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EP3080067A1 - Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine - Google Patents

Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine

Info

Publication number
EP3080067A1
EP3080067A1 EP14805929.8A EP14805929A EP3080067A1 EP 3080067 A1 EP3080067 A1 EP 3080067A1 EP 14805929 A EP14805929 A EP 14805929A EP 3080067 A1 EP3080067 A1 EP 3080067A1
Authority
EP
European Patent Office
Prior art keywords
acid
reaction
alkylamine
amine
tertiary
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.)
Withdrawn
Application number
EP14805929.8A
Other languages
German (de)
English (en)
Inventor
Rudolf Burghardt
Steffen Krill
Torsten Balduf
Eduard Rundal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Evonik Roehm GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Evonik Roehm GmbH filed Critical Evonik Roehm GmbH
Priority to EP14805929.8A priority Critical patent/EP3080067A1/fr
Publication of EP3080067A1 publication Critical patent/EP3080067A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C07C45/61—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
    • 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
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester

Definitions

  • the present invention relates to an improved process for the preparation of methacrolein from propionaldehyde and formalin.
  • This novel process is characterized in that the catalyst system used for this reaction is modified such that the synthesis is more efficient and less
  • Methacrolein is used in chemical synthesis in particular as an intermediate for the production of methacrylic acid, methyl methacrylate or even active,
  • Odors or flavors used There is a great interest in the simplest possible, economical and environmentally friendly production processes.
  • the present invention relates to the modification of the large-scale process for the production of methacrolein, starting from propanal and
  • Formaldehyde or formalin is via a Mannich reaction.
  • Mannich reaction Such a process for the preparation of methacrolein, is inter alia in the
  • Reaction mixture is separated by distillation. At the head of the column becomes one
  • Methacrolein-water obtained by heteroazeotrope.
  • an aqueous solution with the homogeneous catalysts, traces of methacrolein and high boilers is separated.
  • a part, for example about 50%, of the aqueous discharge can be recycled again.
  • the catalytically active amines required for the reaction form under the
  • the inventive method is used to optimize the amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing amine-containing
  • Methacrolein is reacted.
  • the process according to the invention is characterized in particular in that the organic base is a mixture of a secondary alkylamine and a tertiary alkylamine in a substance ratio between 20: 1 and 1: 3, preferably between 10 to 1 and 1 to 2, more preferably between 7 to 1 and 1 to 1, and most preferably between 5 to 1 and 2.5 to 1.
  • the organic base is a mixture of a secondary alkylamine and a tertiary alkylamine in a substance ratio between 20: 1 and 1: 3, preferably between 10 to 1 and 1 to 2, more preferably between 7 to 1 and 1 to 1, and most preferably between 5 to 1 and 2.5 to 1.
  • the secondary and the tertiary alkyl amines of the plant are added as a mixture.
  • the ratio of the two components is either as indicated or the proportion of tertiary alkyl amines at the entrance of the reaction is reduced compared to
  • Reactor outlet as they are formed during the reaction itself.
  • only secondary alkylamines are added to the system.
  • the tertiary alkylamines are formed during operation of the plant and accumulate in circulation.
  • Alkylamines continuously or regularly determined, for example by sampling. On the basis of this determination, the amine-containing catalyst solution falls below the ratio of secondary to tertiary amine components below 1 to 3, preferably below 1 to 2 and particularly preferably below 1 to 1
  • This renewal is carried out by discharging the aqueous reaction phase and / or by adding fresh secondary alkylamine to
  • the plant is designed such that the reaction mixture is continuously discharged from the reaction space and separated via a phase separator or preferably via a distillation column.
  • the organic phase containing the methacrolein is recovered and removed, for example, as a distillate.
  • distillation bottoms including, inter alia, residues of the methacrolein, are recycled wholly or partly to the reaction space.
  • parts of the aqueous phase can be removed to renew the catalyst components, in particular the amine components. The removal over one
  • Phase separator is analog. By taking this takes place not only the
  • the supply of the reaction solution to be worked up from the reaction space into the distillation column can take place above, inside or below the separation section of the column.
  • a sump which predominantly consists of water of reaction or which contains quantities of water which enter the cycle process with the formalin solution collects.
  • This sump additionally contains the catalyst components, such as, for example, the organic acid and the secondary and the tertiary amine or the salts formed therefrom, as well as by-products of the reaction or the combination of the two.
  • This aqueous catalyst solution can preferably be withdrawn below the feed to the column at the bottom of the column.
  • the present total water is made up of the water, which was added as a catalyst solution, in the
  • sources of water are components of the technical starting materials such as propional and water, which is formed in various side reactions of the catalyst components with reactants, by-products and reaction products, and water of reaction of all these
  • the aqueous phase of the reaction taken in this way continuously, semicontinuously or batchwise is then preferably removed, optionally separated via a membrane into two phases, and the amine-containing wastewater (retentate) thus obtained is incinerated in a thermal oxidizer.
  • the wastewater can be further separated by means of an additional distillation, in order in this way, for example, to lead with discharged product back into the reaction cycle or product work-up.
  • the retentate of the membrane separation stage can be wholly or partly fed back into the reactor or work-up.
  • the aqueous phase of the reaction is removed and separated via a membrane into two phases.
  • the amine-containing wastewater thus obtained is then incinerated in a thermal oxidizer or otherwise disposed of, eg in a biological work-up, and the membrane separation retentate is partially recycled to the reactor.
  • a thermal oxidizer or otherwise disposed of, eg in a biological work-up e.g., a thermal oxidizer or otherwise disposed of, eg in a biological work-up, and the membrane separation retentate is partially recycled to the reactor.
  • the concentrate thus obtained can then be partially returned to the reactor.
  • the aqueous phase of the reaction can be removed and separated in a distillation.
  • the recovered distillation bottoms are then fed back to the reactor.
  • the aqueous phase is removed for disposal. This disposal may be, for example, combustion in a thermal oxidizer or biological work-up.
  • the recovered methacrolein in turn is in particular preferably converted to methacrylic acid or methyl methacrylate after purification in a second process which is continuously subsequent to the process.
  • the invention relates before the supply of the amine-containing
  • Patent application is disclosed with the Anmeldeakten Stand 13002076.1.
  • Such, particularly preferred Mannich reaction is in the presence of 0.1 to 20 mol% of organic base, preferably a secondary amine, and 0.1 to 20 mol% acid, based on the propanal used, at a temperature of 100 to 300 ° C and carried out at a pressure of 5 to 100 bar.
  • the acids are generally inorganic acids or organic mono-, di- or polycarboxylic acids, preferably monocarboxylic acids, in particular aliphatic monocarboxylic acids.
  • Particular preference is given to using at least one organic acid, particularly preferably acetic acid, for the reaction of propanal and formaldehyde.
  • the proportion of acid is between 0.1 and 20, advantageously from 0.5 to 10, preferably 1 to 5 mol%, based on propanal.
  • inorganic acids are in particular sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid or boric acid in question.
  • Suitable organic compounds besides acetic acid are also formic acid, propionic acid, isobutyric acid, n-butyric acid, oxalic acid, adipic acid, caprylic acid, phenylformic acid and 2-ethylhexylic acid.
  • mixtures of two or more acids can be used.
  • mixtures of organic and inorganic acids, in particular of acetic acid and sulfuric acid are also well suited.
  • an organic acid or a mixture of an organic acid and sulfuric acid is used. Particular preference is given to using only formic acid, acetic acid or propionic acid.
  • Examples of secondary amines which are added to the system as catalyst are: dimethylamine, diethylamine, methylethylamine,
  • the secondary amine is preferably dimethylamine or diethylamine, more preferably dimethylamine.
  • Suitable tertiary amines which are added to the system as catalyst or formed during the process are, for example: trimethylamine, triethylamine, dimethylethylamine, diethylmethylamine, dimethylpropylamine,
  • the tertiary amine is trimethylamine or triethylamine, more preferably trimethylamine.
  • the secondary alkylamine is dimethylamine and at the same time the tertiary alkylamine is trimethylamine.
  • the proportion of organic base is between 0.1 and 30, advantageously from 0.5 to 20, preferably 1 to 10 mol%, based on propanal.
  • the ratio of the equivalents of amine to acid is preferably chosen such that a pH of 2.5 to 9 results in the reaction mixture before the reaction.
  • Wastewater quantity can be carried out. Surprisingly, since the tertiary alkylamine does not have to be continuously discharged from the system and at the same time the secondary amine has to be renewed to a lesser extent, the continuous production process can be carried out with this reduced amount of wastewater.
  • a great advantage of the method according to the invention is that this can be carried out with relatively simple and cost-effective or in already existing systems.
  • the systems are easy to maintain and cause low maintenance costs.
  • the following examples serve to illustrate more preferred
  • the catalyst solution consisting of the amines and acids mentioned, is driven into the preheater (12). Both streams are heated to a temperature of 170 ° C prior to combining.
  • the preheated streams are combined in a T-mixer directly with a T-mixer
  • Flow tube reactor (1/16 inch pipe with a length of 4.2 m) is connected.
  • the thermostating of the reactor is carried out with an oil bath, which is operated at 180 ° C, the residence time is less than 10 s (see Table 1), the pressure in the tubular reactor 70 bar.
  • the mixture is expanded in valve (14) and fed to the column (15). 335 g / h of the bottom effluent are returned to the reactor (13), disposed of 370 g / h of the bottom effluent as wastewater.
  • Examples 5 and 6 and Comparative Example 5 again show that, with particularly high amine concentrations, it is expected that a particularly high conversion and high MAL yields can be achieved. However, it is surprising and in great contradiction to the state of the art that these high conversions are achieved even if there is so much trimethylamine in the reactor that the ratio of trimethylamine to dimethylamine is only slightly below 0.8.
  • Fig. 1 Schematic representation of an apparatus suitable for carrying out the method according to the invention

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour produire de la méthacroléine à partir de propionaldéhyde et de formol. Ce nouveau procédé est caractérisé en ce que le système catalytique utilisé pour cette réaction est modifié par la présence simultanée d'amines secondaires et tertiaires et en ce que la synthèse peut être réalisée plus efficacement et avec une exigence de purification moins importante.
EP14805929.8A 2013-12-12 2014-12-03 Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine Withdrawn EP3080067A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14805929.8A EP3080067A1 (fr) 2013-12-12 2014-12-03 Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13196810.9A EP2883859A1 (fr) 2013-12-12 2013-12-12 Alkylamines tertiaires comme cocatalyseurs pour la synthèse de méthacroléine
EP14805929.8A EP3080067A1 (fr) 2013-12-12 2014-12-03 Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine
PCT/EP2014/076326 WO2015086386A1 (fr) 2013-12-12 2014-12-03 Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine

Publications (1)

Publication Number Publication Date
EP3080067A1 true EP3080067A1 (fr) 2016-10-19

Family

ID=49816793

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13196810.9A Withdrawn EP2883859A1 (fr) 2013-12-12 2013-12-12 Alkylamines tertiaires comme cocatalyseurs pour la synthèse de méthacroléine
EP14805929.8A Withdrawn EP3080067A1 (fr) 2013-12-12 2014-12-03 Alkylamines tertiaires employées comme cocatalyseur pendant la synthèse de la méthacroléine

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP13196810.9A Withdrawn EP2883859A1 (fr) 2013-12-12 2013-12-12 Alkylamines tertiaires comme cocatalyseurs pour la synthèse de méthacroléine

Country Status (8)

Country Link
US (1) US20160280624A1 (fr)
EP (2) EP2883859A1 (fr)
JP (1) JP2017502943A (fr)
KR (1) KR20160098374A (fr)
CN (1) CN105722814A (fr)
SG (1) SG11201602880UA (fr)
TW (1) TW201536732A (fr)
WO (1) WO2015086386A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2714899T3 (es) 2016-09-30 2019-05-30 Oxea Gmbh Método de producción continuo para 2-metilenos-alcanales
JP7065118B2 (ja) * 2017-05-25 2022-05-11 ローム アンド ハース カンパニー メタクロレインを調製するための方法
CN110882722A (zh) * 2019-11-22 2020-03-17 淄博诺奥化工股份有限公司 一种酸碱复合催化剂以及使用其制备甲基丙烯醛的方法
CN117916217A (zh) 2021-09-06 2024-04-19 罗姆化学有限责任公司 甲基丙烯醛合成中优化的催化剂后处理和再循环
CN115894200A (zh) * 2022-10-19 2023-04-04 东南大学 一种基于胺酸高效耦合催化的脂肪族烯醛制备方法
KR20250119549A (ko) * 2022-12-08 2025-08-07 롬 앤드 하스 캄파니 메틸 메타크릴레이트 및 메타크릴산의 동시 제조를 위한 방법

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US2848499A (en) 1956-05-09 1958-08-19 Celanese Corp Preparation of unsaturated aldehydes
JPS55105111A (en) * 1979-02-08 1980-08-12 Nittetsu Kakoki Kk Process for combustion of fluid
DE3106557A1 (de) 1981-02-21 1982-09-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von (alpha)-alkylacroleinen
DE3213681A1 (de) 1982-04-14 1983-10-27 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von (alpha)-alkylacroleinen
US4562901A (en) 1983-10-12 1986-01-07 Miguel C. Junger Sound absorptive structural block with sequenced cavities
DE3740293A1 (de) 1987-11-27 1989-06-01 Hoechst Ag Verfahren zur herstellung von alpha-alkylacroleinen
JP2922674B2 (ja) * 1991-06-25 1999-07-26 ダイセル化学工業株式会社 α−アルキルアクロレインの製造方法
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
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

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
KR20160098374A (ko) 2016-08-18
CN105722814A (zh) 2016-06-29
JP2017502943A (ja) 2017-01-26
EP2883859A1 (fr) 2015-06-17
SG11201602880UA (en) 2016-05-30
US20160280624A1 (en) 2016-09-29
TW201536732A (zh) 2015-10-01
WO2015086386A1 (fr) 2015-06-18

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