Hydrotreating Unit

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Impurities: Origins and effects

2 Objectives of hydrotreating

3 Hydrotreating reaction

4 Hydrotreating catalyst

5 Operating variables

6 Process technology
2
 Impurities and their Origins
 Heteroatoms and Metals?
 Crude oil naturally contains impurities, particalarly sulfur, nitrogen, metals
such as nickel, iron and vanadium and sommes oxygen. These impurities are
an integral part of various heteroatomic compounds, whose nature and amount
depend greatly on the origins of the crude.
 In general, the impurities content increases after distillation from light cuts to
heavy cuts.

Arabian
Light
Crude
 Impurities and their Origins
 Heteroatoms
and Metals?

Non HC compounds:
Molecules contain
atoms other that C
and H.
 Impurities and their Origins
 Heteroatoms and Metals?
 Sulfur compounds: 0.04-6%wt
 Nitrogen compounds : 0.01- 1%kl
 Oxygen compounds : 0,1 - 0,5 %kl
 Metals:0,005-0,01 %wt
 Impurities and their Origins
 Sulfur compounds?

• Mercaptan R-S-H • Benzotiophene

• Sulfide R-S-R’
• Dibenzotiophene
• Disulfide R-S-S-R’
• Thiophene
• Naphta benzotiophen
 Impurities and their Origins
 Sulfur compounds?
Typical distribution of Sulfur Compounds in fractionations of CDU unit.
 Impurities and their Origins
 Nitrogen compounds?

Basic nitrogen compounds

Non-Basic nitrogen compounds

 Impurities and their Origins
 Oxygen compounds?

Acidic Oxygen compounds Non Acidic Oxygen compounds

 Impurities and their Origins
 Metals?
 Nickel, vanadium and iron are essentially
chelated in organometallic compounds
such as resins and asphaltenes and in
particular structures of the porphyrin
type pressnt in the heavy oil fraction.

 Other impurities are present in very small amounts, such as mercury

and arsenic in the form of alkyl-mercury and alkyl-arsenic
 Another type of impurities is sodium chloride, even though it is
usually removed by desalting
 Impurities and their Origins
 Unsaturated products?
 Aromatics.
 Polyaromatics
 Olefines, diolefines
 Impurities and their effects
 Metals?

Origin of impurities
and their effects on
hydrotreating
catalysts. Maximum
content on spent
catalysts
 Impurities and their effects
 Effects of sulfur compounds
• Sulfur compounds can lead to many disadvantages:
1. Pollution (acid rain);

2. Poison catalyst in refinery;

3. Corrosion directly (H2S, RSH);

4. Corrosion (SOx);

5. Decreased activity of three way catalyst;

6. Increased acidity of lubricant oil;

7. Increased pollutants in the exhaust gas;

8. Decreased heat value of fuel.

 Impurities and their effects
 Effects of sulfur compounds

Experimental result :
• [S]=0,06% wt → PM, soot : 2,1%*.
• [S]=0,85%wt → PM, soot :5,8% *.
• [S]=2,9% wt → PM, soot : 12,2% *.
* deposited on piston and segment
 Impurities and their effects
 Effects of nitrogen compounds
Basic nitrogen compounds

 Effects of oxygen compounds

Acidic Oxygen compounds
 Impurities and their effects
 Effects of unsaturated compounds

 Aromatics.
 Polyaromatics  Soot
 Olefines, diolefines  PM
 CONTENTS

1 Impurities: Origins and effects

2 Objectives of hydrotreating

3 Hydrotreating reaction

4 Hydrotreating catalyst

5 Operating variables

6 Process technology
17
 Objectives of hydrotreating

 Hydro-treating is a process to catalytically stabilize petroleum

products and/or remove impurities (sulfur, nitrogen, metal…)
from products or feed-stocks by reacting them with hydrogen;

 Stabilization usually involves converting unsaturated

hydrocarbons such as olefins and gum-forming unstable
dioleffins to paraffins.
 Objectives of hydrotreating

 Removing impurities, such as sulphur, nitrogen and oxygen

for the control of a final product specification or for the
preparation of feed for further processing;
 Removal of metals, usually in a separate guard catalytic
reactor when the organo-metallic compounds are hydrogenated
and decomposed, resulting in metal deposition on the catalyst
pores;
 Saturation of olefins, aromatic ring and their unstable
compounds.
 Objectives of hydrotreating

 Why?

Removal impurities from hydro-treated products shall help:

 To achieve the product specifications;

 To protect the catalysts in down stream processes;

 To achieve the environment aspects (SOx, PM, Soot).

 Objectives of hydrotreating

Ensure the quality of the finished products.

 Kerosene hydroteating:
• Reduces mercaptans, sulfur, aromatics
• Improve smoke point
 Gas oil hydroteating:
• Reduces sulfur, nitrogen, aromatics, olefins
• Improve cetane number, thermal stability
 Lube oil hydrofinishing:
• Reduces sulfur, Condrason Carbon Residue (CCR)
• Improve color, oxidation stability
 Objectives of hydrotreating

Prepare feeds for other refining processes.

 Pretreament of fluid catalytic cracking feed:
• Reduces sulfur, nitrogen, polyaromatics, olefins, metals (Ni, V)
and Condrason Carbon Residue (CCR)
• Improves hydrogen content, crackability
• Results increased conversion, reduced impurities in products.
 Pretreatment of hydrocracking feeds (or the first stage in the
hydrocracking processes):
• Reduces nitrogen (<10ppm) and aromatics content.
 Pretreatment of Naphtha for CR and ISOM:
• Reduces sulfur (<0.5ppmwt) and olefins (0.1%wt).
Location of hydrotreating units in an oil refinery
Location of hydrotreating units in an oil refinery
Location of hydrotreating units in an oil refinery

NSRP
 Feedstock of hydrotreating

 Hydro-treating is applied to a wide range of feedstock, from

naphtha to reduced crude.

Processes Feedstocks

Naphtha Hydrotreating Straight Run, Visbreaker, Coker

Kerosene Hydrotreating Straight Run Kerosene

Straight Run LGO, Visbreaker

Diesel Hydrotreating
LGO, FCC LCO, Coker LGO

Straight Run VGO, Coker Heavy

VGO Hydrotreating
Gas Oil, DAO
 Feedstock of hydrotreating
 Feeds ans products objectives for different kinds of hydrotreaters
Typical catalytic hydrotreating scheme