Hydrogen production with reduced carbon dioxide generation and complete capture

1. A method of reducing the carbon dioxide production and shifting balance from a reformer furnace flue gas to a high pressure syngas exit water gas shift reaction unit, the method comprising the steps of:

a) providing a first gas mixture;

b) heating said first stream mixture to a first temperature, then introducing said heated first gas mixture into a pre-reforming chamber to produce a pre-reformed mixture;

c) further heating said pre-reformed mixture in a primary reformer, thereby generating a second gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, and a flue gas, wherein said primary reformer comprises a reformer furnace and tubes filled with catalyst, wherein the second mixture and/or the flue a provides said heating for step b);

d) introducing said second gas mixture into at least one isothermal shift reactor, or a combination of high followed by a low temperature shift reactor, or a medium temperature shift reactor, thereby generating a third gas mixture;

e) introducing said third gas mixture into an amine wash, thereby producing an carbon dioxide enriched stream and a sweet syngas stream;

f) introducing said sweet syngas stream into a PSA unit, wherein said sweet syngas stream is separated into a hydrogen enriched stream and a PSA tail gas stream; and

g) introducing said PSA tail gas stream as fuel into the reformer furnace along with natural gas, a portion of the feed hydrocarbon stream, a portion of the hydrogen enriched stream, or any other external make-up fuel for the reformer furnace,

wherein step b) is repeated in a second pre-reforming chamber and a third pre-reforming chamber, for a total of three pre-reforming steps, such that the resulting temperature of the pre-reformed mixture is higher after each repetition,

wherein each pre-reforming chamber comprises a bed of pre-reformer catalyst

wherein an outlet gas from each pre-reforming chamber is heated up in a coil in exchange with flue gas or the second gas mixture before going to the next pre-reforming chamber or before entering the tubes of the primary reformer,

wherein a portion of the PSA tail gas stream is compressed and recycled to the PSA unit.

2. The method of claim 1 , wherein the three beds of pre-reformer catalyst are stacked in one vessel with internal heads.

3. The method of claim 1 , wherein the carbon dioxide enriched stream represents greater than 80% of the overall CO2 generated in the primary reformer.

4. The method of claim 3 , wherein the carbon dioxide enriched stream represents greater than 90% of the overall CO2 generated in the primary reformer.

5. The method of claim 1 , wherein there is no steam exported from the primary reformer.

6. The method of claim 1 , wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the primary reformer.

7. The method of claim 1 , wherein the catalyst in the first pre-reforming chamber include conventional pre-reforming catalyst and the second and third pre-reforming chambers includes typical main catalyst bed reforming catalyst.

8. The method of claim 1 , wherein the flue gas from the primary reformer is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the primary reformer.

9. The method of claim 8 , wherein the flue gas is compressed and used for Enhanced Oil Recovery.

10. The method of claim 9 , further comprising the step of passing the flue gas through a drier comprising of adsorbent to remove water from the flue gas.

11. The method of claim 10 , wherein the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

12. The method of claim 1 , wherein each of the pre-reforming chamber includes of a bank of tubes filled with catalyst that are configured to be heated in counter-current contact with the flue gas for heating with syngas.

13. The method of claim 12 , wherein the carbon dioxide enriched stream represents greater than 85% of the overall CO2 generated in the primary reformer.

14. The method of claim 12 , wherein the flue gas from the reformer furnace is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the primary reformer.

15. The method of claim 14 , wherein the flue gas is compressed and used for Enhanced Oil Recovery.

16. The method of claim 15 , further comprising the step of passing the flue gas through a drier comprising a bed of adsorbent to remove water from the flue gas.

17. The method of claim 16 , wherein the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

18. The method of claim 14 , wherein the flue gas is contacted with Hydrogen from the PSA unit and passed over a bed of catalyst to promote combustion.

19. The method of claim 18 , wherein the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

20. The method of claim 19 , further comprising the step of gas passing the flue gas through a drier comprising a bed of adsorbent to remove water from flue gas.

21. The method of claim 20 , wherein the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 99%.

22. The method of claim 13 , wherein the carbon dioxide enriched stream represents greater than 95% of the overall CO2 generated in the primary reformer.

23. The method of claim 12 , wherein no steam is exported from the primary reformer.

24. The method of claim 12 , wherein a portion of the PSA tail gas stream is compressed and recycled to the PSA unit.

25. The method of claim 12 , wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer.

26. The method of claim 12 , wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer and the PSA unit.

27. The method of claim 12 , wherein the catalyst at the top of the tube includes conventional pre-reforming catalyst and at the bottom of tube includes typical main catalyst bed reforming catalyst.

28. The method of claim 27 , wherein the transition between pre-reforming catalyst and main reforming catalyst is done through a series of progressively larger catalyst pellets.

29. The method of claim 12 , wherein the process gas from the exit of the pre-reforming tube is passed through two helical shaped tubes back up the pre-reformer tube.

30. The method of claim 29 , wherein a portion of the heat for the reforming reaction in said tubes is provided by exchange with the exit gas through the helical shaped tubes.

31. The method of claim 30 , wherein the temperature of the exit gas from the top of the helical tubes is between 500 and 1300 Degrees F.

32. The method of claim 30 , wherein the temperature of the exit gas from the top of the helical tubes is between 1200 and 1300 Degrees F.

33. The method of claim 1 , wherein the process gas from the exit of the reforming tube is passed through two helical shaped tubes back up the pre-reformer tube.

34. The method of claim 33 , wherein a portion of the heat for the reforming reaction in said tubes is provided by exchange with the exit gas through the helical shaped tubes.

35. The method of claim 33 , wherein the flue gas from the reformer furnace is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen from the primary reformer.

36. The method of claim 35 , wherein the flue gas is compressed and used for Enhanced Oil Recovery.

37. The method of claim 36 , further comprising the step of passing the flue gas through a drier comprising a bed of adsorbent to remove water from the flue gas.

38. The method of claim 37 , wherein the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

39. The method of claim 35 , wherein the flue gas is contacted with Hydrogen from the PSA and passed over a bed of catalyst to promote combustion.

40. The method of claim 39 , wherein the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

41. The method of claim 40 , further comprising the step of passing the flue gas through a drier comprising a bed of adsorbent to remove water from the flue gas.

42. The method of claim 41 , wherein the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 97%.

43. The method of claim 34 , wherein the carbon dioxide enriched stream represents greater than 80% of the overall CO2 generated in the primary reformer.

44. The method of claim 43 , wherein the carbon dioxide enriched stream represents greater than 90% of the overall CO2 generated in the primary reformer.

45. The method of claim 34 , wherein there is no steam exported from the primary reformer.

46. The method of claim 34 , wherein a portion of the PSA tail gas stream is compressed and recycled to the PSA unit.

47. The method of claim 34 , wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the first pre-reforming chamber.

48. The method of claim 34 , wherein a portion of the PSA tail gas stream is compressed and recycled to the first pre-reforming chamber and to the PSA unit.

49. A method of reducing the carbon dioxide production and shifting balance from a reformer furnace flue gas to a high pressure syngas exit water gas shift reaction unit, the method comprising; the steps of:

a) providing a first gas mixture;

b) heating said first stream mixture to a first temperature, then introducing said heated first gas mixture into a pre-reforming chamber to produce a pre-reformed mixture;

c) further heating said pre-reformed mixture in a primary reformer, thereby generating a second gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, and a flue gas, wherein said primary reformer comprises a reformer furnace and tubes filled with catalyst, wherein the second gas mixture and/or the flue gas provides said heating for step b);

d) introducing said second gas mixture into at least one isothermal shift reactor, or a combination of high followed by a low temperature shift reactor, or a medium temperature shift reactor, thereby generating a third gas mixture;

e) introducing said third gas mixture into an amine wash, thereby producing an carbon dioxide enriched stream and a sweet syngas stream;

f) introducing said sweet syngas stream into a PSA unit, wherein said sweet syngas stream is separated into a hydrogen enriched stream and a PSA tail gas stream; and

g) introducing said PSA tail gas stream as fuel into the reformer furnace along with natural gas, a portion of the feed hydrocarbon stream, a portion of the hydrogen enriched stream, or any other external make-up fuel for the reformer furnace,

wherein step b) is repeated in a second pre-reforming chamber and a third pre-reforming chamber, for a total of three pre-reforming steps, such that the resulting temperature of the pre-reformed mixture is higher after each repetition,

wherein each pre-reforming chamber comprises a bed of pre-reformer catalyst,

wherein an outlet as from each pre-reforming chamber is heated up in a coil in exchange with fine gas or process syngas before going to the next pre-reforming chamber or before entering the tubes of the primary reformer,

wherein the flue gas is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the primary reformer,

wherein the flue gas is contacted with Hydrogen from the PSA unit and passed over a bed of catalyst to promote combustion of oxygen.

50. The method of claim 49 , wherein the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

51. The method of claim 50 , further comprising the step of passing the flue gas through a drier comprising a bed of adsorbent to remove water from the flue gas.

52. The method of claim 51 , wherein Nitrogen+Argon composition of the flue as downstream of the drier is greater than or equal to 99%.