Reforming • Introduction • Thermal Reforming • Catalytic Reforming ➢ Introduction ➢ History ➢ Feedstocks ➢ Reforming Reactions ➢ Reforming catalysts ➢ Deactivation and Regeneration ➢ Reforming Process Variables ➢ Process Flow Schemes ➢ Reformer correlations Catalytic Reforming Deactivation and Regeneration Deactivation forms:
poisoning, coking, and agglomeration of the platinum
Poisoning, is prevented or minimized by the naphtha hydrotreater:
➢ By removing N and S compounds ➢ By adsorbing metal poisons such as Si, As, and Pb. • Fe is a corrosion product, at higher Fe levels, ➢ Fe can plug catalyst pores and/or negatively impact the selectivity of the metal function leading to poorer yields.
• If the metal contaminants on the reforming catalyst become excessive, a catalyst change-out is required. Catalytic Reforming Deactivation and Regeneration Coking, When the coke is burned in the regeneration, ➢ if the Pt is not properly redispersed, ➢ some of the Pt will remain agglomerated. In an SR unit, • When does the catalyst become inactive? ➢ Temperature limit of the reforming unit will be reached, ➢ The selectivity to desired products is too much reduced, or ➢ The ON of the liquid product is decreasing. ➢ The refiner will shut down the SR process unit and regenerate the catalyst in all the reactor positions. In a cyclic unit, In a moving bed unit CCR, • when the coke becomes too high in a particular reactor position, • some of the catalyst is continually being regenerated ➢ A series of valves are switched outside the process and returned to the reactors ➢ Putting the deactivated reactor in a separate regeneration system. • ➢ high selectivity and activity ➢ A “swing” reactor is substituted for the deactivated reactor. Catalytic Reforming Deactivation and Regeneration Regeneration steps for all process units are very similar: 1. coke must be burned from the catalyst, 2. Pt must be well redispersed, 3. Pt must be reduced and sulfided, 4. alumina must be rechlorided to the correct acidity level. • For cyclic or continuous reformers, plant shutdown and start-up are unnecessary, ➢ the remaining steps are accomplished in separate regeneration equipment Catalytic Reforming Deactivation and Regeneration SR Regeneration - coke burning
• Heater temperatures and feed rates are reduced gradually.
• The circulation of recycle gas is continued to strip hydrocarbons from the catalyst, ➢ leaving only coke. • The combustion of coke to CO2 and H2O is exothermic, and ➢ O2 concentration must be kept low ➢ to limit the reaction and temperature rise.
• Excessive temperature can cause:
1. agglomeration of the platinum or, 2. change the desired alumina phase or crystal structure • H2O produced in the combustion also facilitates sintering (agglomeration) of platinum. Coke burning is usually done in the range of 400–500 ºC at O2 concentrations initially in the 1–2 mol% range. Catalytic Reforming Deactivation and Regeneration SR Regeneration - Pt redispersed & chloride to alumina •Halogen acid gas, oxygen, chlorine, and nitric oxide can be used as agents to redisperse Pt catalysts. ➢ dispersion agent: ensuring that almost all the Pt is exposed for reaction. ➢ For example: Platinum oxychlorides or chlorides ➢ Used as dispersion agent and adds chloride to the alumina support to enhance its acidity. Redispersion process typically involves four • Redispersion steps: steps: ➢ increasing temperature to ~ 500 ºC, (1)formation of redispersed Pt complexes ➢ O2 conc. ~ 5–6 mol%, and by the reaction of Pt atoms with dispersion agents; ➢ Injection dispersion agent (into the (2)dissociation and liberation of the complexes air/nitrogen stream) from agglomerated Pt clusters; ➢ For example: chlorine or an (3)migration and deposition of these species organic chloride that breaks on the support surface; and down to HCl and Cl2. (4)the reduction of the complexes to Pt clusters. Catalytic Reforming Deactivation and Regeneration SR Regeneration - reduction & sulfiding the catalyst Catalysts in their pure state are not selective enough to perform their required functions. To make them more selective and controllable, they must be presulfided.
Reduction step: “Platinum oxide is reduced to platinum metal”
➢ in a dry H2 atmosphere. ➢ temperatures > 350 ºC,
• Sulfiding step ➢ by injection of H2S or an organic sulfide into the unit at the end of reduction. ➢ Sulfiding is continued until the specified sulfur level is reached, or ➢ until sulfur is no longer adsorbed by the catalyst Catalytic Reforming Reforming Process Variables Major process variables: ➢ reactor pressure, ➢ reactor temperature, ➢ space velocity, ➢ H2/HC molar ratio (H2/oil ratio), and ➢ catalyst type Reactor pressure ➢ affects reformer yields, reactor temperature requirements, and catalyst stability. • operating pressures: 50–500 psig • As a feed passes through the heaters, reactors, and catalyst beds, the overall pressure drop can be: 50–60 psig. ➢ It is best to: - minimize the pressure drops in the unit as much as possible - operate all the reactors at a lower pressure. • lower pressure is: ➢ increased aromatic, H2, and reformate yields ➢ But: shorten the catalyst cycle because of the increased catalyst coking rate. Catalytic Reforming Reforming Process Variables Reactor temperature • The reactor temperatureis usually expressed as the weighted average inlet temperature (WAIT). ➢ WAIT: is the average of the inlet temperatures multiplied by T11 725ºF (385ºC) T12 700ºF (371ºC) the weight fraction of catalyst in each reactor. T13 680ºF (360ºC) ➢ WAIT for SR units: 490–525 ºC, CCR units: 525–540 ºC.
• Because the main reforming reactions are endothermic, WABT = 385*0.2 + 371*0.3 + 360*0.5 = ➢ a significant drop in temperature along the catalyst beds. 368.3ºC ➢ The drop is largest in the first reactor position due to naphthenes dehydrogenation. ➢ The drop is still substantial in the second reactor position but smaller.
• Weighted average bed temperature (WABT) which accounts for
the temperature drops. ➢ WABT: the summation of the weight fraction of catalyst in a bed multiplied by the average of the inlet and outlet bed temperatures. Catalytic Reforming Reforming Process Variables Hydrogen-to-hydrocarbon (H2/HC) ratio
H2/HC mole ratio is the ratio of moles of H2 in the recycle gas to moles of naphtha charged to the unit. • Recycle H2 is necessary to maintain catalyst life stability by: ➢ removing coke precursors (hydrogenation) from the catalyst. ➢ inhibits polymerization to coke. ➢ Higher ratio reduces the coking rate and increases stability with only a small effect on product quality or yields. ➢ Lower ratio can provide higher C5+
• The recycle gas is a mixture of H2 and light hydrocarbon gases, typically 75–92 mol% H2. • The ratio of total recycle gas to hydrocarbon. Catalytic Reforming Reforming Process Variables Space velocity
Space velocity: point to the residence time or time of contact between reactants and catalyst. • Liquid hourly space velocity (LHSV, h-1): is calculated by dividing the volume of naphtha feed per hour by the total volume of reforming catalyst in the reactors. ➢ The typical commercial LHSVs range from about 1 to 3 h-1. • Weight hourly space velocity (WHSV, h-1): is calculated by dividing the weight of naphtha feed per hour by the total weight of catalyst in the reactors.
➢ The greater the space velocity, the higher the temperature required to achieve a given product target. Catalytic Reforming Reforming Process Variables
• A particular catalyst is typically chosen to meet the yield, activity, and stability requirements of the refiner. ➢ by varying basic catalyst formulation, chloride level, platinum content, and the choice quantity of any additional metals.
• Differences in catalyst types can affect other process variables.
➢ For example, the required temperature to produce a given octane is directly related to the Catalyst selectivity: type of catalyst.
the amount of desired product that can be yielded from a given
feedstock. Catalytic Reforming Process Flow Schemes
Several commercial processes: • Platforming (UOP), • Powerforming (Exxon), • Magna- forming (Engelhard), • Catalytic reforming (IFP), • Rheniforming (Chevron), and • Ultra forming (Amoco) Catalytic Reforming Process Flow Schemes Fixed –bed SR reforming units
(A) : Furnace and reactor layout for fixed bed
reformer.
(B): Variation of temperature in the reactors.
(C): Variation in effluent compositions;
PO, initial Paraffins; NO, initial Napthenes and AO, intial Aromatics
• Cyclic fixed bed process is modified to avoid
shutting down the whole unit during regeneration. ➢ By add an extra-reactor Catalytic Reforming Process Flow Schemes Fixed-bed reactor c a. an internal refractory lining (insulation) b ➢ reduce the required metal thickness. • Metal parts exposed to the high temperature and H2 atmosphere, a ➢ steel containing at least 5% chromium and 0.5% molybdenum d ➢ to resist H2 embrittlement. b. Proper distribution of the inlet vapor is necessary ➢ to make maximum use of the available catalyst volume. c. Thermowell: Temperature sensors - measurement at a d. The catalyst pellets are supported on a bed minimum of three elevations in the catalyst bed of ceramic spheres ~ 30-40 cm deep. ➢ to determine catalyst activity and as an aid in coke burn- ➢ The spheres vary in size from about 25 off operations. mm on the bottom to about 9 mm on the top. • Good distribution of reactants at the reactor inlet and at the top of each subsequent catalyst bed ➢ is essential for optimum catalyst performance.
❖reactor inlet diffuser, or
❖top liquid distribution tray, or ❖reactant mixing device and redistribution tray, ❖as well as the reactor outlet device, or collector. Catalytic Reforming Process Flow Schemes
• Two types of fixed bed reactor:
axial reactor and radial reactor
• Axial reactors: simple internals, less costly
➢ used with pressure greater than 50 bar.
• Radial reactors operated at pressures lower than 25
bar. Catalytic Reforming Process Flow Schemes
Continuous catalyst regeneration
reduction zone before catalyst is entering 1st reactor lifted by N2 Catalytic Reforming Process Flow Schemes
Continuous catalyst regeneration
The IFP continuous reforming units - Institut Francais du Pe´trole - side by side, catalyst transfer through a conveying system with piping between reactors. Catalytic Reforming Process Flow Schemes
Continuous catalyst regeneration
Unit Improvements
• CCR reforming - caustic wash system
➢ to remove all Cl before venting to the atmosphere.
Caustic scrubber for vent gas treating
• UOP’s ChlorsorbTM process introduced in 1998 ➢ A unit is used to adsorb chloride from the regeneration tower vent gas and is then passed to the regeneration vessel as Cl on catalyst. ➢ This reduces the Cl injection requirements for Pt redispersion and chloriding ➢ removing Cl from the regenerator vent gas. ➢ remove more than 97% of chlorides, that it can meet between 1 and 30 vppm of total chlorides in the vent gas.
Chlorsorb system for vent gas treating
Catalytic Reforming Process Flow Schemes Process comparison and economics Operating conditions
ROI: is the net
income divided by the cost of an investment
Economic summary
Product yields for the SR and CCR Platforming units
Catalytic Reforming Reformer correlations Yield correlations for the reformer were developed as given in Table 11. If detailed analysis of the reformer feed is known, the feed conversion can be calculated from the conversion data for each class of compounds as shown in Tables 12 and 13. Naphthenes conversion to aromatics by dehydrogenation Reformer correlations
Paraffin conversion to aromatics by dehydrocyclization
RONF = research octane number of feed;
RONR = research octane number of reformate; C5+ vol% = volume percent of reformate yield; SCFB H2 = standard cubic foot of H2 produced/barrel of feed; K = characterization factor (TB)1/3/SG; TB = absolute mid-boiling of feed, ºR; SG = specific gravity of feed; N = napthenes vol % and A = aromatics vol %.
