Background And: Introducti On

Chapter 1
Introducti on
CHAPTER 01
Background And Introduction
Chapter 1
Introducti on
BACKGROUND
Todays refiner is faced with the need to convert the heavier components of the crude barrel into lighter more valuable products. This situation is a result of increasingly heavier crudes, lower demand for fuel oil, a steady to lower demand for motor gasoline and an increasing demand for mid-distillates particularly diesel. Ultimately new conversion facilities have to be built to upgrade barrel to light products. However neither the available cash flow nor the project economics will support such investment today in most refineries. Redeploying existing facilities to provide the partial solution to residual fuel conversion is an immediately viable move. Mild hydro-cracking is a widely applicable example of such reuse of existing facilities. Other options include fluid catalytic cracking and coking but both of these processes require heavy investments. However, if these units already exist on-site, some of the end products are of such poor quality that further upgrading will be required. Fundamentally the trend towards lower feed grading is related to an increase in the carbon/hydrogen ratio of crudes. This can be overcome by upgrading methods which lower this ratio, by adding hydrogen. Though the technology to upgrade heavy oils exists, selection of the optimum process units is very much dependent on each refiners need and goals. Today, hydro-cracking technology plays the major role in meeting the need for cleanerburning fuels, effective feedstocks for petrochemical operations, and more effective lubricating oils. Only through hydro-cracking can heavy fuel oil components be 2
Chapter 1
Introducti on
converted to transportation fuels and lubricating oils whose quality will meet tightening environmental and market demands. Hydro-processing feedstocksnaphthas, atmospheric gas oils, vacuum gas oils (VGOs), and residuumhave widely different boiling character. Within each of these different
boiling ranges exist a variety of molecular types. This depends on both the crude Source Arabian Light
Density, API Sulphur, wt% Nitrogen, wt% Density, API
Arabian Heavy
Kuwait Iranian Heavy
Venezuelan California
33.3 1.8 0.16
8.0 Sulphur, wt% 3.7 Nitrogen,wt% 0.49 Asphaltenes,wt% 11.3 Nickel+Vanadium, 96

ppm Iron, ppm
Crude oil 28.1 31.3 30.8 2.9 2.5 1.6 0.19 0.09 0.18 0 Residuum 1000 F+ (5380C+ ); 4.6 7.4 6.3 5.6 5.1 3.2 0.67 0.38 0.83 20.6 12.0 14.7 220 116 462
33.3 1.2 0.12 10.9 2.8 0.56 16.0 666
20.9 0.94 0.56 5.4 1.6 1.33 12.0 296
_ 10 0.9 9.0 5.0 90 oil source and whether the material was produced in a cracking reaction or as a straight-run component of the original crude oil. The impurity levels in a variety of crude oils and in their vacuum residua are shown.
Inspection of crude oil and vacuum residua
The vacuum residuum is the lowest-value in the crude oil. Historically it has blended into heavy fuel. The demand for this product, however, has not kept pace with the tremendous increase demand for transportation fuels. Environment pressures have widened this gap restricting the use of high-sulfur fuel oil while 3
Chapter 1
Introducti on
mandating cleaner light products. The products into which the refiner must convert the bottom of the barrel are summarized in the table given
Hydro-processing Objectives
Chapter 1
Introducti on HISTORY
Hydrotreating and hydro-cracking are among the oldest catalytic processes used in petroleum refining. They were originally employed in Germany in 1927 for converting lignite to gasoline and later used to convert petroleum residues to distillable fractions. The first commercial hydro-refining installation in the United States was at Standard Oil Company of Louisiana in Baton Rouge in the 1930s. Following World War II, growth in the use of hydro-cracking was slow. The availability of Middle Eastern crude oils reduced the incentive to convert coal to liquid fuels, and new catalytic cracking processes proved more economical for converting heavy crude fractions to gasoline. In the 1950s, hydrodesulfurization and mild hydrogenation processes experienced a tremendous growth, mostly because large quantities of by-product hydrogen were made available from the catalytic reforming of low-octane naphthas to produce high-octane gasoline. The first modern hydro-cracking operation was placed on-stream in 1959 by Standard Oil Company of California. The unit was small, producing only 1000 barrels per stream day (BPSD). As hydro-cracking units were installed to complement existing fluid catalytic cracking (FCC) units, refiners quickly recognized that the hydro-cracking process had the flexibility to produce varying ratios of gasoline and middle distillate. Thus, the stage was set for rapid growth in U.S. hydro-cracking capacity from about 3000 BPSD in 1961 to about 120,000 BPSD in just 5 years. Between 1966 and 1983, U.S. capacity grew eightfold, to about 980,000 BPSD. Outside the United States, early applications involved production of liquefied petroleum gas (LPG) by hydro-cracking naphtha feedstocks. The excellent quality of distillate fuels produced when hydro-cracking gas oils and other heavy feedstocks 5
Chapter 1
Introducti on
led to the choice of the hydro-cracking process as a major conversion step in locations where diesel and jet fuels were in demand. Interest in high-quality distillate fuels produced by hydro-cracking has increased dramatically worldwide. As of 2002, more than 4 million BPSD of hydro-cracking capacity is either operating or is in design and construction worldwide.
Process Applications
Hydro-cracking is one of the most versatile of all petroleum refining processes. Any fraction from naphtha to non-distillable can be processed to produce almost any desired product with a molecular weight lower than that of the chargestock. At the same time that hydro-cracking takes place, sulfur, nitrogen, and oxygen are almost completely removed, and olefins are saturated so that products are a mixture of essentially pure paraffins, naphthenes, and aromatics. Below given table illustrates the wide range of applications of hydro-cracking by listing typical chargestocks and the usual desired products. The first eight chargestocks are virgin fractions of petroleum crude and gas condensates. The last four are fractions produced from catalytic cracking and thermal cracking. All these streams are being hydrocracked commercially to produce one or more of the products listed. This flexibility gives the hydro-cracking process a particularly important role as refineries attempt to meet the challenges of todays economic climate. The 6
Chapter 1
Introducti on
environmental regulatory pressures, and intense
combined influences of low-quality feed sources, capital spending limitations, hydrogen limitations, competition have created a complex optimization problem for refiners. The hydrocracking process is uniquely suited, with proper optimization, to assist in solving these problems.
Applications of Process
Chapter 1
Introducti on Thermal Cracking History
Because the simple distillation of crude oil produces amounts and types of products that are not consistent with those required by the marketplace, subsequent refinery processes change the product mix by altering the molecular structure of the hydrocarbons. One of the ways of accomplishing this change is through "cracking," a process that breaks or cracks the heavier, higher boilingpoint petroleum fractions into more valuable products such as gasoline, fuel oil, and gas oils. The two basic types of cracking are thermal cracking, using heat and pressure, and catalytic cracking. The first thermal cracking process was developed around 1913. Distillate fuels and heavy oils were heated under pressure in large drums until they cracked into smaller molecules with better antiknock characteristics. However, this method produced large amounts of solid, unwanted coke. This early process has evolved into the following applications of thermal cracking: visbreaking, steam cracking, and coking.
Dieselmax Process Unit

Dieselmax Process Unit is a combination of Mild Hydro-cracking with Thermal Cracking for maximizing High Speed Diesel (HSD) production at relatively low cost. The Dieselmax Process Unit Catalytically desulfurizes and denitrifies a vacuum gas oil (VGO) feedstock and converts the feedstock to a diesel product, Kerosene, naphtha, and light ends including LPG in the presence of hydrogen. Reactor effluent liquid is stripped and fractionated to separate the products from unconverted VGO. The unconverted VGO from the Fractionator is thermally
Chapter 1
Introducti on
cracked and fractionated to provide additional LPG, naphtha, and diesel range materials. The Dieselmax Process Unit consists of three processing sections:

Catalytic Reactor Section Catalytic Fractionation Section Thermal Section.
The Dieselmax process is a combination of catalytic and thermal processes which converts vacuum gas oil to lighter, more valuable middle distillate products. That portion of the Dieselmax feed which is not converted to distillate range products is upgraded by removing contaminants and by hydrogen addition. This unique combination of catalytic and thermal cracking allows a refiner to achieve maximum yields of distillate range product from a vacuum gas oil feed without using higher pressure operations associated with conventional hydro-cracking.
Chapter 2
Present & Future Outlook
CHAPTER 02
Present And future outlook For petroleum sector In Pakistan
10
Chapter 2
REFINERY PROCESS FLOW CHART
11
Chapter 2 Energy Outlook for future
World oil demand growth projections are from 80 million bpd in 2003, to 98 million bpd in 2015, to 118 million bpd in 2030. Non - OECD Asia (including China & India) account for 43% of the total increase. 50% of Projected increase in Oil over the 2003 to 2030 stage, occurs in Transportation sector. Industrial sector accounts for 39% of projected oil demand growth, mostly for Chemical & Petrochemical processes.
World Oil Consumption by Sector showing Projected Demand Growth (2003-2030)
12
Chapter 2
World-wide Activity to Add Refining
Capacity,
Refinery Margins
Estimated $770 billion investment in Oil Refining Capacity by 2030. International Crude Prices are expected to remain well above US $ 90/barrel. New Investments in the Global Refining Industry are expected by 2008-09 coupled with World Oil demand expected to grow at 3%, the prices of Crude & Product shall remain high and new investment in the sector will provide reasonable returns to investors. Based on Long Term Projections, the Refinery Margins are attractive for entering into Refining Business.
Regional Demand
On regional basis, two parts of the world lead the projected growth in world oil demand;

Non - OECD includes China, India & others OECD includes USA, UK, Canada, Japan, France, Germany & others
The fastest growth in Oil demand is projected for the economies of Non - OECD Asia, averaging 3% per year from 2003 to 2030. In Asia Pacific also, beyond 2010 projected strong demand will outpace supply growth.
Necessity to Increase Refining Base

To fulfill the increasing petroleum product demand/supply gap, installation of new refining capacity will have to be undertaken. A Coastal Refinery is therefore necessary to balance the product supply to the country and to export surplus products. The aim is to maximize middle distillates so that configurations can be optimized to meet Pakistans Petroleum needs and to form a nucleus for a Petrochemical complex. 13
Chapter 2 Expanding Refining Capacities Vs
Importing
Refined Products
It is a good time for investment in the Refineries due to strong demand for finished products, especially Gasoline in China. Poor Refining Margin from 1998 to 2002 caused the closure of many refineries in the region. Combination of strong demand growth and decreasing capacity has transformed the Asian Refineries from struggling to Break-Even into improved Refining Margins.
Petroleum Product Outlook for Pakistan
14
Chapter 2
Benefits of Expanding Refining Capacities Vs Importing Refined Products

Direct Benefits Refinery Expansion

Foreign Exchange savings through local production. Strategic Self Reliance for Countrys Energy needs
hence;
Secured Supply Line Strengthening Countrys Infrastructure Assets & Reserves
Trade Opportunity to export Petroleum products from Pakistan to Asia/Asia Pacific.
Indirect benefits
Socio-economic
development
in
relatively
under-developed
areas;
Development of PARCO Mid-Country Refinery is an excellent example where socio-economic development was achieved in districts of Muzaffargarh, D.G Khan, Multan.
Khalifa Coastal Refinery Study

IPIC and PARCO are jointly establishing Khalifa Coastal Refinery. Its capacity will 200,000 to 300,000 BPSD. This project focuses on meeting Pakistans deficit of middle distillates post 2011 and regional export market for surplus products. For maximizing Middle distillates, Delayed Coker/Hydro-cracking processing scheme has been considered. 15
Chapter 2 Future Outlook
Oil Prices have risen to current levels through a much faster mechanism. Regional demand show that strong demand growth across Asia pacific will soak up extra capacity. Security of supply and demand are mutually supportive. Uncertainty over future demand translates into investment opportunity in this sector, while suppliers (OPEC) have risk in meeting this demand.
Projected Refining Gap in Pakistan (2006-2020)
16
Chapter 2
The Way Forward

Enhancing Countrys Refining base Enhancing Energy sources Development of Storage Infrastructure Development of reliable inflow of Energy Supply
Pakistan Existing Refining Capacities
17
Chapter 2
18
Chapter 2
Things that Need to be Done

Conducive & Investor friendly Economic Reforms Legal Protection for Policies & Procedures Implementing De-regulation & Market-related pricing policies Provide security of investment & returns Consistency & continuity of pro-investment policies
Middle Distillate Production:

The quantity and quality of diesel produced is shown in Table ( where, ktpa= thousand [metric] tons per annum). With the exception of ARL diesel, the level of sulfur in diesel is close to 1%. Because of the large quantity of 1-percentsulfur diesel produced at PARCO. The national average for domestically produced diesel is 0.9 percent.
This can be be lowered somewhat by blending kerosene into diesel. Refinery

NRL PRL ARL PARCO
DIESEL ktpa %-sulphur 570 584 217 10 0.9 0.9 0.2 0.5
1142 1 1381 0.8 2523 0.9
19
DHODAK Total without Parco Total with Parco
Chapter 2
Diesel is consumed mainly in four sectors: Power, Industry, Transport, and Other government. On the basis of indications from various consumers in these sectors, OCAC (oil company advisory committee) develops forecasts.
20
Chapter 3
Reaction Chemistry
CHAPTER 03
Hydrocracking And Thermal Cracking Reaction Chemistry
21
Chapter 3
Reaction Chemistry
Hydrocracking Chemistry
Hydrocracking chemistry is bifunctional catalytic chemistry involving acidcatalyzed isomerization and cracking reactions as well as metal-catalyzed hydrogenation reactions. The resulting products are lower in aromatics and contain naphthenes and highly branched paraffins due to the higher stability of the tertiary carbenium ion intermediate. For paraffins, the reaction network, shown below, is postulated to begin with a dehydrogenation step at a metal site forming an olefin intermediate which is quickly protonated at an acid site to yield a carbenium ion. This is quickly followed by a series of isomerization reactions to the most stable tertiary carbenium ions and subsequent cracking to smaller paraffin, which evolves off the catalyst surface and smaller carbenium ion intermediate.
Postulated Paraffin-Cracking Mechanism is shown as.
22
Chapter 3
Postulated Paraffin-Cracking Mechanism
Reaction Chemistry
23
Chapter 3
Reaction Chemistry
The carbenium ion can then eliminate a proton to form an olefinic intermediate, which gets hydrogenated at a metal site or directly abstract a hydride ion from a feed component to form a paraffin and desorb from the surface.
A typical hydrocracking reaction for a cycloparaffin, given on next page 1 is known as a paring reaction, in which methyl groups are rearranged and then selectively removed from the cycloparaffin without severely affecting the ring itself. Normally the main acyclic product is isobutane.
The hydrocracking of multiple-ring naphthene, such as decalin, is more rapid than that of a corresponding paraffin. Naphthenes found in the product contain a ratio of methylcyclopentane to methylcyclohexane that is far in excess of thermodynamic equilibrium.
Reactions during the hydrocracking of alkyl aromatics, shown on next page 2 include isomerization, dealkylation, paring, and cyclization. In the case of alkylbenzenes, ring cleavage is almost absent, and methane formation is at a minimum.
24
Chapter 3
Postulated Cracking-Mechanism for Naphthenes
Reaction Chemistry
Postulated Aromatic Dealkylation Mechanism
25
Chapter 3
Reaction Chemistry
Reaction Mechanism
Sulfur Removal:
Typical feed stocks to the Dieselmax Catalytic Section Unit contains simple mercaptans, sulfides and disulfides. These compounds are easily converted to H2S. However, feed stocks containing aromatic molecules are more difficult to process. Thiophene is considered 15 times more difficult to process compared to diethylsulfide.
Nitrogen Removal:
Denitrogenation is generally more difficult than desulfurization. Side reactions may yield nitrogen compounds more difficult to hydrogenate than the original reactant. 26
Chapter 3
Reaction Chemistry
The reaction mechanism steps are different compared to desulfurization. The denitrogenation of pyridine proceeds by aromatic ring saturation, ring hydrogenolysis, and finally denitrogenation.
Oxygen Removal:
Organically combined oxygen is removed by hydrogenation of the carbonhydroxyl bond forming water and the corresponding hydrocarbon.
27
Chapter 3
Olefin Saturation:
Reaction Chemistry
Olefin saturation reactions proceed very rapidly and have a high heat of reaction. The distillate range recycle stream returning from the thermal section have a high olefin content. It is saturation of this thermally cracked material that greatly upgrades its quality.
Aromatic saturation:
Aromatic saturation reactions are the most difficult. The reactions are influenced by process conditions and are often equilibrium limited. The saturation reaction is very exothermic.
28
Chapter 3
Metals removal:
Reaction Chemistry
The mechanism of the decomposition of organo-metallic compounds is not well understood. However, it is known that metals are retained on the catalyst by a combination of adsorption and chemical reaction. The catalyst has a certain maximum tolerance for retaining metals. Removal of metals normally occurs in plug flow fashion with respect to the catalyst bed. Typical organic metals native to most crude oils are nickel and vanadium. Iron can be found concentrated at the top of catalyst beds as iron sulfides which are corrosion products. The useful life of the catalyst may be determined by the amount of metals that are accumulated on it during the course of operation. Most Dieselmax Units are able to go through several operating cycles without exceeding the ability of the catalyst for removing metals. Metal removal is essentially complete above temperatures of 3160C (6000F) to a metals loading of 2-3 wt% of the total catalyst.
Halides removal:
Organic halides, such as chlorides and bromides, are decomposed in the reactor. The inorganic ammonium halide salts which are produced when the reactants are cooled are then dissolved by injecting water into the reactor effluent or leave with the stripper off-gas.
HCl
NH3
NH4Cl
29
Chapter 3
Reaction Rates:
Reaction Chemistry
The approximate relative heats of reaction per unit of hydrogen consumption for these reactions are: Desulfurization Olefin Saturation Denitrification Aromatics Saturation 1 2 1 1
All of the reactions discussed above are exothermic and result in a temperature rise across the reactor. Olefin saturation and some desulfurization reactions have similarly rapid reaction rates, but it is the saturation of olefins which generates the greatest amount of heat. The temperature rise expected for a given charge stock along with the desired product quality plays a very important role in determining the number, size, and arrangement of the reactors, heat exchange, and hydrogen circulation rate.
Thermal cracking process

Reaction Chemistry
When a hydrocarbon is heated and decomposed under thermal cracking conditions, it may be assumed that it is broken up into two or more free radicals. The free radicals then enter into a series of reactions that result in a total product covering a broad range of molecular weights from hydrogen to bitumen and cokes. In accordance with thermal cracking theory, the reactions may proceed as:
30
Chapter 3
Reaction Chemistry
A portion of the compound disassociates to form free radicals, for example: C10H22 C8H17 + C2H5
The highly reactive radicals do not appear in the thermally cracked product effluent, but depending upon size and environment: (a) react with other hydrocarbons, (b) decompose to olefins, (c) combine with other radicals, and (d) react with metal surfaces. In general, small radicals are more stable than larger radicals, and more readily react with other hydrocarbons by capturing a hydrogen atom, for example; C2H5 + C6H14 C2H6 + C6H13
Large radicals are unstable and decompose to form olefins and smaller radicals, for example; C6H13 C8H17 C4H9 C5H10 + CH3 C4H8 + C4H9 C4H8 + H
The free radical chain reactions are terminated when two radicals combine; for example; C8H17 + H C8H18
The polymerization and condensation reactions that occur at thermal cracking conditions can go all the way to aromatic tars. Coke and bitumen are the ultimate polymers. The molecules become very large with considerable cross linkage. Lack of hydrogen coupled with high molecular weight decreases their solubility in hydrocarbons. 31
Chapter 3
Reaction Chemistry
CATALYST
Hydrocracking catalysts combine acid and hydrogenation components in a variety of types and proportions to achieve the desired activity, yield structure, and product properties. Noble metals as well as combinations of certain base metals are employed to provide the hydrogenation function. Platinum and palladium are commonly used noble metals while the sulfided forms of molybdenum and tungsten promoted nickel or cobalt are the most common basemetal hydrogenation agents. The cracking function is provided by one or a combination of zeolites and amorphous silica-aluminas selected to suit the desired operating and product objectives. A postulated network of reactions that occur in a typical hydrocracker processing a heavy petroleum fraction is shown on next page. The reactions of the multiring species should be noted. These species, generally coke precursors in nonhydrogenative cracking, can be effectively converted to useful fuel products in a hydrocracker because the aromatic rings can be first hydrogenated and then cracked. Amorphous silica-alumina was the first catalyst support material to be used extensively in hydrocracking service. When combined with base-metal hydrogenation promoters, these catalysts effectively converted vacuum gas oil (VGO) feedstocks to products with lower molecular weight. Over three decades of development, amorphous catalyst systems have been refined to improve their performance by adjustment of the type and level of the acidic support as well as the metal function. Catalysts such as UOPs DHC-2 (desulfrization catalyst) and DHC-8 (Hydrocracking catalyst) have a well-established
32
Chapter 3
Reaction Chemistry
performance history in this service, offering a range of activity and selectivity to match a wide range of refiners needs.
Hydrocracking Reactions
Crystalline catalyst support materials, such as zeolites, have been used in hydrocracking catalysts by UOP since the mid-1960s. The combination of selective pore geometry and varying acidity has allowed the development of catalysts that convert a wide range of feedstocks to virtually any desired product slate. UOP now offers catalysts that will selectively produce LPG, naphtha, middle distillates, or lube base oils at high conversion activity using molecularsieve catalyst support materials. The UOP zeolite materials used in hydrocracking service are often grouped according to their selectivity patterns. Base metal catalysts utilized for naphtha applications are HC-24, HC-34, and 33
Chapter 3
Reaction Chemistry
HC-170. Flexible base metal catalysts (naphtha, jet, diesel) include DHC-41, HC43, HC-33, HC-26, and HC-29. The distillate catalysts, which offer a significantly enhanced activity over amorphous catalysts while maintaining the excellent middle-distillate selectivity, are HC-110, HC-115, DHC-32, and DHC-39. Noble metal catalysts are also available for both naphtha (HC-28) and jet/naphtha (HC-35) service. Unlike the amorphous-based catalysts, the zeolite-containing materials are usually more selective to lighter products and thus more suitable when flexibility in product choice is desired. In addition, zeolitic catalysts typically employ a hydroprocessing catalyst upstream, specifically designed to remove nitrogen and sulfur compounds from the feed prior to conversion. UOP catalysts such as HCP, HC-R, HC-T, UF-210, and UF-220 are used for this service. These materials are specifically designed with high hydrogenation activity to effectively remove these compounds, ensuring a clean feed and optimal performance over the zeolitic-based catalyst.
One
important
consideration
for
catalyst
selection
is
regenerability.
Hydrocracking catalysts typically operate for cycles of 2 years between regenerations but can be operated for longer cycles, depending on process conditions. When end-of-run conditions are reached, as dictated by either temperature or product performance, the catalyst is typically regenerated. Regeneration primarily involves combusting the coke off the catalyst in an oxygen environment to recover fresh catalyst surface area and activity. Regenerations can be performed either with plant equipment if it is properly designed or at a vendor regeneration facility. Both amorphous and zeolitic catalysts supplied by UOP are fully regenerable and recover almost full catalyst activity after carbon burn.
34
Chapter 4
Process Selection
CHAPTER 04
Capacity And Process Selection
35
Chapter 4
Process Selection
Processes Available:
Basically there are two processes available for the cracking of vaccum gas oil (VGO). Fluid catalytic cracking Catalytic cracking Thermal cracking
Fluid Catalytic cracking:

Fluid catalytic cracking (FCC) is the most important conversion process used in petroleum refineries. It is widely used to convert the high-boiling, highmolecular weight hydrocarbonfractions of petroleum crude oils to more valuable gasoline, olefinic gases, and other products.Cracking of petroleum hydrocarbons was originally done by thermal cracking, which has been almost completely replaced by catalytic cracking because it produces more gasoline with a higher octane rating. It also produces byproduct gases that are more olefinic, and hence more valuable, than those produced by thermal cracking. The feedstock to an FCC is usually that portion of the crude oil that has an initial boiling point of 340 C or higher at atmospheric pressure and an average molecular weight ranging from about 200 to 600 or higher. This portion of crude oil is often referred to as heavy gas oil. The FCC process vaporizes and breaks the long-chain molecules of the high-boiling hydrocarbon liquids into much shorter molecules by contacting the feedstock, at high temperature and moderate pressure, with a fluidized powdered catalyst. In effect, refineries use fluid catalytic cracking to correct the imbalance between the market demand for gasoline and the excess of heavy, high boiling range products resulting from thedistillation of crude oil. As of 2006, FCC units were in operation at 400 petroleum refineries worldwide and about one-third of the crude oil refined in those refineries is processed in an 36
Chapter 4
Process Selection
FCC to produce high-octane gasoline and fuel oils.During 2007, the FCC units in the United States processed a total of 5,300,000 barrels (834,300,000 litres) per day of feedstock and FCC units worldwide processed about twice that amount. Catalysts Modern FCC catalysts are fine powders with a bulk density of 0.80 to 0.96 g/cc and having a particle size distribution ranging from 10 to 150 m and an average particle size of 60 to 100 m.The design and operation of an FCC unit is largely dependent upon the chemical and physical properties of the catalyst. The desirable properties of an FCC catalyst are:

Good stability to high temperature and to steam High activity Large pore sizes Good resistance to attrition Low coke production
Catalytic Cracking:
The catalytic cracking of hydrocarbons is not restricted to one single reaction. Instead, several reactions occur, all resulting in different product compositions. Here the catalytic cracking of diesel is investigated. Diesel mainly consists of saturated hydrocarbons (CnH2n+2) ranging from C10H22 to C15H32. Therefore, in this study the cracking of dodecane (C12H26) has been taken as the model reaction. Because no hydrogen is added during the cracking process the product mostly comprises of unsaturated hydrocarbons (CnH2n), called olefins. Advantages Advantages of using catalytic cracking of liquid hydrocarbons on-board are:
Increased lower heating value of the fuel by about 6% 37
Chapter 4

Process Selection
Better burning due to usage of gaseous hydrocarbons Reaction conditions comparable with exhaust temperature
Disadvantages Disadvantages of using catalytic cracking of liquid hydrocarbons on-board are:

Incomplete conversion of the fuel Polymerizing by olefins in the system Coking on the catalyst, which leads to deactivation
Solutions To overcome the problem of coking on the catalyst in industrial processes the catalyst is regenerated by heating it up and burning of the cokes. In a car this has to be applied continuously. In another process called hydrocracking the problem of coking is circumvented by adding a high pressure hydrogen stream. This also might work on-board when the cracking system is combined with a hydrogengenerating process. Hydrocracking would provide a solution for the polymerization problem as well. To reuse the unreacted part of the product stream a separation unit has to be incorporated. Possibly the unreacted diesel can be vaporized and introduced to the engine together with the gaseous hydrocarbons. The boiling point of diesel is about 350 C so there is a possibility to run the system in this way. Another option for operating a catalytic cracking process is provided in a US patent from 1985. The catalyst is placed inside the combustion chamber. Liquid fuel is injected into the combustion chamber, where it is cracked right before combustion. It would be interesting to investigate if the engine cycle of such a system corresponds to that of a gas engine
38
Chapter 4
Process Selection
Thermal Cracking:
Reaction Chemistry
When a hydrocarbon is heated and decomposed under thermal cracking conditions, it may be assumed that it is broken up into two or more free radicals. The free radicals then enter into a series of reactions that result in a total product covering a broad range of molecular weights from hydrogen to bitumen and cokes. In accordance with thermal cracking theory, the reactions may proceed as: A portion of the compound disassociates to form free radicals, for example: C10H22 C8H17 + C2H5
The highly reactive radicals do not appear in the thermally cracked product effluent, but depending upon size and environment: (a) react with other hydrocarbons, (b) decompose to olefins, (c) combine with other radicals, and (d) react with metal surfaces. In general, small radicals are more stable than larger radicals, and more readily react with other hydrocarbons by capturing a hydrogen atom, for example; C2H5 + C6H14 C2H6 + C6H13
Large radicals are unstable and decompose to form olefins and smaller radicals, for example; C6H13 C8H17 C4H9 39 C5H10 + CH3 C4H8 + C4H9 C4H8 + H
Chapter 4
Process Selection
The free radical chain reactions are terminated when two radicals combine; for example; C8H17 + H C8H18
The polymerization and condensation reactions that occur at thermal cracking conditions can go all the way to aromatic tars. Coke and bitumen are the ultimate polymers. The molecules become very large with considerable cross linkage. Lack of hydrogen coupled with high molecular weight decreases their solubility in hydrocarbons.
40
Chapter 4
Process Selection
PROCESS SELECTION:
Dieselmax process licensors will need to strike the right balance between complex, expensive, high pressure processes that offer flexibility and products of superior quality and cheap, simple, low pressure designs with more restricted options. In an economic climate of low refining margins and emphasis on high returns on investment, there is a strong incentive to design and construct hydrocrackers with minimum capital investment. This often means simple units, i.e. single reactor operating at moderate conditions. This is the major reason that the mild hydrocracking process is now used. On the other hand, the call for ultra low sulfur and in particular very low aromatics level in finished products cannot easily be satisfied by applying a low hydrogen partial pressure process. Moreover, catalyst activities in mild hydrocracking unit are reduces as well. Therefore, we select mild hydrocracking unit for the conversion of VGO feed stock in our project, which is the best design as proved by above discussion.
Capacity Selection:
We selected 30000 BPSD of VGO feed because as presented by graphs on next pages, these graphs clearly indicate that there is now a large consumption of diesel in all provinces of Pakistan, and we have to maximize the production of diesel and middle distillates.
41
Chapter 4
Process Selection
World Oil Consumption by Sector showing Projected Demand Growth (2003-2030)
Petroleum Product outlook for Pakistan
42
Chapter 4
Process Selection
43
Chapter 5
Process Descriptio n
CHAPTER 05
Process Description
44
Chapter 5
TAGGING OF PLANT EQUIPTMENTS
45
Chapter 5
PROCESS DESCRIPTION
The Dieselmax process Unit can be divided into three (3) sections. These are termed as follows:

Catalyst Reactor Section Catalyst Fractionation Section Thermal Section
Catalyst Reactor Section:

Fresh Feed System: The VGO feed coming from an upstream vacuum distillation unit is sent to the feed surge drum (D1) along with some recycled distillate coming from the thermal section. The VGO feed stream is filtered by automatic backwash filters (F1). The contaminated oil from the backwash contains solids and is sent to backwash surge drum (D2) to refinery tanks. The reactor charge pump (P1) takes suction from the feed surge drum (D1) and pump the raw oil to the reactor effluentcombined feed exchangers (E1, 2). Feed Preheating: The temperature of the VGO feed from the feed surge drum (D1) is below to Hydrocracker reactor (R1) inlet temperature. So, first feed is preheated by reactor effluent-combined feed exchange (E1, 2) with hot reactor effluent coming from hydrocracker and then heating in a fired heater (FH1).
46
Chapter 5
Catalytic Reactor: When the VGO feed has been heated to the desired temperature, the reactants enter the top of the catalytic reactor (R1). As the reactants flow downward through the catalyst bed, exothermic chemical reactions occur and the temperature increases. Reactor Effluent Cooling System: Due to the exothermic nature of the reactions taking place in the reactor (R1), the temperature of the material leaving is greater than the reactor inlet temperature. The heat of reaction as well as a large portion of the heat contained in the reactor feed is recovered with the help of heat exchanger (E3) which is used to preheat the stripper feed. After exiting the heat exchanger (E3), wash water is injected into the reactor effluent and this combined water-effluent stream is further cooled in air cooled exchanger (AE1) before entering the high pressure separator (T1). Vapor / Liquid Separation System: After cooling the reactor effluent, the desired liquid products must be separated from the recycle gas. The reactor effluent exits the air cooled exchanger (AE1) and goes to the separator (T1) where the hydrocarbon liquid is separated from the water and recycle gas and sent to the fractionation section. The water collected in the boot attached to the separator (T1) is removed and sour water is sent to treating unit. The hydrogen-rich recycle gas from the separator (T1) is sent to the recycle gas scrubber for removal of H2S. Reactor Effluent Water Wash System: The sulfur and nitrogen contained in the VGO feed are converted to hydrogen sulfide (H2S) and ammonia (NH3) in the reactor (R1). These two reaction products 47
Chapter 5
combine to form ammonium salts which can solidify and precipitate as the reactor effluent is cooled. Reactor effluent is cooled in the air cooled exchanger (AE1). Water is injected into the stream before it enters the air cooled condenser in order to prevent the deposition of salts that can corrode and foul the condenser tubes.
Recycle Hydrogen Scrubbing System: H2S is present in the recycle gas stream because it is a reaction by-product. So, a recycle gas scrubber (S1) is used to remove H2S from the recycle gas. After separation of the gas and liquid phases in the separator (T1), the gas leaves from the top of the separator (T1), passes through the recycle gas cooler (E4), and flows to the knock out drum (D4), where condensed liquid is removed. The gas from the knock out drum (D4) enters the bottom section of the recycle gas scrubber (S1) and is contacted counter-current with amine, entering from top of the column. The amine flowing down and the gas flowing up the tower come into contact over the trays. Intimate mixing between the two is achieved and the amine absorbs the H2S from the gas. The "rich" amine falls to the bottom of the recycle gas scrubber (S1). The H2S-free gas leaves the top of the tower (S1) and goes through the centrifugal compressor (C1) before joining with the makeup hydrogen. Recycle Gas System: After the recycle gas compressor (C1) discharge, some recycle gas is used as quench gas between catalyst beds. Quench gas streams are used to reduce reactor interbed temperatures. 48
Chapter 5
49
Chapter 5
Catalyst fractionation section:

The function of the Catalyst Fractionation Section is to separate the reactor liquid product into the un-stabilized naphtha, kerosene, diesel and product fractionator (R2) bottoms product. Liquid product from the reactor section is sent to the stripper (S2) for the removal of H2S and light gas components. Stripper overhead vapor are partially condensed and sent to the stripper receiver (T2). The liquid from the receiver is pumped again to the feed stream to S2 From the stripper (S2) bottom the reactor liquid product is fed through stripper bottoms-kerosene product exchanger (E5), stripper bottoms-diesel product exchanger (E6), and product fractionator feed heater (FH2) to product fractionator (R2). The design operation feed temperature to product fractionator is 375oC. A kerosene side draw from the Product Fractionator (R2) is stripped for light ends removal in the reboiled kerosene stripper (S3). The overhead vapor from the kerosene stripper (S3) is returned to the Product Fractionator (R2). The bottoms are pumped by kerosene product pumps (P3) and go through stripper bottomskerosene product exchanger (E5). Then Kerosene product is stored. A diesel side draw from the product fractionator (R2) is steam stripped for light ends removal in the diesel stripper (S4). The overhead vapor from the diesel stripper (S4) is returned to the product fractionator (R2). The bottoms are pumped by diesel product pumps (P4) and go through a stripper bottoms-diesel product exchanger (E6), after which it is stored. Overhead vapor of product fractionator are partially condensed and sent to the product fractionator receiver (T3). The liquid from the receiver is returned to product
50
Chapter 5
fractionator (R2) top section. The net liquid product, un-stabilized naphtha, is sent to treating unit.
CATALYTIC FRACTIONATING SECTION
51
Chapter 5
Thermal section
The Dieselmax Thermal Section consists of two main operating systems. The Thermal Cracking system and Fractionation system. Bottom fractionating feed is passed through the thermal cracker heaters (FH3). The heater effluents combine and pass into a reactor chamber (R3). The thermally cracked material exiting the reactor chamber (R3) is fed into the flash fractionator (R4). The function of the flash fractionator system is to separate the reactor chamber effluent into the desired products. The overheads from the flash fractionator (R4) leave the top of the flash fractionator and are condensed and collect in the flash fractionator receiver (T4). The condensed un-stabilized naphtha is directed to treating unit. A distillate side draw from the flash fractionator (R4) is steam stripped for light ends removal in the distillate stripper (S5). The overhead vapor from the distillate stripper (S5) is returned to the flash fractionator (R4). The distillate is normally recycled back the catalytic reactor section for hydrogenation. The flash fractionator (R4) bottoms product is pumped by the flash fractionator bottoms pumps (P5) and approximately 40 percent side stream of this fractionator bottoms product is recycled. The remaining 60 percent of flash fractionator bottoms product sent towards storage tanks.
52
Chapter 5
53
Chapter 6
Material Balance
CHAPTER 06
Material Balance
54
Chapter 6
Material Balance
Operation Basis = 1 hr Feed Design Capacity = 40000 BPSD Feed is VGO, from Vacuum Distillation Unit = 264.6 m3/hr (equivalent to 40000 BPSD) Because given feed has API =22.3 Specific Gravity = 141.5 (API + 131.5) So, the sp. Gr. Is = 0.92 Hence, the density of feed = 920 kg/m3
Also, Fresh Distillate from Thermal Cracker Section = 40000 kg/hr So, total fresh feed = (40000 + 243432) = 283432 kg/hr
Chemical Hydrogen Consumption

The hydrogen is consumed in the saturation, desulfurization, denitrification and hydrocracking reactions. Chemical Hydrogen Consumption = 126 m3 H2 / m3 of fresh VGO feed Because VGO feed = 264.6 m3/hr
= 33339.6 m3/hr 55
Chapter 6
Density of Hydrogen = 0.185 kg/m3
Material Balance
So, Hydrogen Consumption flow rate = (33339.6 m3/ hr) * (0.185Kg / m3) = 6167.826 kg/hr Because from plat-forming Unit, The Hydrogen flow = 20000 to 30000 Nm3/hr So, converting it into mass flow rate = 5000 kg/hr Recycle Hydrogen Gas = 25000 kg/hr Total recycle gas = (25000 + 5000) = 30000 kg/hr Recycle hydrogen to fresh VGO = 45% of total recycle gas = 13500 kg/hr Recycle gas as Quench gas to catalytic reactor = 55% of total recycle gas = 16500 kg/hr Combined feed to catalytic reactor = (283432 + 13500) = 296932 kg/hr ---------- IN Also, the reactor effluent = 296932 kg/hr ---------- OUT Hence, for Hydrocarcker ; IN = OUT
56
Chapter 6
Material Balance
57
Chapter 6
Reactor effluent = 296932 kg/hr
Material Balance
Wash water injected to reactor effluent = 5 vol. % of fresh feed = (0.05*264.6) = 13.23 m3/hr = (13.23*1000) = 13230 kg/hr Total input to separator = 299632 kg/hr Sour water collected from separator = 10000 kg/hr Gases from separator = 30000 kg/hr Liquid leaves the separator = 299632 (10000 + 30000) = 259632 kg/hr So, for separator; 299632 = 259632 + 10000 + 30000 IN =OUT
Recycle Gas Scrubber
Input gas to scrubber = 30000 kg/hr Amine Solution to scrubber = 150000 kg/hr H2S free gas outlet flow rate = 25000 kg/hr Rich amine outlet = 155000 kg/hr
58
Chapter 6
Material Balance
Stripper and Receiver

Liquid coming from separator = 259632 kg/hr Liquid from receiver = 2500 kg/hr Total feed to stripper = 259632 + 2500 = 262132 kg/hr MP steam flow rate = 3000 kg/hr Vapors leave the separator = 10000 kg/hr Liquid leaves the separator = 191160 kg/hr Feed to receiver = 10000 kg/hr Liquid outlet from receiver = 2500 kg/hr Off-gases leave = 5500 kg/hr, Sour water = 2000 kg/hr
Off gases Molecular wt. =27.8 g/gmole Gas density = 1.2 kg/m3 Gas volumetric flow rate = (5500kg/hr) * (m 3 /1.2kg) = 4580 m3/hr
Product Fractionator
Feed to product fractionator = 191160 kg/hr Steam flow rate = 4000 kg/hr Product fractionator bottoms = 100160 kg/hr
Receiver Section
Feed to receiver = 70000 kg/hr 59
Chapter 6
Water outlet from receiver = 6000 kg/hr
Material Balance
Volumetric flow rate of water = (6000kg/hr) x (m3 / 999kg) = 6.0 m3/hr Un-stabilized naphtha from receiver = 64000 kg/hr Un-stabilized naphtha taken as product or returning to gas concentration unit = 4000 kg/hr Un-stabilized naphtha refluxed back to product fractionator = (64000 4000) = 60000 kg/hr Un-stabilized naphtha taken as product, having mol. Wt. = 89.2 g/gmole Density of Un-stabilized naphtha taken as product = 695 kg/m3 Volumetric flow rate of Un-stabilized naphtha taken as product = 5.75 m3/hr
60
Chapter 6
Material Balance
61
Chapter 6
Material Balance
Diesel Stripper
Feed to Diesel Stripper = 58000 kg/hr Stripper steam to diesel stripper = 1000 kg/hr Volumetric flow rate of stripper steam = (1000kg/hr)x(m3 / 0.8kg) = 1250 m3/hr Diesel taken as product = 40000 kg/hr Mol. Wt. of diesel product obtained = 249.3 g/gmole Volumetric flow rate of diesel product =(40000kg/hr) x (m3 / 868kg) = 46 m3/hr Vapor returned to product fractionator = (58000 + 1000) 40000 = 19000 kg/hr
Kerosene Stripper
Feed to kerosene stripper = 55000 kg/hr Kerosene taken as product = 45000 kg/hr Volumetric flow rate of kerosene product = (45000kg/hr) x (m3 / 821kg) = 55 m3/hr Vapor returned to product fractionator = (55000 45000) = 10000 kg/hr Now, Total feed to fractionator system = 191160 + 4000 = 195160 kg/hr Total output products from fractionating section 4000 + 6000) = (100160 + 40000 + 45000 + = 195160 kg/hr
62
Chapter 6 Thermal Section

Feed to flash fractionator column = 100160 kg/hr Recycled bottom product = 30000 kg/hr Total feed entering = (100160 + 30000) = 130160 kg/hr
Material Balance
Fractionator Receiver
Feed to Fractionator Receiver = 57160 kg/hr Off gases leave = 6000 kg/hr Sour water = 3160 kg/hr Net liquid obtained = 48000 kg/hr Un-stabilized naphtha obtained as product or sent to gas concentration unit = 18000 kg/hr Un-stabilized naphtha recycled to flash fractionator = (48000 18000) = 30000 kg/hr
Distillate stripper
Feed to distillate stripper = 38000 kg/hr Vapors leave = 9000 kg/hr MP steam injection flow rate = 1000 kg/hr Distillate recycled back to cat. Reactor section = 30000 kg/hr MP steam injection to bottom of flash fractionator = 2000 kg/hr Flash fractionator bottoms = 75000 kg/hr Flash fractionator bottoms sent to storage tank = 60% of Flash fractionator bottoms = (0.6*75000) = 45000 kg/hr
63
Chapter 6
Material Balance
Recycled back to feed to flash fractionator = (0.4*75000) = 30000 kg/hr
Flash fractionator IN = 100160 + 30000 + 2000 = 132160 kg/hr Flash fractionator products obtained = 6000 + 3160 + 18000 + 30000 + 75000 = 132160 kg/hr = OUT So, IN=OUT
Percentage of feed evaporated in Diesel stripper of Catalytic Fractionating Section:

64
Chapter 6
Assume, specific heat of diesel = 0.6 btu/lbm.F 100 is the latent heat; The reduction in sensible heat of the diesel product equals; (316 290)*0.6 = 15.6
btu/lbm
Material Balance
The percent of the feed to the stripper that evaporates is then; (15.6 btu/lbm) / (100 btu/lbm. ) = 15.6% I neglected the heat picked up by the steam in the preceding calculations, because steam flow rate is quite small to the stripper feed, so this effect may be disregarded.
65
Chapter 8
Equipmen t Design
CHAPTER 07
Energy Balance
66
Chapter 8
Equipmen t Design
Catalytic Reactor Section:

Reactor effluent feed exchanger
E1: Cold fluid: T1 = 656.60F T2 = 714.20F Cp = 0.7 Btu/lb0F m = 248524 lb/hr Heat gain: Q = m*Cp*T = 248524 (0.7) (714.2 - 656.6) = 10E+06 Btu/hr Hot fluid: T1 = 757.40F T2 = 707 0F Cp = 0.8 Btu/lb0F m = 248524 lb/hr Heat loss: Q = m*Cp*T = 248524 (0.8) (757.4 -707) 67
Chapter 8
= 10E+06 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Reactor effluent feed exchanger

E2: Cold fluid: T1 = 656.60F T2 = 714.20F Cp = 0.7 Btu/lb0F m = 248524 lb/hr Heat gain: Q = m*Cp*T = 248524 (0.7) (714.2 - 656.6) = 10E+06 Btu/hr Hot fluid:
T1 = 757.40F T2 = 7070F Cp = 0.8 Btu/lb0F m = 248524 lb/hr Heat loss: Q = m*Cp*T = 248524 (0.8) (757.4 - 707) 68
Chapter 8
= 10E+06 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Reactor Effluent/Separator liquid exchanger:

E3: Cold fluid (shell side) T1 = 138.20F T2 = 325.40F Cp = 0.798 Btu/lb0F m = 430969.2 lb/hr Heat gain: Q = m*Cp*T = 430969.2 (0.798) (325.4 - 138.2) = 64417480 Btu/hr Hot fluid (tube side, reactor effluent):
T1 = 7160F T2 = 5000F Cp = 0.6 Btu/lb0F m = 497048 lb/hr Heat loss: Q = m*Cp*T 69
Chapter 8
= 497048 (0.6) (716 - 500) = 64417480 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Recycle gas cooler:

E4: Cold fluid: (cooling water, tube side) T 1= 94.10F T 2= 105.80F Cp = 1.0 Btu/lb0F m = 77092.51 lb/hr Heat gain: Q = m*Cp*T = 77092.514 (1.0) (105.8 - 94.1) = 901982.4 Btu/hr Hot fluid ( recycle Hydrogen gas, shell side):
T1 = 1400F T2 = 105.80F Cp = 0.4 Btu/lb0F m = 66079.3 lb/hr Heat loss: 70
Chapter 8
Q = m*Cp*T = 66079.3 (0.4) (140 - 105.8) = 903964.8 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Stripper bottom kerosene product exchanger:

E5: Cold fluid (stripper bottom ,shell side) m = 421057.3lb/hr Cp = 0.576 Btu/lb0F T1 = 3290F T2 = 3470F Heat gain: Q = m*Cp*T = 421057.3(0.576)(347 329) = 4365522 Btu/hr Hot fluid (Kerosene product ,tube side) m = 99118.9 lb/hr Cp = 0.7 T1 = 442.40F T2 = 379.40F Heat loss 71
Chapter 8
Q = m*Cp*T = 99118.9 (0.7)(442.4 349.4) = 4365522 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Stripper bottom Diesel product Exchanger

E6: Cold fluid (Stripper bottom ,shell side) m = 421057.3 lb/hr T1 = 3470F T2 = 386.60F Cp = 0.496 Heat gain Q = m*Cp*T = 421057.3 (0.496)(386.6 347) = 8270238 Btu/hr Hot fluid (Diesel product ,tube side): m = 88105 lb/hr Cp = 0.6 T1 = 5540F T2 = 397.40F 72
Chapter 8
Heat loss Q = m*Cp*T = 88105 (0.6)(554 397.4) = 8278414 Btu/hr Therefore, Heat gain = Heat loss
Equipmen t Design
Fired Heaters:
FH1: T1 = 714.20F T2 = 728.60F Cp = 0.7 Btu/lb0F m = 497048.5 lb/hr Q = m*Cp*T = 497048.5 (0.7) (728.6 -7 14.3) = 5010248 Btu/hr FH-2: T1 = 386.60F T2 = 7070F Cp = 0.6 Btu/lb0F m= 421057.3 lb/hr Q = m*Cp*T = 421057.3 (0.6) (707 - 386.6) 73
Chapter 8
= 80944049 Btu/hr FH-3: T1 = 609.80F T2 = 924.80F Cp = 0.8 Btu/lb0F m = 220616.7 lb/hr Q = m*Cp*T = 220616.7 (0.8) (924.8-609.8) = 55595419 Btu/hr
Equipmen t Design
Catalytic Reactor:
T1 = 728.60F T2 = 757.40F Cp = 0.7 Btu/lb0F m = 497048.5 lb/hr Q = m*Cp*T = 497048.5 (0.7) (757.4 - 728.6) = 10020497 Btu/hr
Product Fractionator:
Inlet Streams: 1: Feed Stream: T1 = 7070F 74
Chapter 8
T2 = 770F Cp = 0.8 Btu/lb0F m = 421057.26 lb/hr Q = m*Cp*T = 421057.26 (0.8) (707 - 77) = 2.12E+08 Btu/hr 2: Overhead Reflux: T1 = 1580F T2 = 770F Cp = 0.5 Btu/lb0F m = 132158.6 lb/hr Q = m*Cp*T = 132158.6 (0.5) (158 - 77) = 5352413 Btu/hr 3: Kerosene Reflux: T1 = 402.80F T2 = 770F Cp = 0.6 Btu/lb0F m = 22026.43 lb/hr Q = m*Cp*T = 22026.43 (0.6) (402.8 - 77) = 4305727 Btu/hr 75
Equipmen t Design
Chapter 8
4: Diesel Reflux: T1 = 588.20F T2 = 770F Cp = 0.7 Btu/lb0F m = 41850.22 lb/hr Q = m*Cp*T = 41850.22 (0.7) (588.2 - 77) = 14975683 Btu/hr 4: Steam: T = 1500C m = 4000 kg/hr = 8810.57 lb/hr at 1500C = 2113.99 kJ/kg
Equipmen t Design
= 909.16 Btu/lbm Q = m = 8810.57 lb/hr *909.16 Btu/lb = 8E+06 Btu/hr Outlet Streams: 1: Overhead: T1 = 201.20F T2 = 770F Cp = 0.6 Btu/lb0F 76
Chapter 8
m = 154185 lb/hr Q = m*Cp*T = 154185 (0.6) (201.2 - 77) = 11489868 Btu/hr 2: Fractionator Bottoms: T1 = 609.80F T2 = 770F Cp = 0.8 Btu/lb0F m = 220616.7 lb/hr Q = m*Cp*T = 220616.7 (0.8) (609.9 - 77) = 94035679 Btu/hr
Equipmen t Design
3: Diesel Draw off: T1 = 600.80F T2 = 770F Cp = 0.75 Btu/lb0F m = 127753.3 lb/hr Q = m*Cp*T = 127753.3 (0.75) (600.8 - 77) = 50187885 Btu/hr 4: Kerosene Draw off: 77
Chapter 8
T1 = 3830F T2 = 770F Cp = 0.6 Btu/lb0F m = 121145.4 lb/hr Q = m*Cp*T = 121145.4 (0.6) (383 - 77) = 22242291 Btu/hr Diesel Stripper: Inlet Stream: 1: Diesel Inlet: T1 = 600.80F T2 = 770F Cp = 0.25 Btu/lb0F
Equipmen t Design
m = 127753.3 lb/hr Q = m*Cp*T = 127753.3 (0.25) (600.8 - 77) = 50187885 Btu/hr 2: Steam: T = 1500C m = 2202.64 lb/hr = 909.16 Btu/lb at 1500F 78
Chapter 8
Q = m =2202.64*909.16 = 2002552.18 Btu/hr Outlet Streams: 1: Diesel Reflux: T1 = 588.20F T2 = 770F Cp = 0.7 Btu/lb0F m = 41850.22 lb/hr Q = m*Cp*T = 41850.22 (0.7) (588.2 - 77) = 14975683 Btu/hr 2: Diesel Product: T1 = 5540F T2 = 770F Cp = 0.7 Btu/lb0F m = 88105.73 lb/hr
Equipmen t Design
Q = m*Cp*T = 88105.73 (0.7) (554 - 77) = 29418502 Btu/hr Rebolier Kerosene Stripper: 79
Chapter 8
Inlet Stream: 1: Kerosene Inlet: T1 = 3830F T2 = 770F Cp = 0.6 Btu/lb0F m = 121145.4 lb/hr Q = m*Cp*T = 121145.4 (0.6) (383 - 77) = 22242291 Btu/hr Outlet Streams: 1: Kerosene Reflux: T1 = 402.80F T2 = 770F Cp = 0.6 Btu/lb0F m = 22026.43 lb/hr Q = m*Cp*T = 22026.43 (0.6) (402.8 - 77) = 4305727 Btu/hr
Equipmen t Design
2: Kerosene Product: T1 = 442.40F T2 = 770F Cp = 0.7 Btu/lb0F 80
Chapter 8
m = 99118.94 lb/hr Q = m*Cp*T = 99118.94 (0.7) (442.4 - 77) = 25352643 Btu/hr
Equipmen t Design
Thermal Section:
Flash Fractionating Column: 1: Feed Stream: T1 = 750.20F T2 = 770F Cp = 0.7 Btu/lb0F m = 286696 lb/hr Q = m*Cp*T = 286696 (0.7) (750.2 - 77) = 1.35E+08 Btu/hr 2: Un-stabilized Naphtha Recycled back:
T1 = 1580F T2 = 770F Cp = 0.6 Btu/lb0F m = 66079.3 lb/hr Q = m*Cp*T = 66079.3 (0.6) (150-77) 81
Chapter 8
= 3211454 Btu/hr 3: Distillate Reflux: T1 = 4640F T2 = 770F Cp = 0.5 Btu/lb0F m = 19823.79 lb/hr Q = m*Cp*T = 19823.79 (0.5) (464 - 77) = 3068722 Btu/hr 4: MP Stream: T = 1500C m = 1000 kg/hr Q = m = 2002552.18 Btu/hr Outlet Stream: 1: Overhead: T1 = 291.20F T2 = 770F Cp = 0.65 Btu/lb0F m = 125903.1 lb/hr Q = m*Cp*T = 125903.1 (0.65) (291.2 - 77) = 17529486 Btu/hr 82
Equipmen t Design
Chapter 8
2: Flash Fractionator Bottom: T1 = 719.60F T2 = 770F Cp = 0.8 Btu/lb0F m = 165198.2 lb/hr Q = m*Cp*T = 165198.2 (0.8) (719.6 - 77) = 84925110 Btu/hr 3: Feed to Distillate Stripper: T1 = 494.60F T2 = 770F Cp = 0.75 Btu/lb0F m = 83700.44 lb/hr Q = m*Cp*T = 83700.44 (0.75) (494.6 - 77) = 26214978 Btu/hr Distillate Stripper: Inlet Stream: Distillate stripper feed rate , Q = 26214978 Btu/hr MP steam = 2202lb/hr, T= 1500C,
Equipmen t Design
MP steam, Q = 2002552.18 Btu/hr
Outlet Stream: 83
Chapter 8
1: Distillate Reflux:
Equipmen t Design
m = 19823.7 lb/hr Q = 3068722 Btu/hr 2: Distillate To Catalytic Reactor Section: m = 66079.3 lb/hr Cp = 0.7 Btu/lb0F T1 = 656.60F T2 = 770F Q = m*Cp*T This implies, Q = 26809692 Btu/hr
84
Chapter 8
Equipmen t Design
85
Chapter 8
Equipmen t Design
CHAPTER 08
Equipment Design
86
Chapter 8
PUMPS
Equipmen t Design
Pumps of all types are used in every phase of petroleum production, transportation, and refining. Production pumps include reciprocating units for mud circulation during drilling and motor driven submersible centrifugal units for lifting crude to the surface. The most common use of centrifugal pumps in production is for water flooding (secondary recovery, subsidence prevention, or pressure maintenance). Transportation pumps include units for gathering, for on and offshore production, for pipelining crude and refined products, for loading and unloading tankers, tank cars, or tank trucks, and for servicing airport fueling terminals. The majority of the units are centrifugal.
Refining units vary from single stage centrifugal units to horizontal and vertical multistage barrel type pumps handling a variety of products over a full range of temperatures and pressures. Centrifugal pumps are also used for auxiliary services, such as cooling towers and cooling water.
Major refinery processes are crude distillation, vacuum tower separation, catalytic :onversion, alkylation, hydrocracking, catalytic reforming, coking, and hydrotreatment or the removal of sulfur and nitrogen. The products resulting from these processes nclude motor gasoline, commercial jet fuel and kerosene, distillate fuel oil, residual fuel II and lubricating oils. The American Petroleum Institute Standard 610, "Centrifugal umps for Petroleum, Heavy Duty Chemical, and Gas Industry Services" (API 610), has stablished specifications for the design features required for centrifugal pumps used )r general refinery service.
hydrocracking unit, centrifugal pumps have been employed. It is the most common ed type in the chemical process industry. It can be constructed in a wide range of corrosion resistance materials. In it, basically the velocity energy is converted into pressure energy.
87
Chapter 8
Pump Design (P1)
According to mechanical energy balance equation; g/gc dZ + VidVi/gc + vdP = W0 + F Neglecting Kinetic term, and re-writing again; g/gc (Z2 Z1) + v(P2 P1) + F = Wo Assume for pump (P1) (Z2 Zi) = 35 ft Sp. Gr. Of liquid being pumped = 0.92 Density of liquid = 57.4 lbm / ft3 Suction pressure = P1 = 4 kgf/cm2 Suction pressure absolute = P1 = 4+1 = 5 kgf/cm2a Discharge pressure = P2 = 103 kgf/cm2 Discharge pressure absolute =P2 = 103+1 =104 kgf/cm2 a Pressure difference = AP = 99 kgf/cm2 a vdP = 3539.8 ft.lbf / Ibm Flow rate of liquid = 212160 kg/hr Mass flow rate of liquid = (212160) / (0.454*3600) = m = 129.8 Ibm/sec
Equipmen t Design
Volumetric flow rate of liquid = (212160)/(0.454*57.4*0.454*3600) = 2.264 ft3/sec
F= 2 * f *(L+Le) * v2
/ D*gc
88
Chapter 8
Assume; f = 0.005 Diam. Of pipe = 6 in. = 0.5 ft Area of pipe = 0.196 ft2 Velocity of liquid in pipe = (2.264/0.196) = 11.52 fps Assume; equivalent length = Le = 30 ft Assume length of pipe = L = 400 ft F= 35.48 ft . lbf / lbm Total work done; = 35 + 3539.8 + 35.48 = 3610.28 ft lbf / lbm
Equipmen t Design
Hp = m*Wo / efficiency
Calculated horsepower = 1420 hp
89
Chapter 8
Equipmen t Design
90
Chapter 8
Catalytic Reactor:
Equipmen t Design
In a large number of industrially important processes, reactions are involved that require the simultaneous contacting of a gas, a liquid and solid particles e.g. hydro-cracking reactions.
The design of a gas-liquid-solid reactor is very much dependent upon the size of the solid particles chosen for the reactions. Particles smaller than about lmm in diameter cannot however be used in the form of a fixed bed , the pressure drop would be too great and the possibility of the interstices between the particles to be blocked too troublesome.
Since the size of the selected catalyst is greater than imm, a fixed bed reactor will be used for the conversion in the hydro-cracking.
Fixed Bed reactor:

Apart from the particles size, the main choice to be made with the fixed bed reactor is the direction of flow, i.e. upwards or downward flow of gas and liquid phases.
The configuration being used in our reactor is liquid and gas in co-current down-flow which is sometimes called a trickle bed reactor, because at low to moderate gas and liquid flows, the gas phase is continuous and the liquid flows as a thin film over the surface of the catalyst. At higher gas flow rates there is more interaction between the liquid and gas flow patterns.
Advantages:
Trickle bed reactors are widely used in the oil refinery because of the reliability of the operation. The flow pattern is close to plug flow and relatively high reaction conversion can be achieved in a single reactor.
91
Chapter 8
Equipmen t Design
Pressure drop with co-current down-flow is smaller and there is no problem of flooding as compared with upward flow.
The particles of the bed are held firmly in place against the bottom support plate as a result of the combined effect of the forces attributable to gravity and fluid drag.
The conversion in the hydro-cracking reactor is Garried out at high temperatures and the reactions are exothermic as well so the temperature rise is controlled by using hydrogen as a quench gas.
Reactor design:
Total fresh feed entering to the top of reactor = 225660 kg/hr Sp. Gr of liquid = 0.92 = 920 kg/m3 Volumetric flow rate = 225660/920 = 245 m3/hr Liquid hourly space velocity (LHSV) = 0.5 to 2.5 hr-1 Assume; LHSV = 0.7 hr-1 Space time = 1/0.7 = 1.428 hr Volume of the reactor = 245 (m3/hr)* 1.428 hr; = 350 m3 Assume; L /D = 9.0 L = 9.0 D; Because, Volume = Area*Length = (0.785 D2* 9.0 D)
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Volume = 7.065 D3 350= 7.065 D3; D = 3.67m Now, length = L= (9.0 * 3.67) = 33m Using four (4) catalyst beds of height 5, 6, 8.75 and 8.75m Spacing between beds = 1.5m So, total height of the reactor = 33m
Equipmen t Design
Because it's a high pressure vessel, operating about 70 kgf/cm2 = 7091 kPa Now, assuming that this vessel has hemispherical head because it has to withstand high pressure, using formula to calculate the thickness of head for hemispherical head type;
t = (Pi*Di) / (4fJ -1.2Pi)

Pi = Design pressure = 5 to 10% of working pressure
Working pressure = 7091 kPa
Design pressure = (7091 * 1.1) = 7800 kPa
Diam. Of the vessel = 3.67m
J= welded joint efficiency factor = 0.85
F= design stress = 500E+03 kPa
t = (7800*3.67) / (4*0.85*500E+03-1.2*780) = 16mm 93
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Including corrosion allowances of 2mm, total thickness of the head material = 18mm For calculation of the thickness of the shell, we used "Pressure Vessel Design Manual" by DENNIS MOSS, Vessel diameter = 145 in
Internal pressure = 1029 PSI
From Figure; The thickness of the shell = 96mm (ref. Dennis Moss)
First two beds of catalytic reactor contain guard catalysts (metallic), where hydrogenation reaction sulfide and halide removal takes place. While the third and fourth catalyst beds contain Zeolites catalysts (Amorphous Silica-alumina), which promote hydro cracking and cracking reactions.
High Pressure Separator:

The separation of liquid droplets is essential from gas and liquid phases. When some carry-over of fine droplets can be tolerated, it s sufficient to rely on gravity in vertical or horizontal separation vessels. For the improved separation of liquid 94
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droplets from the gas stream, vessels are equipped with a full diameter stainless steel mesh blanket. Here, the purpose of the separator is to separate the recycle gas, water and hydrocarbon in the reactor effluent. The mesh blanket helps remove liquid droplets from the recycle gas and help coalesce water droplets out of the hydrocarbon phase. In case of water removal from the mixture, a water boot is also available. The liquid level will also depend on the hold up time required for smooth operation and control, typically 10 minutes is allowed.
Separator Design:
Total input (hydrocarbon + liquid water + recycle hydrogen gas) to separator = 235660 kg/hr = 519074 lb/hr Flow rate of liquid (water+ hydrocarbon) = 205660 kg/hr = 452995.6 lb/hr Liquid density = 57.7 IbM3 (sp.gr. =0.924) Q= 452995.6 / 57.7 = 7850.87 ft3/hr Assume residence time = 10 mins = 0.167 hr
Volume = 7850.87 (ft3 / hr)*0.167 hr; = 1311 ft3 95
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Assume, separator is half filled with liquid, Liquid space = vapor space Total volume of separator = 2*(volume of liquid in separator) = 2*1131 = 2622 ft3 By taking 6% allowance; Volume of separator = Q = 2780 ft3 Assuming, diam. Of separator = 12 ft Including corrosion allowances of 2mm Total diam. Of separator = 14mm Volume of separator = 0.785 D2*L 2780 = 0.785 (12)2*L Length of separator = 25 ft
Equipmen t Design
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Stripper
Stripping is an operation used to remove lights ends from a fraction of product. There are generally two methods used to carry out stripping action, these are Steam stripping Reboiler stripping S2 is the steam stripper. Steam does the same job as reboiler. It is used when high bottom temperatures are undesirable. Steam lowers the partial pressure of the components in the bottoms liquid mixture and thus lowers the boiling point of the bottom liquid. This is a vertical vessel. Feed is introduced towards the top of the column via distributor and stripping steam is injected below the bottom tray. This stripping steam provides the needed lift to remove H2S and light components from the stripper bottoms product.
Stripper Design:
MP steam flow rate = 3000 kg/hr Liquid feed to stripper = 198160 kg/hr Gm = 3000 /18 = 166.67 kgmole/hr Lm = 198160 / 211.8 = 935.59 kgmole/hr Stripper feed molecular weight = 211.8 kg/kgmole The expression for a stripping operation is:
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Where; X2 = mole ratio of solute gas in liquid at top X1= mole ratio of solute gas in liquid at bottom Y1 = mole ratio of impurity in gas (steam) at bottom 1/A = mGm / Lm = Stripping factor N = no. of plates in column Assume, the equilibrium relationship is Ye = 8.0 Xe; Ye = m Xe (straight line equation) 1/A = 8*166.67 / 935.59 = 1.425; So, assume feed oil containing 5 mole% hydrocarbon and we have to reduce the hydrocarbon content to 0.05 mole% by assuming that the oil is non-volatile. X2= 5 mole % = 0.05 = .05 /(1 - 0.05) = 0.052 X1=0.05 mole % = 0.0005 Putting values in equation (1);
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Solving above relationship, a = 43.5; Having, In (43.5) / In (1.425) = N+1 This implies; N = 10 plates Now, maximum allowable superficial vapor velocity (based on cross-sectional area of empty tower) is;
L G
= 800 kg/m3 = 49.92 lb/ft3 = 0.597 kg/m3; from steam table at 1 atm and 100C
Selecting a tray spacing of 12 in. = 0.304 m; From graph, The value of ic = 0.18 (ref. TIMMERHAUS)
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Recycle Gas scrubber (Si)

This is a column uses trays to contact recycle gas and amine. Recycle hydrogen enters in the middle of the scrubbing section and flows up through the sieve trays contacting the amine solution. Assume H2S in inlet gas = 0.03 kmole H2S / kmole of gas;
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Equipmen t Design
The target is to reduce the H2S conc. In the outlet stream to 1% of present value; Assume the equilibrium relationship is; Y = 2X; It is estimated that the rich amine leaves the scrubber with 0.013 kmole H2S / kmole of solvent. Its is also known that the gas phase resistance controls the process. Yi = Mole ratio of H2S in inlet gas stream = 0.03 Y2 = Mole ratio H2S of in
outlet gas stream = 0.0003
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Fired Heaters
Most of the furnaces / fired heaters used in the petroleum refinery are pipe still heaters, which are designed to heat the process fluids in tubes effectively by burning fuels. The function of heater is similar to that of steam generating boiler except that process fluids are heated instead of water. The heat is supplied by 103
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Equipmen t Design
gas or oil burners located in the floor or in walls of the combustion chamber. The process fluid is fed and passed through tubes inside the heater. The feed is heated to the required temperature and fed to the next unit in the process. The purpose of the furnace is to raise the temperature of the process fluid. Box type furnace and cylindrical furnaces are two major types of furnaces. The major furnace parts are Walls, Refractory lining, Tubes, Burners, The air registor etc. When a furnace is operating in a fuel gas only mode of firing, the excess air is usually in the range of 10-20% is used. I think that the efficiency of the fired heater is the most critical factor in saving or making money for the process plant.
Fired Heater (FH1):

Inlet temp. = T= 379C = 714.2F Outlet temp. = T2 = 387C = 728.6F Flow rate = 225660 kg/hr = 497048.5 lb/hr Cp = 0.7 Btu / Ibm.F' Q = m*cp*(T2 T1) = 5010248 Btu/hr Heating value of fuel oil = 19000 Btu/lbm (ref. NELSON) Consumption of fuel oil = (5010248 / 19000) = 264 lb/hr
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105
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SPECIFICATION SHEET
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Equipmen t Design
Distillation column (fractionator)

Column design: Designing of a distillation column constitutes the following steps; Specify the degree of separation required, set product specifications Select operating conditions Select type of contacting assembly Determine stages and reflux requirements Size of column, no. of real stages Design of column internals Mechanical design, vessel and internals
Plate spacing:
The overall height of the column depends on the plate spacing. Plate spacing from 0.15 1 m (6 -36 in.) are normally used. The spacing chosen depends on column diam. And operating conditions. Close spacing is used with small diameter column. For columns above 1m diam., plate spacing of 0.6 m is normally used .A large plate spacing is needed between certain plate to accommodate fed and side streams arrangements. The product fractionators is a vertical column. In operation, feed enters from the product fractionator feed heater to the flash zone of the column which is typically several trays above the bottom of the column. The vaporized lighter material rises up through the column trays and the heavier oil condenses and falls down 107
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Equipmen t Design
the column. Low pressure stripping steam is injected into the column below the bottom tray to provide additional lift for fractionation and aids in the stripping of light material from the bottoms product. The bottoms material is removed out from the bottom of the column for routing to the thermal section of Dieselmax Unit.
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109
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Equipmen t Design
Shell and Tube Heat Exchangers

Equipment for transferring heat is used in essentially all the process industries. Modern heat exchangers range from simple concentric-pipe exchangers to complex surface condensers with thousands of square feet of heating area. Between these two extremes are found the conventional shell-and-tube exchangers, coil heaters, bayonet heaters, extended-surface finned exchangers, plate exchangers, furnaces, and many varieties of other equipment. Exchangers of the shell-and-tube type are used extensively in industry and are often identified by their characteristic design features. For example, U-tube, fin-tube, fixed-tube sheet, and floating-head exchangers are common types of shell-and tube exchangers. When designing heat-transfer equipment, it is necessary to consider the basic process-design variables and also many other factors, such as temperature strains, thickness of tubes and shell, types of baffles, tube pitch, and standard tube lengths. Under ordinary conditions, the mechanical design of an exchanger should meet the requirements of the ASME or API-ASME Safety Codes. The standard length of tubes in a shell-and-tube heat exchanger is 8, 12, or 16 ft, and these standard-length tubes are available in a variety of different diameters and wall thickness. Tube-wall thickness is usually specified by the Birmingham wire gauge, and variations from the nominal thickness may be 10 percent for "average-wall" tubes and + 22 percent for "minimum-wall" tubes. Pressure, temperature, corrosion, and allowances for expanding the individual tubes into the tube sheets must be taken into consideration when the thickness is determined.
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Tube pitch:
Equipmen t Design
The shortest center-to-center distance between adjacent tubes, while the shortest distance between two tubes is designated as the clearance. In most shell-and-tube exchangers, the pitch is in the range of 1.25 to 1.50 times the tube diameter. The clearance should not be less than one-fourth of the tube diameter, and & in. is usually considered to be a minimum clearance. Tubes are commonly laid out on a square pattern or on a triangular pattern. Although a square pitch has the advantage of easier external cleaning, the triangular pitch is sometimes preferred because it permits the use of more tubes in a given shell diameter.
Shell Size:
For shell diameters up to 24 in., nominal pipe sizes apply to the shell. Inside diameters are usually indicated, and schedule number or wall thickness should also be designated. In general, a shell thickness of % in. is used for shell diameters between 12 and 24 in. unless the fluids are extremely corrosive or the operating pressure on the shell side exceeds 300 psig. Thermal Strains: Thermal expansion can occur when materials, such as the metal components of a heat exchanger, are heated. In a shell-and-tube heat exchanger, thermal expansion can cause an elongation of both the tube bundle and the shell as the temperature of the unit is increased. Temperature stresses due to tube elongation can be avoided by using U-shaped tubes. Baffles: Although the presence of baffles in the shell side of a shell-and-tube exchanger increases the pressure drop on the shell side, the advantage of better mixing of the fluid
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Equipmen t Design
and increased turbulence more than offsets the pressure-drop disadvantage. The distance between baffles is known as the Baffle spacing. In general, baffle spacing is not greater than a distance equal to the diameter of the shell or less than one-fifth of the shell diameter.
112
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113
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114
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115
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116
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117
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118
Chapter 9
Instrumentat ion & Control
CHAPTER 9
Plant Instrumentation And Control
119
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INTRODUCTION
No plant can be operated unless it is adequately instrumented. The monitoring of flow, pressure, temperature and level is necessary in almost every process in order that the plant operator can see that all parts of plants are functioning as required. Additionally it may be necessary to record and display many other quantities, which are more specific to the particular process in question, e.g., the composition of process stream, the heat radiation produced or humidity of a gas stream.
Objectives:
The primary objectives of the designer when specifying instrumentation and control scheme are:
Safe Plant Operation:

To keep the process variables within known safe operating limit. To detect dangerous situation as they develop and to provide alarms and automatic shut down systems.
Production Rate:
To achieve the design product output.
Product Quality:
To maintain the product composition within specified quality standards.
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Hardware Elements of Process Control System:
It represents the material together with equipment, with physical and chemical operation that occurs. 1.
The chemical process:
It represents the material equipment together with the physical or chemical operations that occur. 2. The measuring instruments or sensors: Such instruments are used to measure the disturbances, the controlled output variables or to measure secondary variables, and are the main sources of information about what is going on in the process. Characteristic examples are: thermocouples temperature, Venturi meters, for measuring the flow rate, gas chromatographs, for measuring the composition of a stream, etc. Since good measurements are very crucial for good control, the measuring devices should be rugged and reliable for an industrial environment. 3. Transducers or transmitters: Many measurements cannot be used for control until they are converted to physical quantities (like electric voltage or current, or a pneumatic signal, i.e. compressed air or liquid) which can be transmitted easily. The transducers or transmitters are used for that purpose. For example, the Strain Gauges are metallic conductors which change their resistance when subjected to mechanical strain. Thus, they can be used to convert a pressure signal to an electric one. 121 or resistance thermometers, for measuring the
Chapter 9
4. Transmission lines:
They are used to carry the measurement signal from the measuring device to the controller. In the past the transmission lines were pneumatic (compressed air or compressed liquids) but with the advent of the electronic analog controllers and especially the expanding usage of digital computers for control, the transmission lines carry electric signals. Many times the measurement signal coming out from a measuring device is very weak, and it cannot be transmitted over a long distance. In such cases the transmission lines are equipped with amplifiers which raise the level of the signal. For example, the output of a thermocouple is of the order of a few (milli-volts) mV. Before it is transmitted to the controller, it is amplified to the level of a few volts. 5. The controller: This is the hardware element that has "intelligence". It receives the information from the measuring devices and decides what action should be taken. The older controllers were of limited ,"intelligence", could perform very simple operations and implement simple control laws. Today with the increasing usage of digital computers as controllers the available machine intelligence has expanded tremendously, and very complicated control laws can be implemented. 6. The final control element: This is the hardware element that implements in real life the decision taken by the controller. For example, if the controller decides that the flow rate of the outlet stream should be increased (or decreased) in order to keep the liquid level in the tank at, the desired value, it is the valve (on the effluent stream) that will implement this decision, opening (or closing) by the commanded amount.
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The control valve is the most frequently encountered final control element but not the only one. Other typical final control elements for a chemical processes are; Relay switches, providing on-off control variable speed pumps variable speed compressors
Instruments and Controllers:

Locally mounted controllers means that the controller and display is located out on plant near to the sensing instrument location. Main panel controller is in the control room. Except on small plants, most controllers are mounted in the control room. All the instruments of the Dieselmax Unit are main panel mounted.
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Types of instruments:
Property Measured First
Indicating Recording Controlling Indicating Only Only And Controlling FIC LIC PIC RIC TIC WIC
Recording And Controlling FRC LRC PRC PRC TRC WRC
Letter Only
Flow rate Level Pressure Radiation Temperature Weight
F L P R T W
FI LI PI RI TI WI
FR LR PR RP TR WR
FC LC PC RC TC WC
The first letter indicates the property measured; for example, F=flow, Subsequent letters indicate the function; for example, I = Indicating RC= Recording Controlling. The suffixes E and A can be added to indicate emergency action and/or alarm functions. Instruments are provided to monitor the key process variables during Plant operation. They may be incorporated in automatic control loops, or used for the manual monitoring of the process operation. It is desirable that the process variable to be monitored be measured directly; Often, however this is impractical to measure, is monitored in its place. For example , in the control of distillation columns the continuous online, analysis of the overhead product is desirable but difficult and expensive, so temperature is often monitored as an indication of composition. The temperature instrument may from part of a control loop controlling, say, reflux flow, with the composition of overheads checked frequently by sampling and laboratory analysis.
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Level Control:
In any equipment where an interface exists between two phases (e.g. Liquidvapor), some means of maintaining the interface at the Required level must be provided. This may be incorporated in the design of the equipment. Pressure Control: Pressure control will be necessary for most system handling vapors or gas. This method of control will depend on nature of the process. Flow Control: Flow control is usually associated with inventory control in a storage tank or other equipment. There must be a reservoir to take up the changes in flow rate. Distillation Column Control: The primary objective of distillation column control is to maintain the specified composition of the top and bottom products, and any side streams; correcting for the effect of disturbances in,

Feed flow rate, composition and temperature. Steam supply pressure. Cooling water pressure and header temperature. Ambient conditions, which cause change in internal reflux.
125
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Typical control Systems:
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127
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128
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129
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The Use of digital computers in process control:

The rapid technological development of digital computers in the last 10 years, coupled with significant reduction of cost, had a very pro-found effect on how the chemical plants are controlled. The expected future improvements along with the growing sophistication of the control design technique make the digital computer center piece for the development of a control system for chemical processes. Already large chemical plants like petroleum refineries, ethylene plants and many others are under digital control. The effects have been very substantial, leading to better control and reduced operating costs.
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Cost Estimatio n
CHAPTER 10
Cost Estimation
134
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Cost Estimatio n
COST ESTIMATION
In cost analysis of industrial process capital investment costs, manufacturing costs and general expenses including income taxes are taken into consideration.
Fixed Capital Investment

Manufacturing fixed-capital investment represents the capital necessary for the installed process equipment with all auxiliaries that are needed for complete process operation. Expenses for piping, instruments, insulation, foundations, and site preparation are examples of costs included in the manufacturing fixed-capital investment.
Working Capital
The working capital for an industrial plant consists of the total amount of money invested in

Raw materials and supplies carried in stock, Finished products in stock and semi-finished products in the process of being manufactured,
accounts receivable, Cash kept on hand for monthly payment of operating expenses, such as salaries, wages, and raw-material purchases,
Accounts payable, and Taxes payable
Types of Capital Cost Estimates

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Cost Estimatio n
An estimate of the capital investment for a process may vary from a pre-design estimate based on little information except the size of the proposed project to a detailed estimate prepared from complete drawings and specifications. Between these two extremes of capital-investment estimates, there can be numerous other estimates which vary in accuracy depending upon the stage of development of the project. We used here, Study estimate (factored estimate) based on knowledge of major items of equipment; probable accuracy of estimate up to 30 percent.
Methods for estimating capital investment

Various methods can be employed for estimating capital investment. The choice of any one method depends upon the amount of detailed information available and the accuracy desired. There are about seven methods, we used here, Percentage of Delivered Equipment Cost. This method for estimating the fixed or total-capital investment requires determination of the delivered-equipment cost. The other items included in the total direct plant cost are then estimated as percentages of the deliveredequipment cost. The additional components of the capital investment are based on average percentages of the total direct plant cost, total direct and indirect plant costs, or total capital investment. Estimating by percentage of delivered-equipment cost is commonly used for preliminary and study estimates. It yields most accurate results when applied to projects similar in configuration to recently constructed plants.
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Cost Estimatio n
Estimation of purchased equipment cost

The purchased equipment cost of the unit is calculated by using graphs and table given in Plant design and Economics for Chemical Engineers by Peters and Timmerhaus. The base index for these graphs and tables 924 in January 1990 (Marshall and Swift installed equipment index). So to bring the values up to date, we used the cost index for Dec. 2007, i.e. 1362.2. These prices can be used for preliminary design estimates; firm estimates should be based on manufacturers quotations. The formula by which the present cost of the equipment from previous cost can be determined as follows;
Cost indexes is used to give a general estimate, but no index can take into account all factors, such as special technological advancements or local conditions.
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Cost Estimatio n
Purchased Equipment Cost:

Back wash Filters, F1 From Timmerhaus, p-554, 4th ed., Fig. 14-62, Assume, Filter area = 50 ft2, for filter unit, mild steel; The purchased cost = 65000 dollars (Jan. 1990) The present value = 109261 dollars Feed surge drum, D1 From Timmerhaus, p-539, 4th ed., Fig. 14-56, Because feed flow rate = 30000 BPSD; i.e. 1.26E+06 gal/day or 52500 gal/hr Assume 50000 gal/hr, also, for 304 stainless steel storage tank, Purchased cost = 70000 dollars (Jan. 1990) Present value = 117666 dollars Back wash surge drum, D2 Assume, storage tank carbon steel, Assume capacity = 50000 gal/hr The purchased cost = 45000 dollars ( Jan. 1990) Now, the present value = 75643 dollars Centrifugal Pump, P1 From Timmerhaus, p-527, Fig. 14-41; 138
Chapter 10
Cost Estimatio n
Because the volumetric flow rate = 2.264 ft3/sec On x-axis, there should be (gal*PSI) = capacity factor;
= 1470000; For, API-610, Cast steel casing up to 150 PSI, horizontal; Purchased cost = 100000 dollars; (Jan. 1990); The present value = 168095 dollars Centrifugal pump, P2 Capacity factor = 151000; From same graph as used for P1; Purchased cost = 15000 dollars (Jan. 1990)
The present cost = 25214 dollars Centrifugal pump, P3 Capacity factor = 37000; From same graph as used for P1; Purchased cost = 7600 dollars (Jan. 1990) The present cost = 12775 dollars
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Cost Estimatio n
Centrifugal pump, P4
Capacity factor = 34160; From same graph as used for P1;
Purchased cost = 6500 dollars (Jan. 1990) The present cost = 10926 dollars Centrifugal pump, P5 Capacity factor = 51400; From same graph as used for P1; Purchased cost = 9000 dollars (Jan. 1990) The present cost = 15128 dollars
Heat exchangers:
E1 From Timmerhaus, p-616, Fig. 15-13, The purchased cost = 6000 dollars (Jan. 1990) The present value = 10085 dollars From same fig. we found the cost of E2 is same as that for E1. For E3, the purchased cost = 10000 dollars (Jan. 1990) The present value for E3 = 16809 dollars
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Cost Estimatio n
For E4, the purchased cost = 5000 dollars (Jan. 1990) The present value for E4 = 8404 dollars
Compressor Cost, C1 From Timmerhaus, Fig. 14-48; Because centrifugal turbine driven, Assume brake horsepower = 1000 The purchased cost = 400000 dollars (Jan. 1990) The present value = 672380 dollars
Air cooled Exchanger, AE1 From Timmerhaus, Fig. 15-18, p-618; Assume, bare tube surface area = 102 ft2 , for 8 tube rows,
The purchased cost = 15000 dollars (Jan. 1990) The present value = 25214 dollars
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Cost Estimatio n
Air cooled Exchanger, AE2
Assume for 12 tube rows; The purchased cost = 10000 dollars (Jan. 1990) The present value = 16809 dollars
Fired Heaters;
FH 1; From Timmerhaus, p-625, Fig. 15-30; Heat duty for fired heater (FH1) = 6E+06 Btu/hr Assume for Carbon steel tubes, 500 PSI, The purchased cost = 80000 dollars (Jan. 1900) The present value = 134476 dollars FH2; Because its heat duty = 8E+06 Btu/hr The purchased cost = 90000 dollars (Jan. 1990) The present cost = 151285 dollars FH3; Because its heat duty is = 55.59 E+06 Btu/hr The purchased cost = 700000 dollars (Jan. 1990) 142
Chapter 10
Cost Estimatio n
The present worth = 1176666 dollars Reactor, R1; Assume for packed towers; Fig. 16-28; The purchased cost = 100000 dollars (Jan. 1990) The present value = 168095 dollars R2; For 152 in. diameter, and for sieve tray towers; The purchased cost = 349000 dollars (Jan. 1990) The present cost = 586652 dollars R4; Assume diameter = 140 in. And for sieve tray tower; The purchased cost = 196000 dollars (Jan. 1990) The present cost = 329466 dollars Recycle gas scrubber, S1; Because diameter = 8 ft; Height of tower = 23 m For sieve tray tower, 143
Chapter 10
Cost Estimatio n
The purchased cost = 370000 dollars (Jan. 1990) The present cost = 621952 dollars Stripper, S2; Because the diameter of the stripper = 0.942 m = 37 in. For sieve tray towers; The purchased cost = 14700 dollars (Jan. 1990) The present cost = 24710 dollars S4; Because the diameter = 0.602 m = 23.7 in. Height = 1.37 m = 4.49 ft The purchased cost = 4041 dollars (Jan. 1990) The present cost = 6792 dollars Reboiler kerosene stripper, S3; The purchased cost = 6000 dollars (Jan. 1990) The present cost = 15128 dollars K.O. Drums, D3; From Fig. 14-56; Assume 10000 gallons, 304 stainless steel, 144
Chapter 10
Cost Estimatio n
The purchased cost = 30000 dollars (Jan. 1990) The present cost = 50428 dollars
K.O. Drums, D4; From Fig. 14-56; Assume 10000 gallons, 304 stainless steel, The purchased cost = 30000 dollars (Jan. 1990) The present cost = 50428 dollars Separator,T1 Separator cost = 42000 dollars (Jan. 1990) The present value of the separator = 70600 dollars Three receiver; T2, T3, T4 Receiver cost = 84000 dollars (Jan. 1990) The present value = 141200 dollars There are three receivers in our unit. Reaction Chamber, R3 From fig. 14-56, Assume 30 PSIg carbon steel tank, Assume the capacity = 100 gal; The purchased cost = 4000 dollars (Jan. 1990) 145
Chapter 10
Cost Estimatio n
The present cost = 6723 dollars Purchased Equipment Cost Unit Feed surge drum Back wash filter Back wash surge drum Pump, P1 Pump, P2 Pump, P3 Pump, P4 Pump, P5 Exchanger, E1 Exchanger, E2 Exchanger, E3 Exchanger, E4 Exchanger, E5 Exchanger, E6 Centrifugal Compressor, C1 Air cooled exchanger, AC1 Air cooled exchanger, AC2 Fired heater, FH1 Fired heater, FH2 146 2009 Cost in Dollar 109261 117666 75643 168095 25214 12775 10926 15128 10085 16809 16809 8404 6723 7228 672380 25214 16809 134476 151285
Chapter 10
Cost Estimatio n
Fired heater, FH3
1176666
Reactor, R1 Reactor, R2 Reactor, R4 Scrubber, S1 Stripper, S2 Diesel stripper, S4 Kerosene stripper, S3 K.O.Drum, D3 K.O.Drum, D4 Separator, T1 Receivers, T2, T3, T4 Reaction chamber, R3
168095 586652 329466 621952 24710 6792 15128 50428 50428 70600 141200 (each) 6723
147
Chapter 10
Cost Estimatio n
Capital Investment Estimation: (Based on Delivered Equipment Cost) Direct Cost, D Item Percent of delivered Cost Equipment Cost (dollars) 4505100 2162448 810918 2973366 495561 810918 450510 3153570 270306 15632700
Purchased Equipment delivered Cost 100 Purchased equipment installation Instrumentation Control Piping (installed) Electrical (installed) Building (including Services) Yard improvements Service Facilities Land
48 18 66 11 18 10 70 6
Total Direct Plant Cost Indirect Cost, I Engineering Supervision 148 32
1441632
Chapter 10
Cost Estimatio n
40 1802040
Construction Expenses
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Cost Estimatio n
Total direct & indirect Cost = (D+I) = 18876370 dollars
Contraction Fee Contingency
5% 0f (D+I) 10% of (D+I)
943818 1887637
Fixed Capital Investment = 21707830 dollars Working Capital OR = 15% of total Capital investment = 85% of Purchased equipment cost = 3829335 dollars Total Capital Investment = Fixed Capital Investment + Working Capital = 25537165 dollars = 25.5 million dollars
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Chapter 11
Material Selection
CHAPTER 11
Material Selection
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MATERIAL SELECTION
Material Selection
Many factors have to be considered when selecting engineering materials, but for chemical process plant, much consideration is usually given for the ability to resist corrosion. Material selected should be suitable for the process conditions i.e. the material selected must have sufficient strength and be easily worked; it should give lowest cost over the working life of the plant, allowing for maintenance and replacement.
Procedure for selection of materials

1. Preliminary Selection It is done by experience, manufacturers data, relevant literature, availability, safety aspects and preliminary laboratory test. 2. Laboratory Testing It is the re-evaluation of apparently suitable materials under process conditions. In laboratory tests, a study of the effect of excess temperature, excess pressure, agitation, presence of possible impurities other factors are tested. 3. Economic and Final Selection The cost of material to be selected and the maintenance cost effect the final selection of material.
Material Properties
1. 152 Mechanical Properties Strength tensile strength Stiffness Elastic Modulus Toughness Fracture resistance
Chapter 11
Hardness wear resistance Fatigue resistance Creep resistance
Material Selection
2. The effect of high and low temperatures 3. Corrosion resistance 4. Any special properties required; such as, thermal conductivity, electrical resistance magnetic properties 5. Ease of fabrication forming, welding, casting. 6. Availability in standard sizes plate sections, tubes. 7. Cost Effect of Temperature on the Mechanical Properties: The tensile strength and elastic modulus of metals decreases with increasing temperature. For example, the tensile strength of mild steel (low carbon steel, C < 0.25 percent) is 450 N/mm2 at 25C falling to 21 N/mm2 at 500C and the value of Yong's modulus 200,000 N/mm2 at 25C falling to 150,000 N/mm2 at 500C. If equipment is being designed to operate at high temperatures, materials that retain their strength must be selected. The stainless steel is superior in this respect to plain carbon steel. Creep resistance will he important if material is subjected to high stresses at elevated temperatures. Corrosion Resistance: The conditions that cause corrosion can arise in variety of ways. The selection of materials is convenient to classify corrosion into the following categories: 1. General wastage of material - uniform corrosion. 2. Galvanic corrosion - dissimilar metal in contact. 3. Pitting Localized attack. 153
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4. Inter-granular corrosion. 5. Stress corrosion. 6. Erosion - corrosion. 7. Corrosion fatigue. 8. High temperature oxidation. 9. Hydrogen embrittlement.
Material Selection
Metallic corrosion is essentially an electrochemical process. Four components are necessary to set up an electrochemical cell. 1. Anode - the corroding electrode. 2. Cathode - the passive, non-corroding electrode. 3. The conducting medium - the electrolyte - corroding fluid. 4. Completion of the electrical circuit - through the material. Cathodic areas can arise in many ways:

Dissimilar metals. Corrosion products. Inclusion in the metal, such as slag. Less well aerated areas. Areas of differential concentration. Differentially strained area.
Commonly Used Material of Construction: Materials of construction may be divided into the two general classifications of metals and non-metals. Pure metals and alloys are included under the first classification.
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Metals:

Material Selection
Iron and steel Stainless steel Mild Steel Cast Iron Hastelloy Copper and its alloys Copper and its alloys Nickel and its alloys Aluminium Silver Lead (Amphoteric)
Non Metals:

Glass and Glassed steel Carbon and Graphite Stoneware and porcelain Rubber and elastomers Plastics Wood
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Metals: Material Iron and Steel Mild Steel Cast Iron Hastelloy Nickel and its alloys Aluminium -
Material Selection
Properties Easily available Low cost of fabrication Good Tensile strength and ductility Non corrosion resistant Used in non-corrosive atmosphere reactors, vessels Corrosion resistant material Expensive Heat and temperature resistant Available in different types with respect to their micro structure Low carbon steel Most common engineering material Available in large range of standard forms. It can be easily worked and moulded It has good tensile strength and ductility High carbon - iron alloy containing silicon Least expensive of engineering material. Can be readily cast with intricate shapes. It is an alloy of nickel, molybdenum, and chromium. Highly corrosion resistant material. Expensive. Used in valves, piping exchangers, vessels. High corrosion resistance particularly to alkalis. Good mechanical strength and hard as carbon steel. Monel (Nickel alloy) is used in the food indust Light metal. Easy fabrication. i.e.
Stainless Steel
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Material Selection
Silver Lead Non-Metals: Glass and Glassed Steel Carbon and Graphite Stoneware and porcelain Brick and Cement material 157
Resists attack of acid due to surface film of inert hydrated aluminium oxide. Low mechanical strength. High cost. Used in the form of lining. Resistant to alkalis and organic acids. Amphoteric in nature. Low creep. Fatigue resistant. Used as coating.
Borosilicate glass (pyrex) is good resistant to thermal and chemical attack Used in laboratory equipment Glassed steel is strongly resistant to corrosive acid Inert to oxidising conditions. Good heat transfer medium. Threshold oxidation temp is 400C for graphite. Used in pipes pumps heat exchangers, as brick. Used as coating. Poor thermal conductivity. Low tensile strength Brick lined construction is used for corrosive conditions. Cement materials are used with brick. Acid proof refractories can be used up to 900C. Sulphur based cements are limited up to 95C. Resins can be used to about 175C.
Chapter 11
Rubber and Elastomers Plastics -
Material Selection
Used as linings or structural components. Natural rubber is resistant to mineral acids, alkalies and salts. Oxidizing media, oil, benzene and ketones will attack it. These are light in weight and have low friction factor. Good thermal and electrical insulators. Easy to fabricate. Examples are Teflon, polyethene, butadiene, PVC.
About Materials of Construction used: 1. Stainless Steel: There are many different types of stainless steels. These materials are high chromium or high nickel-chromium alloys of iron containing small amounts of other essential constituents. The most common stainless steels, such as type 303 or type 304, contain approximately 18% chromium and 80% nickel, and are designated as 18-8 stainless steels. The addition of molybdenum to the alloy, as in type 316, increases the corrosion resistance and high temperature strength. If nickel is not included, the low temperature brittleness of the material is increased and the ductility and pit type corrosion resistance are reduced. The presence of chromium in the alloy gives resistance to oxidizing agents. Thus, type 430 which contains chromium but no nickel or molybdenum, exhibits excellent corrosion resistance to nitric acid and other oxidizing agents. Although fabricating operation on stainless steels are more difficult than on standard carbon steels, all types of stainless steels can be fabricated 158
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Material Selection
successfully. The properties of the type 430 F, 416, 410, 310, 309, and 303 make these materials particularly well suited for machining or other fabricating operations. In general machine-ability is improved if small quantities of phosphorus, selenium or sulfur is present in the alloy. The type of stainless steel included in the 300 series are harden-able only by cold working; those included in 400 series are either non harden-able or hardenable by heat-treating. As an example, type 410, containing 12% chromium and no nickel, can be heat treated for hardening and has good mechanical properties when heat-treated. Carbon Steel: Carbon steel is the most common cheapest and most versatile metal used in industry. It has excellent ductility permitting many cool-forming operations. It is easy to fabricate and is resistant to corrosion. The low carbon steel has a carbon content of 0.2% and other elements present are manganese 0.5% to 0.8%. Their tensile strength varies from 40000 to 70000 Ib/in2. Medium carbon steel has a carbon content of 0.2 to 0.5%, phosphorus 0.5% maximum. Their tensile strength varies from 65000 to 105000 lb/in. High carbon steel has a carbon content of more than 0.5%. And also contains manganese 0.5 to 1.0%, silicon 0.2% to 0.7% and phosphorus & sulfur 0.05% maximum. Fully annealed high carbons steel exhibit a tensile strength of 95000 to 125000 Ib/in2. A small increase in the carbon content of a steel even as little as a tenth of a 1% has a strong effect on all the properties of steel. If the carbon content is increased there are some of the effects. The melting point of the steel is lowered

The steel becomes harder The steel has a higher tensile strength. The steel is less ductile. The steel becomes more wear resistant.
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Material Selection
The steel becomes less easily machined. The steel is more difficult to weld without cracking. The steel becomes heat treatable. The steel is more expensive due to small volume of production.
The higher carbon steel however will have higher yield stress, higher tensile strength and less elongation at rupture, carbon has a powerful effect on the melting point of steels. A pure iron melts at 1537 oC increasing carbon residues the melting point until at 4.3% carbon the melting point falls at 1129.4 oC, the high melting pint of pure iron makes severe demand on the refractory lining of steel melting furnaces and is one reason why pure iron is not in common use.
Carbon above 0.8% gives increased wear resistant of the steel and is necessary in such tools as files, knives, wood cutting tools and facing welding electrodes. If steel is cooled to room temperature the carbon is found to be combined with iron as iron carbide (Fe3C) distributed through the steel. If a hard or wear resistant steel is required, this is obtained by high carbon content to increase the amount of hard ceramic carbide. Other different materials, which are used in chemical process industry for the construction of different equipments, pipes, burners, storage tanks, reactors, vessels etc. are as under: Iron and steel although many materials have greater corrosion resistance than iron and steel, cost aspects favor the use of iron and steel. They are often used as a material of construction when it is known that some corrosion will occur. Hastelloy (alloy formed by the combination of nickel 56%, chromium 16%, molybdenum 17%, iron 5%, tungsten 4%) is used as a construction of equipment for which the structure strength and good corrosion resistance are necessary under condition of high temperature. 160
Chapter 11
Material Selection
Copper and its alloys they are relatively less expensive, possess fair mechanical strength, and can be fabricated easily into a wide variety of shapes.
Killed Carbon Steel: Mechanical properties of steel are largely dependent upon the amount and form of oxygen & suffer in the steel. In killed steels, with low oxygen content, such as when aluminium is used for deoxidation and grain size control, suffer combines with manganese as highly deformable manganese sulfides. These manganese sulfides have low M.P and as the last liquid to solidify in the steel, collect as films at grain boundaries. During hot rolling, the manganese sulfides are plastically deformed into elongated stringers extending parallel to the rolling direction. This shape and distribution of sulfides can have a marked effect on the directional properties of steel.
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Material Selection
Materials Selected for the Equipment of DIESELMAX Unit:
Sr. No. 1 2
Equipment Feed surge drum Reactor
Material of Construction Carbon steel. 11/4 Cr - 1/2 Mo base metal. The material of construction of all internals is to be austenitic stainless steel. Killed carbon steel. Killed carbon steel trays constructed of austenitic steel. Killed carbon steel. Killed carbon steel Carbon steel. Carbon steel Austenitic stainless steel materials used in the hottest heat exchangers, especially (E1,2) and its associated piping
3 4 5 6 7 8 9
Separator Stripper Receivers Fractionator Kerosene stripper Diesel Stripper Heat exchangers
162
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Environmental Health & Safety Consideration
CHAPTER 13
Environment Health And Safety Considerations
163
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INTRODUCTION
Industrial environment is very hazardous by its nature. Advancement of technology has brought various new hazards. The challenge we have to face in industry is to eliminate hazard, as to know where and what the hazards are, and how to handle them, to help us to meet the challenge Maximum Concentration Name of Material Ammonia Carbon Disulphide Carbon monoxide Chlorine Gasoline Hydrogen chloride Hydrogen sulfide Methanol Chloro Benzene Nitro Benzene Sulphur Dioxide Phosphine Toluene Coal Tar Naphthalene All manufacturing processes are, to some extent hazardous but in chemical processes there are additional hazards associate with chemicals used the process conditions. If healthy hazards are to be controlled, they must be 164 (ppm) otherwise stated 100 10 100 1 500 10 20 200 75 1 5 0.5 100 200
Chapter 12
recognized and evaluated. Other materials such as catalysts, additives, cleaning agents and maintenance materials need to be identified to complete the inventory. Every attempt should be made to corporate facilities for health and safety protection of plant personnel in the original design. This includes but is not limited to, protected walkways, platforms, stairs and work areas. Physical hazards if unavoidable must be clearly defined. All machinery must be guarded with protective devices. In all cases medical services and first-aid must be readily available for all workers. In this project only the particular hazards associated with Dieselmax process will be considered.
The Hazards
Toxicity:
The most common and most significant source of workplace exposure to chemicals and also the most difficult to control is inhalation. Workers become exposed when the contaminant is picked up by the air they breathe. A highly toxic material that causes immediate injury such as phosgene or chlorine would be classified as safety hazard. Whereas a materials, such as vinyl chloride, would be classified as industrial health and hygiene hazards. The most toxic gas produced by the hydro cracking reactions due to presence of sulfur in the VGO feedstock.
Hydrogen Sulfide
H2S is a colorless gas slightly heavier than air (it accumulates in low spots). It is highly flammable and a dangerous five risk. Hydrogen sulfide is an explosive gas which will explode in concentration of 4.3% (3.4% at 150 0C) to 45% by volume in air, H2S is easily identified in very low, non fatal concentrations (0.13 ppm) by the strong
165
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pungent odor of rotten eggs. However, since H2S deadens the sense of smell, its odor cannot be considered as a warning of its presence in lethal concentrations.
Precautions
H2S monitors have been provided to detect H2S leaks in particular areas of moderate to high concentrations. Working in any concentration of H 2S is not desirable. Some other are gases encountered during operation and maintenance. N2 is an inert gas used for purging equipment or maintaining a positive pressure inert gas blanket or a vessel. N2 is neither poisonous nor flammable, but care must be exercised when working inside equipment that has been N2 purged. Adequate ventilation must be provided and appropriate breathing devices worn. Rapid vaporization of liquid nitrogen can cause severe burns on contact with the skin.
Ammonia
Ammonia is a colorless gas with extremely pungent odor, may cause varying degrees of irritation to the eyes, skin or mucous membranes. Ammonia exposure for short term and under 100 ppm has caused nose and throat irritation. Over 500ppm exposure for 30 minutes has caused upper respiratory irritation, tearing, increased pulse rate and blood pressure. High level exposures can cause long term respiratory problems and or death. Where ammonia concentrations exist in concentrations above standard, respiratory, eye and skin protection should be provided.
Safety Demonstration:
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Fire:
A combustible chemical reaction between oxygen and any other element accompanied by the evolution of heat, light and flame is called fire. The element, which takes part in the combustible reaction, is termed as a fuel and the temperature at which this reaction proceeds is known as ignition temperature and it is different for different substances. Hence for a fire to start there are three prerequisites:

fuel oxygen Ignition temperature.
Given below are some characteristics relevant to fire hazards of some combustible material i.e. gases, liquids, and solids. Combustible Material / fuel Methane Hydrogen Acetylene Propane Acetone Diethyl ether Petrol Kerosene oil (Water=1) 0.5 0.8 0.7 0.7-0.8 0.8-0.9 (Air=1) 0.554 0.100 0.90 1.6 2.0 2.6 4.0 -180 -250 -84 -42 -19 -45 <20 40 540 560 305 465 465 170 220 220-300 Relative Density Relative Vapor Flash Point Ignition Temp. Density (0C) (0C)
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Explosion:
A violent and rapid increase in pressure in a confined space, which may occur as a result of physical or chemical reaction. The substance that undergoes a rapid chemical change with the production of gas on being heated or being struck is called explosive. Physical explosion: An explosion that occurs as a result of a physical change i.e. compression or heating is known as physical explosion. Chemical explosion: A chemical explosion is that which occurs as a result of pressure increase caused by the energy released during a chemical reaction. Chemical explosion may also occur as result of release of internal energy during an uncontrolled nuclear reaction. When a piece of metal is put in water, it react violently producing sodium hydroxide and hydrogen. The temperature rises so high that the hydrogen produced bursts into flame and explosive occurs. On next page, there are explosion limits and explosive ranges of some explosive fuels.
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Lower Fuel Explosion Upper
Explosion Explosive Range in Vol. % 61.5 10 70 79 7 10.2 34.3 7 30 16 6.8 5 59
Limit in Vol. % LEL 12.5 5 4 2 2.5 2.6 1.7 1 6 3 1.2 1 1
Limit in Vol. % UEL 74 15 74 81 9.5 12.8 36 8 36 19 8 6 60
Carbon monoxide Methane Hydrogen Acetylene Propane Acetone Diethyl ether Petrol Methanol Ethanol Benzene Xylene Carbon disulphide Safety Helmet: Purpose:
It is used for protection against head injury. Its useful life is affected by heat, cold, chemical and sunlight. Helmet provides limited protection, it reduce the effect of force of falling object.
Safety Shoes:
Purpose: It protects feet from injury.
Oil , acid and alkali resistant. 169
Chapter 12

anti slip PVC sole. The steel toe caps impact resistant up to 200 joules are fitted with rubber protection strips, which eliminate pressure across your toes.
Ear Protection:
Purpose: It is used for the protection against high noise level. It is designed to reduce the effect of high noises found typically in factories and plants. It protects the eardrums by means of a plastic shell insulated with urethane cushioned with a soft vinyl seal. It reduces the noise level up to 30dB in the frequency range from 125-8000 Hz. Ear Plugs: Noise reduction 22 dB. Ear plug should be regularly inspected and always protect the plug from dirt, grease etc. Safety Goggles: Have impact resistant lenses and strong frames to protect from flying particles, encountered like chips, or sparks of high inertial energy at work with machines or during transport.

Lens is also resistant to chemical attack. Lens can absorb 99.9% of UV radiation.
Face Shields:
Give full face protection against sparks, splashes and splatter. They provide secondary protection and must be worn with protective glasses or goggles. 170
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Splash Goggles:
Designed to provide a shield around the entire eye area, to protect against hazard from many directions. Eye Washer Shower: The combined eye and face wash fountain and shower are used for washing eyes, face and body at the same time. Its use make it an essential first aid facility.
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Chapter 1

Background And Introduction

Kuwait Iranian Heavy

33.3 1.8 0.16

8.0 Sulphur, wt% 3.7 Nitrogen,wt% 0.49 Asphaltenes,wt% 11.3 Nickel+Vanadium, 96

33.3 1.2 0.12 10.9 2.8 0.56 16.0 666

20.9 0.94 0.56 5.4 1.6 1.33 12.0 296

Inspection of crude oil and vacuum residua

Introducti on Thermal Cracking History

Dieselmax Process Unit

Catalytic Reactor Section Catalytic Fractionation Section Thermal Section.

Present & Future Outlook

Present And future outlook For petroleum sector In Pakistan

Present & Future Outlook

REFINERY PROCESS FLOW CHART

Chapter 2 Energy Outlook for future

Present & Future Outlook

World Oil Consumption by Sector showing Projected Demand Growth (2003-2030)

Present & Future Outlook

Necessity to Increase Refining Base

Chapter 2 Expanding Refining Capacities Vs

Present & Future Outlook

Petroleum Product Outlook for Pakistan

Present & Future Outlook

Benefits of Expanding Refining Capacities Vs Importing Refined Products

Secured Supply Line Strengthening Countrys Infrastructure Assets & Reserves

Trade Opportunity to export Petroleum products from Pakistan to Asia/Asia Pacific.

Khalifa Coastal Refinery Study

Chapter 2 Future Outlook

Present & Future Outlook

Projected Refining Gap in Pakistan (2006-2020)

Present & Future Outlook

The Way Forward

Pakistan Existing Refining Capacities

Present & Future Outlook

Present & Future Outlook

Things that Need to be Done

Middle Distillate Production:

This can be be lowered somewhat by blending kerosene into diesel. Refinery

1142 1 1381 0.8 2523 0.9

DHODAK Total without Parco Total with Parco

Present & Future Outlook

Hydrocracking And Thermal Cracking Reaction Chemistry

Postulated Paraffin-Cracking Mechanism is shown as.

Postulated Aromatic Dealkylation Mechanism

Thermal cracking process

Capacity And Process Selection

Fluid Catalytic cracking:

Increased lower heating value of the fuel by about 6% 37

Disadvantages Disadvantages of using catalytic cracking of liquid hydrocarbons on-board are:

World Oil Consumption by Sector showing Projected Demand Growth (2003-2030)

Petroleum Product outlook for Pakistan

TAGGING OF PLANT EQUIPTMENTS

Catalyst Reactor Section Catalyst Fractionation Section Thermal Section

Catalyst Reactor Section:

Catalyst fractionation section:

CATALYTIC FRACTIONATING SECTION

Chemical Hydrogen Consumption

Recycle Gas Scrubber

Stripper and Receiver

Chapter 6 Thermal Section

Recycled back to feed to flash fractionator = (0.4*75000) = 30000 kg/hr

T1 = 7160F T2 = 5000F Cp = 0.6 Btu/lb0F m = 497048 lb/hr Heat loss: Q = mCpT 69

Volumetric flow rate of liquid = (212160)/(0.45457.40.454*3600) = 2.264 ft3/sec

t = (78003.67) / (40.85500E+03-1.2780) = 16mm 93