Petroleum and Gas Processing(TKK-2136) 16/17 Semester Petroleum and Gas Processing(TKK-2136) Instructor: Rama Oktavian Email: Oktavian.rama2@gmail.com Office Hr.: M.10-15, Tu. 08-12, W. 13-15, Th. 13-15, F. 09-11

Outlines 1. Catalytic reforming 2. Reformer configuration 3. Reformer material balance 4. Isomerization

Catalytic reforming

Catalytic reforming

Catalytic reforming Catalytic reforming process a catalytic process which converts low octane naphthenic into higher octane reformate products. It is a highly endothermic process requiring large amounts of energy. the process of transforming C7–C10 hydrocarbons with low octane numbers to aromatics and iso-paraffins which have high octane numbers gasoline blending and aromatic rich reformate for aromatic production

Catalytic reforming Catalytic reforming chemistry

Catalytic reforming Reformer feed characterization

Catalytic reforming FEED PRODUCT Paraffins 30-70 30-50 Olefins 0-2 Reformer feed and product characterization FEED PRODUCT Paraffins 30-70 30-50 Olefins 0-2 Naphthenes 20-60 0-3 Aromatics 7-20 45-60

Catalytic reforming Research Octane Number (RON) the percentage by volume of iso-octane in a mixture of iso-octane and n-heptane

Catalytic reforming Role of reformer

Catalytic reforming Role of reformer The catalytic reformer is one of the major units for gasoline production in refineries. It can produce 37 wt% of the total gasoline pool. Other units - fluid catalytic cracker (FCC) - alkylation unit - isomerization unit

Catalytic reforming Reforming reaction Naphthene Dehydrogenation of Cyclohexanes Paraffin Dehydrogenation Dehydrocyclization Isomerization Hydrocracking Reactions Coke Deposition Reforming reaction network

Catalytic reforming Calculating dehydrogenation reaction

Catalytic reforming Reforming reaction Naphthene Dehydrogenation of Cyclohexanes Paraffin Dehydrogenation Dehydrocyclization Isomerization Hydrocracking Reactions Coke Deposition

Catalytic reforming Process step in catalytic reforming Feed preparation: Naphtha Hydrotreatment removal of the various catalyst poisons - sulfur, nitrogen, halogens, oxygen, water, olefins, di olefins, arsenic and other metals

Catalytic reforming Process step in catalytic reforming 2. Preheating: Temperature Control 3. Catalytic Reforming and Catalyst Circulation and Regeneration incase of continuous reforming process 4. Product separation: Removal of gases and Reformate by fractional Distillation 5. Separation of aromatics in case of Aromatic production

Catalytic reforming Process step in catalytic reforming

Catalytic reforming Classification of process Semi-Regenerative Fixed Bed reactors Cyclic Fixed Bed Reformers - Adding an extra-reactor to avoid shutting down the whole unit during regeneration. Three reactors can be running while the forth is being regenerated Continuous Reformers

Catalytic reforming

Catalytic reforming

Catalytic reforming Classification of process Semi-Regenerative Fixed Bed reactors

Catalytic reforming Semi-Regenerative Fixed Bed reactors Reactions such as dehydrogenation of paraffins and naphthenes which are very rapid and highly endothermic first reactor

Catalytic reforming Semi-Regenerative Fixed Bed reactors Reactions that are considered rapid, such as paraffin isomerization and naphthens dehydroisomerization, give moderate temperature decline second reactor

Catalytic reforming Semi-Regenerative Fixed Bed reactors slow reactions such as dehydrocyclization and hydrocracking give low temperature decline. Third reactor

Catalytic reforming Classification of process Semi-Regenerative Fixed Bed reactors

Catalytic reforming Classification of process 3. Continuous Reformers Licensed by CCR Platforming UOP Process Process description The catalyst moves downwards by gravity from the first reactor (R1) to the forth reactor (R4) The catalyst is sent to the regenerator to burn off the coke and then sent back to the first reactor R1 The final product from R4 is sent to the stabilizer and gas recovery section Process variable operated at lower hydrogen partial pressure (PH2 = 3 bar) reformate yield gain of nearly 10 vol%

Catalytic reforming Classification of process 3. Continuous Reformers

Catalytic reforming Variable process Catalyst type – affect basic catalyst formulation (metal-acid loading), chloride level, platinum level, and activator level - The catalyst used for reforming is a bifunctional catalyst composed of platinum metal on chlorinated alumina Reaction temperature – control the reaction rate and product, usually operates at 560 C, above that temperature will form petroleum coke Space velocity – higher space velocity will decrease residence time and lower Octane number of product Reactor pressure – will affect to yield of product or hydrogen formation Hydrogen/Hydrocarbon ratio

Catalytic reforming Catalyst type The catalyst used for reforming is a bifunctional catalyst composed of platinum metal on chlorinated alumina. the centre for the dehydrogenation reaction Platinum an acidic site to promote structure changes - cyclization of paraffins - isomerization of the naphthenes. chlorinated alumina

Catalytic reforming Catalyst type Impurities that might cause deactivation or poisoning of the catalyst include: coke, sulphur, nitrogen, metals and water. The reformer should be operated at high temperature and low pressure to minimize coke deposition.

Catalytic reforming Process comparison

Catalytic reforming Calculating material balance in catalytic reformer Yield correlations for the reformer were developed as given

Catalytic reforming Calculating material balance in catalytic reformer Example Solution

Catalytic reforming Calculating material balance in catalytic reformer Solution

Isomerization Isomerization of Light Naphtha Isomerization is the process in which light straight chain paraffins of low RON (C6, C5 and C4) are transformed with proper catalyst into branched chains with the same carbon number and high octane numbers. Light naphtha from the hydrotreated naphtha (HTN) C5=80 ˚C is used as a feed to the isomerization unit.

Isomerization Isomerization reaction Isomerization is a reversible and slightly exothermic reaction: The conversion to iso-paraffin is not complete since the reaction is equilibrium conversion limited. It does not depend on pressure, but it can be increased by lowering the temperature. However operating at low temperatures will decrease the reaction rate. For this reason a very active catalyst must be used.

Isomerization Two types of isomerization catalysts The standard Pt/chlorinated alumina with high chlorine content The Pt/zeolite catalyst

Isomerization Standard isomerization catalysts This bi-functional nature catalyst consists of highly chlorinated alumina responsible for the acidic function of the catalyst. Platinum is deposited (0.3–0.5 wt%) on the alumina matrix. Platinum in the presence of hydrogen will prevent coke deposition, thus ensuring high catalyst activity. The reaction is performed at low temperature at about 130 ˚C to improve the equilibrium yield.

Isomerization Zeolite catalyst Zeolites are used to give an acidic function to the catalyst. Metallic particles of platinum are impregnated on the surface of zeolites and act as hydrogen transfer centres. The zeolite catalyst can resist impurities and does not require feed pretreatment, but it does have lower activity and thus the reaction must be performed at a higher temperature of 250 ˚C (482 F).

Isomerization Isomerization catalyst comparison

Isomerization Isomerization yield The reformate yield from light naphtha isomerization is usually very high (>97 wt%). Typical yields are given in Table

Isomerization Isomerization yield balance

Isomerization Solution Isomerization yields