Naphtha Hydrotreating Unit

Prepared by : Mohamed Fathy Mohamed

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Naphtha

Naphtha is a complex mixture of liquid hydrocarbons, with boiling ranges of about 38 to 205 C and with vapour pressures of about 0.69 bar. Crude distillation, catalytic cracking, delayed coking and visbreaking units produce naphtha with low octane number and contains deferent types of contaminants at the same time .

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Octane no. Improvement

As more demand for high Gasoline Octane no. to match with modern motor. Chemical structure modification is achieved on an expensive Platinum catalyst at Catalytic reforming and Isomerization unit. Sulfur, Nitrogen, Oxygen and other impurities in Naphtha work as a poisonous for Pt catalyst activity. Hydrotreating is used to prepare a clean feedstock to protect catalyst used in naphtha reforming.

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History of Naphtha Hydrotreating

1897 : Paul Sabatier, French chemist discovered the fixation of hydrogen on hydrocarbon (ethylene, benzene) double bonds using nickel containing catalyst. 1903 : Wilhelm Normann, German chemist applied catalytic hydrogenation to Saturate Organic acids. 1950's : First catalytic reforming process was commercialized. At the same time, the catalytic hydrodesulfurization of the naphtha feed to such reformers was also commercialized. Currently : All petroleum refineries world-wide have one or more HDS units.

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Straight Run Naphtha Catalytic cracking Naphtha. Delayed Coking Naphtha. Visbreaking Naphtha. FCC Naphtha

Naphtha Hydrotreating

Catalytic Reforming Unit Gasoline Light Naphtha Isomerization

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Catalytic Reforming Unit

Using expensive Platinium catalyst on chlorinated alumina. Dehydrogenation of Nahthenes , Dehydrocyclization & Isomerization of Paraffins.

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Light Naphtha Isomerization

Using Pt catalyst on highly chlorinated alumina. Isomerization of Pentane and Hexane

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Impurities Removal
Sulfur Removal Nitrogen Removal Oxygen Removal Metallic Compounds Unsaturated Products Halide Removal

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Sulfur Removal

Mercaptans: Sulfides: Disulfide: Cyclic sulfide:

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Sulfur Removal

Thiophenes:

Benzothiophenes: Dibenzothiophenes

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Sulfur Removal

Distribution of sulfur compounds in the cuts from distillation of a crude with 1.2%wt sulfur.

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Nitrogen Removal

Pyridines:

Quinoline:

Isoquinolines:

Pyrroles:

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Nitrogen Removal

Indoles:

Carbazoles:

Methylamine:

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Oxygen Removal

Phenols:

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Oxygen Removal

Naphthenic acids:

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Metallic Compounds
Impurities Ni,V As Hg NaCl Fe Si Pb Source
Crude Crude Crude Crude

Main Cut
Distillates Residues All Naphtha Residues

Catalyst Poison
Strong, deposit inside catalyst and plugging Strong, deposit at top of reactor Slight, only slightly retained Strong, deposit at top of reactor, generates pressure loss Slight, deposit at top of reactor, generates pressure loss Very slight, deposit inside catalyst and plugging Strong, deposit at top of bed

Maximum content (%wt)

10 0.2-2 Traces 1

Crude and corrosion Anti-foaming agents Recycled gasoline

All

Distillates Gasoline

0.1-0.5 5-10

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Unsaturated Products

Linear olefin:

Cyclic olefin:

Aromatics Saturation: the-main unsaturated compounds present in oil, The number of aromatic rings increases with the distillation temperature of the cut.

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Halide Removal

Organic halides can be decomposed in the Naphtha Hydrotreating Unit to the corresponding hydrogen halide, which is either absorbed in the reactor effluent water wash or taken overhead in the stripper gas.

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Hydrotreating Processes
The Naphtha Hydrotreating Process is : Catalytic refining process employing a selected catalyst and a hydrogen-rich gas stream Decompose organic sulfur, oxygen and nitrogen compounds contained in hydrocarbon fractions. In addition, hydrotreating removes Organometallic compounds and saturates olefinic compounds.

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Feeds and Products for Hydrotreating Unit

Straight Run Naphtha Off Gas to Amine Treat Coker Naphtha

FCC Naphtha

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LPG to Amine Treat

Light Naphtha to Isomerization

Hydrocracked Naphtha Visbreaking Naphtha

Heavy Naphtha to Platforming

Sour water to Water Stripper H2 Make up from CRU

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Hydrotreating Process
Product Condenser 02E-02 Feed Surge Drum 02V-01 Charge Heater 02H-01 T=301 oC Reactor 02-R-01 P=45.5 barg T=325 oC T=55 oC 02-K-01 T=50 oC P=10.4barg Separator 02V-02 HCK DCU CDU T=154 oC Stripper 02T-01 HP Steam Condensat e Recycle Gas Sour water to U15 T=120 oC R.C.Suction Drum 02-V-03 Stripper Condenser 02-E-05 Sour Gas To U-12 T=99 oC P=7.1 barg T=48 oC Stripper Receiver 02V-04

P=3.7 barg T=102 oC

T=343 oC Tank-0809

T=201 oC

Stripper Reboiler 02-E-04 Unit 03

P=52.3 barg T=77 oC Combined Feed Exchanger 02E-01

Makeup H2 Gas from CCR

Stripper Feed Bottom Exchanger 02-E03

T=86 oC Naphtha Splitter Condenser 03-E03

P=0.7 barg T=72 oC Naphtha Splitter 03-T-01

Naphtha Splitter Receiver 03-V-01

Sour Water to U15 P=1.9 barg T=124 oC Hydrotreated Light Naphtha

T=159 oC

T=148 oC Naphtha splitter feedBottom Exchange 03-E01 Hydrotreated Heavy Naphtha P=10.3 barg T=124 oC

Unit 02 Naph. Splitter. Bottom Cooler 03E-02

CCR Feed 51-TK-8

Naph. Splitter Reboiler Heater 03H-01

Naph. Splitter OV.HD Cooler 03E-04

51-TK-9

Penex Feed

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Hydrotreating Process
1.

Fixed Bed Reactor

Feed System Reactor System Wash Water System Separator System

Recycle Gas Fractionation section Stripper Section Naphtha Splitter Section

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Hydrotreating Process
2.

Fluidized Naphtha Hydrotreating

Maintain catalyst in its active form. Limited Applications due to its complicated design.

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Other Naphtha treating Units

MERCAPTAN OXIDATION MEROX.

Low operating cost and investment requirement. Ease of operation. Limited Mercaptan treating not less than 5ppm.

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Objectives of Hydrotreating Processes

Meeting finished product specifications Kerosene hydrotreating: a) Reduces mercaptans, sulfur, aromatics, b) Improves smoke point. Gas oil hydrotreating: a) Reduces sulfur, nitrogen, aromatics, olefins, b) Improves cetane number, thermal stability. Lube oil hydrofinishing: a) Reduces sulfur, Conradson carbon (CCR), b) Improves colour, oxidation stability.

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Objectives of Hydrotreating Processes

Preparing the feed for other refinery processes. Naphtha hydrotreating : is a pre-treatment for isomerization and catalytic reforming processes. The objective is to reduce sulfur, nitrogen (<0.5 ppm wt), and olefins (< 0.1% wt). Vacuum distillates: such as straight run, visbreaking, coking and deasphalted oil are hydrotreated as pre-treatment for FCC and hydrocrackers. Improves hydrogen content, crack ability, results increased conversion, reduced impurities in products, lower SOx and NOx emissions in gases exiting the regenerator.

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Hydrotreating Process

Distillate hydrotreating processes incorporated in a refinery flow scheme

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Hydrotreating Process

Typical operating conditions, for Distillate and Residue hydrodesulfurization.

Cut Point ,C 70 -180 160240 230-350 350-550 350+ 550+ Space velocity,hr-1 1.0 5.0 1.0 4.0 1.0 3.0 0.72 2.0 0.3 - 0.5 0.15 - 0.3 H2 Pressure, bar 14 28 35 55 100 - 130 120 - 160 Temperature at Start of Run 260-300 300-340 320-350 360-380 360-380 360-380 H2/HC ratio , nm3/m3 100 150 150-300 300-500 1000 1000

Petroleum Cut Naphtha Kerosene Gas Oil Vacuum Gas Oil Atmospheric residue Vacuum residue

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Hydrotreating Process

Hydrotreating Capacity Worldwide.

Regions United States Europe Asia/Pacific Rest of the world Total
> 200 No. of units

Capacity (Mt/year) 320 180 140 260 900

200 54 23

Naphtha

Residuals

VGO

Distillate

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Hydrotreating Process

Egypt has eight petroleum refining companies distributed around the country. In Cairo, Alexandria, Suez, Asyut and Tanta. Six of eight companies have constructed a naphtha hydrotreating unit.
Barrel/Day 35000 30000 25000 20000 15000 10000 5000 0 Midor Alexandria Suez Ameria Cairo Asyut

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Process Variables
Temperature Reactor Pressure Hydrogen to Hydrocarbon Ratio Space Velocity

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Temperature

The treating severity increases directly with temperature to decrease the content of sulfur, nitrogen, oxygen, and metallic compounds in the treated product. Factors affect selecting treating temperature: Feed Quality Changes. Changes in Feed Rate. Catalyst End-Of-Run. Maximum temperature catalyst can withstand , after this temprature , it will not give the required product quality .

a) b) c)

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Temperature

When operating at too high temperature for maximum sulfur removal. Recombination of hydrogen sulfide with small amounts of olefins can result, producing mercaptans in the product

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Reactor Pressure
1)

As the partial pressure of hydrogen increases: Rate of hydrogenation increases, the treating reactions are brought to a greater degree of completion. Catalyst is generally effective for a longer time owing to less formation of carbonaceous deposits which deactivate the catalyst activity.

2)

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Hydrogen to Hydrocarbon Ratio

1) 2)

Increasing the hydrogen charge rate: Increases the rates of hydrogenation reactions. Reduce the tendency of coke formation on the catalyst. Calculation:
Recycle Gas to Reactor (Nm3 /h) x H 2 Purity (Mole Fraction) H 2 /HC Naphtha Feed (m3 /h)

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Hydrogen to Hydrocarbon Ratio

Effect of injecting hydrogen between two catalyst beds

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Space Velocity

The severity of the operation is determined by the relative volumes of fresh feed and catalyst. Operating with low S.V. means low capacity of the unit, which has bad effect on flow distribution of feed in the catalyst bed with the result of higher rate of cake formation High S.V. will require increased temperature for the same reaction severity with the result of high coke formation. Calculation: volume of charge per hour (m 3 /h) S.V. volume of catalyst (m 3 )

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Reactions Kinetics

Relative reaction rates.

Desulfurization Olefin Saturation Denitrification 100 80 20

Relative heats of reaction.

Olefin Saturation Desulfurization Denitrification 100 20 2

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Reactions Kinetics
1)

Reaction Mechanisms for aliphatic Hydrocarbons. Elimination

2)

Substitution

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Reactions Kinetics
1)

Reaction Mechanisms for Aromatic Hydrocarbons. Hydro-desulfurization of dibenzothiophene

2)

Denitrogenation of Quinoline

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Catalyst of Naphtha Hydrotreating

Catalyst Protection, Aging and Poisonous. Catalyst sulfiding. Regenerating the Catalyst. Reactors Technology weight Average Catalytic Bed Temperature

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Catalyst of Naphtha Hydrotreating

Typical Composition of Hydrotreating Catalyst.

Species Cobalt Oxide Nickel Oxide Molybdenum Oxide Aluminium Oxide Range, wt% 15 1-5 6 25 Balance Typical, wt% 3 2.5 12 Balance

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Catalyst of Naphtha Hydrotreating

1) 2)

The primary causes of catalyst deactivation are: Rate of carbon deposition on the catalyst. The gradual accumulation of inorganic species picked up from the charge stock, ex: arsenic, lead, calcium, sodium, silicon and phosphorus

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Catalyst of Naphtha Hydrotreating

Catalyst sulfiding The active phase of hydrotreating catalysts is produced by sulfurizing the oxide form.

Reactions:

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Catalyst of Naphtha Hydrotreating

Catalyst Regenerating : Hydrotreating catalysts become deactivated with time mainly because of coke deposition Regeneration Reaction:

Lifetime of hydrotreating catalyst.

Petroleum Cut Gasoline/Kerosene Gas Oil, Vacuum Gas Oil Residue Life time , yrs 4 to 10 2 to 6 3 months to 1 year

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Catalyst of Naphtha Hydrotreating

Hydrotreating reactors and its internals :

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Catalyst of Naphtha Hydrotreating

Weight Average Catalytic Bed Temperature (WABT) :

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