METHOD FOR IMPROVED REACTVE MONOMER PRODUCTION WITH MEMBRANE FILTRATION

Abstract

The present invention relates to production processes for reactive monomer species. The method described herein may be used in a variety of reactive monomer production processes to optimise the use of polymerisation inhibitor compounds, which may lead to further advantages such as debottlenecking or elimination of process plant separation unit(s). The method provides for the separation of oligomeric/polymeric species, inhibitor compounds and reactive monomer, optionally in the presence of unreacted raw materials or solvent(s), within the production process by means of membrane filtration, particularly through the use of solvent stable membranes, and in particular by applying organic solvent nanofiltration membranes.

Claims

1-14. (canceled)

15. An apparatus for the production of reactive monomers, comprising: a) at least one inhibitor feed port; b) a primary purification unit PPU, separating a feed stream comprising reactive monomers into RM-stream 1, enriched in reactive monomers and RM-depleted stream, depleted in reactive monomers, wherein enriched means that the concentration of the reactive monomers in RM-stream 1 is higher than in the feed stream of the PPU and depleted means, that the concentration of the reactive monomers in the RM-depleted stream is lower than in the feed stream of the PPU; c) an inhibitor separation unit ISU, separating RM-stream 1, or an intermediate modified RM-stream 1, into RM-stream 2, enriched in the reactive monomers, and an inhibitor stream, enriched in inhibitors and depleted in reactive monomers, wherein enriched means that the concentration of reactive monomers in RM stream 2 is higher than in the feed stream of the ISU and that the concentration of inhibitors in the inhibitor stream is higher than in the feed stream of the ISU; and wherein the apparatus is designed such that the inhibitor stream is recycled to at least one inhibitor feed port, and the ISU is a membrane separation unit comprising OSN nanofiltration membranes having a molecular weight cut off from 150 to 900 g/mol.

16. The apparatus of claim 15, further comprising a polymer separation unit PSU, producing a polymer/oligomer waste stream, and a second stream, depleted in polymers and/or oligomers compared to the feed stream of the PSU.

17. The apparatus of claim 16, wherein the PSU is a membrane separation unit, comprising membranes with a molecular weight cut off from 500 to 1000 Da or of from 1 to 5 kDa.

18. The apparatus of claim 16, wherein: a) the polymer/oligomer waste stream can be withdrawn from the apparatus; and/or b) the PSU can be switched on and off during operation of the apparatus.

19. The apparatus of claim 15, further comprising a reactive monomer separation unit RMSU, which separates the main amount of reactive monomers from the feed stream of the RMSU to produce RM stream 2b and which, in addition, produces an RM residue stream, which is depleted in reactive monomers compared to the feed stream of the RMSU.

20. The apparatus of claim 19, further comprising a polymer separation unit PSU, producing a polymer/oligomer waste stream, and a second stream, depleted in polymers and/or oligomers compared to the feed stream of the PSU and wherein the PSU is a membrane separation unit comprising membranes with a molecular weight cut off from 500 to 1000 Da or of from 1 to 5 kDa.

21. The apparatus of claim 19, wherein: a) RM stream 1 is fed into the RMSU; or b) RM stream 1 is fed to a PSU and the polymer/oligomer depleted stream of the PSU is fed into the RMSU or the ISU.

22. The apparatus of claim 19, wherein: a) the RM residue stream is fed into the ISU; or b) the RM residue stream is fed to a PSU and that the polymer and/or oligomer depleted stream of the PSU is fed to the ISU.

23. The apparatus of claim 19, wherein: a) RM stream 2 is recycled to the RMSU or further processed or withdrawn; or b) RM stream 2 is fed to a PSU and the polymer and/or oligomer depleted stream of the PSU is recycled to the RMSU.

24. A process for the production of reactive monomers, comprising the steps: I. separating a feed stream comprising reactive monomers within a PPU to obtain RM-stream 1 and an RM-depleted stream; II. adding at least one inhibitor to a process stream or device used in the process during, before or after step I via at least one inhibitor feed port; III. separating RM-stream 1, or an intermediately modified RM-stream 1, into RM-stream 2 and an inhibitor stream within an ISU; wherein: a) the inhibitor stream obtained from the ISU is recycled to at least one inhibitor feed port; and b) a membrane separation unit is used as the ISU, comprising OSN nanofiltration membranes having a molecular weight cut off from 150 to 900 g/mol.

25. The process of claim 24, further comprising: IV. separating oligomers and/or polymers from the process with a PSU to produce a polymer/oligomer waste stream, and a second stream, depleted in polymers and/or oligomers compared to the feed stream of the PSU; and/or V. separating reactive monomers from the process with a RMSU.

26. The process of claim 25, wherein the PSU is a membrane separation unit comprising membranes with a molecular weight cut off from 500 to 1000 Da or of from 1 to 5 kDa.

27. The process of claim 25, wherein: a) the polymers and/or oligomers separated with the PSU are withdrawn from the apparatus; and/or b) that the PSU is switched on or off during operation of the apparatus, if the polymer and/or oligomer content in at least one process stream or device exceeds a specified value.

28. The process of claim 25, wherein process steps are carried out in one of the following sequences: a) II, I, III; b) II, I, III, IV; c) II, I, IV, III; e) II, I, IV, V, III; f) II, I, V, IV, III; or g) II, I, V, III, IV.

29. The process of claim 28, wherein the inhibitors are added during step II and reach a concentration in a process stream upstream of the ISU of from 1-100000 parts per million.

30. The process of claim 24, wherein the inhibitors are added during step II and reach a concentration in a process stream upstream of the ISU of from 1-100000 parts per million.

31. The process of claim 28, wherein: a) the reactive monomers are selected from the group consisting of: styrene; (meth)acrylic acid; (meth)acrylic acid esters; acrylonitrile; butadiene; isoprene; chloroprene; vinyl acetate; ethylene; and propylene; and/or b) the inhibitors are selected from the group consisting of: hydroxylamines; oximes; sterically hindered stable nitroxyl radicals; quinone methide inhibitors; nitroaromatics; nitrosoaromatics; benzoquinones; hydroquinones; phenothiazines; phenolic antioxidants; N,N-dialkyl-p-phenylene diamines; and N,N-dialkyl-p-benzoquinone diimides.

32. The process of claim 24, wherein: a) the reactive monomers are selected from the group consisting of: styrene; (meth)acrylic acid; (meth)acrylic acid esters; acrylonitrile; butadiene; isoprene; chloroprene; vinyl acetate; ethylene; and propylene; and/or b) the inhibitors are selected from the group consisting of: hydroxylamines; oximes; sterically hindered stable nitroxyl radicals; quinone methide inhibitors; nitroaromatics; nitrosoaromatics; benzoquinones; hydroquinones; phenothiazines; phenolic antioxidants; N,N-dialkyl-p-phenylene diamines; and N,N-dialkyl-p-benzoquinone diimides.

33. The process of claim 24, wherein said process is carried out using an apparatus comprising: a) at least one inhibitor feed port; b) a primary purification unit PPU, separating a feed stream comprising reactive monomers into RM-stream 1, enriched in reactive monomers and RM-depleted stream, depleted in reactive monomers, wherein enriched means that the concentration of the reactive monomer in RM-stream 1 is higher than in the feed stream of the PPU and depleted means, that the concentration of the reactive monomers in the RM-depleted stream is lower than in the feed stream of the PPU; c) an inhibitor separation unit ISU, separating RM-stream 1, or an intermediate modified RM-stream 1, into RM-stream 2, enriched in the reactive monomer, and an inhibitor stream, enriched in inhibitors and depleted in reactive monomers, wherein enriched means that the concentration of reactive monomers in RM stream 2 is higher than in the feed stream of the ISU and that the concentration of inhibitors in the inhibitor stream is higher than in the feed stream of the ISU; and wherein the apparatus is designed such that the inhibitor stream is recycled to at least one inhibitor feed port, and the ISU is a membrane separation unit comprising OSN nanofiltration membranes having a molecular weight cut off from 150 to 900 g/mol.

34. The process of claim 33, wherein said process is used on a stream of reactive monomer raw material comprising, at least one reactive monomer selected from the group consisting of styrene, (meth)acrylic acid and (meth)acrylic acid esters, acrylonitrile, butadiene, isoprene, chloroprene, vinyl acetate, ethylene and propylene.

Description

DESCRIPTION OF THE FIGURES

[0279] FIG. 1: Apparatus and process for production of reactive monomers with inhibitor recycling (Inhibitor feed port not shown in the Figure).

[0280] FIG. 2a: Apparatus and process for production of reactive monomers with inhibitor recycling. A polymer separation unit, which allows to separate and withdraw polymers and/or oligomers from the apparatus/process, is arranged upstream of the inhibitor separation unit. (Inhibitor feed port not shown in the Figure).

[0281] FIG. 2b: Apparatus and process for production of reactive monomers with Inhibitor recycling and, compared to FIG. 2a alternative arrangement, of the polymer separation unit which allows to separate and withdraw polymers and/or oligomers from the apparatus from RM stream 2 (Inhibitor feed port not shown in the Figure).

[0282] FIG. 3: Apparatus and process for production of reactive monomers with inhibitor recycling. A primary purification unit and a reactive monomer separation unit are arranged upstream of an inhibitor separation unit (inhibitor feed port not shown in the Figure)

[0283] FIG. 4a: Apparatus and process for production of reactive monomers with inhibitor recycling. A primary purification unit, a polymer separation unit and a reactive monomer separation unit are arranged upstream of the inhibitor separation unit (Inhibitor feed port not shown in the Figure).

[0284] FIG. 4b: Apparatus and process for production of reactive monomers with inhibitor recycling. A primary purification unit and a reactive monomer separation unit are arranged upstream and a polymer separation unit downstream of the inhibitor separation unit (Inhibitor feed port not shown in the Figure).

[0285] FIG. 4c: Apparatus and process for production of reactive monomers with inhibitor recycling. A reactive monomer purification unit and a polymer separation unit are arranged downstream of the primary purification unit and upstream of the inhibitor separation unit (Inhibitor feed port not shown in the Figure). RM stream 2, which might comprise reactive monomers, is recycled to the RMSU. Polymers and oligomers are withdrawn via the polymer/oligomer waste stream.

[0286] FIG. 4d: Apparatus and process for production of reactive monomers with inhibitor recycling. A reactive monomer separation unit and a polymer separation unit are arranged downstream of the primary purification unit and upstream of the inhibitor separation unit. The inhibitor stream is recycled and RM stream 2 withdrawn or further processed. Preferably PPU and/or RMSU are distillation devices in this embodiment (Inhibitor feed port not shown in the Figure).

[0287] FIG. 4e: Apparatus and process for production of reactive monomers with inhibitor separation unit arranged downstream of the reactive monomer separation unit. The inhibitor stream is recycled and RM stream 2 withdrawn or further processed. Preferably PPU and/or RMSU are distillation devices in this embodiment (Inhibitor feed port not shown in the Figure).

[0288] FIG. 5: Cross Flow filtration apparatus as used in the examples.

[0289] FIG. 6: Results of Example 2.