METHOD FOR PRODUCTION OF BLUE AMMONIA

Abstract

The present invention provides a method and system for producing blue ammonia, providing for a higher percentage of carbon capture. The method and system of the invention may be used in any ammonia plant.

Claims

1. Process for producing ammonia comprising the steps of: a) preheating a hydrocarbon feed in a fuel system; b) removing sulphur and other contaminants from the preheated hydrocarbon feed; c) reforming the preheated hydrocarbon feed from step b) and obtaining a synthesis gas comprising CO, CO.sub.2, H.sub.2, H.sub.2O and CH.sub.4; d) sending the synthesis gas from step c) through a shift reaction step reducing the CO content; e) sending the gas from step d) to a CO.sub.2 removal step where it is split in at least a CO.sub.2 rich stream; and a hydrogen rich stream and optional a flash gas; f) sending the hydrogen rich stream from step e) through: i) a hydrogen purification and nitrogen wash, where H.sub.2O, CO, CO.sub.2, CH.sub.4 are removed in an off-gas stream and obtaining a purified hydrogen stream and wherein nitrogen is added to obtain an ammonia synthesis gas stream comprising nitrogen and hydrogen; or ii) a PSA, resulting in a hydrogen stream containing more than 99.5% hydrogen to which nitrogen is added to obtain a synthesis gas stream comprising nitrogen and hydrogen and an off-gas stream; or iii) a methanation, converting the CO and CO.sub.2 together with hydrogen into CH.sub.4 and H.sub.2O, to obtain a synthesis gas stream, comprising nitrogen, hydrogen and inerts comprising CH.sub.4; g) sending a part of the synthesis gas stream from step f) through an ammonia synthesis section, where it is converted to ammonia and another part of the synthesis gas stream to the preheating system; wherein the fuel system comprises at least two or more separate fired heaters and wherein at least one of the fired heaters is equipped with a unit which removes 80% or more CO.sub.2 from the resulting flue gas and wherein said fired heater is using the off-gasses from step f) and the flash-gas from step e) and off gases in case of f) iii) from step g) as fuel.

2. Process according to claim 1, wherein the reforming step c) is performed in an autothermal reformer or in a tubular reformer, followed by a step in an autothermal reformer or in a tubular reformer and followed by an air blown secondary reformer.

3. Process according to claim 1, wherein a hydrocarbon fuel, flash gas from step e), off-gas from step f) and part of the synthesis gas streams from step f) are either premixed or fed separately to the fuel system.

4. Process according to claim 1, comprising an adiabatic pre-reforming step co) of the hydrocarbon stream from step b).

5. Process according to claim 1, wherein in step f) i) the hydrogen purification and nitrogen addition are performed by sending the hydrogen rich stream to a PSA, then nitrogen is added to the resulting hydrogen stream and at least part of the resulting off-gas stream is sent to the preheating in step a).

6. Process according to claim 1, wherein in the methanation step f) iii) CO, CO.sub.2 and hydrogen are converted to CH.sub.4 and H.sub.2O and wherein a purge gas stream, comprising the CH.sub.4 from the ammonia synthesis, is added.

7. Process according to claim 6, wherein the CH.sub.4 is captured from a stream of non-reacted components from the ammonia synthesis section in a hydrogen recovery unit resulting in a stream containing more than 99% hydrogen, which is sent to the ammonia synthesis section in step g) and/or the preheating system in step a), and an off-gas containing more than 95% of the CH.sub.4 content in the synthesis gas stream into the ammonia synthesis section in step g), which is used as fuel in the one or more fired heaters equipped with a flue gas CO.sub.2 removal unit.

8. Process according to claim 2, wherein the amount of air to the air blown secondary reformer is adjusted to obtain a molar ratio of N.sub.2 and H.sub.2 between 1 to 2.5 and 1 to 3.5, in the stream from the methanation in step f iii).

9. Process according to claim 1, wherein the synthesis gas stream obtained from step f) comprises N.sub.2 and H.sub.2 in a ratio of 1 to between 2.9 and 3.1.

10. System for producing ammonia according to the process in claim 1, comprising: a) a preheating unit b) a desulfurization unit; c) a reforming unit; d) a shift unit; e) a CO.sub.2 removal unit; f) a nitrogen washing unit or a pressure swing adsorption unit or a methanation unit, g) an ammonia synthesis section; and h) fuel system(s) which supplies fuel to at least two or more separate heaters in the preheating unit and wherein at least one heater is equipped with a unit which removes 80% or more CO.sub.2 from the resulting flue gas.

11. System according claim 10, wherein a pre-reforming unit is arranged upstream to the reforming unit c).

12. System according to claim 10, wherein the reforming unit c) comprises an autothermal reformer or a tubular reformer followed by an autothermal reformer or a tubular reformer followed by an air blown secondary reformer.

13. System according to claim 10, wherein the reforming unit c) comprises an autothermal reformer and f) is a CO.sub.2 and H.sub.2O drier followed by a nitrogen wash unit.

14. System according to claim 10, wherein the reforming unit c) comprises an autothermal reformer and f) is a PSA.

15. System according to claim 10, wherein the reforming unit c) comprises a tubular steam reformer followed by an autothermal reformer and f) is a CO.sub.2 and H.sub.2O drier followed by a nitrogen wash.

16. System according to claim 10, wherein the reforming unit c) comprises a tubular steam reformer followed by an autothermal reformer and f) is a PSA.

17. System according to claim 10, wherein the reforming unit c) comprises a tubular steam reformer followed by an air blown secondary reformer and f) is a methanation unit.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0062] FIG. 1 shows an overview for producing ammonia according to a state of the art method. [0063] a) Desulphurization [0064] b.sub.0) Pre-reforming [0065] b) Reforming (SMR) [0066] b) Secondary reformer (air blown ATR) [0067] c) Shift section [0068] d) CO.sub.2 removal section [0069] e) Methanation [0070] f) Ammonia synthesis [0071] g) Fuel system(s) [0072] i) Ammonia recovery [0073] Stream (9). Hydrogen rich fuel comprising nitrogen (replacing use of natural gas as fuel) Stream (2) Flash gas from CO.sub.2 removal

[0074] FIG. 2 shows an overview of a method to produce Ammonia using Topsoe SynCOR Ammonia process: [0075] a) Desulphurization [0076] b.sub.0) Pre-reforming [0077] b) Reforming (ATR) [0078] c) Shift section [0079] d) CO.sub.2 Removal [0080] e) Nitrogen wash or PSA [0081] f) Ammonia synthesis [0082] g) Fuel system(s) [0083] Stream (4,8). Recycle off-gas stream. [0084] Stream (5,7). Hydrogen rich fuel comprising nitrogen (replacing use of natural gas as fuel) [0085] Stream 2. Flash gas from CO.sub.2 removal

[0086] FIG. 3 shows an overview for producing ammonia using a steam reformer followed by an autothermal reformer in the synthesis gas generation: [0087] a) Desulphurization [0088] b) Pre-reforming [0089] b) Reforming (SMR) [0090] b) Reforming (ATR) [0091] c) Shift section [0092] d) CO.sub.2 removal [0093] e) Nitrogen wash or PSA [0094] f) Ammonia synthesis [0095] g) Fuel system(s) [0096] Stream (4,8). Recycle off-gas stream. [0097] Stream (5,7). Hydrogen rich fuel comprising nitrogen (replacing use of natural gas as fuel) [0098] Stream (2). Flash gas from CO.sub.2 removal

[0099] FIG. 4 is an exploded view of the fuel system(s) g): [0100] FH) Fired heater [0101] CCU) Flue gas carbon capture unit [0102] Stream (2,4,8) Flash gas from CO.sub.2 removal in unit d) and recycle off-gas stream from unit e) [0103] Stream (5,7,9) hydrogen rich fuel comprising nitrogen split stream

[0104] References used to represent the different steps of in the method of the present invention are: [0105] a) Desulphurization [0106] b.sub.0) Pre-reforming [0107] b) Reforming (SMR) [0108] b) Reforming (ATR) [0109] b) Reforming (Air blown secondary reformer) [0110] c) Shift [0111] d) CO.sub.2 Removal [0112] e) Nitrogen wash or PSA or Methanation [0113] f) Ammonia synthesis [0114] g) Fuel system(s) [0115] i) Ammonia recovery [0116] Stream (4,8,10): Recycle off-gas stream. [0117] Stream (9): Hydrogen rich fuel (replacing use of natural gas as fuel) [0118] Stream (5,7): Hydrogen rich fuel (replacing use of natural gas as fuel) [0119] Stream (2): Flash gas from CO.sub.2 removal

Example 1

[0120] Table 1 shows the benefits of the proposed layout in the present invention, in terms of carbon recovery (%).

[0121] Traditional ammonia production involves utilization of off gases from ammonia recovery and syngas preparation steps to supplement natural gas as main fuels for fired heater/process furnaces. This would result in carbon emissions from flue gas stack which could partly be recovered by using a solution based carbon capture technology. The recovery rate for such a plant, including carbon recovery from flue gases would not be higher than 90% and is a capital intensive process. With the proposed layout including firing of hydrogen rich fuel and utilization of off gases in the main process results in significant carbon emission reduction, more than 98% recovery. This process will be significantly cheaper and would require minimum steps and will have lower footprint on plot. Better than 99% recovery can be obtained by recycling at least part of streams (4,8) to the reforming step b

TABLE-US-00001 TABLE 1 Syncor Ammonia Proposed layout: (existing process) Blue Ammonia Ammonia production, MTPD 3500 3500 CO.sub.2 in Flue gas, Nm.sup.3/h 26,200 2030 CO.sub.2 as 100%, captured for 98000 130100 storage/utilization, Nm.sup.3/h Carbon recovery, %, approx 80 >98