Bimodal acetic acid manufacture

• US 6,531,630 B2
• Filed: 12/29/2000
• Issued: 03/11/2003
• Est. Priority Date: 12/29/2000
• Status: Active Grant

• Current Assignee: Kenneth Ebenes Vidalin
• Original Assignee: Kenneth Ebenes Vidalin
• Inventors: Vidalin, Kenneth Ebenes
• Primary Examiner(s): Padmanabhan, Sreeni
• Assistant Examiner(s): Forohar, Farhad
• Application Number:
  US09/751,240
• Publication Number:
  US 20020085963A1
• Time in Patent Office: 802 Days
• Field of Search: 518/713, 518/702, 518/700, 560/206, 562/519, 422/148
• US Class Current: 562/519
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 2219/00024 Revamping, retrofitting or modernisation of existing plants
• CPC Class Codes: C01B 2203/061 Methanol production
• CPC Class Codes: C01B 2203/068 Ammonia synthesis
• CPC Class Codes: C01B 3/025 Preparation or purification of gas mixtures for ammonia synthesis
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C07C 29/152 characterised by the reactor used
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 53/08 Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The converting of an existing methanol plant to make acetic acid is disclosed. The converted plant utilizes the steam reformer (10) to which (a) a hydrocarbon ,e.g., natural gas, or a lower alkanol, e.g., methanol, and (b) steam (water) are fed. Syngas is formed in the reformer (10). All or part of the syngas is processed to separate out carbon dioxide (24), carbon monoxide (30) and hydrogen (32), and the separated carbon dioxide (24) is fed either to the existing methanol synthesis loop (12) for methanol synthesis, or back into the feed to the reformer (10) to enhance carbon monoxide formation in the syngas (18). When a lower alkanol is fed to the reformer (10), the methanol synthesis loop (12) is shutdown and isolated from the rest of the plant. Any remaining syngas (38) not fed to the carbon dioxide separator (22) can be converted to methanol in the existing methanol synthesis loop (12) along with carbon dioxide (24) from the separator (22) and/or imported carbon dioxide (25), and hydrogen (35) from the separator (28). The separated carbon monoxide (30) is then reacted with the methanol (36) to produce acetic acid (40) or an acetic acid precursor by a conventional process. When the methanol synthesis loop (12) is shutdown, an imported source of methanol is used.

Claims

1. A method for converting an original methanol plant to a converted plant having bimodal operation, the method comprising the steps of:

providing the original methanol plant having

at least one steam reformer for converting a hydrocarbon to a syngas stream containing hydrogen, carbon monoxide, and carbon dioxide, and

a methanol synthesis loop for converting hydrogen and carbon monoxide from the syngas stream to methanol;

providing for selectively supplying a gaseous feed to the at least one steam reformer, wherein in a first mode the gaseous feed is a hydrocarbon and in a second mode the gaseous feed is a vaporized lower alkanol;

installing a vaporizer for vaporizing a lower alkanol from an imported source into the vaporized lower alkanol;

loading the at least one steam reformer with a hydrocarbon reformation catalyst for syngas generation;

installing a separation unit for separating all or part of the syngas stream into respective streams rich in carbon dioxide, carbon monoxide and hydrogen;

providing for diverting all or part of the syngas stream originally fed to the methanol synthesis loop to the separation unit;

providing for supplying at least a portion of the carbon dioxide-rich stream to the at least one steam reformer, to the methanol synthesis loop, or to a combination thereof;

installing isolation valves for isolating the methanol synthesis loop from the remainder of the converted plant when operated in the second mode;

installing a reactor for reacting carbon-monoxide and methanol to form a product selected from the group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and combinations thereof;

providing for supplying at least a portion of the carbon monoxide-rich stream from the separation unit to the reactor; and

providing for selectively supplying a methanol stream to the reactor in the first mode from the methanol synthesis loop and in the second mode from an imported source.

2. A method for operating the converted plant of claim 1, the method comprising the steps of:

selecting between the first mode and the second mode of operation; and

operating the converted plant in the selected mode,

wherein the first mode of operation has at least the following steps;

feeding the hydrocarbon to the at least one steam reformer, operating the at least one steam reformer to generate syngas,

separating at least a portion of the syngas stream in the separation unit into respective streams rich in carbon dioxide, carbon monoxide and hydrogen,

operating the methanol synthesis loop with a feed comprising (1) carbon dioxide and (2) hydrogen,

reacting at least a portion of the carbon monoxide-rich stream from the separation unit with methanol from the methanol synthesis loop to form the product, and

wherein the second mode of operation has at least the following steps;

vaporizing the lower alkanol,

feeding the vaporized lower alkanol to the at least one steam reformer,

operating the at least one steam reformer to generate syngas,

separating all or part of the syngas stream in the separation unit into respective streams rich in carbon dioxide, carbon monoxide and hydrogen,

isolating the methanol synthesis loop from the remainder of the converted plant, and

reacting at least a portion of the carbon monoxide-rich stream from the separation unit with methanol from an imported source to form the product.

3. The method of claim 2, wherein the first mode is selected and the feed to the methanol synthesis loop comprises imported carbon dioxide.

4. The method of claim 2, wherein the first mode is selected and the feed to the methanol synthesis loop includes a portion of the syngas.

5. The method of claim 2, wherein the first mode is selected and essentially all of the syngas stream is supplied to the separation step.

6. The method of claim 2, wherein the first mode is selected and the hydrogen supplied to the methanol synthesis loop is provided by supplying at least a portion of the hydrogen-rich stream to the methanol synthesis loop.

7. The method of claim 6, wherein the first mode is selected and the amount of the hydrogen-rich stream is in excess of the stoichiometric hydrogen required by the methanol synthesis loop.

8. The method of claim 2, wherein the first mode is selected and essentially all of the carbon dioxide-rich stream is supplied to the methanol synthesis loop.

9. The method of claim 2, wherein essentially all of the carbon monoxide-rich stream is supplied to the reaction step.

10. The method of claim 2, wherein the second mode is selected.

11. The method of claim 10, wherein the lower alkanol is methanol.

12. The method of claim 2, wherein the feed to the at least one steam reformer includes a carbon dioxide-rich stream.

13.The method of claim 2, wherein the feed to the at least one steam reformer includes steam.

13. The method of claim 2, wherein the product is acetic acid.

14. The method of claim 2, wherein

the first mode is selected,

a major portion of the syngas stream is supplied to the separation unit, and

the feed of carbon dioxide and hydrogen to the methanol synthesis loop comprises at least

the carbon dioxide-rich stream from the separation unit,

a minor amount of the syngas stream, and

carbon dioxide from an additional source.

16.The method of claim 2, wherein:

the first mode is selected, all of the syngas stream is supplied to the separation unit, the feed of carbon dioxide and hydrogen to the methanol synthesis loop is selected from;

the carbon dioxide-rich stream from the separation unit,

a portion of the hydrogen-rich stream from the separation unit,

a minor portion of the syngas stream, and

carbon dioxide from an additional source, and

reacting the carbon monoxide-rich stream from the separation unit with the methanol in essentially stoichiometric proportions to form the product.

15. The process of claim 15, wherein the reaction step comprises the intermediate formation of methyl formate and isomerization of the methyl formate to acetic acid.

16. The process of claim 15, wherein the reaction step comprises the intermediate reaction of one mole of CO and two moles of methanol to form methyl acetate and hydrolysis of the methyl acetate to acetic acid and methanol.

17. A method for converting an original methanol plant into a converted plant, the method comprising the steps of:

providing an original methanol plant having at least one steam reformer for converting a hydrocarbon to a syngas stream containing hydrogen and carbon monoxide,

a heat recovery section for cooling the syngas stream,

a compression unit for compressing the syngas stream, and

a methanol synthesis loop for converting at least a portion of the hydrogen and carbon monoxide in the syngas stream to methanol;

providing for selectively supplying a gaseous feed to the at least one steam reformer, wherein in a first mode the gaseous feed is a hydrocarbon and in a second mode the gaseous feed is vaporized lower alkanol;

installing a vaporizer for vaporizing the lower alkanol from an imported source;

loading the at least one steam reformer with a hydrocarbon reformation catalyst for syngas generation;

installing a separation unit for separating the syngas fed thereto into respective streams rich in carbon dioxide, carbon monoxide and hydrogen;

installing isolation valves for isolating the methanol synthesis loop from the remainder of the converted plant when operated in the second mode;

modifying the flow of the syngas stream to allow diverting at least a portion of the syngas stream from the at least one reformer as a diverted syngas stream to the separation unit;

wherein the separation unit is configured to separate the diverted syngas stream into at least a carbon monoxide-rich stream and a hydrogen-rich stream, wherein the quantity of hydrogen in the hydrogen-rich stream is greater than any net hydrogen production of the original methanol plant;

modifying the operation of the methanol synthesis loop when in the first mode by changing the feed thereto to include at least the remaining syngas stream to produce less methanol than the original methanol plant;

installing a reactor for reacting the carbon monoxide-rich stream from the separation unit with methanol to form a product selected from the group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and combinations thereof,

wherein when in the first mode the diversion of the syngas stream is balanced for the approximately stoichiometric production of the methanol from the methanol synthesis loop and the carbon monoxide-rich stream from the separation unit for conversion to the product;

providing for supplying at least a portion of the carbon dioxide-rich stream to the at least one steam reformer, to the methanol synthesis loop, or to a combination thereof;

providing for supplying at least a portion of the carbon monoxide-rich stream from the separation unit to the reactor; and

providing for selectively supplying methanol to the reactor in the first mode from the methanol synthesis loop and in the second mode from an imported source.

21. A method for converting an original methanol plant into a converted plant, the method comprising the steps of:

providing an original methanol plant having

at least one steam reformer for converting a feed comprising hydrocarbon and steam essentially free of carbon dioxide into a syngas stream containing hydrogen and carbon monoxide,

a heat recovery section for cooling the syngas stream,

a compression unit for compressing the syngas stream, and

a methanol synthesis loop for converting at least a portion of the hydrogen and carbon monoxide in the syngas stream to methanol;

providing for selectively supplying a gaseous feed to the at least one steam reformer, wherein in a first mode the gaseous feed is a hydrocarbon and in a second mode the gaseous feed is vaporized methanol from an imported source;

installing a methanol vaporizer for vaporizing the methanol to be fed to the at least one steam reformer;

loading the at least one steam reformer with a hydrocarbon reformation catalyst for syngas generation;

installing a separation unit for separating syngas into a carbon dioxide-rich stream, carbon monoxide-rich stream and a hydrogen-rich stream;

providing for diverting at least a portion of the syngas stream originally fed to the methanol synthesis loop to the separation unit;

providing for recycling at least a portion of the carbon dioxide-rich stream from the separation unit to the at least one steam reformer to increase the carbon monoxide formation relative to the original methanol plant and increase the molar ratio of carbon monoxide to hydrogen;

installing isolation valves for isolating the methanol synthesis loop from the remainder of the converted plant when operated in the second mode;

installing a reactor for reacting carbon monoxide and methanol to form a product selected from the group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and combinations thereof;

providing for supplying at least a portion of the carbon monoxide-rich stream from the separation unit to the reactor; and

providing for selectively supplying methanol to the reactor in the first mode from the methanol synthesis loop and in the second mode from an imported source,

wherein in the first mode the diversion of the syngas stream is balanced for the approximately stoichiometric production of the methanol from the methanol synthesis loop using the remaining portion of the syngas stream and the carbon monoxide-rich stream from the separation unit for conversion to acetic acid in the reactor.

18. The method of claim 19, further comprising modifying the at least one steam reformer to increase carbon monoxide production in the syngas stream.

19. The method of claim 20, wherein the syngas stream comprises carbon dioxide and the separation unit produces a carbon dioxide-rich stream that is recycled to the at least one steam reformer to increase the carbon monoxide production.

20. The method of claims 21, wherein the syngas stream in the original plant has a molar ratio R ((H₂—

CO₂)/(CO+CO₂)) less than about 2.0 or greater than about 2.9 and wherein the syngas stream in the acetic acid plant has an R ratio from about 2.0 to about 2.9.

23. The method of claim 23, wherein the separation unit comprises a solvent absorber and stripper for carbon dioxide recovery and a cryogenic distillation unit for carbon monoxide hydrogen recovery.

22. The method of claim 23, wherein the at least one steam reformer is modified to operate at a higher temperature.

24. The method of claim 23, Wherein the compression unit comprises a three-stage compressor and the syngas stream diversion occurs between the second and third compression stages.

25. The method of claim 26, further comprising modifying the third compressor stage for operation at lower throughput than the original methanol plant.

26. The method of claim 23, wherein the methanol synthesis loop of the original methanol plant comprises a recycle loop compressor, wherein the recycle loop compressor is modified for operation at a lower throughput.

27. A method for converting an original methanol plant to a converted plant, the method comprising the steps of:

providing the original methanol plant having

at least one steam reformer for converting a hydrocarbon to a syngas stream containing hydrogen, carbon monoxide, and carbon dioxide, and

a methanol synthesis loop for converting hydrogen and carbon monoxide from the syngas stream to methanol;

providing for supplying a gaseous feed to the at least one steam reformer, wherein the gaseous feed is a vaporized lower alkanol;

installing a vaporizer for vaporizing a lower alkanol from an imported source into the vaporized lower alkanol;

loading the at least one steam reformer with a hydrocarbon reformation catalyst for syngas generation;

installing a separation unit for separating all or part of the syngas stream into respective streams rich in carbon dioxide, carbon monoxide and hydrogen;

providing for diverting all of the syngas stream originally fed to the methanol synthesis loop to the separation unit;

providing for supplying at least a portion of the carbon dioxide-rich stream to the at least one steam reformer;

installing isolation valves for isolating the methanol synthesis loop from the remainder of the converted plant;

installing a reactor for reacting carbon monoxide and methanol to form a product selected from the group consisting of acetic acid, acetic anhydride, methyl formate, methyl acetate and combinations thereof;

providing for supplying at least a portion of the carbon monoxide-rich stream from the separation unit to the reactor; and

providing for supplying a methanol stream from an imported source.

30. The method of claim 30, wherein the product is acetic acid.

28. A method for operating the converted plant of claim 29, the method comprising the steps of:

vaporizing the lower alkanol, feeding the vaporized lower alkanol to the at least one steam reformer,

operating the at least one steam reformer to generate syngas,

separating all or part of the syngas stream in the separation unit into respective streams rich in carbon dioxide, carbon monoxide and hydrogen,

isolating the methanol synthesis loop from the remainder of the converted plant, and

reacting at least a portion of the carbon monoxide-rich stream from the separation unit with methanol from an imported source to form the product.

29. The method of claim 30, wherein the lower alkanol is methanol.