INSPECTION TRAINING MANUAL DELAYED COKING UNIT709001 XVI-1 XVI. __COKING PROCESS A._Introduction Petroleum coke is a bottom-of-the barrel product from the refining of crude oi1. Production of petroleum coke has had a considerahle Growth in volume in the past decade. In 1959, total feed rate to delayed coking units was approximately 360,000 barrels per stream day producing 10,500 tons per day of coke. In 1965, the corres- Ponding figures were 530,000 BPD and 17,000 tons of coke. Petroleum coking capacity world-wide is currently estimated to exceed 1,100,000 BPD and 62,000 tons of coke per day. Of this, about 85% 15 1m the USA. In earlier years, the economic incentive to the refiner for installation of coking facilities lay mainly in the reduction of heavy fuel oi] yield by upgrading heavy residuals and bottom-of-the- barrel materials into more valuable distillate products. In addition to coking, this end can be achieved through application of other processes such as thermal cracking, visbreaking, deasphalting or vacuum fractionation; however, all but coking produce a heavy, refractory liquid bottoms which requires tankage and cutter stock. In many instances, the economic justification for coking assumed that coke either had zero value or, because it represented a disposal problem, a negative value. In recent years, intensive cultivation of non-fuel markets for coke has made it a petroleum product in its own right. At the present ‘time in the USA, the use of coke for fuel purposes has decreased to less than 15% of total coke production, the largest end use being in the making of carbon anodes required in aluminum manufacture. Other established coke uses are for producing silicon carbide, titanium, calcium carbide, electrodes for arc furnaces in making stainless steels, as a recarburizing agent in iron and steel, and in709001 XVI-2 the cement industry. More recent developments have included the use of nigh purity grapnite for aerospace components and as a moderator in nuclear reactors. Large potential markets are anticipated for converting coke into regenerable activated carbon to be used for purifying air and water. B._ Process Description Coking units may be grouped into three classes: ultimate, partial recycle and delayed coking. The first refers to a relatively high- pressure operation (above 175 psig and up to 1,000°F) with recycling of coker gas oi] to extinction; normally two separate coil heaters are employed. The last refers to a low-pressure operation (about 30 psig) and employs a minimum recycle consistent with coker gas oi] end point requirement. The partial recycle coking operation is intermediate between ultimate and delayed coking. Normally the operating pressure is about 60 psig and maximum recycle is employed consistent with one coil operation. The use of ultimate coking techniques was largely phased out in the 1940’s with the development and rapid commercial application of fluid catalytic cracking, which was capable of yielding a superior product slate. Except for a special application it is not expected that a modern refiner will even consider the ultimate coking process. The main source of coker feedstock is reduced crude from either atmospheric or vacuum distillation. Clarified oils from fluid catalytic operations and thermal cracking tars have assumed a more recent importance as improvements in coke quality are necessitated by more sophisticated market applications.709001 XVI-3 Coking units will normally produce gas, gasoline and distillates in addition to coke product and these products may require treating or additional processing due to the unsaturated nature and/or other contaminants present in the feedstock. Their utilization and treatment are not covered in this discussion, but it should be noted that the a hydrocracking process may be employed to produce addi- tional distillate products and to reduce the sulfur content of the coker feedstock thus resulting in recovery of lower sulfur content coke and co-products. Coking yields and product properties are dependent on teedstock characteristics and source as well as the operating conditions employed. Dy judicious selection of feedstocks and processing conditions, the refiner can produce high quality coke for many sperialty ond ucoc Properties that contribute to a superior coke are low sulfur, ow volatile material, low metals and ash content, low porosity, low coefficient of thermal expansion (CTE) and good conductivity. The latter three properties are measured after calcination of the green coke. ‘A high sulfur content in coke is objectionable for manufacturing of anodes. During the graphitization process, evolution of sulfur from the carbon-sulfur complex can lead to fracturing of the anodes. High metals content of the coke is detrimental to both its elec- trical and mechanical properties. Volatile material, ash content and porosity are related mainly to the mechanical properties of the coke. ‘The Conradson carbon content of the feedstock is the predominant property affecting the yield of coke. The carbon residue from the test 1s a carbonaceous material formed during evaporation and709001 XvI-4 pyrolysis of the residuum feedstock sample and is a direct measure of the coke-forming potential of a given feedstock. As related to coking operations, the most common classification used to describe the constituents of residua are asphaltenes, resins and aromatics. The asphaltene fraction is a non-volatile, high-molecular weight, amorphous substance which exists as highly dispersed colloid in the oil. Asphaltenes are mainly composed of carbon, hydrogen, nitrogen, oxygen, sulfur, vanadium and nickel molecules arranged in complex clusters or layers. The resin fraction of the residua is similar in structure to aephaltonoe. Howover, rocine are viscous, tacky materiale of partial volatility. They are slightly lower in molecular weight than asphaltenes and have more concentrated amounts of nitrogen and sulfur. Compared to resins and asphaltenes, aromatics are simple structures composed of polycyclic six carbon aromatics. In the delayed coking process, the feed is heated to 900 to 950°F over a short time interval. High tube velocity rates are necessary to prevent the deposition of coke in the heater tubes. The thormally-cracked offluent leaving the heater discharges into a coke chamber. Under heat and "delayed" time conditions, coke is thus slowly formed. Two different reaction mechanisms form coke at these time- temperature conditions. In one, the colloidal suspension of the asphaltene and resin compounds is distorted resulting in the precipitation of the compounds to form a highly cross-linked structure of amorphous coke. The compounds are also subjected to ain i i 709001 XVI-5 cleavage of the aliphatic groups. Due to its amorphous nature and high impurities concentration, the coke produced from the recin asphaltene compounds is undesirable for manufacturing high grade carbon anodes. The second reaction mechanism involves the polymerization and con- densation of aromatics, grouping a large number of these compounds to such a degree that coke is eventually formed. The coke produced in this manner contains few cross-linkages and has a more crystal- Tine appearance than the resin-asphaltene type coke. Those petro- Jeum cokes formed from feedstocks containing a high concentration of aromatics and low concentration of impurities, as characterized by thermal tar, decant oi] and residua having low concentrations of resin-asphaltene compounds, possess the crystallographic structure most desirable for carbon and graphite manufacture. A choice of feeds fron among a multitude of stocks usually will be available to the refiner for charging to a coker -- either by mixing charge stocks in varying combinations, changing the selection of crude oils or varying the crude of7 blends. Consequently the feeds will exhibit varying properties resulting in different yields and coke characteristics. Depending on the design limitations of the coker, the refiner, to some extent, also can vary the coke yields and characte stics hy changing the operating conditions. The three general classifications of product coke are sponge, honeycomb and needle. Sponge coke is produced from high resin-asphaltene feedstock. Due to its impurities and low electrical conductivity, sponge coke is not suitable tor manuracturing anodes. In physical appearance, the coke contains small pores separated by thick walls.er i Sn 709001 XVI-6 Honeycomb coke is produced from low resin-asphaltene feeds and upon calcining and graphitization can produce caticfactory quality anodes. The ellipsoidal pores are unifomnly distributed. The pores are unidirectional and when cut across the minor diameter show a honeycomb structure. Needle coke is produced from highly aromatic thermal tar or de- canted oi1 stocks. The graphitized product yields a premium grade anode. In appearance, the unidirectional pores are very slender, elliptical in shape and connected at the major diameter. The coke surrounding Une vulds ty frayile and upon fracturing breaks inty splintery or needle shaped pieces. To improve coke quality, the high resin-asphaltene feedstock can either be blended with large quantities of thermal tar or decanted oi] to yield the more desirable honeycomb coke. However, in a typical refinery, the production of cracked stocks would not be sufficient for this requirement. Consequently, cracked stocks would only be effective in upgrading the total quantity of coke if the basic feedstock did not itself have a high resin-asphaltene content. Intermediate resin-asphaltene stocks which produce the sponge coke at lower operating severities can also yield the honeycomb coke by increasing the recycle rate or operating pressure. Since the resin-asphaltene compounds are completely precipitated from the effluent, even at low operating severities, an increase in severity causes virtually all the additional coke to be formed by the most desirable reaction, through the condensation of aromatics. There- fore, when a feed yields a coke having a quality near the transi- tion region of sponge and honeycomb type coke, a slight increase in recycle or drum pressure can promote the change to produce the better quality, honeycomb type coke. Raising the operating pressure suppresses vaporization of the gas oils in the drum, thus extending709001 XVI-7 the retention time of the aromatic compounds which favors the formation of the more desirable type coke. Increasing the recycle rate lowers the combined feed resin-asphaltene content and in turn also provides a higher concentration of aromatics in the drum. Higher pressures and recycle rates improve the coke quality primarily by lowering the coefficient of themal expansion and electrical resistivity properties of the coke. The economics for increasing the pressure or recycle rate generally depend on the increnental profitability of producing an improved quality coke. For ‘increased pressure, there 1s an additional capital investment cost attributed to the increased pressure rating of equipment. For added recycle, there is an incremental capital investment cost attributed to the additional heater duty rating and increased fuel consumption. However. operating at the higher severity also results in destruction of coker gas of] and additional production of gas (butanes and lighter) and naphtha. To perform a meaningful economic analysis, it is necessary to study the delayed coking unit with respect to the entire refinery operation. Sulfur generally exists in larger amounts in the sponge coke Produced from the high resin-aphallene stuck> Uren in honeycomb coke Produced from the low resin-asphaltene stocks. The asphaltene sulfur atoms are distributed in the interior of the aromatic sheets and also on the surface of the cluster of molecules. As these compounds are precipitated to coke in the coking reactions, few sulfur atoms are fragmented from the surface and all the interior atoms are retained in the coke. Thus, for two equal sulfur bearing stocks, the sulfur content in coke increases with the concentration ot asphaltenes and Conradson carbon content of the feed.700001 XVI-8 The coke chamber temperature effect is governed by the degree of heavy oils vaporized off the coke. The heavy oils, as measured by the volatile carbon matter test, contain lesser amounts of sulfur ‘than the coke mass. Consequently, an increase in the drum temper- ature vaporizes the lower sulfur bearing ofls from the coke, leaving a more concentrated sulfur bearing residue. Besides sulfur and ash (metals) contents, organic volatile matter is another coke property which influences the price of green coke to the electrode manufacturing industry. This material consists of very heavy hydrocarbons deposited in the coke matrix. During the coke calcining step, these heavy hydrocarbons are almost completely volatilized resulting in a dense calcined coke product with fixed carbon exceeding 98 percent thus making it very suitable for finishing into graphite electrodes (current conductor) and graphite anodes (e.g., when graphite is part of an electro-chemical cell like in the electrolysis of brine, or is providing a source of electrons at a surface as in cells, batteries, vacuum tubes). Drum temperature is the primary variable affecting the volatile carbon matter content in the coke. Increasing the drum temperature enhances the vaporization of heavy hydrocarbons, in turn reducing the volatile carbon matter. Consequently, as the volatile matter i removed from the coke. a harder coke is produced. The ease of handling and removing the coke from the drum or the grindability characteristics required in preparing the coke for calcining would dictate the maximum coke drum temperature at which the unit would operate. ‘B._Process Flow Generally speaking, a coking unit will consist of the following three sections:709001 XVI-9 1, Goke Chamber Section -- Contains the coker heater, and coke chambers where the coke is formed and recovered. 2. Fractionation Section -- Distillate products formed in the coking reaction are recovered. The fractionator may contain several product side draws dependent on the desired product split. 3. as Jon -- Co-product light gases and stabt- lized gasoline range material are recovered in this section of the unit Coker charge is fed to the lower section of the fractionator where material lighter than the desired end point of the heavy gas iT is flashed off. The remainder combines with recycle and is pumped from the botton of the fractionator to the coking heater where it is heated to about 900°F. This scheme is true for both delayed coking and single-coil partial recycling coking. The design of the coking heater must be done carefully to prevent premature coking in the heater tubes which limits the Tength of the run. ‘The liquid vapor mixtura leaving the coking heater passes to a cake chamber. A unit usually has two coke chambers, one being filled while the other is being decoked. Large units may have more than ‘two chambers. These chambers are most often sized so that each chamber operates on a 48-hour cycle. This arrangement permits decoking of one drum to be scheduled at the same time each day on a 24-hour coking-24-hour decoking cycle. Under time-temperature conditions in the chamber, coke is formed and allowed lv accumulate in the vessel. The overhead vapors pass into the lower section of the fractionating tower for separation inte gas, gasoline, gas oils and recycle stock. Gas oils are yielded as sidecut products from the fractionator. The recycle709001 XVI-10 stock is either slumped into the fractionator bottoms for charging te the heater in the case af a single coil design or taken as a separate fractionator cut and charged through a separate coil to the heater in a two coil coker unit design. Fractionator overhead vapors are condensed and flow to an overhead receiver, Both the unstabilized gasoline and the uncondensed Tight co-products are directed to the gas concentration section. Although variations are possible dependent on customer require- ments, the gaz con section ic nomnally designed to recover separately a light gas stream which is usually sent to fuel, and olefin-rich C3/C4 product which can be directed to polymerization or alkylation operations, and a stabilized gasoline for direct blending into gasoline pool or for further processing as required. Essentially the same process flow (see schematic flow diagram) is used in the case of the ultimate coking process unit with the following “exceptions”. 1. Use of two-coil scheme for more efficient conversion required for recycling gas oils to extinction 2. Addition of a reaction chamber to provide the necessary coking ‘time-temperature relationship. Since gas oil is recycled to extinction, this is essentially the maximum coke process. Only products are coke and 400°F minus material. The 400°F minus products are considerably more than that produced in the delayed and partial recycle coking process and consequently will require a correspondingly larger gas concen- tration unit.709001 Wi Vere the refiner has @ central gas concentration such as that used for thermal or catalytt¢ cracking unita, {t 4¢ ueual to include the coker light products recovery in its duty.NOTIOAS WAGNVID TaHOS709001 XVI-14 B.__ Process Variables 1, Crude Sources and Type of Charge Stock A coking unit can be operated either to produce high quality coke or to maximize the yield of gas, gasoline, and distillate products. As discussed in the process description, the crude source and type of charge stock have a major effect on the coke yield and quality. The Conradson carbon content of the feedstock is the predominant property determining the yield of coke: the higher the con carbon content of the feed, the higher the coke yield. The nature of the feedstock, that is its relative proportions of asphaltenes, resins, and aromatics and ite impurities levels, affect the quality of the coke. 2. Coke Chamber Temperature The coke chamber temperature, adjusted by varying the coking heater transfer temperature, has an important effect on both the yield and quality of coke. Heater transfer temperatures should be maintained between 485°C and 510°C. At lower temperatures a tarry coke is produced, at higher temperatures the rate of coke fomnation in the heater is greatly increased. Within the temperature range discussed for a given feedstock, an increase in temperature will decrease the yield of coke and gas plus gasoline. ‘An increase in temperature generally results in an improvement in coke quality. Increasing the drum temperature increases the vaporization of heavy hydrocarbon, thus reducing the coke volatile carbon matter content. As the volatile matter is removed, a harder coke is produced. The material vaporized, however, contains less metals and sulfur than the bulk of the coke, so as these materials700001 XVI-15 are removed, the impurities level of the coke tends to increase. Harder coke makes coke removal more difficult. The eace of handling and the grindability characteristics which affect the preparation of the green coke for calcining will determine the maximum coke drum temperature at which the unit can operate. 3. sure The thermal cracking reactions upon which the process 1s based are « function of time and temperature. The effect of the two variables 18 related. The urum pressure which determines the degree of vapor- ization and, hence, the velocity through the heater and coke chamber ean be ucad to vary the residence time. The effect of increased residence time is that the yield of coke is increased. The pressure is controlled by the fractionator overhead receiver pressure con- troller. uring normal operation, the pressure is maintained constant and the temperature is varied to adjust coke yield. 4. Combined Feed Ratio ‘The combined feed ratio is the volume of fractionator bottoms (fresh feed plus recycle) divided by the volume of fresh feed As the com- bined feed ratio is decreased, the heavy gas oi] product rate increases at the expense of all other products. The coke produced will be softer and have a higher VCM and impurities Jevel. ‘The combined feed ratio can be varied by altering the gas oi] draw rate. An increase in the gas oil draw will decrease the ratio.ruguur XVI-16 )KE_CHAMBER OPERATION 1. Gycle Schedule In the case were a unit 1s designed to operate on a 48 hour cycle, each chamber will be staggered by 12 hours. (See Figure XI-1). For example, one chamber will start filling, one chamber will have been filled for 12 hours, one chamber will start decoking, and the last chamber will have been decoked for 12 hours. A typical cycle schedule for one chamber is as follows: Coking 24.0 hours Initial Steamout to Fractionator 1A Steamout to Dlowdown Ls Water Quench to Blowdown 6.0 Water Filling Lo Block in Drum, Vent, Drain, and Unhead 2.0 Decoke Drum, maximum as Head Up 10 Air Purge and Steam Pressure Test 1.0 Warn Up, minimum 5.0 Switching and Line Out 19 48.0 During the operation of the plant, delays will often occur requiring changes in the planned schodula The enking period of 24 hours. however, should not be varied; major problems can occur if the drum is allowed to fill completely or if the foam layer runs over into the fractionator. If possible the decoking steps should be performed as quickly as possible in order to allow excess time for inspection and warm up.INSPECTION OF COKING UNITS Inspection of the coking unit will fall along guidelines established for the crude unit. As with any other unit, care should be taken when checking Piping thicknesses and inspecting vessels, heaters and exchangers during turnaround after equipment has been thoroughly cleaned for the inspector. Of particular interest will be the coker heater, coke drums, fractionator and associated transfer piping. The coking unit is a "bottoms" stream processing section and as a result could see large quantities of sulfur and nitrogen compounds, olefins and heavy metal contaminants depending on quality of the crude unit feedstock. Also, the coking unit could receive recycled streams or "slop* returns which could contain any variety of rerining adaitives or undesirable contaminants. The coker heater tubes will generally consist of 9% Cr. tubes and are susceptible to coking, over- heating and corrosion. Transfer piping, depending on temperature and sulfur levels could be 5% Cr. material but still should be checked for thinning Coke drums might be 1-1/4 Cr. with 405 or 410S- type clad. The drums experience thermal stresses and shocks and as a result can have problems such as bulging of the vessel walls as well as cracking of weld areas. The fractionator will probably be a killed carbon steel vessel with 405 or 410S-type Cladding in the Tower section. Inspection will involve checking the internals closely as well as the clad lining and unlined areas of the vessel wall. ‘The remaining fractionator section should be inspected per standard procedures. The gas concen- tration section could be susceptible to hydrogen blistering among other things, just as are most gas concentration units of a refinery. A typical gas concentration unit is covered in another chapter of this book.