CHM 3602 Petroleum Refining Process Hydrocracking High pressure hydrogenation of petroleum fractions with the object of the

production of saturated lower boiling material Interest : Demand for high ratios of gasoline (compared to the usages of middle distillates) Byproduct hydrogen at low cost (large amount) Advantages of Hydrocracking 1. better balance of gasoline and distillate production 2. greater gasoline yielImproved gasoline pool octane quality & sensitivity 3. high amounts of isobutane in the butane fraction 4. supplements - upgrade cracking stocks, jet fuels, light fuels oils, aromatics etc Hydrocracking reactions Catalytic cracking scission of a C-C single bond and hydrogenation is the addition of H2 to a C=C double bond Cracking - olefins , Hydrogenation - heat Heat exothermic (xs) T = 300-400C, P = 1,200 2,000 psig H2 (xs) prevent cat. fouling & permit long run Feed preparation Hydrocracking catalyst poisoning by metallic salts, O, organic N, and S in feedstocks Hydrotreated to saturate the olefins and remove O, N, S - to reduce water content (steam) - agglomerate - water removal by passing through silica gel or sieve N & S conversion to NH3 & H2S H2S (low conc.) inhibit the saturation of aromatic rings Hydrotreater high heat release - olefin saturation & aromatic ring saturation

process of hydrocracking in refining process based on Unicracking Process/fixed bed catalytic system Single or two stages system: - dependent upon the size of the unit & product desired - contain several bed of catalysts a.provide locations for injecting cold recycled H2 into reactors for T control. b.uniform utilisation of the catalyst single stage total conversion of the feed material to gasoline and lighter products by recycling the heavier material back to reactor

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CHM 3602 Petroleum Refining Process two stages Fresh feed is mixed with makeup H2 and recycle gas and passed through a heater to the first reactor. Liquid products is sent to a distillation column (gasoline and lighter products taken overhead) Bottoms from distillation are sent to a second stage (total conversion of unconverted oil, T is maintained)

Hydrocracking Catalysts Crystalline of silica-alumina with rare-earth metals (Ni, W, Pt or Pd) A dual functions High cracking (silica-alumina) and high P hydrogenation (metal) activities Catalyst activity decrease with time / age T is raised to maintain the conversion Regeneration : 2-4 years, accumulation of coke and other deposits Burning off the catalyst deposits Activity could be restored Acid function HF treated Montmorillonite clay, alumina, silica alumina and zeolite being used to support the hydrogenation Very sensitive to nitrogen compounds Catalyst contains Pt or Pd on a zeolite base (less sensitive to N2, 40 ppm N2) Operation conditions Pressure Space velocity Hydrogen recycle Temperature

65 130 atm 0.1 1.0 v/v/hr 8 000 15 000 SCF/B 340 420 C

Obtain a high degree of cracking and hydrogenation Result : Very high hydrogen absorption in the process 2 000 SCF/B Problems In processing high S and N feedstocks: Appearance of H2S and NH3 Can be removed from the recycle gas by Injection of water, dissolve much of the H2S and NH3 under the high pressure conditions applied. Design of the Reactors High severity of the conditions, P, PA (H2,H2S and NH3 ) and T (highly exothermic) To maintain temp, dividing the catalyst into beds Heats can be removed by 2 Dr Basyar Rahman

CHM 3602 Petroleum Refining Process 1. Injection of cold recycle gas (increasing the vapourisation) 2. Injection of cold recycle liquid (difficulties in distribution) 3. Interbed exchangers (mechanical design problems) Moving-Bed Hydrocracking Processes H-Oil (Cities Service R & D) - process residium or other heavy feed charge - use hydrogenating catalyst HY-C (Hydrocarbon Research, Inc.) - takes feeds having end points up to 500C- use dual function catalyst Preheated feed, recycle, and makeup hydrogen are charged to the first reactor. Effluent is sent to the second reactor for additional conversion. The product passes through heat exchange to a high-P separator (gas removal). The liquid stream then goes to separation column into products.

Process Variables Measured by the degree of conversion of the feed to lighter products Conversion : Volume percent of the feed which disappears to form products boiling below the desired product end point Temperature : Primary conversion control 10C increase almost double the reaction rate Have been converted & loss of catalyst activity Pressure : Primary effect PA of H2 and NH3 Conversion increases - PA H2 Conversion decreases - PA NH3 Total pressure - increases - PA H2 Space velocity : Ratio of liquid flow rate in barrels per hour to catalyst volume in barrels Varies with feed rate Feed increases catalyst contact time will decreased and conversion is lowered How? By increasing the T, when feed is increased H2S concentration : Low T : catalyst for aromatic saturation 3 Dr Basyar Rahman

CHM 3602 Petroleum Refining Process Conserves H2 and produces a product with a higher octane number

Steam reforming The general equation for the reaction is

20-30% of carbon oxides appeared from steam reforming furnace (product) Must be removed if high purity of H2 is required CO is converted into CO2 Ni catalyst, nickel oxide of 25-30% wt Incorporation with an alkaline promoter in the base prevents deposition of carbon on the catalyst Made in form of cylinders or Raschig rings 12-18 mm diameter Very sensitive to S poisoning , desulphurised to < 2 ppm e.g. Naphtas (0.1% wt S) desulphurisation by treatment H2 over Co-Mo LPG (< 0.05% wt S) passing over ZnO cat at 400C or ZnO / Co-Mo / ZnO system (ZnO must be replaced no longer absorb S) Highly endothermic (226 kJ mol-1 for CH4) High purity of H2 (95%) high T, low P, high steam ratio (to avoid CH4 production) or higher P (28 bar) can be used Typical condition for reforming natural gas 10 bar steam /oil ratio of 3:1 T = 900C 10 cm diameter tubes space velocity of 2 000 (volume of H2 per hour per volume of catalyst)

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