WO2015065610A1 - Process for separating methacrolein - Google Patents
Process for separating methacrolein Download PDFInfo
- Publication number
- WO2015065610A1 WO2015065610A1 PCT/US2014/056268 US2014056268W WO2015065610A1 WO 2015065610 A1 WO2015065610 A1 WO 2015065610A1 US 2014056268 W US2014056268 W US 2014056268W WO 2015065610 A1 WO2015065610 A1 WO 2015065610A1
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- WO
- WIPO (PCT)
- Prior art keywords
- stream
- methacrolein
- water
- product stream
- phase
- Prior art date
Links
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 82
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 28
- 230000018044 dehydration Effects 0.000 claims description 24
- 238000006297 dehydration reaction Methods 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 21
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000012074 organic phase Substances 0.000 claims description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000006709 oxidative esterification reaction Methods 0.000 claims description 17
- 239000008346 aqueous phase Substances 0.000 claims description 15
- 238000007037 hydroformylation reaction Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 34
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 12
- 238000000895 extractive distillation Methods 0.000 description 10
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- 150000001299 aldehydes Chemical class 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- -1 dimethylamine Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 101500021165 Aplysia californica Myomodulin-A Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KXZIYFLCCFPHAX-UHFFFAOYSA-N (2,3-dicyclohexylphenyl)-phenylphosphane Chemical compound C1(CCCCC1)C=1C(=C(C=CC=1)PC1=CC=CC=C1)C1CCCCC1 KXZIYFLCCFPHAX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- ITPOKAFWZBFZCV-UHFFFAOYSA-N 3-diphenylphosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 ITPOKAFWZBFZCV-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RRBTXJVVJCYBQH-UHFFFAOYSA-N formaldehyde propanal Chemical compound C=O.CCC=O RRBTXJVVJCYBQH-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003842 industrial chemical process Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/83—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by extractive distillation
-
- 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
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- 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
-
- 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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/21—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C47/22—Acryaldehyde; Methacryaldehyde
-
- 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
Definitions
- the invention relates to a process for preparing dry methacrolein, and to a process for making methyl methacrylate.
- Methacrolein (MA) is a common intermediate in methyl methacrylate (MMA) production.
- MA can be produced from the more abundant ethylene (C 2 ) feedstock, such as via liquid phase propionaldehyde condensation as disclosed in US 4,496,770, or from less abundant isobutylene or tert-butanol (C 4 ) feedstocks, such as via vapor phase C 4 oxidation as disclosed in US 5,969,578.
- the methacrolein product stream contains significant amounts of water for both C 2 - and C 4 -based methacrolein production methods.
- US 5,969,578 describes a method for dehydrating a gaseous methacrolein-containing product stream produced by a C 4 oxidation process. Water contained in the gaseous stream is removed by partial condensation, while the methanol and methacrolein components are allowed to remain gaseous. The gaseous methacrolein-containing mixture is then contacted with a very dry cooled methanol-containing stream to absorb the methacrolein. The resulting absorber bottoms product mixture contains 25-69% methacrolein in methanol, and ⁇ 1% water. This mixture is sufficiently dry to feed a downstream oxidative esterification reactor. However, this scheme suffers from a number of disadvantages.
- US 5,969,578 discourages the use of methods involving the use of water as a contacting solvent for methacrolein production and goes to significant lengths to entirely avoid the co-condensation of water and methacrolein.
- Another method of treating a gaseous methacrolein-containing product of a C 4 oxidation process is described in US 3,597,880, which discloses a process in which the gaseous methacrolein containing mixture is contacted with methanol to absorb methacrolein and water.
- the resulting liquid mixture contains methanol, methacrolein, and a modest amount of water, e.g., 5.8% indicated in Example 1.
- the liquid mixture is then subjected to extractive distillation with water, where the concentration of water in a liquid phase in an absorbing section of the extractive distillation zone is controlled to a concentration of from 50 to 90 mole%.
- concentration of water is targeted in order to avoid the formation of a methacrolein-methanol azeotrope, and to enable the separation of methacrolein from excess methanol that is recycled for use in the upstream absorption step.
- Methacrolein is thus recovered as a top distillate, whereas the bottom liquid of the extractive distillation column is further distilled to separate methanol from water.
- the top distillate stream of the extractive distillation column which is an azeotrope of water and
- methacrolein (azeotropic point 63.6°C; methacrolein/water weight ratio 100/7.9, per US 5,969,578) containing about 7% water, is allowed to phase separate to give an organic liquid phase containing mostly methacrolein and a level of water dictated by liquid-liquid equilibrium, about 3% water.
- the aqueous liquid phase contains mostly water and a level of methacrolein dictated by liquid-liquid equilibrium, namely about 6% methacrolein.
- the process is not concerned with drying the methacrolein product further, thus producing methacrolein containing approximately 3% water.
- the patent states that the methacrolein product can be further purified by additional distillation or the like.
- the process is intended to capture methacrolein from a gaseous C 4 oxidation product stream, with the associated absorber bottoms containing mostly methanol, methacrolein, and only a modest amount of water, e.g., 5.8% water indicated in Example 1.
- This process is not practical for a highly- aqueous, e.g., 65% water, liquid methacrolein product stream of a propionaldehyde condensation process, such as described in US 4,496,770, used with C 2 feedstock.
- US 2,514,966 and US 2,514,967 disclose a method in which a gas that contains acrolein (or other unsaturated aldehydes) and steam is absorbed into water.
- This method is carried out by scrubbing an acrolein-containing gaseous mixture with a large amount of water under high pressure to form an aqueous solution containing about 2 wt% of acrolein, and then subjecting the aqueous acrolein solution to stripping, rectification and extractive distillation to recover the acrolein.
- Such a process is disadvantageous in that an extremely large amount of water must be used under high pressure to absorb acrolein from the gaseous reaction mixture, due to the inherently low solubility of acrolein in water (21.4 wt under 20°C per US 3,957,880).
- methacrolein would be recovered in the form of an azeotropic mixture of methacrolein and water [azeotropic point: 63.6°C & 100:7.9 per US 5,969,578].
- azeotropic point 63.6°C & 100:7.9 per US 5,969,578.
- US 2,514,966 and US 2,514,967 teach the importance of avoiding heterogeneous extractive distillation configurations, thus advocating high levels of water.
- the invention is such a process comprising (a) providing a first stream comprising water, methacrolein and, optionally, methanol to a phase separator, with the proviso that the first stream comprises at least 8 weight percent water; (b) allowing the first stream to phase separate into an organic phase that comprises primarily methacrolein and an aqueous phase that comprises primarily water; (c) distilling the organic phase in a dehydration column to produce a product stream comprising primarily methacrolein.
- the process of the invention surprisingly produces a concentrated (>90 ) methacrolein stream with less than 2 wt.% water, and avoids many disadvantages of the prior art.
- the invention is a process for the production of MM A from ethylene, the process comprising (1) contacting ethylene with CO and 3 ⁇ 4 in the presence of a hydroformylation catalyst under reaction conditions sufficient to produce propionaldehyde;
- FIG. 1 is a schematic of an embodiment of the invention.
- FIG. 2 is a schematic of another embodiment of the invention.
- the use of the term "(meth)” followed by another term such as acrylate refers to both acrylates and methacrylates.
- the term "(meth)acrylate” refers to either acrylate or methacrylate;
- the term “(meth)acrylic” refers to either acrylic or methacrylic; and
- the term “(meth) acrylic acid” refers to either acrylic acid or methacrylic acid.
- wppm means parts per million by weight.
- the use of the term "fed to the top of the column” means that the relevant stream is fed to the relevant column at a point at or above the highest point of the column internals, which may comprise, e.g., packing or trays.
- all parts and percentages are based on weight and all test methods are current as of the filing date of this application.
- the contents of any referenced patent, patent application or publication are incorporated by reference in their entirety (or its equivalent U.S. version is so incorporated by reference) especially with respect to the disclosure of definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and general knowledge in the art.
- the process of the invention employs a wet MA feed stream.
- the feed stream comprises MA and water, and may contain other materials, such as residual catalyst from an upstream process.
- the feed stream comprises at least 10 wt.% water, based upon the weight of the stream, and in other embodiments the feed stream comprises at least 20, or at least 40, wt.% water.
- the source of wet methacrolein is not particularly important.
- the process of the invention is preferably employed with highly-aqueous C 2 -based methacrolein streams, such as those produced from propionaldehyde by the method of US 4,496,770.
- the process of the invention can be used to dehydrate, following condensation, dilute gaseous C 4 -based methacrolein streams, such as those produced by the method of US 5,969,178.
- FIG. 1 A wet MA feed stream 10 is fed to decanter 100, wherein the feed stream 10 is allowed to separate into aqueous and organic phases.
- the organic phase is used as the feed stream 20 to MA dehydration column 200, which is equipped with a condenser 201 and a reboiler 202.
- stream 20 is distilled or stripped to remove light components, which are condensed in condenser 201. If advantageous to the operation of column 200, a portion 31 of the condensed stream can be refluxed to column 200.
- the condensed overhead stream 30 can be integrated into the process recycle scheme as desired.
- stream 30 can be recycled to decanter 100, while another portion 31 of stream 30 can be used as reflux to column 200.
- stream 30 can be fed to a separate decanter (not shown), whose organic product can be fed to column 200 (either via stream 20 or via reflux), and whose aqueous product can be combined with stream 50 for further processing.
- the bottoms stream of column 200 is recovered as the final MA product stream 40 comprising MA with a small amount of water.
- the MA product stream 40 can be used, in whole or in part, as a feed to other industrial chemical processes, either directly or after additional processing.
- the MA product stream 40 can be used as a feed to an oxidative esterification process to produce MMA.
- the aqueous phase from decanter 100 is removed via line 50.
- FIG. 2 Another embodiment of the invention is shown in FIG. 2, which builds upon the process of FIG. 1.
- the aqueous phase from decanter 100 is sent via line 50 to water purge column 300, which is equipped with a condenser 301 and a reboiler 302.
- the overhead stream from column 300 is condensed in condenser 301 to produce condensed overhead stream 80, at least a portion 82 of which is recycled to decanter 100. If advantageous to the operation of column 300, a portion 81 of the condensed stream 80 can be refluxed to column 300.
- a water purge stream 60 is taken as a side draw stream from column 300.
- the bottoms stream 70 can be used as a recycle stream, either directly or after further work-up, to send material, such as catalyst, back to the reaction step that is the source of stream 10.
- purge stream 60 is not employed and bottoms stream 70 is distilled separately to remove excess water.
- phase separation devices e.g., decanters, 203 and 303 (not shown) that are supplied by the liquid condensate streams leaving condensers 201 and 301, respectively.
- a portion of the organic phase of separation device 203 is refluxed to column 200 and another portion is combined with stream 40 as MA product.
- the aqueous phase from device 203 is sent to phase separation device 303.
- device 303 its organic phase is sent to column 200, either directly or via stream 20, and its aqueous phase is refluxed to column 300.
- a 2 nd distillation column which can be, e.g. column 300 described hereinabove, the aqueous phase from the phase separator to produce: (1) a 2 nd distillation column bottoms stream comprising primarily water and (2) a 2 nd distillation column overhead stream; and
- the MA dehydration column advantageously is operated under conditions sufficient to produce an MA product stream having the desired amount of water.
- the temperature at the bottom of the column is from 65 to 90°C.
- the pressure in the column will be a function of the temperature employed and the composition of the material being distilled.
- the water purge column advantageously is operated under conditions sufficient to recover MA from the aqueous phase and to remove the water of reaction and undesired organic compounds from the process.
- the temperature at the bottom of water purge column is from 80 to 110°C.
- the pressure in the water purge column will be a function of the temperature employed and the composition of the material being distilled.
- the process of the invention advantageously does not require any methanol to achieve methacrolein dehydration, uses a single distillation column for methacrolein dehydration, and does not require a recycle from downstream process units, although recycling from downstream units is not excluded.
- the dehydration process of the invention is an inherently simple process that is more self-contained and robust to operation upsets in surrounding process units compared to dehydration processes of the prior art.
- the process can employ any suitable equipment prepared from any suitable materials of construction, as is well known to those skilled in the art.
- the columns can use packing, trays, or a combination of both.
- the MA product stream advantageously comprises less than 2 weight percent water, based on the weight of the final MA product stream, preferably less than 1 weight percent water, and more preferably less than 0.5 weight percent water.
- the product MA stream is used as the feed stream to an oxidative esterification process wherein the MA is converted to MMA via the reaction of MA with methanol and an oxygen-containing gas in the presence of a catalyst.
- the oxidative esterification process is well known. See, e.g., U.S. Patents 5,969,178, US 6,107,515, 6,040,472, 5,892,102, 4,249,019, 4,518,796.
- copending US Patent Application Ser. Nos. 61/859,526, 61/859,539, 61/859,544, and 61/859,551 discuss oxidative esterification and catalysts therefor.
- the molar ratio of methanol employed to the amount of methacrolein employed in the MA oxidative esterification reaction is not particularly limited, and the reaction may be conducted over a wide range of molar ratios such as 1: 10 to 1,000: 1, preferably from 1: 1 to 10: 1 methanol to methacrolein.
- the oxygen-containing gas for the oxidative esterification may be either oxygen gas or a mixed gas comprising oxygen gas and a diluent inert to the reaction such as, for example, nitrogen, carbon dioxide or the like. Air may be used as the oxygen-containing gas.
- the quantity of oxygen present in the reaction system advantageously is not less than the stoichiometric quantity required for the reaction, and preferably is not less than 1.2 times the stoichiometric quantity.
- Hydrogen peroxide may be introduced into the reaction system as an oxidizer.
- Catalysts that can be used for the MA oxidative esterification are well known to those skilled in the art, including palladium-based, gold-based, and other intermetallics containing combinations of two or more metals.
- the catalytic elements are typically present in the reaction system in such a form that they can have some interaction with each other.
- the oxidative esterification patents cited hereinabove give several examples of suitable oxidative esterification catalysts.
- the catalytic elements may be supported on a carrier, such as silica or alumina, and the amount of the catalytic constituents supported on the carrier advantageously may be from 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the weight of the carrier.
- suitable carriers include silica, alpha alumina and gamma alumina.
- the earner may be modified, as is known by those skilled in the art.
- a silica carrier may be modified with alumina and/or magnesia. Combinations of carriers may be employed.
- the catalyst constituents may also be used in the metallic form or in the form of compounds without supporting them on a carrier.
- the oxidative esterification catalyst is employed in a catalytic amount.
- the amount of the catalyst i.e., catalytic elements and optional carrier, may be varied freely depending on the kind and amount of the starting materials, the method of preparing the catalyst, process operating conditions and the like, although the weight ratio of catalyst to the starting MA generally is from 1 : 1000 to 20: 1.
- the weight ratio of catalyst to MA is from 1: 100 to 2: 1.
- the catalyst may be used in an amount outside this range.
- the oxidative esterification reaction may be conducted at a temperature of from 0°C to 120°C, preferably from 40°C to 90°C.
- the reaction may be conducted at reduced pressure, at atmospheric pressure, or at superatmospheric pressure, it is possible to produce the desired product by a very simple method of blowing the oxygen-containing gas into the reaction system at ambient pressure.
- the reaction may be conducted in a batch, semi-batch or continuous manner.
- the reaction is conducted in the liquid phase.
- a polymerization inhibitor can be employed in the process when the product and/or reactants comprise one or more polymerizable compounds.
- a wide variety of inhibitors are known and commercially available.
- the first stream comprising water, methacrolein and, optionally, methanol comes from a process that converts propionaldehyde to MA.
- formaldehyde in the presence of an amine or amine-acid catalyst in the liquid phase is well known to those skilled in the art. See, e.g., U.S. Patents 4,496,770 and 7,141,702.
- Mannich condensation of propionaldehyde and formaldehyde to methacrolein can be carried out in the presence of a secondary amine, e.g., dimethylamine, and in the presence or absence of an acid, e.g., acetic acid.
- the reaction can be carried out under any suitable conditions at which the reaction proceeds.
- the reaction can be conducted at a temperature of at least 20°C and at least atmospheric pressure.
- the reaction is conducted in the liquid phase at above 150°C, e.g., 160-210°C, and at superatmospheric pressure, e.g., 40-80 bar.
- the molar ratio of propionaldehyde to formaldehyde is not particularly limited, but advantageously can be maintained at around 1: 1.
- the reaction residence time preferably is not more than 25 minutes, and more preferably is from 0.05 to 0.3 minutes, e.g., 9 seconds.
- the molar ratio of the amine to the acid is preferably such that the resulting pH is from 2.5 to 7.
- the propionaldehyde used as a feedstock for preparing MA is prepared by the hydroformylation of ethylene.
- the hydroformylation process is well known. See, e.g., U.S. Patents 4,247,486, 5,087,763, 4,716,250, 4,731,486, and 5,288,918. It involves contacting an olefin with CO and hydrogen in the presence of a hydroformylation catalyst under reaction conditions sufficient to produce the corresponding aldehyde(s). In the case of ethylene, the corresponding aldehyde is propionaldehyde.
- Hydroformylation catalysts are well known and any suitable such catalyst may be employed.
- the hydroformylation catalyst advantageously comprises a metal- organophosphorous ligand complex.
- Suitable organophosphorous ligands include organophosphines, organophosphites, and organophosphoramidites.
- the organophosphine may be a triorganophosphine such as, for example, triphenylphosphine, tris-p- tolylphosphine, tris-p-methoxyphenylphosphine, cyclohexyldiphenylphosphine, dicyclohexyldiphenylphosphine, tribenzylphosphine and the like; as well as alkali and alkaline earth metal salts of sulfonated triphenylphospines such as, for example salts of (tri- m-sulfophenyl)phosphine and of (m-sulfophenyl)diphenylphosphine and the
- Organophosphites that may serve as the ligand include monoorganophosphites, diorganophosphites, and triorganophosphites, and their use and preparation are well known in the art. Examples of illustrative organophosphoramidites may be found in EP 2 740 535.
- the reaction conditions of the hydroformylation process are also well known and may include any suitable hydroformylation conditions employed for producing aldehydes.
- the total gas pressure of hydrogen, carbon monoxide and olefin starting compound of the hydroformylation process may range from 1 to 69,000 kPa. In general, however, it is preferred that the process be operated at a total gas pressure of hydrogen, carbon monoxide and olefin starting compound of less than 14,000 kPa and more preferably less than 3,400 kPa.
- the minimum total pressure is limited predominantly by the amount of reactants necessary to obtain a desired rate of reaction.
- the carbon monoxide partial pressure of the hydroformylation process is preferably from 1 to 6,900 kPa, and more preferably from 21 to 5,500 kPa, while the hydrogen partial pressure is preferably from 34 to 3,400 kPa and more preferably from 69 to 2,100 kPa.
- the molar ratio of gaseous H 2 :CO may range from 1 : 10 to 100: 1 or higher, the more preferred molar ratio being from 1: 10 to 10:1.
- the hydroformylation process may be conducted at any operable reaction temperature.
- the hydroformylation process is conducted at a reaction temperature from -25°C to 200°C, preferably from 50°C to 120°C.
- the invention is a process for the production of MM A from ethylene, the process comprising
- phase separator (3) providing at least a portion of the first stream to a phase separator; (4) allowing at least a portion of the first stream to phase separate in the phase separator into an organic phase that comprises primarily methacrolein and an aqueous phase that comprises primarily water;
- (6) providing at least a portion of the product stream to a process comprising contacting the methacrolein with methanol and an oxygen-containing gas in the presence of an oxidative esterification catalyst under reaction conditions sufficient to produce MMA.
- the process unit operations involved may be less than 100% efficient and may involve less than complete conversion of starting materials to desired products, e.g., some by-products may be produced, as would be expected by one skilled in the art, or a separation step may provide less than a perfect separation of components of its feed stream.
- a liquid methacrolein reactor effluent comprising 31.2% methacrolein, 61.2% water, 4.1% methanol, 0.9% dimethylamine, 1.3% acetic acid, 600 wppm hydroquinone and 600 wppm phenothiazine is fed at 671 g/h into a liquid-liquid decanter.
- the temperature and pressure of the decanter are 5°C and 1 atm, respectively.
- the feed splits into two phases in the decanter, with an organic to aqueous phase mass ratio of ca. 1 :2.5.
- the organic phase effluent from the decanter comprising 94.8% methacrolein, 2.8% water and 0.9% methanol, is accumulated.
- the accumulated organic phase effluent from the decanter is fed to a methacrolein dehydration column at a rate of 760 g/h.
- the dehydration column is a glass, 20 tray, 33 mm Oldershaw column equipped with a forced circulation reboiler and an overhead chilled water cooled condenser.
- the organic phase effluent from the decanter is fed to the dehydration column at the top tray and no reflux is returned to the column; thus, the dehydration column is operated as a stripper.
- Inhibitor consisting of 2% hydroquinone and 2% phenothiazine dissolved in the same organic phase effluent from the decanter is pumped to the overhead condenser at the rate of 6.5 g/h.
- the column is operated continuously for a period of 4 h at a condenser pressure of 7.7 psig and a bottoms temperature of ca. 80°C.
- the bottoms product comprises ca. 98% methacrolein, 0.5% methanol, and 0.2% water.
- the weight ratio of bottoms product to column feed is 0.66: 1.
- the aqueous phase effluent of the decanter is accumulated for subsequent treatment.
- the example demonstrates that the process of this invention is effective at drying a methacrolein stream with a high amount of water to produce a product stream with a high methacrolein concentration and a low water concentration.
- the water concentration in the methacrolein product stream is substantially lower than that achieved by the various methods of the prior art.
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Abstract
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Priority Applications (9)
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US14/917,114 US9765007B2 (en) | 2013-10-28 | 2014-09-18 | Dehydration process |
CN201480057700.2A CN105683142B (en) | 2013-10-28 | 2014-09-18 | Method for detaching methacrolein |
SG11201601819WA SG11201601819WA (en) | 2013-10-28 | 2014-09-18 | Process for separating methacrolein |
MX2016005046A MX369608B (en) | 2013-10-28 | 2014-09-18 | Process for separating methacrolein. |
EP14778025.8A EP3063117B1 (en) | 2013-10-28 | 2014-09-18 | Process for preparing methyl methacrylate |
KR1020167011984A KR102291247B1 (en) | 2013-10-28 | 2014-09-18 | Process for separating methacrolein |
CA2928807A CA2928807C (en) | 2013-10-28 | 2014-09-18 | Process for separating methacrolein |
JP2016525086A JP6382969B2 (en) | 2013-10-28 | 2014-09-18 | Method for separating methacrolein |
SA516371005A SA516371005B1 (en) | 2013-10-28 | 2016-04-23 | Process for separating methacrolein |
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US201361896378P | 2013-10-28 | 2013-10-28 | |
US61/896,378 | 2013-10-28 |
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EP (1) | EP3063117B1 (en) |
JP (1) | JP6382969B2 (en) |
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CN (1) | CN105683142B (en) |
CA (1) | CA2928807C (en) |
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EP3613726A1 (en) * | 2018-08-21 | 2020-02-26 | Röhm GmbH | Continuous process for preparing methacrolein |
JP2020521733A (en) * | 2017-05-25 | 2020-07-27 | ローム アンド ハース カンパニーRohm And Haas Company | Process for preparing methacrolein |
EP3786147A1 (en) | 2019-08-30 | 2021-03-03 | Röhm GmbH | Method for producing methacrolein from formaldehyde and propionaldehyde and production plant therefor |
EP3786146A1 (en) | 2019-08-30 | 2021-03-03 | Röhm GmbH | Method for producing methacrolein from formaldehyde and propionaldehyde and production plant therefor |
WO2023031386A1 (en) | 2021-09-06 | 2023-03-09 | Röhm Gmbh | Optimized catalyst processing and recycling in the synthesis of methacrolein |
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KR102567215B1 (en) * | 2017-05-25 | 2023-08-16 | 롬 앤드 하아스 컴패니 | Method for preparing methacrolein |
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US9765007B2 (en) | 2017-09-19 |
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MX2016005046A (en) | 2016-08-03 |
CN105683142A (en) | 2016-06-15 |
US20160229779A1 (en) | 2016-08-11 |
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