EP4034519A1 - Procédé permettant d'éliminer le méthacrylate de méthyle de constituants à bas point d'ébullition - Google Patents
Procédé permettant d'éliminer le méthacrylate de méthyle de constituants à bas point d'ébullitionInfo
- Publication number
- EP4034519A1 EP4034519A1 EP20767827.7A EP20767827A EP4034519A1 EP 4034519 A1 EP4034519 A1 EP 4034519A1 EP 20767827 A EP20767827 A EP 20767827A EP 4034519 A1 EP4034519 A1 EP 4034519A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- distillation column
- methacrolein
- mma
- reactor
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- 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
- 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
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/60—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
Definitions
- MMA methyl methacrylate
- C2 C3 or C 4 building blocks.
- MMA is obtained by a direct oxidative esterification reaction of methacrolein using methanol.
- methacrolein is obtained from propanal and formaldehyde. Such a method is described in WO 2014/170223.
- the process according to the invention comprises the production of methacrolein by the so-called C2 process from formalin and propionaldehyde in the presence of a secondary amine and an acid, mostly an organic acid.
- the conversion takes place via a Mannich-like reaction with subsequent release of the catalytic secondary amine.
- Processes of this kind for the production of methacrolein are described, inter alia, in US Pat. No. 7,141,702, US Pat. No. 4,408,079, JP 3069420, JP 4173757, EP 0317909 and US Pat. No. 2,848,499. Depending on the process, yields between 91 and 98% can be achieved.
- the IBSME is partially separated into the respective water phase, which leads to a relevant MMA loss each time.
- An important setting parameter is the addition of water in relation to the IBSME content in the inlet. Optimization can reduce MMA loss, but not avoid it.
- the organic stream from the decanter of the second column is obtained as a waste stream or, in a process variant, can optionally be distilled in a third column, with MMA being recovered as the bottom of the columns.
- this variant of the process is very expensive, particularly with regard to the energy requirement and the number of separating devices required.
- the process achieves MMA purity between 98.99% by weight and 99.70% by weight.
- the MMA recovery is between 95.0 and 98.94%.
- the alkyl methacrylate is particularly preferably MMA. It was then the task to remove propionic acid methyl ester PRAME, isobutyric acid methyl ester IBSME, methacrolein MAL from this MMA in a particularly efficient manner while using as little energy as possible.
- an alkyl isobutyrate is formed in at least one of these reactors.
- the resulting crude alkyl methacrylate stream is worked up in a work-up process to give pure alkyl methacrylate. This work-up process goes through several distillative separation columns and at least one extractive separation.
- the raw alkyl methacrylate stream initially contains alkyl propionate and alkyl isobutyrate.
- an alkyl methacrylate with a respective content of alkyl propionate or alkyl isobutyrate of less than 0.1% by weight is preferably obtained.
- the top fraction from distillation column I is passed into a phase separator I and there separated into an aqueous and an organic fraction (see FIG. 1).
- a phase separator I Particularly preferably, water is additionally passed into this phase separator I, it being possible for the water to be fresh water and / or a water-containing recycling stream from one or more other process steps.
- organic phase from phase separator I which contains the by-products methacrolein, alkyl isobutyrate and alkyl propionate, is partially or completely recycled into the distillation column I.
- distillation column II it is also preferred to route the overhead stream from distillation column I and / or the organic phase from phase separator I wholly or partially into a distillation column II for fractionation (see FIG. 2).
- this distillation column II there is then a separation into a low-boiling by-product fraction containing methacrolein and alkyl isobutyrate and / or alkyl propionate, and an alkyl methacrylate-containing fraction in the bottom, which has a respective content of methacrolein, isobutyrate and alkyl propionate less than 0.1 wt % having.
- At least one bottom fraction containing alkymethacrylate is also preferably passed from distillation column I or from distillation column II into a distillation column III for the separation of high-boiling constituents.
- this fraction which has been purified from high boilers, can then be further purified in a further distillation column to separate off further low-boiling components (not part of the schemes in the appendix).
- distillation in distillation column I can optionally be carried out in the presence of an additional solvent acting as an entrainer.
- the top fraction from distillation column I and / or the aqueous phase from phase separator I is passed into a reactor IV. Acid hydrolysis takes place in this reactor IV.
- a particularly preferred variant of the process according to the invention is further characterized in that the extractive separation takes place in an extraction I before introduction into the distillation column I.
- this extractive separation a fraction containing water and alkali and / or alkaline earth salts is separated off.
- One process option is the distillation of the organic phase of extraction I in a distillation column IV to separate high boilers from the crude MMA.
- the high boiling bottom fraction produced can then be distilled again in a distillation column V.
- the distillate of the distillation column V can be returned to the distillation column IV to minimize MMA losses.
- the distillate of the distillation column IV is the feed to the distillation column I.
- the propionaldehyde content of the methacrolein from process step a is preferably between 100 ppm by weight and 2% by weight.
- the content of alkyl isobutyrate in the alkyl methacrylate from process step c is just as preferably below 2000 ppm.
- the distillation stage I which is a low boiler column, can be designed in various ways in order to achieve the required separation of the mentioned by-products alkyl propionate and alkyl isobutyrate, and the remaining methacrolein. It has proven to be practicable to use a multi-stage distillation column with a decanter in the distillate.
- the distillation column is generally operated at an internal pressure between 100 mbar and 1 bar, preferably between 150 and 500 mbar and particularly preferably between 200 and 400 mbar. This results in sump temperatures that are around 55 to 100 ° C. Since secondary reactions, such as polymerization, can occur at higher temperatures, it is advisable to set the pressure so that the bottom temperature is below 80 ° C, preferably below 70 ° C.
- the column is preferably designed and operated in such a way that the top temperature is 7 to 15 ° C. lower than the bottom temperature.
- the phase separator can be operated at a temperature below 50 ° C.
- the temperature is preferably between 4 and 30 ° C, as a rule between 15 and 25 ° C.
- the water-to-feed ratio at the phase separator is generally between 0 (no additional water) and 0.5, preferably between 0.1 and 0.2.
- the aqueous stream mainly contains H2O, methanol and some of the organic substances MMA, PRAME, IBSME, etc.
- the aqueous stream is either treated as waste water or can be subjected to an optional by-product treatment such as acid hydrolysis.
- the process according to the invention allows methyl isobutyrate to be separated off and, at the same time, methacrolein and methyl propionate to be separated off in a single distillation column with MMA recovery rates of over 99% by weight at the same time.
- the distillate stream (31) of the high boiler column is 11,000 g / h and contains 98.0% by weight of MMA, 1.0% by weight of H 2 0, 0.2% by weight of MAL, 0.1% by weight of PRAME, 0 , 1 wt% IBSME and 0.5 wt% remainder, this remainder being predominantly methanol.
- a reflux-to-feed ratio of 1.1 is set and the discharge flow is fixed at 112 g / h.
- the rate of addition of water into the phase separator is 1285 g / h. This results in a top temperature of 53 ° C and a bottom temperature of 61 ° C.
- the aqueous stream (36) of the phase separator is 1858 g / h and contains 1.6 wt% MMA, 91.8 wt% H2O, 0.4 wt% MAL, 0.4 wt% PRAME, 0.5 wt% IBSME and 4.9 wt% remainder.
- the bottom discharge (40) is 11035 g / h with the composition 99.91 wt% MMA, 35 ppm PRAME, 315 ppm IBSME and 0.06 wt% process stabilizer. This procedure described achieves an MMA retention of 99.71%.
- the process circuitry used in Examples 1 to 3 is supplemented by a further distillation column II (44), the so-called discharge column (FIG. 2).
- the discharge stream (35) is introduced into this column as a feed and purified by distillation.
- the distillate (45) produced contains the low-boiling components (MAL, PRAME and IBSME).
- the bottom fraction contains MMA with a process stabilizer and is returned to the low boiler column.
- the discharge column is operated at an absolute pressure of 250 mbar.
- the column is equipped with the high-performance laboratory packing DX from Sulzer (diameter 50 mm, packing height 2000 mm).
- the operating conditions of the low boiler column and the phase separator are the same as in Example 1.
- the feed into the low boiler column is 11,000 g / h and contains 96.7% by weight of MMA, 1.8% by weight of H2O, 0.1% by weight of MAL, 0.1% by weight % PRAME, 0.2% by weight IBSME and 1.1% by weight remainder.
- the reflux-to-feed ratio is set to 1.0 and the addition of water to the phase separator is 1530 g / h. This results in a top temperature of 54 ° C and a bottom temperature of 62 ° C.
- the discharge stream (35), which functions as a feed into the discharge column, is fixed at 110 g / h.
- the aqueous stream (36) of the phase separator is 1858 g / h and contains 1.2 wt% MMA, 93.8 wt% H2O, 1 wt% MAL, 0.4 wt% PRAME, 0.1 wt% IBSME and 3, 5% by weight remainder.
- the top temperature of the discharge column is 34.degree. C. and a bottom temperature of 61.degree.
- a distillate stream (45) falls from the discharge column of 22 g / h containing 2.1% by weight of MMA, 7.9% by weight of H2O, 39.9% by weight of MAL, 26.6% by weight of PRAME, 19.5% by weight IBSME and 4.0 wt% remainder.
- the bottom (46) of the discharge column is completely returned to the low boiler column.
- Example 1 The process circuitry used in Example 1 is supplemented by a stirred tank reactor (reactor IV) (37) with a reaction volume of 250 ml (FIG. 1).
- the stirrer is operated at 500 rpm and the operating temperature is 40 ° C.
- the aqueous phase (36) of the phase separator is introduced into this reactor (37). This stream consists of 1.2 wt% MMA, 93.8 wt% H2O, 1 wt%
- FIG. 1 Overall flow diagram of the production of MMA starting from formalin and propanal
- FIG. 2 Overall flow diagram of the production of MMA starting from formalin and propanal with an optional discharge column
- Alcohol feed usually methanol feed
- Acid feed usually sulfuric acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
La présente invention concerne un nouveau procédé permettant de purifier par distillation du méthacrylate de méthyle (MMA) contaminé par des constituants à bas point d'ébullition, ledit MMA ayant été produit par utilisation d'une estérification oxydative et, en tant que produit brut, contenant de l'ester méthylique de l'acide propionique (PRAME), de l'ester méthylique de l'acide isobutyrique (IBSME) et de la méthacroléine (MAL) en tant que constituants à bas point d'ébullition. Le procédé peut être utilisé sur un MMA qui a été produit à partir de méthacroléine obtenue lors de la production en C2, et qui contient les constituants à bas point d'ébullition mentionnés ci-dessus. Cependant, en théorie, le procédé peut aussi être utilisé sur un MMA qui a été produit à partir de méthacroléine obtenue lors de la production en C4, et qui contient du PRAME et du MAL, mais pas une quantité significative de IBSME.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19199547.1A EP3798202A1 (fr) | 2019-09-25 | 2019-09-25 | Procédé de purification du méthacrylate de méthyle des composants à bas point d'ébullition |
PCT/EP2020/075351 WO2021058293A1 (fr) | 2019-09-25 | 2020-09-10 | Procédé permettant d'éliminer le méthacrylate de méthyle de constituants à bas point d'ébullition |
Publications (1)
Publication Number | Publication Date |
---|---|
EP4034519A1 true EP4034519A1 (fr) | 2022-08-03 |
Family
ID=68069539
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19199547.1A Pending EP3798202A1 (fr) | 2019-09-25 | 2019-09-25 | Procédé de purification du méthacrylate de méthyle des composants à bas point d'ébullition |
EP20767827.7A Pending EP4034519A1 (fr) | 2019-09-25 | 2020-09-10 | Procédé permettant d'éliminer le méthacrylate de méthyle de constituants à bas point d'ébullition |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19199547.1A Pending EP3798202A1 (fr) | 2019-09-25 | 2019-09-25 | Procédé de purification du méthacrylate de méthyle des composants à bas point d'ébullition |
Country Status (6)
Country | Link |
---|---|
US (1) | US11731931B2 (fr) |
EP (2) | EP3798202A1 (fr) |
JP (1) | JP2022549485A (fr) |
CN (1) | CN114450264A (fr) |
TW (1) | TW202124351A (fr) |
WO (1) | WO2021058293A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115974668A (zh) * | 2022-12-02 | 2023-04-18 | 重庆道为低碳科技有限公司 | 一种甲基丙烯酸甲酯生产中甲基丙烯醛的分离方法 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
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US2848499A (en) | 1956-05-09 | 1958-08-19 | Celanese Corp | Preparation of unsaturated aldehydes |
JPS51146418A (en) | 1975-06-10 | 1976-12-16 | Nippon Zeon Co Ltd | Purification of methacrylic esters |
EP0044409B1 (fr) | 1980-06-20 | 1984-01-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Procédé pour la purification d'acrylate de méthyle |
DE3106557A1 (de) | 1981-02-21 | 1982-09-16 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von (alpha)-alkylacroleinen |
DE3740293A1 (de) | 1987-11-27 | 1989-06-01 | Hoechst Ag | Verfahren zur herstellung von alpha-alkylacroleinen |
JP3069420B2 (ja) | 1991-11-05 | 2000-07-24 | ダイセル化学工業株式会社 | 反応器および反応方法 |
SG71815A1 (en) | 1997-07-08 | 2000-04-18 | Asahi Chemical Ind | Method of producing methyl methacrylate |
DE10144490A1 (de) * | 2001-09-10 | 2003-03-27 | Basf Ag | Verfahren zur Herstellung von (Meth)acrylsäureestern |
WO2003053570A1 (fr) | 2001-12-21 | 2003-07-03 | Asahi Kasei Chemicals Corporation | Composition catalytique d'oxyde |
JP4173757B2 (ja) | 2003-03-26 | 2008-10-29 | ジヤトコ株式会社 | ロックアップクラッチの寿命判定方法及びスリップロックアップ領域設定方法並びに寿命判定装置 |
US7141702B2 (en) | 2004-03-26 | 2006-11-28 | Council Of Scientific And Industrial Research | Process for the synthesis of α-substituted acroleins |
SG189244A1 (en) * | 2010-10-07 | 2013-05-31 | Rohm & Haas | Process for production of methacrylic acid ester |
US9890105B2 (en) | 2013-04-19 | 2018-02-13 | Evonik Roehm Gmbh | Method for producing methylmethacrylate |
CN105683148B (zh) * | 2013-09-26 | 2017-11-24 | 赢创罗姆有限公司 | 甲基丙烯醛的制备方法及其调理/脱水以用于直接氧化酯化 |
EP2886528A1 (fr) | 2013-12-20 | 2015-06-24 | Evonik Industries AG | Procédé de fabrication d'esters non saturés à partir d'aldéhydes par estérisation oxydative directe |
FR3024143B1 (fr) * | 2014-07-28 | 2016-07-15 | Arkema France | Procede perfectionne de fabrication de (meth)acrylates d'alkyle |
EP3144291A1 (fr) | 2015-09-16 | 2017-03-22 | Evonik Röhm GmbH | Synthese d'acide methacrylique a partir de methacrylate d'alkyle a base de methacroleine |
TWI715627B (zh) * | 2015-09-16 | 2021-01-11 | 德商羅伊姆公司 | 含鈉鹽之mma-甲醇混合物的萃取後處理 |
CN116514657A (zh) | 2017-05-09 | 2023-08-01 | 罗姆化学有限责任公司 | 将醛氧化酯化成羧酸酯的方法 |
EP3450422A1 (fr) | 2017-08-29 | 2019-03-06 | Evonik Röhm GmbH | Procédé de fabrication des matières à mouler optiques |
EP3587390A1 (fr) | 2018-06-26 | 2020-01-01 | Röhm GmbH | Procédé de fabrication de mma en grandes quantités |
-
2019
- 2019-09-25 EP EP19199547.1A patent/EP3798202A1/fr active Pending
-
2020
- 2020-09-10 CN CN202080067155.0A patent/CN114450264A/zh active Pending
- 2020-09-10 JP JP2022519041A patent/JP2022549485A/ja active Pending
- 2020-09-10 WO PCT/EP2020/075351 patent/WO2021058293A1/fr active Application Filing
- 2020-09-10 US US17/754,096 patent/US11731931B2/en active Active
- 2020-09-10 EP EP20767827.7A patent/EP4034519A1/fr active Pending
- 2020-09-22 TW TW109132743A patent/TW202124351A/zh unknown
Also Published As
Publication number | Publication date |
---|---|
US20220388942A1 (en) | 2022-12-08 |
TW202124351A (zh) | 2021-07-01 |
JP2022549485A (ja) | 2022-11-25 |
CN114450264A (zh) | 2022-05-06 |
EP3798202A1 (fr) | 2021-03-31 |
US11731931B2 (en) | 2023-08-22 |
WO2021058293A1 (fr) | 2021-04-01 |
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