Hydrotreating

Hydrotreating is a process to stabilize, remove

objectionable elements by reacting them with hydrogen j y g y g (do not change the boiling range) .
Stabilization - converting unsaturated hydrocarbons (olefins and diolefins) to paraffins. Element removed : sulfur, nitrogen, oxygen, halides, and trace metals. Aromatic reduction

Feedstocks: naphtha to reduced crude. Reactions are exothermic. Name exp: for S removal - hydrodesulfurization, or HDS.

Catalytic hydrodesulfurizer.

Process
Oil feed is mixed with hydrogen-rich gas and enters the top of the fixed-bed reactor. Reactions temperature range 260 427C to minimize cracking. 260427 C cracking Hydrogen reacts with the oil to produce hydrogen sulfide, ammonia, saturated hydrocarbons, and free metals. Metals remain on the surface of the catalyst and other products leave the reactor effluent stream. Reactor effluent is cooled before separating oil from hydrogen rich gas. Oil is stripped of remaining H2S and light ends in a stripper stripper. Gas may be treated to remove H2S and recycled to reactor.

HYDROTREATING CATALYSTS
Common catalyst: Nickel, Cobalt and molybdenum based oxides on alumina catalysts CoMo catalysts - selective for S removal NiCoMo or NiMo catalysts - selective for N removal, aromatic reduction Nitrogen is more difficult to remove than sulfur. C t l t activated by sulfidation: Catalysts ti t d b lfid ti
By presulfiding with carbon disulfide, mercaptans, or dimethyl sulfide before bringing up to reaction temperature; By injecting the sulfiding chemical into the oil feed during startup.

AROMATICS REDUCTION
PH2 -key parameter. Hydrogenation is an exothermic reaction. Equilibrium yields are favored by low temperatures. Reaction rates increase with temperature temperature. Compromise between using low reactor temperatures to achieve maximum reduction of aromatic content and a high temperature to give high reaction rates and a min amt of catalyst charge per barrel of feed. Maximum aromatic reduction 375385C. For a given P, the optimum T is a function of the types of aromatic p p y compounds in the feed and space velocity. Hydrogenation of tri- and di-aromatics are easier. Saturation of the final aromatic ring is difficult because of the resonance stabilization of the mono-aromatic ring.

Kinetic rate and thermodynamic equilibrium effects on aromatics reduction.

Reactions
The main hydrotreating reaction is hydrodesulfurization. Lower-boiling compounds are desulfurized more easily than higherboiling ones. ones The difficulty of S removal increases in the order paraffins, naphthenes, aromatics

Desulfurization: Thiols or Mercaptans: R-SH + H2 RH + H2S Sulfides: R-S-R + 2H2 2RH + H2S Disulfides: R S S R + 3H2 2RH 2H2S R-S-S-R Thiophenes: + 4H2 C4H10 + H2S
S

Reactions
Denitrogenation
Pyrrole:
N H

+ 4H2 C4H10 + NH3

Pyridine:
N

+ 5H2 C5H12 + NH3

Deoxidation

Phenol: C6H5OH + H2 C6H6 + H2O Peroxides: C7H13OOH + 3H2 C7H16 + 2H2O

Dehalogenation
Chlorides: RCl + H2 RH + HCl

Hydrogenation:
Pentene: C5H10 + H2 C5H12

Hydrocracking: C10H22 + H2 C4H10 C6H14

PROCESS VARIABLES
The principal operating variables: Temperature H d Hydrogen partial pressure ti l Space velocity Increasing T and H2 partial pressure increases S and N removal and H2 consumption. Increasing P increases hydrogen saturation and reduces coke formation. Increasing space velocity reduces X, H2 consumption, and coke formation. Excessive T must be avoided because of the increased coke formation.

Typical ranges of process variables in hydrotreating operations

Temperature : Pressure : H2, per unit of feed: Recycle: Consumption: Space velocity (LHSV) : 270 340 C 270340C 0.720.7 MPag (1003,000 psig)

360 m3/m3 36142 m3/m3 1.58.0

Catalytic Reforming
The main goal: to increase the octane number of motor gasolines. f t li In catalytic reforming, hydrocarbon molecular structures are rearranged to form higher-octane aromatics with only a minor amount of cracking.

Feedstock and Product

Typical feedstocks: heavy straight-run (HSR) gasolines and naphthas. heavy hydrocracker naphthas naphthas.

Paraffins Olefins Naphthenes Aromatics

Feedstock: Heavy Naphtha 45-55 % 02 0-2 % 30-40 % 5-10 %

Product: High Octane Gasoline: 30-50 % 0% 5 10 % 45-60 %

Catalytic Reforming
The ease and probability of these occurring increases with no. of carbon atoms in the molecules, therefore only the HSR gasoline is used for reformer feed. feed

C5-180F (C5-82C) > 180375F (82190C) > 400F (204C) Crack to butane and lighter fractions f ti Heavy naphtha (reformer feed) Easily hydrocracked and cause an excessive carbon laydown on the catalyst.

Reactions
There are 4 main reactions taking place during reforming: (1) Dehydrogenation of naphthenes to aromatics (2) Deh droc cli ation of paraffins to aromatics Dehydrocyclization (3) Isomerization (4) Hydrocracking Paraffins and naphthenes undergo two types of reactions in being converted to higher octane components: cyclization and isomerization. isomerization

Reactions
Desirable reactions lead to the formation of aromatics and
isoparaffins:

Isoparaffins (i) Paraffins (ii) Olefins (iii) Naphthenes (iv) Aromatics Naphthenes Paraffins Aromatics unchange Aromatics (i)

Reactions
Undesired reaction:
1. naphthenes & aromatics Dealkylation butane & lighter paraffins

2. paraffins & p naphthenes

Cracking

butane & lighter paraffins

1.Dehydrogenation
highly endothermic and have the highest reaction rates of the reforming reactions.
The major dehydrogenation reactions are: 1. Dehydrogenation of alkylcyclohexanes to aromatics: + 3H2 2. Dehydroisomerization of alkylcyclopentanes to aromatics: + 3H2 3. 3 Dehydrocyclization of paraffins to aromatics:

n-C7H16 All three reactions take place simultaneously.

+ 4H2

2. Isomerization
Rapid reactions with small heat effects to increase the un-isomerized materials. Isomerization of paraffins and cyclopentanes results in a lower octane product than does conversion t aromatics. d t th d i to ti 1. Isomerization of normal paraffins to isoparaffins:

2. Isomerization of alkylcyclopentanes to cyclohexanes, plus subsequent conversion t b i to benzene:

91 RON

83 RON

100 RON

10

3. Hydrocracking Reactions
Unwanted, led to production of lighter liquid and gas products. The major hydrocracking reactions involve the cracking and saturation of paraffins.
+ H2 +

decane

isohexane

n-butane

Hydrocracking yields are increased by: 1. High temperature 2. High pressure 3. Low space velocity

FEED PREPARATION
Active material in catalyst: platinum. Feed pretreatment: hydrotreating, hydrotreating
to remove metals, hydrogen sulfide, ammonia, and organic nitrogen and sulfur compounds that will deactivate the catalyst.

Hydrogen needed for the hydrotreater is obtained f bt i d from th catalytic reformer. the t l ti f

11

CATALYTIC REFORMING PROCESSES

Reforming processes are classified depending upon the frequency of catalyst regeneration. y p g Continuous : The catalyst is removed and replaced during normal operation. The catalyst can be regenerated continuously and maintained at a high activity. Need high capital costs. Semiregenerative : Minimum capital costs. Regeneration requires the unit to be taken off-stream every 3 to 24 months. High hydrogen recycle rates and operating pressures are utilized to minimize coke laydown and consequent loss of catalyst activity. C li : Ch Cyclic Cheaper th continuous b t more expensive th than ti but i than semigenerative. A swing reactor is used to replace an on-stream reactor once its catalyst activity drops to a point below the desired level. The catalyst in the replaced reactor is then regenerated by admitting hot air into the reactor to burn the carbon off the catalyst.

Semiregenerative Process
Typical of fixed-bed reactor reforming operations. The pretreated feed and recycle hydrogen are heated to 498524C before entering the first reactor. In the 1st reactor, the major reaction is the dehydrogenation of naphthenes to aromatics The endothermic reactions causes a large temperature drop. To maintain the reaction rate, the gases are reheated before being passed into the 2nd reactor. As the charge proceeds through the reactors, the reaction rates decrease and the reactors become larger, and the reheat needed becomes less. The effluent from the last reactor is cooled and liquid products condensed. The H2- rich gas is separated from the liquid p g p q phase in a separation drum. p The liquid from the separator is sent to a fractionator to be debutanized. The hydrogen-rich gas stream is split into a hydrogen recycle stream and a net hydrogen by-product which is used in hydrotreating or hydrocracking operations or as fuel.

12

Process Diagram

Catalytic reforming, semiregenerative process

An exp of a typical gas composition leaving each of the reactors in a four reactor system, with a HSR naphtha feed (180380F):

T i l reforming processes conditions: Typical f i diti pressures :50 to 350 psig (3452415 kPa) hydrogen charge ratios: 38 mol H2/mol feed Liquid hourly space velocities (LHSV) : 1 to 3 hr-1

13

Continuous catalyst regeneration catalytic reformer process

The sequence of flow of the reactants is similar to semiregenerative system except for the continuous catalyst regeneration steps. Fresh regenerated catalyst is introduced in the top of the upper reactor and flows by gravity from top to bottom. The reactants, naphtha are introduced on the outside of the outer cylinder and flow radially through the catalyst to the center of the inner cylinder. The reactant is reheated before discharging into the following reactors to maintain the kinetic rate. Partially aged catalyst is removed from the bottom of the lowest reactor and sent to an external regenerator In the regenerator, carbon is burned from the catalyst, and the catalyst is reduced and acidified before being returned to the upper reactor.

Continuous catalyst regeneration catalytic reformer

14

REFORMING CATALYST
The main catalyst: Pt/Al2O3 , Pt/SiO2-Al2O3 Sometimes, rhenium is used as a promoter, Pt-Re/Al2O3 Pt Re/Al a more stable catalyst, operation at lower pressures. Platinum - serve as a catalytic site for hydrogenation and dehydrogenation reactions Chlorinated alumina - acid site for isomerization, cyclization, and hydrocracking reactions. Catalyst deactivation - coke deposition and chloride loss. Regeneration - high temperature oxidation of the carbon followed by chlorination.

Typical fixed-bed downflow catalytic reformer

15

REACTOR DESIGN
Basic features of fixed-bed reactors used for semiregenerative and cyclic catalytic reforming. Very similar reactors are used for hydrotreating, isomerization, and hydrocracking. Internal refractory lining - to insulate the shell from the high reaction temperatures and thus reduce the required metal thickness. Vapor distributor to provide maximum contact time between reactants and catalyst, to prevent channeling and to maximize the use of the available catalyst volume. Thermowell to measure catalyst bed temperature for determining the catalyst activity and as an aid in coke burn-off operations. Inert ceramic spheres bed - 30 to 40 cm deep. To support catalyst pellet in the reactor. Metal parts exposed to the high temperature hydrogen atmosphere are constructed from steel containing at least 5% chromium and 0.5% molybdenum to resist hydrogen embrittlement.

ISOMERIZATION
To improve octane numbers of the LSR naphtha [C5-180 F (C5 82C)] isomerization [C5 180F (C5-82 C)] -isomerization process to convert normal paraffins to their isomers.
Reaction temperatures: 200400F (95205C) Catalyst: platinum on various bases.

16