CATALYTIC HYDROCRACKING

INTRODUCTION: Hydrogenation is one of the oldest catalytic processes used in refining Petroleum, only in recent years has catalytic hydrocracking developed to any Great extent in this country. This interest in the use of hydrocracking has been caused by several factors. The demand for petroleum products has shifted to high ratios of gasoline and jet fuel compared with the usages of diesel fuel and home heating oils. By-product hydrogen at low cost and in large amounts has become available from catalytic reforming operations. Environmental concerns limiting sulfur and aromatic compound concentrations in motor Fuels have increased.

The hydrocracking process was commercially developed by I. G. Farben Industries in 1927 for converting lignite into gasoline and was brought to this country by Esso Research and Engineering Company in the early 1930s for use in upgrading petroleum feedstocks and products, but the first modern distillate hydrocracker was put into commercial operation by Chevron in 1958. Improved catalysts have been developed which permit operations at relatively low pressures, and the demand for high-octane unleaded gasolines and kerosenetype jet fuels plus a decrease in demand for distillate fuel oils has promoted the conversion of higher-boiling petroleum materials to gasoline and jet fuels. Product balance is of major importance to any petroleum refiner. There are a number of things that can be done to balance the products made with the demand, but there are relatively few operations that offer the versatility of catalytic hydrocracking. Some of the advantages of hydrocracking are: Better balance of gasoline and distillate production Greater gasoline yield Improved gasoline pool octane quality and sensitivity Production of relatively high amounts of isobutane in the butane fraction Supplementing of fluid catalytic cracking to upgrade heavy cracking stocks, aromatics, cycle oils, and coker oils to gasoline, jet fuels, and light fuel oils

In a modern refinery catalytic cracking and hydrocracking work as a team. The catalytic cracker takes the more easily cracked paraffinic atmospheric and vacuum gas oils as charge stocks, while the hydrocracker uses more aromatic cycle oils and coker distillates as feed. These streams are very refractory and resist catalytic cracking, while the higher pressures and hydrogen atmosphere make them relatively easy to hydrocrack. The new zeolite cracking catalysts help improve the gasoline yields and octane from catalytic crackers as well as reduce the cycle stock and gas make. However, the cycle oil still represents a difficult
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fraction to crack catalytically to extinction. One alternative is to use the cycle stock as a component for fuel oil blending, but this is limited as it is a relatively poor burning stock and burns with a smoky flame. For this reason a limit is placed on the percentage that can be blended into distillate fuel oils. The cycle oils that result from cracking operations with zeolite catalysts tend to be highly aromatic and therefore make satisfactory feedstocks for hydrocracking. Vacuum and coker gas oils are also used as hydrocracker feed. Sometimes diesel boiling range material is included in hydrocracker feed to make jet and motor gasoline products. Both straight-run and FCC LCO can be used and in some cases 100% LCO is used. In cases where 100% LCO is the feed, there is a follow-up with a highpressure hydrotreater to reduce the aromatic content and increase the smoke point to meet specifications. When the feed contains large amounts of LCO, the major effects are increased heat release and lower smoke point of the jet fuel product. In addition to middle distillates and cycle oils used as feed for hydrocracking units, it is also possible to process residual fuel oils and reduced crude by hydrocracking. This usually requires a different technology and for the purposes of our discussion the hydrocracking operation is broken into two general types of processes; those which operate on distilled feed (hydrocracking) and those which process residual materials (hydro processing). These processes are similar and some licensed processes have been adapted to operate on both types of feedstocks. There are major differences, however, between the two processes in regard to the type of catalyst and operating conditions. During the design stages of the hydrocracker the process can be tailored to convert heavy residue into lighter oils or to change straight-run naphthas into liquefied petroleum gases. This is difficult to do after the unit is built as the processing of residual oil requires special consideration with respect to such factors as asphaltenes, ash, and metal contents of the feedstocks.

HYDROCRACKING As the name implies, Hydrocracking is cracking in presence of hydrogen. It is a catalytic process at high temperature and high pressure. The initial development of the process had the limitation of operation at very high pressures (above 200 bar). The development of improved catalyst made it possible to operate the process at considerably lower pressure, about 70-150 bar at temperatures of 350 to 430oC. The main advantages of hydrocracking process are:

its flexibility with respect to production of gasoline and middle distillates, quality of its products ability to handle a wider range of feedstock like cycle oils from other cracking units does not yield any coke as by-product Better conversion of the gas oil and residues into useful products.

Although more expensive than other cracking processes, it is competitive and often advantageous compared to other cracking processes depending on market parameters.
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TYPICAL FEEDSTOCKS AND PRODUCTS FOR HYDROCRACKERS ARE GIVEN IN TABLE 1:

SERIOL NO.

FEED Kerosene Straight-run diesel Atmospheric gas oil Vacuum gas oil FCC LCO FCC HCO Cocker LCGO CockerHCGO

PRODUCTS Naphtha Naphtha and/or jet fuel Naphtha, jet fuel, and/or diesel Naphtha, jet fuel, diesel, lube oil Naphtha Naphtha and/or distillates Naphtha and/or distillates Naphtha and/or distillates

1 2 3 4 5 6 7 8

HYDROCRACKING REACTIONS:

Most hydrocrackers use fixed beds of catalyst with down flow of reactants. The H-Oil process developed by Hydrocarbon Research Corp and Cities Service R & D employs a fluidized bed reactor. The main reactions in hydrocracking are:

cracking, saturation of aromatics And further cracking of it.

The other reactions occurring are:

Saturation of any olefinic material present in feedstock. The reaction of desulphurization, denitrogenation and de-oxygenation.

The latter reactions are essentially treating processes, which are used as a separate processing step when other types of cracking units are used. Thus there are two steps of reactions in Hydrocracking the cracking step and the treating step.

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A combination of catalysts is used. The cracking function is provided by Silica Alumina catalyst or Zeolite catalyst. Zeolite catalyst permits operation at lower temperatures for the same conversion. Tungsten oxide or nickel oxide catalysts promote hydrogenation reaction. Although there are hundreds of simultaneous chemical reactions occurring in hydrocracking, it is the general opinion that the mechanism of hydrocracking is that of catalytic cracking with hydrogenation superimposed. Catalytic cracking is the scission of a carboncarbon single bond, and hydrogenation is the addition of hydrogen to a carboncarbon double bond. An example of the scission of a carboncarbon single bond followed by hydrogenation is the following:

This shows that cracking and hydrogenation are complementary, for cracking provides olefins for hydrogenation, while hydrogenation in turn provides heat for cracking. The cracking reaction is endothermic and the hydrogenation reaction is exothermic. The overall reaction provides an excess of heat because the amount of heat released by the exothermic hydrogenation reactions is much greater than the amount of heat consumed by the endothermic cracking reactions. This surplus of heat causes the reactor temperature to increase and accelerate the reaction rate. This is controlled by injecting cold hydrogen as quench into the reactors to absorb the excess heat of reaction. Another reaction that occurs and illustrates the complementary operation of the hydrogenation and cracking reactions is the initial hydrogenation of a condensed aromatic compound to a cycloparaffin. This allows subsequent cracking to proceed to a greater extent and thus converts a low-value component of catalytic cycle oils to a useful product. Isomerisation is another reaction type that occurs in hydrocracking and accompanies the cracking reaction. The olefinic products formed are rapidly hydrogenated, thus maintaining a high concentration of high octane isoparaffins and preventing the reverse reaction back to straight-chain molecules. An interesting point in connection with the hydrocracking of these compounds is the relatively small amounts of propane and lighter materials that are produced as compared with normal cracking processes. The volumetric yield of liquid products can be

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as high as 125% of the feed because the hydrogenated products have a higher API gravity than the feed.

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THE HYDROCRACKING PROCESS: There are a number of hydrocracking processes available for licensing and some of these are given in Table With the exception of the H-Oil and LC-Fining processes, all hydrocracking and hydro processing processes in use today are fixed-bed catalytic processes with liquid down flow. The hydrocracking process may require either one or two stages, depending upon the process and the feed-stocks used. The process flows of most of the fixed-bed processes are similar and the GOFining process will be described as a typical fixed-bed hydrocracking Process.

Hydrocracking Processes Available for License: TABLE 2: SERIOL NO. 1 2 3 4 5 6 7 Process Isomax Unicracking GOFining Ultra cracking Shell BASF-IFP hydrocracking Unibon Company Chevron and UOP, LLC UOP Exxon Research and Engineering BP Amoco Shell Development Co. Badische Aniline und Soda Fabric, and Institute Francais Petrol UOP, LLC

The GOFining process is a fixed-bed regenerative process employing a molecular-sieve catalyst impregnated with a rare-earth metal. The process employs either single-stage or twostage hydrocracking with typical operating conditions ranging from 660 to 785F and from 1000 to 2000 psig (350420C and 690013,800 kPa). The temperature and pressure vary with the age of the catalyst, the product desired, and the properties of the feedstock. The decision to use a single- or two-stage system depends upon the size of the unit and the product desired. For most feedstocks the use of a single stage will permit the total conversion of the feed material to gasoline and lighter products by recycling the heavier material back to the reactor. The process flow for a two-stage reactor is shown in Figure. If only one stage is used, the process flow is the same as that of the first stage of the two-stage plant except the fractionation tower bottoms is recycled to the reactor feed.

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PROCESS FLOW DIAGRAM:

Fig (1) Two stage hydrocracker

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PROCESS DESCRIPTION:

The fresh feed is mixed with makeup hydrogen and recycles gas (high in hydrogen content) and passed through a heater to the first reactor. If the feed has not been hydrotreated, there is a guard reactor before the first hydrocracking reactor. The guard reactor usually has a modified hydrotreating catalyst such as cobalt-molybdenum on silica-alumina to convert organic sulfur and nitrogen compounds to hydrogen sulphide, ammonia, and hydrocarbons to protect the precious metals catalyst in the following reactors. The hydrocracking reactor(s) is operated at a sufficiently high temperature to convert 40 to 50 vol% of the reactor effluent to material boiling below 400F (205C). The reactor effluent goes through heat exchangers to a high-pressure separator where the hydrogen-rich gases are separated and recycled to the first stage for mixing both makeup hydrogen and fresh feed. The liquid product from the separator is sent to a distillation column where the C4 and lighter gases are taken off overhead, and the light and heavy naphtha, jet fuel, and diesel fuel boiling range streams are removed as liquid side streams. The fractionator bottoms are used as feed to the second-stage reactor system. The unit can be operated to produce all gasoline and lighter products or to maximize jet fuel or diesel fuel products. The bottoms stream from the fractionator is mixed with recycle hydrogen from the second stage and sent through a furnace to the second-stage reactor. Here the temperature is maintained to bring the total conversion of the unconverted oil from the first-stage and second-stage recycle to 50 to 70 vol% per pass. The second-stage product is combined with the first-stage product prior to fractionation. Both the first- and second-stage reactors contain several beds of catalysts. The major reason for having separate beds is to provide locations for injecting cold recycled hydrogen into the reactors for temperature control. In addition, redistribution of the feed and hydrogen between the beds helps to maintain a more uniform utilization of the catalyst. When operating hydrocrackers for total conversion of distillate feeds to gasoline, the butaneand-heavier liquid yields are generally from 120 to 125 vol% of fresh feed. UTILITIES: Utilities consumption also vary typical ranges (per bbl of feed processed) are:

Power: Fuel: Cooling Water (100 C rise):

10 - 18 KWH 80,000 - 120,000 BTU 150 - 250 US gal

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HYDROCRACKING CATALYST: There are a number of hydrocracking catalysts available and the actual composition is tailored to the process, feed material, and the products desired. Most of the hydrocracking catalysts consist of a crystalline mixture of silica-alumina with a small uniformly distributed amount of rare earths contained within the crystalline lattice. The silica-alumina portion of the catalyst provides cracking activity while the rare-earth metals promote hydrogenation. Catalyst activity decreases with use, and reactor temperatures are raised during a run to increase reaction rate and maintain conversion. The catalyst selectivity also changes with age and more gas is made and less naphtha produced as the catalyst temperature is raised to maintain conversion. With typical feedstocks it will take from two to four years for catalyst activity to decrease from the accumulation of coke and other deposits to a level which will require regeneration. Regeneration is accomplished by burning off the catalyst deposits, and catalyst activity is restored to close to its original level. The catalyst can undergo several regenerations before it is necessary to replace it. Almost all hydrocracking catalysts use silica-alumina as the cracking base but the rare-earth metals vary according to the manufacturer. Those in most common use are platinum, palladium, tungsten, and nickel.

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