System and method for producing renewable natural gas from biogas
A system and method for generating renewable natural gas from raw biogas streams, such as biogas from landfills or biogas from controlled anaerobic digestion of biomass, provides for the efficient removal of acid gases and other impurities, including oxygen and nitrogen from biogas. The biogas is treated in a multi-stage membrane gas separation system integrated with a pressure swing adsorption system to generate pipeline-specification renewable natural gas. The combined system provides for efficient acid gas removal while simultaneously limiting oxygen carryover into the product stream.
1. A process for purification of a raw biogas stream comprised of methane, carbon dioxide, oxygen, nitrogen and hydrogen sulfide available at a substantially atmospheric pressure, said process comprising the steps of:
(i) compressing a feed gas stream comprising said raw biogas stream in a compressor to a pressure from 6 to 25 barg, thereby forming a first effluent stream;
(ii) passing the first effluent stream into a first membrane separation unit, wherein a membrane removes a portion of carbon dioxide, oxygen and nitrogen from the first effluent stream, thereby forming a retentate second effluent stream having a lower carbon dioxide content and a lower oxygen content than the first effluent stream and a permeate third effluent stream enriched in carbon dioxide and oxygen as compared to the first effluent stream;
(iii) passing the retentate second effluent stream to a second membrane separation unit, wherein a membrane removes a portion of carbon dioxide from the retentate second effluent stream, thereby forming a retentate fourth effluent stream having a lower carbon dioxide and oxygen content than the retentate second effluent stream and a permeate fifth effluent stream enriched in carbon dioxide and oxygen content as compared to the retentate second effluent stream;
(iv) passing the permeate third effluent stream to a third membrane separation unit wherein a membrane removes a portion of carbon dioxide from the permeate third effluent stream, thereby forming a retentate sixth effluent stream having a lower carbon dioxide content than the permeate third effluent stream and a higher oxygen and nitrogen content than the permeate third effluent stream and a permeate seventh effluent stream enriched in carbon dioxide content and depleted in oxygen, nitrogen and methane content as compared to the permeate third effluent stream, wherein the permeate seventh effluent stream is at substantially atmospheric pressure or at a sub-atmospheric pressure;
(v) passing the retentate sixth effluent stream to a pressure swing adsorption separation unit containing an adsorbent selective for removal of oxygen and nitrogen from a mixture of methane and carbon dioxide, wherein the pressure swing adsorption separation unit generates an eighth effluent stream depleted in nitrogen and oxygen content as compared to the retentate sixth effluent stream, and a blow-off gas ninth effluent stream comprised substantially of nitrogen and oxygen, wherein the eighth effluent stream is at an intake pressure of said compressor and the blow-off gas ninth effluent stream is at a pressure above atmospheric pressure;
(vi) passing the eighth effluent stream containing recoverable methane to an intake side of said compressor, wherein the eighth effluent stream is mixed with the raw biogas stream to define the feed gas stream;
(vii) passing the permeate fifth effluent stream containing recoverable methane to the intake side of said compressor, wherein the permeate fifth effluent stream is mixed with the raw biogas stream to define the feed gas stream; and
(viii) collecting the retentate fourth effluent stream generated by the second membrane separation unit as a methane product.
2. The process of claim 1 wherein the eighth effluent stream contains a nitrogen concentration below a nitrogen concentration of the raw biogas stream.
3. The process of claim 1 wherein the feed gas stream is treated in a biological desulfurization unit prior to being compressed.
4. The process of claim 3 wherein the blow-off gas ninth effluent stream is mixed with the raw biogas stream to define the feed gas stream prior to treatment of the feed gas stream in the biological desulfurization unit.
5. The process of claim 1 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 25.
6. The process of claim 5 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 35.
7. The process of claim 6 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 45.
8. The process of claim 5 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 5.
9. The process of claim 8 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 7.
10. The process of claim 9 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 9.
11. The process of claim 1 wherein the membrane in the third membrane separation unit is a polymeric membrane with a carbon dioxide/methane separation factor above 50.
12. The process of claim 8 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a nitrogen/methane separation factor above 2.
13. The process of claim 12 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a nitrogen/methane separation factor above 2.7.
14. The process of claim 1 wherein the membrane in each of the first, second and third membrane separation units is a polymeric membrane that possesses different gas separation characteristics as compared to one another.
15. The process of claim 1 wherein the retentate second effluent stream is treated in a deoxygenation unit prior to being passed to the second membrane separation unit.
16. The process of claim 1 wherein the retentate fourth effluent stream is treated in a deoxygenation unit prior to being collected as a methane product.
17. The process of claim 1 wherein a pressure booster or a second compressor is provided between the first and third membrane separation units.
18. The process of claim 1 wherein the feed gas stream is treated in an adsorption unit designed to remove hydrogen sulfide from the feed gas stream prior to the feed gas stream being passed to an intake side of said compressor.
19. The process of claim 18 wherein the permeate fifth effluent stream is recycled to an intake side of the adsorption unit and combined with the raw biogas stream to define the feed gas stream.
20. The process of claim 1 wherein an adsorption unit designed to remove hydrogen sulfide is positioned to treat the first effluent stream before the first effluent stream enters the first membrane separation unit.
21. The process of claim 20 wherein a portion of the permeate fifth effluent stream is used to regenerate the adsorption unit.
22. The process of claim 1 wherein said pressure swing adsorption separation unit comprises two to four adsorption beds.
23. The process of claim 1 wherein the permeate seventh effluent stream is collected at a sub-atmospheric pressure above 0.2 bara by way of a vacuum pump.
24. The process of claim 1 wherein the eighth effluent stream is removed at a sub-atmospheric pressure from the pressure swing adsorption separation unit by way of a vacuum pump prior to being conveyed to an intake side of said compressor.
25. The process of claim 1 wherein a caloric value of the blow-off gas ninth effluent stream is adjusted to meet a power generation specification and the blow-off gas ninth effluent stream is used for heat or power generation.
26. The process of claim 1 further comprising the step of:
(ix) collecting the permeate seventh effluent stream generated by the third membrane separation unit as a carbon dioxide product.
27. The process of claim 1 wherein the raw biogas stream is treated in a biological desulfurization unit.
28. An apparatus for purification of a raw biogas stream comprised of methane, carbon dioxide, oxygen, nitrogen and hydrogen sulfide available at a substantially atmospheric pressure, said apparatus comprising:
(i) a compressor that compresses a feed gas stream comprising said raw biogas stream to a pressure from 6 to 25 barg, thereby forming a first effluent stream;
(ii) a first membrane separation unit that receives the first effluent stream, the first membrane separation unit comprising a membrane that removes a portion of carbon dioxide, oxygen and nitrogen from the first effluent stream, thereby forming a retentate second effluent stream having a lower carbon dioxide content and a lower oxygen content than the first effluent stream and a permeate third effluent stream enriched in carbon dioxide and oxygen as compared to the first effluent stream;
(iii) a second membrane separation unit that receives the retentate second effluent stream, the second membrane separation unit comprising a membrane that removes a portion of carbon dioxide from the retentate second effluent stream, thereby forming a retentate fourth effluent stream having a lower carbon dioxide and oxygen content than the retentate second effluent stream and a permeate fifth effluent stream enriched in carbon dioxide and oxygen content as compared to the retentate second effluent stream;
(iv) a third membrane separation unit that receives the permeate third effluent stream, the third membrane separation unit comprising a membrane that removes a portion of carbon dioxide from the permeate third effluent stream, thereby forming a retentate sixth effluent stream having a lower carbon dioxide content than the permeate third effluent stream and a higher oxygen and nitrogen content than the permeate third effluent stream and a permeate seventh effluent stream enriched in carbon dioxide content and depleted in oxygen, nitrogen and methane content as compared to the permeate third effluent stream, wherein the permeate seventh effluent stream is at substantially atmospheric pressure or at a sub-atmospheric pressure;
(v) a pressure swing adsorption separation unit that receives the retentate sixth effluent stream, the pressure swing adsorption separation unit containing an adsorbent selective for removal of oxygen and nitrogen from a mixture of methane and carbon dioxide, wherein the pressure swing adsorption separation unit generates an eighth effluent stream depleted in nitrogen and oxygen content as compared to the retentate sixth effluent stream, and a blow-off gas ninth effluent stream comprised substantially of nitrogen and oxygen, wherein the eighth effluent stream is at an intake pressure of said compressor and the blow-off gas ninth effluent stream is at a pressure above atmospheric pressure;
(vi) wherein the eighth effluent stream containing recoverable methane is passed to an intake side of said compressor, wherein the eighth effluent stream is mixed with the raw biogas stream to define the feed gas stream;
(vii) wherein the permeate fifth effluent stream containing recoverable methane is passed to the intake side of said compressor, wherein the permeate fifth effluent stream is mixed with the raw biogas stream to define the feed gas stream; and
(viii) wherein the retentate fourth effluent stream generated by the second membrane separation unit is collected as a methane product.
29. The apparatus of claim 28 wherein the eighth effluent stream contains a nitrogen concentration below a nitrogen concentration of the raw biogas stream.
30. The apparatus of claim 28 further comprising a biological desulfurization unit that treats the feed gas stream prior to the feed gas stream being compressed.
31. The apparatus of claim 30 wherein the blow-off gas ninth effluent stream is mixed with the raw biogas stream to define the feed gas stream prior to treatment of the feed gas stream in the biological desulfurization unit.
32. The apparatus of claim 28 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 25.
33. The apparatus of claim 32 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 35.
34. The apparatus of claim 33 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a carbon dioxide/methane separation factor above 45.
35. The apparatus of claim 32 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 5.
36. The apparatus of claim 35 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 7.
37. The apparatus of claim 36 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with an oxygen/methane separation factor above 9.
38. The apparatus of claim 28 wherein the membrane in the third membrane separation unit is a polymeric membrane with a carbon dioxide/methane separation factor above 50.
39. The apparatus of claim 35 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a nitrogen/methane separation factor above 2.
40. The apparatus of claim 39 wherein the membrane in the first, second and third membrane separation units is a polymeric membrane with a nitrogen/methane separation factor above 2.7.
41. The apparatus of claim 28 wherein the membrane in each of the first, second and third membrane separation units is a polymeric membrane that possesses different gas separation characteristics as compared to one another.
42. The apparatus of claim 28 further comprising a deoxygenation unit that treats the retentate second effluent stream prior to being passed to the second membrane separation unit.
43. The apparatus of claim 28 further comprising a deoxygenation unit that treats the retentate fourth effluent stream prior to being collected as a methane product.
44. The apparatus of claim 28 further comprising a pressure booster or a second compressor disposed between the first and third membrane separation units.
45. The apparatus of claim 28 further comprising an adsorption unit that removes hydrogen sulfide from the feed gas stream prior to the feed gas stream being passed to an intake side of said compressor.
46. The apparatus of claim 45 wherein the permeate fifth effluent stream is recycled to an intake side of the adsorption unit and combined with the raw biogas stream to define the feed gas stream.
47. The apparatus of claim 28 further comprising an adsorption unit designed to remove hydrogen sulfide positioned to treat the first effluent stream before the first effluent stream enters the first membrane separation unit.
48. The apparatus of claim 47 wherein a portion of the permeate fifth effluent stream is used to regenerate the adsorption unit.
49. The apparatus of claim 28 wherein said pressure swing adsorption separation unit comprises two to four adsorption beds.
50. The apparatus of claim 28 further comprising a vacuum pump that collects the permeate seventh effluent stream at a sub-atmospheric pressure above 0.2 bara.
51. The apparatus of claim 28 further comprising a vacuum pump that removes the eighth effluent stream at a sub-atmospheric pressure from the pressure swing adsorption separation unit prior to being conveyed to an intake side of said compressor.
52. The apparatus of claim 28 wherein a caloric value of the blow-off gas ninth effluent stream is adjusted to meet a power generation specification and the blow-off gas ninth effluent stream is used for heat or power generation.
53. The apparatus of claim 28 wherein:
(ix) the permeate seventh effluent stream generated by the third membrane separation unit is collected as a carbon dioxide product.
54. The apparatus of claim 28 further comprising a biological desulfurization unit that treats the raw biogas stream.