The devices, systems, and methods described herein relate generally to fluid separations. More particularly, the devices, systems, and methods described herein relate to desiccation and stripping components from fluids.
Desiccation and stripping of compounds from fluids, gases or liquids, is often accomplished using solid desiccants and stripping agents. Solid desiccants, such as molecular sieves, and solid stripping agents, such as activated carbon, are useful but are required to be in certain temperature regimes to run optimally. Existing desiccants and stripping agents tend to be optimized for temperatures at or near ambient. Devices, methods, and systems capable of operating at a temperature higher than that of the process flow without significant heat losses would be beneficial.
Devices, systems, and methods for removing a component from a fluid are disclosed. A feed fluid is heated by passing the feed fluid through a heating path of a first indirect-contact heat exchanger (ICHE). The feed fluid contains a first component. The fluid is heated from a first temperature to a second temperature, resulting in a heated feed fluid. The heated feed fluid is passed through a desiccator, containing a desiccant. The first component is bound up to the desiccant, resulting in a stripped-heated feed fluid. The stripped-heated feed fluid is cooled by passing the stripped-heated feed fluid through a cooling path of the first indirect-contact heat exchanger (ICHE). The stripped-heated feed fluid is cooled from a second temperature to a third temperature, the third temperature being greater than the first temperature, producing a product fluid.
The second temperature may be maintained substantially at an ambient temperature. The feed fluid may be passed below a feed rate at which a first sensible heat transfer from the feed fluid to the desiccant is greater than a second sensible heat transfer from an ambient environment around the desiccator into the desiccant. The desiccator may have heat exchange surfaces mounted to the desiccator that increase the second sensible heat transfer from the ambient environment around the desiccator into the desiccant.
A difference between the first temperature and the third temperature may be between 0° C. and 20° C. The first temperature may be between −80° C. and −25° C.
The feed fluid may be a liquid. The liquid may consist of water, hydrocarbons, liquid ammonia, liquid carbon dioxide, cryogenic liquids, or a combination thereof. The first component may be carbon dioxide, nitrogen oxide, sulfur dioxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, hydrogen cyanide, water, mercury, hydrocarbons, pharmaceuticals, soot, dust, minerals, microbes, precipitated salts, precious metals, base metals, or a combination thereof.
The feed fluid may be a carrier gas. The carrier gas may consist of flue gas, syngas, producer gas, natural gas, steam reforming gas, hydrocarbons, light gases, refinery off-gases, organic solvents, steam, ammonia, or a combination thereof. The first component may be carbon dioxide, nitrogen oxide, sulfur dioxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, hydrogen cyanide, water, mercury, hydrocarbons, pharmaceuticals, soot, dust, minerals, microbes, precipitated salts or a combination thereof. A preliminary gas may be passed through a brine dryer, wherein a fraction of the preliminary gas consists of water and the brine dryer removes a portion of the water from the preliminary gas, producing the carrier gas. The product fluid may be cooled to a fourth temperature by passing the product fluid through a second ICHE, producing a cooled product fluid. The fourth temperature is below the first temperature. The cooled product fluid may be passed through a desublimating direct-contact heat exchanger, the desublimating direct-contact heat exchanger removing a second component from the product fluid.
The desiccant may be activated alumina, aerogel, benzophenone, Bentonite clay, calcium chloride, calcium oxide, calcium sulfate, cobalt(ii) chloride, copper(ii) sulfate, lithium chloride, lithium bromide, magnesium sulfate, magnesium perchlorate, molecular sieve, potassium carbonate, potassium hydroxide, silica gel, sodium chlorate, sodium chloride, sodium hydroxide, sodium sulfate, sucrose, activated carbon, biochar, ion-exchange resins, diatomaceous earth, porous membranes, xeolites, conjugated microporous polymers, porous ceramics, or a combination thereof.
In order that the advantages of the described devices, systems, and methods will be readily understood, a more particular description of the described devices, systems, and methods briefly described above will be rendered by reference to specific embodiments illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the described devices, systems, and methods and are not therefore to be considered limiting of its scope, the devices, systems, and methods will be described and explained with additional specificity and detail through use of the accompanying drawings, in which:
It will be readily understood that the described devices, systems, and methods, as generally described and illustrated in the Figures herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description of the embodiments of the described devices, systems, and methods, as represented in the Figures, is not intended to limit the scope of the described devices, systems, and methods, as claimed, but is merely representative of certain examples of presently contemplated embodiments in accordance with the described devices, systems, and methods.
The term desiccant, as used herein, is not limited to a hygroscopic substance that attracts and absorbs water. Rather, desiccation is defined herein as the removal of a component or components out of a fluid—gas, liquid, or slurry. The first component or components removed are not limited to water, but can include any substance being stripped, absorbed out of, removed from, or bound out of a fluid. A desiccant is, therefore, a solid that captures the first component or components out of the fluid. The term “stripped” is equivalent to the term “desiccated” herein. As such, desiccators can include traditional desiccators, strip vessels, filters, or any other system where solids are used to extract components.
Ambient temperature is vaguely and inconsistently defined in industry and literature. In general, this temperature is assumed to be 20 to 25° C. However, when used herein, ambient temperature is defined as a temperature between the freezing point of water and 60° C.
As cryogenic processes often require temperatures far below the freezing point of water, water is generally removed as early as possible in a cryogenic process, before it has a chance to freeze out in sensitive, low temperature equipment, potentially blocking or damaging that equipment. However, water is very difficult to remove. Processes like distillation require heat and are, therefore, heading the wrong direction. Brine drying (which operates at below ambient temperatures, for example) is an excellent solution, but incomplete (as it generally leaves a few parts per million of water in the process stream, for example). However, even a few parts per million of water can freeze up equipment at low cryogenic temperatures. As such, the devices, systems, and methods disclosed herein were developed to enable further drying of the process stream (using desiccation, for example). It is appreciated that the described devices, systems, and methods have much broader application than removing just water from the process stream. For example, the described devices, systems, and methods may be used to remove any of a variety of components (e.g., water, mercury, acid gases, and hydrocarbons) which are referred to generally as a component. It is further appreciated that the described devices, systems, and methods have broader application than cryogenics, including electrowinning, reverse-Arrhenius reactions involving solids, or any situation where a process needs to be warmed up for a single unit operation but then be cooled again after.
In short, the concepts herein involve pre-heating a process stream (i.e., using a stripped process stream from a desiccator) before it passes through the desiccator to remove a component from the process stream, binding that component to the solids in the desiccator (resulting in the stripped process stream, for example). The stripped process stream is then used to preheat the process stream. In the case of cryogenics, the source of heat can be as simple as the ambient environment. In other cases, some amount of heat would be added to the desiccator. In all instances, the amount of heat needed in the desiccator is reduced by the recuperative heat exchange step. In the case of cryogenics, the sensible heat requirements to reheat a desiccator are far less than the sensible heat requirements to preheat a process gas, making this solution critical for success.
Combustion flue gas consists of the exhaust gas from a fireplace, oven, furnace, boiler, steam generator, or other combustor. The combustion fuel sources include coal, hydrocarbons, and bio-mass. Combustion flue gas varies greatly in composition depending on the method of combustion and the source of fuel. Combustion in pure oxygen produces little to no nitrogen in the flue gas. Combustion using air leads to the majority of the flue gas consisting of nitrogen. The non-nitrogen flue gas consists of mostly carbon dioxide, water, and sometimes unconsumed oxygen. Small amounts of carbon monoxide, nitrogen oxides, sulfur dioxide, hydrogen sulfide, and trace amounts of hundreds of other chemicals are present, depending on the source. Entrained dust and soot will also be present in all combustion flue gas streams. The method disclosed applies to any combustion flue gases. Dried combustion flue gas has had the water removed.
Syngas consists of hydrogen, carbon monoxide, and carbon dioxide.
Producer gas consists of a fuel gas manufactured from materials such as coal, wood, or syngas. It consists mostly of carbon monoxide, with tars and carbon dioxide present as well.
Steam reforming is the process of producing hydrogen, carbon monoxide, and other compounds from hydrocarbon fuels, including natural gas. The steam reforming gas referred to herein consists primarily of carbon monoxide and hydrogen, with varying amounts of carbon dioxide and water.
Light gases include gases with higher volatility than water, including hydrogen, helium, carbon dioxide, nitrogen, and oxygen. This list is for example only and should not be implied to constitute a limitation as to the viability of other gases in the process. A person of skill in the art would be able to evaluate any gas as to whether it has higher volatility than water.
Refinery off-gases comprise gases produced by refining precious metals, such as gold and silver. These off-gases tend to contain significant amounts of mercury and other metals.
Referring now to the Figures,
In another embodiment, the partially-dried flue gas 120 has about 200 ppm water at −35° C. The temperature can range between −35° C. and −70° C. in various embodiments. In other embodiments, flue gas 118 may be replaced by syngas, producer gas, natural gas, steam reforming gas, hydrocarbons, light gases, refinery off-gases, organic solvents, steam, ammonia. Each of these alternatives would require different temperatures for the second cooled-dried gas 128 and the desublimating DCE 108. The temperature of the desublimating direct-contact exchanger 108 would be at or below the temperature at which the component to be removed desublimates. The temperature of the second cooled-dried gas 128 would be above that temperature.
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In some embodiments, the second temperature is maintained substantially at an ambient temperature. In one instance, the feed fluid is passed below a feed rate at which a first sensible heat transfer from the feed fluid to the desiccant is greater than a second sensible heat transfer from the ambient environment around the desiccator into the desiccant. In some instances, such as when a higher feed rate is needed than the second sensible heat transfer can accomplish, the desiccator further comprises heat exchange surfaces mounted to the desiccator that increase the second sensible heat transfer from the ambient environment around the desiccator into the desiccant. These may be fins, radiators, or other attachments that increase surface area for convection and conduction with the ambient environment.
In some embodiments, a difference between the first temperature and the third temperature is between 0° C. and 20° C. In some embodiments, the first temperature is between −80° C. and −25° C.
In some embodiments, the feed fluid may be a liquid, the liquid being water, hydrocarbons, liquid ammonia, liquid carbon dioxide, cryogenic liquids, or a combination thereof. In some embodiments, the hydrocarbons may be 1,1,3-trimethylcyclopentane, 1,4-pentadiene, 1,5-hexadiene, 1-butene, 1-methyl-1-ethylcyclopentane, 1-pentene, 2,3,3,3-tetrafluoropropene, 2,3-dimethyl-1-butene, 2-chloro-1,1,1,2-tetrafluoroethane, 2-methylpentane, 3-methyl-1,4-pentadiene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-methylpentane, 4-methyl-1-hexene, 4-methyl-1-pentene, 4-methylcyclopentene, 4-methyl-trans-2-pentene, bromochlorodifluoromethane, bromodifluoromethane, bromotrifluoroethylene, chlorotrifluoroethylene, cis 2-hexene, cis-1,3-pentadiene, cis-2-hexene, cis-2-pentene, dichlorodifluoromethane, difluoromethyl ether, trifluoromethyl ether, dimethyl ether, ethyl fluoride, ethyl mercaptan, hexafluoropropylene, isobutane, isobutene, isobutyl mercaptan, isopentane, isoprene, methyl isopropyl ether, methylcyclohexane, methylcyclopentane, methylcyclopropane, n,n-diethylmethylamine, octafluoropropane, pentafluoroethyl trifluorovinyl ether, propane, sec-butyl mercaptan, trans-2-pentene, trifluoromethyl trifluorovinyl ether, vinyl chloride, bromotrifluoromethane, chlorodifluoromethane, dimethyl silane, ketene, methyl silane, perchloryl fluoride, propylene, vinyl fluoride, or combinations thereof.
In some embodiments, the first component comprises carbon dioxide, nitrogen oxide, sulfur dioxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, hydrogen cyanide, water, mercury, hydrocarbons, pharmaceuticals, soot, dust, minerals, microbes, precipitated salts, precious metals, base metals, or a combination thereof.
In some embodiments, the feed fluid may be a carrier gas, the carrier gas comprising flue gas, syngas, producer gas, natural gas, steam reforming gas, hydrocarbons, light gases, refinery off-gases, organic solvents, steam, ammonia, or a combination thereof. In some embodiments, the first component may be carbon dioxide, nitrogen oxide, sulfur dioxide, nitrogen dioxide, sulfur trioxide, hydrogen sulfide, hydrogen cyanide, water, mercury, hydrocarbons, pharmaceuticals, soot, dust, minerals, microbes, precipitated salts or a combination thereof.
In some embodiments, the desiccant may be activated alumina, aerogel, benzophenone, Bentonite clay, calcium chloride, calcium oxide, calcium sulfate, cobalt(ii) chloride, copper(ii) sulfate, lithium chloride, lithium bromide, magnesium sulfate, magnesium perchlorate, molecular sieve, potassium carbonate, potassium hydroxide, silica gel, sodium chlorate, sodium chloride, sodium hydroxide, sodium sulfate, sucrose, activated carbon, biochar, ion-exchange resins, diatomaceous earth, porous membranes, xeolites, conjugated microporous polymers, porous ceramics, or a combination thereof.
This invention was made with government support under DE-FE0028697 awarded by the Department of Energy. The government has certain rights in the invention.