Hydrotreating

By: Seyyed Rasoul Habiby Teacher`s name: Dr. Azin Islamic azad university

Introduction

The Chevron Lummus Global (CLG) Residuum Desulfurization (RDS) and Vacuum Residuum Desulfurization (VRDS) Hydrotreating processes are used by refiners to produce low-sulfur fuel oils, and to prepare feeds for vacuum gas oil (VGO) fluid catalytic crackers (FCCs), residuum FCCs (RFCCs), visbreakers, and delayed cokers. Over half of the fixedbed residuum hydrotreaters in operation use CLGs RDS/VRDS Hydrotreating technology. Hydrotreating refers to a relatively mild operation whose primary purpose is to saturate olefins and/or reduce the sulfur and/or nitrogen content (and not to change the boiling range) of the feed. Sulfur removal greater than 95 percent, metal removal (primarily nickel and vanadium) greater than 98 percent, nitrogen removal greater than 70 percent, carbon residue reduction

greater than 70 percent, and cracking of vacuum residue (538C+ material converted to 538C) as high as 60 liquid volume percent (LV%) have been commercially demonstrated.

Objectionable elements removed by hydrotreating

1-sulfur 2-nitrogen 3-oxygen 4-halides 5-trace metals 6-carbon residue 7-nickel 8-vanadium from the oil and cracking heavy VR molecules to VGO, distillates, and naphtha products.

HYDROTREATING FLOW DIAGRAMS

Simplified RDS/VRDS flow scheme.

HYDROTREATING CATALYSTS

Catalysts developed for hydrotreating include cobalt and molybdenum oxides on alumina, nickel oxide, nickel thiomolybdate, tungsten and nickel sulfides, and vanadium oxide.

Olefin Saturation

Although desulfurization is the most common of the reactions, olefin saturation also proceeds quite rapidly. Hydrogen is added to an olefin, and the corresponding saturated compound is the product. This reaction is quite fast and highly exothermic. If a significant quantity of olefins is present in the feed, the resulting heat release must be accounted for in the unit design. The ease with which this reaction takes place allows for operation at lower temperatures than the other hydrotreating reactions discussed in this section.

Aromatic Saturation

Aromatic saturation occurs according to the same principles as olefin saturation in that hydrogen is added to saturate the double bonds in the aromatic or benzene ring. The aromatic or benzene ring is a six-carbon atom ring that contains three double bonds. Because this ring structure is quite prominent in many of the materials found in the refinery, the symbol for this benzene ring is simplified and indicated as a hexagon with a circle inside. Because these aromatic-saturation reactions are highly exothermic, maintaining a proper temperature profile in the reactor is important. As the catalyst deactivates, the temperatures are raised to maintain conversion until end-of-run (EOR) conditions are approached. In the case of aromatic saturation, EOR occurs when the equilibrium no longer favors aromatic saturation.

AROMATICS REDUCTION

Hydrogen partial pressure is the most important parameter controlling aromatic saturation. Even the most difficult hydro dearomatizations can be achieved to levels of less than 10 vol% aromatics with nickeltungsten on gamma-alumina catalysts.

Kinetic rate and thermodynamic equilibrium effects on aromatics reduction

REACTIONS

Typical petroleum molecules that contain sulfur atoms.

Typical desulfurization reaction. Sulfur can usually be removed without having to saturate aromatic rings.

Typical petroleum molecules that contain nitrogen atoms. Nitrogen atoms usually have complex, aromatic bonds in petroleum.

Typical denitrification reaction. Nitrogen can seldom be removed without saturating aromatic rings.

Typical vanadyl-porphyrin molecule. Porphyrin structures are very flat and vanadium is easily removedif the molecules can diffuse through the catalysts pores.

Typical olefin saturation reactions.

Typical aromatic saturation reactions

PROCESS VARIABLES

The principal operating variables are temperature, hydrogen partial pressure, and space velocity.