Ammonia production with enriched air reforming and nitrogen injection into the synthesis loop

• US 5,736,116 A
• Filed: 10/25/1995
• Issued: 04/07/1998
• Est. Priority Date: 10/25/1995
• Status: Expired due to Term

• Current Assignee: MW Kellogg Limited (KBR Incorporated)
• Original Assignee: MW Kellogg Limited (KBR Incorporated)
• Inventors: Knez, Stan A., LeBlanc, Joseph Ray
• Primary Examiner(s): LANGEL, WAYNE A
• Application Number:
  US08/547,853
• Time in Patent Office: 895 Days
• Field of Search: 423/359, 423/362
• US Class Current: 423/359
• CPC Class Codes: C01B 2203/143 Three or more reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/147 Three or more purification steps in series
• CPC Class Codes: C01B 2203/82 Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/025 Preparation or purification of gas mixtures for ammonia synthesis
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01C 1/0405 from N2 and H2 in presence of a catalyst
• CPC Class Codes: C01C 1/0482 Process control; Start-up or cooling-down procedures
• CPC Class Codes: F25J 2215/50 Oxygen or special cases, e.g. isotope-mixtures or low purity O2
• CPC Class Codes: F25J 3/04539 for the H2/CO synthesis by partial oxidation or oxygen consuming reforming processes of fuels
• CPC Class Codes: F25J 3/04587 for the NH3 synthesis, e.g. for adjusting the H2/N2 ratio
• CPC Class Codes: F25J 3/04593 The air gas consuming unit is also fed by an air stream
• CPC Class Codes: F25J 3/04969 Retrofitting or revamping of an existing air fractionation unit
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

A retrofit method for increasing production capacity of an ammonia plant having a front end including in series primary and secondary reformers and a shift converter for reacting a hydrocarbon feed, steam and air to form a make-up syngas stream comprising hydrogen and nitrogen at about design stoichiometry, and a synthesis loop wherein a recycle syngas stream is combined with the make-up gas to form a syngas feed to ammonia converters. The retrofit involves the installation of an air separation unit to supply oxygen and nitrogen streams. The oxygen is used to enrich air supplied to the secondary reformer and increase the hydrogen content of the make-up gas substantially above the design stoichiometry and capacity. The nitrogen stream is supplied to the synthesis loop to obtain a desired hydrogen to nitrogen ratio in the syngas feed to the ammonia converters and compensate for the excess hydrogen in the make-up gas. The synthesis loop, if desired, is upgraded to include a high activity catalyst converter for increased ammonia production.

Claims

1. A retrofit method for increasing the production capacity of an ammonia plant having a front end including in series primary and secondary reformers and high and low temperature shift converters for reacting a hydrocarbon feed, steam and air to form a makeup syngas stream comprising hydrogen and nitrogen at a design stoichiometry of about 3, and a synthesis loop wherein a recycle syngas stream is combined with the makeup gas to form a syngas feed to ammonia converters, comprising the steps of:

enriching air supplied to the secondary reformer to an oxygen content of 25 to 40 volume percent and increasing the hydrogen content of the makeup syngas stream above the design stoichiometry;

supplying a substantially pure nitrogen stream to the synthesis loop to obtain a desired hydrogen to nitrogen ratio in the syngas feed to the ammonia converters.

2. The method of claim 1, including installing an air separation unit to form oxygen-rich and nitrogen-rich streams, wherein the oxygen-rich stream is added to air in the enrichment step, and wherein the nitrogen-rich stream is used as a source for the substantially pure nitrogen stream.

3. The method of claim 2, wherein the existing synthesis loop capacity of the ammonia plant exceeds the existing front end capacity prior to the retrofit.

4. The method of claim 1, further comprising the step of modifying the synthesis loop to increase the capacity of the synthesis loop to exceed the capacity of the front end existing before the retrofit.

5. The method of claim 1, wherein the ammonia plant includes a methanator for removing carbon oxides to condition the makeup syngas stream for the synthesis loop, and the nitrogen supply step comprises injecting a nitrogen stream into the makeup syngas stream upstream from the methanator.

6. The method of claim 1, wherein the nitrogen stream is essentially free of oxygen and oxygen compounds and is added to the makeup syngas stream.

7. The method of claim 1, wherein the nitrogen stream is essentially free of oxygen and oxygen compounds and is injected into the syngas feed.

8. A retrofit method for increasing the production capacity of an ammonia plant having (1) a front end including a primary reformer, a secondary reformer, an air compressor, and a CO₂ removal unit for reacting a hydrocarbon feed stream with steam and compressed air to produce a makeup syngas stream having a HN ratio at a pre-existing capacity, and (2) a synthesis loop wherein a recycle syngas stream is combined with the makeup syngas stream to form a syngas feed to ammonia converters for producing ammonia at a pre-existing capacity, comprising the steps of:

installing an air separation unit to produce oxygen-rich and nitrogen-rich streams;

injecting the oxygen-rich stream into the compressed air to form an oxygen enriched stream for feed to the secondary reformer containing from 25 to 40 volume percent oxygen and operating the front end at an increased capacity relative to its pre-existing capacity wherein a raw syngas stream from the CO₂ removal unit has an increased HN ratio relative to the ratio at the pre-existing capacity;

supplying the nitrogen-rich stream to the synthesis loop; and

modifying the synthesis loop to increase the ammonia production capacity of the synthesis loop.

9. The retrofit method of claim 8, wherein the oxygen-rich stream contains from 40 to 100 volume percent oxygen.

10. The retrofit method of claim 8, wherein the oxygen-rich stream contains from 50 to 80 volume percent oxygen.

11. The retrofit method of claim 8, wherein the nitrogen-rich stream contains less than 1 volume percent oxygen, the nitrogen-rich stream is injected into the raw syngas stream and the method includes passing the nitrogen-enriched raw syngas stream through a methanator to form the makeup syngas stream essentially free of oxygen and oxygen-containing compounds.

12. The retrofit method of claim 10, wherein the nitrogen-rich stream is essentially free of oxygen and the nitrogen-rich stream is injected into the makeup syngas stream downstream from a methanator.

13. The retrofit method of claim 10, wherein the nitrogen-rich stream is essentially free of oxygen and the nitrogen-rich stream is injected into the syngas feed to the ammonia converters.

14. The retrofit method of claim 8, wherein the modification of the synthesis loop includes the installation of ammonia conversion capacity based on high activity catalyst comprising a platinum group metal supported on graphite-containing carbon.

15. A process for ammonia synthesis, comprising the steps of:

(a) separating air into oxygen-rich and nitrogen-rich streams;

(b) mixing air with the oxygen-rich stream from step (a) to form an oxygen-enriched stream containing 25-40 mole percent oxygen;

(c) injecting the oxygen-enriched stream from step (b) into an autothermal reformer of a syngas unit including a primary reformer upstream from the autothermal reformer and a downstream shift converter, CO₂ removal unit and methanator, to produce a syngas stream;

(d) supplying the syngas stream from step (c) and the nitrogen-rich stream from step (a) as makeup gas to an ammonia synthesis loop;

(e) operating the ammonia synthesis loop to (1) convert nitrogen and hydrogen in an ammonia synthesis reactor feed stream to form an ammonia-rich stream, (2) recover ammonia from the ammonia rich stream to form a recycle gas stream, (3) remove a purge stream from the synthesis loop, (4) recover a hydrogen-rich gas from the purge stream, and (5) combine the hydrogen-rich gas with the recycle stream and the makeup gas from step

(d) to form the ammonia synthesis reactor feed stream.