Method and plant for the purification of carbon dioxide using liquid carbon dioxide
11287183 · 2022-03-29
Assignee
Inventors
Cpc classification
B01D53/1493
PERFORMING OPERATIONS; TRANSPORTING
F25J2200/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02P70/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F25J2210/80
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2250/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2200/76
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2235/80
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D2257/704
PERFORMING OPERATIONS; TRANSPORTING
F25J2205/30
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2230/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2205/40
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J3/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2200/50
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D3/106
PERFORMING OPERATIONS; TRANSPORTING
F25J2220/84
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2230/80
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25J2215/80
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D3/007
PERFORMING OPERATIONS; TRANSPORTING
Y02C20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
F25J3/0204
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
F25J3/08
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01D3/00
PERFORMING OPERATIONS; TRANSPORTING
B01D53/00
PERFORMING OPERATIONS; TRANSPORTING
F25J3/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
The present invention relates to an improved method for removing contaminants from a gaseous stream substantially comprising carbon dioxide. More specifically, the method comprises the step of subjecting the gaseous stream to an absorption step in which the absorbent is liquid carbon dioxide wherein the waste of carbon dioxide is minimized by utilizing a compressing means for generating a pressure difference between two streams in a reboiler.
Claims
1. A carbon dioxide purification system, comprising: a purification column having a top with an outlet and a bottom; a reboiler in fluid communication with the outlet of the top of the purification column via a first pathway consisting of one or more pipes that carry a contaminant lean gaseous stream; a compressor in fluid communication with the reboiler and the purification column, wherein the compressor is provided downstream of the reboiler; a depressurizing valve in fluid communication with the bottom of the purification column and the reboiler; and a product line in fluid communication with the reboiler.
2. The carbon dioxide purification system of claim 1, the purification column defining: a bottom outlet at the bottom; a feed inlet between the top and the bottom; and a compression inlet between the feed inlet and the bottom.
3. The carbon dioxide purification system of claim 2, wherein: the compressor is in fluid communication with the purification column via the compression inlet; and the depressurizing valve is in fluid communication with the bottom of the purification column via the bottom outlet.
4. The carbon dioxide purification system of claim 1, wherein the depressurizing valve is in fluid communication with the compressor via the reboiler.
5. The carbon dioxide purification system of claim 1, wherein the purification column is in fluid communication with the product line via the reboiler.
6. The carbon dioxide purification system of claim 1, wherein the reboiler defines a first fluid flow path and a second fluid flow path, the first and second fluid flow paths being fluidly isolated from one another.
7. The carbon dioxide purification system of claim 6, wherein the first and second fluid flow paths are arranged to exchange heat with one another.
8. The carbon dioxide purification system of claim 6, wherein the top of the purification column and the product line are in fluid communication with the first fluid flow path; and the depressurizing valve and the compressor are in fluid communication with the second flow path.
9. The carbon dioxide purification system of claim 8, wherein fluid from a bottom cools fluid from the top in the reboiler.
10. The carbon dioxide purification system of claim 1, wherein the depressurizing valve is provided upstream of the reboiler.
11. A carbon dioxide purification system, consisting essentially of: a reboiler; a purification column having a top and a bottom; a compressor; a product line; a plurality of pipes; and optionally, one or more pumps, valves and combinations thereof; wherein a first fluid flow path consists essentially of the purification column, the reboiler, pipes and, optionally, the one or more pumps, valves and combinations thereof and a second fluid flow path consists essentially of the purification column, the reboiler, the compressor, pipes and, optionally, the one or more pumps, valves and combinations thereof, wherein the top of the purification column is in fluid communication with the first fluid flow path and the bottom of the purification column is in fluid communication with the second fluid flow path, wherein the compressor is downstream of the reboiler, and wherein the first and second fluid flow paths are fluidly isolated from each other and in a heat exchange relationship with each other.
12. The carbon dioxide purification system of claim 11, wherein the purification column defines a feed inlet between the top and the bottom; and a compression inlet between the feed inlet and the bottom.
13. The carbon dioxide purification system of claim 11, wherein the compressor is designed to produce a pressure differential between the purification column and the reboiler.
14. The carbon dioxide purification system of claim 13, wherein a first fluid pressure in the purification column is greater than a second fluid pressure in the second fluid flow path.
15. The carbon dioxide purification system of claim 14, wherein the compressor acts to draw fluid from the bottom through the second flow path.
16. The carbon dioxide purification system of claim 11, wherein fluid in the second flow path cools fluid in the first flow path.
17. A method for producing purified carbon dioxide, the method comprising: feeding a first unpurified stream of carbon dioxide into a purification column having a top and a bottom; circulating a second unpurified stream of carbon dioxide from the bottom through a first fluid flow path consisting of the purification column, a reboiler heat exchanger, a compressor, pipes, and, optionally, one or more pumps, valves, and combinations thereof, wherein the compressor is downstream of the reboiler; and passing a purified stream of carbon dioxide from the top through a second fluid flow path consisting of the purification column, the reboiler heat exchanger, pipes, and, optionally, one or more pumps, valves, and combinations thereof, wherein the first and second fluid flow paths are fluidly isolated from one another and exchange heat with one another; wherein circulating the second unpurified stream of carbon dioxide from the bottom through the first fluid flow path of the reboiler heat exchanger comprises compressing the second unpurified stream of carbon dioxide downstream of the reboiler heat exchanger.
Description
FIGURES
(1)
(2)
(3)
DETAILED DESCRIPTION OF THE INVENTION
(4) According to the present invention, a substantially pure CO.sub.2 stream and/or feed stream comprises more than 80 weight-% CO.sub.2.
(5) Throughout the description, unless otherwise indicated, all contents are given as weight-%.
(6) Throughout the description and claims the reference numerals are the same when referring to a stream (for methods) and influent/effluent (for purification units). Each stream assigned the same reference will have the same prefix and then being denoted stream or influent/effluent respectively depending on the context.
(7) It is contemplated that all embodiments and variations of the method and purification unit apply equally to both said method and unit.
(8) Thus, when referring to the method the suffix applied is “stream” when referring to the purification unit the suffix “influent/effluent” is applied. It is contemplated that streams/influents/effluents having the same prefix correspond, this is further detailed below.
(9) Streams and Influents/Effluents
(10) Feed stream (f); Product stream (p); Contaminant lean gaseous stream (g2); Gaseous stream (g3); Second gaseous stream (g3a); Compressed gaseous stream (g4); Cooled compressed gaseous stream (g4′); Filtered gas stream (g5); Non-condensable gases (g6); Water inhibitor and/or scavenger stream (l0); Liquid carbon dioxide stream (l1); Contaminant rich liquid stream (l2); First contaminant rich liquid stream (l2a); Second contaminant rich liquid stream (l2″); Waste liquid stream (l3); Second waste liquid stream (l3a); Split second liquid stream (l3b) Carbon dioxide stream (l5); Condensed/distilled liquid carbon dioxide (l6).
(11) Components
(12) Purification column (A1); Compression means (A2); Reboiler (A3); Valve (A4); condenser (A5); Filter (A6); Condenser/distillation column (A7); Pump (A8); Heat exchanger (A9).
(13) Throughout the description and the claims the terms impurity and contaminant may be used interchangeably having the same meaning in the context of the present invention and both cover undesired substances in a carbon dioxide stream that should be removed.
(14) Throughout the description and the claims the terms water activity reducing agent, agent and water inhibitor and/or scavenger may be used interchangeably having the same meaning in the context of the present invention, and all cover a substance that is capable of removing water from a carbon dioxide stream.
(15) Throughout the description and the claims the term water free or dry gaseous stream is a gaseous stream in which the water content is so low so as not to cause process related problems, such as freezing within pipes, containers etc. More specifically a water free or dry gaseous stream may be defined as a stream wherein the dew point temperature of water under the prevailing process conditions is lower than the temperature of the stream.
(16) The purification process described in greater details below typically takes place in a traditional column of the absorber, scrubber or rectification type. The specific choice of column depends on the size of the facility, the nature of the feed stream and other factors; this is within the skill of the art.
(17) All illustrations appended to the present description should be understood as a section of a larger facility. All features and variants of each of the embodiments and aspects described herein apply equally to all embodiments and aspects, i.e. both the method and the plant.
(18) The method of the present invention can be applied in any carbon dioxide recovery process at a point where the pressure of the feed gas is higher than the triple point pressure of carbon dioxide. Thus, preferably the method is used on a feed gas having a high carbon dioxide content.
(19) The method can be applied to but is not limited to streams originating from a flue gas, a fermentation gas, petrochemical combustion gases and carbon dioxide from natural sources.
(20) If the gaseous source is a flue gas the method of the present invention will typically be preceded by an amine absorption step optionally followed by flash distillation, and stripping as described in EP 1 907 319 B 1. Alternatively, the flue gas is condensed and subsequently absorbed in a physical absorbing agent as described in EP 1804956 A.
(21) In applications where the source gas is from a natural source, a fermentation process or a petrochemical process, the method of the present invention will typically be preceded by compression and optionally drying. The applications described above are examples and the invention should not be limited to these specific applications.
(22) Detailed descriptions based of the drawings apply equally to the method and purification unit of the present invention.
(23) Referring now to
(24) In
(25) The streams shown are the feed stream f, a liquid carbon dioxide stream l1, a contaminant lean gas stream g2 leaving at the top of the purification column, a contaminant rich liquid stream l2 leaving at the bottom of the purification column, a compressed gaseous stream g4 leaving the compressing means, a gaseous stream g3 leaving the reboiler, a waste liquid stream l3 leaving the reboiler, and a product stream p, leaving the reboiler.
(26) The interaction of streams in the reboiler is as follows: The colder contaminant rich liquid stream l2 enters the reboiler in which it is heated by the warmer compressed gaseous stream g4. After the heat exchange, the contaminant rich liquid stream l2 turns into the gaseous stream g3 and the waste liquid stream l3 (i.e. the portion of l2 that is not re-evaporated). The warmer compressed gaseous stream g4 becomes the product stream p, which may be liquid, gaseous or both.
(27) Hence, l2 is the contaminant rich liquid carbon dioxide stream comprising the absorbed/washed/scrubbed out contaminants. The contaminant rich stream l2 is fed to the reboiler A3 where it is reboiled providing the gaseous stream g3 and the waste liquid l3, which is optionally discarded. The contaminant lean gaseous stream g2 is compressed by means of a compressor or blower providing the compressed gas g4, which is fed to the reboiler A3.
(28) The product stream p may be both gaseous, liquid and a mixture depending on the conditions. The product stream may be further purified as desired for example by, but not limited to, heat exchanging and flash distillation and/or condensation to provide high purity liquid carbon dioxide to be stored in a tank or used directly. This high purity liquid dioxide directly obtained by any of the methods is also contemplated.
(29) Before entering the purification column A1, the feed stream f may be passed through a filter and/or a heat exchanger in order to condition the feed stream f for entering the purification column. The feed stream f may be both gaseous and/or liquid, thus the preconditioning depends on whether a gaseous and/or liquid feed stream is desired.
(30) Normally, the feed stream is gaseous when the method of the invention is part of a complete carbon dioxide production plant. A liquid feed stream will most likely be relevant when non-pure carbon dioxide is supplied from an external source and is to be further purified according to the method of the present invention.
(31) In one embodiment it may be desirable to prepare the feed stream f so that the temperature is well above the dew point temperature of carbon dioxide at the given conditions. The pressure in the purification column will typically be around 6 to 25 bar in the food and beverage industry, such as between 15 and 23 bar, e.g. 22.8 bar. In other applications, pressures are, however, also contemplated such as up to 60 bar, e.g. 40 to 55 bar, or even higher. The dew point temperature of carbon dioxide at 10 bar is −40° C.; therefore, at that pressure the temperature of the stream entering the column should preferably be higher than this temperature.
(32) When the appropriate pressure has been chosen it is within the skill of the art to choose the appropriate temperature of the feed stream. When the temperature of the feed stream is well above the dew point of carbon dioxide when entering the column, the amount of liquid carbon dioxide in the bottom stream is minimized.
(33) It is also contemplated that the gaseous feed stream is cooled, and optionally liquefied before entering the purification column; in this embodiment the contaminant rich liquid stream will comprise a higher amount of carbon dioxide than when the feed stream is gaseous.
(34) The contaminant lean gaseous stream leaving the purification column is fed to a compressor in which the difference in pressure is provided.
(35) Referring now to
(36) In this embodiment the compressing means is situated after the reboiler so that the gaseous stream g3 is compressed before entering the purification column. In this embodiment a valve A4 is placed to depressurize the contaminant rich liquid stream l2 before entering the reboiler, providing the necessary difference in pressure. In this embodiment the duty of the compressing means may be lower as compared to the first embodiment. This is due to the lower amount of carbon dioxide passing through in the gaseous stream g3 as compared to the contaminant lean gaseous stream g2. Furthermore, a cheaper compressor may be used, e.g. an oil lubricated compressor, as the compressed gaseous stream provided, g4′, is immediately purified removing any traces of oil from the stream.
(37) Referring now to
(38) Additionally, in
(39) When the feed stream originates from a bioethanol or fermentation plant the stream may comprise ethanol and it may not be necessary to add additional water inhibitor to the purification column. Thus, in a particular embodiment the feed stream originates from a bioethanol plant or a fermentation process and the water inhibitor is fed together with the feed stream.
(40) In principle the water inhibitor/scavenger may be fed at any position of the column, however it is preferred that it is fed at the lower section of the column in order to minimize contamination of the contaminant lean gaseous stream g2.
(41) In the embodiment shown the contaminant rich liquid stream l2 leaves the column at a position above the inlets of the feed stream and the water inhibitor/scavenger, respectively. In this embodiment the waste liquid stream l3 re-enters the column for use in the lower section, where it is used to scrub out impurities of the incoming gaseous streams fed to the lower part of the column A1.
(42) In the embodiment shown a first contaminant rich liquid stream l2a is partly recirculated to the column, this recirculation may be omitted. Thus, at the bottom section of the column the first contaminant rich liquid stream l2a is withdrawn and at least a portion of the stream is fed to the purification column as a split liquid stream l3b. A second waste stream, l3a, is discarded. The split liquid stream l3b may optionally be subjected to a heat exchanging step (not shown), providing, if heated, either a gaseous stream g3a or a gas liquid mixture or, if cooled, the split liquid stream further cooled. The provision of the recirculation provides either a higher degree of purity when a liquid stream is provided, i.e. the heat exchanger cools, or a higher yield, when the heat exchanger provides heat. This set up will result in a very pure product steam p and a very low degree of waste carbon dioxide (ultimately l3a) without using excessive water inhibitor/scavenger otherwise used if the increased contact between contaminant rich and contaminant lean fluids were to be conducted at the upper part of the purification column.
(43) In the embodiment shown the product is further purified by filtrating (A4), optionally through an activated carbon filter, liquefaction by means of a condenser (A5) and/or a distillation column (A5′—not shown) providing a condensed/distilled liquid carbon dioxide stream l6 and the stream of non-condensable gases g6.
(44) It is also contemplated that liquid carbon dioxide may be withdrawn at a position above the inlet of the water inhibitor/scavenger and the contaminant rich liquid stream (l2) outlet. This stream is denoted a carbon dioxide stream l5 (not shown) The advantage of this embodiment is that the water inhibitor/scavenger is not contaminated with an impurity from which the water inhibitor/scavenger cannot be recovered. In this embodiment the contaminant rich liquid stream is preferably situated at the lower part of the column.
(45) In a further embodiment (not shown) the contaminant rich liquid stream l2 leaving the column is split into the streams l2a the first liquid stream and l2″ a second liquid stream. l2″ is fed to a second reboiler and l2a is mixed with the water inhibitor/scavenger stream l0 and re-enters the column in a mixture as the water inhibitor/scavenger. l2a comprises carbon dioxide, contaminants, water and the water inhibitor/scavenger stream. This looping of the water inhibitor/scavenger is feasible despite the fact that pure inhibitor is mixed with the first liquid stream l2a because pure inhibitor will often have a water binding capacity which exceeds the amount of water present in the feed stream f. Therefore, by looping the liquid stream l2a to the stream l0, both consumption of water inhibitor/scavenger and the volume of the first liquid stream l2a will be reduced, both resulting in overall savings. The ratio of the first liquid stream l2a that is mixed with the water inhibitor/scavenger stream l0 to the contaminant rich stream l2 depends on the water inhibitor/scavenger used. The skilled person will be able to determine the optimal ratio.
(46) In this embodiment the second liquid stream l2″ is fed to the reboiler A3 and re-evaporated and purified according to the invention.
(47) It is, however, also contemplated by the present invention that the first liquid stream l2a is fed to the column again, optionally after being re-evaporated, i.e. the stream l2a is not mixed with l0. This embodiment may be desirable if unexpectedly large amounts of water are present in the feed stream f, or if the stream l0 is diluted beforehand so that the concentration of water inhibitor/scavenger is low.
(48) Another situation where l2a is not mixed with l0 could be if the first liquid stream (l2a) comprises contaminants which react with the water inhibitor/scavenger creating undesired side-products.
(49) The absorbent liquid carbon dioxide may be fully or partially originating from the gaseous feed stream to be purified. This embodiment is suitable when the amount of liquid carbon dioxide to be used is relatively low, such as 400-2000 kg/hour, alternatively it can be used as a supplement to externally supplied liquid carbon dioxide, and is particularly used when the feeding stream is gaseous. In this embodiment the purification column, in which the method is taking place, is provided with a condensing means, preferably in the top section of the column. When the, preferably gaseous, carbon dioxide feed stream contacts the condensing means, a fraction of the gas will condense and, due to the higher density, run in the opposite direction than the gaseous stream and act as the absorbent/rectification liquid. This construction has several advantages; first of all, the set up is relatively simple and part of the absorbent originates from the feed stream to be purified.
(50) The present invention will now be illustrated in more details by way of the following non-limiting example.
Comparative Example
(51) Purification of gaseous carbon dioxide according to the method of the prior art at a constant pressure of 22.8 bar in the column, at a constant feeding gas temperature of 10.70° C. and at a constant liquid carbon dioxide temperature of −18.20° C. is illustrated in the table below with varying flow rates of the liquid absorbent carbon dioxide stream. The number given in the column TB (° C.) is the boiling point of each of the components at 1 bar(a). The loss of carbon dioxide indicated in the top row is loss without any provisions for recovery of the contaminant rich liquid stream (l2).
(52) TABLE-US-00001 Carbon dioxide loss (4/hour) 1562.8 1066.1 817.9 718.6 619.4 173.8 74.9 2.9 Liquid CO.sub.2 fed to column (Kg/h) Feed 2000 1500 1250 1150 1050 600 500 400 Flow rates (kmole/h) gas % Recovery to waste liquid outlet TB ° C. Nitrogen 0.01 1.43 0.97 0.75 0.65 0.56 0.15 0.06 0.00 −195.8 Oxygen 0.01 2.68 1.83 1.41 1.23 1.06 0.30 0.13 0.01 −182.98 Methane 0.01 3.15 2.15 1.65 1.45 1.25 0.35 0.15 0.01 −161.49 Carbon Dioxide 100.00 24.41 18.07 14.47 12.95 11.36 3.47 1.53 0.06 −78.48 Hydrogen Sulfide 0.01 43.41 30.14 23.29 20.53 17.77 5.28 2.49 0.19 −60.35 Carbonyl Sulfide 0.01 95.43 86.96 77.41 71.93 65.30 21.36 9.52 0.32 −50.15 Dimethyl Ether 0.01 99.87 99.46 98.71 98.09 97.07 67.01 37.51 0.66 −24.84 n-Pentane 0.01 99.90 99.60 99.03 98.55 97.78 74.15 49.36 1.81 36.07 Nitrogen Dioxide 0.01 100.00 100.00 99.99 99.99 99.98 99.56 98.04 2.72 20.85 n-Hexane 0.01 100.00 100.00 99.99 99.99 99.98 99.61 98.52 5.01 68.73 Acetaldehyde 0.01 100.00 100.00 100.00 100.00 100.00 99.98 99.89 4.81 20.85 Ethyl Acetate 0.01 100.00 100.00 100.00 100.00 100.00 99.99 99.98 61.40 77.06 Dimethyl Sulfide 0.01 100.00 100.00 100.00 100.00 100.00 100.00 99.99 10.61 37.33 Benzene 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 60.87 80.09 Acetone 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 69.76 56.25 Toluene 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 99.40 110.63 Methanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 99.71 64.7 Ethanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 99.88 78.29 Isobutanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 99.99 107.66 n-Propanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 97.2 Feed gas temp ° C. 10.70 Gas Outlet temp ° C. −19.01 −19.01 −19.00 −19.01 −19.00 −18.97 −18.95 −17.68 Liquid Feed temp. ° C. −18.20 Liquid outlet temp. ° C. −18.83 −18.75 18.74 −18.75 −18.57 −17.66 −16.28 5.24 Liquid outlet flow of CO.sub.2. kmole/hr 35.51 24.22 18.58 16.33 14.07 3.95 1.70 0.07 % CO.sub.2 loss of liquid 78.14 71.07 65.43 62.49 58.99 28.96 14.97 0.74 inlet.sup.a % CO.sub.2 loss of total CO.sub.2 24.41 18.07 14.47 12.95 11.36 3.47 1.53 0.06 amount.sup.b .sup.aThe percentage CO.sub.2 loss of liquid inlet is calculated as the molar flow of liquid CO.sub.2 leaving the column divided by the kg CO.sub.2 fed to the column divided by the molar mass of CO.sub.2 (i.e. 44 g/mole) and multiplied by 100. .sup.bThe percentage CO.sub.2 loss of total CO.sub.2 amount is calculated as the molar flow of liquid CO.sub.2 leaving the column divided by the sum of the gas and liquid inlet (kg liquid CO.sub.2 divided by 44 kmole gas) and multiplied by 100. The percentage
(53) The feed stream f was fed at the bottom of the purification column A1 at a flow of approximately 100 kmole/hour. The major component was carbon dioxide contaminated with minor amounts of the components as indicated in the table.
(54) The liquid absorbent carbon dioxide stream l0 was fed at the top of the purification column at different flow rates in the range 400-2000 kg/hour as indicated in the table above.
(55) The contaminant rich liquid l2 left the purification column at the bottom section and was discarded or re-boiled according to the prior art method and fed to the gaseous feed stream again and fed to the purification column.
(56) The contaminant lean carbon dioxide enriched stream leaving the column at the top section was stored or further processed before being stored, e.g. by filtration and distillation.
(57) From the table it is evident that under the above conditions the lowest applicable flow rate of liquid carbon dioxide was approximately 400 kg/hour. At this flow rate only n-propane was completely reduced; toluene, methanol, ethanol and iso-butanol to over 99%.
(58) Increasing flow rates increased the number of components that were washed out. Thus, depending on the composition of the feed gas the flow rate must be adjusted for optimal results. In the top row the amount of carbon dioxide waste is illustrated. Thus, it can be seen that increasing the flow of liquid carbon dioxide effectuated a more efficient washing out of contaminants, however the amount of waste carbon dioxide in the contaminant rich stream increased dramatically from 1.53% at 500 kg/hour to 24.41% at 2000 kg/hour. Though not shown, increasing the amount of liquid carbon dioxide above 2000 kg/hour would result in even higher percentages of carbon dioxide in the contaminant rich fraction.
(59) Recirculating this contaminant rich carbon dioxide by means of a reboiler as suggested in the prior art would require a large energy input as outlined in table 3 below.
Example 1
(60) A feed stream was treated according to the method described in the comparative example. In addition a blower, i.e. compressing means, was inserted in accordance with alternative 1 according to the present invention.
(61) TABLE-US-00002 TABLE 2 Absorbent liquid carbon dioxide fed to column (kg/hour) Pressure in column bar 22.8 12,000 10,500 9000 7500 6000 4500 3000 1500 Flowrates in feed gas (kmole/hour) % Recovery to liquid outlet Nitrogen 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Oxygen 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Methane 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 Carbon Dioxide 100.00 0.67 0.74 0.82 0.92 1.05 1.23 1.46 1.76 Hydrogen Sulfide 0.01 1.53 1.62 1.72 1.85 2.00 2.20 2.52 2.98 Carbonyl Sulfide 0.01 89.39 89.03 88.37 87.43 85.16 80.73 70.44 42.99 Dimethyl Ether 0.01 99.95 99.95 99.94 99.91 99.91 99.86 99.72 98.81 N-Pentane 0.01 99.97 99.97 99.96 99.94 99.94 99.92 99.83 99.30 Nitrogen Dioxide 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 N-Hexane 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Acetaldehyde 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Ethyl Acetate 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Dimethyl Sulfide 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Benzene 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Acetone 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Toluene 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Methanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Ethanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Isobutanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 N-Propanol 0.01 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Feed gas temp ° C. 10.70 Gas Outlet temp ° C. −19.0 −19.0 −19.0 −19.0 −19.0 −19.0 −19.0 -19.0 Liquid Feed temp. ° C. −18.20 −22.0 −22.0 −22.0 −22.0 −22.0 −22.0 −22.0 -22.0 Liquid outlet temp. ° C. 18.74 −18.75 −18.57 −17.66 −16.28 5.24
(62) From table 2 it can be seen that the amount of carbon dioxide in the overall process was substantially reduced as compared to the comparative example for which the results are shown in table 1. Thus, the waste liquid (l3) comprised only minor volumes of carbon dioxide.
(63) The energy consumption that would be required by the prior art method and the method of the present invention respectively has been compared.
(64) In a recovery unit of the size illustrated, i.e. processing 100 kmole feed gas per hour, approximately 30 kWh internal energy is available (“internal energy” means energy that is neutral to the refrigeration load). The internal energy available will increase with the size of the unit.
(65) In table 3 below the energy consumption is analysed. In a plant operating at 100 kmole feed stream/hour the internal heat available typically corresponds to 30 kWh. “Additional power prior art” in table 3 is the extra power required in order to reduce the CO.sub.2 loss to the same level as for the present invention. Heat required above this value must be supplied from external sources.
(66) TABLE-US-00003 TABLE 3 Absorbent liquid carbon dioxide (kg/hour) 12,000 10,500 9,000 7,500 6,000 4,500 3,000 1,500 Reboiler duty (kWh) 881.2 765.3 649.5 533.6 417.7 301.8 186.0 70.4 Additional power prior 425.61 3676.7 309.73 251.78 193.84 135.90 78.00 20.22 art (kWh) Additional power for 12.3 10.7 9.0 7.4 5.8 4.2 2.6 1.0 refrigeration (kWh) Additional power for 24.5 21.3 18.1 14.9 11.6 8.4 5.2 2.0 blower (kWh) Total additional power 36.8 32.0 27.1 22.3 17.5 12.6 7.8 3.0 present invention (kWh)
(67) From the table it is clearly seen that when applying the solution provided by the present invention the overall energy needed for providing a clean product stream without compromising the yield of carbon dioxide is markedly reduced.