User:Milton Beychok/Sandbox: Difference between revisions

From Citizendium
Jump to navigation Jump to search
imported>Milton Beychok
No edit summary
No edit summary
 
Line 1: Line 1:
'''Hydrodesulfurization''' (HDS) is a [[catalytic]] chemical process widely used to remove [[sulfur]] (S) from [[natural gas]] and from [[oil refinery|refined petroleum products]] such as [[gasoline|gasoline or petrol]], [[jet fuel]], [[kerosene]], [[diesel fuel]], and [[fuel oil]]s.<ref name=Gary>{{cite book|author=Gary, J.H. and Handwerk, G.E.|title=Petroleum Refining Technology and Economics|edition=2nd Edition|publisher=Marcel Dekker, Inc|year=1984|id=ISBN 0-8247-7150-8}}</ref><ref>[http://www.theicct.org/documents/Yamaguchi_Mexico_2003.pdf ''Hydrodesulfurization Technologies and Costs''] Nancy Yamaguchi, Trans Energy Associates, William and Flora Hewlett Foundation Sulfur Workshop, Mexico City, May 29-30, 2003</ref>  The purpose of removing the sulfur is to reduce the sulfur dioxide (SO<sub>2</sub>) emissions that result from using those fuels in automotive [[vehicles]], [[aircraft]], railroad [[locomotives]], [[ships]], gas or oil burning [[power plants]], residential and industrial [[furnaces]], and other forms of fuel [[combustion]].  
{{AccountNotLive}}
__NOTOC__
[[File:Crude oil-fired power plant.jpg|thumb|right|225px|Industrial air pollution source]]
Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.  


Another important reason for removing sulfur from the [[naphtha]] streams within a petroleum refinery is that sulfur, even in extremely low concentrations, [[catalyst poisoning|poisons]] the [[noble metal]] catalysts ([[platinum]] and [[rhenium]]) in the [[catalytic reforming]] units that are subsequently used to upgrade the [[octane rating]] of the [[naphtha]] streams.
Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.<ref>J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", ''JAPCA'', Vol. 21, No. 7, 1971.</ref> 


The industrial hydrodesulfurization processes include facilities for the capture and removal of the resulting [[hydrogen sulfide]] (H<sub>2</sub>S) gas. In [[oil refinery|petroleum refineries]], the hydrogen sulfide gas is then subsequently converted into byproduct elemental sulfur. In fact, the vast majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was byproduct sulfur from refineries and other hydrocarbon processing plants.<ref>[http://minerals.usgs.gov/minerals/pubs/commodity/sulfur/sulfumcs06.pdf Sulfur production report] by the [[United States Geological Survey]]</ref><ref>[http://www.agiweb.org/geotimes/july03/resources.html Discussion of recovered byproduct sulfur]</ref>
Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.


An HDS unit in the petroleum refining industry is also often also referred to as a '''Hydrotreater'''.
The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:


==History==
* Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
Although reactions involving catalytic hydrogenation of organic substances were known prior to 1897, the property of finely divided nickel to catalyze the fixation of hydrogen on hydrocarbon (ethylene, benzene) double bonds was discovered by the [[France|French]] [[chemist]], [[Paul Sabatier (chemist)|Paul Sabatier]].<ref>C.R.Acad.Sci. 1897, 132, 210</ref><ref>C.R.Acad.Sci. 1901, 132, 210</ref> Thus, he found that unsaturated hydrocarbons in the vapor phase could be converted into saturated hydrocarbons by using hydrogen and a catalytic metal. His work was the foundation of the modern catalytic hydrogenation process.
* The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
* Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
* The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).


Soon after Sabatier's work, a [[Germany|German]] chemist, [[Wilhelm Normann]], found that catalytic hydrogenation could be used to convert unsaturated fatty acids or glycerides in the liquid phase into saturated ones. He was awarded a patent in Germany in 1902<ref>[http://v3.espacenet.com/textdoc?DB=EPODOC&IDX=DE141029&F=0 DE Patent DE141029 (Espacenet, record not available)]</ref> and in Britain in 1903,<ref>[http://v3.espacenet.com/textdoc?DB=EPODOC&IDX=GB190301515&F=0 UK Patent GB190301515 GB190301515 (Espacenet)]</ref> which was the beginning of what is now a worldwide industry.
Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.


In the mid-1950's, the first [[noble metal]] catalytic reforming process (the [[Platforming|Platformer process]]) was commercialized. At the same time, the catalytic hydrodesulfurization of the naphtha feed to such reformers was also commercialized. In the decades that followed, various proprietary catalytic hydrodesulfurization processes such as the one depicted in the [[Process flow diagram|flow diagram]] below have been commercialized.  Currently, virtually all of the petroleum refineries world-wide have one or more HDS units.
The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.


By 2006 miniature [[microfluidic]] HDS units had been implemented for treating [[JP-8]] jet fuel to produce clean feed stock for a [[fuel cell]] [[hydrogen reformer]].<ref>[http://www.greencarcongress.com/2006/03/microchannel_de.html Microchannel HDS (March 2006)]</ref>  By 2007 this had been integrated into an operating 5kW fuel cell generation system.<ref>[http://www.pnl.gov/topstory.asp?id=282 Fuel cells help make noisy, hot generators a thing of the past (December 2007) Pacific Northwest National Laboratory]</ref>
==Atmospheric layers==


==The process chemistry==
Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the ''troposphere''. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The ''stratosphere'' is the next layer and extends from 18 km up to about 50 km. The third layer is the ''mesosphere'' which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.


[[Hydrogenation]] is a class of [[chemical reaction]]s in which the net result is the addition of [[hydrogen]] (H). [[Hydrogenolysis]] is a type of hydrogenation and results in the cleavage of the C-X [[chemical bond]], where C is a [[carbon]] atom and X is a sulfur, [[nitrogen]] (N) or [[oxygen]] (O) atom. The net result of a hydrogenolysis reaction is the formation of C-H and H-X chemical bonds. Thus, hydrodesulfurization is a hydrogenolysis reaction. Using [[ethanethiol]] (C<sub>2</sub>H<sub>5</sub>SH), a sulfur compound present in some petroleum products, as an example, the hydrodesulfurization reaction can be simply expressed as
The lowest part of the troposphere is called the ''atmospheric boundary layer (ABL)'' or the ''planetary boundary layer (PBL)'' and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the ''inversion layer'' (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the ''free troposphere'' and it extends up to the 18 km height of the troposphere.
:{| cellpadding="0" cellspacing="0"
|align="center"| Ethanethiol + Hydrogen
| &nbsp;→&nbsp;
|align="center"| [[Ethane]] + [[Hydrogen sulfide]]
|-
|align="center"| C<sub>2</sub>H<sub>5</sub>SH + H<sub>2</sub>
| &nbsp;→&nbsp;
|align="center"| C<sub>2</sub>H<sub>6</sub> + H<sub>2</sub>S
|}


For the mechanistic aspects of, and the catalysts used in this reaction see the section [[#Catalysts and mechanisms|catalysts and mechanisms]]
The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the ''mixing layer''. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.


==Process description==
In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as ''boundary layer models'' because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as ''mesoscale models'' have dispersion modeling capabilities that can extend horizontally as much as  a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.
In an industrial hydrodesulfurization unit, such as in a refinery, the hydrodesulfurization reaction takes place in a fixed-bed [[chemical reactor|reactor]] at elevated [[temperatures]] ranging from 300 to 400 °C and elevated [[pressures]] ranging from 30 to 130 [[atmosphere (unit)|atmosphere]]s of absolute pressure, typically in the presence of a [[catalyst]] consisting of an [[alumina]] base impregnated with [[cobalt]] and [[molybdenum]].


The image below is a schematic depiction of the equipment and the process flow streams in a typical refinery HDS unit.
==Gaussian air pollutant dispersion equation==
[[Image:HDS Flow.png|frame|center|Schematic diagram of a typical Hydrodesulfurization (HDS) unit in a petroleum refinery]]


The liquid feed (at the bottom left in the diagram) is [[pump|pumped]] up to the required elevated pressure and is joined by a stream of hydrogen-rich recycle gas. The resulting liquid-gas mixture is preheated by flowing through a [[heat exchanger]]. The preheated feed then flows through a [[furnace|fired heater]] where the feed mixture is totally [[vaporized]] and heated to the required elevated temperature before entering the reactor and flowing through a fixed-bed of catalyst where the hydrodesulfurization reaction takes place.
The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.<ref>C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", ''Trans. Faraday Soc.'', 32:1249, 1936.</ref> Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.


The hot reaction products are partially cooled by flowing through the heat exchanger where the reactor feed was preheated and then flows through a water-cooled heat exchanger before it flows through the pressure controller (PC) and undergoes a pressure reduction down to about 3 to 5 atmospheres.  The resulting mixture of liquid and gas enters the gas separator [[pressure vessel|vessel]] at about 35 °C and 3 to 5 atmospheres of absolute pressure.
Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947<ref>O.G. Sutton, "The problem of diffusion in the lower atmosphere", ''QJRMS'', 73:257, 1947.</ref><ref>O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", ''QJRMS'', 73:426, 1947.</ref> which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.


Most of the hydrogen-rich gas from the gas separator vessel is recycle gas which is routed through an [[amine gas treating|amine contactor]] for removal of the reaction product H<sub>2</sub>S that it contains. The H<sub>2</sub>S-free hydrogen-rich gas is then recycled back for reuse in the reactor section. Any excess gas from the gas separator vessel joins the [[sour gas]] from the stripping of the reaction product liquid.
Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the '''Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes''' shown below:<ref name=Beychok>{{cite book|author=M.R. Beychok|title=Fundamentals Of Stack Gas Dispersion|edition=4th Edition| publisher=author-published|year=2005|isbn=0-9644588-0-2}}.</ref><ref>{{cite book|author=D. B. Turner| title=Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling| edition=2nd Edition |publisher=CRC Press|year=1994|isbn=1-56670-023-X}}.</ref>


The liquid from the gas separator vessel is routed through a [[reboiler|reboiled]] stripper [[Continuous distillation|distillation]] tower.  The bottoms product from the stripper is the final desulfurized liquid product from hydrodesulfurization unit.


The overhead sour gas from the stripper contains hydrogen, [[methane]], [[ethane]], hydrogen sulfide, [[propane]] and perhaps some [[butane]] and heavier components. That sour gas is sent to the refinery's central gas processing plant for removal of the hydrogen sulfide in the refinery's main [[amine gas treating]] unit and through a series of distillation towers for recovery of propane, butane and [[pentane]] or heavier components. The residual hydrogen, methane, ethane and some propane is used as refinery fuel gas. The hydrogen sulfide removed and recovered by the amine gas treating unit is subsequently converted to elemental sulfur in a [[Claus  process]] unit.
<math>C = \frac{\;Q}{u}\cdot\frac{\;f}{\sigma_y\sqrt{2\pi}}\;\cdot\frac{\;g_1 + g_2 + g_3}{\sigma_z\sqrt{2\pi}}</math>


Note that the above description assumes that the HDS unit feed contains no [[olefin]]s.  If the feed does contain olefins (for example, the feed is a naphtha derived from a refinery fluid catalytic cracker (FCC) unit), then the overhead gas from the HDS stripper may also contain some [[ethene]], [[propene]], [[butene]]s and [[pentene]]s or heavier components.
{| border="0" cellpadding="2"
|-
|align=right|where:
|&nbsp;
|-
!align=right|<math>f</math> 
|align=left|= crosswind dispersion parameter
|-
!align=right|&nbsp;
|align=left|= <math>\exp\;[-\,y^2/\,(2\;\sigma_y^2\;)\;]</math>
|-
!align=right|<math>g</math>
|align=left|= vertical dispersion parameter = <math>\,g_1 + g_2 + g_3</math>
|-
!align=right|<math>g_1</math>
|align=left|= vertical dispersion with no reflections
|-
!align=right|&nbsp;
|align=left|= <math>\; \exp\;[-\,(z - H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_2</math>
|align=left|= vertical dispersion for reflection from the ground
|-
!align=right|&nbsp;
|align=left|= <math>\;\exp\;[-\,(z + H)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|<math>g_3</math>
|align=left|= vertical dispersion for reflection from an inversion aloft
|-
!align=right|&nbsp;
|align=left|= <math>\sum_{m=1}^\infty\;\big\{\exp\;[-\,(z - H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z + H - 2mL)^2/\,(2\;\sigma_z^2\;)\;]</math>
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; <math>+\, \exp\;[-\,(z - H + 2mL)^2/\,(2\;\sigma_z^2\;)\;]\big\}</math>
|-
!align=right|<math>C</math>
|align=left|= concentration of emissions, in g/m³, at any receptor located:
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; x meters downwind from the emission source point
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; y meters crosswind from the emission plume centerline
|-
!align=right|&nbsp;
|align=left|&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; z meters above ground level
|-
!align=right|<math>Q</math>
|align=left|= source pollutant emission rate, in g/s
|-
!align=right|<math>u</math>
|align=left|= horizontal wind velocity along the plume centerline, m/s
|-
!align=right|<math>H</math>
|align=left|= height of emission plume centerline above ground level, in m
|-
!align=right|<math>\sigma_z</math>
|align=left|= vertical standard deviation of the emission distribution, in m
|-
!align=right|<math>\sigma_y</math>
|align=left|= horizontal standard deviation of the emission distribution, in m
|-
!align=right|<math>L</math>
|align=left|= height from ground level to bottom of the inversion aloft, in m
|-
!align=right|<math>\exp</math>
|align=left|= the exponential function
|}


It should also be noted that the amine solution to and from the recycle gas contactor comes from and is returned to the refinery's main amine gas treating unit.
The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.


==Sulfur compounds in refinery HDS feedstocks==
The sum of the four exponential terms in <math>g_3</math> converges to a final value quite rapidly. For most cases, the summation of the series with '''''m''''' = 1, '''''m''''' = 2 and '''''m''''' = 3 will provide an adequate solution.


The refinery HDS feedstocks (naphtha, kerosene, diesel oil and heavier oils) contain a wide range of [[Organic compound|organic]] sulfur compounds, including [[thiols]], [[thiophenes]], organic [[sulfides]] and [[disulfides]], and many others. These organic sulfur compounds are products of the degradation of sulfur containing biological components, present during the natural formation of the [[fossil fuel]], petroleum crude oil.
<math>\sigma_z</math> and <math>\sigma_y</math> are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.


When the HDS process is used to desulfurize a refinery naphtha, it is necessary to remove the the total sulfur down to the parts per million range or lower in order to prevent poisoning the noble metal catalysts in the subsequent catalytic reforming of the naphthas.
Whereas older models rely on stability classes for the determination of <math>\sigma_y</math> and <math>\sigma_z</math>, more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.


When the process is used for desulfurizing diesel oils, the latest environmental regulations in the United States and Europe, requiring  what is referred to as ''ultra-low sulfur diesel'' (ULSD), in turn requires that very deep hydrodesulfurization is needed. In the very early 2000's, the governmental regulatory limits for highway vehicle diesel was within the range of 300 to 500 ppm by weight of total sulfur. As of 2006, the total sulfur limit for highway diesel is in the range of 15 to 30 ppm by weight.<ref>[http://www.npradc.org/issues/fuels/diesel_sulfur.cfm ''Diesel Sulfur''] published online by the National Petrochemical & Refiners Association (NPRA)</ref>
==Briggs plume rise equations==


===Thiophenes===
The Gaussian air pollutant dispersion equation (discussed above) requires the input of ''H'' which is the pollutant plume's centerline height above ground level. ''H'' is the sum of ''H''<sub>s</sub> (the actual physical height of the pollutant plume's emission source point) plus Δ''H'' (the plume rise due the plume's buoyancy).


A family of substrates that are particularly common in petroleum are the aromatic sulfur-containing heterocycles called thiophenes. Many kinds of thiophenes occur in petroleum ranging from thiophene itself to more condensed derivatives called [[benzothiophene]]s and [[dibenzothiophene]]s.  Thiophene itself and its alkyl derivatives are easier to hydrogenolyse, whereas dibenzothiophene, especially its 4,6-disubstituted derivatives, are considered the most challenging substrates.  Benzothiophenes are midway between the simple thiophenes and dibenzothiophenes in their susceptibility to HDS.
[[File:Gaussian Plume.png|thumb|right|333px|Visualization of a buoyant Gaussian air pollutant dispersion plume]]


==Catalysts and mechanisms==
To determine Δ''H'', many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.<ref>G.A. Briggs, "A plume rise model compared with observations", ''JAPCA'', 15:433–438, 1965.</ref> In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.<ref>G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", ''Atmos. Envir.'', 2:228–232, 1968.</ref> In that same year, Briggs also wrote the section of the publication edited by Slade<ref>D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.</ref> dealing with the comparative analyses of plume rise models. That was followed in 1969 by his classical critical review of the entire plume rise literature,<ref>G.A. Briggs, "Plume Rise", ''USAEC Critical Review Series'', 1969.</ref> in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations"Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.<ref>G.A. Briggs, "Some recent analyses of plume rise observation", ''Proc. Second Internat'l. Clean Air Congress'', Academic Press, New York, 1971.</ref><ref>G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", ''Atmos. Envir.'', 6:507–510, 1972.</ref>
The main HDS catalysts are based on [[Molybdenum disulfide|MoS<sub>2</sub>]] together with smaller amounts of other metals.<ref>Topsøe, H.; Clausen, B. S.; Massoth, F. E., Hydrotreating Catalysis, Science and Technology, Springer-Verlag: Berlin, 1996.</ref> The nature of the sites of catalytic activity remains an active area of investigation, but it is generally assumed basal planes of the MoS<sub>2</sub> structure are not relevant to catalysis, rather the edges or rims of these sheet.<ref> Daage, M.; Chianelli, R. R., "Structure-Function Relations in Molybdenum Sulfide Catalysts - the Rim-Edge Model", J. of Catalysis, 1994, 149, 414-427.</ref>  At the edges of the MoS<sub>2</sub> crystallites, the molybdenum centre can stabilize a coordinatively unsaturated site (CUS), also known as an anion vacancySubstrates, such as thiophene, bind to this site and undergo a series a reactions that result in both C-S scission and C=C hydrogenation. Thus, the hydrogen serves multiple roles - generation of anion vacancy by removal of sulfide, hydrogenation, and hydrogenolysis. A simplified diagram for the cycle is shown:
[[Image:HDS.png|thumb|450px|center|Simplified diagram of a HDS cycle for thiophene]]


===Catalysts===
Briggs divided air pollution plumes into these four general categories:
Most metals catalyse HDS, but it is those at the middle of the transition metal series that are most active.  [[Ruthenium disulfide]] appears to be the single most active catalyst, but binary combinations of cobalt and molybdenum are also highly active.<ref>Chianelli, R. R.; Berhault, G.; Raybaud, P.; Kasztelan, S.; Hafner, J. and Toulhoat, H., "Periodic trends in hydrodesulfurization: in support of the Sabatier principle", Applied Catalysis, A, 2002, volume 227, pages 83-96</ref>  Aside from the basic cobalt-modified MoS<sub>2</sub> catalyst, nickel and tungsten are also used, depending on the nature of the feed.  For example, Ni-W catalysts are more effective for hydrodenitrification (HDN).
* Cold jet plumes in calm ambient air conditions
* Cold jet plumes in windy ambient air conditions
* Hot, buoyant plumes in calm ambient air conditions
* Hot, buoyant plumes in windy ambient air conditions


===Supports===
Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportantAlthough Briggs proposed plume rise equations for each of the above plume categories, '''''it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes'''''.
Metal sulfides are "supported" on materials with high surface areas.  A typical support for HDS catalyst is &gamma;-[[alumina]].  The support allows the more expensive catalyst to be more widely distributed, giving rise to a larger fraction of the MoS<sub>2</sub> that is catalytically activeThe interaction between the support and the catalyst is an area of intense interest, since the support is often not fully inert but participates in the catalysis.


==Other uses==
In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants.  Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).


The basic hydrogenolysis reaction has a number of uses other than hydrodesulfurization.
A logic diagram for using the Briggs equations<ref name=Beychok/> to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:
 
[[Image:BriggsLogic.png|none]]
===Hydrodenitrogenation===
:{| border="0" cellpadding="2"
 
|-
The hydrogenolysis reaction is also used to reduce the nitrogen content of a petroleum stream and, in that case, is referred to '''Hydrodenitrogenation''' (HDN). The process flow scheme is the same as for an HDS unit.
|align=right|where:
 
|&nbsp;
Using [[pyridine]] (C<sub>5</sub>H<sub>5</sub>N), a nitrogen compound present in some petroleum fractionation products, as an example, the hydrodenitrogenation reaction has been postulated as occurring in three steps:<ref>[https://dspace.mit.edu/bitstream/1721.1/27892/1/03740017.pdf ''Kinetics and Interactions of the Simultaneous Catalytic Hydrodenitrogenation of Pyridine and<br> Hydrodesulfurization of Thiophene''](John Wilkins, PhD Thesis, [[MIT]], 1977)</ref><ref>[http://pubs.acs.org/cgi-bin/abstract.cgi/iepdaw/1980/19/i01/f-pdf/f_i260073a027.pdf?sessid=6006l3 ''Simultaneous Catalytic Hydrodenitrogenation of Pyridine and Hydrodesulfurization of<br> Thiophene''](Satterfield,C.N., Modell, M. and Wilkens, J.A., Ind. Eng. Chem. Process Des. Dev., 1980 Vol. 19, pages 154-160)</ref>
|-
:{| cellpadding="0" cellspacing="0"
!align=right| Δh
|align="center"| Pyridine + Hydrogen
|align=left|= plume rise, in m
| &nbsp;&nbsp;  
|-
|align="center"| [[Piperdine]] + Hydrogen
!align=right| F<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
| &nbsp;→&nbsp;
|align=left|= buoyancy factor, in m<sup>4</sup>s<sup>−3</sup>
|align="center"| [[Amine|Amylamine]] + Hydrogen
|-
| &nbsp;→&nbsp;
!align=right| x
|align="center"| Pentane + [[Ammonia]]
|align=left|= downwind distance from plume source, in m
|-
!align=right| x<sub>f</sub>
|align=left|= downwind distance from plume source to point of maximum plume rise, in m
|-
|-
|align="center"| C<sub>5</sub>H<sub>5</sub>N + 5H<sub>2</sub>
!align=right| u
| &nbsp;→&nbsp;
|align=left|= windspeed at actual stack height, in m/s
|align="center"| C<sub>5</sub>H<sub>11</sub>N + 2H<sub>2</sub>
| &nbsp;→&nbsp;
|align="center"| C<sub>5</sub>H<sub>11</sub>NH<sub>2</sub> + H<sub>2</sub>
| &nbsp;→&nbsp;
|align="center"| C<sub>5</sub>H<sub>12</sub> + NH<sub>3</sub>
|}
 
and the overall reaction may be simply expressed as:
:{| cellpadding="0" cellspacing="0"
|align="center"| Pyridine + Hydrogen
| &nbsp;→&nbsp;
|align="center"| Pentane + Ammonia
|-
|-
|align="center"| C<sub>5</sub>H<sub>5</sub>N + 5H<sub>2</sub>
!align=right| s<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->  
| &nbsp;→&nbsp;
|align=left|= stability parameter, in s<sup>−2</sup>
|align="center"| C<sub>5</sub>H<sub>12</sub> + NH<sub>3</sub>
|}
|}
The above parameters used in the Briggs' equations are discussed in Beychok's book.<ref name=Beychok/>


Many HDS units for desulfurizing naphthas within petroleum refineries are actually simultaneously denitrogenating to some extent as well.
==References==
{{reflist}}


===Saturation of olefins===
== Further reading==


The hydrogenolysis reaction may also be used to [[saturation (chemistry)|saturate]] or convert [[olefins]] ([[alkenes]]) into [[paraffin]]s ([[alkane]]s). The process used is the same as for an HDS unit.
*{{cite book | author=M.R. Beychok| title=Fundamentals Of Stack Gas Dispersion | edition=4th Edition | publisher=author-published | year=2005 | isbn=0-9644588-0-2}}


As an example, the saturation of the olefin, pentene, can be simply expressed as:
*{{cite book | author=K.B. Schnelle and P.R. Dey| title=Atmospheric Dispersion Modeling Compliance Guide  | edition=1st Edition| publisher=McGraw-Hill Professional | year=1999 | isbn=0-07-058059-6}}
:{| cellpadding="0" cellspacing="0"
|align="center"| Pentene + Hydrogen
| &nbsp;→&nbsp;
|align="center"| Pentane
|-
|align="center"| C<sub>5</sub>H<sub>10</sub> + H<sub>2</sub>
| &nbsp;→&nbsp;
|align="center"| C<sub>5</sub>H<sub>12</sub>
|}
 
Some hydrogenolysis units within a petroleum refinery or a petrochemical plant may be used solely for the saturation of olefins or they may be used for simultaneously desulfurizing as well as denitrogenating and saturating olefins to some extent.
 
===Hydrogenation in the food industry===
{{see|Hydrogenation|Wilhelm Normann|Trans fat}}
The food industry uses hydrogenation to completely or partially [[saturated fat|saturate]] the [[unsaturated fat|unsaturated]] [[fatty acids]] in liquid [[vegetable fats and oils]] to convert them into solid or semi-solid fats, such as those in [[margarine]] and [[shortening]].
 
==References==
{{reflist}}


==External links==
*{{cite book | author=D.B. Turner| title=Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling | edition=2nd Edition | publisher=CRC Press | year=1994 | isbn=1-56670-023-X}}


*[http://www.albemarle.com/Products_and_services/Catalysts/ Albemarle Catalyst Company] (Petrochemical catalysts supplier)
*{{cite book | author= S.P. Arya| title=Air Pollution Meteorology and Dispersion | edition=1st Edition | publisher=Oxford University Press | year=1998 | isbn=0-19-507398-3}}
*[http://www.uop.com/refining/1060.html UOP Company] (Engineering design and construction of large-scale, industrial HDS plants)
*[https://portal.mustangeng.com/pls/portal30/docs/FOLDER/MUSTANGENG/TECHNICAL_ARTICLES_CONTENT/USDLHYDROTREATER.PDF Mustang Engineering Company] (Description and flow diagram of an HDS unit, from an article published in the Oil & Gas Journal)
*[http://members.ift.org/NR/rdonlyres/27B49B9B-EA63-4D73-BAB4-42FEFCD72C68/0/crfsfsv4n1p00220030ms20040577.pdf ''Hydrogenation for Low Trans and High Conjugated Fatty Acids''] by E.S. Jang, M.Y. Jung, D.B. Min, Comprehensive Reviews in Food Science and Food Safety, Vol.1, 2005
*[http://www.akerkvaerner.com/Internet/IndustriesAndServices/Process/Petrochemicals/ChemicalImtermediates/OxoAlcohols.htm Oxo Alcohols]  (Engineered and constructed by Aker Kvaerner)
*[http://www.jmcatalysts.com/pct/marketshome.asp?marketid=10&id=373 Catalysts and technology for Oxo-Alcohols]


[[Category:Chemical engineering]]
*{{cite book | author=R. Barrat| title=Atmospheric Dispersion Modelling | edition=1st Edition | publisher=Earthscan Publications | year=2001 | isbn=1-85383-642-7}}
[[Category:Oil refineries]]
[[Category:Chemical processes]]
[[Category:Unit processes]]


*{{cite book | author=S.R. Hanna and R.E. Britter| title=Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites  | edition=1st Edition | publisher=Wiley-American Institute of Chemical Engineers | year=2002 | isbn=0-8169-0863-X}}


[[de:Hydrodesulfurierung]]
*{{cite book | author=P. Zannetti| title=Air pollution modeling : theories, computational methods, and available software | edition= | publisher= Van Nostrand Reinhold | year=1990 | isbn=0-442-30805-1 }}
[[fr:Hydrodésulfuration]]
[[ja:脱硫]]

Latest revision as of 04:25, 22 November 2023


The account of this former contributor was not re-activated after the server upgrade of March 2022.


Industrial air pollution source

Atmospheric dispersion modeling is the mathematical simulation of how air pollutants disperse in the ambient atmosphere. It is performed with computer programs that solve the mathematical equations and algorithms which simulate the pollutant dispersion. The dispersion models are used to estimate or to predict the downwind concentration of air pollutants emitted from sources such as industrial plants, vehicular traffic or accidental chemical releases.

Such models are important to governmental agencies tasked with protecting and managing the ambient air quality. The models are typically employed to determine whether existing or proposed new industrial facilities are or will be in compliance with the National Ambient Air Quality Standards (NAAQS) in the United States or similar regulations in other nations. The models also serve to assist in the design of effective control strategies to reduce emissions of harmful air pollutants. During the late 1960's, the Air Pollution Control Office of the U.S. Environmental Protection Agency (U.S. EPA) initiated research projects to develop models for use by urban and transportation planners.[1]

Air dispersion models are also used by emergency management personnel to develop emergency plans for accidental chemical releases. The results of dispersion modeling, using worst case accidental releases and meteorological conditions, can provide estimated locations of impacted areas and be used to determine appropriate protective actions. At industrial facilities in the United States, this type of consequence assessment or emergency planning is required under the Clean Air Act (CAA) codified in Part 68 of Title 40 of the Code of Federal Regulations.

The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:

  • Meteorological conditions such as wind speed and direction, the amount of atmospheric turbulence (as characterized by what is called the "stability class"), the ambient air temperature, the height to the bottom of any inversion aloft that may be present, cloud cover and solar radiation.
  • The emission parameters such the type of source (i.e., point, line or area), the mass flow rate, the source location and height, the source exit velocity, and the source exit temperature.
  • Terrain elevations at the source location and at receptor locations, such as nearby homes, schools, businesses and hospitals.
  • The location, height and width of any obstructions (such as buildings or other structures) in the path of the emitted gaseous plume as well as the terrain surface roughness (which may be characterized by the more generic parameters "rural" or "city" terrain).

Many of the modern, advanced dispersion modeling programs include a pre-processor module for the input of meteorological and other data, and many also include a post-processor module for graphing the output data and/or plotting the area impacted by the air pollutants on maps. The plots of areas impacted usually include isopleths showing areas of pollutant concentrations that define areas of the highest health risk. The isopleths plots are useful in determining protective actions for the public and first responders.

The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.

Atmospheric layers

Discussion of the layers in the Earth's atmosphere is needed to understand where airborne pollutants disperse in the atmosphere. The layer closest to the Earth's surface is known as the troposphere. It extends from sea-level up to a height of about 18 km and contains about 80 percent of the mass of the overall atmosphere. The stratosphere is the next layer and extends from 18 km up to about 50 km. The third layer is the mesosphere which extends from 50 km up to about 80 km. There are other layers above 80 km, but they are insignificant with respect to atmospheric dispersion modeling.

The lowest part of the troposphere is called the atmospheric boundary layer (ABL) or the planetary boundary layer (PBL) and extends from the Earth's surface up to about 1.5 to 2.0 km in height. The air temperature of the atmospheric boundary layer decreases with increasing altitude until it reaches what is called the inversion layer (where the temperature increases with increasing altitude) that caps the atmospheric boundary layer. The upper part of the troposphere (i.e., above the inversion layer) is called the free troposphere and it extends up to the 18 km height of the troposphere.

The ABL is the most important layer with respect to the emission, transport and dispersion of airborne pollutants. The part of the ABL between the Earth's surface and the bottom of the inversion layer is known as the mixing layer. Almost all of the airborne pollutants emitted into the ambient atmosphere are transported and dispersed within the mixing layer. Some of the emissions penetrate the inversion layer and enter the free troposphere above the ABL.

In summary, the layers of the Earth's atmosphere from the surface of the ground upwards are: the ABL made up of the mixing layer capped by the inversion layer; the free troposphere; the stratosphere; the mesosphere and others. Many atmospheric dispersion models are referred to as boundary layer models because they mainly model air pollutant dispersion within the ABL. To avoid confusion, models referred to as mesoscale models have dispersion modeling capabilities that can extend horizontally as much as a few hundred kilometres. It does not mean that they model dispersion in the mesosphere.

Gaussian air pollutant dispersion equation

The technical literature on air pollution dispersion is quite extensive and dates back to the 1930s and earlier. One of the early air pollutant plume dispersion equations was derived by Bosanquet and Pearson.[2] Their equation did not assume Gaussian distribution nor did it include the effect of ground reflection of the pollutant plume.

Sir Graham Sutton derived an air pollutant plume dispersion equation in 1947[3][4] which did include the assumption of Gaussian distribution for the vertical and crosswind dispersion of the plume and also included the effect of ground reflection of the plume.

Under the stimulus provided by the advent of stringent environmental control regulations, there was an immense growth in the use of air pollutant plume dispersion calculations between the late 1960s and today. A great many computer programs for calculating the dispersion of air pollutant emissions were developed during that period of time and they were commonly called "air dispersion models". The basis for most of those models was the Complete Equation For Gaussian Dispersion Modeling Of Continuous, Buoyant Air Pollution Plumes shown below:[5][6]


where:  
= crosswind dispersion parameter
  =
= vertical dispersion parameter =
= vertical dispersion with no reflections
  =
= vertical dispersion for reflection from the ground
  =
= vertical dispersion for reflection from an inversion aloft
  =
           
           
           
= concentration of emissions, in g/m³, at any receptor located:
            x meters downwind from the emission source point
            y meters crosswind from the emission plume centerline
            z meters above ground level
= source pollutant emission rate, in g/s
= horizontal wind velocity along the plume centerline, m/s
= height of emission plume centerline above ground level, in m
= vertical standard deviation of the emission distribution, in m
= horizontal standard deviation of the emission distribution, in m
= height from ground level to bottom of the inversion aloft, in m
= the exponential function

The above equation not only includes upward reflection from the ground, it also includes downward reflection from the bottom of any inversion lid present in the atmosphere.

The sum of the four exponential terms in converges to a final value quite rapidly. For most cases, the summation of the series with m = 1, m = 2 and m = 3 will provide an adequate solution.

and are functions of the atmospheric stability class (i.e., a measure of the turbulence in the ambient atmosphere) and of the downwind distance to the receptor. The two most important variables affecting the degree of pollutant emission dispersion obtained are the height of the emission source point and the degree of atmospheric turbulence. The more turbulence, the better the degree of dispersion.

Whereas older models rely on stability classes for the determination of and , more recent models increasingly rely on Monin-Obukhov similarity theory to derive these parameters.

Briggs plume rise equations

The Gaussian air pollutant dispersion equation (discussed above) requires the input of H which is the pollutant plume's centerline height above ground level. H is the sum of Hs (the actual physical height of the pollutant plume's emission source point) plus ΔH (the plume rise due the plume's buoyancy).

Visualization of a buoyant Gaussian air pollutant dispersion plume

To determine ΔH, many if not most of the air dispersion models developed between the late 1960s and the early 2000s used what are known as "the Briggs equations." G.A. Briggs first published his plume rise observations and comparisons in 1965.[7] In 1968, at a symposium sponsored by CONCAWE (a Dutch organization), he compared many of the plume rise models then available in the literature.[8] In that same year, Briggs also wrote the section of the publication edited by Slade[9] dealing with the comparative analyses of plume rise models. That was followed in 1969 by his classical critical review of the entire plume rise literature,[10] in which he proposed a set of plume rise equations which have become widely known as "the Briggs equations". Subsequently, Briggs modified his 1969 plume rise equations in 1971 and in 1972.[11][12]

Briggs divided air pollution plumes into these four general categories:

  • Cold jet plumes in calm ambient air conditions
  • Cold jet plumes in windy ambient air conditions
  • Hot, buoyant plumes in calm ambient air conditions
  • Hot, buoyant plumes in windy ambient air conditions

Briggs considered the trajectory of cold jet plumes to be dominated by their initial velocity momentum, and the trajectory of hot, buoyant plumes to be dominated by their buoyant momentum to the extent that their initial velocity momentum was relatively unimportant. Although Briggs proposed plume rise equations for each of the above plume categories, it is important to emphasize that "the Briggs equations" which become widely used are those that he proposed for bent-over, hot buoyant plumes.

In general, Briggs's equations for bent-over, hot buoyant plumes are based on observations and data involving plumes from typical combustion sources such as the flue gas stacks from steam-generating boilers burning fossil fuels in large power plants. Therefore the stack exit velocities were probably in the range of 20 to 100 ft/s (6 to 30 m/s) with exit temperatures ranging from 250 to 500 °F (120 to 260 °C).

A logic diagram for using the Briggs equations[5] to obtain the plume rise trajectory of bent-over buoyant plumes is presented below:

BriggsLogic.png
where:  
Δh = plume rise, in m
F  = buoyancy factor, in m4s−3
x = downwind distance from plume source, in m
xf = downwind distance from plume source to point of maximum plume rise, in m
u = windspeed at actual stack height, in m/s
s  = stability parameter, in s−2

The above parameters used in the Briggs' equations are discussed in Beychok's book.[5]

References

  1. J.C. Fensterstock et al, "Reduction of air pollution potential through environmental planning", JAPCA, Vol. 21, No. 7, 1971.
  2. C.H. Bosanquet and J.L. Pearson, "The spread of smoke and gases from chimneys", Trans. Faraday Soc., 32:1249, 1936.
  3. O.G. Sutton, "The problem of diffusion in the lower atmosphere", QJRMS, 73:257, 1947.
  4. O.G. Sutton, "The theoretical distribution of airborne pollution from factory chimneys", QJRMS, 73:426, 1947.
  5. 5.0 5.1 5.2 M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. .
  6. D. B. Turner (1994). Workbook of atmospheric dispersion estimates: an introduction to dispersion modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. .
  7. G.A. Briggs, "A plume rise model compared with observations", JAPCA, 15:433–438, 1965.
  8. G.A. Briggs, "CONCAWE meeting: discussion of the comparative consequences of different plume rise formulas", Atmos. Envir., 2:228–232, 1968.
  9. D.H. Slade (editor), "Meteorology and atomic energy 1968", Air Resources Laboratory, U.S. Dept. of Commerce, 1968.
  10. G.A. Briggs, "Plume Rise", USAEC Critical Review Series, 1969.
  11. G.A. Briggs, "Some recent analyses of plume rise observation", Proc. Second Internat'l. Clean Air Congress, Academic Press, New York, 1971.
  12. G.A. Briggs, "Discussion: chimney plumes in neutral and stable surroundings", Atmos. Envir., 6:507–510, 1972.

Further reading

  • M.R. Beychok (2005). Fundamentals Of Stack Gas Dispersion, 4th Edition. author-published. ISBN 0-9644588-0-2. 
  • K.B. Schnelle and P.R. Dey (1999). Atmospheric Dispersion Modeling Compliance Guide, 1st Edition. McGraw-Hill Professional. ISBN 0-07-058059-6. 
  • D.B. Turner (1994). Workbook of Atmospheric Dispersion Estimates: An Introduction to Dispersion Modeling, 2nd Edition. CRC Press. ISBN 1-56670-023-X. 
  • S.P. Arya (1998). Air Pollution Meteorology and Dispersion, 1st Edition. Oxford University Press. ISBN 0-19-507398-3. 
  • R. Barrat (2001). Atmospheric Dispersion Modelling, 1st Edition. Earthscan Publications. ISBN 1-85383-642-7. 
  • S.R. Hanna and R.E. Britter (2002). Wind Flow and Vapor Cloud Dispersion at Industrial and Urban Sites, 1st Edition. Wiley-American Institute of Chemical Engineers. ISBN 0-8169-0863-X. 
  • P. Zannetti (1990). Air pollution modeling : theories, computational methods, and available software. Van Nostrand Reinhold. ISBN 0-442-30805-1.