
CA3233785A1 (en) | 2021-10-08 | 2023-04-13 | Reetam Chakrabarti | Process for an oxidative esterification reactor |
US12017987B2 (en) | 2021-11-12 | 2024-06-25 | Röhm Gmbh | Process for eliminating interfering by-products in the direct oxidative esterification of methacrolein |
WO2024123528A1 (en) | 2022-12-08 | 2024-06-13 | Dow Global Technologies Llc | Process for preparing alkyl methacrylates |
WO2024123526A1 (en) | 2022-12-08 | 2024-06-13 | Dow Global Technologies Llc | Process for preparing alkyl methacrylates |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57150628A (en) * | 1981-02-21 | 1982-09-17 | Basf Ag | Manufacture of alpha-alkylacrolein |
JPS58154534A (ja) * | 1982-03-09 | 1983-09-14 | Asahi Chem Ind Co Ltd | 不飽和脂肪酸メチルエステルの製造法 |
JPH05252944A (ja) * | 1992-03-12 | 1993-10-05 | Fuji Shirishia Kagaku Kk | 組織培養方法 |
JPH0616587A (ja) * | 1992-03-31 | 1994-01-25 | Kuraray Co Ltd | α−メチレンアルデヒドの製造法 |
JPH0680611A (ja) * | 1992-09-03 | 1994-03-22 | Asahi Chem Ind Co Ltd | カルボン酸エステルの製造方法 |
WO2003022425A1 (fr) * | 2001-09-10 | 2003-03-20 | Kuraray Chemical Co., Ltd. | Article particulaire composite et procede de preparation associe |
JP2003260357A (ja) * | 2002-03-12 | 2003-09-16 | Asahi Kasei Corp | カルボン酸エステル製造用触媒および製造方法 |
JP2004345972A (ja) * | 2003-05-20 | 2004-12-09 | Asahi Kasei Chemicals Corp | カルボン酸エステルの製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55151533A (en) * | 1979-05-17 | 1980-11-26 | Asahi Chem Ind Co Ltd | Preparation of carboxylic acid ester |
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 |
JP3577361B2 (ja) * | 1995-06-06 | 2004-10-13 | 旭化成ケミカルズ株式会社 | 強度、耐腐食性に優れたカルボン酸エステル製造用触媒 |
MY119415A (en) | 1995-07-18 | 2005-05-31 | Asahi Chemical Ind | Catalyst for use in producing carboxylic esters |
JP3503777B2 (ja) * | 1995-07-19 | 2004-03-08 | 旭化成ケミカルズ株式会社 | パラジウム及び鉛を含む表面制御担持触媒 |
JP3498102B2 (ja) * | 1995-08-16 | 2004-02-16 | 旭化成ケミカルズ株式会社 | 強度に優れたカルボン酸エステル製造用触媒 |
JPH09192495A (ja) * | 1996-01-17 | 1997-07-29 | Asahi Chem Ind Co Ltd | カルボン酸エステル製造用触媒 |
SG71815A1 (en) | 1997-07-08 | 2000-04-18 | Asahi Chemical Ind | Method of producing methyl methacrylate |
AU2002354236A1 (en) | 2001-12-21 | 2003-07-09 | Asahi Kasei Chemicals Corporation | Oxide catalyst composition |
JP2004345974A (ja) | 2003-05-20 | 2004-12-09 | Asahi Kasei Chemicals Corp | カルボン酸エステルの連続的製造方法 |
JP4127522B2 (ja) | 2003-05-20 | 2008-07-30 | 旭化成ケミカルズ株式会社 | カルボン酸エステルの連続的製造方法 |
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 |
CN101148406B (zh) * | 2007-11-02 | 2011-04-20 | 中国科学院过程工程研究所 | 一种以醛、醇和氧化剂为原料制备羧酸酯的新方法 |
JP5336235B2 (ja) * | 2009-03-19 | 2013-11-06 | 旭化成ケミカルズ株式会社 | 貴金属担持物及びそれを触媒として用いるカルボン酸エステルの製造方法 |
-
2013
- 2013-12-20 EP EP13198873.5A patent/EP2886529A1/en not_active Withdrawn
-
2014
- 2014-12-11 JP JP2016541531A patent/JP6835583B2/ja active Active
- 2014-12-11 US US15/037,212 patent/US9963417B2/en active Active
- 2014-12-11 CN CN201480068152.3A patent/CN105814011B/zh active Active
- 2014-12-11 ES ES14821533.8T patent/ES2670553T3/es active Active
- 2014-12-11 EP EP14821533.8A patent/EP3083550B1/en active Active
- 2014-12-11 KR KR1020167019656A patent/KR20160102485A/ko not_active Application Discontinuation
- 2014-12-11 WO PCT/EP2014/077302 patent/WO2015091173A1/en active Application Filing
- 2014-12-11 SG SG11201603274YA patent/SG11201603274YA/en unknown
- 2014-12-17 TW TW103144090A patent/TW201538475A/zh unknown
-
2020
- 2020-10-29 JP JP2020181637A patent/JP2021038231A/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57150628A (en) * | 1981-02-21 | 1982-09-17 | Basf Ag | Manufacture of alpha-alkylacrolein |
JPS58154534A (ja) * | 1982-03-09 | 1983-09-14 | Asahi Chem Ind Co Ltd | 不飽和脂肪酸メチルエステルの製造法 |
JPH05252944A (ja) * | 1992-03-12 | 1993-10-05 | Fuji Shirishia Kagaku Kk | 組織培養方法 |
JPH0616587A (ja) * | 1992-03-31 | 1994-01-25 | Kuraray Co Ltd | α−メチレンアルデヒドの製造法 |
JPH0680611A (ja) * | 1992-09-03 | 1994-03-22 | Asahi Chem Ind Co Ltd | カルボン酸エステルの製造方法 |
WO2003022425A1 (fr) * | 2001-09-10 | 2003-03-20 | Kuraray Chemical Co., Ltd. | Article particulaire composite et procede de preparation associe |
JP2003260357A (ja) * | 2002-03-12 | 2003-09-16 | Asahi Kasei Corp | カルボン酸エステル製造用触媒および製造方法 |
JP2004345972A (ja) * | 2003-05-20 | 2004-12-09 | Asahi Kasei Chemicals Corp | カルボン酸エステルの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN105814011A (zh) | 2016-07-27 |
ES2670553T3 (es) | 2018-05-30 |
EP2886529A1 (en) | 2015-06-24 |
US20160280628A1 (en) | 2016-09-29 |
US9963417B2 (en) | 2018-05-08 |
EP3083550A1 (en) | 2016-10-26 |
EP3083550B1 (en) | 2018-02-28 |
JP2017507903A (ja) | 2017-03-23 |
WO2015091173A1 (en) | 2015-06-25 |
JP6835583B2 (ja) | 2021-02-24 |
CN105814011B (zh) | 2018-10-26 |
KR20160102485A (ko) | 2016-08-30 |
SG11201603274YA (en) | 2016-05-30 |
TW201538475A (zh) | 2015-10-16 |
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