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'''Catalytic reforming''' is a chemical process used to convert [[petroleum refinery]] [[naphtha]]s, typically having low [[Octane rating|octane ratings]], into high-octane liquid products called '''reformates''' which are components of high-octane [[Gasoline|gasoline]] (also known as petrol). Basically, the process re-arranges or re-structures the [[hydrocarbon]] [[molecules]] in the naphtha feedstocks as well as breaking some of the molecules into smaller molecules. The overall effect is that the product reformate contains hydrocarbons with more complex molecular shapes having higher octane values than the hydrocarbons in the naphtha feedstock. In so doing, the process separates [[hydrogen]] [[atoms]] from the hydrocarbon molecules and produces very significant amounts of byproduct hydrogen gas for use in a number of the other processes involved in a modern petroleum refinery. Other byproducts are small amounts of [[methane]], [[ethane]], [[propane]] and [[butanes]].  
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[[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.  


This process is quite different from and not to be confused with the catalytic [[steam reforming]] process used industrially to produce various products such as hydrogen, [[ammonia]] and [[methanol]] from natural gas, naphtha or other petroleum-derived feedstocks. Nor is this process to be confused with various other catalytic reforming processes that use methanol or [[biomass|biomass-derived]] feedstocks to produce hydrogen for [[fuel cells]] or other uses.
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> 


==History==
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.


[[Universal Oil Products]] (also known as UOP) is a multi-national company developing and delivering technology to the [[petroleum refining]], [[natural gas]] processing, [[petrochemical]] production and other manufacturing industries. In the 1940s, an eminent research chemist named Vladimir Haensel<ref>[http://newton.nap.edu/html/biomems/vhaensel.pdf A Biographical Memoir of Vladimir Haensel] written by Stanley Gembiki, published by the National Academy of Sciences in 2006.</ref> working for UOP developed a [[catalytic]] reforming process using a [[catalyst]] containing [[platinum]]. Haensel's process was subsequently commercialized by UOP in 1949 for producing a high octane gasoline from low octane naphthas and the UOP process become known as the Platforming process.<ref>[http://www.uop.com/refining/1030.html Platforming described on UOP's website]</ref> The first Platforming unit was built in 1949 at the refinery of the Old Dutch Refining Company in [[Muskegon]], [[Michigan]].
The dispersion models vary depending on the mathematics used to develop the model, but all require the input of data that may include:


In the years since then, many other versions of the process have been developed by some of the major oil companies and other organizations. Today, the large majority of gasoline produced worldwide is derived from the catalytic reforming process.  
* 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).


To name a few of the other catalytic reforming versions that were developed, all of which utilized  a platinum and/or a [[rhenium]] catalyst:
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.


*Rheniforming: Developed by [[Chevron Oil Company]].
The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.
*Powerforming: Developed by [[Esso|Esso Oil Company]], now known as [[ExxonMobil]].
*Magnaforming: Developed by Englehard Catalyst Company and [[ARCO|Atlantic Richfield Oil Company]].
*Ultraforming: Developed by [[Standard Oil of Indiana]], now a part of the [[British Petroleum|British Petroleum Company]].
*Houdriforming: Developed by the Houdry Process Corporation.
*CCR Platforming: A Platforming version, designed for continuous catalyst regeneration, developed by UOP.
*Octanizing: A catalytic reforming version developed by Axens, a subsidiary of [[Institut francais du petrole]] (IFP), designed for continuous catalyst regeneration.


==Chemistry==
==Atmospheric layers==


Before describing the reaction chemistry of the catalytic reforming process as used in petroleum refineries, the typical naphthas used as catalytic reforming feedstocks will be discussed.
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.


===Typical naphtha feedstocks===
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.


A petroleum refinery includes many [[unit operations]] and [[unit processing|unit processes]]. The first unit operation in a refinery is the [[Continuous distillation#Continuous distillation of crude oil|continuous distillation]] of the [[petroleum|petroleum crude oil]] being refined. The overhead liquid distillate is called naphtha and will become a major component of the refinery's gasoline (petrol) product after it is further processed through a [[Hydrodesulfurization|catalytic hydrodesulfurizer]] to remove [[sulfur]]-containing hydrocarbons and a catalytic reformer to reform its hydrocarbon molecules into more complex molecules with a higher octane rating value. The naphtha is a mixture of very many different hydrocarbon compounds. It has an initial [[boiling point]] of about 35 °C and a final boiling point of about 200 °C, and it contains [[paraffin]], [[naphthene]] (cyclic paraffins) and [[aromatic]] hydrocarbons ranging from those containing 4 [[carbon]] atoms to those containing about 10 or 11 carbon atoms.
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.


The naphtha from the crude oil distillation is often further distilled to produce a "light" naphtha containing most (but not all) of the hydrocarbons with 6 or less carbon atoms and a "heavy" naphtha containing most (but not all) of the hydrocarbons with more than 6 carbon atoms. The heavy naphtha has an initial boiling point of about 140 to 150 °C and a final boiling point of about 190 to 205 °C. The naphthas derived from the distillation of crude oils are referred to as "straight-run" naphthas.
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.


It is the straight-run heavy naphtha that is usually processed in a catalytic reformer because the light naphtha has molecules with 6 or less carbon atoms which, when reformed, tend to crack into butane and lower molecular weight hydrocarbons which are not useful as high-octane gasoline blending components. Also, the molecules with 6 carbon atoms tend to form aromatics which is undesirable because governmental environmental regulations in a number of countries limit the amount of aromatics (most particularly [[benzene]]) that gasoline may contain.<ref>[http://www.ec.gc.ca/CEPARegistry/regulations/detailReg.cfm?intReg=1 Canadian regulations on benzene in gasoline]</ref><ref>[http://www.ukpia.com/industry_issues/environment_air_quality_health_safety/benzene_in_petrol.aspx United Kingdom regulations on benzene in gasoline]</ref><ref>[http://www.washingtonpost.com/wp-dyn/content/article/2006/03/01/AR2006030102113.html USA regulations on benzene in gasoline]</ref>
==Gaussian air pollutant dispersion equation==


It should be noted that there are a great many petroleum [[List of oil fields|crude oil sources]] worldwide and each crude oil has its own unique composition or [[Crude oil assay|"assay"]]. Also, not all refineries process the same crude oils and each refinery produces its own straight-run naphthas with their own unique initial and final boiling points. In other words, naphtha is a generic term rather than a specific term.  
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 table just below lists some fairly typical straight-run heavy naphtha feedstocks, available for catalytic reforming, derived from various crude oils. It can be seen that they differ significantly in their content of paraffins, naphthenes and aromatics:
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.


{| class="wikitable"
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>
|+ Typical Heavy Naphtha Feedstocks
 
 
<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>
 
{| border="0" cellpadding="2"  
|-
|-
! Crude oil name <math>\Rightarrow</math><br>Location <math>\Rightarrow</math>
|align=right|where:
! Barrow Island<br>Australia<ref>[http://www.santos.com/library/barrow_crude.pdf Barrow Island crude oil assay]</ref>
|&nbsp;
! Mutineer-Exeter<br>Australia<ref>[http://www.santos.com/library/refining_characteristics.pdf Mutineer-Exeter crude oil assay]</ref>
! CPC Blend<br>Kazakhstan<ref>[http://crudemarketing.chevron.com/overview.asp?cpc CPC Blend crude oil assay]</ref>
! Draugen<br>North Sea<ref>[http://www.statoil.com/STATOILCOM/crude/svg02659.nsf/UNID/C9AC3EF9CE76B0DFC1256B5600528D6D/$FILE/Dra4kv02.pdf Draugen crude oil assay]</ref>
|-
|-
| Initial boiling point, °C ||align=center|149||align=center|140||align=center|149||align=center|150
!align=right|<math>f</math> 
|-
|align=left|= crosswind dispersion parameter
| Final boiling point, °C ||align=center|204||align=center|190||align=center|204||align=center|180
|-
|-
| Paraffins, liquid volume % ||align=center|46||align=center|62||align=center|57||align=center|38
!align=right|&nbsp;
|align=left|= <math>\exp\;[-\,y^2/\,(2\;\sigma_y^2\;)\;]</math>
|-
|-
| Naphthenes, liquid volume % ||align=center|42||align=center|32||align=center|27||align=center|45
!align=right|<math>g</math>
|align=left|= vertical dispersion parameter = <math>\,g_1 + g_2 + g_3</math>
|-
|-
| Aromatics, liquid volume % ||align=center|12||align=center|6||align=center|16||align=center|17
!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
|}
|}


Some refinery naphthas include [[olefins|olefinic hydrocarbons]], such as naphthas derived from the [[Cracking (chemistry)|fluid catalytic cracking]] and [[coking]] processes used in many refineries. Some refineries may also [[hydrodesulfurization|desulfurize]] and catalytically reform those naphthas. However, for the most part, catalytic reforming is mainly used on the straight-run heavy naphthas, such as those in the above table, derived from the distillation of crude oils.
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 reaction chemistry===
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.


There are a good many chemical reactions that occur in the catalytic reforming process, all of which occur in the presence of a catalyst and a high [[partial pressure]] of hydrogen. Depending upon the type or version of catalytic reforming used as well as the desired reaction severity, the reaction conditions range from temperatures of about 495 to 525 °C and from pressures of about 5 to 45 [[atmosphere|atm]].<ref>[http://www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html#3 OSHA  Technical Manual, Section IV, Chapter 2, ''Petroleum refining Processes''] (A publication of the [[Occupational Safety and Health Administration]])</ref>
<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.


The commonly used catalytic reforming catalysts contain [[noble metals]] such as platinum and/or rhenium, which are very susceptible to [[Catalyst poisoning|poisoning]] by sulfur and [[nitrogen]] compounds. Therefore, the naphtha feedstock to a catalytic reformer is always pre-processed in a [[hydrodesulfurization]] unit which removes both the sulfur and the nitrogen compounds.
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.


The four major catalytic reforming reactions are:<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>
==Briggs plume rise equations==


:1: The [[dehydrogenation]] of naphthenes to convert them into aromatics as exemplified in the conversion methylcyclohexane (a naphthene) to [[toluene]] (an aromatic), as shown below:
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).


[[Image:CatReformerEq1.png|center]]<br>
[[File:Gaussian Plume.png|thumb|right|333px|Visualization of a buoyant Gaussian air pollutant dispersion plume]]


:2: The [[isomerization]] of normal paraffins to [[isoparaffin]]s as exemplified in the conversion of [[Octane|normal octane]] to 2,5-Dimethylhexane (an isoparaffin), as shown below:
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>


[[Image:CatReformerEq3.PNG|center]]<br>
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


:3: The dehydrogenation and [[aromatization]] of paraffins to aromatics (commonly called dehydrocyclization) as exemplified in the conversion of [[Heptane|normal heptane]] to toluene, as shown below:
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'''''.


[[Image:CatReformerEq2.png|center]]<br>
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).


:4: The [[hydrocracking]] of paraffins into smaller molecules as exemplified by the cracking of normal heptane into [[isopentane]] and ethane, as shown below:
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]]
:{| border="0" cellpadding="2"
|-
|align=right|where:
|&nbsp;
|-
!align=right| Δh
|align=left|= plume rise, in m
|-
!align=right| F<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= buoyancy factor, in m<sup>4</sup>s<sup>−3</sup>
|-
!align=right| x
|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=right| u
|align=left|= windspeed at actual stack height, in m/s
|-
!align=right| s<sup>&nbsp;</sup> <!-- The HTML is needed to line up characters. Do not remove.-->
|align=left|= stability parameter, in s<sup>−2</sup>
|}
The above parameters used in the Briggs' equations are discussed in Beychok's book.<ref name=Beychok/>


[[Image:CatReformerEq4.png|center]]<br>
==References==
 
{{reflist}}
The hydrocracking of paraffins is the only one of the above four major reforming reactions that consumes hydrogen. The isomerization of normal paraffins does not consume or produce hydrogen. However, both the dehydrogenation of naphthenes and the dehydrocyclization of paraffins  produce hydrogen. The overall net production of hydrogen  in the catalytic reforming of petroleum naphthas ranges from about 50 to 200 [[cubic meter]]s of hydrogen gas (at 0 °C and 1 atm) per cubic meter of liquid naphtha feedstock. In the [[United States customary units]], that is equivalent to 300 to 1200 [[cubic foot|cubic feet]] of hydrogen gas (at 60 °F and 1 atm) per [[barrel (unit)|barrel]] of liquid naphtha feedstock.<ref>[http://www.freepatentsonline.com/5011805.html US Patent 5011805, ''Dehydrogenation, dehydrocyclization and reforming catalyst''] (Inventor: Ralph Dessau, Assignee: Mobil Oil Corporation)</ref>  In many petroleum refineries, the net hydrogen produced in catalytic reforming supplies a significant part of the hydrogen used elsewhere in the refinery (for example, in hydrodesulfurization processes).
 
==Process description==
 
The most commonly used type of catalytic reforming unit has three [[Chemical reactor|reactors]], each with a fixed bed of catalyst, and all of the catalyst is regenerated [[In situ#Chemistry and chemical engineering|''in situ'']] during routine catalyst regeneration [[shutdown]]s which occur approximately once each 6 to 24 months. Such a unit is referred to as a [[SRR|semi-regenerative catalytic reformer (SRR)]].
 
Some catalytic reforming units have an extra ''spare'' or ''swing'' reactor and each reactor can be individually isolated so that any one reactor can be undergoing in situ regeneration while the other reactors are in operation. When that reactor is regenerated, it replaces another reactor which, in turn, is isolated so that it can then be regenerated.  Such units, referred to as ''cyclic'' catalytic reformers, are not very common. Cyclic catalytic reformers  serve to  extend the period between required shutdowns.
 
The latest and most modern type of catalytic reformers are called continuous catalyst regeneration reformers (CCR). Such units are characterized by continuous in-situ regeneration of part of the catalyst in a special regenerator, and by continuous addition of the regenerated catalyst to the operating reactors. As of 2006, two CCR versions available: UOP's CCR Platformer process<ref>[http://www.uop.com/objects/CCR%20Platforming.pdf CCR Platforming] (UOP website)</ref> and Axen's Octanizing process.<ref>[http://www.axens.net/upload/news/fichier/ptq_q1_06_octanizing_reformer_options.pdf Octanizing Options] (Axens website)</ref> The installation and use of CCR units is rapidly increasing.
 
Many of the earliest catalytic reforming units (in the 1950's and 1960's) were non-regenerative in that they did not perform in situ catalyst regeneration. Instead, when needed, the aged catalyst was replaced by fresh catalyst and the aged catalyst was shipped to catalyst manufacturer's to be either regenerated or to recover the platinum content of the aged catalyst. Very few, if any, catalytic reformers currently in operation are non-regenerative.
The [[process flow diagram]] below depicts a typical semi-regenerative catalytic reforming unit.
 
[[Image:CatReformer.png|frame|center|Schematic diagram of a typical semi-regenerative catalytic reformer unit in a petroleum refinery]]
 
The liquid feed (at the bottom left in the diagram) is [[pump|pumped]] up to the reaction pressure (5 to 45 atm) 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 mixture is then totally [[vaporized]] and heated to the reaction temperature (495 to 520 °C) before the vaporized reactants enter the first reactor. As the vaporized reactants flow through the fixed bed of catalyst in the reactor, the major reaction is the dehydrogenation of naphthenes to aromatics (as described earlier herein) which is highly [[endothermic]] and results in a large temperature decrease between the inlet and outlet of the reactor. To maintain the required reaction temperature and the rate of reaction, the vaporized stream is reheated in the second fired heater before it flows through the second reactor. The temperature again decreases across the second reactor and the vaporized stream must again be reheated in the third fired heater before it flows through the third reactor. As the vaporized stream proceeds through the three reactors, the reaction rates decrease and the reactors therefore become larger.  At the same time, the amount of reheat required between the reactors becomes smaller. Usually, three reactors are all that is required to provide the desired performance of the catalytic reforming unit.
 
Some installations use three separate fired heaters as shown in the schematic diagram and some installations use a single fired heater with three separate heating coils.
 
The hot reaction products from the third reactor are partially cooled by flowing through the heat exchanger where the feed to the first reactor is preheated and then flow through a water-cooled heat exchanger before flowing through the pressure controller (PC) into the gas separator.
 
Most of the hydrogen-rich gas from the gas separator vessel returns to the suction of the recycle hydrogen [[gas compressor]] and the net production of hydrogen-rich gas from the reforming reactions is exported for use in other the other refinery processes that consume  hydrogen (such as hydrodesulfurization units and/or a [[Cracking (chemistry)#Hydrocracking|hydrocracker unit]]).
 
The liquid from the gas separator vessel is routed into a [[fractionating column]] commonly called a ''stabilizer''. The overhead offgas product from the stabilizer contains the byproduct methane, ethane, propane and butane gases produced by the hydrocracking reactions as explained in the above discussion of the reaction chemistry of a catalytic reformer, and it may also contain  some small amount of hydrogen. That offgas is routed to the refinery's central gas processing plant for removal and recovery of propane and butane. The residual gas after such processing becomes part of the refinery's fuel gas system.
 
The bottoms product from the stabilizer is the high-octane liquid reformate that will become a component of the refinery's product gasoline.
 
==Catalysts and mechanisms==
 
Most catalytic reforming catalysts contain platinum or rhenium on a [[Silicon dioxide|silica]] or silica-[[Aluminum oxide|alumina]] support base, and some contain both platinum and rhenium. Fresh catalyst is [[chloride|chlorided]] (chlorinated) prior to use.


The noble metals (platinum and rhenium) are considered to be catalytic sites for the dehydrogenation reactions and the chlorinated alumina provides the [[acid]] sites needed for isomerization, cyclization and hydrocracking reactions.<ref name=Gary/>
== Further reading==


The activity (i.e., effectiveness) of the catalyst in a semi-regenerative catalytic reformer is reduced over time during operation by [[Carbon|carbonaceous coke]] deposition and chloride loss. The activity of the catalyst can be periodically regenerated or restored by in situ high temperature oxidation of the coke followed by chlorination. As stated earlier herein, semi-regenerative catalytic reformers are regenerated about once per 6 to 24 months.
*{{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}}


Normally, the catalyst can be regenerated perhaps 3 or 4 times before it must be returned to the manufacturer for reclamation of the valuable platinum and/or rhenium content.<ref name=Gary/>
*{{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}}


==References==
*{{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}}
{{reflist}}


==External links==
*{{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.processengr.com/ppt_presentations/oil_refinery_processes.pdf Oil Refinery Processes, A Brief Overview]
*{{cite book | author=R. Barrat| title=Atmospheric Dispersion Modelling | edition=1st Edition | publisher=Earthscan Publications | year=2001 | isbn=1-85383-642-7}}
*[http://www.jechura.com/ChEN409/09%20Reforming.pdf Colorado School of Mines, Lecture Notes] (''Chapter 10, Refining Processes, Catalytic Refinery'' by John Jechura, Adjunct Professor)
*[http://www.cheresources.com/refining3.shtml Students' Guide to Refining]] (scroll down to ''Platforming'')
*[http://www.dct.tudelft.nl/race/education/smst/smst200303.pdf Modern Refinery] Website of [[Delft University of Technology]], [[Netherlands]] (use search function for ''Reforming'')
*[http://www.ifp.fr/IFP/fr/IFP02OGS.nsf/(VNoticesOGST)/AD4A1392D20E5AAEC1256CDE0055399E/$file/decroocq_52n5.pdf?openelement Major scientific and technical challenges about development of new refining processes] (IFP website)


[[Category:Chemical engineering]]
*{{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}}
[[Category:Oil refineries]]
[[Category:Chemical processes]]
[[Category:Unit processes]]


[[ar:مصلح حفزي]]
*{{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 }}
[[es:Reformado catalítico]]
[[ja:接触改質]]
[[ru:Каталитический риформинг]]

Latest revision as of 03:25, 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.