Pressure swing adsorption

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Schematic drawing of the PSA process ("aria" = air input). Note the symmetry in a vertical plane between the left and the right sketches. Adsorbimento - layout rigenerazione.svg
Schematic drawing of the PSA process ("aria" = air input). Note the symmetry in a vertical plane between the left and the right sketches.
Nitrogen generator using PSA Pressure Swing Adsorption oxygen concentrator.jpg
Nitrogen generator using PSA

Pressure swing adsorption (PSA) is a technique used to separate some gas species from a mixture of gases (typically air) under pressure according to the species' molecular characteristics and affinity for an adsorbent material. It operates at near-ambient temperature and significantly differs from the cryogenic distillation commonly used to separate gases. Selective adsorbent materials (e.g., zeolites, (aka molecular sieves), activated carbon, etc.) are used as trapping material, preferentially adsorbing the target gas species at high pressure. The process then swings to low pressure to desorb the adsorbed gas.

Contents

Process

Animation of pressure swing adsorption, (1) and (2) showing alternating adsorption and desorption.
I
compressed air input
A
adsorption
O
oxygen output
D
desorption
E
exhaust Pressure swing adsorption principle.svg
Animation of pressure swing adsorption, (1) and (2) showing alternating adsorption and desorption.
Icompressed air inputAadsorption
Ooxygen outputDdesorption
Eexhaust

The pressure swing adsorption (PSA) process is based on the phenomenon that under high pressure, gases tend to be trapped onto solid surfaces, i.e. to be "adsorbed". The higher the pressure, the more gas is adsorbed. When the pressure is dropped, the gas is released, or desorbed. PSA can be used to separate gases in a mixture because different gases are adsorbed onto a given solid surface more or less strongly. For example, if a gas mixture such as air is passed under pressure through a vessel containing an adsorbent bed of zeolite that attracts nitrogen more strongly than oxygen, a fraction of nitrogen will stay in the bed, and the gas exiting the vessel will be richer in oxygen than the mixture entering. When the bed reaches the limit of its capacity to adsorb nitrogen, it can be regenerated by decreasing the pressure, thus releasing the adsorbed nitrogen. It is then ready for another cycle of producing oxygen-enriched air.

Using two adsorbent vessels allows for near-continuous production of the target gas. It also allows a pressure equalisation, where the gas leaving the vessel being depressurised is used to partially pressurise the second vessel. This results in significant energy savings, and is a common industrial practice.

Adsorbents

Aside from their ability to discriminate between different gases, adsorbents for PSA systems are usually very porous materials chosen because of their large specific surface areas. Typical adsorbents are zeolite, activated carbon, silica gel, alumina, or synthetic resins. Though the gas adsorbed on these surfaces may consist of a layer only one or at most a few molecules thickness, surface areas of several hundred square meters per gram enable the adsorption of a large portion of the adsorbent's weight in gas. In addition to their affinity for different gases, zeolites and some types of activated carbon may utilize their molecular sieve characteristics to exclude some gas molecules from their structure based on the size and shape of the molecules, thereby restricting the ability of the larger molecules to be adsorbed.

Applications

Gas separator membrane skid used in landfill gas utilization process Gas separator membrane skid for PSA process of landfill gas.jpg
Gas separator membrane skid used in landfill gas utilization process

Aside from its use to supply medical oxygen, or as a substitute for bulk cryogenic or compressed-cylinder storage, which is the primary oxygen source for any hospital, PSA has numerous other uses. One of the primary applications of PSA is in the removal of carbon dioxide (CO2) as the final step in the large-scale commercial synthesis of hydrogen (H2) for use in oil refineries and in the production of ammonia (NH3). Refineries often use PSA technology in the removal of hydrogen sulfide (H2S) from hydrogen feed and recycle streams of hydrotreating and hydrocracking units. Another application of PSA is the separation of carbon dioxide from biogas to increase the methane (CH4) ratio. Through PSA the biogas can be upgraded to a quality similar to natural gas. This includes a process in landfill gas utilization to upgrade landfill gas to utility-grade high purity methane gas to be sold as natural gas. [1]

PSA is also used in:

In the frame of carbon capture and storage (CCS), research is also currently underway to capture CO2 in large quantities from coal-fired power plants prior to geosequestration, in order to reduce greenhouse gas production from these plants. [4] [5]

PSA has also been discussed as a future alternative to the non-regenerable sorbent technology used in space suit primary life support systems, in order to save weight and to extend the operating time of the suit. [6]

This is the process used in medical oxygen concentrators used by emphysema and COVID-19 patients and others requiring oxygen-enriched air for breathing.[ citation needed ]

Variations of PSA technology

Double Stage PSA

(DS-PSA, sometimes also referred to as Dual Step PSA)
With this variant of PSA developed for use in laboratory nitrogen generators, nitrogen gas is produced into two steps: in the first step, the compressed air is forced to pass through a carbon molecular sieve to produce nitrogen at a purity of approximately 98%; in the second step this nitrogen is forced to pass into a second carbon molecular sieve and the nitrogen gas reaches a final purity up to 99.999%. The purge gas from the second step is recycled and partially used as feed gas in the first step.

In addition, the purge process is supported by active evacuation for better performance in the next cycle. The goals of both of these changes is to improve efficiency over a conventional PSA process.

DS-PSA can also be applied to increase the oxygen concentration. In this case, an aluminum silica based zeolite adsorbs nitrogen in the first stage reaching 95% oxygen in the outlet, and in the second stage a carbon-based molecular sieve adsorbs the residual nitrogen in a reverse cycle, concentrating oxygen up to 99%.

Rapid PSA

Rapid pressure swing adsorption, or RPSA, is frequently used in portable oxygen concentrators. It allows a large reduction in the size of the adsorbent bed when high purity is not essential and when the feed gas (air) can be discarded. [7] It works by quickly cycling the pressure while alternately venting opposite ends of the column at the same rate. This means that non-adsorbed gases progress along the column much faster and are vented at the distal end, while adsorbed gases do not get the chance to progress and are vented at the proximal extremity. [8]

Vacuum swing adsorption

Vacuum swing adsorption (VSA) segregates certain gases from a gaseous mixture at near ambient pressure; the process then swings to a vacuum to regenerate the adsorbent material. VSA differs from other PSA techniques because it operates at near-ambient temperatures and pressures. VSA typically draws the gas through the separation process with a vacuum. For oxygen and nitrogen VSA systems, the vacuum is typically generated by a blower. Hybrid vacuum pressure swing adsorption (VPSA) systems also exist. VPSA systems apply pressurized gas to the separation process and also apply a vacuum to the purge gas. VPSA systems, like one of the portable oxygen concentrators, are among the most efficient systems measured on customary industry indices, such as recovery (product gas out/product gas in) and productivity (product gas out/mass of sieve material). Generally, higher recovery leads to a smaller compressor, blower, or other compressed gas or vacuum source and lower power consumption. Higher productivity leads to smaller sieve beds. The consumer will most likely consider indices which have a more directly measurable difference in the overall system, like the amount of product gas divided by the system weight and size, the system initial and maintenance costs, the system power consumption or other operational costs, and reliability.

See also

Related Research Articles

<span class="mw-page-title-main">Haber process</span> Industrial process for ammonia production

The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. The German chemists Fritz Haber and Carl Bosch developed it in the first decade of the 20th century. The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using an iron metal catalyst under high temperatures and pressures. This reaction is slightly exothermic (i.e. it releases energy), meaning that the reaction is favoured at lower temperatures and higher pressures. It decreases entropy, complicating the process. Hydrogen is produced via steam reforming, followed by an iterative closed cycle to react hydrogen with nitrogen to produce ammonia.

<span class="mw-page-title-main">Zeolite</span> Microporous, aluminosilicate mineral

Zeolite is a family of several microporous, crystalline aluminosilicate materials commonly used as commercial adsorbents and catalysts. They mainly consist of silicon, aluminium, oxygen, and have the general formula Mn+
1/n
(AlO
2
)
(SiO
2
)
x
・yH
2
O
where Mn+
1/n
is either a metal ion or H+. These positive ions can be exchanged for others in a contacting electrolyte solution. H+
exchanged zeolites are particularly useful as solid acid catalysts.

<span class="mw-page-title-main">Adsorption</span> Phenomenon of surface adhesion

Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid is dissolved by or permeates a liquid or solid. While adsorption does often precede absorption, which involves the transfer of the absorbate into the volume of the absorbent material, alternatively, adsorption is distinctly a surface phenomenon, wherein the adsorbate does not penetrate through the material surface and into the bulk of the adsorbent. The term sorption encompasses both adsorption and absorption, and desorption is the reverse of sorption.

<span class="mw-page-title-main">Activated carbon</span> Form of carbon with an extremely high surface area

Activated carbon, also called activated charcoal, is a form of carbon commonly used to filter contaminants from water and air, among many other uses. It is processed (activated) to have small, low-volume pores that greatly increase the surface area available for adsorption or chemical reactions that can be thought of as a microscopic "sponge" structure.. Activation is analogous to making popcorn from dried corn kernels: popcorn is light, fluffy, and its kernels have a high surface-area-to-volume ratio. Activated is sometimes replaced by active.

<span class="mw-page-title-main">Membrane gas separation</span> Technology for splitting specific gases out of mixtures

Gas mixtures can be effectively separated by synthetic membranes made from polymers such as polyamide or cellulose acetate, or from ceramic materials.

An oxygen concentrator is a device that concentrates the oxygen from a gas supply by selectively removing nitrogen to supply an oxygen-enriched product gas stream. They are used industrially, to provide supplemental oxygen at high altitudes, and as medical devices for oxygen therapy.

<span class="mw-page-title-main">Molecular sieve</span> Filter material with homogeneously sized pores in the nanometer range

A molecular sieve is a material with pores of uniform size. These pore diameters are similar in size to small molecules, and thus large molecules cannot enter or be adsorbed, while smaller molecules can. As a mixture of molecules migrates through the stationary bed of porous, semi-solid substance referred to as a sieve, the components of the highest molecular weight leave the bed first, followed by successively smaller molecules. Some molecular sieves are used in size-exclusion chromatography, a separation technique that sorts molecules based on their size. Another important use is as a desiccant. Most of molecular sieves are aluminosilicate zeolites with Si/Al molar ratio less than 2, but there are also examples of activated charcoal and silica gel.

<span class="mw-page-title-main">Industrial gas</span> Gaseous materials produced for use in industry

Industrial gases are the gaseous materials that are manufactured for use in industry. The principal gases provided are nitrogen, oxygen, carbon dioxide, argon, hydrogen, helium and acetylene, although many other gases and mixtures are also available in gas cylinders. The industry producing these gases is also known as industrial gas, which is seen as also encompassing the supply of equipment and technology to produce and use the gases. Their production is a part of the wider chemical Industry.

The sorption pump is a vacuum pump that creates a vacuum by adsorbing molecules on a very porous material like molecular sieve which is cooled by a cryogen, typically liquid nitrogen. The ultimate pressure is about 10−2 mbar. With special techniques this can be lowered till 10−7 mbar. The main advantages are the absence of oil or other contaminants, low cost and vibration free operation because there are no moving parts. The main disadvantages are that it cannot operate continuously and cannot effectively pump hydrogen, helium and neon, all gases with lower condensation temperature than liquid nitrogen. The main application is as a roughing pump for a sputter-ion pump in ultra-high vacuum experiments, for example in surface physics.

A nitrogen rejection unit (NRU) selectively removes nitrogen from a gas. The name can be applied to any system that removes nitrogen from natural gas.

<span class="mw-page-title-main">Carbon dioxide scrubber</span> Device which absorbs carbon dioxide from circulated gas

A carbon dioxide scrubber is a piece of equipment that absorbs carbon dioxide (CO2). It is used to treat exhaust gases from industrial plants or from exhaled air in life support systems such as rebreathers or in spacecraft, submersible craft or airtight chambers. Carbon dioxide scrubbers are also used in controlled atmosphere (CA) storage. They have also been researched for carbon capture and storage as a means of combating climate change.

Supercritical adsorption also referred to as the adsorption of supercritical fluids, is the adsorption at above-critical temperatures. There are different tacit understandings of supercritical fluids. For example, “a fluid is considered to be ‘supercritical’ when its temperature and pressure exceed the temperature and pressure at the critical point”. In the studies of supercritical extraction, however, “supercritical fluid” is applied for a narrow temperature region of 1-1.2 or to +10 K, which is called the supercritical region.

<span class="mw-page-title-main">Nitrogen generator</span>

Nitrogen generators and stations are stationary or mobile air-to-nitrogen production complexes.

A biogas upgrader is a facility that is used to concentrate the methane in biogas to natural gas standards. The system removes carbon dioxide, hydrogen sulphide, water and contaminants from the biogas. One technique for doing this uses amine gas treating. This purified biogas is also called biomethane. It can be used interchangeably with natural gas.

Oxygen plants are industrial systems designed to generate oxygen. They typically use air as a feedstock and separate it from other components of air using pressure swing adsorption or membrane separation techniques. Such plants are distinct from cryogenic separation plants which separate and capture all the components of air.

An air separation plant separates atmospheric air into its primary components, typically nitrogen and oxygen, and sometimes also argon and other rare inert gases.

Gas separation can refer to any of a number of techniques used to separate gases, either to give multiple products or to purify a single product.

Solid sorbents for carbon capture include a diverse range of porous, solid-phase materials, including mesoporous silicas, zeolites, and metal-organic frameworks. These have the potential to function as more efficient alternatives to amine gas treating processes for selectively removing CO2 from large, stationary sources including power stations. While the technology readiness level of solid adsorbents for carbon capture varies between the research and demonstration levels, solid adsorbents have been demonstrated to be commercially viable for life-support and cryogenic distillation applications. While solid adsorbents suitable for carbon capture and storage are an active area of research within materials science, significant technological and policy obstacles limit the availability of such technologies.

Sorption enhanced water gas shift (SEWGS) is a technology that combines a pre-combustion carbon capture process with the water gas shift reaction (WGS) in order to produce a hydrogen rich stream from the syngas fed to the SEWGS reactor.

A zeolite membrane is a synthetic membrane made of crystalline aluminosilicate materials, typically aluminum, silicon, and oxygen with positive counterions such as Na+ and Ca2+ within the structure. Zeolite membranes serve as a low energy separation method. They have recently drawn interest due to their high chemical and thermal stability, and their high selectivity. Currently zeolites have seen applications in gas separation, membrane reactors, water desalination, and solid state batteries. Currently zeolite membranes have yet to be widely implemented commercially due to key issues including low flux, high cost of production, and defects in the crystal structure.

References

  1. "SWANA 2012 Excellence Award Application "Landfill Gas Control" Seneca Landfill, Inc" (PDF): 8. Retrieved 13 October 2016.{{cite journal}}: Cite journal requires |journal= (help)
  2. Propylene Production via Propane Dehydrogenation, Technology Economics Program. Intratec. 2012. ISBN   9780615661025.
  3. Air Products and Chemicals, Inc (2009). "Systèmes de production de gaz PRISM®" (PDF) (in French).
  4. http://www.co2crc.com.au Archived August 19, 2006, at the Wayback Machine
  5. Grande, Carlos A.; Cavenati, Simone, eds. (2005), "Pressure Swing Adsorption for Carbon Dioxide Sequesteration", 2nd Mercosur Congress on Chemical Engineering
  6. Alptekin, Gokhan (2005-01-08). "An Advanced Rapid Cycling CO2 and H2O Control System for PLSS". NASA. Retrieved 2007-02-24.
  7. Chai, S. W.; Kothare, M. V.; Sircar, S. (2011). "Rapid Pressure Swing Adsorption for Reduction of Bed Size Factor of a Medical Oxygen Concentrator". Industrial & Engineering Chemistry Research. 50 (14): 8703. doi:10.1021/ie2005093.
  8. Ruthven, Douglas M.; Shamsuzzman Farooq, Kent S. Knaebel (1993). Pressure Swing Adsorption. Wiley-VCH. ISBN   9780471188186.

Further reading