SYNTHESIS OF METHACRYLIC ACID FROM METHACROLEIN-BASED ALKYL METHACRYLATE

Abstract

The present invention relates to a process for preparing alkyl methacrylates, especially MMA, and methacrylic acid, based on methacrolein, which has been oxidatively esterified in a second process stage. Methacrolein is obtainable in principle from C.sub.2 and C.sub.4 units. The present process has the advantage that the alkyl methacrylate and methacrylic acid can be obtained in a simple manner, in high yields and high purities, either as a mixture or as isolated product streams. In particular, the process of the invention has the great advantage that especially the ratio of the desired methacrylic acid and alkyl methacrylate, especially MMA, products can be adjusted freely within a wide range and varied by chemical engineering measures and operating parameters.

Claims

1. A process for preparing at least one alkyl methacrylate and methacrylic acid, the process comprising: a) synthesizing methacrolein in a reactor I, b) carrying out oxidative esterification of methacrolein with an alcohol and oxygen to give an alkyl methacrylate in a reactor II and e) reacting at least a portion of the alkyl methacrylate with water to give methacrylic acid in a reactor III.

2. The process according to claim 1, comprising: c) removing excess methacrolein and at least partially removing the alcohol, optionally followed by treating with an acid and/or by carrying out phase separation of an alkyl methacrylate-containing composition, d) of separating the alkyl methacrylate-containing composition and optionally a methacrylic acid-containing composition with supply of water as an organic phase from an aqueous phase in an extraction I, f) transferring a composition comprising the methacrylic acid and the alkyl methacrylate from e) into the extraction I and g) of optionally separating the methacrylic acid from the alkyl methacrylate in a separation stage M.

3. The process according to or 2 claim 1, wherein water of reaction formed in b) is separated from the alkyl methacrylate between b) and e) and fed wholly or partly back to the reactor III for hydrolysis step e).

4. The process according to claim 1, wherein an alcohol formed in e) is wholly or partly removed and wholly or partly fed back to the reactor II for oxidative esterification in b).

5. The process according to claim 2, wherein the alkyl methacrylate-containing composition from c) is passed into the reactor III for performance of e) and, after e), f), d) and g) are conducted in succession.

6. The process according to claim 2, wherein the alkyl methacrylate-containing composition from c) is passed into the extraction I for performance of d), and the organic phase from d) is then fed in a substream to the reactor III for performance of e) and in another substream to the separation stage M for performance of g).

7. The process according to claim 2, wherein the alkyl methacrylate-containing composition from c) is passed into the extraction I for performance of d), and the organic phase from d) is then guided into the separation stage M for performance of g), in which case a substream of an alkyl methacrylate phase from the separation stage M is then fed to the reactor III for performance of e).

8. The process according to claim 5, wherein the aqueous phase from d) is separated into water, an alcohol and a waste stream, the water being fed wholly or partly into the reactor III, the alcohol wholly or partly into the reactor II, and the waste stream to a disposal.

9. The process according to claim 2, wherein the methacrolein is prepared in a) from propionaldehyde and formaldehyde via a Mannich condensation, and the methacrolein removed in c) and the alcohol are recycled into the reactor II.

10. The process according to claim 2, wherein the separation stage M in g) is at least one distillation.

11. The process according to claim 1, wherein the reacting in e) in the reactor III is effected in the presence of at least one heterogeneous catalyst selected from the group consisting of a zeolite, an ion exchange resin and an amorphous acid catalyst at a temperature of 50 to 200? C. and at a pressure of 1.1 to 10 bar.

12. The process according to claim 1, wherein the reacting in e) in the reactor III is effected in the presence of at least one homogeneous catalyst selected from the group consisting of a mineral, and an organic acid at a temperature of 50 to 200? C. and at a pressure of 1.1 to 10 bar.

13. The process according to claim 1, wherein the alcohol is methanol and the alkyl methacrylate is methyl methacrylate.

14. The process according to claim 1, wherein an introduction of a respective stream into the reactor III to obtain pure alkyl methacrylate is preceded either by withdrawal of a substream for transfer into a workup or diversion of an entire stream at least temporarily upstream of the reactor III into the workup.

15. The process according to claim 1, wherein the process is operated in such a way that a molar proportion of isolated methacrylic acid in a sum total of isolated methacrylic acid and isolated alkyl methacrylate is between 0.02 and 1.

16. A plant for preparing an alkyl methacrylate and methacrylic acid, the plant comprising: a) a reactor I for synthesis of methacrolein, b) a reactor II for oxidative esterification of methacrolein to give an alkyl methacrylate in the presence of an alcohol and oxygen, c) a distillation column for distillation of a reactor output from reactor II, an optional treatment with an acid and optionally subsequent phase separation of an alkyl methacrylate-containing phase from the distillation, d) an extraction I for separation of an alkyl methacrylate-containing composition and optionally an methacrylic acid-containing composition with supply of water into an organic phase and an aqueous phase, e) a reactor III for partial hydrolysis of the alkyl methacrylate to methacrylic acid, f) a pipeline from the reactor III which leads directly or indirectly into the extraction I and g) at least one distillation column for separation of the alkyl methacrylate from the methacrylic acid.

17. The process according to claim 11, wherein the at least one heterogeneous catalyst is a cationic ion exchange resin.

18. The process according to claim 12, wherein the at least one heterogeneous catalyst is sulphuric acid, methanesulphonic acid or toluenesulphonic acid.

Description

LIST OF REFERENCE NUMERALS

[0088] FIG. 1 shows a process regime according to embodiment 1. This embodiment is configured such that, after operating step e), the further operating steps are conducted in the sequence f), d) and g).

[0089] FIG. 2 shows a process regime according to embodiment 2. This embodiment is configured such that, after operating step c), the further operating steps are conducted in the sequence d), e), f) and g), this mode of connection resulting in a circulation regime of operating steps d), e) and f).

[0090] FIG. 3 shows a process regime according to embodiment 3. Here, the reaction is effected, after operating step c), in the sequence d), g), e) and f), these operating steps d), g), e) and f) being operated at least partly and/or temporarily in a circulation regime.

[0091] (1) Formaldehyde feed [0092] (2) Propionaldehyde feed [0093] (3) Inlet for a base [0094] (4) Inlet for an acid I [0095] (5) Inlet for an acid (II) [0096] (6) Reactor I (synthesis of methacrolein; operating step a) [0097] (7) Catalyst removal [0098] (8) Isolation of methacrolein [0099] (9) Reactor II (oxidative esterification; operating step b) [0100] (10) Alcohol feed (e.g. methanol) [0101] (11) Oxygen or air inlet [0102] (12) Removal of methacrolein and alcohol (e.g. methanol) (operating step c) [0103] (13) Isolated methacrolein/alcohol mixture [0104] (14) Admixing with acid and optional phase separation [0105] (15) Optional water and acid (II) addition [0106] (16) Reactor III (hydrolysis to methacrylic acid; operating step e) [0107] (17) Extraction I (operating step d) [0108] (18) Separation of the isolated alcohol/H.sub.2O mixture (from operating step d) [0109] (19) Removed H.sub.2O (for recycling or disposal) [0110] (20) Isolated alcohol (e.g. methanol) [0111] (21) Separation stage M (separation of alkyl methacrylate and methacrylic acid; operating step g) [0112] (22) Isolated alkyl methacrylate for further purification [0113] (23) Isolated methacrylic acid for further purification [0114] (24) Disposal [0115] Special conduits: [0116] (A) Catalyst recycling into reactor I [0117] (B) Optional transfer of the methacrolein stream into the methacrolein purification (12) [0118] (C) Recycling of methacrolein removed (with methanol) into (9) [0119] (D) Recycling of methanol into (9) [0120] (E) Optional transfer of the aqueous phase from (14) into (18) [0121] (F) Optional transfer of the water from (18) into (16) [0122] (G) Optional transfer of the water from (18) into (17) [0123] (H) Transfer of product stream from (16) into (17) (operating step f) [0124] In FIG. 2 only: [0125] (I) Substream from (17) into (21) [0126] (J) Substream from (17) into (16) [0127] In FIG. 3 only: [0128] (K) Substream of the alkyl methacrylate phase (22) from (21) into (16)