User:Milton Beychok/Sandbox: Difference between revisions

From Citizendium
Jump to navigation Jump to search
imported>Milton Beychok
No edit summary
 
Line 1: Line 1:
{{Image|Hydrocracker 1.jpg|right|250px|A hydrocracking unit in a petroleum refinery.}}
{{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.  


'''Hydrocracking''' is a [[catalytic]] chemical process used in [[petroleum refining processes|petroleum refineries]] for converting the [[Boiling point|high-boiling]] constituent [[hydrocarbon]]s in [[petroleum]] crude oils to more valuable lower-boiling products such as [[gasoline]], [[kerosene]], [[jet fuel]] and [[diesel oil]]. The process takes place in a [[Hydrogen|hydrogen-rich]] atmosphere at elevated [[temperature]]s (260 – 425  [[Celsius|°C]]) and [[pressure]]s (35 – 200 [[Bar (unit)|bar]]).<ref name=Jones>{{cite book|author=David S.J. Jones and Peter P.Pujado (Editors)|title=Handbook of Petroleum Processing|edition=First Edition|publisher=Springer|year=2006|id=ISBN 1-4020-2819-9}}</ref><ref name=Gary>{{cite book|author=James H. Gary and Glenn E. Handwerk|title=Petroleum Refining: Technology and Economics|edition=2nd Edition|publisher=Marcel Dekker|year=1984|id=ISBN 0-8247-7150-8}}</ref><ref>{{cite journal| author=Editorial Staff|title=Refining Processes 2002|journal=Hydrocarbon Processing|volume= &nbsp;|issue=| pages=pages 115 – 117|date=November 2002|id=}}</ref>  
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>


Basically, the process cracks the high-boiling, high [[molecular weight]] hydrocarbons into lower-boiling, lower molecular weight [[Hydrocarbons|olefinic]] and [[Hydrocarbons|aromatic]] hydrocarbons and then [[Hydrodesulfurization|hydrogenates]] them. Any [[sulfur]] and [[nitrogen]] present in the hydrocracking feedstock are, to a large extent, also hydrogenated and form gaseous [[hydrogen sulfide]] (H<sub>2</sub>S) and [[ammonia]] (NH<sub>3</sub>) which are subsequently removed. The result is that the hydrocracking products are essentially free of sulfur and nitrogen impurities and consist mostly of [[Hydrocarbons|paraffinic]] hydrocarbons.
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.


Hydrocracking plants are capable of processing a wide variety of feedstocks of different characteristics to produce a broad range of products. They can be designed and operated to maximize the production of a gasoline blending component (called '''''hydrocrackate''''') or to maximize the production of diesel oil.
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.
* 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.
Hydrocracking was first developed in [[Germany]] as early as 1915 to provide liquid fuels derived from their domestic [[coal]] deposits. The first plant that might be considered as a commercial hydrocracking unit began operation in Leuna, Germany in 1927. Similar efforts to convert coal to liquid fuels took place in the [[United Kingdom|Great Britain]], [[France]] and other countries.<ref>{{cite book|author=Julius Scherzer and A.J. Gruia|title=Hydrocracking Science and Technology|edition=1st Edition|publisher=CRC Press|year=1996|id=ISBN 0-8247-9760-4}}  (This book was the source for most of the History section of this article)</ref><ref>[http://www.cheresources.com/refining5.shtml Hydrocracking] (From the website of Chemical Engineering Resources, which also provided some of this historical information)</ref>
* 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).


Between 1925 and 1930, [[Standard  Oil of New Jersey]] collaborated with [[I.G. Farbenindustrie]] of Germany to develop hydrocracking technology capable of converting heavy petroleum oils into fuels. Such processes required pressures of 200 – 300 bar and temperatures of over 375 °C and were very expensive.
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 1939, [[Imperial Chemical Industries]] of Great Britain developed a two-stage hydrocracking process. During [[World War II]] (1939 – 1945), two-stage hydrocracking processes played an important role in producing  aviation gasoline in Germany, Great Britain and the [[United States]].  
The atmospheric dispersion models are also known as atmospheric diffusion models, air dispersion models, air quality models, and air pollution dispersion models.


After World War II, hydrocracking technology became less important. The availability of petroleum crude oil from the [[Middle East]] removed the motivation to convert coal into liquid fuels. Newly developed [[fluid catalytic cracking]] processes were much more economical than hydrocracking for converting high-boiling petroleum oils to fuels.
==Atmospheric layers==


In the early 1960s, hydrocracking become economical for a number of reasons:
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 automobile industry began manufacturing higher-performing automobiles that required [[Gasoline|high-octane gasoline]].
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.


:* Fluid catalytic cracking expanded rapidly to meet the demand for high-octane gasoline. However, fluid catalytic cracking, in addition to producing gasoline, produces a by-product high-boiling oil called ''cycle oil'' that is very difficult to recycle for further cracking. However, hydrocracking can crack that cycle oil.  
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 switch from railroad steam engines to diesel engines and the introduction of commercial jet aircraft in the 1950's increased the demand for diesel oil and for jet fuel. The flexibility of hydrocracking to produce either gasoline, jet fuel or diesel oil made it desirable for petroleum refineries to install hydrocrackers.
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.


:* [[Zeolite|Zeolite-based catalysts]], developed and commercialized during the period from about 1964 to 1966, performed much better than the earlier [[catalyst]]s. Most importantly, they permitted operation at lower pressures than possible with the earlier catalysts. The higher performance and lower operating pressures made possible by  the new catalysts resulted in significantly more economical hydrocrackers. 
==Gaussian air pollutant dispersion equation==


Hydrocracking enjoyed rapid growth in the United States during the late 1960s and the early 1970s. By the mid-1970s, hydrocracking had become a mature process and its growth began to moderate. From then on, hydrocracking growth in the United States proceeded at a slow pace. However, at the same time, hydrocracking enjoyed significant growth in [[Europe]], the [[Asia-Pacific]] region and the Middle East.
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.


As of 2001, there were about 155 hydrocracker units operating worldwide<ref name=Jones/> and processing about 4,000,000 barrels (550,000 metric tons) per day of feedstock.<ref>{{cite book|author=J.G. Speight and Baki Ozum|title=Petroleum Refining Processes|edition=|publisher=Marcel Dekker|year=2002|id=ISBN 0-8247-0599-8}}</ref> As of 2009, The feedstock processing capacity of the hydrocrackers in the United States was 1,740, 000 barrels (238,000 metric tons) per day.<ref>[http://tonto.eia.doe.gov/dnav/pet/pet_pnp_cap1_a_(na)_8CH0_BpSD_a.htm Number and Capacity of Petroleum Refineries] From the website of the [[U.S. Energy Information Administration]] (U.S. EIA), using the drop down Data Series menu to select Catalytic Hydrocracking Charge Capacity.</ref>
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.


==Process configurations and a typical flow diagram==
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>
{{Image|Hydrocracker Types.png|right|260px|Three hydrocracker configurations.}}  


There are a good many different proprietary hydrocracker designs available for use under license as is the case for many of the other processes used in petroleum refineries. There are also a number of different hydrocracker process equipment configurations, the most common of which are depicted in the adjacent diagram:


:* '''''Single stage, once through hydrocracker''''': This configuration uses only one reactor and any uncracked residual hydrocarbon oil from the bottom of the reaction product [[Continuous distillation|fractionation (distillation) tower]] is not recycled for further cracking. For single stage hydrocracking, either the feedstock must first be hydrotreated to remove ammonia and hydrogen sulfide or the catalyst used in the single reactor must be capable of both [[hydrotreating]] and hydrocracking.<ref name=Jones/>
<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>


:* '''''Single stage hydrocracker with recycle''''': This is the most commonly used configuration. The uncracked residual hydrocarbon oil from the bottom of reaction product fractionation tower is recycled back into the single reactor for further cracking. Again, for single stage hydrocracking, either the feedstock must first be hydrotreated to remove ammonia and hydrogen sulfide or the catalyst used in the single reactor must be capable of both hydrotreating and hydrocracking.<ref name=Jones/>
{| 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
|}


:* '''''Two stage hydrocracker''''': This configuration uses two reactors and the residual hydrocarbon oil from the bottom of reaction product fractionation tower is recycled back into the second reactor for further cracking. Since the first stage reactor accomplishes both hydrotreating and hydrocracking, the second stage reactor feed is virtually free of ammonia and hydrogen sulfide. This permits the use of high performance [[noble metal]] ([[palladium]], [[platinum]]) catalysts which are susceptible to [[poisoning]] by sulfur or nitrogen compounds.<ref name=Jones/>
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.


===Typical flow diagram of a two stage hydrocracker===
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 high-boiling, high molecular weight hydrocarbons used as feedstocks for catalytic hydrocrackers include what are commonly referred to as '''''atmospheric gas oil''''' from [[Petroleum refining processes#The atmospheric crude oil distillation unit|atmospheric crude oil distillation]] units, '''''vacuum gas oil''''' from [[vacuum distillation]] units, and '''''cycle oil''''' from [[fluid catalytic cracking]] units. For describing the hydrocracking process depicted in the typical flow diagram below, the feedstock will be referred to as simply '''''gas 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.


The gas oil from the feedstock pump is mixed with a stream of high-pressure hydrogen and then flows through a [[heat exchanger]] where it is heated by the hot effluent reaction products from the hydrocracker's first stage reactor. The feedstock is then heated further in a fuel-fired heater before it enters the top of first stage reactor and flows downward through three beds of catalyst. The temperature and pressure conditions in the first stage reactor depend upon the specific licensed hydrocracker design, the feedstock properties, the desired products, the catalyst being used and other variables. As a broad generality, the pressure in the first stage reactor may range from 35 to 200 [[Bar (unit)|bar]] and the temperature may range from 260 to 480 °C.
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.


After the effluent reaction product stream from the reactor bottom is cooled by the incoming gas oil feedstock, it is injected with ''wash water'', partially [[Condensation|condensed]] in a water-cooled [[condenser]] and routed into a high-pressure [[vapor-liquid separator]] for separation into three phases: hydrogen-rich gas, hydrocarbon liquid and water. Sulfur and nitrogen compounds in the gas oil feedstock are converted into gaseous hydrogen sulfide and ammonia by the [[Hydrodesulfurization|hydrogenation]] that takes place in the first stage reactor. The purpose of the wash water is to dissolve some of the hydrogen sulfide and ammonia gases present in the first stage reaction product stream. The resulting aqueous solution of [[ammonium hydrosulfide]] (NH<sub>4</sub>HS) is referred to as ''sour water'' and is typically routed to a ''[[sour water stripper]]'' elsewhere in the petroleum refinery. The sour water stripper removes hydrogen sulfide from the sour water and that hydrogen sulfide is subsequently converted to endproduct elemental sulfur in a [[Claus proces unit]].
==Briggs plume rise equations==


The hydrogen-rich gas from the high-pressure separator is routed through an [[Amine gas treating|amine scrubber]] where it is contacted with an aqueous [[amine]] solution<ref>The amines most commonly used for removing hydrogen sulfide from refinery gases area [[monoethanol amine]] (MEA), [[diethanolamine]] (DEA) and [[methyldiethanolamine]] (MDEA)</ref> to absorb and remove residual hydrogen sulfide in the gas. The rich amine solution (containing the absorbed hydrogen sulfide) is typically routed to a central [[amine gas treating]] unit elsewhere in the refinery.
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).


The hydrocarbon liquid phase from the high-pressure separator flows through a pressure letdown (i.e., pressure reduction) valve and into a low-pressure separator. The reduction in pressure partially vaporizes (see [[flash evaporation]]) the liquid. The resulting vapor (referred to as ''offgas'') is routed to a central [[amine gas treating]] unit elsewhere in the refinery. The hydrocracked the enproducts of hydrocarbon liquid phase from the low-pressure separator is heated in a fuel-fired heater and fed into the fractionator.
[[File:Gaussian Plume.png|thumb|right|333px|Visualization of a buoyant Gaussian air pollutant dispersion plume]]


The fractionator is a [[continuous distillation]] tower that that separates the hydrocracked hydrocarbon stream into [[naphtha]], jet fuel (or kerosene) and diesel oil. The offgas from the tower's associated reflux drum joins the offgas from the low-pressure separator.  
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>


Not all of the feedstock hydrocarbons to the first stage reactor are hydrocracked (i.e., converted) into lower-boiling, lower molecular weight hydrocarbons. The bottom stream from the fractionator consists of the unconverted hydrocarbons from the first stage reactor and that stream is mixed with high pressure hydrogen and recycled as feed to the second stage reactor. It is first heated by the hot effluent reaction products from the second stage reactor. The recycled feed is then heated further in a fuel-fired heater before it enters the top of second stage reactor and flows downward through three beds of catalyst. The temperature and pressure conditions in the second stage reactor depend upon the same variables as determine the conditions in the first stage reactor. As a broad generality, the prNessure in the second stage reactor may range from 80 to 200 [[Bar (unit)|bar]] and the temperature may range from 345 to 425 °C.
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


After the effluent reaction product stream from the second stage reactor bottom is cooled by the incoming recycle feed, it is partially condensed in a water-cooled condenser and routed into second high-pressure vapor-liquid separator for separation into two phases: hydrogen-rich gas and hydrocarbon. No water washing of the second stage reactor effluent is needed because the second stage reactor effluent is essentially free of
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'''''.
hydrogen sulfide and ammonia gases. For the same reason, the gas from the second high-pressure separator does not require amine scrubbing to remove hydrogen sulfide.


The two hydrogen-rich gas streams (the amine-scrubbed gas from the first high-pressure separator and the gas from second high-pressure separator) are joined and then compressed and recycled for use in both the first and second stage reactor systems.  
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 hydrogenation of sulfur and nitrogen compounds in the first stage reactor requires the consumption of hydrogen. Likewise, the saturation of olefins and aromatics, in both the first stage and second stage reactors, to form paraffinic hydrocracked products consumes hydrogen. To a large extent, the amount of hydrogen consumption depends to the the feedstock content of sulfur, nitrogen, olefins and aromatics. As a broad generality, the consumption of hydrogen in a hydrocracker may range from 1,000 to 3,000 standard cubic feet per barrel of feedstock (195 to 585 normal cubic metres per metric ton of feedstock).<ref>The standard cubic feet hydrogen are at 60 °F and the normal cubic metres are at 0 °C, both at 1 atmosphere of absolute temperature.</ref>  
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|Hydrocracking process.png|center|650px|Schematic flow diagram of a typical hydrocracker.}}
==References==
 
{{reflist}}
==Chemistry==
 
Basically, catalytic hydrocracking involves three primary chemical processes:
 
:* Cracking of high-boiling, high molecular weight hydrocarbons found in petroleum crude oil into lower-boiling, lower molecular weight hydrocarbons.
 
:*Hydrogenating unsaturated hydrocarbons (whether present in the original feedstock or formed during the cracking of the high-boiling, high molecular weight feedstock hydrocarbons) to obtain saturated hydrocarbons usually referred to as paraffins or [[Hydrocarbon|alkane]]s.
 
:*Hydrogenating any sulfur, nitrogen or oxygen compounds in the original feedstock into gaseous hydrogen sulfide, ammonia and water.
 
The above primary processes include too many complex reactions to describe each of them in detail. The following four reactions are provided as examples of those complex reactions:<ref>{{cite book|author=John S. Mgee and Geoffrey E. Dolbear|title=Petroleum Catalysts in Nontechnical Language|Edition=1st Edition|publisher=Pennwell Books|id=0-87814-661-X}}</ref>
 
:* Reaction 1: Addition of hydrogen to aromatics converts them into hydrogenated rings. These are then readily cracked using [[acid catalyst]]s.
 
:* Reaction 2: Acid catalyst cracking opens paraffinic rings, breaks larger paraffins into smaller pieces and creates double bonds.


==Catalyst==
== Further reading==


Hydrocracking catalysts dual function catalysts, specifically a cracking function and a hydrogenation function. The cracking function is provided by an acid catalyst support and the hydrogenation function is provided by metals
*{{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}}


The acidic support consiste of amorphous oxides such as [[silica-alumina]], crystalline [[zeolite]] or a mixture of amorphous oxides and crystalline zeolite. Cracking and isomerization reactions
*{{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}}


*{{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}}


*{{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}}


:* Reaction 3: Addition of hydrogen to olefinic double bonds to obtain paraffins.
*{{cite book | author=R. Barrat| title=Atmospheric Dispersion Modelling | edition=1st Edition | publisher=Earthscan Publications | year=2001 | isbn=1-85383-642-7}}
 
:* Reaction 4: Isomerization of branched and straight-chain paraffins.
 
==References==
{{reflist}}


*{{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}}


------------------------------------
*{{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 }}
*{{cite journal|author= Naveen Bhutani, Ajay K. Ray and G.P. Rangaiah|title=Modeling, Simulation and Multi-objective Optimization of an Industrial Hydrocracking Unit|journal=Ind. Eng. Res.|volume=45|issue=4|pages=pages 1354 – 1372|date=2006|id= }}

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.