The present disclosure relates generally to systems and methods for purifying and liquefying gas and, more particularly, to a system and method that purifies and liquefies gas using liquid nitrogen.
Industrial gases, such as natural gas or other gases containing high levels of methane, are advantageously stored or transported in a liquid state because they occupy a much smaller volume (liquified natural gas for instance is 1/600th the gaseous state). The liquified gases are then vaporized back to a gaseous state for use at a site or system.
Natural gas, biogas and other gases with high methane content are typically recovered with contaminants or impurities. Such contaminants or impurities may include water and carbon dioxide (CO2). Further contaminants or impurities may include hydrogen sulfide (H2S) or heavy hydrocarbons. These contaminants or impurities can negatively affect the liquification (such as by causing freeze up of the liquifying heat exchanger) and/or utilization of the gas. It is, therefore, important to remove as many of these contaminants or impurities as possible before liquefying and/or storing the gas for use.
Purification of such gases prior to liquefaction often involves a multi-step process that can have high equipment and operational costs. Increases in efficiency are desirable.
There are several aspects of the present subject matter which may be embodied separately or together in the methods, devices and systems described and claimed below. These aspects may be employed alone or in combination with other aspects of the subject matter described herein, and the description of these aspects together is not intended to preclude the use of these aspects separately or the claiming of such aspects separately or in different combinations as set forth in the claims appended hereto.
In one aspect, a system for purifying and liquefying a feed gas stream includes a water condenser having a cooling passage that receives the feed gas stream and cools the feed gas stream so that a cooled gas stream is formed. The water condenser also has a water outlet for removing liquid water from the water condenser. A first cooler has a first cooler cooling passage that further cools the cooled gas stream to separate a first contaminants stream. The first cooler has a first contaminants outlet for removing the first contaminants stream from the first cooler so that a partially purified cooled gas stream is produced. The first cooler further includes a first warming passage that receives a nitrogen stream, warms the nitrogen stream to cool the cooled gas stream and releases a nitrogen vapor stream through a first cooler nitrogen vapor stream outlet. A second cooler has a second cooler cooling passage that further cools the partially purified cooled gas stream to separate a second contaminants stream. The second cooler has a second contaminants outlet for removing the second contaminants stream from the second cooler so that a purified cooled gas stream is produced. The second cooler further includes a second warming passage configured to receive the nitrogen stream, warm the nitrogen stream so to further cool the partially purified cooled gas stream and release the warmed nitrogen stream through a second cooler nitrogen outlet. A liquifier has a liquifier cooling passage that liquifys the purified cooled gas stream and produces a liquid product. The liquefier further includes a liquefier warming passage that receives the nitrogen stream, warms the nitrogen stream so that the purified cooled gas stream is liquified and releases the warmed nitrogen stream through a liquefier nitrogen outlet.
In another aspect, a method for purifying and liquifying a feed gas stream includes the steps of: cooling the feed gas stream and removing liquid water to form a cooled gas stream; cooling the cooled gas stream in a first cooler and removing a first contaminant stream from the first cooler forming a partially purified cooled gas stream; cooling the partially purified cooled gas stream in a second cooler and removing a second contaminant stream from the second cooler to form a purified cooled gas stream; liquefying the purified cooled gas stream to form a liquid product and directing liquid nitrogen through the liquefier and second and first coolers to provide refrigeration therein.
In accordance with the present disclosure, liquid nitrogen is used to provide cooling to a gas purification and liquefication system. As explained below, the nitrogen may exit the system as a vapor stream.
A process flow diagram and schematic illustrating a first embodiment of the gas purification and liquefication system and method of the disclosure is provided in
It should be noted herein that the lines, conduits, piping, passages and similar structures and the corresponding streams are sometimes both referred to by the same element number set out in the figures. Also, as used herein, and as known in the art, a heat exchanger is that device or an area in the device wherein indirect heat exchange occurs between two or more streams at different temperatures, or between a stream and the environment. In addition, all heat exchangers referenced herein may be incorporated into one or more heat exchanger devices or may each be individual heat exchanger devices. As used herein, the terms “communication”, “communicating”, and the like generally refer to fluid communication unless otherwise specified. And although two fluids in communication may exchange heat upon mixing, such an exchange would not be considered to be the same as heat exchange in a heat exchanger, although such an exchange can take place in a heat exchanger. As used herein, the terms, “high”, “middle”, “warm”, “cold” and the like are relative to comparable streams, as is customary in the art.
As shown in
A first solid formation cooler or heat exchanger 24 receives stream 22 and will remove contaminants such as water in the form of solid ice. Heat exchanger 24 may have a mechanism for continuously scraping the heat exchange surfaces in order to remove the solids formed. Examples of such heat exchanger scrapers are provided below with reference to
A second solid formation cooler or heat exchanger 30 receives stream 28 and may be another solid formation cooler similar in design, though not necessarily identical, to that of heat exchanger 24. Another solid contaminant, such as CO2 (dry ice) is removed in second heat exchanger 30. Remaining trace amounts of the contaminant removed in the first heat exchanger 24 may also solidify in heat exchanger 30. The solids may again be scraped from the heat exchange surfaces and collected at the bottom of the exchanger. The CO2 contaminant is removed in a second contaminant stream 32 either in dry ice form, sublimated into vapor CO2, or melted into liquid.
The remaining vapor leaving second heat exchanger 30 in purified cooled gas stream 34 may be relatively free of contaminants that would form solids above the bubble point of biomethane/natural gas and thus freezing in the liquefier 36. As examples only, stream 34 may have a pressure of ˜3 bar and a temperature of ˜−140° C. Liquefier 36, which may be a heat exchanger, liquefies the remaining vapor in stream 34 at a low or near atmospheric pressure. The liquid product known as liquefied biogas (LBG) or liquefied natural gas (LNG) is removed via stream 38 to a storage tank, tanker, or other transportation mode. As examples only, stream 38 may have a pressure of ˜2 bar and a temperature of ˜−165° C.
Pressurized liquid nitrogen enters the process via stream 40 and flows countercurrent to the vapor stream being purified and liquified. As examples only, the liquid nitrogen in stream 40 may have a pressure of ˜10 bar and a temperature of its bubble point of ˜−196° C. As an example only, the nitrogen may be sourced from an onsite liquid nitrogen tank that is able to be periodically refilled from a truck with liquid nitrogen purchased from a commercial supplier or other local sources. Liquefied waste nitrogen from a nearby air separation unit (ASU) or other device or system is another possible source of the liquid nitrogen.
The liquid nitrogen from stream 40 is warmed and vaporized as it flows through liquefier 36 as the vapor from stream 34 is liquified. The warmed nitrogen is further warmed as it passes through, and provides refrigeration in, second heat exchanger 30, and then first heat exchanger 24 via streams 50 and 52. The nitrogen stream is fully vaporized at or before it leaves first heat exchanger 24 via stream 42. As examples only, stream 42 may have a pressure of ˜2 bar and a temperature of ˜−21° C. The warm nitrogen vapor stream 42, which may still be below ambient temperature, can either be vented to a safe location via stream 44 or it can be routed via stream 46 to cooler 18 in order to supplement or replace air or water cooling within cooler 18. If the warm nitrogen is used in cooler 18, it will be further warmed and then vented to a safe location via stream 48.
Turning now to the embodiment of
In
If the liquid from second heat exchanger 154 is sent to first heat exchanger 124 then the liquid/solid slurry is removed via first contaminant stream 126 and stream 160 and may be further processed in separator 156 to produce first separate contaminant product stream 162 and second separate contaminant product stream 164. The separator 156, as in the case of any of the separators disclosed herein, may be an accumulation drum or any other separation vessel or other type of separation device known in the art including, but not limited to a cyclonic separator, a distillation unit, a coalescing separator or a mesh or vane type mist eliminator.
Potential separation methods that can be used in separator 156 will be obvious to one skilled in the art and may include filtering the solid contaminants such as ice from the liquid contaminant as well as boiling the liquid contaminant from the solid contaminant. Boiling can be accomplished through addition of heat and/or reduction of pressure. For some contaminant dispositions separation in separator 156 may not be necessary. Separator 156 may also include pumps, heat exchangers, and other equipment necessary to preform the separation of the two contaminants, as would be obvious to one skilled in the art.
To liquify CO2 in second heat exchanger 154, the pressure may need to be above ˜5.1 bar and the temperature below ˜−56 C. In such an embodiment, all of the pressures and temperatures in stream 116, cooler 118, stream 122, first heat exchanger 124, and stream 128 would be higher than ˜5.1 bar and −56 C, or a compressor and possibly an air or water cooler could be placed along stream 128 between first heat exchanger 124 and second heat exchanger 154.
In the embodiment of
It is to be understood that the embodiment of
The liquid/solid slurry in stream 266 and/or a liquid/solid slurry stream 260 originally from cooler 224 may be sent via stream 270 to separator 256 for separation similar to that in separator 156. Separator 256 may produce first separate contaminant product stream 262 and second separate contaminant product stream 264.
To liquify CO2 in second heat exchanger 230, the pressure may need to be above ˜5.1 bar and the temperature below ˜−56° C. Therefore, in this embodiment, all of the pressures and temperatures in stream 216, cooler 218, stream 222, first heat exchanger 224, and stream 228 would be higher than ˜5.1 bar and −56° C., or a compressor and possibly an air or water cooler could be placed along stream 228 between first heat exchanger 224 and second heat exchanger 230.
As noted previously, in some embodiments, it is desirable for the heat exchangers with solids formation to be continuously scraped while the gas is flowing to maintain a near constant heat transfer coefficient on the exchanger walls, with either periodic or continuous dumping of solids collected at the bottom. For removal of the solids scraped from the side of the exchangers, the bottom of the exchanger may open to a screw press that continuously packs the solids into a sealable chamber (with a closing door, gate, valve or similar) away from the exchanger such that vapor is kept out of the sealable chamber, and any heating would not affect the exchanger. In this case, the solids may be recovered and melted or sublimated in batches. Alternately, sealing may not be necessary, other than around the screw blades, allowing for continuous melting and/or sublimation of the removed solids in a chamber at the end of the screw press. Heating, possibly electric, of the screw blades may be used in some embodiments to prevent solids build-up.
Creating a liquid slurry, either by co-producing ice and liquid CO2 in the same exchanger or washing the ice collected at the bottom of one exchanger with liquid CO2 created elsewhere (either as melted dry ice or condensed from vapor) are also solutions to this. As another option, heating a sealing device or dump valve at the bottom of the exchanger to ensure proper opening and closing can be done. Some degassing might be necessary in this case if the solids aren't sufficiently packed at the bottom of the exchanger.
A sectional or cutaway view (taken along the longitudinal axis) of a portion of one potential configuration of a scraping heat exchanger suitable, indicated in general at 300, for use with the system and method of the disclosure is presented in
Scraper blades 308 are distributed along the length of a central axle 312 and are attached thereto by blade arms 314 in a fixed fashion so that all of the heat transfer surface of the inner wall may be scraped by the blades 308 when the central axle 312 is rotated. The blades and blade arms illustrated are not necessarily drawn to scale. The blades 308 may be attached perpendicularly or at an angle with regard to the central axle 312. Blades 308 are attached at multiple degrees of rotation around the axle 312 such that there are no two blades touching. The axle may be continuously rotated buy a motor, gears, or another method at one or both ends of the heat exchanger. The blades may rotate, for example at a 30-60 RPM, but faster and slower rotational speeds have been contemplated.
The scraper blades 308 can feature many alternative shapes including, but not limited to, triangular or rectangular. The blades 308 and their arms 314 may have an anti-stick coating, be made from anti-stick materials, be made in whole or in part from a polymer, and/or heated to prevent solids from sticking to the blades and ensured that the solids scraped from the inner wall of the inner pipe 302 drop to the bottom of the heat exchanger. The blades may or may not be spring loaded (optional springs illustrated at 315 in
Flow path arrows 316 and 318 indicate possible flow directions of the coolant and process gas flow, respectively, but may vary based on specific application needs. Indeed, the coolant and process gas flow directions may be opposite those indicated by arrows 316 and 318 in
An embodiment of a solids and liquids collection section, indicated in general at 320, is presented schematically in
Further non-limiting details and/or non-limiting screw press designs for the screw 324 and housing 325 arrangement may be found in U.S. Patent Application Publication No. US20180172346A1 to Baxter et al. and U.S. Patent Application Publication No. US20180170784A1 to Baxter et al., the contents of both of which are hereby incorporated by reference.
After all the solids are compacted and effectively degassed, solids and any collected liquids can be removed from conduit 325 through a valve 326 or other openable sealing mechanism. The valve or sealing mechanism may be normally open or may open and close as needed to ensure that only packed, degassed solids and/or liquids are removed from that location.
A valved line 328 (illustrated in
Any portion of the solids collection section such as the walls, screw, valve or sealing mechanism may have an anti-stick coating, be made from anti-stick materials, be made in whole or in part from a polymer, and/or be heated to prevent solids from sticking and clogging this section.
Furthermore, solid scraping of heat exchangers has been previously described in the art, particularly in U.S. Pat. No. 10,780,460 and European application no. EP3791125A1, each of which are incorporated by reference in their entirety. European application no. EP3791125A1 describes a condensate extraction device for a heat exchanger, including a condensate drain opening and a lock device having a condensate collection chamber wherein the lock device can be arranged in a collection position and in a drain position. U.S. Pat. No. 10,780,460 describes a heat exchanger with a cylindrical tube with guiding grooves and a lead screw with a cleaning element in which a rotating movement of the lead screw moves the cleaning element in the axial direction along the guiding grooves.
It is possible to recover a partially pure water stream under certain configurations and conditions. However, if some hydrates are expected to form in the water freezing cooler, the melted water stream can be recycled to the liquid section of one or more compressor knockout drums or free water knockout drums to allow the methane trapped as hydrate to be recovered. Frozen water or hydrate in the CO2 recovery stream (liquid or solid) may require additional processing, depending on the disposition of the CO2 stream. If the maximum amount of water is removed in an exchanger prior to the exchanger which removes CO2, then the contamination of water and hydrates in the CO2 stream should be minimal and may not require removal for most dispositions of CO2.
It is possible and may be desirable to include pressure drops, such as by Joule-Thomson (JT) or other expansion valves or devices, along the path of the gas being purified and liquefied. For example, such expansion devices may be included at streams 22, 28, 34, and 38 and/or streams 50, 52, and 42 and/or corresponding streams in
If the recovered solid and/or liquid contaminants are not required to be maintained at cold temperatures for their final sale or disposition, the recovered streams maybe heat integrated into any of the cooling steps.
While first and second coolers and a single water condenser are illustrated, the number of coolers and condensers may vary from what is illustrated in the above embodiments.
In the above embodiments, a refrigerant loop is not necessary, with the systems using only liquid nitrogen and air/water cooling. All cooling below what can be achieved with air/water cooling is done with liquid nitrogen, but the liquid nitrogen can also be used for higher temperature cooling. Pressurized liquid nitrogen enters the liquefier first, and is vaporized in the liquefier, at least partially, and then the nitrogen continues to the coldest stage of cooling and freeze out. Once the nitrogen is fully vaporized it continues to cool the gas feed stream as the nitrogen warms. In the above embodiments, the nitrogen cooling should be sufficient to remove the desired impurities as either solid or liquid and still be cold enough to provide some additional cooling near ambient temperatures.
While the preferred embodiments of the disclosure have been shown and described, it will be apparent to those skilled in the art that changes and modifications may be made therein without departing from the spirit of the disclosure, the scope of which is defined by the following claims.
This application claims the benefit of U.S. Provisional Application No. 63/271,388, filed Oct. 25, 2021, the contents of which are hereby incorporated by reference.
Number | Date | Country | |
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63271388 | Oct 2021 | US |