Hydrocracking is a catalytic refining process that upgrades petroleum feedstocks using hydrogen. It removes impurities and cracks molecules to a desired boiling range, typically producing distillate products like diesel rather than gasoline. Hydrocracking units operate at specific conditions depending on the feed and desired products. The process involves hydrogenation, cracking, and isomerization reactions. It consumes hydrogen to saturate and crack carbon bonds, convert heteroatoms, and suppress condensation reactions. Hydrocracking became commercially important in the 1950s with the availability of by-hydrogen from catalytic reforming.
Hydrocracking is a catalytic refining process that upgrades petroleum feedstocks using hydrogen. It removes impurities and cracks molecules to a desired boiling range, typically producing distillate products like diesel rather than gasoline. Hydrocracking units operate at specific conditions depending on the feed and desired products. The process involves hydrogenation, cracking, and isomerization reactions. It consumes hydrogen to saturate and crack carbon bonds, convert heteroatoms, and suppress condensation reactions. Hydrocracking became commercially important in the 1950s with the availability of by-hydrogen from catalytic reforming.
Hydrocracking is a catalytic refining process that upgrades petroleum feedstocks using hydrogen. It removes impurities and cracks molecules to a desired boiling range, typically producing distillate products like diesel rather than gasoline. Hydrocracking units operate at specific conditions depending on the feed and desired products. The process involves hydrogenation, cracking, and isomerization reactions. It consumes hydrogen to saturate and crack carbon bonds, convert heteroatoms, and suppress condensation reactions. Hydrocracking became commercially important in the 1950s with the availability of by-hydrogen from catalytic reforming.
Hydrocracking is a catalytic refining process that upgrades petroleum feedstocks using hydrogen. It removes impurities and cracks molecules to a desired boiling range, typically producing distillate products like diesel rather than gasoline. Hydrocracking units operate at specific conditions depending on the feed and desired products. The process involves hydrogenation, cracking, and isomerization reactions. It consumes hydrogen to saturate and crack carbon bonds, convert heteroatoms, and suppress condensation reactions. Hydrocracking became commercially important in the 1950s with the availability of by-hydrogen from catalytic reforming.
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HYDROCRACKING
CHAPTER 02 Hydro-cracking Processes
Hydro-Cracking processes
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HYDROCRACKING
CHAPTER
02 Hydro-cracking Processes
Recent Advances in Hydro-cracking:
Hydrocracking is a versatile catalytic refining process that upgrades petroleum feedstocks by adding hydrogen, removing impurities and cracking to a desired boiling range. Hydrocracking requires the conversion of a variety of types of molecules and is characterized by the fact that the products are of significantly lower molecular weight than the feed. Hydrocracking feeds can range from heavy vacuum gas oils and coker gas oils to atmospheric gas oils. Products usually range from heavy diesel to light naphtha. Hydrocrackers are designed for and run at a variety of conditions depending on many factors such as type of feed, desired cycle length, expected product slate but in general they will operate at the following range of conditions: LHSV - 0.5-2.0 hr-1, H2 circulation - 5,000-10,000 SCFB (850-1,700 NM3/M3), H2PP 1,500- 2,000 Pisa (103-138 bars) and SOR temperatures ranging between 675 and 725 F (357-385 C). Hydrocracking is particularly well suited to generating products that meet or exceed all of the present tough environmental regulations.
Brief History: The large scale industrial development of hydrogenation in Europe, Particularly in Germany, was due entirely to military considerations. Germany used hydrogenation extensively during World War II to produce Gasoline: 3.5 million tons were produced in 1944.The emergent availability of Middle Eastern crude after World War II removed the incentive to convert coal to liquid fuels, so continuing the development of hydro cracking technology became less important. Even though hydrogenation has been of interest to the petroleum industry for many years, little commercial use of hydrogen-consuming processes has been made because of the lack of low-cost hydrogen. That changed in the early 1950s with the advent of Hydro-Cracking processes
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catalytic reforming, which made available byproduct hydrogen. That brought up an
extensive and increased interest in processes that will utilize this hydrogen to upgrade petroleum stocks. Another factor was that in the mid-1950 the automobile industry started manufacturing high performance cars with high-compression ratio engines, which required high-octane gasoline. Thus catalytic cracking expanded rapidly and generated, in addition to gasoline, large quantities of refractory cycle stock that was difficult to convert to gasoline and lighter products. This need to convert refractory stock to gasoline was filled by hydro cracking. Furthermore, the switch of railroads from steam to diesel engines after World War II and the introduction of commercial jet aircraft in the late 1950s increased the demand for diesel fuel and jet fuel. The flexibility of the newly developed hydro cracking processes made possible the production of such fuels from heavier feed stocks.
Flow Schemes: Various licensors have slightly different names for their hydrocracking units flow schemes, but in general, they can be grouped into major two categories: single stage and two stages. Table below shows the general evolution of flows schemes, generally driven by improvements in catalysts.
Single Stage Once-Through Hydrocracking:
Figure below shows a schematic of a single stage, once through hydrocracking unit, which is the simplest configuration for a hydrocracker. It is a variation of the single stage hydrocracking with recycle configuration . The feed mixes with hydrogen and goes to the reactor. The effluent goes to fractionation, with the unconverted material being taken out of the unit as unconverted material. This type of unit is the lowest cost hydrocracking unit, can process heavy, high boiling feed stocks and produces high value unconverted material which becomes feed stock for FCC units, ethylene plants or lube oil units. In general, the conversion of the feed stock to products is 60-70 vol%, but can range as high as 90 vol%.
Hydro-Cracking processes
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Single Stage with Recycle Hydrocracking:
The most widely found hydrocracking unit is the single stage with recycle in which the unconverted feed is sent back to the reactor section for further conversion. Figure below depicts this type unit. It is the most cost-effective design for 100% (or near 100%) conversion and is especially used to maximize diesel product.
Two Stage Recycle Hydrocracking
The two stage hydrocracking process configuration is also widely used, especially for large throughput units. In two stage units, the hydrotreating and some cracking takes place in the first stage. The effluent from the first stage is separated and fractionated, with
Hydro-Cracking processes
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the unconverted oil going to the second stage. The unconverted oil from the second stage reaction section goes back hydrocracker is shown in Figure 4. The catalysts in the first stage are the same types as those used in the single stage configuration. The catalyst in the second stage is operating in near absence of ammonia, and depending on the particular design, in the absence or presence of hydrogen sulfide. The near absence of NH3 and H2S allows the use of either noble metal or base metal sulfide hydrocracking catalysts.
Separate Hydrotreat Two Stage Hydrocracking
A variation of the typical two stage hydrocracking with common hydrogen circulation loop is the separate hydrotreat hydrocracking shown in Figure in which each stage has a separate hydrogen circulation loop, allowing for operation of the second stage in the near absence of hydrogen sulfide (and ammonia).
Hydro-Cracking processes
HYDROCRACKING
Characteristics of Petroleum Products
Hydrocracking
Purpose: process gas oil to break carbon-carbon bonds of large
carbon bonds of large aromatic compounds & remove contaminants. Hydrogenation (addition of hydrogen) Cracking (carbon-carbon scission) of aromatic bonds
Typically creates distillate range products, not gasoline range products.
Typical feeds Cat cracker cycle oil i) Highly aromatic with sulfur, small ring & polynuclear aromatics, catalyst fines; usually has high viscosity ii) Hydrocracked to form high yields of jet fuel, kerosene, diesel, & heating oil Gas oils from visbreaker (a) Aromatic Gas oil from the delayed coker a) Aromatic, olefinic, with sulfur b) Usually more economical to route atmospheric & vacuum gas oils to the c) cat cracker to produce primarily gasoline & some diesel
Gas Oil Hydrocracker Feed
Hydrocracking does a better job of processing aromatic rings without
coking than catalytic cracking. o Hydrogen used to hydrogenate polynuclear aromatics (PNAs) o Reduces frequency of aromatic condensation Hydrocracking not as attractive as delayed coking for resids high in resins, asphaltenes & heteroatom compounds o Heteroatoms & metals prevalent in resins & asphaltenes poison hydroprocessing catalysts o High concentrations of resins & asphaltenes will still ultimately coke Feeds limited to a Conradson Carbon Number (CCR) of 8 wt% Feeds require high pressures & large amounts of hydrogen
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Gas Oil Hydrocracker Products
Hydrocracking primarily to make distillates.
o In US hydrocracking normally a specialized operation used to optimize catalytic cracker operation o In US cat cracking preferred to make gasoline from heavier fractions Hydrocracking capacity is only about 8% of the crude distillation Capacity o Not all refineries have hydrocrackers Intent is to minimize the production of heavy fuel oil o Light ends are approximately 5% of the feed. o Middle distillates (kerosene, jet fuel, diesel, heating oil) still contain uncracked polynuclear aromatics All liquid fractions are low in sulfur & olefins
Hydrocracking Chemistry Cracking reactions Saturated paraffins cracked to form lower molecular weight olefins & paraffins Side chains cracked off small ring aromatics (SRA) & cycloparaffins (naphthenes) Side chains cracked off resins & asphaltenes leaving thermally stable polynuclear aromatics (PNAs) But condensation (dehydrogenation) also occurs if not limited by Hydrogenation
Hydro-Cracking processes
Hydrogenation Reactions
Isomerization Reactions
Condensation Reactions
Exothermic giving off heat
Hydrogen inserted to saturate newly formed molecule from aromatic cracking Olefins are saturated to form light hydrocarbons, especially butane Aromatic rings hydrogenated to cycloparaffins (naphthenes) Carbon-carbon bonds cleaved to open aromatic & cycloparaffins (naphthenes) rings Heteroatoms form hydrogen sulfide, ammonia, water, hydrogen chloride
Isomerization provides branching of alkyl groups of paraffins and opening of naphthenic rings
Suppressed by hydrogen
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Hydrogen Consumption
Carbon bonds with heteroatom broken & saturated
o Creates light ends Heavier distillates make more light ends from breaking more compl ex molecules o Sulfur converted to hydrogen sulfide o Nitrogen converted to ammonia o Oxygen converted to water o Organic chlorides converted to hydrogen chloride Saturation of carbon-carbon bonds o Olefins saturated to form light hydrocarbons. Consumption stoichiometric one hydrogen molecule added for each double bond o Aromatic rings hydrogenated to cycloparaffins (naphthenes). Severe operation hydrogen consumption strong function of complexity of the aromatics Isomerization reactions generally not present Metals deposited directly on the catalysts o Excess metals reduce catalyst activity & promote dehydrogenation (produces coke & hydrogen) Have cracking of carbon-carbon bonds o Severe operation hydrogen consumption strong function of complexity of the aromatics Hydrogen lost in mixture with products o Equilibrium with light gases Significant may double amount required for sulfur removal o Absorbed in liquid products Usually small compared to hydrogen used for sulfur removal o Lost with purge gas
Status of Macro and Micro Nutrients in Selected Soils of Moshi Rural District, Kilimanjaro Tanzania: Case Study of Mboni, Kyou and Makami Chini Villages.
Status of Macro and Micro Nutrients in Selected Soils of Moshi Rural District, Kilimanjaro Tanzania: Case Study of Mboni, Kyou and Makami Chini Villages.
