PRODUCTION SYSTEM/PRODUCTION PROCESS FOR ACRYLIC ACID AND PRECURSORS THEREOF

• US 20170029352A1
• Filed: 07/29/2016
• Published: 02/02/2017
• Est. Priority Date: 07/31/2015
• Status: Active Grant

• Current Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Original Assignee: Novomer, Inc (Danimer Scientific, Inc.)
• Inventors: Vinograd, Dmitry, Slowik, Michael A., Sookraj, Sadesh H., Pokrovski, Konstantin A., Ruhl, John B.
• Granted Patent: US 10,703,702 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01J 19/1862 placed in series
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/785 characterised by the apparatus used
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

Provided herein are systems, and methods of using such systems, for producing acrylic acid from ethylene oxide and carbon monoxide on an industrial scale. The production system/production process has various unit operations, including, for example, a β-propiolactone production system/production process configured to produce β-propiolactone from ethylene oxide and carbon monoxide; a polypropiolactone production system/production process configured to produce polypropiolactone from β-propiolactone; and a glacial acrylic acid production system/production process configured to produce acrylic acid with a high purity by thermolysis of polypropiolactone.

Claims

1. A process for producing acrylic acid from a source of β

-propiolactone, comprising;

contacting a BPL feed stream with a polymerization initiator in a polypropiolactone reaction zone having at least one polymerization reactor that produces a polypropiolactone outlet stream comprising polypropiolactone and β

-propiolactone; and

,

passing at least a portion of the polypropiolactone outlet stream to an acrylic acid production zone comprising a thermolysis reactor that receives the at least a portion of the polypriolactone outlet stream and produces an acrylic acid stream comprising acrylic acid.

2. The process of claim 1 wherein the polymerization initiator is selected from the group consisting of quaternary ammonium salts, alkali metal salts of carboxylic acids, ammonium acrylate, ammonium acetate, phosphonium acrylate, phosphonium salts, sodium acrylate, potassium acrylate, phosphonium acetate, tetra-n-butylammonium acrylate, sodium acetate, potassium acetate, tetra-n-butylammonium acetate, trimethylphenylammonium acrylate, trimethylphenylammonium acetate, or tetraphenyl phosphonium acrylate.

3. The process of claim 1 wherein a radical polymerization inhibitor is present in the polypropiolactone reaction zone.

4. The process of claim 3 wherein the radical polymerization inhibitor comprises phenothiazine preferably in a concentration of 50-500 ppmw and more preferably in a concentration of 150 to 250 ppm.

5. The process of claim 1 wherein the polypropiolactone reactor zone comprises a first polymerization reactor and a second polymerization reactor;

the first polymerization reactor produces an intermediate mixture comprising polypropiolactone, β

-propiolactone and polymerization initiator;

the intermediate mixture and additional polymerization initiator passes to the second polymerization reactor that produces at least a portion of the polypropiolactone outlet stream; and

at least a portion of the polypropiolactone outlet stream comprises polypropiolactone, β

-propiolactone, and polymerization initiator.

6. The process of claim 5 wherein polypropiolactone is separated from the portion of the polypropiolactone outlet stream produced by the second reaction zone in at least one of an evaporator, flash tank evaporator wiped film evaporator or a distillation apparatus.

7. The process of claim 1 wherein the polypropiolactone outlet stream comprises a solid polypropiolactone.

8. The process of claim 1 wherein the at least one polymerization reaction zone contains at least one of a continuous reactor, semi-batch reactor, a continuous-flow stirred-tank reactor, a loop reactor, or plug-flow reactor.

9. The process of claim 1 wherein acrylic acid reaction zone comprises at least one of a thermolysis reactor in the form of a continuous stirred tank reactor, plug flow reactor, wiped film evaporator, a moving bed reactor;

kneader reactor, and fluidized bed reactor for receiving molten polypropiolactone.

10. The process of claim 1 wherein at least a portion of the acrylic acid stream is separated into (i) an acrylic acid stream comprises acrylic acid having a purity of at least 90%, and (ii) an organic heavies stream.

18. The process of claim 10 wherein the carbonylation reactor operates at a temperature from −

20°

C. to 160°

C. and operates at a pressure from 100 psig to 5000 psig, and produces β

-propiolactone with a selectivity of at least 90% and preferably at least 99%.

11. A process for producing acrylic acid from ethylene oxide and carbon monoxide, comprising:

contacting input components comprising carbon monoxide feed, an ethylene oxide feed, and a catalyst recycle stream with a carbonylation catalyst and a solvent in a carbonylation reaction zone and producing a BPL outlet stream comprising β

-propiolactone, ethylene oxide and carbonylation catalyst;

passing at least a portion the BPL outlet stream to a carbonylation catalyst recycling zone and separating said portion into i) BPL separation stream comprising a portion of the BPL outlet stream from which at least some carbonylation catalyst has been removed and ii) the recycle stream stream, comprising β

-propiolactone, solvent, ethylene oxide, carbonylation catalyst, succinic anhydride, and acetaldehyde;

passing at least a portion of the recycle stream to the carbonylation reaction zone;

purifying at least a portion of the BPL separation stream in a BPL purification zone comprising at least one separator, wherein the BPL purification zone produces a purified BPL stream and rejects a portion of β

-propiolactone and rejects solvent, ethylene oxide, and carbonylation catalyst, succinic anhydride and acetaldehyde in one or more rejection streams;

streams comprising at least one of β

-propiolactone, solvent, ethylene oxide, and carbonylation catalyst, succinic anhydride and acetaldehyde;

passing at least a portion of the purified BPL stream and a polymerization initiator to a polypropiolactone reaction zone having at least one polymerization reactor that contacts the mixed bottoms with the polymerization initiator and produces a polypropiolactone outlet stream comprising polypropiolactone and β

-propiolactone; and

,

passing at least a portion of the polypropiolactone outlet stream to an acrylic acid production zone comprising a thermolysis reactor that receives the at least a portion of the polypriolactone outlet stream and produces an acrylic acid stream comprising acrylic acid.

12. The process of claim 11 wherein the BPL purification zone produces an EO rejection stream as one of the rejection streams, said EO rejection stream comprising ethylene oxide and at least a portion of the EO rejection is passed to the carbonylation reaction zone.

13. The process of claim 11 wherein the BPL purification zone produces a solvent recovery stream as one of the EO rejection streams, said solvent recovery stream comprising solvent at least a portion of the solvent recovery stream is passed to the carbonylation reaction zone.

14. The process of claim 11 wherein I) the carbonylation catalyst recycling zone comprises one or more membrane systems from which the catalyst recycle stream is recovered as a retentate and BPL separation stream is recovered as a permeate;

and II) the BPL purification zone comprises a.) an EO recovery section comprising at least one distillation column that receives at least a portion of the BPL separation stream and produces an EO stream containing ethylene oxide that is passed to the carbonylation reactor and a solvent bottoms stream containing solvent and β

-propiolactone, b.) a solvent recovery section comprising at least one distillation column that receives at least a portion of the solvent bottoms stream and produces a overhead recovered solvent stream comprising solvent that is passed to the carbonylation zone and a BPL bottoms stream comprising β

-propiolactone, and c.) a BPL concentration section comprising at least one distillation column that receives the BPL bottoms stream and produces an bottoms rejection stream and produces the purified BPL as an overhead stream.

15. The process of claim 11, wherein at least one of the carbon monoxide feed and the ethylene oxide from the carbon monoxide source have at least one of an oxygen level of less than 5 ppm and a water level of less than 5 ppm.

16. The process of claim 11 wherein the carbonylation catalyst is at least one of a cobalt-aluminum catalyst;

a carbonyl cobaltate in combination with an aluminum porphyrin compound, a carbonyl cobaltate in combination with an aluminum salen compound, a carbonyl cobaltate in combination with an aluminum salophen compound, and Al(TPP)Co(CO)4).

17. The process of claim 11 wherein the carbonylation catalyst is at least partially dissolved in a catalyst solvent and the solvent comprises at least one an ether, a hydrocarbon, tetrahydrofuran, hexane, 2,5-dimethyl tetrahydrofuran, sulfolane, N-methyl pyrrolidone, 1,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ethers, methyl tertbutyl ether, diethylether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxy ethane, acetone, and methylethyl ketone.

19. The process of claim 11 wherein the carbonylation reactor zones contains at least one reactor selected from the group consisting of a continuous reactor or a semi-batch reactor a continuous-flow stirred-tank reactor or a loop reactor.

20. The process of claim 11 wherein the BPL outlet stream satisfies on a mass fraction basis the condition of having;

at least 0.1 β

-propiolactone;

at most 0.9 solvent;

at most 0.07 ethylene oxide;

between 0.0005 to 0.04 of carbon monoxide;

at most 0.005 catalyst;

at most 0.07 acetaldehyde;

or at most 0.07 succinic anhydride.

21. The process of claim 11 wherein the BPL outlet stream satisfies on a mass fraction basis the condition of having;

at least 0.1 and at most 0.4 β

-propiolactone;

at least 0. and at most 0.9 solvent;

at least 0.005 and at most 0.07 ethylene oxide;

between 0.0005 to 0.001 of carbon monoxide;

at least 0.0001 and at most 0.005 catalyst;

at least 0.0001 and at most 0.06 acetaldehyde;

or at least 0.0001 and at most 0.06 succinic anhydride.

22. The process of claim 11 wherein the carbonylation catalyst recycling zone includes a ceramic membrane or a polymeric membrane preferably with at least one of a carbonylation catalyst rejection rate greater than 95% or a permeability of greater than 1.0 L·

m-2·

hr-1 bar-1.

23. The process of claim 11 wherein the BPL concentration section includes a vacuum column and the purified BPL stream is recovered as a vacuum column overhead stream having a β

-propiolactone purity of at least 99% and preferably at least 99.5% and most preferably 99.9%.

24. A process for producing acrylic acid from ethylene oxide and carbon monoxide, comprising:

contacting carbon monoxide feed, an ethylene oxide feed, an CO overhead stream and a BPL recycle stream with a carbonylation catalyst and a solvent in a carbonylation reaction zone and producing a BPL outlet stream comprising β

-propiolactone, solvent, ethylene oxide, carbon monoxide, carbonylation catalyst, acetaldehyde, and succinic anhydride;

passing at least a portion of the BPL outlet stream to a CO/EO separator and recovering i.) the CO separator overhead stream wherein the CO separator overhead stream comprises ethylene oxide and carbon monoxide and ii.) an CO separator bottoms stream comprising β

-propiolactone, solvent, carbonylation catalyst, acetaldehyde, succinic anhydride, and ethylene oxide;

passing at least a portion of the CO separator overhead stream to the carbonylation reaction zone;

passing at least a portion the CO separator bottoms stream to a membrane separation section of a carbonylation catalyst recycling zone and separating said at least a portion of the CO separator bottoms stream into i) a BPL recycle stream comprising a retentate containing separated carbonylation catalyst, solvent, and β

-propiolactone and ii) a BPL separation stream comprising a permeate containing β

-propiolactone, solvent, acetaldehyde, succinic anhydride, ethylene oxide and carbonylation catalyst;

passing at least a portion of the BPL recycle stream to the carbonylation reaction zone;

passing at least a portion of the BPL separation stream to a BPL purification zone comprising at least one separation zone that separates the BPL separation stream into a solvent recycle stream comprising solvent, and a purified BPL stream comprising β

-propiolactone and carbonylation catalyst;

passing at least a portion of the purified BPL stream and a polymerization initiator to a polypropiolactone reaction zone having at least one polymerization reactor that contacts the at least a portion of the purified BPL stream with the polymerization initiator and produces a polypropiolactone outlet stream comprising polypropiolactone and β

-propiolactone;

passing at least a portion of the polypropiolactone outlet stream to a PPL/BPL processing zone having at least one separation zone to produce i.) an PPL/BPL overhead stream that increases the concentration of β

-propiolactone relative to the polypropiolactone outlet stream and ii) a PPL/BPL separator bottoms stream that comprises polypropiolactone;

passing at least a portion of the PPL/BPL overhead stream to the polypropionate reaction zone;

passing at least a portion of the a PPL/BPL bottoms stream to an acrylic acid production zone comprising a thermolysis reactor that receives the at least a portion of the a polypropiolactone outlet stream and produces an acrylic acid stream; and

,

separating at least a portion of the acrylic acid stream in a separator into (i) acrylic acid stream comprising acrylic acid having a purity of at least 90%, and (ii) an organic heavies stream.

25. The process of claim 24 wherein the acrylic acid stream has a acrylic acid purity of greater than 99.5% and comprises glacial acrylic acid.

26. The process of claim 24 wherein the at least one polymerization reactor produces polypropiolactone at a polypropiolactone conversion of at least 50%.

27. The process of claim 24 wherein the at least one separation zone in the PPL/BPL processing zone comprises at least one flash tank and/or at least one evaporator.

28. The process of claim 27 wherein the at least one evaporator is at least one wiped film evaporator, thin film evaporator, or falling film evaporator.

29. The process of claim 24 wherein the carbonylation reactor zone operates at a temperature between 30°

C. and 160°

C. and a pressure between 100 psig and 5000 psig.

30. The process of claim 24 wherein the CO separator is a flash tank.

31. The process of claim 24, wherein the membrane separation section comprises at least one membrane selected from the group consisting of ceramic membranes and/or polymeric membranes wherein the at least one membrane has a rejection rate of greater than 95% and/or a permeability of greater than 1.0 L·

m-2·

hr-1 bar-1

32. The process of claim 24 wherein the at least one distillation column operates at or below atmospheric pressure and at a temperature of less than 120°

C.

33. The process of claim 24 wherein the solvent recycle stream comprises solvent and less than 15 wt % of β

-propiolactone, ethylene oxide, carbon monoxide, acetaldehyde, or succinic anhydride, or any combinations thereof.

34. The process of claim 24 wherein the purified BPL stream comprises (i) β

-propiolactone and (ii) less than 1 wt % of solvent, ethylene oxide, carbon monoxide, acetaldehyde, or succinic anhydride, or any combinations thereof.

35. A process for producing glacial acrylic acid from ethylene oxide and carbon monoxide, comprising:

contacting carbon monoxide feed, an ethylene oxide feed, an CO overhead stream and a BPL recycle stream with a carbonylation catalyst and a solvent in a carbonylation reaction zone and producing a BPL outlet stream comprising β

-propiolactone, solvent, ethylene oxide, carbon monoxide, carbonylation catalyst, acetaldehyde, and succinic anhydride;

passing at least a portion of the BPL outlet stream to a CO separator and recovering i.) the CO overhead stream wherein the CO overhead stream comprises ethylene oxide and carbon monoxide and ii.) a CO bottoms stream comprising β

-propiolactone, solvent, carbonylation catalyst, acetaldehyde, succinic anhydride, ethylene oxide and carbon monoxide;

passing at least a portion of the CO overhead stream to the carbonylation reaction zone;

passing at least a portion the CO bottoms stream to a membrane separation section of a carbonylation catalyst recycling zone and separating said at least a portion of the CO bottoms stream into i) a BPL recycle stream comprising a retentate containing separated carbonylation catalyst, solvent and β

-propiolactone and ii) a BPL separation stream comprising a permeate containing β

-propiolactone, solvent, acetaldehyde, succinic anhydride, ethylene oxide, carbon monoxide, and carbonylation catalyst;

passing at least a portion of the BPL recycle stream to the carbonylation reaction zone;

purifying the BPL separation stream in a BPL purification zone comprising at least one distillation column that further separates the BPL separation stream into a solvent recycle stream comprising solvent and a purified BPL stream comprising β

-propiolactone;

passing at least a portion of the purified BPL stream and a polymerization initiator to a polypropiolactone reaction zone having at least one polymerization reactor that contacts the at least a portion of the purified BPL stream with the polymerization initiator and produces a polypropiolactone outlet stream comprising polypropiolactone and β

-propiolactone; and

,

passing at least a portion of the polypropiolactone outlet stream to an acrylic acid production zone comprising a thermolysis reactor that receives the at least a portion of the polypropiolactone outlet stream and produces an acrylic acid stream; and

,

separating at least a portion of the acrylic acid stream in a condenser into (i) a acrylic acid stream comprises acrylic acid having a purity of at least 90%, and (ii) an organic heavies stream.

36. The process of claim 35 wherein the acrylic acid stream has a acrylic acid purity of greater than 99.5% and comprises glacial acrylic acid.

37. The process of claim 35 wherein the at least a portion of the polypropiolactone outlet stream that passes to the acrylic acid production zone first passes to a polypropiolactone purification zone, comprising a PPL ion exchange zone comprising a resin column that purifies the at least a portion of the polypropiolactone outlet stream that passes to the acrylic acid production zone so that it comprises at least 90 wt % of polypropiolactone and removes an ionic species stream comprising cationic carbonylation catalyst species and anionic carbonylation catalyst species.

38. The process of claim 35 wherein at least a portion of the polypropiolactone outlet stream that passes to the acrylic acid production zone passes from the polypropiolactone purification zone first passes to a polypropiolactone processing zone before passing to the acrylic acid production zone and the polypropiolactone processing zone converts the at least a portion of the purified polypropiolactone outlet stream that passes to the acrylic acid production zone to solid form.

39. The process of claim 35 wherein a.) at least a portion of the polypropiolactone outlet stream that passes to the acrylic acid production zone passes from the polypropiolactone purification zone to a PPL/BPL processing zone before passing to the acrylic acid production zone and the PPL/BPL processing zone has at least one separation zone to produce i.) an overhead stream that increases the concentration of β

-propiolactone in the at least a portion of the polypropiolactone outlet stream that passes to the acrylic acid production zone and ii.) a PPL/BPL bottoms stream that comprises polypropiolactone and b.) a condensate ion exchange zone comprising a resin column receives at least a portion of the organic heavies and separates the organic heavies into a heavies output stream and an ionic species stream comprising cationic carbonylation catalyst species and anionic carbonylation catalyst species.

40. A method for continuously producing polypropiolactone, comprising:

continuously feeding β

-propiolactone into a first reactor;

continuously feeding polymerization initiator into the first reactor;

producing a first mixture comprising polypropiolactone and unreacted β

-propiolactone in the first reactor,

wherein the first reactor comprises;

a β

-propiolactone inlet to receive the β

-propiolactone from a β

-propiolactone source,

a first initiator inlet to receive the initiator from a initiator source, and

a first mixture outlet to output the first mixture; and

transferring the first mixture from the first reactor to a second reactor;

optionally feeding additional initiator from the initiator source to the second reactor;

producing a second mixture comprising polypropiolactone and unreacted β

-propiolactone,

wherein the second reactor comprises;

a mixture inlet to receive the first mixture from the first reactor,

optionally, a second initiator inlet to receive the additional initiator from the initiator source, and

a second mixture outlet to output the second mixture.

41. A polypropiolactone production system, comprising:

a β

-propiolactone source;

a first reactor comprising;

a β

-propiolactone inlet to receive β

-propiolactone from the β

-propiolactone source,

a bed of supported catalyst or supported catalyst precursor,

a first mixture outlet to output a first mixture, wherein the first mixture comprises polypropiolactone and unreacted β

-propiolactone; and

optionally, a second reactor positioned after the first reactor, comprising;

a mixture inlet to receive the first mixture from the first reactor,

a second bed of supported catalyst or supported catalyst precursor,

a second mixture outlet to output a second mixture, wherein the second mixture comprises polypropiolactone and unreacted β

-propiolactone.

42. A solid transportable polymer composition, comprising:

at least 95 wt % of polypropiolactone;

less than 1 ppm of cobalt or ions thereof;

less than 10 ppm of aluminum or ions thereof;

less than 10 ppm acetic acid;

less than 500 ppm of tetrahydrofuran; and

less than 10 ppm of succinic anhydride

less than 10 ppm β

-propiolactone

less than 6000 ppm water

43. A β

-propiolactone composition, comprising;

at least 99 wt % of β

-propiolactone;

less than 10 ppm of cobalt or ions thereof;

less than 10 ppm of aluminum or ions thereof;

less than 300 ppm of acetic acid;

less than 500 ppm of succinic anhydride;

less than 500 ppm of tetrahydrofuran;

less than 100 ppm Ethylene Oxide;

less than 100 ppm acetaldehyde;

an average molecular weight of polypropiolactone of between 800 and 100000 g/mol.

44. A β

-propiolactone production system, comprising;

a carbon monoxide source;

an ethylene oxide source;

a carbonylation catalyst source;

a solvent source;

a recycled solvent storage tank;

a reactor comprising;

at least one inlet to receive carbon monoxide from the carbon monoxide source, ethylene oxide from the ethylene oxide source, carbonylation catalyst from the carbonylation catalyst source, and solvent from the solvent source and the recycled solvent storage tank,

an outlet to output a mixture, wherein the mixture comprises β

-propiolactone, solvent, unreacted carbon monoxide, unreacted ethylene oxide, and carbonylation catalyst; and

a purification apparatus configured to;

separate solvent from the mixture, and

transfer the separated solvent to the recycled solvent reservoir.

45. A glacial acrylic acid production system, comprising:

a polypropiolactone source comprising;

at least 99 wt % of polypropiolactone;

less than 1 ppm of cobalt or ions thereof;

less than 10 ppm of aluminum or ions thereof;

less than 10 ppm of acetic acid;

less than 10 ppm of succinic anhydride;

less than 1 wt % β

-polypropiolactone;

less than 10 ppm of tetrahydrofuran; and

less than 200 ppm of water; and

a reactor comprising;

an inlet configured to receive the polypropiolactone from the polypropiolactone source, and

an outlet configured to output a mixture, wherein the mixture comprises glacial acrylic acid.