The invention relates to membrane-based gas separation processes, and specifically the concurrent separation of acidic gases, such as SO2, NOx, and CO2, from combustion gases.
Presented below is background information on certain aspects of the present invention as they may relate to technical features referred to in the summary of the invention, but not necessarily described in detail. The discussion below should not be construed as an admission as to the relevance of the information to the claimed invention or the prior art effect of the material described.
Combustion of many fuels, such as coal, petroleum coke, or municipal solid waste produces flue gas containing nitrogen, some oxygen, carbon dioxide, and 100 to 20,000 ppm of sulfur dioxide and up to 200 ppm of NOx. Since the clean air act of 1990, the United States and other countries have controlled the emission of the most acidic gases: SO2, NOx, and in some cases HCl and HF. In the last few years, emissions of CO2 have also been the subject of research and regulation because of the contribution of CO2 to global warming.
A simple block diagram of coal-burning power fitted with emission control equipment is shown in
Coal feed stream (101) and air stream (102) are combined in boiler (103) that produces high temperature steam used to drive a steam turbine. Because the coal contains 0.5 to 2% sulfur and up to 1% nitrogen, the flue gas, 104, produced contains CO2 (typically 10-15 mol %), SO2 (0.2 to 1 mol %), and as much as 1,000 ppm NO2. Almost all U.S. power plants have electrostatic preceptors (105) sometimes supplanted by bag house filters to control particulate emissions. U.S. coal power plants are also fitted with SO2/NOx control systems (107) to remove SO2 and NOx. CO2 control systems (108) are installed on only one or two plants. The CO2 control systems installed to date are based on amine absorption technology. Because amine absorbents react with SO2 and NOx to form inert salt precipitates, the amine systems installed to date are all positioned after the particulate and SO2/NOx separating systems.
In many parts of the world, however, the power plants being operated are not fitted with SO2/NOx separating systems and the flue gas emitted (109) contains high levels of CO2, SO2 and NOx. Thus, it would be beneficial to develop a separation process that was able to remove SO2, NOx, and CO2 concurrently in the same separation unit.
In the embodiments of the present invention, all of these components are removed concurrently with the CO2 from the flue gas into a single concentrate stream. In this way, the costs of CO2, SO2 and NOx removal and final segregation are significantly reduced.
The embodiments of the invention are for coal power plant flue gas, which is the largest and most important flue-gas source, but the process can also be applied to other gas streams, including but not limited to those produced by burning petroleum, coke, catalysis regeneration in FCC crackers and refineries, or flue gas emitted in cement plants, steel mills, or by municipal solid waste incinerators.
The invention is a process for concurrently removing CO2 and SO2 from flue gas produced by a combustion process, comprising:
(a) performing a combustion process by combusting a fuel and air in a combustion apparatus, thereby creating an exhaust stream comprising CO2 and SO2;
(b) compressing the exhaust stream in a first compression step, thereby producing a first compressed gas stream;
(c) providing a first membrane having a feed side and a permeate side, and being selectively permeable to CO2 and SO2 over nitrogen and to CO2 and SO2 over oxygen;
(d) passing at least a portion of the first compressed gas stream across the feed side;
(e) withdrawing from the feed side a CO2- and SO2-depleted residue stream;
(f) withdrawing from the permeate side at a lower pressure than the first compressed gas stream, a first permeate stream enriched in CO2 and SO2;
(g) passing the second compressed gas stream to separation process that produces a stream enriched in CO2 and a stream enriched in SO2.
The invention is a process for concurrently removing CO2 and SO2 from flue gas produced by a combustion process, comprising:
(a) performing a combustion process by combusting a fuel and air in a combustion apparatus, thereby creating an exhaust stream comprising CO2 and SO2;
(b) compressing the exhaust stream in a first compression step, thereby producing a first compressed gas stream;
(c) providing a first membrane having a feed side and a permeate side, and being selectively permeable to CO2 and SO2 over nitrogen and to CO2 and SO2 over oxygen;
(d) passing at least a portion of the first compressed gas stream across the feed side;
(e) withdrawing from the feed side a CO2- and SO2-depleted residue stream;
(f) withdrawing from the permeate side at a lower pressure than the first compressed gas stream, a first permeate stream enriched in CO2 and SO2;
optionally, compressing the first permeate stream in a second compression step to form a second compressed gas stream; and
(g) passing the first permeate stream (or the second compressed gas stream, where appropriate) to a separation process that produces a stream enriched in CO2 and a stream enriched in SO2.
A basic embodiment of the present invention is shown in
Treated residue gas (214) can then be sent to the chimney for disposal as vent gas (209). Membrane permeate stream (215) is typically about 10-15% of the volume of the original flue gas and is then sent to downstream CO2, NOx, SOx separation step (210) via compressor (207) producing CO2 concentrate stream (211) and SO2/NOx concentrate stream (212).
Because the SO2 and NOx concentration in the treated flue gas is 5 to 20 times more concentrated than in the original flue gas, a number of low-cost separation processes (not practical when treating the total flue gas streams) can be used.
SO2 and NOx are both strong, acid gases and so wet or dry scrubbing can be used. In dry scrubbing, the reactive component is powdered CaCO3, which reacts
CaCO3 (solid)+SO2 (gas) CaSO3 (solid)+CO2 (gas)
in wet scrubbing processes, the reactant is a Ca(OH)2 hydrated lime. In some cases, Na(OH) is used or Ca(OH)2 and Mg(OH)2 mixtures. The reaction is then
Na(OH) solid+SO2 (gas) Na2SO3 (solid)+H2O (liquid)
The CaSO3 can be further oxidized with air to produce CaSO4, which is more marketable as gypsum for wallboards. Flue gas separation with these processes is subject to scaling and precipitation of the gypsum reactant, and careful process system design is needed to minimize these issues. Acid gas scrubbing is a simple, reliable and relatively economical process, but the products of this process are of little value.
Because the membranes process shown in
The SNOx process as used in this embodiment may include the following steps:
The final cooling/condensation step often uses combustion air to the boiler as the heat sink, which significantly increases the energy efficiency of the process.
In the SNOx process shown in
Another separation process, possible because of the relatively high SO2 and NOx concentration in the gas to be treated is the Wellman-Lord sodium sulfite absorption process. The Wellman-Lord process is a regenerable process to remove sulfur dioxide from the flue gas concentrate without creating a throwaway sludge product as produced by the lime precipitation process. In the Wellman Loral process, sulfur dioxide in the concentrate gas is absorbed in a sodium sulfite solution in water forming sodium bisulfite; other components of flue gas are not absorbed. After lowering the temperature, the bisulfite is converted to sodium pyrosulfite, which precipitates.
Upon heating, the two previously described chemical reactions are reversed, sodium pyrosulfite is converted to a concentrated stream of sulfur dioxide and sodium sulfite. The sulfur dioxide can be used for further reactions (e.g., the production of sulfuric acid), and the sulfite is reintroduced into the process.
A diagram showing how the Wellman-Lord process could be combined with membrane separation of the present invention is shown in
CO2 stream (419), free of NOx and SO2, is removed from the top of reactor (420). The bisulfite and pyrosulfite-containing solution is then sent to second heated reactor (421) where the SO2 absorption reaction is reversed, producing concentrated SO2 stream (422) and regenerated sodium sulfite stream (426), which is recycled back to the reactor (420).
Another separation process that may be used in this step is the LICONOX® (Linde Cold DeNOx) process. LICONOX is used for the reduction NOx (NO and NO2) SOx in a flue gas from an oxyfuel power plant.
The CO2 removed from the processes of the invention may be used for a number of applications, including but not limited to sequestration, enhanced oil/natural gas recovery (EOR/ENGR), enhanced coal bed methane recovery (ECBMR), submarine extraction of methane from hydrate, or for use in chemicals and fuels.
The SO2 contained in the SO2 concentrate stream can also be used, for example, to make sulphuric acid.
A final separation process is fractional condensation of the SO2 and NOx streams. A process of this type is shown in
An example calculation to show the efficacy of the approach described in
For this process to be successful, membranes are required that selectivity permeate CO2, SO2 and NOx, and are stable in the pressure of these components. We have found a number of membranes that meet this requirement.
A preferred type of membrane that could be used is a composite membrane made from polar rubbery polymers, such as Pebax® or Polaris™ membranes. Both of these polymers include blocks of polyethylene oxide in their structures that make the membranes very permeable to gases, such as CO2, NO2SO2, and relatively impermeable to other gases, such as oxygen and nitrogen. Typical selectivities that are possible with flue gas are:
SO2/N2: 50-100
NOx/N2: 50-100
CO2/N2: 20-50
O2/N2: 2.
This type of membrane is described, for example in papers by H. Lin and Freeman, J. Molec Struct, vol. 739, pp 57-74 (2005), and Lin, et al., Macromolecules, vol. 38, pp 8381-8393 (2005). Even more selective membranes can be used if needed, such as the membrane incorporating amine groups and working by facilitated transport, for example, Zhao, et al., J. Mater. Chem A. vol. 1, pp 246-249 (2013), Zou and Ho, J. Memb. Sci vol. 286, pp 310-321 2006), and Chen and Ho, J. memb. Sci. vol. 514, pp 376-384 (2016) In general, these polar rubbery membranes have good selectivities for CO2 over nitrogen, SO2 and NO2 because they are more condensable than CO2 and have even higher selectivities over nitrogen. Typically SO2 and NOx are 2 to 3 times more permeable than CO2. This means that a membrane process designed to remove, for example 50% of the CO2 from the flue gas stream will generally remove 70 to 80% of the SO2 and NO2 at the same time.
A number of membrane processes to separate CO2 from flue gas have been suggested. These processes, if fitted with the right membrane that permeate NOx and SO2, as well as CO2, could be used in the total process. Examples of certain embodiments of potential process designs are shown below in
A calculation was performed to model the performance of the process of the invention shown in
The membrane used for this process has a CO2 permeance of 1,000 gpu, an SO2 permeance of 3,000 gpu, an NOx permeance of 3,000 gpu, a nitrogen permeance of 25 gpu and an oxygen permeance of 50 gpu. Membranes with these permeances and selectivities are well known.
Another membrane separation process that can be used is the MTR membrane contactor design shown in
This is a U.S. national stage application based on PCT application PCT/GB2017/053742 filed Dec. 14, 2017 and claims priority to application U.S. Provisional application No. 62/434,197, filed Dec. 14, 2016, the entire disclosures of which are expressly incorporated herein by reference.
Filing Document | Filing Date | Country | Kind |
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PCT/GB2017/053742 | 12/14/2017 | WO | 00 |
Number | Date | Country | |
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62434197 | Dec 2016 | US |